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Toward Understanding Drug Incorporation and Delivery from Biocompatible Metal–Organic Frameworks in View of Cutaneous Administration
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  • Sara Rojas
    Sara Rojas
    Institut Lavoisier, CNRS UMR 8180, UVSQ, Université Paris-Saclay, 45, Avenue Des Etats Unis, 78035 Versailles Cedex, France
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    Orcidhttp://orcid.org/0000-0002-7874-2122
  • Isabel Colinet
    Isabel Colinet
    Institut Lavoisier, CNRS UMR 8180, UVSQ, Université Paris-Saclay, 45, Avenue Des Etats Unis, 78035 Versailles Cedex, France
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  • Denise Cunha
    Denise Cunha
    Institut Lavoisier, CNRS UMR 8180, UVSQ, Université Paris-Saclay, 45, Avenue Des Etats Unis, 78035 Versailles Cedex, France
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  • Tania Hidalgo
    Tania Hidalgo
    Institut Lavoisier, CNRS UMR 8180, UVSQ, Université Paris-Saclay, 45, Avenue Des Etats Unis, 78035 Versailles Cedex, France
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  • Fabrice Salles
    Fabrice Salles
    Institut Charles Gerhardt Montpellier, CNRS UMR 5253, UM, ENSCM, Place E. Bataillon, 34095 Montpellier Cedex 05, France
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    Orcidhttp://orcid.org/0000-0001-8069-533X
  • Christian Serre
    Christian Serre
    Institut Lavoisier, CNRS UMR 8180, UVSQ, Université Paris-Saclay, 45, Avenue Des Etats Unis, 78035 Versailles Cedex, France
    Institut des Matériaux Poreux de Paris, FRE 2000 CNRS Ecole Normale Supérieure, Ecole Supérieure de Physique et de Chimie Industrielles de Paris, PSL Research University, 24 rue Lhomond, 75005 Paris, France
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  • Nathalie Guillou
    Nathalie Guillou
    Institut Lavoisier, CNRS UMR 8180, UVSQ, Université Paris-Saclay, 45, Avenue Des Etats Unis, 78035 Versailles Cedex, France
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  • Patricia Horcajada*
    Patricia Horcajada
    Institut Lavoisier, CNRS UMR 8180, UVSQ, Université Paris-Saclay, 45, Avenue Des Etats Unis, 78035 Versailles Cedex, France
    IMDEA Energy, Avenue Ramón de la Sagra 3, 28935 Móstoles, Madrid, Spain
    *E-mail: [email protected]
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    Orcidhttp://orcid.org/0000-0002-6544-5911
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ACS Omega

Cite this: ACS Omega 2018, 3, 3, 2994–3003
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https://doi.org/10.1021/acsomega.8b00185
Published March 12, 2018

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Abstract

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Although metal–organic frameworks (MOFs) have widely demonstrated their convenient performances as drug-delivery systems, there is still work to do to fully understand the drug incorporation/delivery processes from these materials. In this work, a combined experimental and computational investigation of the main structural and physicochemical parameters driving drug adsorption/desorption kinetics was carried out. Two model drugs (aspirin and ibuprofen) and three water-stable, biocompatible MOFs (MIL-100(Fe), UiO-66(Zr), and MIL-127(Fe)) have been selected to obtain a variety of drug–matrix couples with different structural and physicochemical characteristics. This study evidenced that the drug-loading and drug-delivery processes are mainly governed by structural parameters (accessibility of the framework and drug volume) as well as the MOF/drug hydrophobic/hydrophilic balance. As a result, the delivery of the drug under simulated cutaneous conditions (aqueous media at 37 °C) demonstrated that these systems fulfill the requirements to be used as topical drug-delivery systems, such as released payload between 1 and 7 days. These results highlight the importance of the rational selection of MOFs, evidencing the effect of geometrical and chemical parameters of both the MOF and the drug on the drug adsorption and release.

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1. Introduction

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Once administered, therapeutic drugs should be in a concentration at which full efficacy is achieved with no associated side effects. (1) For that purpose, several drug-delivery systems (DDS) have been formulated and/or are being investigated for drug administration (e.g., intravenous, oral, nasal). (2,3) Among them, metal–organic frameworks (MOFs) have recently emerged as original promising DDS. (4−7) MOFs are crystalline solids based on metal ions subunits coordinated to organic polydentate ligands, leading to the formation of highly porous structures. (8) Their structural/chemical diversity and exceptional porosity (Brunauer–Emmett–Teller (BET) surface (SBET) up to 7000 m2·g–1) together with their amphiphilic internal microenvironment are thus well adapted to the adsorption of a large variety of guest molecules, including the therapeutic ones (e.g., drugs, cosmetics, biological gases, enzymes). (4,7,9)
Although MOFs have been extensively investigated for drug administration, (4,7,9,10) the large versatility of these solids makes it difficult to predict which is the best MOF material for a given drug molecule. Although the pore size, chemical composition, and stability of MOFs play an essential role in controlling the drug incorporation/delivery processes and the total cargo capacity, (10−13) studies focusing on the systematic understanding of the encapsulation and delivery processes using MOFs still remain very limited. To the best of our knowledge, only three works have focused on the understanding of the drug incorporation and delivery processes, which is crucial to improve and/or control their performances. In this regard, Maurin and co-workers have pioneered and reported a quantitative–structure activity relationship approach to predict the encapsulation rate as a function of the physicochemical properties of MOFs, validating this strategy using a series of functionalized porous flexible Fe(III) terephthalates (MIL-88B; MIL = Materials of Institut Lavoisier) (14) or functionalized rigid Zr(IV) terephthalates (UiO-66; UiO = University of Oslo) (15) and two model active ingredients (caffeine and ibuprofen). The drug uptake was analyzed as a function of the polarity, polarizability, and H-donor capacity of the functionalized organic linkers. Later, Serre and co-workers followed an experimental and computational strategy to rationalize the encapsulation and release of the cosmetic amphiphilic molecule, caffeine, highlighting the importance of the encapsulation conditions and the MOF topology and polarity on the drug uptake and delivery kinetics. (16) However, all of these works are focused on the influence of the MOF properties on the drug encapsulation, and the effect of the drug nature on the encapsulation and delivery is not systematically considered. So, there is no comparative study determining the main requirements/parameters of MOFs and drug to be considered for a suitable cutaneous MOF carrier. Thus, there is still a need to better understand the mechanisms of drug incorporation and delivery, particularly the influence of the drug properties on the drug sorption processes.
Taking this into account, we have selected two topical nonsteroidal anti-inflammatory and analgesic drugs, exhibiting different physicochemical properties: (i) acetylsalicylic acid (also known as aspirin, AAS) as a hydrophilic model cargo (log P = 1.19) and (ii) isobutylphenylpropanoic acid (or ibuprofen, IBU) as hydrophobic drug (log P = 3.97), to analyze, through a combined experimental and computational systematic study, how these features will affect the drug adsorption/desorption kinetics in MOF matrixes. Besides, the well-known and common gastric mucosal damage of these orally administered drugs, (17,18) together with their unquestioned value in the treatment of various symptoms (e.g., fever, pain) and inflammatory diseases (e.g., rheumatoid arthritis, pericarditis), shows that alternative formulations need to be undertaken. (17,19) In this regard, the simple and noninvasive cutaneous route is very convenient whether for a local (topical) or systemic (transdermal) administration. (20) We note here that the desired properties of MOFs for a cutaneous treatment significantly differ from those required for other administration routes (stability, delivery time, etc.). To date, MOFs have been mostly proposed for intravenous administration, (4) and only three works have been reported dealing with the potential use of MOFs in cutaneous applications. The first described the use of a NO-loaded Ni carboxylate CPO-27 with two different hydrocolloids (cellulose and polyisobutanol) for the topical (local) delivery of NO. (21) The second is the study of Ni-CPO-27 or HKUST(Cu) nanoparticles with poly(tetrafluoroethylene) patches for the local co-delivery of NO and an antibiotic (metronidazole). (22) Finally, Horcajada and co-workers have recently reported the skin bypass of the cosmetic caffeine by using cutaneous patches based on biocompatible MIL-100(Fe) nanoparticles associated with different biopolymers. (23) Therefore, to gain further fundamental understanding, we analyze here the performances of several MOF–drug systems for the cutaneous delivery of AAS and IBU. These results will be further compared to those of the previously published studies on caffeine-containing MIL-100, MIL-127, UiO-66, and MIL-53 solids. (16)
In addition to the MOFs and drug structural characteristics, hydrophobic/hydrophilic balance is another key parameter, taking into account that MOFs possess both a polar part (metal clusters) and a nonpolar fraction (aromatic ligands). Previous water sorption experiments provide an appropriate tool to probe the hydrophilic/hydrophobic properties of MOFs and their stability to moisture. (24,25) Hence, we have selected three MOF architectures with different hydrophilic/hydrophobic balance (Figure 1): (i) the more hydrophilic mesoporous MIL-100, (26) or [Fe3O(H2O)2OH(BTC)2]·nH2O (H3BTC = 1,3,5-benzenetricarboxylic acid or trimesic acid) based on iron(III) octahedra trimers and trimesate anions leading to a very high porosity (SBET ∼ 2000 m2·g–1, Vp ∼ 1.2 cm3·g–1), associated with two types of mesoporous cages (25 and 29 Å) accessible through microporous windows (ca. 4.8–5.8 and 8.6 Å, respectively); (27) (ii) the microporous hydrophilic/hydrophobic MIL-127 structure, or [Fe3O(OH)0.88Cl0.12(C16N2O8H6)1.5(H2O)3]·nH2O (SBET > 1200 m2·g–1, Vp ∼ 0.7 cm3·g–1) based on iron octahedra trimers and 3,3′,5,5′-azobenzenetetracarbozylate anions, associated with two types of pores, namely, an accessible hydrophobic one-dimensional (1D) channel system (∼6 Å) and more hydrophilic cages of ∼10 Å, accessible through narrow apertures of ∼3 Å; (28,29) and (iii) the microporous slightly hydrophobic UiO-66 solid or [Zr6O4(OH)4(BDC)6]·nH2O (H2BDC = 1,4-benzenedicarboxilic acid), (SBET ∼ 1200 m2·g–1, Vp ∼ 0.5 cm3·g–1) based on zirconium(IV) oxoclusters and terephthalate anions, possessing octahedral and tetrahedral cavities (∼ 11 and ∼8 Å, respectively) accessible through triangular micropores (ca. 5–7 Å). (30,31)

Figure 1

Figure 1. Schematic view of the structure of UiO-66, MIL-100, and MIL-127 (zirconium polyhedra, iron polyhedra, nitrogen, oxygen, and carbon are represented in cyan, green, blue, red, and gray, respectively; hydrogen atoms are omitted for clarity). Structures of AAS and IBU drugs are also given.

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2. Results and Discussion

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2.1. Drug Incorporation

The impregnation of the porous materials with ethanolic solutions of both drugs led in all cases to an efficient incorporation. The drug-loaded matrixes MIL-100@AAS, MIL-100@IBU, UiO-66@AAS, UiO-66@IBU, MIL-127@AAS, and MIL-127@IBU reached a maximum capacity after 24 h for all MOF–drug systems. X-ray powder diffraction (XRPD) patterns evidence that the drug-loading process does not alter the crystalline structure of the porous materials (Supporting Information (SI), Figure S6). In addition, the absence of Bragg peaks corresponding to free AAS or IBU rules out the presence of free recrystallized drug out of the pores.
The drug content, estimated by thermogravimetric analysis (TGA) and high-performance liquid chromatography (HPLC), was high regardless of the nature of the MOF (Table 1 and SI, Section 3). Remarkably, higher drug loadings were obtained for UiO-66, reaching up to 35.5 and 25.5 wt % for IBU and AAS, respectively, corresponding to 3.7 and 3.0 mol of drug per mol of material, with high efficiencies of ca. 92 and 75% (compared to the total drug available in the starting solution). This is particularly significant because MIL-100 and MIL-127 possess larger pore volumes than UiO-66 (Table 1). However, these results are in agreement with the previously obtained ones for the caffeine encapsulation, where the following classification from the highest to the lowest caffeine loading capacity was obtained: UiO-66 > MIL-100 > MIL-127. (16) Moreover, the high IBU loading capacity for UiO-66 supported the recently published results obtained using CD-MOF-1 and the porous carbon derived from MOF PCDM-1000 (35.5 vs 26 and 32 wt %, respectively). (32,33) Finally, increasing initial drug concentrations and/or successive impregnations did not lead to any improvement in the drug capacity.
Table 1. Textural Properties of MOFs before and after Drug Adsorption Processa
  before encapsulationafter drug encapsulation  
MOFdrugVp (cm3·g–1)SBET (m2·g–1)Vp (cm3·g–1)SBET (m2·g–1)drug wt % (mol·mol–1)drug occupancy volume (A3·molecule–1)
MIL-100IBU1.4219400.3450930.6 ± 0.9 (1.0)1078 (474)b
AAS0.57107224.8 ± 0.8 (1.0)763 (336)b
UiO-66IBU0.6413490.1238335.5 ± 3.2 (3.7)347
AAS0.3272425.5 ± 3.7 (3.0)199
MIL-127IBU0.4713040.0910513.6 ± 0.7 (0.5)1272 (250)b
AAS0.378364.4 ± 0.6 (0.2)1224 (241)b
a

Total drug loading (wt % and mol·mol–1) and estimated occupancy volume of a single drug molecule (A3·molecule–1).

b

Estimated considering a selective occupation of the porosity.

The incorporation of AAS and IBU into the MIL-100, UiO-66, and MIL-127 cavities was further demonstrated by the dramatic reduction of the N2 sorption capacity of the MOFs (SI, Section 4, Figure S8). In this regard, to shed some light on the influence of porosity on drug adsorption, we have estimated the volume occupied by one drug molecule inside the MOF by taking into account the variation of the MOF pore volume after the drug encapsulation and the total amount of loaded drug (SI, Section 4, eq 1). The larger occupancy volume of both drugs in MIL-100 and MIL-127 (IBU: 1078 and 797 Å3, AAS: 1522 and 1438 Å3, respectively) compared to the free drug molecular volume (∼372 and 155 Å3 for IBU and AAS, respectively, as estimated under vacuum by ChemDraw) might be due to the partial occupancy of the porosity, as confirmed by the important remaining porosity after drug insertion (Table 1). This could be related to a selective adsorption of the drug that might occur only within the larger cages of MIL-100 (accessible via hexagonal windows of ∼8.6 Å) and the channels of MIL-127 (∼6 Å). In contrast, the dimensions of both IBU (11.0 × 5.0 × 4.3 Å3) and AAS (7.8 × 5.8 × 2.3 Å3) might prevent their loading into the smaller cages of MIL-100 (exclusively accessible by pentagonal windows of ca. 4.8–5.8 Å) and the hydrophilic cages of MIL-127, accessible through apertures of ∼3 Å (note that van der Waals radius has been considered).
Furthermore, in the case of MIL-100, it is known that ethanol (used as solvent in the impregnation) can bind the coordinatively unsaturated iron(III) metal sites (CUS), pointing to the center of the window, then considerably reducing the free diameter of the hexagonal (from 8.2 to 4.1 Å) and pentagonal (from 4.5 to 1.7 Å) windows, and therefore, drastically reducing the diffusion of the drugs into the pores, particularly into the smaller cages. (34) This suggests the absence of any encapsulation within the smaller cage of MIL-100, in agreement with the selective location of IBU within the larger cages of MIL-100(Cr), as previously proposed. (10) We note here the similar IBU uptake of the Cr-based MIL-100 and its iron-based analogue (35 vs 31 wt %), ruling out any significant influence of the metal on the drug adsorption process. Thus, excluding the drug adsorption within the smaller pores, this gives a more realistic volume of the MIL-100 occupied by IBU or AAS (44%), corresponding to drug occupancy volumes of 474 and 336 Å3.
A theoretical maximum loading was estimated by assuming a selective adsorption within the larger cavities of MIL-100. Such predictions, corresponding to 1.0 (IBU) and 1.6 (AAS) mol·mol–1, illustrate two different situations: in the case of IBU the maximal capacity is reached (1 mol·mol–1), whereas it is not the case for MIL-100@AAS (1.6 vs 1.0 mol·mol–1). Lin et al. (35) have recently reported an exceptionally high loading of 1.8 g of AAS per gram of MIL-100 (6.5 mol·mol–1) with however a residual porosity of 64% after encapsulation. This high residual porosity (SBET = 1141 m2·g–1, Vp = 0.62 cm3·g–1), in agreement with a partial occupation of the MIL-100 porosity, was however not consistent with the location of the drug exclusively within the pores. Even considering a full occupancy of both cavities, the maximum theoretical amount of encapsulated AAS in MIL-100 shall indeed not exceed 1.09 g·g–1 (3.9 mmol·mol–1). In addition, drug estimation from Lin’s TGA fits better with a lower “more realistic” encapsulation rate of around 21.0 wt % (ca. 40 wt loss % corresponding to both AAS and linker), in line with our results (25.5 wt %).
Similarly to MIL-100, one could expect a selective adsorption of the drug within the microporous channels of MIL-127. Here, only ca. 19% of the total free volume can be occupied by IBU and AAS, which corresponds to occupancy volumes of 250 and 241 Å3, respectively, which is also, on the whole, in agreement with the free drug volumes (∼372 and 155 Å3, respectively).
Estimating the theoretical maximum loading by assuming a selective adsorption within the channels, we find that the theoretical maximum AAS cargo is higher than the experimental data (1.01 vs 0.27 mol·mol–1), suggesting that the maximum drug capacity is not reached. On the other hand, the experimental data of IBU adsorption (0.5 mol·mol–1) fit well with the theoretical data of IBU cargo (0.42 mol·mol–1). We note here that IBU seems to occupy a lower volume when encapsulated in MIL-127 than in the free state, suggesting an improved packing probably due to the formation of weak interactions between drug molecules and the ABTC ligand.
Finally, both UiO-66@IBU and UiO-66@AAS solids keep a significant residual porosity (383 and 735 m2·g–1, respectively). We note that octahedral and tetrahedral cavities in UiO-66 are accessible through a unique type of windows, which favors a higher loading than that in MIL-100 or MIL-127. Moreover, the presence of functional groups on the benzene ring of AAS or IBU (ester, carboxylic acids, and an alkyl side chain) might lead to various weak interactions (e.g., hydrogen bonding, van der Waals, π–π staking) within the pores of UiO-66, which may further enhance their loading into the pores. This should also explain the difference between the free AAS molecular volume (155 Å3) and that inside the UiO-66 framework (199 Å3) consistent with a more efficient AAS packing to minimize free volume. As an intermediate conclusion, although the pore volume and surface area of MOFs as well as the nature of solvent (see below) used for the encapsulation are key parameters to drive the encapsulation capacity, one has also to consider the correlation between the size and shape of both the pores and the drug to determine whether the drug can be adsorbed and to which extent.
Apart from these important geometrical parameters, other factors such as the chemical nature of both the MOF and the drug strongly influence the drug loading. As previously mentioned, despite the general amphiphilic character of MIL-100, MIL-127, and UiO-66 solids, one could comparatively propose the following order from the more hydrophilic to the more hydrophobic material: MIL-100 > MIL-127 > UiO-66. Thus, in the case of UiO-66 and MIL-127, we observe an influence of the hydrophilic/hydrophobic balance of the matrix: the lipophilic IBU (3.7 and 0.5 mol·mol–1, respectively) is retained higher than the hydrophilic AAS (3.0 and 1.0 mol·mol–1, respectively). In contrast, the drug uptake in the hydrophilic MIL-100 matrix does not depend on the differences of polarity of these drugs because both molecules are similarly adsorbed (1.0 mol·mol–1 in both cases). Structural reasons may explain these results. The larger cage in the MIL-100 framework, in which the drug adsorption process preferentially occurs, might be large enough to allow interaction with both the hydrophobic (linker) and hydrophilic (metal trimers) parts of the pores, regardless of the nature of the cargo. These results are in agreement with the exceptional ability of this MOF to adsorb molecules bearing very different polarities (e.g., IBU (hydrophobic); caffeine and busulfan (amphiphilic); RAPTA-C, urea, and phosphorylated nucleoside analogues (hydrophilic); etc.). (36,37)
To gain further understanding of the drug adsorption process, we studied in detail the solid–liquid adsorption isotherms (at 25 °C) of IBU (hydrophobic) and AAS (hydrophilic) in the materials showing an extreme hydrophobic/hydrophilic nature: MIL-100 (hydrophilic) and UiO-66 (hydrophobic) (Figure 2). A relatively fast drug uptake was observed in all cases, with a maximum drug loading reached after ∼6 and 24 h for UiO-66 and MIL-100, respectively. In the case of UiO-66, loadings higher than ca. 24 wt % are even obtained during the first hour, corresponding to 97% (IBU) and 77% (AAS) of its total drug capacity. We note that the drug incorporation process in MIL-100 is prolonged, with loading rates of ca. 14% during the first 3 h, which corresponds to total drug capacities of 53% (IBU) and 56% (AAS).

Figure 2

Figure 2. IBU (hydrophobic) and AAS (hydrophilic) encapsulation kinetics in MIL-100 (hydrophilic) and UiO-66 (hydrophobic) matrixes. Adjustment of the drug adsorption data to a zero-order kinetic equation, with different zero-order kinetic constants (K), regression factors (R2), and total drug loadings (wt %).

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The data obtained after 1 or 3 h (UiO-66 and MIL-100, respectively) can be empirically adjusted to a zero-order kinetics (Figure 2, eq 2), where [drug] is the concentration of the drug into the ethanolic solution (M) at equilibrium and at the time t (h) and K is the zero-order kinetic constant (M·h–1). By estimating the K values, we confirmed a drug adsorption process more than 6 times faster in UiO-66 than in MIL-100, consistent with a better drug–MOF affinity. Differences in terms of pore accessibility might be at the origin of these differences. As previously mentioned, AAS and IBU fit in both octahedral and tetrahedral cavities of UiO-66, but not into the smaller cages of MIL-100. In addition, the ethanol molecules considerably reduce the accessibility of the hexagonal windows in MIL-100, through coordination on the iron metal sites pointing at the center of the windows, leading to a slower diffusion of the drug, as seen before with caffeine in MIL-100. (16) Moreover, as previously studied in the use of MOFs for the separation of racemic mixtures of (±)-IBU, (38,39) one expects here host–guest interactions associated with the presence of −CO2H or C═O moieties from the drugs able to interact with the hexameric or trimeric oxoclusters of the hybrid solids. Indeed, the 13C NMR spectra of the MIL-100(Cr)@IBU analogue showed previously the possible coordination of IBU to the MIL-100 structure. (6) Fourier transform infrared (FTIR) spectra of both drug-loaded materials confirmed a shift in the wavelengths in comparison to the pure AAS and IBU, characteristic of the ν(C═O) groups, suggesting the formation of interactions between drugs moieties and the hybrid framework (SI, Section 5, Figure S9 and Table S2). These results are in agreement with those previously published for the caffeine loaded MIL-100, UiO-66, and MIL-127, where a shift in the wavelengths of the ν(C═O) groups of caffeine was also observed. (16) Molecular simulations confirm such results when the configurations of the drugs are extracted (see Figure S16). In fact, interactions of C═O from AAS can be observed as predominant in UiO-66. All of these results evidence the importance of the selection of the right MOF (pores and windows dimensions) to be used as DDS.
When one considers the configuration of the AAS adsorbed in MIL-127, the main interactions are between the C═O of the drug and coordinated water molecules. This is in agreement with the saturation of metal centers with water molecules. However, in the case of IBU-loaded material, the benzene rings of the drug mainly interact with the N═N moieties of the framework (see Figure S17). In contrast to MIL-100, π-stacking is not observed here due to the smaller pore size of MIL-127.
In conclusion, drug–matrix interactions are rather weak here. It should be noted however that our simulations do not take into account any possible coordination of the metal sites, as suggested before for MIL-100(Cr) and IBU, or the impact of the solvent, which certainly affects the nature of the drug–matrix interactions.

2.2. Drug Release

Once the porous matrixes were loaded, we evaluated their ability to deliver AAS or IBU to consider them as topical DDS. The delivery of the cargoes was performed in distilled water at 37 °C, under continuous bidimensional stirring, to evaluate a potential cutaneous administration, mimicking the hydration of a cutaneous patch to evaluate and compare the delivery kinetics of these solids as a function of their features. In addition, the high stability of these MOFs might rule out any impact of the MOF degradation on the release profiles, thus allowing a better understanding of the effect of other parameters (polarity, interactions, etc.). To confirm the stability of the MOF matrixes, the leaching of ligands to the water medium was further monitored by HPLC (Figure S10), confirming the stability of all MOFs (<2%). In particular, only 1.65, 1.02, and 0.04% of degradation were observed for UiO-66, MIL-100, and MIL-127, respectively, after 3 days, which could also correspond to the release of residual free linker initially trapped in the pores of these MOFs.
The release kinetics were determined by quantifying the amount of delivered drug in the medium by HPLC as a function of time (Figure 3). According to the drug-release profiles, the MOF–drug systems can be divided into two groups: a complete and fast release for MIL-100@IBU, MIL-100@AAS, and UiO-66@AAS, against a partial and slower release for MIL-127@AAS, MIL-127@IBU, and UiO-66@IBU (Figure 3). In particular, and considering its high aqueous stability, the slow and sustained cargo release from MIL-127 is probably governed by the slow diffusion of the drugs through its 1D channels. We note that the total amounts of released drug are only 48 ± 2% (IBU) and 37 ± 2% (AAS) after 1 day of release. In the case of MIL-100, both drugs are released faster regardless of the nature of the cargo (hydrophilic or hydrophobic). In 1 day, MIL-100 progressively releases almost the total amount of both drugs (99 ± 1 and 84 ± 5% of the total amount of AAS and IBU, respectively). This is likely due to the larger pores (windows, cages) facilitating the diffusion of the drugs, although direct coordination of these drugs on the metal sites is likely to occur in MIL-100, as said before. In the case of UiO-66, the delivery seems more influenced by the degree of hydrophobicity of the adsorbate because a significant difference between the delivery of AAS and IBU is observed. After 1 day, UiO-66@AAS releases indeed 96 ± 2% of the total AAS amount, whereas only 46 ± 2% of its cargo is delivered from UiO-66@IBU. The concomitant hydrophobicities of UiO-66 and IBU probably lead to even slower water diffusion into the porosity and, subsequently, a slower release of the drug. In contrast, the hydrophilic AAS molecule leads to faster delivery, similar to the one observed in MIL-100.

Figure 3

Figure 3. AAS and IBU released from the different MOFs under simulated cutaneous conditions (aqueous media at 37 °C).

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As a whole, one can conclude that the drug delivery in water is mainly governed by the drug hydrophobic/hydrophilic balance as well as the accessibility of the pores as highlighted here: (i) the more hydrophilic MIL-100 with very large interconnected cavities, in which the delivery process is mainly governed by the very open character of the structure (fast delivery); (ii) the hydrophobic/hydrophilic environment of MIL-127 together with narrow 1D channels (slow delivery), and finally, (iii) the more hydrophobic UiO-66 matrix with interconnected microporous cavities, leading to rather different rates of delivery, depending on the hydrophobic/hydrophilic nature of the cargo
Furthermore, the possible clinical translation of these MOF@drug systems as cutaneous DDS requires considering the total time and the total amount of the released drug. As mentioned before, specific features, differing from other administration routes, are desired for DDS for cutaneous route. In this regard, cutaneous systems are designed normally to deliver drugs from 1 to 7 days. (40) In this regard, some examples of other materials (silicon microneedles, mesoporous silica) have shown promising results in the dermal delivery of bioactive compounds (nonviral gene, methotrexate anticancer drug) for 24 h. (41,42) The total amounts of AAS and IBU are released from MIL-100 within 1 and 4 days, respectively (Figure S11), being of interest for the topical and/or transdermal administration of analgesic and anti-inflammatory drugs. As previously mentioned, nanoscale MIL-100 combined with different biopolymers has been recently reported for its use as cutaneous patches for the delivery of caffeine, evidencing a successful drug skin bypass dependent on the nature of the biopolymer. (23) We note here that IBU was released from this composite patch in a similar way to the micrometric pure MIL-100 (e.g., 40% of IBU is released in 3 h), suggesting that the release from the patch is mainly controlled by the MOF. UiO-66-loaded materials released 96 ± 2 and 81 ± 6% of the total AAS and IBU cargo in 1 and 7 days, respectively, and the MIL-127@IBU and MIL-127@AAS delivered 92 ± 5 and 61 ± 4% of the drug in 4 and 6 days, respectively. So, besides being biocompatible and highly stable, (43−45) MIL-100, UiO-66, and MIL-127 materials are good candidates as cutaneous DDS.
The release profiles in play here lie within the same range when further compared to previous delivery studies of AAS and/or IBU from Fe-CPO-27@IBU (100%, 4 days, phosphate-buffered saline (PBS)), (46) MIL-100(Cr)@IBU (100%, 3 days, simulated body fluid (SBF)), MIL-101(Cr)@IBU (100%, 6 days, SBF), (10) MIL-100(Fe)@AAS (33%, 10 days, PBS; 2%, 7 days, pH 1.2), (35) or Zn3(BTC)2@IBU (34%, 1 day, PBS), (47) except for the flexible MOFs, in which much longer delivery times were observed: MIL-53(Cr)@IBU (100%, 18 days, SBF) and MIL-53(Fe)@IBU (100%, 20 days, SBF). (48) However, as most of the studies described in the literature were performed under different conditions (e.g., simulated gastric conditions (pH 1.2) or intravenous conditions (e.g., PBS, SBF)), a direct comparison is not possible because it is known that the composition of the media (e.g., ions, proteins) strongly affects the drug release kinetics.
On the basis of the previous drug-delivery results obtained with the amphiphilic cosmetic caffeine and the ones obtained here for the AAS and IBU, we can further see the influence of the nature of the active pharmaceutical ingredient on the delivery process. In this regard, when one considers studies dealing with the delivery of caffeine from MIL-100, UiO-66, and MIL-127 in water at 37 °C, similar results (from fast to slow release: MIL-100 ≥ UiO-66 ≥ MIL-127) were obtained. (16) This indicates that the delivery from MIL-100 and MIL-127 is less affected by the hydrophilic/hydrophobic balance of the adsorbate, whereas in the cases of UiO-66, the nature of the adsorbate molecule strongly determines its interaction with the matrix and, consequently, its release. When comparing all studied drugs in the case of UiO-66, the release rate can indeed be classified as follows (from the faster to the slower): AAS (hydrophilic, 1 day) > caffeine (amphiphilic, 2 days) ≫ IBU (hydrophobic, 7 days).
To shed some light on the release kinetics and to gain further understanding on the involved mechanism, the first hours of delivery (up to 1 h for AAS and 6 h for IBU) were fitted to a mathematical model. In particular, the Higuchi model, which defines the short time behavior of the release of a dispersed drug from a homogeneous matrix, (49) has been used to describe the diffusion of drugs from porous materials. (6,50,51) This commonly used equation perfectly describes release processes through which the drug is dispersed in stable monolithic systems (with no changes during the release process, which is the case when using these aqueous stable MOFs), being the release purely controlled by diffusion. (49,52) Considering that the external diffusion process around the MOF particles is minimized by continuous stirring during the delivery assay, the desorption process is only due to the drug movements through the pores of the frameworks. Therefore, the AAS and IBU delivery from the studied matrixes can be explained by the following equation
(1)
where [drug] corresponds to the concentration of released drug (mg·g–1), t is the time (h), and K is the kinetic constant (g·mg–1·h–1/2).
Except for MIL-127@IBU, with regression factor (R2) value slightly below 0.99, the rest of the drug releases can be empirically adjusted in the first hour (AAS) and the sixth hour (IBU) to the Higuchi model with R2 > 0.99 (Table 2; Figure S12). Therefore, the drug release is here mainly governed by a diffusion process, predictable by the Higuchi model and dependent on several factors such as the structure (dimensionality, interconnectivity, pore size) and composition (polarity, interactions). The initial delivery rate can be easily compared by estimating the constant diffusion coefficients (Table 2), observing the following classification from the faster to the slower initial release kinetics: UiO-66@AAS > MIL-100@AAS ≫ MIL-100@IBU ≫ UiO-66@IBU ≫> MIL-127@IBU ≫> MIL-127@AAS. In addition, kinetic constants associated with the IBU delivery are always lower than those of AAS, in agreement with the hydrophobicity of IBU.
Table 2. Release Kinetics Including the Kinetic Model Used in the Data Fitting, the Kinetics Constant of Release, the Total Release Time, and the Total Drug Releasea
 drug
 AASIBU
materialkinetic modelbk (mg·g–1·h–1/2)release time (days) and delivered drug (%)kinetic modelbk (mg·g–1·h–1) or (mg·g–1·h–1/2)release time (days) and delivered drug (%)
MIL-100H81.21 (99 ± 1%)H53.24 (100 ± 2%)
UiO-66H94.71 (96 ± 2%)H29.27 (81 ± 6%)
MIL-127H2.646 (61 ± 4%)05.044 (92 ± 5%)
a

Comparison of the results obtained in this study in the delivery of IBU and AAS.

b

H = Higuchi model; 0 = zero-order kinetics.

