Enantioselective Discrimination of Histidine by Means of an Achiral Cubane-Bridged Bis-Porphyrin
- Simona BettiniSimona BettiniDepartment of Biological and Environmental Sciences and Technologies, DISTEBA, University of Salento, Via per Arnesano, Lecce 73100, ItalyConsorzio Interuniversitario Nazionale per la Scienza e, Tecnologia dei Materiali, INSTM, Via G. Giusti, 9, Firenze 50121, ItalyMore by Simona Bettini
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- Nitika GroverNitika GroverSchool of Chemistry, Chair of Organic Chemistry, Trinity Biomedical Sciences Institute, Trinity College Dublin, The University of Dublin, 152−160 Pearse Street, Dublin 2, IrelandMore by Nitika Grover
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- Michela OttoliniMichela OttoliniDepartment of Engineering of Innovation, Campus University Ecotekne, University of Salento, Via per Monteroni, Lecce 73100, ItalyMore by Michela Ottolini
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- Cornelia MatternCornelia MatternSchool of Chemistry, Chair of Organic Chemistry, Trinity Biomedical Sciences Institute, Trinity College Dublin, The University of Dublin, 152−160 Pearse Street, Dublin 2, IrelandMore by Cornelia Mattern
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- Ludovico ValliLudovico ValliDepartment of Biological and Environmental Sciences and Technologies, DISTEBA, University of Salento, Via per Arnesano, Lecce 73100, ItalyConsorzio Interuniversitario Nazionale per la Scienza e, Tecnologia dei Materiali, INSTM, Via G. Giusti, 9, Firenze 50121, ItalyMore by Ludovico Valli
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- Mathias O. Senge*Mathias O. Senge*Email: [email protected]School of Chemistry, Chair of Organic Chemistry, Trinity Biomedical Sciences Institute, Trinity College Dublin, The University of Dublin, 152−160 Pearse Street, Dublin 2, IrelandMore by Mathias O. Senge
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- Gabriele Giancane*Gabriele Giancane*Email: [email protected]Consorzio Interuniversitario Nazionale per la Scienza e, Tecnologia dei Materiali, INSTM, Via G. Giusti, 9, Firenze 50121, ItalyDepartment of Cultural Heritage, University of Salento, Via D. Birago, Lecce 73100, ItalyMore by Gabriele Giancane
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Abstract
A Langmuir film of cubane-bridged bisporphyrin (H2por-cubane-H2por) at the air/water interface was developed and characterized. The floating film was successfully employed for the chiral discrimination between l- and d-histidine. The enantioselective behavior persisted after the deposition of the film on a solid support using the Langmuir–Schaefer method. Distinct absorption and reflection spectra were observed in the presence of l- or d-histidine, revealing that conformational switching was governed by the interaction between H2por-cubane-H2por and the histidine enantiomer. The mechanism of chiral selection was investigated using an ad hoc modified nulling ellipsometer, indicating the anti-conformation was dominant in the presence of l-histidine, whereas the presence of d-histidine promoted the formation of tweezer conformation.
This publication is licensed under
CC-BY 4.0.
License Summary*
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Attribution (BY): Credit must be given to the creator.
*Disclaimer
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License Summary*
You are free to share (copy and redistribute) this article in any medium or format and to adapt (remix, transform, and build upon) the material for any purpose, even commercially within the parameters below:
Creative Commons (CC): This is a Creative Commons license.
Attribution (BY): Credit must be given to the creator.
*Disclaimer
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License Summary*
You are free to share (copy and redistribute) this article in any medium or format and to adapt (remix, transform, and build upon) the material for any purpose, even commercially within the parameters below:
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Introduction
ARTICLE SECTIONS
Chiral discrimination is a chemical interaction phenomenon, by which a receptor recognizes a specific enantiomer of substrate molecules. (1) Different enantiomers of the same molecule may exhibit different properties under physiological conditions. Furthermore, the human olfactory and gustatory systems use chiral interactions. Hence, d-asparagine tastes sweet, and l-asparagine tastes bitter. The toxicity and/or efficacy of a molecule depends upon the ratio of enantiomers or the presence of a specific enantiomer in a sample. The true medical importance of a pure enantiomer was realized through the thalidomide tragedy, a global medical disaster in the late 1950s. (2) In 1979, Blaschke and co-workers discovered that R-thalidomide exhibits a therapeutic effect, whereas S-enantiomer is a teratogen. (3) Hence, the birth defects could have been avoided if only the R-enantiomer had been used instead of a racemic mixture. Since then, chemists from all over the world have devoted tremendous efforts to the field of chiral discrimination and enantiomeric excess (ee) analysis. (1,4)
In nature, many biomolecules such as amino acids and sugars are present in a chiral form. More than 20 proteinogenic amino acids (5) are listed and, except for glycine, all of them are chiral molecules. In humans and other vertebrates, proteins are mainly composed of l-amino acids. (6)l-amino acids participate in several biological processes such as impulse neurotransmission (7) and regulatory functions of cells. (8) Nature preferentially uses the l-amino acids for the ontogenesis of living organisms. Exceptionally, d-amino acids are present in deep ocean microorganisms (9) and cell walls of Gram-positive bacteria. (10) The reason for the asymmetric chiral approach used in many natural processes is fascinating, controversial, and still unknown.