In the particular case of MIL-127@IBU, a better fit can be obtained by using a zero-order kinetic
(2)
where [drug] corresponds to the concentration of released drug (mg·g–1), t is the time (h), and K is the kinetic constant (g·mg–1·h–1, Figure S12). This means that the release process takes place at a constant rate, regardless of the remaining drug concentration, with an incomplete release of 92%. Therefore, it can be assumed that MIL-127 leads to a well-controlled drug release, which might be associated to a good control of drug concentration and higher efficacy.
Taking into account that optimal cutaneous systems are designed to deliver drugs from 1 to 7 days, the structural stability of the obtained matrixes after 3 days of delivery (denoted as MOF@drug_del) and the evaluation of the residual amount of drug were studied by XRPD, FTIR, TGA, and N2 sorption measurements. In the MIL-100 materials after drug delivery, the absence of vibrational bands at around 1697 and 1694 cm–1, characteristic of the (C═O) groups of AAS and IBU, respectively, confirms the complete release of both drugs (Figure S13). These results are in agreement with the TGA, exhibiting a similar composition to the starting material considering 1% of matrix degradation (Figures S10 and S14, Table S3). The structural integrity of MIL-100@drug_del in water after 3 days monitored by XRPD indicates a partial loss of crystallinity, probably due to the creation of some defects within the matrix or the difference in the water content (Figure S15). Furthermore, N2 sorption experiments of MIL-100@AAS_del confirm the complete recovery of the porosity after the delivery of the cargo (Figure S16). In contrast, the porosity of MIL-100 is not completely recovered after the release of IBU. This discrepancy may find its origin in a partial amorphization of the framework and may be misleading because crystallinity might be retained while a part of the solid is degraded (amorphization, hydrolysis, or residual traces of IBU that block the access to the porosity).
On the other hand, the FTIR spectrum of UiO-66@IBU_del shows a vibrational band at around 1700 cm–1, which could be assigned to the ν(C═O) groups of IBU or even the BDC ligand (Figure S13). It is known that the BDC ligand shows a low solubility in water (25 °C, 1.7 mg·100 mL–1). However, the HPLC measurements confirm that only 1.65% of the total BDC is released after 24 h in water, ruling out the presence of the ligand and supporting the presence of residual traces of drug. TGA indicates that the residual drug contents are about 9 and 35% for UiO-66@AAS_del and UiO-66@IBU_del, respectively (Figure S14, Table S3). These results are in good agreement with the total amount of released drug after 3 days from the UiO-66 material, as studied by HPLC (96 ± 2% of AAS and 68 ± 3% of IBU). After drug release, XRPD patterns showed that the structural stability is maintained, although a partial loss of crystallinity or disorder into the pores of the matrix is observed (Figure S15). The presence of residual drug molecules inside the UiO-66 matrixes might explain the reduction of the N2 uptake at 77 K after the drug-delivery process compared to the pristine materials (Figure S16). After the drug delivery, 64% (UiO-66@IBU_del) and 88% (UiO-66@AAS_del) of the pore volume are recovered, values near to the expected values of 68 and 96% of the IBU and AAS release, respectively (Table S4).
Finally, for MIL-127, both drugs are only partially released. In the case of MIL-127@AAS_del, the amount of remaining drug inside the pores is rather high, i.e., 53%, deduced from HPLC (Figure S11), IR spectra (see band at ca. 1700 cm–1 on Figure S13), TGA (around 50% of residual AAS, Figure S14, Table S3), and BET (see lower surface area in Figure S16) with only 62% of the pore volume recovered, which is close to the expected pore volume (84%, Table S4). Similarly, MIL-127@IBU_del also contains residual IBU but to a much lower extent than with AAS, i.e., around 18%. This is confirmed by IR spectra (see band at 1703 cm–1 in Figure S13), TGA, and HPLC (Figure S14, Table S3). As the percentage of residual IBU is here rather low, the N2 uptake at 77 K after IBU release is higher, although not totally recovered (74% of the initial pore volume, see Table S4). In both cases, the structural integrity of the MOF is kept after release, as shown by XRPD patterns (Figure S15). Therefore, one can conclude that MIL-127 remains stable during the delivery process, which makes this material interesting for its potential use as cutaneous drug-delivery system.

3. Conclusions

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To gain further understanding of the drug adsorption and delivery from MOFs, three rigid MOF architectures with different hydrophilic/hydrophobic balance have been selected for the encapsulation and release of two model drugs. The loadings of the hydrophilic aspirin and the hydrophobic ibuprofen have been performed in the MIL-100, UiO-66, and MIL-127 structures, resulting in six different loaded matrixes. One could establish that the drug uptake is here governed by the hydrophilic/hydrophobic balance between cargo and matrix (UiO-66 and MIL-127) and the accessibility of the drug through the framework (MIL-100 and MIL-127). Their controlled release under cutaneous conditions follows different kinetics profiles depending on: (i) the structure of the framework, with either a fast delivery from the very open structure MIL-100 or a slower drug release from the narrow 1D pore system of MIL-127 or (ii) the hydrophobic/hydrophilic nature of the cargo, with a fast (AAS) and slow (IBU) release from the UiO-66 matrix.
As a whole, all loaded materials fit well as cutaneous drug-delivery systems because of their high drug loading and good aqueous stability, which is associated with drug releases in less than 7 days. These results highlight the importance on the rational selection of MOFs and the physicochemical properties of cargoes on the encapsulation and release process.

4. Experimental Section

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All reactants were commercially obtained and used without further purification. The synthesis of starting materials was performed under solvothermal or reflux conditions following similar procedures as previously reported.

4.1. Synthesis of Ethyl Ester 1,3,5-Benzenetricarboxylic (EE-BTC)

1,3,5-Benzenetricarboxylic acid (H3BTC; 5 g, 2.4 mmol) was dispersed in 100 mL of absolute ethanol. H2SO4 (95%, 2 mL) was added to this suspension, and the resulting mixture was stirred under reflux for 24 h to give, upon cooling, a white precipitate, which was filtered off (filter funnel no. 4) and cleaned with water and ether. 1H NMR (300 MHz, CDCl3) δ: 8.84 (s, 3H), 4.45 (q, 6H), 1.43 (t, 9H).

4.2. Synthesis of 3,3′,5,5′-Azobenzenetetracarboxylic Acid (ABTC) (53)

5-Nitroisophthalic acid (19 g) was dispersed in 250 mL of distilled water. NaOH (50 g) was added, and the resulting mixture was heated at 60 °C under stirring. A pink slurry was thus formed. Subsequently, 100 g of glucose dissolved in 150 mL of water was slowly added to the previously obtained pink slurry. The solution turned from yellow to orange and then to brown. The heating was stopped, and air was bubbled through the solution overnight at room temperature. The mixture was then cooled with an ice bath to optimize the amount of precipitate, before recovering the disodium salt by filtration. The filtrate was then redissolved in 200 mL of distilled water and then this solution was acidified to pH = 1 using HCl (37%). This yielded a bright orange precipitate, which was recovered by filtration and washed with ethanol. 1H NMR (DMSO-d6) δ: 8.62 (6H).

4.3. Synthesis of MIL-100 [Fe3O(H2O)2OH(C9H3O6)2]·nH2O (27)

FeCl3·6H2O (2.7 g, 10 mmol) and EE-BTC (2.24 g, 6.66 mmol) were dispersed in 50 mL of H2O. The mixture was placed in a Teflon-lined autoclave at 130 °C for 3 days. Then, the orange solid was recovered by filtration and washed with absolute ethanol (3 × 10 mL). The solid was then suspended in 1 L of EtOH, refluxed under stirring for 3 h, and then the same procedure was carried out in deionized water. The solid was recovered by filtration. The particle size is ∼460 ± 80 nm (polydispersity index (PdI) > 0.3).

4.4. Synthesis of UiO-66 [Zr6O4(OH)4(C8O4H4)6]·nH2O (15,54,55)

ZrCl4 (0.23 g, 1 mmol) and terephthalic acid (H2BDC; 0.16 g, 1 mmol) were dispersed in 3 mL of dimethylformamide (DMF) placed in a Teflon-lined autoclave and heated at 220 °C for 12 h. The resulting solid was recovered by filtration. After filtration, activation was carried out by solvent exchange by suspending 200 mg of solid in 100 mL of DMF under stirring for 12 h and then in 100 mL of MeOH under stirring for 12 h. The particle size is ∼240 ± 40 nm (PdI > 0.3).

4.5. Synthesis of MIL-127 [Fe3O(OH)0.88Cl0.12(C16N2O8H6)1.5(H2O)3]·n(H2O) (29)

Fe(ClO4)3·nH2O (9.9 g, 28 mmol) and ABTC (5.0 g, 14 mmol) were dispersed in 100 mL of DMF. The mixture was refluxed under stirring at 150 °C for 20 h. The solid was recovered as a brown crystalline solid by filtration and washed with EtOH. The solid was then suspended in 1 L of EtOH and refluxed overnight under stirring. Then, the solid was recovered by filtration. The particle size is ∼2 ± 1 μm (PdI > 0.3).

4.6. Drug Encapsulation

Ibuprofen or aspirin was entrapped into the porous solids by suspending the previously dehydrated powdered MOFs (100 °C/overnight) in 20 mL of a 20 mg·mL–1 drug solution in ethanol at room temperature under magnetic stirring for 24 h, using 30 mL vessels with magnetic stirring (300 rpm). In all cases, the MOF/drug ratio was 1:4. The drug-loaded materials were recovered by filtration (filter funnel no. 4) and cleaned with 5 mL of ethanol.
The amount of adsorbed drug was quantified by thermogravimetric analysis (TGA) and high-performance liquid chromatography (HPLC). Pristine solids and drug-encapsulated solids were characterized by X-ray powder diffraction (XRPD), Fourier transform infrared spectroscopy (FTIR), and N2 sorption measurements.
For the evaluation of the kinetics of the drug adsorption within the MIL-100 and UiO-66, the concentration of the remaining free drug in the impregnation solution was checked by HPLC at different times (0.5, 1, 2, 3, 6, 16, 24, and 72 h).

4.7. Drug Release

Drug-containing material (5 mg) was placed in 40 mL of deionized water at 37 °C under bidimensional continuous stirring (80 × 80 rpm). At different incubation times, 20 mL of supernatant was recovered by centrifugation (10 500 rpm for 15 min) and replaced with the same volume of fresh deionized water at 37 °C. This procedure was performed in triplicate. The amount of released drug was determined by HPLC. After the drug-delivery process, the samples were characterized by XRPD, FTIR spectroscopy, TGA, and N2 sorption.

4.8. HPLC Measurement Conditions

The amount of encapsulated and released drug, as well as the release of the corresponding organic linker was determined using a reversed-phase HPLC system Waters Alliance e2695 Separations Module (Waters, Milford, MA), equipped with a variable-wavelength photodiode array detector Waters 2998 and controlled by Empower software. SunFire-C18 reverse-phase column (5 μm, 4.6 × 150 mm2, Waters) or Hypersil GOLD C18 (5 μm, 150 × 4.6 mm2, Thermo Fisher) were employed. For the quantification of all of the chemical species, isocratic conditions were used. The flow rate was 0.8 mL·min–1, and the column temperature was fixed at 25 °C. In all cases, the injection volume was 50 μL.
Different HPLC measurement conditions were used for the quantification of drugs and ligands: AAS (85:15 MeOH/buffer solution (0.04 M, pH = 2.5), retention time (RT) = 5.6 min and absorption maximum λ = 227.9 nm); IBU (85:15 MeOH/buffer solution (0.04 M, pH = 2.5), RT = 4.9 min and λ = 219.6 nm); H3BTC (50:50 MeOH/buffer solution (0.04 M, pH = 2.5), RT = 3.3 min and λ = 225 nm); H2BDC (5:95 MeOH/buffer solution (0.04 M, pH = 9), RT = 3.6 min and λ = 240 nm); ABTC (5:95 MeOH/buffer solution (0.04 M, pH = 9), RT = 2.9 min and λ = 225 nm) (SI, Section 1; Figures S1–S5).

4.8.1. Preparation of the Buffer Solution (0.04 M, pH = 2.5)

NaH2PO4 (2.4 g, 0.02 mol) and Na2HPO4 (2.84 g, 0.02 mol) were dissolved in 1 L of Milli-Q water. The pH was then adjusted to 2.5 with H3PO4 (≥85%).
1H NMR spectra for the characterization of the synthesized ligands were recorded on an Bruker Avance Instrument (300 MHz). FTIR spectra were recorded using a Nicolet 6700 FTIR Thermo Scientific spectrometer in the 400–4000 cm–1 region. XRPD patterns were collected in a Siemens D5000 diffractometer (θ–2θ) using Cu Kα radiation with a step size of 0.04° (2θ) and 4 s per step in continuous mode. TGA was performed under oxygen flow (20 mL·min–1) using a PerkinElmer Diamond TGA/DTA STA 6000 running from room temperature to 600 °C with a scan rate of 2 °C·min–1. N2 isotherms were obtained at 77 K using a BELSORP-mini (Bel, Japan). Prior to the analysis, approximately 40–60 mg of material was evacuated under vacuum at different times and temperatures taking into account the decomposition temperature of AAS (140 °C) and IBU (160 °C); the drug-loaded materials and the materials obtained after the drug-delivery process were evacuated at 110 °C for 24 h. HPLC measurements were performed using a HPLC system Waters Alliance e2695 Separations Module (Waters, Milford, MA) equipped with a variable-wavelength photodiode array detector Waters 2998 and controlled by Empower software.

4.9. Computational Section

To estimate the configuration of the drug molecules in the selected solids, Grand Canonical Monte Carlo (GCMC) calculations were performed at 300 K with a simulation box large enough to use a cutoff equal to 12.5 Å with typically 10 × 106 Monte Carlo steps for both equilibration and production steps. Partial charges have been evaluated using qEq method (included in Materials Studio software), (56) whereas universal force field is considered for Lennard-Jones interatomic potentials. (57)
Initial structures for MIL-100, MIL-127, and UiO-66 were obtained from the literature and then optimized classically. (27,28,58) Regarding GCMC calculations, the structure of the solid was supposed to be rigid with fixed unit cell parameters. The adsorbed drug molecules were optimized using density functional theory (DMol3 using PW91 functional and DNP basis set) calculations and considered in the GCMC calculations as rigid. We note also that drug coordination to the metal sites was not taken into consideration.
In complement, from the solid structures, free volume was calculated using a method of trial insertions within the entire volume of the unit cell. A probe size of 0 Å was used to enable us to determine this total free volume of the unit cell that was not occupied by the atoms of the framework. (59) The maximum saturation loading for UiO-66 and ibuprofen was determined by dividing the free volume of the structure by the volume of the IBU molecule (212 Å3 determined using software available in Materials Studio). In addition, specific surface area can be calculated for each structure using the approach developed by Düren et al., (59) considering the center of a N2 probe molecule rolling across the surface (with a diameter equal to 3.681 Å).

Supporting Information

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsomega.8b00185.

  • HPLC determinations, characterization of all materials (PXRD, FTIR spectroscopy, TGA, and N2 sorption measurements), stability studies, and complete drug-delivery studies (PDF)

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Author Information

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  • Corresponding Author
    • Patricia Horcajada - Institut Lavoisier, CNRS UMR 8180, UVSQ, Université Paris-Saclay, 45, Avenue Des Etats Unis, 78035 Versailles Cedex, France;  IMDEA Energy, Avenue Ramón de la Sagra 3, 28935 Móstoles, Madrid, Spain;  Orcidhttp://orcid.org/0000-0002-6544-5911;  Email: [email protected]
  • Authors
    • Sara Rojas - Institut Lavoisier, CNRS UMR 8180, UVSQ, Université Paris-Saclay, 45, Avenue Des Etats Unis, 78035 Versailles Cedex, France;  Orcidhttp://orcid.org/0000-0002-7874-2122
    • Isabel Colinet - Institut Lavoisier, CNRS UMR 8180, UVSQ, Université Paris-Saclay, 45, Avenue Des Etats Unis, 78035 Versailles Cedex, France
    • Denise Cunha - Institut Lavoisier, CNRS UMR 8180, UVSQ, Université Paris-Saclay, 45, Avenue Des Etats Unis, 78035 Versailles Cedex, France
    • Tania Hidalgo - Institut Lavoisier, CNRS UMR 8180, UVSQ, Université Paris-Saclay, 45, Avenue Des Etats Unis, 78035 Versailles Cedex, France
    • Fabrice Salles - Institut Charles Gerhardt Montpellier, CNRS UMR 5253, UM, ENSCM, Place E. Bataillon, 34095 Montpellier Cedex 05, France;  Orcidhttp://orcid.org/0000-0001-8069-533X
    • Christian Serre - Institut Lavoisier, CNRS UMR 8180, UVSQ, Université Paris-Saclay, 45, Avenue Des Etats Unis, 78035 Versailles Cedex, France;  Institut des Matériaux Poreux de Paris, FRE 2000 CNRS Ecole Normale Supérieure, Ecole Supérieure de Physique et de Chimie Industrielles de Paris, PSL Research University, 24 rue Lhomond, 75005 Paris, France
    • Nathalie Guillou - Institut Lavoisier, CNRS UMR 8180, UVSQ, Université Paris-Saclay, 45, Avenue Des Etats Unis, 78035 Versailles Cedex, France
  • Notes
    The authors declare no competing financial interest.

Acknowledgments

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This work was supported by EU funding through the ERC-2007-209241-BioMOFs ERC. S.R. acknowledges the Marie Sklodowska-Curie Programme (MSCA-IF-EF-ST-2015-705529). PH acknowledges the Spanish Ramon y Cajal Programme (grant agreement no. 2014-16823) and the People Programme (Marie Curie Actions) of the European Union’s Seventh Framework Programme (FP7/2007-2013) under REA grant agreement no. 291803.

References

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This article references 59 other publications.

  1. 1
    Chien, Y. W.; Lin, S. Drug Delivery: Controlled Release. In Encyclopedia of Pharmaceutical Technology; Swarbrick, J., Ed.; CRC Press, 2007; pp 1082– 1103.
    Google Scholar
    There is no corresponding record for this reference.
  2. 2
    Qu, H.; Bhattachayya, S.; Ducheyne, P. Sol-Gel Processed Oxide Controlled Release Materials. In Comprehensive Biomaterials I; Ducheyne, P.; Ducheyne, P.; Healy, K.; Hutmacher, D. E.; Grainger, D. W.; Kirkpatrick, C. J., Eds.; Elsevier, 2011; pp 476– 493.
    Google Scholar
    There is no corresponding record for this reference.
  3. 3
    Malmsten, M. Soft Drug Delivery Systems. Soft Matter 2006, 2, 760– 769,  DOI: 10.1039/b608348j
    Google Scholar
    3
    Soft drug delivery systems
    Malmsten, Martin
    Soft Matter (2006), 2 (9), 760-769CODEN: SMOABF; ISSN:1744-683X. (Royal Society of Chemistry)
    This brief review aims at providing some illustrative examples on the use of soft drug delivery systems formed by surfactants, polymers, and lipids. Such delivery systems are discussed and exemplified regarding both more traditional soft drug delivery systems such as micelles, liq. cryst. phases, liposomes and polymer gels, as well as more novel structures, e.g., carbon nanotubes, polyelectrolyte multilayer capsules, and liq. cryst. particles.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XpvVGgtLs%253D&md5=217a980927b8ecfbcb7030b71c8901a2
  4. 4
    Giménez-Marqués, M.; Hidalgo, T.; Serre, C.; Horcajada, P. Nanostructured Metal–organic Frameworks and Their Bio-Related Applications. Coord. Chem. Rev. 2015, 307, 1– 19,  DOI: 10.1016/j.ccr.2015.08.008
    Google Scholar
    There is no corresponding record for this reference.
  5. 5
    Imaz, I.; Rubio-Martínez, M.; An, J.; Solé-Font, I.; Rosi, N. L.; Maspoch, D. Metal-Biomolecule Frameworks (MBioFs). Chem. Commun. 2011, 47, 7287– 7302,  DOI: 10.1039/c1cc11202c
    Google Scholar
    5
    Metal-biomolecule frameworks (MBioFs)
    Imaz, Inhar; Rubio-Martinez, Marta; An, Jihyun; Sole-Font, Isabel; Rosi, Nathaniel L.; Maspoch, Daniel
    Chemical Communications (Cambridge, United Kingdom) (2011), 47 (26), 7287-7302CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
    A review. Biomols. are the building blocks of life. Nature has evolved countless biomols. that show promise for bridging metal ions. These mols. have emerged as an excellent source of biocompatible building blocks that can be used to design Metal-Biomol. Frameworks (MBioFs). This feature article highlights the advances in the synthesis of this class of MOFs. Special emphasis is provided on the crystal structures of these materials, their miniaturization to the submicron length scale, and their new potential storage, catalytic, and biomedical applications.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXnslSntLk%253D&md5=c64900429dfda43a9c3d190fe8600eb2
  6. 6
    Horcajada, P.; Serre, C.; Vallet-Regí, M.; Sebban, M.; Taulelle, F.; Férey, G. Metal-Organic Frameworks as Efficient Materials for Drug Delivery. Angew. Chem., Int. Ed. 2006, 45, 5974– 5978,  DOI: 10.1002/anie.200601878
    Google Scholar
    6
    Metal-organic frameworks as efficient materials for drug delivery
    Horcajada, Patricia; Serre, Christian; Vallet-Regi, Maria; Sebban, Muriel; Taulelle, Francis; Ferey, Gerard
    Angewandte Chemie, International Edition (2006), 45 (36), 5974-5978CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    The metal carboxylates MIL-100 and MIL-101 (MIL = Materials of Institut Lavoisier) act as porous matrixes for drug-delivery systems using ibuprofen as a model substrate. Very large amts. of the drug could be incorporated, up to an unprecedented capacity of 1.4 g of drug per g of porous solid for MIL-101, and the total release of ibuprofen was achieved under physiol. conditions in 3 (MIL-100) and 6 days (MIL-101).
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XhtVSrtLfF&md5=b88dbd1aeef6086fe4f1a6f9195d2054
  7. 7
    He, C.; Liu, D.; Lin, W. Nanomedicine Applications of Hybrid Nanomaterials Built from Metal–Ligand Coordination Bonds: Nanoscale Metal–Organic Frameworks and Nanoscale Coordination Polymers. Chem. Rev. 2015, 115, 11079– 11108,  DOI: 10.1021/acs.chemrev.5b00125
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    7
    Nanomedicine Applications of Hybrid Nanomaterials Built from Metal-Ligand Coordination Bonds: Nanoscale Metal-Organic Frameworks and Nanoscale Coordination Polymers
    He, Chunbai; Liu, Demin; Lin, Wenbin
    Chemical Reviews (Washington, DC, United States) (2015), 115 (19), 11079-11108CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
    A review. Topics covered include synthesis and properties of nanoscale metal-org. frameworks (NMOFs) and nanoscale coordination polymers (NCPs) and their uses in biomedical imaging and delivery of therapeutic agents for cancer treatment.
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  8. 8
    Zhou, H.-C. J.; Kitagawa, S. Metal–Organic Frameworks (MOFs). Chem. Soc. Rev. 2014, 43, 5415– 5418,  DOI: 10.1039/C4CS90059F
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    8
    Metal-Organic Frameworks (MOFs)
    Zhou, Hong-Cai "Joe"; Kitagawa, Susumu
    Chemical Society Reviews (2014), 43 (16), 5415-5418CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
    A review. Recent advances in the chem. of porous coordination polymers are discussed.
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  9. 9
    Carné, A.; Carbonell, C.; Imaz, I.; Maspoch, D. Nanoscale Metal-Organic Materials. Chem. Soc. Rev. 2011, 40, 291– 305,  DOI: 10.1039/C0CS00042F
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    9
    Nanoscale metal-organic materials
    Carne, Arnau; Carbonell, Carlos; Imaz, Inhar; Maspoch, Daniel
    Chemical Society Reviews (2011), 40 (1), 291-305CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
    A review. Metal-org. materials are a fascinating novel class of functional nanomaterials. The limitless combinations between inorg. and org. building blocks enable researchers to synthesize 0- and 1-dimensional metal-org. discrete nanostructures with varied compns., morphologies and sizes, fabricate 2-dimensional metal-org. thin films and membranes, and even structure them on surfaces at the nanometer length scale. In this tutorial review, the synthetic methodologies for prepg. these miniaturized materials as well as their potential properties and future applications are discussed. This review wants to offer a panoramic view of this embryonic class of nanoscale materials that will be of interest to a cross-section of researchers working in chem., physics, medicine, nanotechnol., materials chem., etc., in the next years.
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  10. 10
    Horcajada, P.; Serre, C.; Vallet-Regí, M.; Sebban, M.; Taulelle, F.; Férey, G. Metal-Organic Frameworks as Efficient Materials for Drug Delivery. Angew. Chem., Int. Ed. 2006, 45, 5974– 5978,  DOI: 10.1002/anie.200601878
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    10
    Metal-organic frameworks as efficient materials for drug delivery
    Horcajada, Patricia; Serre, Christian; Vallet-Regi, Maria; Sebban, Muriel; Taulelle, Francis; Ferey, Gerard
    Angewandte Chemie, International Edition (2006), 45 (36), 5974-5978CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    The metal carboxylates MIL-100 and MIL-101 (MIL = Materials of Institut Lavoisier) act as porous matrixes for drug-delivery systems using ibuprofen as a model substrate. Very large amts. of the drug could be incorporated, up to an unprecedented capacity of 1.4 g of drug per g of porous solid for MIL-101, and the total release of ibuprofen was achieved under physiol. conditions in 3 (MIL-100) and 6 days (MIL-101).
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  11. 11
    Sun, C.-Y.; Qin, C.; Wang, X.-L.; Su, Z.-M. Metal-Organic Frameworks as Potential Drug Delivery Systems. Expert Opin. Drug Delivery 2013, 10, 89– 101,  DOI: 10.1517/17425247.2013.741583
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    11
    Metal-organic frameworks as potential drug delivery systems
    Sun, Chun-Yi; Qin, Chao; Wang, Xin-Long; Su, Zhong-Min
    Expert Opinion on Drug Delivery (2013), 10 (1), 89-101CODEN: EODDAW; ISSN:1742-5247. (Informa Healthcare)
    A review. Introduction: Metal-org. frameworks (MOFs) are a unique class of hybrid porous solids based on metals and org. linkers. Compared to traditional porous materials, they possess predominance of large surface areas, tunable pore size and shape, adjustable compn. and functionalized pore surface, which enable them unique advantages and promises for applications in adsorption and release of therapeutic agents. Areas covered: This review addresses MOFs as a new avenue for drug delivery and exhibits their ability to efficiently deliver various kinds of therapeutic agents. It also details the requirements that MOFs need to satisfy for biomedical application, such as toxicol. compatibility, stability, particle size, and surface modification. In addn., several approaches used to enhance encapsulation efficiency are summarized and parameters influencing delivery efficiency are also discussed. Expert opinion: Benefiting from the unique advantages of MOFs materials, efficient delivery of various kinds of drugs has been achieved in some MOF materials. However, it is only the outset of MOFs in drug delivery system, and numerous work need to be done before clin. applications, for example, studying their in vivo toxicity, exploring degrdn. mechanisms so as to establish real stability of MOFs in body's liq., providing appropriated surface modification avenue for MOFs, and researching in vivo efficiency and pharmacokinetics of drug-loaded MOFs.
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  12. 12
    Carmona, F. J.; Rojas, S.; Sánchez, P.; Jeremias, H.; Marques, A. R.; Romão, C. C.; Choquesillo-Lazarte, D.; Navarro, J. A. R.; Maldonado, C. R.; Barea, E. Cation Exchange Strategy for the Encapsulation of a Photoactive CO-Releasing Organometallic Molecule into Anionic Porous Frameworks. Inorg. Chem. 2016, 55, 6525– 6531,  DOI: 10.1021/acs.inorgchem.6b00674
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    12
    Cation Exchange Strategy for the Encapsulation of a Photoactive CO-Releasing Organometallic Molecule into Anionic Porous Frameworks
    Carmona, Francisco J.; Rojas, Sara; Sanchez, Purificacion; Jeremias, Helia; Marques, Ana R.; Romao, Carlos C.; Choquesillo-Lazarte, Duane; Navarro, Jorge A. R.; Maldonado, Carmen R.; Barea, Elisa
    Inorganic Chemistry (2016), 55 (13), 6525-6531CODEN: INOCAJ; ISSN:0020-1669. (American Chemical Society)
    The encapsulation of the photoactive, nontoxic, water-sol., and air-stable cationic CORM [Mn(tacn)(CO)3]Br (tacn = 1,4,7-triazacyclononane) in different inorg. porous matrixes, namely, the metalorg. framework bio-MOF-1, (NH2(CH3)2)2[Zn8(adeninate)4(BPDC)6]·8DMF·11H2O (BPDC = 4,4'-biphenyldicarboxylate), and the functionalized mesoporous silicas MCM-41-SO3H and SBA-15-SO3H, is achieved by a cation exchange strategy. The CO release from these loaded materials, under simulated physiol. conditions, is triggered by visible light. The results show that the silica matrixes, which are unaltered under physiol. conditions, slow the kinetics of CO release, allowing a more controlled CO supply. In contrast, bio-MOF-1 instability leads to the complete leaching of the CORM. Nevertheless, the degrdn. of the MOF matrix gives rise to an enhanced CO release rate, which is related to the presence of free adenine in the soln.
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  13. 13
    Oh, H.; Li, T.; An, J. Drug Release Properties of a Series of Adenine-Based Metal-Organic Frameworks. Chem. - Eur. J. 2015, 21, 17010– 17015,  DOI: 10.1002/chem.201501560
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    13
    Drug Release Properties of a Series of Adenine-Based Metal-Organic Frameworks
    Oh, Hyojae; Li, Tao; An, Jihyun
    Chemistry - A European Journal (2015), 21 (47), 17010-17015CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)
    The drug uptake and release properties of a series of biomol.-based metal-org. frameworks (bMOF-1, bMOF-4, bMOF-100, and bMOF-102) have been studied. The bMOFs were loaded with the small mol. etilefrine hydrochloride and release profiles were collected in both Nanopure water and simulated body fluid (SBF). Each bMOF exhibited an initial burst of drug release at the initial stages of the expt. followed by a gradual release of the remaining drug mols. over time. bMOF-1 released 50 % of the drug after 15 days and complete release at 80 days in SBF. bMOF-4 released 50 % of the drug within two days and complete release at 49 days in SBF. bMOF-100 and bMOF-102 released 50 % of the drug after 4 h and complete release at 69 and 54 days in SBF, resp.
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  14. 14
    Gaudin, C.; Cunha, D.; Ivanoff, E.; Horcajada, P.; Chevé, G.; Yasri, A.; Lobet, O.; Serre, C.; Maurin, G. A Quantitative Structure Activity Relationship Approach to Probe the Influence of the Functionalization on the Drug Encapsulation of Porous Metal-Organic Frameworks. Microporous Mesoporous Mater. 2012, 157, 124– 130,  DOI: 10.1016/j.micromeso.2011.06.011
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    14
    A quantitative structure activity relationship approach to probe the influence of the functionalization on the drug encapsulation of porous metal-organic frameworks
    Gaudin, C.; Cunha, D.; Ivanoff, E.; Horcajada, P.; Cheve, G.; Yasri, A.; Loget, O.; Serre, C.; Maurin, G.
    Microporous and Mesoporous Materials (2012), 157 (), 124-130CODEN: MIMMFJ; ISSN:1387-1811. (Elsevier Inc.)
    A series of 10 MIL-88B(Fe) iron(III) dicarboxylate MOFs wherein the org. linker is functionalized by a large variety of polar and apolar functional groups (-H, -Br, -F, -CF3, -CH3, -NH2, -NO2, -OH) was investigated as a potential carrier for encapsulating drugs, using the cosmetic amphiphilic caffeine as a model mol. Encapsulation using impregnation followed by thermogravimetric anal. (TGA) and high performance liq. chromatog. (HPLC) measurements to quant. est. the caffeine uptake, have been first performed on the functionalized MIL-88B(Fe) samples. This set of exptl. data was further used as an ideal platform to conduct a quant. structure activity relationship approach based on multiple linear regression (MLR) method with the aim to find out the most relevant chem. and structural features of the MIL-88B(Fe) that significantly affect the therapeutic mol. uptake. Individual QSAR models showed that tuning the polarity and the H-donor capacity of the org. linker can enhance the caffeine encapsulation, suggesting that the functional groups serve as anchoring points for the drug mol., consistent with previous conclusions drawn from mol. simulations performed on similar functionalized MOFs. Consensus modeling approach based on the selection of the most diverse individual models was also employed to build more representative QSAR models over the chem. space that could be further used to predict the drug encapsulation performance of the MOFs grafted by other functional groups.
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  15. 15
    Cunha, D.; Gaudin, C.; Colinet, I.; Horcajada, P.; Maurin, G.; Serre, C. Rationalization of the Entrapping of Bioactive Molecules into a Series of Functionalized Porous Zirconium Terephthalate MOFs. J. Mater. Chem. B 2013, 1, 1101– 1108,  DOI: 10.1039/c2tb00366j
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    15
    Rationalization of the entrapping of bioactive molecules into a series of functionalized porous zirconium terephthalate MOFs
    Cunha, D.; Gaudin, C.; Colinet, I.; Horcajada, P.; Maurin, G.; Serre, C.
    Journal of Materials Chemistry B: Materials for Biology and Medicine (2013), 1 (8), 1101-1108CODEN: JMCBDV; ISSN:2050-7518. (Royal Society of Chemistry)
    The encapsulation of two different bioactive mols., the cosmetic caffeine and the analgesic and anti-inflammatory ibuprofen, has been evaluated by combining impregnation and advanced characterization exptl. tools in a series of microporous rigid zirconium(iv) terephthalates UiO-66 bearing different polar or apolar functional groups (-H, -Br, -NH2, -2OH, -NO2, -Cl, -2CF3, -CH3, -2CH3). It has been first evidenced that these hybrid solids exhibit drug payloads that significantly outperform those obtained using current drug formulations or other conventional porous solids. A quant. structure-activity relationship strategy has been further conducted with the aim of rationalizing the exptl. drug uptakes and further emphasizing the most relevant chem. and structural features that significantly impact their encapsulation performances. Indeed, it appears that the caffeine loading is optimized when the functionalized org. linker both shows a large octanol-water partition coeff. and contains grafted functions with low hydrogen bond acceptor abilities, whereas the ibuprofen entrapping is enhanced when the org. linker contains functional groups with a large solvent surface area and free vol., and to a lesser extent low hydrogen bond acceptor abilities. Moreover, it has been shown that the solvent used as media for the biomol. impregnation plays a crucial role in the encapsulation performance due to the formation of a competitive adsorption process between the solvent and the active mol.
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  16. 16
    Cunha, D.; Yahia, M. B.; Hall, S.; Miller, S. R.; Chevreau, H.; Elka, E.; Maurin, G.; Horcajada, P.; Serre, C. Rationale of Drug Encapsulation and Release from Biocompatible Porous Metal–Organic Frameworks. Chem. Mater. 2013, 25, 2767– 2776,  DOI: 10.1021/cm400798p
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    16
    Rationale of Drug Encapsulation and Release from Biocompatible Porous Metal-Organic Frameworks
    Cunha, Denise; Ben Yahia, Mouna; Hall, Shaun; Miller, Stuart R.; Chevreau, Hubert; Elkaim, Erik; Maurin, Guillaume; Horcajada, Patricia; Serre, Christian
    Chemistry of Materials (2013), 25 (14), 2767-2776CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
    A joint exptl. and computational systematic exploration of the driving forces that govern (i) encapsulation of active ingredients (solvent, starting material dehydration, drug/material ratio, immersion time, and several consecutive impregnations) and (i) its kinetics of delivery (structure, polarity,...) was performed using a series of porous biocompatible metal-org. frameworks (MOFs) that bear different topologies, connectivities, and chem. compns. The liporeductor cosmetic caffeine was selected as the active mol. Its encapsulation is a challenge for the cosmetic industry due to its high tendency to crystallize leading to poor loadings (<5 wt. %) and uncontrolled releases with a subsequent low efficiency. It was evidenced that caffeine entrapping reaches exceptional payloads up to 50 wt. %, while progressive release of this cosmetic agent upon immersion in the simulated physiol. media (phosphate buffer soln. pH = 7.4 or distd. water pH = 6.3, 37 °C) occurred mainly depending on the degree of MOF stability, caffeine mobility, and MOF-caffeine interactions. Thus, MIL-100 and UiO-66 appear as very promising carriers for topical administration of caffeine with both spectacular cosmetic payloads and progressive releases within 24 h.
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  17. 17
    Lanza, F.; Royer, G.; Nelson, R. An Endoscopic Evaluation of the Effects of Non-Steroidal Anti-Inflammatory Drugs on the Gastric Mucosa. Gastrointest. Endosc. 1975, 21, 103– 105,  DOI: 10.1016/S0016-5107(75)73812-9
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    17
    An endoscopic evaluation of the effects of non-steroidal anti-inflammatory drugs on the gastric mucosa
    Lanza F; Royer G; Nelson R
    Gastrointestinal endoscopy (1975), 21 (3), 103-5 ISSN:0016-5107.
    There is no expanded citation for this reference.
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  18. 18
    Schoen, R. T.; Vender, R. J. Mechanisms of Nonsteroidal Anti-Inflammatory Drug-Induced Gastric Damage. Am. J. Med. 1989, 86, 449– 458,  DOI: 10.1016/0002-9343(89)90344-6
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    18
    Mechanisms of nonsteroidal anti-inflammatory drug-induced gastric damage
    Schoen, Robert T.; Vender, Ronald J.
    American Journal of Medicine (1989), 86 (4), 449-58CODEN: AJMEAZ; ISSN:0002-9343.
    A review with 136 refs. on the effects of nonsteroidal anti-inflammatory drugs (NSAIDs) on the gastric mucosa. Current knowledge about the normal function of the gastric mucosal barrier, the role of prostaglandins in cytoprotection and repair, the mechanisms by which aspirin and other weak org. acids are absorbed by the stomach, and the subsequent cascade of events (including ion trapping and back diffusion of H+) that leads to gastric erosion and bleeding are discussed. A hypothesis describing NSAIDs' dual insult on the stomach is advanced.
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  19. 19
    Ammar, H. O.; Ghorab, M.; El-Nahhas, S. A.; Kamel, R. Design of a Transdermal Delivery System for Aspirin as an Antithrombotic Drug. Int. J. Pharm. 2006, 327, 81– 88,  DOI: 10.1016/j.ijpharm.2006.07.054
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    19
    Design of a transdermal delivery system for aspirin as an antithrombotic drug
    Ammar, H. O.; Ghorab, M.; El-Nahhas, S. A.; Kamel, R.
    International Journal of Pharmaceutics (2006), 327 (1-2), 81-88CODEN: IJPHDE; ISSN:0378-5173. (Elsevier Ltd.)
    Aspirin has become the gold std. to which newer antiplatelet drugs are compared for reducing risks of cardiovascular diseases, while keeping low cost. Oral aspirin has a repertoire of gastrointestinal side effects even at low doses and requires high frequent dosing because it undergoes extensive presystemic metab. Transdermal delivery offers an alternative route that bypasses the gut and may be more convenient and safer for aspirin delivery esp. during long-term use. This study comprised formulation of aspirin in different topical bases. Release studies revealed that hydrocarbon gel allowed highest drug release. In vitro permeation studies revealed high drug permeation from hydrocarbon gel. Several chem. penetration enhancers were monitored for augmenting the permeation from this base. Combination of propylene glycol and alc. showed max. enhancing effect and, hence, was selected for biol. investigation. The biol. performance of the selected formulation was assessed by measuring the inhibition of platelet aggregation relevant to different dosage regimens aiming to minimize both drug dose and frequency of application. The results demonstrated the feasibility of successfully influencing platelet function and revealed that the drug therapeutic efficacy in transdermal delivery system is dose independent. Biol. performance was re-assessed after storage and the results revealed stability and persistent therapeutic efficacy.
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  20. 20
    Prausnitz, M. R.; Langer, R. Transdermal Drug Delivery. Nat. Biotechnol. 2008, 26 (11), 1261– 1268,  DOI: 10.1038/nbt.1504
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    20
    Transdermal drug delivery
    Prausnitz, Mark R.; Langer, Robert
    Nature Biotechnology (2008), 26 (11), 1261-1268CODEN: NABIF9; ISSN:1087-0156. (Nature Publishing Group)
    A review. Transdermal drug delivery has made an important contribution to medical practice, but has yet to fully achieve its potential as an alternative to oral delivery and hypodermic injections. First-generation transdermal delivery systems have continued their steady increase in clin. use for delivery of small, lipophilic, low-dose drugs. Second-generation delivery systems using chem. enhancers, noncavitational ultrasound and iontophoresis have also resulted in clin. products; the ability of iontophoresis to control delivery rates in real time provides added functionality. Third-generation delivery systems target their effects to skin's barrier layer of stratum corneum using microneedles, thermal ablation, micro-dermabrasion, electroporation and cavitational ultrasound. Microneedles and thermal ablation are currently progressing through clin. trials for delivery of macromols. and vaccines, such as insulin, parathyroid hormone and influenza vaccine. Using these novel second- and third-generation enhancement strategies, transdermal delivery is poised to significantly increase its impact on medicine.
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  21. 21
    Horcajada, P.; Gref, R.; Baati, T.; Allan, P. K.; Maurin, G.; Couvreur, P.; Férey, G.; Morris, R. E.; Serre, C. Metal-Organic Frameworks in Biomedicine. Chem. Rev. 2012, 112, 1232– 1268,  DOI: 10.1021/cr200256v
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    21
    Metal-Organic Frameworks in Biomedicine
    Horcajada, Patricia; Gref, Ruxandra; Baati, Tarek; Allan, Phoebe K.; Maurin, Guillaume; Couvreur, Patrick; Ferey, Gerard; Morris, Russell E.; Serre, Christian
    Chemical Reviews (Washington, DC, United States) (2012), 112 (2), 1232-1268CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
    A review. Coordination polymers or MOFs (metal-org. frameworks) as porous solids for biomedical are reviewed.
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  22. 22
    McKinlay, A. C.; Allan, P. K.; Renouf, C. L.; Duncan, M. J.; Wheatley, P. S.; Warrender, S. J.; Dawson, D.; Ashbrook, S. E.; Gil, B.; Marszalek, B.; Düren, T.; Williams, J. J.; Charrier, C.; Mercer, D. K.; Teat, S. J.; Morris, R. E. Multirate Delivery of Multiple Therapeutic Agents from Metal-Organic Frameworks. APL Mater. 2014, 2, 124108  DOI: 10.1063/1.4903290
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    22
    Multirate delivery of multiple therapeutic agents from metal-organic frameworks
    McKinlay, Alistair C.; Allan, Phoebe K.; Renouf, Catherine L.; Duncan, Morven J.; Wheatley, Paul S.; Warrender, Stewart J.; Dawson, Daniel; Ashbrook, Sharon E.; Gil, Barbara; Marszalek, Bartosz; Duren, Tina; Williams, Jennifer J.; Charrier, Cedric; Mercer, Derry K.; Teat, Simon J.; Morris, Russell E.
    APL Materials (2014), 2 (12), 124108/1-124108/8CODEN: AMPADS; ISSN:2166-532X. (American Institute of Physics)
    The highly porous nature of metal-org. frameworks (MOFs) offers great potential for the delivery of therapeutic agents. Here, we show that highly porous metal-org. frameworks can be used to deliver multiple therapeutic agents-a biol. active gas, an antibiotic drug mol., and an active metal ion-simultaneously but at different rates. The possibilities offered by delivery of multiple agents with different mechanisms of action and, in particular, variable timescales may allow new therapy approaches. Here, we show that the loaded MOFs are highly active against various strains of bacteria. (c) 2014 American Institute of Physics.
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  23. 23
    Márquez, A. G.; Hidalgo, T.; Lana, H.; Cunha, D.; Blanco-Prieto, M. J.; Álvarez-Lorenzo, C.; Boissière, C.; Sánchez, C.; Serre, C.; Horcajada, P. Biocompatible Polymer–metal–organic Framework Composite Patches for Cutaneous Administration of Cosmetic Molecules. J. Mater. Chem. B 2016, 4, 7031– 7040,  DOI: 10.1039/C6TB01652A
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    23
    Biocompatible polymer-metal-organic framework composite patches for cutaneous administration of cosmetic molecules
    Marquez, Alfonso Garcia; Hidalgo, Tania; Lana, Hugo; Cunha, Denise; Blanco-Prieto, Maria Jose; Alvarez-Lorenzo, Carmen; Boissiere, Cedric; Sanchez, Clement; Serre, Christian; Horcajada, Patricia
    Journal of Materials Chemistry B: Materials for Biology and Medicine (2016), 4 (43), 7031-7040CODEN: JMCBDV; ISSN:2050-7518. (Royal Society of Chemistry)
    Despite increasing interest in metal-org. frameworks (MOFs) in the biomedical field, developing specific formulations suitable for different administration routes is still a main challenge. Here, we propose a simple, fast and bio-friendly press-molding method for the prepn. of cutaneous patches based on composites made from the drug nanocarrier MIL-100(Fe) and biopolymers. The physicochem. properties of the patches (structure, hydration, bioadhesive and swelling properties), as well as their encapsulation and release capabilities (both in ex vitro and ex vivo models), were evaluated using active ingredients such as the challenging cosmetic liporeductor, caffeine, and the model analgesic and anti-inflammatory drug, ibuprofen. In particular, very high caffeine loadings were entrapped within these cutaneous devices with progressive releases under simulated cutaneous physiol. conditions as a consequence of the swelling of the hydrophilic patches. Despite the absence of any cutaneous bioadhesive character, these patches provided progressive and suitable permeation of their cosmetic cargo through the skin, interestingly reaching the targeted adipose tissue. This makes these cosmetic-contg. composite MOF-based patches promising candidates for new cutaneous devices in cosmetic applications.
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  24. 24
    Canivet, J.; Fateeva, A.; Guo, Y.; Coasne, B.; Farrusseng, D. Water Adsorption in MOFs: Fundamentals and Applications. Chem. Soc. Rev. 2014, 43, 5594– 5617,  DOI: 10.1039/C4CS00078A
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    24
    Water adsorption in MOFs: fundamentals and applications
    Canivet, Jerome; Fateeva, Alexandra; Guo, Youmin; Coasne, Benoit; Farrusseng, David
    Chemical Society Reviews (2014), 43 (16), 5594-5617CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
    A review. This review article presents the fundamental and practical aspects of water adsorption in Metal-Org. Frameworks (MOFs). The state of the art of MOF stability in water, a crucial issue to many applications in which MOFs are promising candidates, is discussed here. Stability in both gaseous (such as humid gases) and aq. media is considered. By considering a non-exhaustive yet representative set of MOFs, the different mechanisms of water adsorption in this class of materials are presented: reversible and continuous pore filling, irreversible and discontinuous pore filling through capillary condensation, and irreversibility arising from the flexibility and possible structural modifications of the host material. Water adsorption properties of more than 60 MOF samples are reported. The applications of MOFs as materials for heat-pumps and adsorbent-based chillers and proton conductors are also reviewed. Some directions for future work are suggested as concluding remarks.
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  25. 25
    Cychosz, K. A.; Matzger, A. J. Water Stability of Microporous Coordination Polymers and the Adsorption of Pharmaceuticals from Water. Langmuir 2010, 26, 17198– 17202,  DOI: 10.1021/la103234u
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    25
    Water Stability of Microporous Coordination Polymers and the Adsorption of Pharmaceuticals from Water
    Cychosz, Katie A.; Matzger, Adam J.
    Langmuir (2010), 26 (22), 17198-17202CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)
    The stability of a variety of microporous coordination polymers (MCPs) to water-contg. solns. was studied using powder x-ray diffraction. The stability of the MCP is related to the metal cluster present in the structure with trinuclear chromium clusters more stable than copper paddlewheel clusters which are more stable than basic zinc acetate clusters. Zn(2-methylimidizolate)2 is more water stable than zinc MCPs with carboxylate linkers; however, extended exposure to water led to decompn. of all zinc-based MCPs. Materiaux de l'Institut Lavoisier (MIL)-100 also is completely water stable and was used to adsorb the pharmaceuticals furosemide and sulfasalazine from water with large uptakes achievable at low concns., indicating that the adsorption of wastewater contaminants may be a feasible application for these materials.
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  26. 26
    Küsgens, P.; Rose, M.; Senkovska, I.; Fröde, H.; Henschel, A.; Siegle, S.; Kaskel, S. Characterization of Metal-Organic Frameworks by Water Adsorption. Microporous Mesoporous Mater. 2009, 120, 325– 330,  DOI: 10.1016/j.micromeso.2008.11.020
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    26
    Characterization of metal-organic frameworks by water adsorption
    Kuesgens, Pia; Rose, Marcus; Senkovska, Irena; Froede, Heidrun; Henschel, Antje; Siegle, Sven; Kaskel, Stefan
    Microporous and Mesoporous Materials (2009), 120 (3), 325-330CODEN: MIMMFJ; ISSN:1387-1811. (Elsevier)
    The water physisorption properties and the water stability of the metal-org. frameworks HKUST-1 (=(Cu3(BTC)2) (BTC = benzene-1,3,5-tricarboxylate)), ZIF-8, MIL-101, MIL-100(Fe) and DUT-4 (=Al(OH)(NDC)) (NDC = naphthalene-2,6-dicarboxylate) were studied. The water physisorption isotherms were compared to nitrogen physisorption isotherms and the chem. stability after water adsorption was investigated. Water adsorption does not only provide information about sp. surface area, pore size and pore vol., but can also be used to est. hydrophobicity and stability towards moisture. Both HKUST-1 and DUT-4 turned out to be unstable in direct contact with water, whereas the MIL-materials and ZIF-8 do show stability. The highest water adsorption affinity was obsd. for HKUST-1. Even though unstable in liq. water, for applications in trace water removal or mol. sensing HKUST-1 is a promising material. ZIF-8 is highly inert but hydrophobic. The MIL-materials are both likely candidates for water adsorption applications, but higher concns. of the adsorbate are needed to attain an effective adsorption. DUT-4 shows insufficient adsorption capacity, but stability at ambient conditions is given.
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  27. 27
    Horcajada, P.; Surblé, S.; Serre, C.; Hong, D.-Y.; Seo, Y.-K.; Chang, J.-S.; Grenèche, J.-M.; Margiolaki, I.; Férey, G. Synthesis and Catalytic Properties of MIL-100(Fe), an iron(III) Carboxylate with Large Pores. Chem. Commun. 2007, 2820– 2822,  DOI: 10.1039/B704325B
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    27
    Synthesis and catalytic properties of MIL-100(Fe), an iron(III) carboxylate with large pores
    Horcajada, Patricia; Surble, Suzy; Serre, Christian; Hong, Do-Young; Seo, You-Kyong; Chang, Jong-San; Greneche, Jean-Marc; Margiolaki, Irene; Ferey, Gerard
    Chemical Communications (Cambridge, United Kingdom) (2007), (27), 2820-2822CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
    The large-pore iron(III) carboxylate MIL-100(Fe) with a zeotype architecture was isolated under hydrothermal conditions. Its structure was solved from synchrotron x-ray powder diffraction data and the complex is formulated as [Fe3O(H2O)2F(BTC)2]·nH2O (n ≈ 14.5; BTC = 1,3,5-benzenetricarboxylate). Friedel-Crafts benzylation catalytic tests indicate a high activity and selectivity for MIL-100(Fe).
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  28. 28
    Liu, Y.; Eubank, J. F.; Cairns, A. J.; Eckert, J.; Kravtsov, V. C.; Luebke, R.; Eddaoudi, M. Assembly of Metal-Organic Frameworks (MOFs) Based on Indium-Trimer Building Blocks: A Porous MOF with Soc Topology and High Hydrogen Storage. Angew. Chem., Int. Ed. 2007, 46, 3278– 3283,  DOI: 10.1002/anie.200604306
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    28
    Assembly of metal-organic frameworks (MOFs) based on indium-trimer building blocks: a porous MOF with soc topology and high hydrogen storage
    Liu, Yunling; Eubank, Jarrod F.; Cairns, Amy J.; Eckert, Juergen; Kravtsov, Victor Ch.; Luebke, Ryan; Eddaoudi, Mohamed
    Angewandte Chemie, International Edition (2007), 46 (18), 3278-3283CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    The synthesis and structure of two MOFs based on oxo-bridged trinuclear indium carboxylate clusters are reported. The one MOF has a cubic structure with a CaB6 topol. and the other with an unprecedented soc topol. (soc = square-octahedron). The results obtained indicate that MOFs possessing the characteristics of these two MOFs, combined with the modularity of their construction which allows higher surface areas to be obtained, will permit the attainment of the US DOE target for H2 uptake.
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  29. 29
    Chevreau, H.; Permyakova, A.; Nouar, F.; Fabry, P.; Livage, C.; Ragon, F.; Garcia-Marquez, A.; Devic, T.; Steunou, N.; Serre, C.; Horcajada, P. Synthesis of the Biocompatible and Highly Stable MIL-127(Fe): From Large Scale Synthesis to Particle Size Control. CrystEngComm 2016, 18, 4094– 4101,  DOI: 10.1039/C5CE01864A
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    29
    Synthesis of the biocompatible and highly stable MIL-127(Fe): from large scale synthesis to particle size control
    Chevreau, Hubert; Permyakova, Anastasia; Nouar, Farid; Fabry, Paul; Livage, Carine; Ragon, Florence; Garcia-Marquez, Alfonso; Devic, Thomas; Steunou, Nathalie; Serre, Christian; Horcajada, Patricia
    CrystEngComm (2016), 18 (22), 4094-4101CODEN: CRECF4; ISSN:1466-8033. (Royal Society of Chemistry)
    Controlled-sized crystals, from the nano to the microscale, of the biocompatible and highly stable porous iron(III) 3,3,'5,5'-azobenzenetetracarboxylate MIL-127(Fe) MOF have been successfully prepd. with very high space-time-yields using different synthetic routes.
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  30. 30
    Ghosh, P.; Colón, Y. J.; Snurr, R. Q. Water Adsorption in UiO-66: The Importance of Defects. Chem. Commun. 2014, 50, 11329– 11331,  DOI: 10.1039/C4CC04945D
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    30
    Water adsorption in UiO-66: the importance of defects
    Ghosh, Pritha; Colon, Yamil J.; Snurr, Randall Q.
    Chemical Communications (Cambridge, United Kingdom) (2014), 50 (77), 11329-11331CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
    Simulated adsorption isotherms for water in UiO-66 illustrate that defects in the form of missing linkers make this MOF more hydrophilic. Heats of adsorption and d. plots further confirm the effect of defects on adsorption of water in UiO-66 at low loadings. In addn., water and CO2 isotherms indicate that not only the amt. of defects but their locations within the material affect the loading of guest mols.
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  31. 31
    Cavka, J. H.; Jakobsen, S.; Olsbye, U.; Guillou, N.; Lamberti, C.; Bordiga, S.; Lillerud, K. P. A New Zirconium Inorganic Building Brick Forming Metal Organic Frameworks with Exceptional Stability. J. Am. Chem. Soc. 2008, 130, 13850– 13851,  DOI: 10.1021/ja8057953
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    31
    A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability
    Cavka Jasmina Hafizovic; Jakobsen Soren; Olsbye Unni; Guillou Nathalie; Lamberti Carlo; Bordiga Silvia; Lillerud Karl Petter
    Journal of the American Chemical Society (2008), 130 (42), 13850-1 ISSN:.
    Porous crystals are strategic materials with industrial applications within petrochemistry, catalysis, gas storage, and selective separation. Their unique properties are based on the molecular-scale porous character. However, a principal limitation of zeolites and similar oxide-based materials is the relatively small size of the pores, typically in the range of medium-sized molecules, limiting their use in pharmaceutical and fine chemical applications. Metal organic frameworks (MOFs) provided a breakthrough in this respect. New MOFs appear at a high and an increasing pace, but the appearances of new, stable inorganic building bricks are rare. Here we present a new zirconium-based inorganic building brick that allows the synthesis of very high surface area MOFs with unprecedented stability. The high stability is based on the combination of strong Zr-O bonds and the ability of the inner Zr6-cluster to rearrange reversibly upon removal or addition of mu3-OH groups, without any changes in the connecting carboxylates. The weak thermal, chemical, and mechanical stability of most MOFs is probably the most important property that limits their use in large scale industrial applications. The Zr-MOFs presented in this work have the toughness needed for industrial applications; decomposition temperature above 500 degrees C and resistance to most chemicals, and they remain crystalline even after exposure to 10 tons/cm2 of external pressure.
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  32. 32
    Hartlieb, K. J.; Ferris, D. P.; Holcroft, J. M.; Kandela, I.; Stern, C. L.; Nassar, M. S.; Botros, Y. Y.; Stoddart, J. F. Encapsulation of Ibuprofen in CD-MOF and Related Bioavailability Studies. Mol. Pharm. 2017, 14, 1831– 1839,  DOI: 10.1021/acs.molpharmaceut.7b00168
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    32
    Encapsulation of Ibuprofen in CD-MOF and Related Bioavailability Studies
    Hartlieb, Karel J.; Ferris, Daniel P.; Holcroft, James M.; Kandela, Irawati; Stern, Charlotte L.; Nassar, Majed S.; Botros, Youssry Y.; Stoddart, J. Fraser
    Molecular Pharmaceutics (2017), 14 (5), 1831-1839CODEN: MPOHBP; ISSN:1543-8384. (American Chemical Society)
    Although ibuprofen is one of the most widely used nonsteroidal anti-inflammatory drugs (NSAIDs), it exhibits poor soly. in aq. and physiol. environments as a free acid. In order to improve its oral bioavailability and rate of uptake, extensive research into the development of new formulations of ibuprofen has been undertaken, including the use of excipients as well as ibuprofen salts, such as ibuprofen lysinate and ibuprofen, sodium salt. The ultimate goals of these studies are to reduce the time required for max. uptake of ibuprofen, as this period of time is directly proportional to the rate of onset of analgesic/anti-inflammatory effects, and to increase the half-life of the drug within the body; i.e., the duration of action of the effects of the drug. Herein, we present a pharmaceutical cocrystal of ibuprofen and the biocompatible metal-org. framework called CD-MOF. This metal-org. framework (MOF) is based upon γ-cyclodextrin (γ-CD) tori that are coordinated to alkali metal cations (e.g., K+ ions) on both their primary and secondary faces in an alternating manner to form a porous framework built up from (γ-CD)6 cubes. We show that ibuprofen can be incorporated within CD-MOF-1 either by (i) a crystn. process using the potassium salt of ibuprofen as the alkali cation source for prodn. of the MOF or by (ii) absorption and deprotonation of the free-acid, leading to an uptake of 23-26 wt % of ibuprofen within the CD-MOF. In vitro viability studies revealed that the CD-MOF is inherently not affecting the viability of the cells with no IC50 value detd. up to a concn. of 100 μM. Bioavailability investigations were conducted on mice, and the ibuprofen/CD-MOF pharmaceutical cocrystal was compared to control samples of the potassium salt of ibuprofen in the presence and absence of γ-CD. From these animal studies, we obsd. that the ibuprofen/CD-MOF-1 cocrystal exhibits the same rapid uptake of ibuprofen as the ibuprofen potassium salt control sample with a peak plasma concn. obsd. within 20 min, and the cocrystal has the added benefit of a 100% longer half-life in blood plasma samples and is intrinsically less hygroscopic than the pure salt form.
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  33. 33
    Bhadra, B. N.; Ahmed, I.; Kim, S.; Jhung, S. H. Adsorptive Removal of Ibuprofen and Diclofenac from Water Using Metal-Organic Framework-Derived Porous Carbon. Chem. Eng. J. 2017, 314, 50– 58,  DOI: 10.1016/j.cej.2016.12.127
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    33
    Adsorptive removal of ibuprofen and diclofenac from water using metal-organic framework-derived porous carbon
    Bhadra, Biswa Nath; Ahmed, Imteaz; Kim, Sunghwan; Jhung, Sung Hwa
    Chemical Engineering Journal (Amsterdam, Netherlands) (2017), 314 (), 50-58CODEN: CMEJAJ; ISSN:1385-8947. (Elsevier B.V.)
    A metal-org. framework (MOF) (here, zeolitic-imidazolate framework-8) was pyrolyzed at different temps. (800, 1000, and 1200 °C) in order to prep. porous carbons derived from MOF (PCDMs). Adsorption of ibuprofen (IBP) and diclofenac sodium (DCF) from aq. solns. was carried out over the produced PCDMs and compared with that over pristine MOF and com. activated carbon (AC). Among the tested adsorbents, the PCDM prepd. at 1000 °C (PCDM-1000) was found to be the best candidate for both IBP and DCF. The max. adsorption capacities of IBP (320 mg/g) and DCF (400 mg/g) over PCDM-1000 were ∼3 and ∼5 times, resp., of that of AC. Interaction mechanisms such as H-bonding (H-donation from PCDM, H-acceptance from IBP or DCF) were suggested based on the effect of soln. pH on the zeta potential of PCDM and the adsorbed quantity of IBP and DCF along with functional groups created on the surface of PCDM-1000. Finally, PCDM-1000 was confirmed to be as a highly efficient and recyclable adsorbent having potential applications in water purifn.
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  34. 34
    García Márquez, A.; Demessence, A.; Platero-Prats, A. E.; Heurtaux, D.; Horcajada, P.; Serre, C.; Chang, J.-S.; Férey, G.; De La Peña-O’Shea, V. A.; Boissière, C.; Grosso, D.; Sanchez, C. Green Microwave Synthesis of MIL-100(Al, Cr, Fe) Nanoparticles for Thin-Film Elaboration. Eur. J. Inorg. Chem. 2012, 100, 5165– 5174,  DOI: 10.1002/ejic.201200710
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    There is no corresponding record for this reference.
  35. 35
    Singco, B.; Liu, L.-H.; Chen, Y.-T.; Shih, Y.-H.; Huang, H.-Y.; Lin, C.-H. Approaches to Drug Delivery: Confinement of Aspirin in MIL-100(Fe) and Aspirin in the de Novo Synthesis of Metal-Organic Frameworks. Microporous Mesoporous Mater. 2016, 223, 254– 260,  DOI: 10.1016/j.micromeso.2015.08.017
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    35
    Approaches to drug delivery: Confinement of aspirin in MIL-100(Fe) and aspirin in the de novo synthesis of metal-organic frameworks
    Singco, Brenda; Liu, Li-Hao; Chen, Ya-Ting; Shih, Yung-Han; Huang, Hsi-Ya; Lin, Chia-Her
    Microporous and Mesoporous Materials (2016), 223 (), 254-260CODEN: MIMMFJ; ISSN:1387-1811. (Elsevier B.V.)
    Aspirin is known as a wonder drug due to its vast therapeutic range. However, side effects after oral administration include gastrointestinal irritation. Shielding of the free aspirin was developed by confining it inside the pores of MIL-100(Fe). This was done by immersion of the metal-org. framework (MOF) in a satd. aspirin soln. which achieved a ∼181% loading efficiency by time-of-flight mass spectrometer (TOF/MS) detection and took about 14 days for the drug release in phosphate buffered saline at 37 °C. The pore vol. of the MOF was found to be the determinant in the loading efficiency of aspirin when variations arise between batches of the encapsulating material. Another approach in the use of MOFs for aspirin delivery was to incorporate aspirin as ligand in the de novo synthesis of the AH-series MOFs (bioactive MOFs). The diffusion of aspirin from the MOFs was slower in acidic medium and was faster in basic medium. This encapsulation technique of aspirin would potentially spare it from enzymic degrdn. and interactions in the stomach that would lessen the amt. of the drug transported into the blood.
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  36. 36
    Horcajada, P.; Chalati, T.; Serre, C.; Gillet, B.; Sebrie, C.; Baati, T.; Eubank, J. F.; Heurtaux, D.; Clayette, P.; Kreuz, C.; Chang, J.-S.; Hwang, Y. K.; Marsaud, V.; Bories, P.-N.; Cynober, L.; Gil, S.; Férey, G.; Couvreur, P.; Gref, R. Porous Metal-Organic-Framework Nanoscale Carriers as a Potential Platform for Drug Delivery and Imaging. Nat. Mater. 2010, 9, 172– 178,  DOI: 10.1038/nmat2608
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    Porous metal-organic-framework nanoscale carriers as a potential platform for drug delivery and imaging
    Horcajada, Patricia; Chalati, Tamim; Serre, Christian; Gillet, Brigitte; Sebrie, Catherine; Baati, Tarek; Eubank, Jarrod F.; Heurtaux, Daniela; Clayette, Pascal; Kreuz, Christine; Chang, Jong-San; Hwang, Young Kyu; Marsaud, Veronique; Bories, Phuong-Nhi; Cynober, Luc; Gil, Sophie; Ferey, Gerard; Couvreur, Patrick; Gref, Ruxandra
    Nature Materials (2010), 9 (2), 172-178CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)
    In the domain of health, one important challenge is the efficient delivery of drugs in the body using non-toxic nanocarriers. Most of the existing carrier materials show poor drug loading (usually less than 5 wt% of the transported drug vs. the carrier material) and/or rapid release of the proportion of the drug that is simply adsorbed (or anchored) at the external surface of the nanocarrier. In this context, porous hybrid solids, with the ability to tune their structures and porosities for better drug interactions and high loadings, are well suited to serve as nanocarriers for delivery and imaging applications. Here we show that specific non-toxic porous iron(III)-based metal-org. frameworks with engineered cores and surfaces, as well as imaging properties, function as superior nanocarriers for efficient controlled delivery of challenging antitumoral and retroviral drugs (i.e., busulfan, azidothymidine triphosphate, doxorubicin or cidofovir) against cancer and AIDS. In addn. to their high loadings, they also potentially assoc. therapeutics and diagnostics, thus opening the way for theranostics, or personalized patient treatments.
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  37. 37
    Rojas, S.; Carmona, F. J.; Maldonado, C. R.; Barea, E.; Navarro, J. A. R. RAPTA-C Incorporation and Controlled Delivery from MIL-100(Fe) Nanoparticles. New J. Chem. 2016, 40, 5690– 5694,  DOI: 10.1039/C5NJ02741A
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    37
    RAPTA-C incorporation and controlled delivery from MIL-100(Fe) nanoparticles
    Rojas, Sara; Carmona, Francisco J.; Maldonado, Carmen R.; Barea, Elisa; Navarro, Jorge A. R.
    New Journal of Chemistry (2016), 40 (7), 5690-5694CODEN: NJCHE5; ISSN:1144-0546. (Royal Society of Chemistry)
    [Fe3F(H2O)2O(btc)2]·nH2O (H3btc: benzene-1,3,5-tricarboxylic acid) (MIL-100(Fe)) in the form of nanoparticles with av. size of 135±70 nm can be used for the adsorption and controlled delivery of metallodrug [Ru(p-cymene)Cl2(pta)] (RAPTA-C) in simulated body fluid (SBF). The results show that the RAPTA-C delivery process takes place in two steps exhibiting half-life times of 1.9 and 30 h. We also found a pos. effect of bovine serum albumine (BSA) in speeding up the RAPTA-C delivery rate, which agrees with the suitability of MIL-100(Fe) as a drug delivery system (DDS) for the controlled release of RAPTA-C.
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  38. 38
    Hailili, R.; Wang, L.; Qv, J.; Yao, R.; Zhang, X. M.; Liu, H. Planar Mn4O Cluster Homochiral Metal-Organic Framework for HPLC Separation of Pharmaceutically Important (±)-Ibuprofen Racemate. Inorg. Chem. 2015, 54, 3713– 3715,  DOI: 10.1021/ic502861k
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    38
    Planar Mn4O Cluster Homochiral Metal-Organic Framework for HPLC Separation of Pharmaceutically Important (±)-Ibuprofen Racemate
    Hailili, Reshalaiti; Wang, Li; Qv, Junzhang; Yao, Ruxin; Zhang, Xian-Ming; Liu, Huwei
    Inorganic Chemistry (2015), 54 (8), 3713-3715CODEN: INOCAJ; ISSN:0020-1669. (American Chemical Society)
    A planar tetracoordinated oxygen contg. a homochiral metal-org. framework (MOF) was synthesized and characterized that can be used as a new chiral stationary phase in HPLC to efficiently sep. racemates such as pharmaceutically important (±)-ibuprofen and (±)-1-phenyl-1,2-ethanediol.
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  39. 39
    Bueno-Perez, R.; Martin-Calvo, A.; Gómez-Álvarez, P.; Gutiérrez-Sevillano, J. J.; Merkling, P. J.; Vlugt, T. J. H.; van Erp, T. S.; Dubbeldam, D.; Calero, S. Enantioselective Adsorption of Ibuprofen and Lysine in Metal–organic Frameworks. Chem. Commun. 2014, 50, 10849– 10852,  DOI: 10.1039/C4CC03745F
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    39
    Enantioselective adsorption of ibuprofen and lysine in metal-organic frameworks
    Bueno-Perez, Rocio; Martin-Calvo, Ana; Gomez-Alvarez, Paula; Gutierrez-Sevillano, Juan J.; Merkling, Patrick J.; Vlugt, Thijs J. H.; van Erp, Titus S.; Dubbeldam, David; Calero, Sofia
    Chemical Communications (Cambridge, United Kingdom) (2014), 50 (74), 10849-10852CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
    This study reveals the efficient enantiomeric sepn. of bioactive mols. in the liq. phase. Chiral structure HMOF-1 separates racemic mixts. whereas heteroselectivity is obsd. for scalemic mixts. of ibuprofen using non-chiral MIL-47 and MIL-53. Lysine enantiomers are only sepd. by HMOF-1. These sepns. are controlled by the tight confinement of the mols.
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  40. 40
    Paudel, K. S.; Milewski, M.; Swadley, C. L.; Brogden, N. K.; Ghosh, P.; Stinchcomb, A. L. Challenges and Opportunities in Dermal/transdermal Delivery. Ther. Delivery 2010, 1, 109– 131,  DOI: 10.4155/tde.10.16
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    40
    Challenges and opportunities in dermal/transdermal delivery
    Paudel, Kalpana S.; Milewski, Mikolaj; Swadley, Courtney L.; Brogden, Nicole K.; Ghosh, Priyanka; Stinchcomb, Audra L.
    Therapeutic Delivery (2010), 1 (1), 109-131CODEN: TDHEA7; ISSN:2041-5990. (Future Science Ltd.)
    A review. Transdermal drug delivery is an exciting and challenging area. There are numerous transdermal delivery systems currently available on the market. However, the transdermal market still remains limited to a narrow range of drugs. Further advances in transdermal delivery depend on the ability to overcome the challenges faced regarding the permeation and skin irritation of the drug mols. Emergence of novel techniques for skin permeation enhancement and development of methods to lessen skin irritation would widen the transdermal market for hydrophilic compds., macromols. and conventional drugs for new therapeutic indications. As evident from the ongoing clin. trials of a wide variety of drugs for various clin. conditions, there is a great future for transdermal delivery of drugs.
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  41. 41
    Chabri, F.; Bouris, K.; Jones, T.; Barrow, D.; Hann, A.; Allender, C.; Brain, K.; Birchall, J. Microfabricated Silicon Microneedles for Nonviral Cutaneous Gene Delivery. Br. J. Dermatol. 2004, 150, 869– 877,  DOI: 10.1111/j.1365-2133.2004.05921.x
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    41
    Microfabricated silicon microneedles for nonviral cutaneous gene delivery
    Chabri, F.; Bouris, K.; Jones, T.; Barrow, D.; Hann, A.; Allender, C.; Brain, K.; Birchall, J.
    British Journal of Dermatology (2004), 150 (5), 869-877CODEN: BJDEAZ; ISSN:0007-0963. (Blackwell Publishing Ltd.)
    The skin represents an accessible somatic tissue for therapeutic gene transfer. The superficial lipophilic layer of the skin, the stratum corneum, however, constitutes a major obstacle to the cutaneous delivery of charged macromols. such as DNA. To det. whether silicon-based microneedles, microfabricated via a novel isotropic etching/BOSCH reaction process, could generate microchannels in the skin of sufficient dimensions to facilitate access of lipid: polycation: pDNA (LPD) nonviral gene therapy vectors. SEM was used to visualize the microconduits created in heat-sepd. human epidermal sheets after application of the microneedles. Following confirmation of particle size and particle surface charge by photon correlation spectroscopy and microelectrophoresis, resp., the diffusion of fluorescent polystyrene nanospheres and LPD complexes through heat-sepd. human epidermal sheets was detd. in vitro using a Franz-type diffusion cell. In-vitro cell culture with quantification by flow cytometry was used to det. gene expression in human keratinocytes (HaCaT cells). The diffusion of 100 nm diam. fluorescent polystyrene nanospheres, used as a readily quantifiable predictive model for LPD complexes, through epidermal sheets was significantly enhanced following membrane treatment with microneedles. The delivery of LPD complexes either into or through the membrane microchannels was also demonstrated. In both cases considerable interaction between the particles and the epidermal sheet was obsd. In-vitro cell culture was used to confirm that LPD complexes mediated efficient reporter gene expression in human keratinocytes in culture when formulated at the appropriate surface charge. These studies demonstrate the utility of silicon microneedles in cutaneous gene delivery.
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  42. 42
    Sapino, S.; Oliaro-bosso, S.; Zonari, D.; Zattoni, A.; Ugazio, E. Mesoporous Silica Nanoparticles as a Promising Skin Delivery System for Methotrexate. Int. J. Pharm. 2017, 530, 239– 248,  DOI: 10.1016/j.ijpharm.2017.07.058
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    42
    Mesoporous silica nanoparticles as a promising skin delivery system for methotrexate
    Sapino, Simona; Oliaro-Bosso, Simonetta; Zonari, Daniele; Zattoni, Andrea; Ugazio, Elena
    International Journal of Pharmaceutics (Amsterdam, Netherlands) (2017), 530 (1-2), 239-248CODEN: IJPHDE; ISSN:0378-5173. (Elsevier B.V.)
    The systemic administration of methotrexate (MTX), a commonly used, antineoplastic drug which is also used in cutaneous disorders, is primarily assocd. with prolonged retention in the body and consequently with side effects. Innovative drug delivery techniques and alternative administration routes would therefore contribute to its safe and effective use. The general objective of this study is thus the development of MTX-based prepns. for the topical treatment of skin disorders. MCM-41-like nanoparticles (MSN), are herein proposed as carriers which can improve the cutaneous absorption and hence the bioavailability and efficacy of MTX. The MTX/MSN complex, prepd. via the impregnation procedure, has been physico-chem. characterized, while its cell cultures have had their biocompatibility and bioactivity tested. Furthermore, a series of stable MTX-based dermal formulations has been developed, some contg. shea butter, a natural fat. Ex-vivo porcine skin absorption and the transepidermal permeation of MTX have also been monitored in a variety of media using Franz diffusion cells. Interestingly, the epidermal accumulation of the active mol. was increased by its inclusion into MSN, regardless of the surrounding medium. Furthermore, the presence of shea butter enhanced the skin uptake of the drug both in the free and in the loaded form.
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  43. 43
    Orellana-Tavra, C.; Marshall, R. J.; Baxter, E. F.; Lázaro, I. A.; Tao, A.; Cheetham, A. K.; Forgan, R. S.; Fairen-Jimenez, D. Drug Delivery and Controlled Release from Biocompatible Metal–organic Frameworks Using Mechanical Amorphization. J. Mater. Chem. B 2016, 7697– 7707,  DOI: 10.1039/C6TB02025A
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    43
    Drug delivery and controlled release from biocompatible metal-organic frameworks using mechanical amorphization
    Orellana-Tavra, Claudia; Marshall, Ross J.; Baxter, Emma F.; Lazaro, Isabel Abanades; Tao, Andi; Cheetham, Anthony K.; Forgan, Ross S.; Fairen-Jimenez, David
    Journal of Materials Chemistry B: Materials for Biology and Medicine (2016), 4 (47), 7697-7707CODEN: JMCBDV; ISSN:2050-7518. (Royal Society of Chemistry)
    We have used a family of Zr-based metal-org. frameworks (MOFs) with different functionalized (bromo, nitro and amino) and extended linkers for drug delivery. We loaded the materials with the fluorescent model mol. calcein and the anticancer drug α-cyano-4-hydroxycinnamic acid (α-CHC), and consequently performed a mech. amorphization process to attempt to control the delivery of guest mols. Our anal. revealed that the loading values of both mols. were higher for the MOFs contg. unfunctionalized linkers. Confocal microscopy showed that all the materials were able to penetrate into cells, and the therapeutic effect of α-CHC on HeLa cells was enhanced when loaded (20 wt%) into the MOF with the longest linker. On one hand, calcein release required up to 3 days from the cryst. form for all the materials. On the other hand, the amorphous counterparts contg. the bromo and nitro functional groups released only a fraction of the total loaded amt., and in the case of the amino-MOF a slow and progressive release was successfully achieved for 15 days. In the case of the materials loaded with α-CHC, no difference was obsd. between the cryst. and amorphous form of the materials. These results highlight the necessity of a balance between the pore size of the materials and the size of the guest mols. to accomplish a successful and efficient sustained release using this mech. ball-milling process. Addnl., the endocytic pathway used by cells to internalize these MOFs may lead to diverse final cellular locations and consequently, different therapeutic effects. Understanding these cellular mechanisms will drive the design of more effective MOFs for drug delivery applications.
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  44. 44
    Abánades Lázaro, I.; Haddad, S.; Sacca, S.; Orellana-Tavra, C.; Fairen-Jimenez, D.; Forgan, R. S. Selective Surface PEGylation of UiO-66 Nanoparticles for Enhanced Stability, Cell Uptake, and pH-Responsive Drug Delivery. Chem 2017, 2, 561– 578,  DOI: 10.1016/j.chempr.2017.02.005
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    44
    Selective Surface PEGylation of UiO-66 Nanoparticles for Enhanced Stability, Cell Uptake, and pH-Responsive Drug Delivery
    Abanades Lazaro, Isabel; Haddad, Salame; Sacca, Sabrina; Orellana-Tavra, Claudia; Fairen-Jimenez, David; Forgan, Ross S.
    Chem (2017), 2 (4), 561-578CODEN: CHEMVE; ISSN:2451-9294. (Cell Press)
    The high storage capacities and excellent biocompatibilities of metal-org. frameworks (MOFs) have made them emerging candidates as drug-delivery vectors. Incorporation of surface functionality is a route to enhanced properties, and here we report on a surface-modification procedure-click modulation-that controls their size and surface chem. The zirconium terephthalate MOF UiO-66 is (1) synthesized as ∼200 nm nanoparticles coated with functionalized modulators, (2) loaded with cargo, and (3) covalently surface modified with poly(ethylene glycol) (PEG) chains through mild bioconjugate reactions. At pH 7.4, the PEG chains endow the MOF with enhanced stability toward phosphates and overcome the "burst release" phenomenon by blocking interaction with the exterior of the nanoparticles, whereas at pH 5.5, stimuli-responsive drug release is achieved. The mode of cellular internalization is also tuned by nanoparticle surface chem., such that PEGylated UiO-66 potentially escapes lysosomal degrdn. through enhanced caveolae-mediated uptake. This makes it a highly promising vector, as demonstrated for dichloroacetic-acid-loaded materials, which exhibit enhanced cytotoxicity. The versatility of the click modulation protocol will allow a wide range of MOFs to be easily surface functionalized for a no. of applications.
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  45. 45
    Tamames-Tabar, C.; Cunha, D.; Imbuluzqueta, E.; Ragon, F.; Serre, C.; Blanco-Prieto, M. J.; Horcajada, P. Cytotoxicity of Nanoscaled Metal–organic Frameworks. J. Mater. Chem. B 2014, 2, 262– 271,  DOI: 10.1039/C3TB20832J
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    45
    Cytotoxicity of nanoscaled metal-organic frameworks
    Tamames-Tabar, Cristina; Cunha, Denise; Imbuluzqueta, Edurne; Ragon, Florence; Serre, Christian; Blanco-Prieto, Maria J.; Horcajada, Patricia
    Journal of Materials Chemistry B: Materials for Biology and Medicine (2014), 2 (3), 262-271CODEN: JMCBDV; ISSN:2050-7518. (Royal Society of Chemistry)
    A series of fourteen porous Metal-Org. Frameworks (MOFs) with different compns. (Fe, Zn, and Zr; carboxylates or imidazolates) and structures have been successfully synthesized at the nanoscale and fully characterised by XRPD, FTIR, TGA, N2 porosimetry, TEM, DLS and ζ-potential. Their toxicol. assessment was performed using two different cell lines: human epithelial cells from fetal cervical carcinoma (HeLa) and murine macrophage cell line (J774). It appears that MOF nanoparticles (NPs) exhibit low cytotoxicity, comparable to those of other commercialised nanoparticulate systems, the less toxic being the Fe carboxylate and the more toxic being the zinc imidazolate NPs. The cytotoxicity values, higher in J774 cells than in HeLa cells, are mainly function of their compn. and cell internalisation capacity. Finally, cell uptake of one of the most relevant Fe-MOF-NPs for drug vectorization has been investigated by confocal microscopy studies, and indicates a faster kinetics of cell penetration within J774 compared to HeLa cells.
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  46. 46
    Hu, Q.; Yu, J.; Liu, M.; Liu, A.; Dou, Z.; Yang, Y. A Low Cytotoxic Cationic Metal-Organic Framework Carrier for Controllable Drug Release. J. Med. Chem. 2014, 57, 5679– 5685,  DOI: 10.1021/jm5004107
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    46
    A Low Cytotoxic Cationic Metal-Organic Framework Carrier for Controllable Drug Release
    Hu, Quan; Yu, Jiancan; Liu, Min; Liu, Aiping; Dou, Zhongshang; Yang, Yu
    Journal of Medicinal Chemistry (2014), 57 (13), 5679-5685CODEN: JMCMAR; ISSN:0022-2623. (American Chemical Society)
    A pos. charged porous drug carrier MOF-74-Fe(III) (1, MOF = metal-org. framework), which could not be directly synthesized using ferric salts, was prepd. through the oxidn. of the neutral crystal MOF-74-Fe(II). This cationic host material exhibits very low cytotoxicity upon PC12 cells by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium (MTT) assay and high drug loading capacity of ibuprofen anions (∼15.9 wt %) through ion exchange and salt penetration procedures. Controlled by anion exchange, two mechanisms were involved in the drug release process with different drug delivery rates due to the presence of coordinated or free ibuprofen anions, making the administration of drug release more flexible.
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  47. 47
    Lestari, W. W.; Arvinawati, M.; Martien, R.; Kusumaningsih, T. Green and Facile Synthesis of MOF and Nano MOF Containing zinc(II) and Benzen 1,3,5-Tri Carboxylate and Its Study in Ibuprofen Slow-Release. Mater. Chem. Phys. 2018, 204, 141– 146,  DOI: 10.1016/j.matchemphys.2017.10.034
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    47
    Green and facile synthesis of MOF and nano MOF containing zinc(II) and benzene 1,3,5-tricarboxylate and its study in ibuprofen slow-release
    Lestari, Witri Wahyu; Arvinawati, Maria; Martien, Ronny; Kusumaningsih, Triana
    Materials Chemistry and Physics (2018), 204 (), 141-146CODEN: MCHPDR; ISSN:0254-0584. (Elsevier B.V.)
    Nano scale and bio-based metal-org. frameworks (MOFs) are an important class of porous materials potentially used in biomedical application. Several green and facile synthetic methods have been developed in this regard. In this study, we have compared green synthetic methods in generating MOF and nano MOF contg. biocompatible metal ion, i.e. zinc(II) and benzene 1,3,5-tricarboxylic acid (H3BTC) as linker to form [Zn3(BTC)2] using electro- and sonochem. method. The electrosynthesis of [Zn3(BTC)2] performed at ambient temp. under voltage of 15 V in the solvent mixt. of ethanol: water (1:1), whereas the sonochem. conducted in the solvent mixt. ethanol: water (1: 1) at ambient temps. and 40 KHz with a time variation of 90, 60 and 30 min. The obtained materials were loaded with ibuprofen for three days. The materials, before and after being loaded with ibuprofen, were fully characterized using x-ray diffraction anal., FTIR, SEM and transmission electron microscopy (TEM), surface area analyzer (SAA) and thermogravimetric anal. (TG/DTA). The electrochem. method tend to produce larger avarage particle size (ca. 18.43 ± 8.10μm) of [Zn3(BTC)2] than sonochem. method (with avarage particle size ca. 87.63 ± 22.86 and 112.23 ± 28.87 nm, for 30 and 60 min, resp.). Slow-release of ibuprofen was conducted in a phosphate buffered saline system (PBS) at 37°C and pH 7.4. The concn. of loaded and released ibuprofen were monitored using UV-Vis spectroscopy. After 24 h, it showed that ibuprofen encapsulated into [Zn3(BTC)2] have av. release ca. 25.6 wt%, while ibuprofen without [Zn3(BTC)2] is released ca. 85.9 wt%, then continued with a const. rate. This study demonstrated that [Zn3(BTC)2] could be afforded as a matrix to assist the slow-release of ibuprofen.
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  48. 48
    Horcajada, P.; Serre, C.; Maurin, G.; Ramsahye, N. A.; Balas, F.; Vallet-Regí, M.; Sebban, M.; Taulelle, F.; Férey, G. Flexible Porous Metal-Organic Frameworks for a Controlled Drug Delivery. J. Am. Chem. Soc. 2008, 130, 6774– 6780,  DOI: 10.1021/ja710973k
    Google Scholar
    48
    Flexible Porous Metal-Organic Frameworks for a Controlled Drug Delivery
    Horcajada, Patricia; Serre, Christian; Maurin, Guillaume; Ramsahye, Naseem A.; Balas, Francisco; Vallet-Regi, Marila; Sebban, Muriel; Taulelle, Francis; Ferey, Geard
    Journal of the American Chemical Society (2008), 130 (21), 6774-6780CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    Flexible nanoporous chromium or iron terephthalates (BDC) MIL-53(Cr, Fe) or M(OH)[BDC] have been used as matrixes for the adsorption and in vitro drug delivery of Ibuprofen (or α-p-isobutylphenylpropionic acid). Both MIL-53(Cr) and MIL-53(Fe) solids adsorb around 20 wt % of Ibuprofen (Ibuprofen/dehydrated MIL-53 molar ratio = 0.22(1)), indicating that the amt. of inserted drug does not depend on the metal (Cr, Fe) constitutive of the hybrid framework. Structural and spectroscopic characterizations are provided for the solid filled with Ibuprofen. In each case, the very slow and complete delivery of Ibuprofen was achieved under physiol. conditions after 3 wk with a predictable zero-order kinetics, which highlights the unique properties of flexible hybrid solids for adapting their pore opening to optimize the drug-matrix interactions.
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  49. 49
    Higuchi, W. I. Analysis of Data on Medicament Release Form Ointments. J. Pharm. Sci. 1962, 51, 802– 804,  DOI: 10.1002/jps.2600510825
    Google Scholar
    There is no corresponding record for this reference.
  50. 50
    Vallet-Regí, M.; Balas, F.; Arcos, D. Mesoporous Materials for Drug Delivery. Angew. Chem., Int. Ed. 2007, 46, 7548– 7558,  DOI: 10.1002/anie.200604488
    Google Scholar
    50
    Mesoporous materials for drug delivery
    Vallet-Regi, Maria; Balas, Francisco; Arcos, Daniel
    Angewandte Chemie, International Edition (2007), 46 (40), 7548-7558CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    A review. Research on mesoporous materials for biomedical purposes has experienced an outstanding increase during recent years. Since 2001, when MCM-41 was first proposed as drug-delivery system, silica-based materials, such as SBA-15 or MCM-48, and some metal-org. frameworks were discussed as drug carriers and controlled-release systems. Mesoporous materials are intended for both systemic-delivery systems and implantable local-delivery devices. The later application provides very promising possibilities in the field of bone-tissue repair because of the excellent behavior of these materials as bioceramics. This Minireview deals with the advances in this field by the control of the textural parameters, surface functionalization, and the synthesis of sophisticated stimuli-response systems.
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  51. 51
    Ke, F.; Yuan, Y.-P.; Qiu, L.-G.; Shen, Y.-H.; Xie, A.-J.; Zhu, J.-F.; Tian, X.-Y.; Zhang, L.-D. Facile Fabrication of Magnetic Metal–organic Framework Nanocomposites for Potential Targeted Drug Delivery. J. Mater. Chem. 2011, 21, 3843– 3848,  DOI: 10.1039/c0jm01770a
    Google Scholar
    51
    Facile fabrication of magnetic metal-organic framework nanocomposites for potential targeted drug delivery
    Ke, Fei; Yuan, Yu-Peng; Qiu, Ling-Guang; Shen, Yu-Hua; Xie, An-Jian; Zhu, Jun-Fa; Tian, Xing-You; Zhang, Li-De
    Journal of Materials Chemistry (2011), 21 (11), 3843-3848CODEN: JMACEP; ISSN:0959-9428. (Royal Society of Chemistry)
    We describe a facile, efficient, and environmentally friendly fabrication of a novel type of magnetic porous metal-org.-framework (MOF)-based nanocomposites that can be potentially used for targeted drug delivery. The magnetic MOF nanocomposites were fabricated by incorporation of Fe3O4 nanorods with nanocrystals of Cu3(BTC)2 (HKUST-1), a 3-dimensional (3D) MOF with a 3D channel system. The as-synthesized materials had both magnetic characteristics and high porosity, making them excellent candidates for targeted drug delivery systems. An anti-cancer drug acting as a selective cyclooxygenase-2 (COX-2) inhibitor for pancreatic cancer treatment, nimesulide, was laden into pores of the nanocomposites. These MOF-based magnetic nanocomposites could adsorb up to 0.2 g of nimesulide per g of composite, and it took as long as 11 days to complete the drug release in physiol. saline at 37°.
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  52. 52
    Tiwari, A.; Patra, H. K.; Wang, X. Advanced Materials Interfaces; Gregory, P., Ed.; Wiley-VCH: Weinheim, 2016.
    Google Scholar
    There is no corresponding record for this reference.
  53. 53
    Dhakshinamoorthy, A.; Alvaro, M.; Chevreau, H.; Horcajada, P.; Devic, T.; Garcia, H.; Serre, C. Iron(III) Metal–organic Frameworks as Solid Lewis Acids for the Isomerization of Alfa-Pinene Oxide. Catal. Sci. Technol. 2012, 3, 324– 330,  DOI: 10.1039/C2CY00376G
    Google Scholar
    There is no corresponding record for this reference.
  54. 54
    Kandiah, M.; Nilsen, M. H.; Usseglio, S.; Jakobsen, S.; Olsbye, U.; Tilset, M.; Larabi, C.; Quadrelli, E. A.; Bonino, F.; Lillerud, K. P. Synthesis and Stability of Tagged UiO-66 Zr-MOFs. Chem. Mater. 2010, 22, 6632– 6640,  DOI: 10.1021/cm102601v
    Google Scholar
    54
    Synthesis and Stability of Tagged UiO-66 Zr-MOFs
    Kandiah, Mathivathani; Nilsen, Merete Hellner; Usseglio, Sandro; Jakobsen, Soren; Olsbye, Unni; Tilset, Mats; Larabi, Cherif; Quadrelli, Elsje Alessandra; Bonino, Francesca; Lillerud, Karl Petter
    Chemistry of Materials (2010), 22 (24), 6632-6640CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
    The assembly of extended structures of the Zr-based MOF UiO-66 was pursued with three different com. available ligands: 2-aminobenzenedicarboxylic acid (H2N-H2BDC), 2-nitrobenzenedicarboxylic acid (ON-H2BDC), and 2-bromobenzenedicarboxylic acid (Br-H2BDC). Three new functionalized MOFs UiO-66-NH2 (1), UiO-66-NO2 (2), and UiO-66-Br (3) was initiated by detg. the reaction conditions necessary to produce MOFs with the same topol. of the parent UiO-66. Thermal and structural stability of the modified MOFs were examd. using powder X-ray diffraction anal. (PXRD) and thermogravimetric anal. (TGA). Langmuir surface areas were also detd. using N2 isotherms at 77 K to examine the porosity of the functionalized materials. Some changes in the surface area because of the presence of addnl. functionality on the BDC ligand were revealed. The results demonstrate the possibility of incorporating active functional groups into the UiO-66 structure almost without losing its exceptionally high thermal and chem. stability.
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  55. 55
    Garibay, S. J.; Cohen, S. M. Isoreticular Synthesis and Modification of Frameworks with the UiO-66 Topology. Chem. Comm. 2010, 46, 7700– 7702,  DOI: 10.1039/c0cc02990d
    Google Scholar
    55
    Isoreticular synthesis and modification of frameworks with the UiO-66 topology
    Garibay, Sergio J.; Cohen, Seth M.
    Chemical Communications (Cambridge, United Kingdom) (2010), 46 (41), 7700-7702CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
    Amino, bromo, nitro, and naphthalene functionalized terephthalates in UiO-66 metal-org. frameworks [Zr6O4(OH)4(p-O2C-Ar-CO2)6]n were synthesized through reticular chem. UiO-66-NH2 is suitable for postsynthetic modification with a variety of anhydrides to generate new, functionalized frameworks.
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  56. 56
    Rappe, A. K.; Iii, W. A. G. Charge Equilibration for Molecular Dynamics Simulations. J. Phys. Chem. 1991, 95, 3358– 3363,  DOI: 10.1021/j100161a070
    Google Scholar
    56
    Charge equilibration for molecular dynamics simulations
    Rappe, Anthony K.; Goddard, William A., III
    Journal of Physical Chemistry (1991), 95 (8), 3358-63CODEN: JPCHAX; ISSN:0022-3654.
    An approach is reported for predicting charge distributions in mols. for use in mol. dynamics simulations. The input data are exptl. at. ionization potentials, electron affinities, and at. radii. An at. chem. potential is constructed by using these quantities plus shielded electrostatic interactions between all charges. Equal chem. potentials leads to equil. charges that depend upon geometry. This Charge Equilibration (QEq) approach leads to charges in excellent agreement with exptl. dipole moments and with the at. charges obtained from the electrostatic potentials of accurate ab initio calcns. QEq can be used to predict charges for any polymer, ceramic, semiconductor, or biol. system, allowing extension of mol. dynamics studies to broad classes of new systems. The charges depend upon environment and changes during mol. dynamics calcns. This approach can also be used to predict IR intensities, dielec. consts., and other charge-related properties.
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    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK3MXhvFaktbo%253D&md5=c7dccc6c65d8935261db5310e8cb0e97
  57. 57
    Rappe, A. K.; Casewit, C. J.; Colwell, K. S.; Goddard, W. A., III; Skiff, W. M. UFF, a Full Periodic Table Force Field for Molecular Mechanics and Molecular Dynamics Simulations. J. Am. Chem. Soc. 1992, 114, 10024– 10035,  DOI: 10.1021/ja00051a040
    Google Scholar
    57
    UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations
    Rappe, A. K.; Casewit, C. J.; Colwell, K. S.; Goddard, W. A., III; Skiff, W. M.
    Journal of the American Chemical Society (1992), 114 (25), 10024-35CODEN: JACSAT; ISSN:0002-7863.
    A new mol. mechanics force field, the Universal force field (UFF), is described wherein the force field parameters are estd. using general rules based only on the element, its hybridization and its connectivity. The force field functional forms, parameters, and generating formulas for the full periodic table are presented.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK38Xmtl2qur8%253D&md5=cf41e8bb9ad299fd5d79f070d690afe1
  58. 58
    Yang, Q.; Wiersum, A. D.; Llewellyn, P. L.; Guillerm, V.; Serre, C.; Maurin, G. Functionalizing Porous Zirconium Terephthalate UiO-66 (Zr) for Natural Gas Upgrading: A Computational Exploration. Chem. Commun. 2011, 47, 9603– 9605,  DOI: 10.1039/c1cc13543k
    Google Scholar
    There is no corresponding record for this reference.
  59. 59
    Düren, T.; Millange, F.; Férey, G.; Walton, K. S.; Snurr, R. Q. Calculating Geometric Surface Areas as a Characterization Tool for Metal-Organic Frameworks. J. Phys. Chem. C 2007, 111, 15350– 15356,  DOI: 10.1021/jp074723h
    Google Scholar
    59
    Calculating Geometric Surface Areas as a Characterization Tool for Metal-Organic Frameworks
    Dueren, Tina; Millange, Franck; Ferey, Gerard; Walton, Krista S.; Snurr, Randall Q.
    Journal of Physical Chemistry C (2007), 111 (42), 15350-15356CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
    Metal-org. frameworks (MOFs) synthesized in a building-block approach from org. linkers and metal corner units offer the opportunity to design materials with high surface areas for adsorption applications by assembling the appropriate building blocks. In this paper, we show that the surface area calcd. in a geometric fashion from the crystal structure is a useful tool for characterizing MOFs. We argue that the accessible surface area rather than the widely used Connolly surface area is the appropriate surface area to characterize cryst. solids for adsorption applications. The accessible surface area calcd. with a probe diam. corresponding to the adsorbate of interest provides a simple way to screen and compare adsorbents. We investigate the effects of the probe mol. diam. on the accessible surface area and discuss the implications for increasing the surface area of metal-org. frameworks by the use of catenated structures. We also demonstrate that the accessible surface area provides a useful tool for judging the quality of a synthesized sample. Exptl. surface areas can be adversely affected by incomplete solvent removal during activation, crystal collapse, or interpenetration. The easily calcd. accessible surface area provides a benchmark for the theor. upper limit for a perfect crystal.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2sXhtFShtLjP&md5=47226155a5817ef357a9b6f941883ee6

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  3. Ioanna Christodoulou, Gilles Patriarche, Christian Serre, Cédric Boissiére, Ruxandra Gref. Advanced Characterization Methodology to Unravel the Biodegradability of Metal–Organic Framework Nanoparticles in Extremely Diluted Conditions. ACS Applied Materials & Interfaces 2024, 16 (11) , 14296-14307. https://doi.org/10.1021/acsami.3c18958
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  8. Neila Pederneira, Kyle Newport, Shane Lawson, Ali A. Rownaghi, Fateme Rezaei. Drug Delivery on Mg-MOF-74: The Effect of Drug Solubility on Pharmacokinetics. ACS Applied Bio Materials 2023, 6 (6) , 2477-2486. https://doi.org/10.1021/acsabm.3c00275
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  12. Jinhua Feng, Junnan Chen, Shuchang Wang, Miaomiao Jia, Zhiyu Zhang, Tongwen Yu, Ming Xue. Rational Design of Inhibitor-Encapsulated Bio-MOF-1 for Dual Corrosion Protection. Inorganic Chemistry 2022, 61 (45) , 18285-18292. https://doi.org/10.1021/acs.inorgchem.2c03151
  13. Muhammad Usman Akbar, Muhammad Badar, Muhammad Zaheer. Programmable Drug Release from a Dual-Stimuli Responsive Magnetic Metal–Organic Framework. ACS Omega 2022, 7 (36) , 32588-32598. https://doi.org/10.1021/acsomega.2c04144
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  19. Shane Lawson, Ali A. Rownaghi, Fateme Rezaei. Combined Ibuprofen and Curcumin Delivery Using Mg-MOF-74 as a Single Nanocarrier. ACS Applied Bio Materials 2022, 5 (1) , 265-271. https://doi.org/10.1021/acsabm.1c01067
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  24. Hao Pham, Kimberly Ramos, Andy Sua, Jessica Acuna, Katarzyna Slowinska, Travis Nguyen, Angela Bui, Mark D. R. Weber, Fangyuan Tian. Tuning Crystal Structures of Iron-Based Metal–Organic Frameworks for Drug Delivery Applications. ACS Omega 2020, 5 (7) , 3418-3427. https://doi.org/10.1021/acsomega.9b03696
  25. Mithun Sarker, Subin Shin, Sung Hwa Jhung. Synthesis and Functionalization of Porous Zr-Diaminostilbenedicarboxylate Metal–Organic Framework for Storage and Stable Delivery of Ibuprofen. ACS Omega 2019, 4 (6) , 9860-9867. https://doi.org/10.1021/acsomega.9b01139
  26. Sara Rojas, Nathalie Guillou, Patricia Horcajada. Ti-Based nanoMOF as an Efficient Oral Therapeutic Agent. ACS Applied Materials & Interfaces 2019, 11 (25) , 22188-22193. https://doi.org/10.1021/acsami.9b06472
  27. Sabrina Panter, Pezhman Zarabadi-Poor. Computational Exploration of IRMOFs for Xenon Separation from Air. ACS Omega 2018, 3 (12) , 18535-18541. https://doi.org/10.1021/acsomega.8b03014
  28. Tayyaba Tariq, Shumaila Bibi, Syed Shoaib Ahmad Shah, Muhammad Ahmad Wattoo, Mohamed A. Salem, Hala El-Haroun, Zeinhom M. El-Bahy, Aziz ur Rehman, Shujuan Bao. MIL materials: Synthesis strategies, morphology control, and biomedical application: A critical review. Journal of Drug Delivery Science and Technology 2025, 104 , 106532. https://doi.org/10.1016/j.jddst.2024.106532
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  30. Akash Vikal, Rashmi Maurya, Preeti Patel, Shivani Rai Paliwal, Raj Kumar Narang, Ghanshyam Das Gupta, Balak Das Kurmi. Exploring metal-organic frameworks (MOFs) in drug delivery: A concise overview of synthesis approaches, versatile applications, and current challenges. Applied Materials Today 2024, 41 , 102443. https://doi.org/10.1016/j.apmt.2024.102443
  31. Shuai Liu, Yuzhu Xiong, Fuping Dong. Cyclodextrin metal–organic framework@SiO 2 nanocomposites for poorly soluble drug loading and release. RSC Advances 2024, 14 (43) , 31868-31876. https://doi.org/10.1039/D4RA04935G
  32. Xuanxuan Wang, Nan Gao, Jiuhong Zhao, Guixia Ling, Peng Zhang. Applications of Material Institute Lavoisier (MIL) based materials as nano drug delivery carriers in biomedicine. Coordination Chemistry Reviews 2024, 517 , 216040. https://doi.org/10.1016/j.ccr.2024.216040
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  36. Javier Salazar, Yoan Hidalgo-Rosa, Pia C. Burboa, Yi-nan Wu, Néstor Escalona, Angel Leiva, Ximena Zarate, Eduardo Schott. UiO-66(Zr) as drug delivery system for non-steroidal anti-inflammatory drugs. Journal of Controlled Release 2024, 370 , 392-404. https://doi.org/10.1016/j.jconrel.2024.04.035
  37. Ngoan Thi Thao Nguyen, Thuy Thi Thanh Nguyen, Shengbo Ge, Rock Keey Liew, Duyen Thi Cam Nguyen, Thuan Van Tran. Recent progress and challenges of MOF-based nanocomposites in bioimaging, biosensing and biocarriers for drug delivery. Nanoscale Advances 2024, 6 (7) , 1800-1821. https://doi.org/10.1039/D3NA01075A
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  39. Pawan Kumar, Ananyaashree Behera, Pranav Tiwari, Sibi Karthik, Mainak Biswas, Avinash Sonawane, Shaikh M. Mobin. Exploring the antimicrobial potential of isoniazid loaded Cu-based metal–organic frameworks as a novel strategy for effective killing of Mycobacterium tuberculosis. Journal of Materials Chemistry B 2023, 11 (45) , 10929-10940. https://doi.org/10.1039/D3TB02292G
  40. Muhammad Usman Akbar, Arslan Akbar, Umair Ali Khan Saddozai, Malik Ihsan Ullah Khan, Muhammad Zaheer, Muhammad Badar. A multivariate metal–organic framework based pH-responsive dual-drug delivery system for chemotherapy and chemodynamic therapy. Materials Advances 2023, 4 (22) , 5653-5667. https://doi.org/10.1039/D3MA00389B
  41. Erika Medel, Jorge Garza, Ilich A. Ibarra, Ana Martínez, Rubicelia Vargas. Non-covalent interactions in biocompatible platforms for drug delivery: Mg2(olsalazine) Metal-Organic Framework with phenylethylamine, dopamine and sertraline. Computational and Theoretical Chemistry 2023, 1228 , 114265. https://doi.org/10.1016/j.comptc.2023.114265
  42. Xiao-Hui Dong, Zhi-Gang Li, Dong-Yan Bian, Tian-Meng Guo, Zi-Ying Li, Wei Li, Hongpeng He. Drug release and solubility properties of two zeolitic metal–organic frameworks influenced by their hydrophobicity/hydrophilicity. Dalton Transactions 2023, 52 (36) , 12909-12917. https://doi.org/10.1039/D3DT01975F
  43. Muhammad Usman Akbar, Saadullah Khattak, Malik Ihsanullah Khan, Umair Ali Khan Saddozai, Nemat Ali, Abdullah F. AlAsmari, Muhammad Zaheer, Muhammad Badar. A pH-responsive bi-MIL-88B MOF coated with folic acid-conjugated chitosan as a promising nanocarrier for targeted drug delivery of 5-Fluorouracil. Frontiers in Pharmacology 2023, 14 https://doi.org/10.3389/fphar.2023.1265440
  44. Fatemeh Parsa, Moslem Setoodehkhah, Seyed Mohammad Atyabi. Loading and release study of ciprofloxacin from silica-coated magnetite modified by iron-based metal-organic framework (MOF) as a nonocarrier in targeted drug delivery system. Inorganic Chemistry Communications 2023, 155 , 111056. https://doi.org/10.1016/j.inoche.2023.111056
  45. Preety Yadav, Priya Bhardwaj, Mulaka Maruthi, Anindita Chakraborty, Prakash Kanoo. Metal–organic framework based drug delivery systems as smart carriers for release of poorly soluble drugs hydrochlorothiazide and dapsone. Dalton Transactions 2023, 52 (33) , 11725-11734. https://doi.org/10.1039/D3DT01301D
  46. Xiao-Wei Yan, Somayeh Tarasi, Su-Juan Wang, Kobra Rostamizadeh, Mao-Lin Hu, Ali Morsali, Ali Ramazani, Roghayeh Tarasi, Yavar Ahmadi. Influence of pore structural properties in metal-organic frameworks on the host-guest interaction in drug delivery. Arabian Journal of Chemistry 2023, 16 (8) , 104887. https://doi.org/10.1016/j.arabjc.2023.104887
  47. Jiaxun Li, Mufeng Lin, Chichao Shen, Zhixuan Zhou. Metal-Organic Framework (MOFs) for Drug Delivery Applications. Highlights in Science, Engineering and Technology 2023, 58 , 304-312. https://doi.org/10.54097/hset.v58i.10113
  48. Erika Medel, Juan L. Obeso, Camilo Serrano-Fuentes, Jorge Garza, Ilich A. Ibarra, Carolina Leyva, A. Ken Inge, Ana Martínez, Rubicelia Vargas. Encapsulation of dopamine within SU-101: insights by computational chemistry. Chemical Communications 2023, 59 (56) , 8684-8687. https://doi.org/10.1039/D3CC02304D
  49. Bao Quang Gia Le, Tan Le Hoang Doan. Trend in biodegradable porous nanomaterials for a nticancer drug delivery. WIREs Nanomedicine and Nanobiotechnology 2023, 15 (4) https://doi.org/10.1002/wnan.1874
  50. Muse Ji, Hongbing Liu, Jingxin Gou, Tian Yin, Haibing He, Yu Zhang, Xing Tang. Recent advances in nanoscale metal–organic frameworks for cancer chemodynamic therapy. Nanoscale 2023, 15 (20) , 8948-8971. https://doi.org/10.1039/D3NR00867C
  51. Syeda Fiza Fatima, Rana Sabouni, Renuka Garg, Hassan Gomaa. Recent advances in Metal-Organic Frameworks as nanocarriers for triggered release of anticancer drugs: Brief history, biomedical applications, challenges and future perspective. Colloids and Surfaces B: Biointerfaces 2023, 225 , 113266. https://doi.org/10.1016/j.colsurfb.2023.113266
  52. J. P. Metherall, R. C. Carroll, S. J. Coles, M. J. Hall, M. R. Probert. Advanced crystallisation methods for small organic molecules. Chemical Society Reviews 2023, 52 (6) , 1995-2010. https://doi.org/10.1039/D2CS00697A
  53. Vihanga K Munasinghe, Dilhan Manawadu, Rohini M de Silva, K M Nalin de Silva. Impact of active sites on encapsulation of curcumin in Metal Organic Frameworks. Materials Research Express 2023, 10 (3) , 035102. https://doi.org/10.1088/2053-1591/acc445
  54. Sandy Elmehrath, Ha L. Nguyen, Sherif M. Karam, Amr Amin, Yaser E. Greish. BioMOF-Based Anti-Cancer Drug Delivery Systems. Nanomaterials 2023, 13 (5) , 953. https://doi.org/10.3390/nano13050953
  55. Ioanna Christodoulou, Pengbo Lyu, Carla Vieira Soares, Gilles Patriarche, Christian Serre, Guillaume Maurin, Ruxandra Gref. Nanoscale Iron-Based Metal–Organic Frameworks: Incorporation of Functionalized Drugs and Degradation in Biological Media. International Journal of Molecular Sciences 2023, 24 (4) , 3362. https://doi.org/10.3390/ijms24043362
  56. Changlei Xia, Xin Jin, Hakim AL. Garalleh, Mazen Garaleh, Yingji Wu, James M. Hill, Arivalagan Pugazhendhi. Optimistic and possible contribution of nanomaterial on biomedical applications: A review. Environmental Research 2023, 218 , 114921. https://doi.org/10.1016/j.envres.2022.114921
  57. Jing Li, Lijun Liang, Hanxing Zhou, Pengzhen Zhang, Zhe Kong, Xing Duan. Molecular dynamics simulation study of drugs adsorption in UiO‐66. Zeitschrift für anorganische und allgemeine Chemie 2023, 649 (1) https://doi.org/10.1002/zaac.202200261
  58. Suzan A. Rashed, Sherif F. Hammad, Moustafa M. Eldakak, Islam A. Khalil, Ahmed Osman. Assessment of the Anticancer Potentials of the Free and Metal-Organic Framework (UiO-66) – Delivered Phycocyanobilin. Journal of Pharmaceutical Sciences 2023, 112 (1) , 213-224. https://doi.org/10.1016/j.xphs.2022.08.038
  59. Ayush Kumar, Rajesh Kumar, Chandan Bhogendra Jha, Rashi Mathur. Metal-organic frameworks (MOFs) nanocarriers-a novel approach for the drug delivery along with other biomedical applications. 2023, 020185. https://doi.org/10.1063/5.0162841
  60. Jinglin Yin, Zhengzhong Kang, Yao Fu, Weicheng Cao, Yiran Wang, Hanxi Guan, Yu Yin, Binbin Chen, Xianfeng Yi, Wei Chen, Wei Shao, Yihan Zhu, Anmin Zheng, Qi Wang, Xueqian Kong. Molecular identification and quantification of defect sites in metal-organic frameworks with NMR probe molecules. Nature Communications 2022, 13 (1) https://doi.org/10.1038/s41467-022-32809-9
  61. Kohei Akagi, Kazuki Ohshima, Shuji Ohsaki, Hideya Nakamura, Satoru Watano. pH dependence of drug release behavior from metal-organic framework particle with different acid-base resistances. Inorganica Chimica Acta 2022, 542 , 121143. https://doi.org/10.1016/j.ica.2022.121143
  62. Liang Qin, Fenglan Liang, Yan Li, Jiana Wu, Shiyuan Guan, Meiyin Wu, Shiling Xie, Manshi Luo, Deyun Ma. A 2D Porous Zinc-Organic Framework Platform for Loading of 5-Fluorouracil. Inorganics 2022, 10 (11) , 202. https://doi.org/10.3390/inorganics10110202
  63. Aftab Alam, Ahmed I. Foudah, Mohammad Ayman Salkini, Mohammad Raish, Jyotiram Sawale. Herbal Fennel Essential Oil Nanogel: Formulation, Characterization and Antibacterial Activity against Staphylococcus aureus. Gels 2022, 8 (11) , 736. https://doi.org/10.3390/gels8110736
  64. Ekaterina Mamontova, Fabrice Salles, Yannick Guari, Joulia Larionova, Jérôme Long. Post-synthetic modification of Prussian blue type nanoparticles: tailoring the chemical and physical properties. Inorganic Chemistry Frontiers 2022, 9 (15) , 3943-3971. https://doi.org/10.1039/D2QI01068B
  65. Guillermo Rodrigo, Rafael Ballesteros-Garrido. Metal–organic frameworks in pursuit of size: the development of macroscopic single crystals. Dalton Transactions 2022, 51 (20) , 7775-7782. https://doi.org/10.1039/D2DT00560C
  66. Mahdi Barjasteh, Manouchehr Vossoughi, Mojtaba Bagherzadeh, Kamran Pooshang Bagheri. Green synthesis of PEG-coated MIL-100(Fe) for controlled release of dacarbazine and its anticancer potential against human melanoma cells. International Journal of Pharmaceutics 2022, 618 , 121647. https://doi.org/10.1016/j.ijpharm.2022.121647
  67. Sima Singh, Hibah M. Aldawsari, Aftab Alam, Mohammed Hamed Saeed Alqarni, Sanjeev Ranjan, Prashant Kesharwani. Synthesis and antimicrobial activity of vancomycin–conjugated zinc coordination polymer nanoparticles against methicillin-resistant staphylococcus aureus. Journal of Drug Delivery Science and Technology 2022, 70 , 103255. https://doi.org/10.1016/j.jddst.2022.103255
  68. Azalea Dyah Maysarah Satya, Agustino Zulys,, Endang Saepudin. Green synthesis of iron based metal-organic framework by microwave and its potential as drug delivery system. 2022, 050002. https://doi.org/10.1063/5.0072883
  69. Kohei Akagi, Shuji Ohsaki, Hideya Nakamura, Satoru Watano. Application of Metal-Organic Frameworks as Ph-Responsive Drug Delivery System. SSRN Electronic Journal 2022, 4 https://doi.org/10.2139/ssrn.4047636
  70. Seyed Dariush Taherzade, Janet Soleimannejad. Controlled API release in azelaic acid coordination compounds with potential dermatological properties. Journal of Molecular Structure 2022, 1248 , 131393. https://doi.org/10.1016/j.molstruc.2021.131393
  71. Minze Zhu, Andrew K. Whittaker, Felicity Y. Han, Maree T. Smith. Journey to the Market: The Evolution of Biodegradable Drug Delivery Systems. Applied Sciences 2022, 12 (2) , 935. https://doi.org/10.3390/app12020935
  72. Fatma Demir Duman, Sophia S. Boyadjieva, Margarita Štrimaite, Rachel Foulkes, Gareth R. Williams, Ross S. Forgan. Inorganic Materials in Drug Delivery. 2021, 14-126. https://doi.org/10.1039/9781788019293-00014
  73. Mehdi Bazi Alahri, Razieh Arshadizadeh, Mohammadali Raeisi, Mehrdad Khatami, Monireh Sadat Sajadi, Walid Kamal Abdelbasset, Ravil Akhmadeev, Siavash Iravani. Theranostic applications of metal–organic frameworks (MOFs)-based materials in brain disorders: Recent advances and challenges. Inorganic Chemistry Communications 2021, 134 , 108997. https://doi.org/10.1016/j.inoche.2021.108997
  74. Márta Kubovics, Sara Rojas, Ana M. López, Julio Fraile, Patricia Horcajada, Concepción Domingo. Fully supercritical CO2 preparation of a nanostructured MOF composite with application in cutaneous drug delivery. The Journal of Supercritical Fluids 2021, 178 , 105379. https://doi.org/10.1016/j.supflu.2021.105379
  75. Shaikha S. Al Neyadi, Afra G. Al Blooshi, Ha L. Nguyen, Mohamed. A. Alnaqbi. UiO-66-NH 2 as an effective solid support for quinazoline derivatives for antibacterial agents against Gram-negative bacteria. New Journal of Chemistry 2021, 45 (43) , 20386-20395. https://doi.org/10.1039/D1NJ03749H
  76. Cristina Fernández-Paz, Estefanía Fernández-Paz, Pablo Salcedo-Abraira, Sara Rojas, Sheila Barrios-Esteban, Noemi Csaba, Patricia Horcajada, Carmen Remuñán-López. Microencapsulated Isoniazid-Loaded Metal–Organic Frameworks for Pulmonary Administration of Antituberculosis Drugs. Molecules 2021, 26 (21) , 6408. https://doi.org/10.3390/molecules26216408
  77. Sara Rojas, Ana Torres, Víctor Dato, Fabrice Salles, David Ávila, Jessica García-González, Patricia Horcajada. Towards improving the capacity of UiO-66 for antibiotic elimination from contaminated water. Faraday Discussions 2021, 231 , 356-370. https://doi.org/10.1039/D1FD00019E
  78. Zhoujing Zhang, Chuang Liu, Ozioma Akakuru, Wenjing Xu, Aiguo Wu, Yewei Zhang. ICG and Sunitinib-loaded NH2-MOFs for Folate-mediated Hepatocellular Carcinoma Dual-modal Therapy. Chemical Research in Chinese Universities 2021, 37 (4) , 967-974. https://doi.org/10.1007/s40242-021-1206-3
  79. A. Ringaci, A.V. Yaremenko, K.G. Shevchenko, S.D. Zvereva, M.P. Nikitin. Metal-organic frameworks for simultaneous gene and small molecule delivery in vitro and in vivo. Chemical Engineering Journal 2021, 418 , 129386. https://doi.org/10.1016/j.cej.2021.129386
  80. Md. Nur Hasan, Arpan Bera, Tuhin Kumar Maji, Samir Kumar Pal. Sensitization of nontoxic MOF for their potential drug delivery application against microbial infection. Inorganica Chimica Acta 2021, 523 , 120381. https://doi.org/10.1016/j.ica.2021.120381
  81. Xin Ma, Mathilde Lepoitevin, Christian Serre. Metal–organic frameworks towards bio-medical applications. Materials Chemistry Frontiers 2021, 5 (15) , 5573-5594. https://doi.org/10.1039/D1QM00784J
  82. Miroslav Almáši. A review on state of art and perspectives of Metal-Organic frameworks (MOFs) in the fight against coronavirus SARS-CoV-2. Journal of Coordination Chemistry 2021, 74 (13) , 2111-2127. https://doi.org/10.1080/00958972.2021.1965130
  83. Christopher Marsh, Greig C. Shearer, Beth T. Knight, Joseph Paul-Taylor, Andrew D. Burrows. Supramolecular aspects of biomolecule interactions in metal–organic frameworks. Coordination Chemistry Reviews 2021, 439 , 213928. https://doi.org/10.1016/j.ccr.2021.213928
  84. Rongrong Yuan, Hongxu Chen, Qian-Qian Zhu, Hongming He. Rational fabrication of a porous Cd-organic framework for chemical fixation of CO2 and selective sorption of p-xylene over other isomers. Journal of Solid State Chemistry 2021, 297 , 122036. https://doi.org/10.1016/j.jssc.2021.122036
  85. Renan Augusto Marson Armando, Marina Paiva Abuçafy, Angelica Ellen Graminha, Roberto Santana da Silva, Regina Célia Galvão Frem. Ru-90@bio-MOF-1: A ruthenium(II) metallodrug occluded in porous Zn-based MOF as a strategy to develop anticancer agents. Journal of Solid State Chemistry 2021, 297 , 122081. https://doi.org/10.1016/j.jssc.2021.122081
  86. Sara Rojas, Patricia Horcajada. Understanding the Incorporation and Release of Salicylic Acid in Metal‐Organic Frameworks for Topical Administration. European Journal of Inorganic Chemistry 2021, 2021 (14) , 1325-1331. https://doi.org/10.1002/ejic.202001134
  87. Jorge Albalad, Christopher J. Sumby, Daniel Maspoch, Christian J. Doonan. Elucidating pore chemistry within metal–organic frameworks via single crystal X-ray diffraction; from fundamental understanding to application. CrystEngComm 2021, 23 (11) , 2185-2195. https://doi.org/10.1039/D1CE00067E
  88. Ioanna Christodoulou, Tom Bourguignon, Xue Li, Gilles Patriarche, Christian Serre, Christian Marlière, Ruxandra Gref. Degradation Mechanism of Porous Metal-Organic Frameworks by In Situ Atomic Force Microscopy. Nanomaterials 2021, 11 (3) , 722. https://doi.org/10.3390/nano11030722
  89. Sara Rojas, Jorge A. R. Navarro, Patricia Horcajada. Metal–organic frameworks for the removal of the emerging contaminant atenolol under real conditions. Dalton Transactions 2021, 50 (7) , 2493-2500. https://doi.org/10.1039/D0DT03637D
  90. Xiao-Qing Wang, Jing Tang, Xuehui Ma, Dan Wu, Jie Yang. A water-stable zinc( ii )–organic framework as an “on–off–on” fluorescent sensor for detection of Fe 3+ and reduced glutathione. CrystEngComm 2021, 23 (5) , 1243-1250. https://doi.org/10.1039/D0CE01741H
  91. Christian Rafael Quijia, Camila Lima, Caroline Silva, Renata Carolina Alves, Regina Frem, Marlus Chorilli. Application of MIL-100(Fe) in drug delivery and biomedicine. Journal of Drug Delivery Science and Technology 2021, 61 , 102217. https://doi.org/10.1016/j.jddst.2020.102217
  92. Bastian Moll, Tim Müller, Carsten Schlüsener, Alexa Schmitz, Philipp Brandt, Secil Öztürk, Christoph Janiak. Modulated synthesis of thiol-functionalized fcu and hcp UiO-66(Zr) for the removal of silver( i ) ions from water. Materials Advances 2021, 2 (2) , 804-812. https://doi.org/10.1039/D0MA00555J
  93. Nurul N. M. Ishak, N. N. M. Khiruddin, N. Nasri, T. B. S. A. Ravoof. Metal-Organic Frameworks (MOFs). 2021, 105-146. https://doi.org/10.1007/978-3-030-62761-4_5
  94. Olivia L. Rose, Cerasela Zoica Dinu. Analysis and correlations of metal-organic frameworks: applications and toxicity. 2021, 253-290. https://doi.org/10.1016/B978-0-12-820505-1.00012-2
  95. Parth Malik, Rachna Gupta, Rakesh Kumar Ameta. Unique attributes of metal-organic frameworks in drug delivery. 2021, 389-415. https://doi.org/10.1016/B978-0-12-822099-3.00016-2
  96. A.M. Chávez, A. Rey, J. López, P.M. Álvarez, F.J. Beltrán. Critical aspects of the stability and catalytic activity of MIL-100(Fe) in different advanced oxidation processes. Separation and Purification Technology 2021, 255 , 117660. https://doi.org/10.1016/j.seppur.2020.117660
  97. Khaled AbouAitah, Imane M. Higazy, Anna Swiderska-Sroda, Reda M. Abdelhameed, Stanislaw Gierlotka, Tarik A. Mohamed, Urszula Szałaj, Witold Lojkowski. Anti-inflammatory and antioxidant effects of nanoformulations composed of metal-organic frameworks delivering rutin and/or piperine natural agents. Drug Delivery 2021, 28 (1) , 1478-1495. https://doi.org/10.1080/10717544.2021.1949073
  98. Ricardo F. Mendes, Flávio Figueira, José P. Leite, Luís Gales, Filipe A. Almeida Paz. Metal–organic frameworks: a future toolbox for biomedicine?. Chemical Society Reviews 2020, 49 (24) , 9121-9153. https://doi.org/10.1039/D0CS00883D
  99. Mahdiyeh Akbari, Mohammad Ali Ghasemzadeh, Manoochehr Fadaeian. Synthesis and Application of ZIF‐8 MOF Incorporated in a TiO 2 @Chitosan Nanocomposite as a Strong Nanocarrier for the Drug Delivery of Acyclovir. ChemistrySelect 2020, 5 (46) , 14564-14571. https://doi.org/10.1002/slct.202003213
  100. Yujia Sun, Liwei Zheng, Yu Yang, Xu Qian, Ting Fu, Xiaowei Li, Zunyi Yang, He Yan, Cheng Cui, Weihong Tan. Metal–Organic Framework Nanocarriers for Drug Delivery in Biomedical Applications. Nano-Micro Letters 2020, 12 (1) https://doi.org/10.1007/s40820-020-00423-3
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  • Abstract

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    Figure 1

    Figure 1. Schematic view of the structure of UiO-66, MIL-100, and MIL-127 (zirconium polyhedra, iron polyhedra, nitrogen, oxygen, and carbon are represented in cyan, green, blue, red, and gray, respectively; hydrogen atoms are omitted for clarity). Structures of AAS and IBU drugs are also given.

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    Figure 2

    Figure 2. IBU (hydrophobic) and AAS (hydrophilic) encapsulation kinetics in MIL-100 (hydrophilic) and UiO-66 (hydrophobic) matrixes. Adjustment of the drug adsorption data to a zero-order kinetic equation, with different zero-order kinetic constants (K), regression factors (R2), and total drug loadings (wt %).

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    Figure 3

    Figure 3. AAS and IBU released from the different MOFs under simulated cutaneous conditions (aqueous media at 37 °C).

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  • References

    This article references 59 other publications.

    1. 1
      Chien, Y. W.; Lin, S. Drug Delivery: Controlled Release. In Encyclopedia of Pharmaceutical Technology; Swarbrick, J., Ed.; CRC Press, 2007; pp 1082– 1103.
      There is no corresponding record for this reference.
    2. 2
      Qu, H.; Bhattachayya, S.; Ducheyne, P. Sol-Gel Processed Oxide Controlled Release Materials. In Comprehensive Biomaterials I; Ducheyne, P.; Ducheyne, P.; Healy, K.; Hutmacher, D. E.; Grainger, D. W.; Kirkpatrick, C. J., Eds.; Elsevier, 2011; pp 476– 493.
      There is no corresponding record for this reference.
    3. 3
      Malmsten, M. Soft Drug Delivery Systems. Soft Matter 2006, 2, 760– 769,  DOI: 10.1039/b608348j
      3
      Soft drug delivery systems
      Malmsten, Martin
      Soft Matter (2006), 2 (9), 760-769CODEN: SMOABF; ISSN:1744-683X. (Royal Society of Chemistry)
      This brief review aims at providing some illustrative examples on the use of soft drug delivery systems formed by surfactants, polymers, and lipids. Such delivery systems are discussed and exemplified regarding both more traditional soft drug delivery systems such as micelles, liq. cryst. phases, liposomes and polymer gels, as well as more novel structures, e.g., carbon nanotubes, polyelectrolyte multilayer capsules, and liq. cryst. particles.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XpvVGgtLs%253D&md5=217a980927b8ecfbcb7030b71c8901a2
    4. 4
      Giménez-Marqués, M.; Hidalgo, T.; Serre, C.; Horcajada, P. Nanostructured Metal–organic Frameworks and Their Bio-Related Applications. Coord. Chem. Rev. 2015, 307, 1– 19,  DOI: 10.1016/j.ccr.2015.08.008
      There is no corresponding record for this reference.
    5. 5
      Imaz, I.; Rubio-Martínez, M.; An, J.; Solé-Font, I.; Rosi, N. L.; Maspoch, D. Metal-Biomolecule Frameworks (MBioFs). Chem. Commun. 2011, 47, 7287– 7302,  DOI: 10.1039/c1cc11202c
      5
      Metal-biomolecule frameworks (MBioFs)
      Imaz, Inhar; Rubio-Martinez, Marta; An, Jihyun; Sole-Font, Isabel; Rosi, Nathaniel L.; Maspoch, Daniel
      Chemical Communications (Cambridge, United Kingdom) (2011), 47 (26), 7287-7302CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
      A review. Biomols. are the building blocks of life. Nature has evolved countless biomols. that show promise for bridging metal ions. These mols. have emerged as an excellent source of biocompatible building blocks that can be used to design Metal-Biomol. Frameworks (MBioFs). This feature article highlights the advances in the synthesis of this class of MOFs. Special emphasis is provided on the crystal structures of these materials, their miniaturization to the submicron length scale, and their new potential storage, catalytic, and biomedical applications.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXnslSntLk%253D&md5=c64900429dfda43a9c3d190fe8600eb2
    6. 6
      Horcajada, P.; Serre, C.; Vallet-Regí, M.; Sebban, M.; Taulelle, F.; Férey, G. Metal-Organic Frameworks as Efficient Materials for Drug Delivery. Angew. Chem., Int. Ed. 2006, 45, 5974– 5978,  DOI: 10.1002/anie.200601878
      6
      Metal-organic frameworks as efficient materials for drug delivery
      Horcajada, Patricia; Serre, Christian; Vallet-Regi, Maria; Sebban, Muriel; Taulelle, Francis; Ferey, Gerard
      Angewandte Chemie, International Edition (2006), 45 (36), 5974-5978CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      The metal carboxylates MIL-100 and MIL-101 (MIL = Materials of Institut Lavoisier) act as porous matrixes for drug-delivery systems using ibuprofen as a model substrate. Very large amts. of the drug could be incorporated, up to an unprecedented capacity of 1.4 g of drug per g of porous solid for MIL-101, and the total release of ibuprofen was achieved under physiol. conditions in 3 (MIL-100) and 6 days (MIL-101).
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XhtVSrtLfF&md5=b88dbd1aeef6086fe4f1a6f9195d2054
    7. 7
      He, C.; Liu, D.; Lin, W. Nanomedicine Applications of Hybrid Nanomaterials Built from Metal–Ligand Coordination Bonds: Nanoscale Metal–Organic Frameworks and Nanoscale Coordination Polymers. Chem. Rev. 2015, 115, 11079– 11108,  DOI: 10.1021/acs.chemrev.5b00125
      7
      Nanomedicine Applications of Hybrid Nanomaterials Built from Metal-Ligand Coordination Bonds: Nanoscale Metal-Organic Frameworks and Nanoscale Coordination Polymers
      He, Chunbai; Liu, Demin; Lin, Wenbin
      Chemical Reviews (Washington, DC, United States) (2015), 115 (19), 11079-11108CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      A review. Topics covered include synthesis and properties of nanoscale metal-org. frameworks (NMOFs) and nanoscale coordination polymers (NCPs) and their uses in biomedical imaging and delivery of therapeutic agents for cancer treatment.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhsVahs73F&md5=d02e7281936960c70a7d52933d0b302f
    8. 8
      Zhou, H.-C. J.; Kitagawa, S. Metal–Organic Frameworks (MOFs). Chem. Soc. Rev. 2014, 43, 5415– 5418,  DOI: 10.1039/C4CS90059F
      8
      Metal-Organic Frameworks (MOFs)
      Zhou, Hong-Cai "Joe"; Kitagawa, Susumu
      Chemical Society Reviews (2014), 43 (16), 5415-5418CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
      A review. Recent advances in the chem. of porous coordination polymers are discussed.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhtFehtr%252FM&md5=bbe8405d4302c49b5bb262abfab0fc10
    9. 9
      Carné, A.; Carbonell, C.; Imaz, I.; Maspoch, D. Nanoscale Metal-Organic Materials. Chem. Soc. Rev. 2011, 40, 291– 305,  DOI: 10.1039/C0CS00042F
      9
      Nanoscale metal-organic materials
      Carne, Arnau; Carbonell, Carlos; Imaz, Inhar; Maspoch, Daniel
      Chemical Society Reviews (2011), 40 (1), 291-305CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
      A review. Metal-org. materials are a fascinating novel class of functional nanomaterials. The limitless combinations between inorg. and org. building blocks enable researchers to synthesize 0- and 1-dimensional metal-org. discrete nanostructures with varied compns., morphologies and sizes, fabricate 2-dimensional metal-org. thin films and membranes, and even structure them on surfaces at the nanometer length scale. In this tutorial review, the synthetic methodologies for prepg. these miniaturized materials as well as their potential properties and future applications are discussed. This review wants to offer a panoramic view of this embryonic class of nanoscale materials that will be of interest to a cross-section of researchers working in chem., physics, medicine, nanotechnol., materials chem., etc., in the next years.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXhsFKisr7P&md5=3c21d9ac0c789e0abfec94bc1a5ea626
    10. 10
      Horcajada, P.; Serre, C.; Vallet-Regí, M.; Sebban, M.; Taulelle, F.; Férey, G. Metal-Organic Frameworks as Efficient Materials for Drug Delivery. Angew. Chem., Int. Ed. 2006, 45, 5974– 5978,  DOI: 10.1002/anie.200601878
      10
      Metal-organic frameworks as efficient materials for drug delivery
      Horcajada, Patricia; Serre, Christian; Vallet-Regi, Maria; Sebban, Muriel; Taulelle, Francis; Ferey, Gerard
      Angewandte Chemie, International Edition (2006), 45 (36), 5974-5978CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      The metal carboxylates MIL-100 and MIL-101 (MIL = Materials of Institut Lavoisier) act as porous matrixes for drug-delivery systems using ibuprofen as a model substrate. Very large amts. of the drug could be incorporated, up to an unprecedented capacity of 1.4 g of drug per g of porous solid for MIL-101, and the total release of ibuprofen was achieved under physiol. conditions in 3 (MIL-100) and 6 days (MIL-101).
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XhtVSrtLfF&md5=b88dbd1aeef6086fe4f1a6f9195d2054
    11. 11
      Sun, C.-Y.; Qin, C.; Wang, X.-L.; Su, Z.-M. Metal-Organic Frameworks as Potential Drug Delivery Systems. Expert Opin. Drug Delivery 2013, 10, 89– 101,  DOI: 10.1517/17425247.2013.741583
      11
      Metal-organic frameworks as potential drug delivery systems
      Sun, Chun-Yi; Qin, Chao; Wang, Xin-Long; Su, Zhong-Min
      Expert Opinion on Drug Delivery (2013), 10 (1), 89-101CODEN: EODDAW; ISSN:1742-5247. (Informa Healthcare)
      A review. Introduction: Metal-org. frameworks (MOFs) are a unique class of hybrid porous solids based on metals and org. linkers. Compared to traditional porous materials, they possess predominance of large surface areas, tunable pore size and shape, adjustable compn. and functionalized pore surface, which enable them unique advantages and promises for applications in adsorption and release of therapeutic agents. Areas covered: This review addresses MOFs as a new avenue for drug delivery and exhibits their ability to efficiently deliver various kinds of therapeutic agents. It also details the requirements that MOFs need to satisfy for biomedical application, such as toxicol. compatibility, stability, particle size, and surface modification. In addn., several approaches used to enhance encapsulation efficiency are summarized and parameters influencing delivery efficiency are also discussed. Expert opinion: Benefiting from the unique advantages of MOFs materials, efficient delivery of various kinds of drugs has been achieved in some MOF materials. However, it is only the outset of MOFs in drug delivery system, and numerous work need to be done before clin. applications, for example, studying their in vivo toxicity, exploring degrdn. mechanisms so as to establish real stability of MOFs in body's liq., providing appropriated surface modification avenue for MOFs, and researching in vivo efficiency and pharmacokinetics of drug-loaded MOFs.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XhvVyntL7M&md5=58cd72bdd2651a1ab172e4afaed97491
    12. 12
      Carmona, F. J.; Rojas, S.; Sánchez, P.; Jeremias, H.; Marques, A. R.; Romão, C. C.; Choquesillo-Lazarte, D.; Navarro, J. A. R.; Maldonado, C. R.; Barea, E. Cation Exchange Strategy for the Encapsulation of a Photoactive CO-Releasing Organometallic Molecule into Anionic Porous Frameworks. Inorg. Chem. 2016, 55, 6525– 6531,  DOI: 10.1021/acs.inorgchem.6b00674
      12
      Cation Exchange Strategy for the Encapsulation of a Photoactive CO-Releasing Organometallic Molecule into Anionic Porous Frameworks
      Carmona, Francisco J.; Rojas, Sara; Sanchez, Purificacion; Jeremias, Helia; Marques, Ana R.; Romao, Carlos C.; Choquesillo-Lazarte, Duane; Navarro, Jorge A. R.; Maldonado, Carmen R.; Barea, Elisa
      Inorganic Chemistry (2016), 55 (13), 6525-6531CODEN: INOCAJ; ISSN:0020-1669. (American Chemical Society)
      The encapsulation of the photoactive, nontoxic, water-sol., and air-stable cationic CORM [Mn(tacn)(CO)3]Br (tacn = 1,4,7-triazacyclononane) in different inorg. porous matrixes, namely, the metalorg. framework bio-MOF-1, (NH2(CH3)2)2[Zn8(adeninate)4(BPDC)6]·8DMF·11H2O (BPDC = 4,4'-biphenyldicarboxylate), and the functionalized mesoporous silicas MCM-41-SO3H and SBA-15-SO3H, is achieved by a cation exchange strategy. The CO release from these loaded materials, under simulated physiol. conditions, is triggered by visible light. The results show that the silica matrixes, which are unaltered under physiol. conditions, slow the kinetics of CO release, allowing a more controlled CO supply. In contrast, bio-MOF-1 instability leads to the complete leaching of the CORM. Nevertheless, the degrdn. of the MOF matrix gives rise to an enhanced CO release rate, which is related to the presence of free adenine in the soln.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XpsFOgsr8%253D&md5=706731d312ae56c22cf62e61012eed53
    13. 13
      Oh, H.; Li, T.; An, J. Drug Release Properties of a Series of Adenine-Based Metal-Organic Frameworks. Chem. - Eur. J. 2015, 21, 17010– 17015,  DOI: 10.1002/chem.201501560
      13
      Drug Release Properties of a Series of Adenine-Based Metal-Organic Frameworks
      Oh, Hyojae; Li, Tao; An, Jihyun
      Chemistry - A European Journal (2015), 21 (47), 17010-17015CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)
      The drug uptake and release properties of a series of biomol.-based metal-org. frameworks (bMOF-1, bMOF-4, bMOF-100, and bMOF-102) have been studied. The bMOFs were loaded with the small mol. etilefrine hydrochloride and release profiles were collected in both Nanopure water and simulated body fluid (SBF). Each bMOF exhibited an initial burst of drug release at the initial stages of the expt. followed by a gradual release of the remaining drug mols. over time. bMOF-1 released 50 % of the drug after 15 days and complete release at 80 days in SBF. bMOF-4 released 50 % of the drug within two days and complete release at 49 days in SBF. bMOF-100 and bMOF-102 released 50 % of the drug after 4 h and complete release at 69 and 54 days in SBF, resp.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhsFGkt7jP&md5=abea1fc34c104670f686f89a26eb1141
    14. 14
      Gaudin, C.; Cunha, D.; Ivanoff, E.; Horcajada, P.; Chevé, G.; Yasri, A.; Lobet, O.; Serre, C.; Maurin, G. A Quantitative Structure Activity Relationship Approach to Probe the Influence of the Functionalization on the Drug Encapsulation of Porous Metal-Organic Frameworks. Microporous Mesoporous Mater. 2012, 157, 124– 130,  DOI: 10.1016/j.micromeso.2011.06.011
      14
      A quantitative structure activity relationship approach to probe the influence of the functionalization on the drug encapsulation of porous metal-organic frameworks
      Gaudin, C.; Cunha, D.; Ivanoff, E.; Horcajada, P.; Cheve, G.; Yasri, A.; Loget, O.; Serre, C.; Maurin, G.
      Microporous and Mesoporous Materials (2012), 157 (), 124-130CODEN: MIMMFJ; ISSN:1387-1811. (Elsevier Inc.)
      A series of 10 MIL-88B(Fe) iron(III) dicarboxylate MOFs wherein the org. linker is functionalized by a large variety of polar and apolar functional groups (-H, -Br, -F, -CF3, -CH3, -NH2, -NO2, -OH) was investigated as a potential carrier for encapsulating drugs, using the cosmetic amphiphilic caffeine as a model mol. Encapsulation using impregnation followed by thermogravimetric anal. (TGA) and high performance liq. chromatog. (HPLC) measurements to quant. est. the caffeine uptake, have been first performed on the functionalized MIL-88B(Fe) samples. This set of exptl. data was further used as an ideal platform to conduct a quant. structure activity relationship approach based on multiple linear regression (MLR) method with the aim to find out the most relevant chem. and structural features of the MIL-88B(Fe) that significantly affect the therapeutic mol. uptake. Individual QSAR models showed that tuning the polarity and the H-donor capacity of the org. linker can enhance the caffeine encapsulation, suggesting that the functional groups serve as anchoring points for the drug mol., consistent with previous conclusions drawn from mol. simulations performed on similar functionalized MOFs. Consensus modeling approach based on the selection of the most diverse individual models was also employed to build more representative QSAR models over the chem. space that could be further used to predict the drug encapsulation performance of the MOFs grafted by other functional groups.
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    15. 15
      Cunha, D.; Gaudin, C.; Colinet, I.; Horcajada, P.; Maurin, G.; Serre, C. Rationalization of the Entrapping of Bioactive Molecules into a Series of Functionalized Porous Zirconium Terephthalate MOFs. J. Mater. Chem. B 2013, 1, 1101– 1108,  DOI: 10.1039/c2tb00366j
      15
      Rationalization of the entrapping of bioactive molecules into a series of functionalized porous zirconium terephthalate MOFs
      Cunha, D.; Gaudin, C.; Colinet, I.; Horcajada, P.; Maurin, G.; Serre, C.
      Journal of Materials Chemistry B: Materials for Biology and Medicine (2013), 1 (8), 1101-1108CODEN: JMCBDV; ISSN:2050-7518. (Royal Society of Chemistry)
      The encapsulation of two different bioactive mols., the cosmetic caffeine and the analgesic and anti-inflammatory ibuprofen, has been evaluated by combining impregnation and advanced characterization exptl. tools in a series of microporous rigid zirconium(iv) terephthalates UiO-66 bearing different polar or apolar functional groups (-H, -Br, -NH2, -2OH, -NO2, -Cl, -2CF3, -CH3, -2CH3). It has been first evidenced that these hybrid solids exhibit drug payloads that significantly outperform those obtained using current drug formulations or other conventional porous solids. A quant. structure-activity relationship strategy has been further conducted with the aim of rationalizing the exptl. drug uptakes and further emphasizing the most relevant chem. and structural features that significantly impact their encapsulation performances. Indeed, it appears that the caffeine loading is optimized when the functionalized org. linker both shows a large octanol-water partition coeff. and contains grafted functions with low hydrogen bond acceptor abilities, whereas the ibuprofen entrapping is enhanced when the org. linker contains functional groups with a large solvent surface area and free vol., and to a lesser extent low hydrogen bond acceptor abilities. Moreover, it has been shown that the solvent used as media for the biomol. impregnation plays a crucial role in the encapsulation performance due to the formation of a competitive adsorption process between the solvent and the active mol.
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    16. 16
      Cunha, D.; Yahia, M. B.; Hall, S.; Miller, S. R.; Chevreau, H.; Elka, E.; Maurin, G.; Horcajada, P.; Serre, C. Rationale of Drug Encapsulation and Release from Biocompatible Porous Metal–Organic Frameworks. Chem. Mater. 2013, 25, 2767– 2776,  DOI: 10.1021/cm400798p
      16
      Rationale of Drug Encapsulation and Release from Biocompatible Porous Metal-Organic Frameworks
      Cunha, Denise; Ben Yahia, Mouna; Hall, Shaun; Miller, Stuart R.; Chevreau, Hubert; Elkaim, Erik; Maurin, Guillaume; Horcajada, Patricia; Serre, Christian
      Chemistry of Materials (2013), 25 (14), 2767-2776CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
      A joint exptl. and computational systematic exploration of the driving forces that govern (i) encapsulation of active ingredients (solvent, starting material dehydration, drug/material ratio, immersion time, and several consecutive impregnations) and (i) its kinetics of delivery (structure, polarity,...) was performed using a series of porous biocompatible metal-org. frameworks (MOFs) that bear different topologies, connectivities, and chem. compns. The liporeductor cosmetic caffeine was selected as the active mol. Its encapsulation is a challenge for the cosmetic industry due to its high tendency to crystallize leading to poor loadings (<5 wt. %) and uncontrolled releases with a subsequent low efficiency. It was evidenced that caffeine entrapping reaches exceptional payloads up to 50 wt. %, while progressive release of this cosmetic agent upon immersion in the simulated physiol. media (phosphate buffer soln. pH = 7.4 or distd. water pH = 6.3, 37 °C) occurred mainly depending on the degree of MOF stability, caffeine mobility, and MOF-caffeine interactions. Thus, MIL-100 and UiO-66 appear as very promising carriers for topical administration of caffeine with both spectacular cosmetic payloads and progressive releases within 24 h.
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    17. 17
      Lanza, F.; Royer, G.; Nelson, R. An Endoscopic Evaluation of the Effects of Non-Steroidal Anti-Inflammatory Drugs on the Gastric Mucosa. Gastrointest. Endosc. 1975, 21, 103– 105,  DOI: 10.1016/S0016-5107(75)73812-9
      17
      An endoscopic evaluation of the effects of non-steroidal anti-inflammatory drugs on the gastric mucosa
      Lanza F; Royer G; Nelson R
      Gastrointestinal endoscopy (1975), 21 (3), 103-5 ISSN:0016-5107.
      There is no expanded citation for this reference.
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    18. 18
      Schoen, R. T.; Vender, R. J. Mechanisms of Nonsteroidal Anti-Inflammatory Drug-Induced Gastric Damage. Am. J. Med. 1989, 86, 449– 458,  DOI: 10.1016/0002-9343(89)90344-6
      18
      Mechanisms of nonsteroidal anti-inflammatory drug-induced gastric damage
      Schoen, Robert T.; Vender, Ronald J.
      American Journal of Medicine (1989), 86 (4), 449-58CODEN: AJMEAZ; ISSN:0002-9343.
      A review with 136 refs. on the effects of nonsteroidal anti-inflammatory drugs (NSAIDs) on the gastric mucosa. Current knowledge about the normal function of the gastric mucosal barrier, the role of prostaglandins in cytoprotection and repair, the mechanisms by which aspirin and other weak org. acids are absorbed by the stomach, and the subsequent cascade of events (including ion trapping and back diffusion of H+) that leads to gastric erosion and bleeding are discussed. A hypothesis describing NSAIDs' dual insult on the stomach is advanced.
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    19. 19
      Ammar, H. O.; Ghorab, M.; El-Nahhas, S. A.; Kamel, R. Design of a Transdermal Delivery System for Aspirin as an Antithrombotic Drug. Int. J. Pharm. 2006, 327, 81– 88,  DOI: 10.1016/j.ijpharm.2006.07.054
      19
      Design of a transdermal delivery system for aspirin as an antithrombotic drug
      Ammar, H. O.; Ghorab, M.; El-Nahhas, S. A.; Kamel, R.
      International Journal of Pharmaceutics (2006), 327 (1-2), 81-88CODEN: IJPHDE; ISSN:0378-5173. (Elsevier Ltd.)
      Aspirin has become the gold std. to which newer antiplatelet drugs are compared for reducing risks of cardiovascular diseases, while keeping low cost. Oral aspirin has a repertoire of gastrointestinal side effects even at low doses and requires high frequent dosing because it undergoes extensive presystemic metab. Transdermal delivery offers an alternative route that bypasses the gut and may be more convenient and safer for aspirin delivery esp. during long-term use. This study comprised formulation of aspirin in different topical bases. Release studies revealed that hydrocarbon gel allowed highest drug release. In vitro permeation studies revealed high drug permeation from hydrocarbon gel. Several chem. penetration enhancers were monitored for augmenting the permeation from this base. Combination of propylene glycol and alc. showed max. enhancing effect and, hence, was selected for biol. investigation. The biol. performance of the selected formulation was assessed by measuring the inhibition of platelet aggregation relevant to different dosage regimens aiming to minimize both drug dose and frequency of application. The results demonstrated the feasibility of successfully influencing platelet function and revealed that the drug therapeutic efficacy in transdermal delivery system is dose independent. Biol. performance was re-assessed after storage and the results revealed stability and persistent therapeutic efficacy.
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    20. 20
      Prausnitz, M. R.; Langer, R. Transdermal Drug Delivery. Nat. Biotechnol. 2008, 26 (11), 1261– 1268,  DOI: 10.1038/nbt.1504
      20
      Transdermal drug delivery
      Prausnitz, Mark R.; Langer, Robert
      Nature Biotechnology (2008), 26 (11), 1261-1268CODEN: NABIF9; ISSN:1087-0156. (Nature Publishing Group)
      A review. Transdermal drug delivery has made an important contribution to medical practice, but has yet to fully achieve its potential as an alternative to oral delivery and hypodermic injections. First-generation transdermal delivery systems have continued their steady increase in clin. use for delivery of small, lipophilic, low-dose drugs. Second-generation delivery systems using chem. enhancers, noncavitational ultrasound and iontophoresis have also resulted in clin. products; the ability of iontophoresis to control delivery rates in real time provides added functionality. Third-generation delivery systems target their effects to skin's barrier layer of stratum corneum using microneedles, thermal ablation, micro-dermabrasion, electroporation and cavitational ultrasound. Microneedles and thermal ablation are currently progressing through clin. trials for delivery of macromols. and vaccines, such as insulin, parathyroid hormone and influenza vaccine. Using these novel second- and third-generation enhancement strategies, transdermal delivery is poised to significantly increase its impact on medicine.
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    21. 21
      Horcajada, P.; Gref, R.; Baati, T.; Allan, P. K.; Maurin, G.; Couvreur, P.; Férey, G.; Morris, R. E.; Serre, C. Metal-Organic Frameworks in Biomedicine. Chem. Rev. 2012, 112, 1232– 1268,  DOI: 10.1021/cr200256v
      21
      Metal-Organic Frameworks in Biomedicine
      Horcajada, Patricia; Gref, Ruxandra; Baati, Tarek; Allan, Phoebe K.; Maurin, Guillaume; Couvreur, Patrick; Ferey, Gerard; Morris, Russell E.; Serre, Christian
      Chemical Reviews (Washington, DC, United States) (2012), 112 (2), 1232-1268CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      A review. Coordination polymers or MOFs (metal-org. frameworks) as porous solids for biomedical are reviewed.
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    22. 22
      McKinlay, A. C.; Allan, P. K.; Renouf, C. L.; Duncan, M. J.; Wheatley, P. S.; Warrender, S. J.; Dawson, D.; Ashbrook, S. E.; Gil, B.; Marszalek, B.; Düren, T.; Williams, J. J.; Charrier, C.; Mercer, D. K.; Teat, S. J.; Morris, R. E. Multirate Delivery of Multiple Therapeutic Agents from Metal-Organic Frameworks. APL Mater. 2014, 2, 124108  DOI: 10.1063/1.4903290
      22
      Multirate delivery of multiple therapeutic agents from metal-organic frameworks
      McKinlay, Alistair C.; Allan, Phoebe K.; Renouf, Catherine L.; Duncan, Morven J.; Wheatley, Paul S.; Warrender, Stewart J.; Dawson, Daniel; Ashbrook, Sharon E.; Gil, Barbara; Marszalek, Bartosz; Duren, Tina; Williams, Jennifer J.; Charrier, Cedric; Mercer, Derry K.; Teat, Simon J.; Morris, Russell E.
      APL Materials (2014), 2 (12), 124108/1-124108/8CODEN: AMPADS; ISSN:2166-532X. (American Institute of Physics)
      The highly porous nature of metal-org. frameworks (MOFs) offers great potential for the delivery of therapeutic agents. Here, we show that highly porous metal-org. frameworks can be used to deliver multiple therapeutic agents-a biol. active gas, an antibiotic drug mol., and an active metal ion-simultaneously but at different rates. The possibilities offered by delivery of multiple agents with different mechanisms of action and, in particular, variable timescales may allow new therapy approaches. Here, we show that the loaded MOFs are highly active against various strains of bacteria. (c) 2014 American Institute of Physics.
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    23. 23
      Márquez, A. G.; Hidalgo, T.; Lana, H.; Cunha, D.; Blanco-Prieto, M. J.; Álvarez-Lorenzo, C.; Boissière, C.; Sánchez, C.; Serre, C.; Horcajada, P. Biocompatible Polymer–metal–organic Framework Composite Patches for Cutaneous Administration of Cosmetic Molecules. J. Mater. Chem. B 2016, 4, 7031– 7040,  DOI: 10.1039/C6TB01652A
      23
      Biocompatible polymer-metal-organic framework composite patches for cutaneous administration of cosmetic molecules
      Marquez, Alfonso Garcia; Hidalgo, Tania; Lana, Hugo; Cunha, Denise; Blanco-Prieto, Maria Jose; Alvarez-Lorenzo, Carmen; Boissiere, Cedric; Sanchez, Clement; Serre, Christian; Horcajada, Patricia
      Journal of Materials Chemistry B: Materials for Biology and Medicine (2016), 4 (43), 7031-7040CODEN: JMCBDV; ISSN:2050-7518. (Royal Society of Chemistry)
      Despite increasing interest in metal-org. frameworks (MOFs) in the biomedical field, developing specific formulations suitable for different administration routes is still a main challenge. Here, we propose a simple, fast and bio-friendly press-molding method for the prepn. of cutaneous patches based on composites made from the drug nanocarrier MIL-100(Fe) and biopolymers. The physicochem. properties of the patches (structure, hydration, bioadhesive and swelling properties), as well as their encapsulation and release capabilities (both in ex vitro and ex vivo models), were evaluated using active ingredients such as the challenging cosmetic liporeductor, caffeine, and the model analgesic and anti-inflammatory drug, ibuprofen. In particular, very high caffeine loadings were entrapped within these cutaneous devices with progressive releases under simulated cutaneous physiol. conditions as a consequence of the swelling of the hydrophilic patches. Despite the absence of any cutaneous bioadhesive character, these patches provided progressive and suitable permeation of their cosmetic cargo through the skin, interestingly reaching the targeted adipose tissue. This makes these cosmetic-contg. composite MOF-based patches promising candidates for new cutaneous devices in cosmetic applications.
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    24. 24
      Canivet, J.; Fateeva, A.; Guo, Y.; Coasne, B.; Farrusseng, D. Water Adsorption in MOFs: Fundamentals and Applications. Chem. Soc. Rev. 2014, 43, 5594– 5617,  DOI: 10.1039/C4CS00078A
      24
      Water adsorption in MOFs: fundamentals and applications
      Canivet, Jerome; Fateeva, Alexandra; Guo, Youmin; Coasne, Benoit; Farrusseng, David
      Chemical Society Reviews (2014), 43 (16), 5594-5617CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
      A review. This review article presents the fundamental and practical aspects of water adsorption in Metal-Org. Frameworks (MOFs). The state of the art of MOF stability in water, a crucial issue to many applications in which MOFs are promising candidates, is discussed here. Stability in both gaseous (such as humid gases) and aq. media is considered. By considering a non-exhaustive yet representative set of MOFs, the different mechanisms of water adsorption in this class of materials are presented: reversible and continuous pore filling, irreversible and discontinuous pore filling through capillary condensation, and irreversibility arising from the flexibility and possible structural modifications of the host material. Water adsorption properties of more than 60 MOF samples are reported. The applications of MOFs as materials for heat-pumps and adsorbent-based chillers and proton conductors are also reviewed. Some directions for future work are suggested as concluding remarks.
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    25. 25
      Cychosz, K. A.; Matzger, A. J. Water Stability of Microporous Coordination Polymers and the Adsorption of Pharmaceuticals from Water. Langmuir 2010, 26, 17198– 17202,  DOI: 10.1021/la103234u
      25
      Water Stability of Microporous Coordination Polymers and the Adsorption of Pharmaceuticals from Water
      Cychosz, Katie A.; Matzger, Adam J.
      Langmuir (2010), 26 (22), 17198-17202CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)
      The stability of a variety of microporous coordination polymers (MCPs) to water-contg. solns. was studied using powder x-ray diffraction. The stability of the MCP is related to the metal cluster present in the structure with trinuclear chromium clusters more stable than copper paddlewheel clusters which are more stable than basic zinc acetate clusters. Zn(2-methylimidizolate)2 is more water stable than zinc MCPs with carboxylate linkers; however, extended exposure to water led to decompn. of all zinc-based MCPs. Materiaux de l'Institut Lavoisier (MIL)-100 also is completely water stable and was used to adsorb the pharmaceuticals furosemide and sulfasalazine from water with large uptakes achievable at low concns., indicating that the adsorption of wastewater contaminants may be a feasible application for these materials.
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    26. 26
      Küsgens, P.; Rose, M.; Senkovska, I.; Fröde, H.; Henschel, A.; Siegle, S.; Kaskel, S. Characterization of Metal-Organic Frameworks by Water Adsorption. Microporous Mesoporous Mater. 2009, 120, 325– 330,  DOI: 10.1016/j.micromeso.2008.11.020
      26
      Characterization of metal-organic frameworks by water adsorption
      Kuesgens, Pia; Rose, Marcus; Senkovska, Irena; Froede, Heidrun; Henschel, Antje; Siegle, Sven; Kaskel, Stefan
      Microporous and Mesoporous Materials (2009), 120 (3), 325-330CODEN: MIMMFJ; ISSN:1387-1811. (Elsevier)
      The water physisorption properties and the water stability of the metal-org. frameworks HKUST-1 (=(Cu3(BTC)2) (BTC = benzene-1,3,5-tricarboxylate)), ZIF-8, MIL-101, MIL-100(Fe) and DUT-4 (=Al(OH)(NDC)) (NDC = naphthalene-2,6-dicarboxylate) were studied. The water physisorption isotherms were compared to nitrogen physisorption isotherms and the chem. stability after water adsorption was investigated. Water adsorption does not only provide information about sp. surface area, pore size and pore vol., but can also be used to est. hydrophobicity and stability towards moisture. Both HKUST-1 and DUT-4 turned out to be unstable in direct contact with water, whereas the MIL-materials and ZIF-8 do show stability. The highest water adsorption affinity was obsd. for HKUST-1. Even though unstable in liq. water, for applications in trace water removal or mol. sensing HKUST-1 is a promising material. ZIF-8 is highly inert but hydrophobic. The MIL-materials are both likely candidates for water adsorption applications, but higher concns. of the adsorbate are needed to attain an effective adsorption. DUT-4 shows insufficient adsorption capacity, but stability at ambient conditions is given.
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    27. 27
      Horcajada, P.; Surblé, S.; Serre, C.; Hong, D.-Y.; Seo, Y.-K.; Chang, J.-S.; Grenèche, J.-M.; Margiolaki, I.; Férey, G. Synthesis and Catalytic Properties of MIL-100(Fe), an iron(III) Carboxylate with Large Pores. Chem. Commun. 2007, 2820– 2822,  DOI: 10.1039/B704325B
      27
      Synthesis and catalytic properties of MIL-100(Fe), an iron(III) carboxylate with large pores
      Horcajada, Patricia; Surble, Suzy; Serre, Christian; Hong, Do-Young; Seo, You-Kyong; Chang, Jong-San; Greneche, Jean-Marc; Margiolaki, Irene; Ferey, Gerard
      Chemical Communications (Cambridge, United Kingdom) (2007), (27), 2820-2822CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
      The large-pore iron(III) carboxylate MIL-100(Fe) with a zeotype architecture was isolated under hydrothermal conditions. Its structure was solved from synchrotron x-ray powder diffraction data and the complex is formulated as [Fe3O(H2O)2F(BTC)2]·nH2O (n ≈ 14.5; BTC = 1,3,5-benzenetricarboxylate). Friedel-Crafts benzylation catalytic tests indicate a high activity and selectivity for MIL-100(Fe).
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    28. 28
      Liu, Y.; Eubank, J. F.; Cairns, A. J.; Eckert, J.; Kravtsov, V. C.; Luebke, R.; Eddaoudi, M. Assembly of Metal-Organic Frameworks (MOFs) Based on Indium-Trimer Building Blocks: A Porous MOF with Soc Topology and High Hydrogen Storage. Angew. Chem., Int. Ed. 2007, 46, 3278– 3283,  DOI: 10.1002/anie.200604306
      28
      Assembly of metal-organic frameworks (MOFs) based on indium-trimer building blocks: a porous MOF with soc topology and high hydrogen storage
      Liu, Yunling; Eubank, Jarrod F.; Cairns, Amy J.; Eckert, Juergen; Kravtsov, Victor Ch.; Luebke, Ryan; Eddaoudi, Mohamed
      Angewandte Chemie, International Edition (2007), 46 (18), 3278-3283CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      The synthesis and structure of two MOFs based on oxo-bridged trinuclear indium carboxylate clusters are reported. The one MOF has a cubic structure with a CaB6 topol. and the other with an unprecedented soc topol. (soc = square-octahedron). The results obtained indicate that MOFs possessing the characteristics of these two MOFs, combined with the modularity of their construction which allows higher surface areas to be obtained, will permit the attainment of the US DOE target for H2 uptake.
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    29. 29
      Chevreau, H.; Permyakova, A.; Nouar, F.; Fabry, P.; Livage, C.; Ragon, F.; Garcia-Marquez, A.; Devic, T.; Steunou, N.; Serre, C.; Horcajada, P. Synthesis of the Biocompatible and Highly Stable MIL-127(Fe): From Large Scale Synthesis to Particle Size Control. CrystEngComm 2016, 18, 4094– 4101,  DOI: 10.1039/C5CE01864A
      29
      Synthesis of the biocompatible and highly stable MIL-127(Fe): from large scale synthesis to particle size control
      Chevreau, Hubert; Permyakova, Anastasia; Nouar, Farid; Fabry, Paul; Livage, Carine; Ragon, Florence; Garcia-Marquez, Alfonso; Devic, Thomas; Steunou, Nathalie; Serre, Christian; Horcajada, Patricia
      CrystEngComm (2016), 18 (22), 4094-4101CODEN: CRECF4; ISSN:1466-8033. (Royal Society of Chemistry)
      Controlled-sized crystals, from the nano to the microscale, of the biocompatible and highly stable porous iron(III) 3,3,'5,5'-azobenzenetetracarboxylate MIL-127(Fe) MOF have been successfully prepd. with very high space-time-yields using different synthetic routes.
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    30. 30
      Ghosh, P.; Colón, Y. J.; Snurr, R. Q. Water Adsorption in UiO-66: The Importance of Defects. Chem. Commun. 2014, 50, 11329– 11331,  DOI: 10.1039/C4CC04945D
      30
      Water adsorption in UiO-66: the importance of defects
      Ghosh, Pritha; Colon, Yamil J.; Snurr, Randall Q.
      Chemical Communications (Cambridge, United Kingdom) (2014), 50 (77), 11329-11331CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
      Simulated adsorption isotherms for water in UiO-66 illustrate that defects in the form of missing linkers make this MOF more hydrophilic. Heats of adsorption and d. plots further confirm the effect of defects on adsorption of water in UiO-66 at low loadings. In addn., water and CO2 isotherms indicate that not only the amt. of defects but their locations within the material affect the loading of guest mols.
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    31. 31
      Cavka, J. H.; Jakobsen, S.; Olsbye, U.; Guillou, N.; Lamberti, C.; Bordiga, S.; Lillerud, K. P. A New Zirconium Inorganic Building Brick Forming Metal Organic Frameworks with Exceptional Stability. J. Am. Chem. Soc. 2008, 130, 13850– 13851,  DOI: 10.1021/ja8057953
      31
      A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability
      Cavka Jasmina Hafizovic; Jakobsen Soren; Olsbye Unni; Guillou Nathalie; Lamberti Carlo; Bordiga Silvia; Lillerud Karl Petter
      Journal of the American Chemical Society (2008), 130 (42), 13850-1 ISSN:.
      Porous crystals are strategic materials with industrial applications within petrochemistry, catalysis, gas storage, and selective separation. Their unique properties are based on the molecular-scale porous character. However, a principal limitation of zeolites and similar oxide-based materials is the relatively small size of the pores, typically in the range of medium-sized molecules, limiting their use in pharmaceutical and fine chemical applications. Metal organic frameworks (MOFs) provided a breakthrough in this respect. New MOFs appear at a high and an increasing pace, but the appearances of new, stable inorganic building bricks are rare. Here we present a new zirconium-based inorganic building brick that allows the synthesis of very high surface area MOFs with unprecedented stability. The high stability is based on the combination of strong Zr-O bonds and the ability of the inner Zr6-cluster to rearrange reversibly upon removal or addition of mu3-OH groups, without any changes in the connecting carboxylates. The weak thermal, chemical, and mechanical stability of most MOFs is probably the most important property that limits their use in large scale industrial applications. The Zr-MOFs presented in this work have the toughness needed for industrial applications; decomposition temperature above 500 degrees C and resistance to most chemicals, and they remain crystalline even after exposure to 10 tons/cm2 of external pressure.
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    32. 32
      Hartlieb, K. J.; Ferris, D. P.; Holcroft, J. M.; Kandela, I.; Stern, C. L.; Nassar, M. S.; Botros, Y. Y.; Stoddart, J. F. Encapsulation of Ibuprofen in CD-MOF and Related Bioavailability Studies. Mol. Pharm. 2017, 14, 1831– 1839,  DOI: 10.1021/acs.molpharmaceut.7b00168
      32
      Encapsulation of Ibuprofen in CD-MOF and Related Bioavailability Studies
      Hartlieb, Karel J.; Ferris, Daniel P.; Holcroft, James M.; Kandela, Irawati; Stern, Charlotte L.; Nassar, Majed S.; Botros, Youssry Y.; Stoddart, J. Fraser
      Molecular Pharmaceutics (2017), 14 (5), 1831-1839CODEN: MPOHBP; ISSN:1543-8384. (American Chemical Society)
      Although ibuprofen is one of the most widely used nonsteroidal anti-inflammatory drugs (NSAIDs), it exhibits poor soly. in aq. and physiol. environments as a free acid. In order to improve its oral bioavailability and rate of uptake, extensive research into the development of new formulations of ibuprofen has been undertaken, including the use of excipients as well as ibuprofen salts, such as ibuprofen lysinate and ibuprofen, sodium salt. The ultimate goals of these studies are to reduce the time required for max. uptake of ibuprofen, as this period of time is directly proportional to the rate of onset of analgesic/anti-inflammatory effects, and to increase the half-life of the drug within the body; i.e., the duration of action of the effects of the drug. Herein, we present a pharmaceutical cocrystal of ibuprofen and the biocompatible metal-org. framework called CD-MOF. This metal-org. framework (MOF) is based upon γ-cyclodextrin (γ-CD) tori that are coordinated to alkali metal cations (e.g., K+ ions) on both their primary and secondary faces in an alternating manner to form a porous framework built up from (γ-CD)6 cubes. We show that ibuprofen can be incorporated within CD-MOF-1 either by (i) a crystn. process using the potassium salt of ibuprofen as the alkali cation source for prodn. of the MOF or by (ii) absorption and deprotonation of the free-acid, leading to an uptake of 23-26 wt % of ibuprofen within the CD-MOF. In vitro viability studies revealed that the CD-MOF is inherently not affecting the viability of the cells with no IC50 value detd. up to a concn. of 100 μM. Bioavailability investigations were conducted on mice, and the ibuprofen/CD-MOF pharmaceutical cocrystal was compared to control samples of the potassium salt of ibuprofen in the presence and absence of γ-CD. From these animal studies, we obsd. that the ibuprofen/CD-MOF-1 cocrystal exhibits the same rapid uptake of ibuprofen as the ibuprofen potassium salt control sample with a peak plasma concn. obsd. within 20 min, and the cocrystal has the added benefit of a 100% longer half-life in blood plasma samples and is intrinsically less hygroscopic than the pure salt form.
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    33. 33
      Bhadra, B. N.; Ahmed, I.; Kim, S.; Jhung, S. H. Adsorptive Removal of Ibuprofen and Diclofenac from Water Using Metal-Organic Framework-Derived Porous Carbon. Chem. Eng. J. 2017, 314, 50– 58,  DOI: 10.1016/j.cej.2016.12.127
      33
      Adsorptive removal of ibuprofen and diclofenac from water using metal-organic framework-derived porous carbon
      Bhadra, Biswa Nath; Ahmed, Imteaz; Kim, Sunghwan; Jhung, Sung Hwa
      Chemical Engineering Journal (Amsterdam, Netherlands) (2017), 314 (), 50-58CODEN: CMEJAJ; ISSN:1385-8947. (Elsevier B.V.)
      A metal-org. framework (MOF) (here, zeolitic-imidazolate framework-8) was pyrolyzed at different temps. (800, 1000, and 1200 °C) in order to prep. porous carbons derived from MOF (PCDMs). Adsorption of ibuprofen (IBP) and diclofenac sodium (DCF) from aq. solns. was carried out over the produced PCDMs and compared with that over pristine MOF and com. activated carbon (AC). Among the tested adsorbents, the PCDM prepd. at 1000 °C (PCDM-1000) was found to be the best candidate for both IBP and DCF. The max. adsorption capacities of IBP (320 mg/g) and DCF (400 mg/g) over PCDM-1000 were ∼3 and ∼5 times, resp., of that of AC. Interaction mechanisms such as H-bonding (H-donation from PCDM, H-acceptance from IBP or DCF) were suggested based on the effect of soln. pH on the zeta potential of PCDM and the adsorbed quantity of IBP and DCF along with functional groups created on the surface of PCDM-1000. Finally, PCDM-1000 was confirmed to be as a highly efficient and recyclable adsorbent having potential applications in water purifn.
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    34. 34
      García Márquez, A.; Demessence, A.; Platero-Prats, A. E.; Heurtaux, D.; Horcajada, P.; Serre, C.; Chang, J.-S.; Férey, G.; De La Peña-O’Shea, V. A.; Boissière, C.; Grosso, D.; Sanchez, C. Green Microwave Synthesis of MIL-100(Al, Cr, Fe) Nanoparticles for Thin-Film Elaboration. Eur. J. Inorg. Chem. 2012, 100, 5165– 5174,  DOI: 10.1002/ejic.201200710
      There is no corresponding record for this reference.
    35. 35
      Singco, B.; Liu, L.-H.; Chen, Y.-T.; Shih, Y.-H.; Huang, H.-Y.; Lin, C.-H. Approaches to Drug Delivery: Confinement of Aspirin in MIL-100(Fe) and Aspirin in the de Novo Synthesis of Metal-Organic Frameworks. Microporous Mesoporous Mater. 2016, 223, 254– 260,  DOI: 10.1016/j.micromeso.2015.08.017
      35
      Approaches to drug delivery: Confinement of aspirin in MIL-100(Fe) and aspirin in the de novo synthesis of metal-organic frameworks
      Singco, Brenda; Liu, Li-Hao; Chen, Ya-Ting; Shih, Yung-Han; Huang, Hsi-Ya; Lin, Chia-Her
      Microporous and Mesoporous Materials (2016), 223 (), 254-260CODEN: MIMMFJ; ISSN:1387-1811. (Elsevier B.V.)
      Aspirin is known as a wonder drug due to its vast therapeutic range. However, side effects after oral administration include gastrointestinal irritation. Shielding of the free aspirin was developed by confining it inside the pores of MIL-100(Fe). This was done by immersion of the metal-org. framework (MOF) in a satd. aspirin soln. which achieved a ∼181% loading efficiency by time-of-flight mass spectrometer (TOF/MS) detection and took about 14 days for the drug release in phosphate buffered saline at 37 °C. The pore vol. of the MOF was found to be the determinant in the loading efficiency of aspirin when variations arise between batches of the encapsulating material. Another approach in the use of MOFs for aspirin delivery was to incorporate aspirin as ligand in the de novo synthesis of the AH-series MOFs (bioactive MOFs). The diffusion of aspirin from the MOFs was slower in acidic medium and was faster in basic medium. This encapsulation technique of aspirin would potentially spare it from enzymic degrdn. and interactions in the stomach that would lessen the amt. of the drug transported into the blood.
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    36. 36
      Horcajada, P.; Chalati, T.; Serre, C.; Gillet, B.; Sebrie, C.; Baati, T.; Eubank, J. F.; Heurtaux, D.; Clayette, P.; Kreuz, C.; Chang, J.-S.; Hwang, Y. K.; Marsaud, V.; Bories, P.-N.; Cynober, L.; Gil, S.; Férey, G.; Couvreur, P.; Gref, R. Porous Metal-Organic-Framework Nanoscale Carriers as a Potential Platform for Drug Delivery and Imaging. Nat. Mater. 2010, 9, 172– 178,  DOI: 10.1038/nmat2608
      36
      Porous metal-organic-framework nanoscale carriers as a potential platform for drug delivery and imaging
      Horcajada, Patricia; Chalati, Tamim; Serre, Christian; Gillet, Brigitte; Sebrie, Catherine; Baati, Tarek; Eubank, Jarrod F.; Heurtaux, Daniela; Clayette, Pascal; Kreuz, Christine; Chang, Jong-San; Hwang, Young Kyu; Marsaud, Veronique; Bories, Phuong-Nhi; Cynober, Luc; Gil, Sophie; Ferey, Gerard; Couvreur, Patrick; Gref, Ruxandra
      Nature Materials (2010), 9 (2), 172-178CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)
      In the domain of health, one important challenge is the efficient delivery of drugs in the body using non-toxic nanocarriers. Most of the existing carrier materials show poor drug loading (usually less than 5 wt% of the transported drug vs. the carrier material) and/or rapid release of the proportion of the drug that is simply adsorbed (or anchored) at the external surface of the nanocarrier. In this context, porous hybrid solids, with the ability to tune their structures and porosities for better drug interactions and high loadings, are well suited to serve as nanocarriers for delivery and imaging applications. Here we show that specific non-toxic porous iron(III)-based metal-org. frameworks with engineered cores and surfaces, as well as imaging properties, function as superior nanocarriers for efficient controlled delivery of challenging antitumoral and retroviral drugs (i.e., busulfan, azidothymidine triphosphate, doxorubicin or cidofovir) against cancer and AIDS. In addn. to their high loadings, they also potentially assoc. therapeutics and diagnostics, thus opening the way for theranostics, or personalized patient treatments.
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    37. 37
      Rojas, S.; Carmona, F. J.; Maldonado, C. R.; Barea, E.; Navarro, J. A. R. RAPTA-C Incorporation and Controlled Delivery from MIL-100(Fe) Nanoparticles. New J. Chem. 2016, 40, 5690– 5694,  DOI: 10.1039/C5NJ02741A
      37
      RAPTA-C incorporation and controlled delivery from MIL-100(Fe) nanoparticles
      Rojas, Sara; Carmona, Francisco J.; Maldonado, Carmen R.; Barea, Elisa; Navarro, Jorge A. R.
      New Journal of Chemistry (2016), 40 (7), 5690-5694CODEN: NJCHE5; ISSN:1144-0546. (Royal Society of Chemistry)
      [Fe3F(H2O)2O(btc)2]·nH2O (H3btc: benzene-1,3,5-tricarboxylic acid) (MIL-100(Fe)) in the form of nanoparticles with av. size of 135±70 nm can be used for the adsorption and controlled delivery of metallodrug [Ru(p-cymene)Cl2(pta)] (RAPTA-C) in simulated body fluid (SBF). The results show that the RAPTA-C delivery process takes place in two steps exhibiting half-life times of 1.9 and 30 h. We also found a pos. effect of bovine serum albumine (BSA) in speeding up the RAPTA-C delivery rate, which agrees with the suitability of MIL-100(Fe) as a drug delivery system (DDS) for the controlled release of RAPTA-C.
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    38. 38
      Hailili, R.; Wang, L.; Qv, J.; Yao, R.; Zhang, X. M.; Liu, H. Planar Mn4O Cluster Homochiral Metal-Organic Framework for HPLC Separation of Pharmaceutically Important (±)-Ibuprofen Racemate. Inorg. Chem. 2015, 54, 3713– 3715,  DOI: 10.1021/ic502861k
      38
      Planar Mn4O Cluster Homochiral Metal-Organic Framework for HPLC Separation of Pharmaceutically Important (±)-Ibuprofen Racemate
      Hailili, Reshalaiti; Wang, Li; Qv, Junzhang; Yao, Ruxin; Zhang, Xian-Ming; Liu, Huwei
      Inorganic Chemistry (2015), 54 (8), 3713-3715CODEN: INOCAJ; ISSN:0020-1669. (American Chemical Society)
      A planar tetracoordinated oxygen contg. a homochiral metal-org. framework (MOF) was synthesized and characterized that can be used as a new chiral stationary phase in HPLC to efficiently sep. racemates such as pharmaceutically important (±)-ibuprofen and (±)-1-phenyl-1,2-ethanediol.
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    39. 39
      Bueno-Perez, R.; Martin-Calvo, A.; Gómez-Álvarez, P.; Gutiérrez-Sevillano, J. J.; Merkling, P. J.; Vlugt, T. J. H.; van Erp, T. S.; Dubbeldam, D.; Calero, S. Enantioselective Adsorption of Ibuprofen and Lysine in Metal–organic Frameworks. Chem. Commun. 2014, 50, 10849– 10852,  DOI: 10.1039/C4CC03745F
      39
      Enantioselective adsorption of ibuprofen and lysine in metal-organic frameworks
      Bueno-Perez, Rocio; Martin-Calvo, Ana; Gomez-Alvarez, Paula; Gutierrez-Sevillano, Juan J.; Merkling, Patrick J.; Vlugt, Thijs J. H.; van Erp, Titus S.; Dubbeldam, David; Calero, Sofia
      Chemical Communications (Cambridge, United Kingdom) (2014), 50 (74), 10849-10852CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
      This study reveals the efficient enantiomeric sepn. of bioactive mols. in the liq. phase. Chiral structure HMOF-1 separates racemic mixts. whereas heteroselectivity is obsd. for scalemic mixts. of ibuprofen using non-chiral MIL-47 and MIL-53. Lysine enantiomers are only sepd. by HMOF-1. These sepns. are controlled by the tight confinement of the mols.
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    40. 40
      Paudel, K. S.; Milewski, M.; Swadley, C. L.; Brogden, N. K.; Ghosh, P.; Stinchcomb, A. L. Challenges and Opportunities in Dermal/transdermal Delivery. Ther. Delivery 2010, 1, 109– 131,  DOI: 10.4155/tde.10.16
      40
      Challenges and opportunities in dermal/transdermal delivery
      Paudel, Kalpana S.; Milewski, Mikolaj; Swadley, Courtney L.; Brogden, Nicole K.; Ghosh, Priyanka; Stinchcomb, Audra L.
      Therapeutic Delivery (2010), 1 (1), 109-131CODEN: TDHEA7; ISSN:2041-5990. (Future Science Ltd.)
      A review. Transdermal drug delivery is an exciting and challenging area. There are numerous transdermal delivery systems currently available on the market. However, the transdermal market still remains limited to a narrow range of drugs. Further advances in transdermal delivery depend on the ability to overcome the challenges faced regarding the permeation and skin irritation of the drug mols. Emergence of novel techniques for skin permeation enhancement and development of methods to lessen skin irritation would widen the transdermal market for hydrophilic compds., macromols. and conventional drugs for new therapeutic indications. As evident from the ongoing clin. trials of a wide variety of drugs for various clin. conditions, there is a great future for transdermal delivery of drugs.
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    41. 41
      Chabri, F.; Bouris, K.; Jones, T.; Barrow, D.; Hann, A.; Allender, C.; Brain, K.; Birchall, J. Microfabricated Silicon Microneedles for Nonviral Cutaneous Gene Delivery. Br. J. Dermatol. 2004, 150, 869– 877,  DOI: 10.1111/j.1365-2133.2004.05921.x
      41
      Microfabricated silicon microneedles for nonviral cutaneous gene delivery
      Chabri, F.; Bouris, K.; Jones, T.; Barrow, D.; Hann, A.; Allender, C.; Brain, K.; Birchall, J.
      British Journal of Dermatology (2004), 150 (5), 869-877CODEN: BJDEAZ; ISSN:0007-0963. (Blackwell Publishing Ltd.)
      The skin represents an accessible somatic tissue for therapeutic gene transfer. The superficial lipophilic layer of the skin, the stratum corneum, however, constitutes a major obstacle to the cutaneous delivery of charged macromols. such as DNA. To det. whether silicon-based microneedles, microfabricated via a novel isotropic etching/BOSCH reaction process, could generate microchannels in the skin of sufficient dimensions to facilitate access of lipid: polycation: pDNA (LPD) nonviral gene therapy vectors. SEM was used to visualize the microconduits created in heat-sepd. human epidermal sheets after application of the microneedles. Following confirmation of particle size and particle surface charge by photon correlation spectroscopy and microelectrophoresis, resp., the diffusion of fluorescent polystyrene nanospheres and LPD complexes through heat-sepd. human epidermal sheets was detd. in vitro using a Franz-type diffusion cell. In-vitro cell culture with quantification by flow cytometry was used to det. gene expression in human keratinocytes (HaCaT cells). The diffusion of 100 nm diam. fluorescent polystyrene nanospheres, used as a readily quantifiable predictive model for LPD complexes, through epidermal sheets was significantly enhanced following membrane treatment with microneedles. The delivery of LPD complexes either into or through the membrane microchannels was also demonstrated. In both cases considerable interaction between the particles and the epidermal sheet was obsd. In-vitro cell culture was used to confirm that LPD complexes mediated efficient reporter gene expression in human keratinocytes in culture when formulated at the appropriate surface charge. These studies demonstrate the utility of silicon microneedles in cutaneous gene delivery.
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    42. 42
      Sapino, S.; Oliaro-bosso, S.; Zonari, D.; Zattoni, A.; Ugazio, E. Mesoporous Silica Nanoparticles as a Promising Skin Delivery System for Methotrexate. Int. J. Pharm. 2017, 530, 239– 248,  DOI: 10.1016/j.ijpharm.2017.07.058
      42
      Mesoporous silica nanoparticles as a promising skin delivery system for methotrexate
      Sapino, Simona; Oliaro-Bosso, Simonetta; Zonari, Daniele; Zattoni, Andrea; Ugazio, Elena
      International Journal of Pharmaceutics (Amsterdam, Netherlands) (2017), 530 (1-2), 239-248CODEN: IJPHDE; ISSN:0378-5173. (Elsevier B.V.)
      The systemic administration of methotrexate (MTX), a commonly used, antineoplastic drug which is also used in cutaneous disorders, is primarily assocd. with prolonged retention in the body and consequently with side effects. Innovative drug delivery techniques and alternative administration routes would therefore contribute to its safe and effective use. The general objective of this study is thus the development of MTX-based prepns. for the topical treatment of skin disorders. MCM-41-like nanoparticles (MSN), are herein proposed as carriers which can improve the cutaneous absorption and hence the bioavailability and efficacy of MTX. The MTX/MSN complex, prepd. via the impregnation procedure, has been physico-chem. characterized, while its cell cultures have had their biocompatibility and bioactivity tested. Furthermore, a series of stable MTX-based dermal formulations has been developed, some contg. shea butter, a natural fat. Ex-vivo porcine skin absorption and the transepidermal permeation of MTX have also been monitored in a variety of media using Franz diffusion cells. Interestingly, the epidermal accumulation of the active mol. was increased by its inclusion into MSN, regardless of the surrounding medium. Furthermore, the presence of shea butter enhanced the skin uptake of the drug both in the free and in the loaded form.
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    43. 43
      Orellana-Tavra, C.; Marshall, R. J.; Baxter, E. F.; Lázaro, I. A.; Tao, A.; Cheetham, A. K.; Forgan, R. S.; Fairen-Jimenez, D. Drug Delivery and Controlled Release from Biocompatible Metal–organic Frameworks Using Mechanical Amorphization. J. Mater. Chem. B 2016, 7697– 7707,  DOI: 10.1039/C6TB02025A
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      Drug delivery and controlled release from biocompatible metal-organic frameworks using mechanical amorphization
      Orellana-Tavra, Claudia; Marshall, Ross J.; Baxter, Emma F.; Lazaro, Isabel Abanades; Tao, Andi; Cheetham, Anthony K.; Forgan, Ross S.; Fairen-Jimenez, David
      Journal of Materials Chemistry B: Materials for Biology and Medicine (2016), 4 (47), 7697-7707CODEN: JMCBDV; ISSN:2050-7518. (Royal Society of Chemistry)
      We have used a family of Zr-based metal-org. frameworks (MOFs) with different functionalized (bromo, nitro and amino) and extended linkers for drug delivery. We loaded the materials with the fluorescent model mol. calcein and the anticancer drug α-cyano-4-hydroxycinnamic acid (α-CHC), and consequently performed a mech. amorphization process to attempt to control the delivery of guest mols. Our anal. revealed that the loading values of both mols. were higher for the MOFs contg. unfunctionalized linkers. Confocal microscopy showed that all the materials were able to penetrate into cells, and the therapeutic effect of α-CHC on HeLa cells was enhanced when loaded (20 wt%) into the MOF with the longest linker. On one hand, calcein release required up to 3 days from the cryst. form for all the materials. On the other hand, the amorphous counterparts contg. the bromo and nitro functional groups released only a fraction of the total loaded amt., and in the case of the amino-MOF a slow and progressive release was successfully achieved for 15 days. In the case of the materials loaded with α-CHC, no difference was obsd. between the cryst. and amorphous form of the materials. These results highlight the necessity of a balance between the pore size of the materials and the size of the guest mols. to accomplish a successful and efficient sustained release using this mech. ball-milling process. Addnl., the endocytic pathway used by cells to internalize these MOFs may lead to diverse final cellular locations and consequently, different therapeutic effects. Understanding these cellular mechanisms will drive the design of more effective MOFs for drug delivery applications.
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    44. 44
      Abánades Lázaro, I.; Haddad, S.; Sacca, S.; Orellana-Tavra, C.; Fairen-Jimenez, D.; Forgan, R. S. Selective Surface PEGylation of UiO-66 Nanoparticles for Enhanced Stability, Cell Uptake, and pH-Responsive Drug Delivery. Chem 2017, 2, 561– 578,  DOI: 10.1016/j.chempr.2017.02.005
      44
      Selective Surface PEGylation of UiO-66 Nanoparticles for Enhanced Stability, Cell Uptake, and pH-Responsive Drug Delivery
      Abanades Lazaro, Isabel; Haddad, Salame; Sacca, Sabrina; Orellana-Tavra, Claudia; Fairen-Jimenez, David; Forgan, Ross S.
      Chem (2017), 2 (4), 561-578CODEN: CHEMVE; ISSN:2451-9294. (Cell Press)
      The high storage capacities and excellent biocompatibilities of metal-org. frameworks (MOFs) have made them emerging candidates as drug-delivery vectors. Incorporation of surface functionality is a route to enhanced properties, and here we report on a surface-modification procedure-click modulation-that controls their size and surface chem. The zirconium terephthalate MOF UiO-66 is (1) synthesized as ∼200 nm nanoparticles coated with functionalized modulators, (2) loaded with cargo, and (3) covalently surface modified with poly(ethylene glycol) (PEG) chains through mild bioconjugate reactions. At pH 7.4, the PEG chains endow the MOF with enhanced stability toward phosphates and overcome the "burst release" phenomenon by blocking interaction with the exterior of the nanoparticles, whereas at pH 5.5, stimuli-responsive drug release is achieved. The mode of cellular internalization is also tuned by nanoparticle surface chem., such that PEGylated UiO-66 potentially escapes lysosomal degrdn. through enhanced caveolae-mediated uptake. This makes it a highly promising vector, as demonstrated for dichloroacetic-acid-loaded materials, which exhibit enhanced cytotoxicity. The versatility of the click modulation protocol will allow a wide range of MOFs to be easily surface functionalized for a no. of applications.
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    45. 45
      Tamames-Tabar, C.; Cunha, D.; Imbuluzqueta, E.; Ragon, F.; Serre, C.; Blanco-Prieto, M. J.; Horcajada, P. Cytotoxicity of Nanoscaled Metal–organic Frameworks. J. Mater. Chem. B 2014, 2, 262– 271,  DOI: 10.1039/C3TB20832J
      45
      Cytotoxicity of nanoscaled metal-organic frameworks
      Tamames-Tabar, Cristina; Cunha, Denise; Imbuluzqueta, Edurne; Ragon, Florence; Serre, Christian; Blanco-Prieto, Maria J.; Horcajada, Patricia
      Journal of Materials Chemistry B: Materials for Biology and Medicine (2014), 2 (3), 262-271CODEN: JMCBDV; ISSN:2050-7518. (Royal Society of Chemistry)
      A series of fourteen porous Metal-Org. Frameworks (MOFs) with different compns. (Fe, Zn, and Zr; carboxylates or imidazolates) and structures have been successfully synthesized at the nanoscale and fully characterised by XRPD, FTIR, TGA, N2 porosimetry, TEM, DLS and ζ-potential. Their toxicol. assessment was performed using two different cell lines: human epithelial cells from fetal cervical carcinoma (HeLa) and murine macrophage cell line (J774). It appears that MOF nanoparticles (NPs) exhibit low cytotoxicity, comparable to those of other commercialised nanoparticulate systems, the less toxic being the Fe carboxylate and the more toxic being the zinc imidazolate NPs. The cytotoxicity values, higher in J774 cells than in HeLa cells, are mainly function of their compn. and cell internalisation capacity. Finally, cell uptake of one of the most relevant Fe-MOF-NPs for drug vectorization has been investigated by confocal microscopy studies, and indicates a faster kinetics of cell penetration within J774 compared to HeLa cells.
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    46. 46
      Hu, Q.; Yu, J.; Liu, M.; Liu, A.; Dou, Z.; Yang, Y. A Low Cytotoxic Cationic Metal-Organic Framework Carrier for Controllable Drug Release. J. Med. Chem. 2014, 57, 5679– 5685,  DOI: 10.1021/jm5004107
      46
      A Low Cytotoxic Cationic Metal-Organic Framework Carrier for Controllable Drug Release
      Hu, Quan; Yu, Jiancan; Liu, Min; Liu, Aiping; Dou, Zhongshang; Yang, Yu
      Journal of Medicinal Chemistry (2014), 57 (13), 5679-5685CODEN: JMCMAR; ISSN:0022-2623. (American Chemical Society)
      A pos. charged porous drug carrier MOF-74-Fe(III) (1, MOF = metal-org. framework), which could not be directly synthesized using ferric salts, was prepd. through the oxidn. of the neutral crystal MOF-74-Fe(II). This cationic host material exhibits very low cytotoxicity upon PC12 cells by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium (MTT) assay and high drug loading capacity of ibuprofen anions (∼15.9 wt %) through ion exchange and salt penetration procedures. Controlled by anion exchange, two mechanisms were involved in the drug release process with different drug delivery rates due to the presence of coordinated or free ibuprofen anions, making the administration of drug release more flexible.
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    47. 47
      Lestari, W. W.; Arvinawati, M.; Martien, R.; Kusumaningsih, T. Green and Facile Synthesis of MOF and Nano MOF Containing zinc(II) and Benzen 1,3,5-Tri Carboxylate and Its Study in Ibuprofen Slow-Release. Mater. Chem. Phys. 2018, 204, 141– 146,  DOI: 10.1016/j.matchemphys.2017.10.034
      47
      Green and facile synthesis of MOF and nano MOF containing zinc(II) and benzene 1,3,5-tricarboxylate and its study in ibuprofen slow-release
      Lestari, Witri Wahyu; Arvinawati, Maria; Martien, Ronny; Kusumaningsih, Triana
      Materials Chemistry and Physics (2018), 204 (), 141-146CODEN: MCHPDR; ISSN:0254-0584. (Elsevier B.V.)
      Nano scale and bio-based metal-org. frameworks (MOFs) are an important class of porous materials potentially used in biomedical application. Several green and facile synthetic methods have been developed in this regard. In this study, we have compared green synthetic methods in generating MOF and nano MOF contg. biocompatible metal ion, i.e. zinc(II) and benzene 1,3,5-tricarboxylic acid (H3BTC) as linker to form [Zn3(BTC)2] using electro- and sonochem. method. The electrosynthesis of [Zn3(BTC)2] performed at ambient temp. under voltage of 15 V in the solvent mixt. of ethanol: water (1:1), whereas the sonochem. conducted in the solvent mixt. ethanol: water (1: 1) at ambient temps. and 40 KHz with a time variation of 90, 60 and 30 min. The obtained materials were loaded with ibuprofen for three days. The materials, before and after being loaded with ibuprofen, were fully characterized using x-ray diffraction anal., FTIR, SEM and transmission electron microscopy (TEM), surface area analyzer (SAA) and thermogravimetric anal. (TG/DTA). The electrochem. method tend to produce larger avarage particle size (ca. 18.43 ± 8.10μm) of [Zn3(BTC)2] than sonochem. method (with avarage particle size ca. 87.63 ± 22.86 and 112.23 ± 28.87 nm, for 30 and 60 min, resp.). Slow-release of ibuprofen was conducted in a phosphate buffered saline system (PBS) at 37°C and pH 7.4. The concn. of loaded and released ibuprofen were monitored using UV-Vis spectroscopy. After 24 h, it showed that ibuprofen encapsulated into [Zn3(BTC)2] have av. release ca. 25.6 wt%, while ibuprofen without [Zn3(BTC)2] is released ca. 85.9 wt%, then continued with a const. rate. This study demonstrated that [Zn3(BTC)2] could be afforded as a matrix to assist the slow-release of ibuprofen.
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    48. 48
      Horcajada, P.; Serre, C.; Maurin, G.; Ramsahye, N. A.; Balas, F.; Vallet-Regí, M.; Sebban, M.; Taulelle, F.; Férey, G. Flexible Porous Metal-Organic Frameworks for a Controlled Drug Delivery. J. Am. Chem. Soc. 2008, 130, 6774– 6780,  DOI: 10.1021/ja710973k
      48
      Flexible Porous Metal-Organic Frameworks for a Controlled Drug Delivery
      Horcajada, Patricia; Serre, Christian; Maurin, Guillaume; Ramsahye, Naseem A.; Balas, Francisco; Vallet-Regi, Marila; Sebban, Muriel; Taulelle, Francis; Ferey, Geard
      Journal of the American Chemical Society (2008), 130 (21), 6774-6780CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      Flexible nanoporous chromium or iron terephthalates (BDC) MIL-53(Cr, Fe) or M(OH)[BDC] have been used as matrixes for the adsorption and in vitro drug delivery of Ibuprofen (or α-p-isobutylphenylpropionic acid). Both MIL-53(Cr) and MIL-53(Fe) solids adsorb around 20 wt % of Ibuprofen (Ibuprofen/dehydrated MIL-53 molar ratio = 0.22(1)), indicating that the amt. of inserted drug does not depend on the metal (Cr, Fe) constitutive of the hybrid framework. Structural and spectroscopic characterizations are provided for the solid filled with Ibuprofen. In each case, the very slow and complete delivery of Ibuprofen was achieved under physiol. conditions after 3 wk with a predictable zero-order kinetics, which highlights the unique properties of flexible hybrid solids for adapting their pore opening to optimize the drug-matrix interactions.
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    49. 49
      Higuchi, W. I. Analysis of Data on Medicament Release Form Ointments. J. Pharm. Sci. 1962, 51, 802– 804,  DOI: 10.1002/jps.2600510825
      There is no corresponding record for this reference.
    50. 50
      Vallet-Regí, M.; Balas, F.; Arcos, D. Mesoporous Materials for Drug Delivery. Angew. Chem., Int. Ed. 2007, 46, 7548– 7558,  DOI: 10.1002/anie.200604488
      50
      Mesoporous materials for drug delivery
      Vallet-Regi, Maria; Balas, Francisco; Arcos, Daniel
      Angewandte Chemie, International Edition (2007), 46 (40), 7548-7558CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      A review. Research on mesoporous materials for biomedical purposes has experienced an outstanding increase during recent years. Since 2001, when MCM-41 was first proposed as drug-delivery system, silica-based materials, such as SBA-15 or MCM-48, and some metal-org. frameworks were discussed as drug carriers and controlled-release systems. Mesoporous materials are intended for both systemic-delivery systems and implantable local-delivery devices. The later application provides very promising possibilities in the field of bone-tissue repair because of the excellent behavior of these materials as bioceramics. This Minireview deals with the advances in this field by the control of the textural parameters, surface functionalization, and the synthesis of sophisticated stimuli-response systems.
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    51. 51
      Ke, F.; Yuan, Y.-P.; Qiu, L.-G.; Shen, Y.-H.; Xie, A.-J.; Zhu, J.-F.; Tian, X.-Y.; Zhang, L.-D. Facile Fabrication of Magnetic Metal–organic Framework Nanocomposites for Potential Targeted Drug Delivery. J. Mater. Chem. 2011, 21, 3843– 3848,  DOI: 10.1039/c0jm01770a
      51
      Facile fabrication of magnetic metal-organic framework nanocomposites for potential targeted drug delivery
      Ke, Fei; Yuan, Yu-Peng; Qiu, Ling-Guang; Shen, Yu-Hua; Xie, An-Jian; Zhu, Jun-Fa; Tian, Xing-You; Zhang, Li-De
      Journal of Materials Chemistry (2011), 21 (11), 3843-3848CODEN: JMACEP; ISSN:0959-9428. (Royal Society of Chemistry)
      We describe a facile, efficient, and environmentally friendly fabrication of a novel type of magnetic porous metal-org.-framework (MOF)-based nanocomposites that can be potentially used for targeted drug delivery. The magnetic MOF nanocomposites were fabricated by incorporation of Fe3O4 nanorods with nanocrystals of Cu3(BTC)2 (HKUST-1), a 3-dimensional (3D) MOF with a 3D channel system. The as-synthesized materials had both magnetic characteristics and high porosity, making them excellent candidates for targeted drug delivery systems. An anti-cancer drug acting as a selective cyclooxygenase-2 (COX-2) inhibitor for pancreatic cancer treatment, nimesulide, was laden into pores of the nanocomposites. These MOF-based magnetic nanocomposites could adsorb up to 0.2 g of nimesulide per g of composite, and it took as long as 11 days to complete the drug release in physiol. saline at 37°.
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    52. 52
      Tiwari, A.; Patra, H. K.; Wang, X. Advanced Materials Interfaces; Gregory, P., Ed.; Wiley-VCH: Weinheim, 2016.
      There is no corresponding record for this reference.
    53. 53
      Dhakshinamoorthy, A.; Alvaro, M.; Chevreau, H.; Horcajada, P.; Devic, T.; Garcia, H.; Serre, C. Iron(III) Metal–organic Frameworks as Solid Lewis Acids for the Isomerization of Alfa-Pinene Oxide. Catal. Sci. Technol. 2012, 3, 324– 330,  DOI: 10.1039/C2CY00376G
      There is no corresponding record for this reference.
    54. 54
      Kandiah, M.; Nilsen, M. H.; Usseglio, S.; Jakobsen, S.; Olsbye, U.; Tilset, M.; Larabi, C.; Quadrelli, E. A.; Bonino, F.; Lillerud, K. P. Synthesis and Stability of Tagged UiO-66 Zr-MOFs. Chem. Mater. 2010, 22, 6632– 6640,  DOI: 10.1021/cm102601v
      54
      Synthesis and Stability of Tagged UiO-66 Zr-MOFs
      Kandiah, Mathivathani; Nilsen, Merete Hellner; Usseglio, Sandro; Jakobsen, Soren; Olsbye, Unni; Tilset, Mats; Larabi, Cherif; Quadrelli, Elsje Alessandra; Bonino, Francesca; Lillerud, Karl Petter
      Chemistry of Materials (2010), 22 (24), 6632-6640CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
      The assembly of extended structures of the Zr-based MOF UiO-66 was pursued with three different com. available ligands: 2-aminobenzenedicarboxylic acid (H2N-H2BDC), 2-nitrobenzenedicarboxylic acid (ON-H2BDC), and 2-bromobenzenedicarboxylic acid (Br-H2BDC). Three new functionalized MOFs UiO-66-NH2 (1), UiO-66-NO2 (2), and UiO-66-Br (3) was initiated by detg. the reaction conditions necessary to produce MOFs with the same topol. of the parent UiO-66. Thermal and structural stability of the modified MOFs were examd. using powder X-ray diffraction anal. (PXRD) and thermogravimetric anal. (TGA). Langmuir surface areas were also detd. using N2 isotherms at 77 K to examine the porosity of the functionalized materials. Some changes in the surface area because of the presence of addnl. functionality on the BDC ligand were revealed. The results demonstrate the possibility of incorporating active functional groups into the UiO-66 structure almost without losing its exceptionally high thermal and chem. stability.
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    55. 55
      Garibay, S. J.; Cohen, S. M. Isoreticular Synthesis and Modification of Frameworks with the UiO-66 Topology. Chem. Comm. 2010, 46, 7700– 7702,  DOI: 10.1039/c0cc02990d
      55
      Isoreticular synthesis and modification of frameworks with the UiO-66 topology
      Garibay, Sergio J.; Cohen, Seth M.
      Chemical Communications (Cambridge, United Kingdom) (2010), 46 (41), 7700-7702CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
      Amino, bromo, nitro, and naphthalene functionalized terephthalates in UiO-66 metal-org. frameworks [Zr6O4(OH)4(p-O2C-Ar-CO2)6]n were synthesized through reticular chem. UiO-66-NH2 is suitable for postsynthetic modification with a variety of anhydrides to generate new, functionalized frameworks.
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    56. 56
      Rappe, A. K.; Iii, W. A. G. Charge Equilibration for Molecular Dynamics Simulations. J. Phys. Chem. 1991, 95, 3358– 3363,  DOI: 10.1021/j100161a070
      56
      Charge equilibration for molecular dynamics simulations
      Rappe, Anthony K.; Goddard, William A., III
      Journal of Physical Chemistry (1991), 95 (8), 3358-63CODEN: JPCHAX; ISSN:0022-3654.
      An approach is reported for predicting charge distributions in mols. for use in mol. dynamics simulations. The input data are exptl. at. ionization potentials, electron affinities, and at. radii. An at. chem. potential is constructed by using these quantities plus shielded electrostatic interactions between all charges. Equal chem. potentials leads to equil. charges that depend upon geometry. This Charge Equilibration (QEq) approach leads to charges in excellent agreement with exptl. dipole moments and with the at. charges obtained from the electrostatic potentials of accurate ab initio calcns. QEq can be used to predict charges for any polymer, ceramic, semiconductor, or biol. system, allowing extension of mol. dynamics studies to broad classes of new systems. The charges depend upon environment and changes during mol. dynamics calcns. This approach can also be used to predict IR intensities, dielec. consts., and other charge-related properties.
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    57. 57
      Rappe, A. K.; Casewit, C. J.; Colwell, K. S.; Goddard, W. A., III; Skiff, W. M. UFF, a Full Periodic Table Force Field for Molecular Mechanics and Molecular Dynamics Simulations. J. Am. Chem. Soc. 1992, 114, 10024– 10035,  DOI: 10.1021/ja00051a040
      57
      UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations
      Rappe, A. K.; Casewit, C. J.; Colwell, K. S.; Goddard, W. A., III; Skiff, W. M.
      Journal of the American Chemical Society (1992), 114 (25), 10024-35CODEN: JACSAT; ISSN:0002-7863.
      A new mol. mechanics force field, the Universal force field (UFF), is described wherein the force field parameters are estd. using general rules based only on the element, its hybridization and its connectivity. The force field functional forms, parameters, and generating formulas for the full periodic table are presented.
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    58. 58
      Yang, Q.; Wiersum, A. D.; Llewellyn, P. L.; Guillerm, V.; Serre, C.; Maurin, G. Functionalizing Porous Zirconium Terephthalate UiO-66 (Zr) for Natural Gas Upgrading: A Computational Exploration. Chem. Commun. 2011, 47, 9603– 9605,  DOI: 10.1039/c1cc13543k
      There is no corresponding record for this reference.
    59. 59
      Düren, T.; Millange, F.; Férey, G.; Walton, K. S.; Snurr, R. Q. Calculating Geometric Surface Areas as a Characterization Tool for Metal-Organic Frameworks. J. Phys. Chem. C 2007, 111, 15350– 15356,  DOI: 10.1021/jp074723h
      59
      Calculating Geometric Surface Areas as a Characterization Tool for Metal-Organic Frameworks
      Dueren, Tina; Millange, Franck; Ferey, Gerard; Walton, Krista S.; Snurr, Randall Q.
      Journal of Physical Chemistry C (2007), 111 (42), 15350-15356CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
      Metal-org. frameworks (MOFs) synthesized in a building-block approach from org. linkers and metal corner units offer the opportunity to design materials with high surface areas for adsorption applications by assembling the appropriate building blocks. In this paper, we show that the surface area calcd. in a geometric fashion from the crystal structure is a useful tool for characterizing MOFs. We argue that the accessible surface area rather than the widely used Connolly surface area is the appropriate surface area to characterize cryst. solids for adsorption applications. The accessible surface area calcd. with a probe diam. corresponding to the adsorbate of interest provides a simple way to screen and compare adsorbents. We investigate the effects of the probe mol. diam. on the accessible surface area and discuss the implications for increasing the surface area of metal-org. frameworks by the use of catenated structures. We also demonstrate that the accessible surface area provides a useful tool for judging the quality of a synthesized sample. Exptl. surface areas can be adversely affected by incomplete solvent removal during activation, crystal collapse, or interpenetration. The easily calcd. accessible surface area provides a benchmark for the theor. upper limit for a perfect crystal.
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  • Supporting Information

    Supporting Information

    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsomega.8b00185.

    • HPLC determinations, characterization of all materials (PXRD, FTIR spectroscopy, TGA, and N2 sorption measurements), stability studies, and complete drug-delivery studies (PDF)


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