l-histidine contains an α-amino group, (−NH3+ under physiological conditions), a carboxyl group (−COO– under physiological conditions), and an imidazole side chain. Histidine is the precursor of histamine, a vital inflammatory agent in immune responses. (11)l-histidine plays several biological roles; it is able to bind to iron centers in hemoglobin and myoglobin; (12) it is often present in the active sites of metalloenzymes (such as carbonic anhydrase and cytochromes) (12) and acts as an antioxidant (13) and a mitochondrial glutamine transporter inhibitor. (14) For a long time, histidine was not considered as an essential amino acid. A lack of histidine in the adult daily diet induces the metabolization of hemoglobin and carnosine, (12) resulting in low hemoglobin concentration in blood and low carnosine in muscular tissues. (15) In pharmacological applications, l-histidine is used to prevent fatigue during physical efforts (16) and to cure aging-related disorders, (17) dermatitis, (18) inflammatory, and ocular diseases. (19)d-Histidine plays a marginal role in physiology. It was proposed as a protecting agent against infections from Bacillus anthracis spores. (20) Antifungal activities of d-histidine were also reported in the literature. (21)
Although l- and d-histidine play different roles in nature, the chiral discrimination between their enantiomers is difficult. The lock and key mechanism is the most common approach used for chiral detection. (22) The three-point interaction model is another method typically used to design active layers for chiral recognition. (23) Additionally, basket molecules (such as cyclodextrins) (24) and supramolecular systems are also used as an enantioselective receptor. (25) Various aromatic systems have been used for the (enantio)differentiation of (di)amines and (amine)alcohols in solution and in the solid state. (26−29) Porphyrins are the pigments of life, performing a variety of roles such as oxygen transport, electron transfer, oxidation reactions, and photosynthesis in nature. (30) The porphyrin scaffolds have been used as “building blocks” in molecular engineering of structurally defined multichromophoric arrays. Furthermore, it has been demonstrated that bismetalloporphyrins act as excellent sensors for the detection of a variety of guests, including aromatic amines. (31) Furthermore, a few reports on chiral detection of amino acids using chiral porphyrins have been published; however, reports on the enantioselective detection using an achiral (free base) porphyrin receptor are scarce. In the present contribution, a method to recognize l-histidine by means of a nonchiral organic molecule is proposed. To this end, we have used an achiral cubane-bridged-bisporphyrin (H2por-cubane-H2por, Figure 1) (32) to form supramolecularly arranged thin films employing the Langmuir–Schaefer (LS) method. (33) The LS film was used as a receptor for the chiral discrimination between l- and d-histidine. The spectroscopic investigations indicate that each enantiomer is able to stabilize only one kind of bisporphyrin conformer. In particular, l-histidine favors the left-handed configuration of the bisporphyrin derivative.
Figure 1
Figure 1. Chemical structure of the cubane-bridged bisporphyrin (H2por-cubane-H2por) and schematic representation of the possible configurations adopted by the H2por-cubane-H2por. (A) Syn-form, (B) tweezer configuration, and (C) anti-form.
Materials and Methods
ARTICLE SECTIONS
The H2por-cubane-H2por and the (Zn)por-cubane-H2por (Figure S1) were synthetized according to the procedure reported in the literature. (32)
A NIMA-KSV trough equipped with a Brewster angle microscope (34) and a reflection spectrophotometer were used to record the isotherm curve surface pressure vs area per molecule of the floating film, and the barrier speed was set at 5 mm min–1 for all the Langmuir experiments. The H2por-cubane-H2por solution was obtained by dissolving 0.1 mg in 10 mL of chloroform (10–4 M), and 150 μL was spread at the air/water subphase interface by means of a glass syringe. Reflection spectra were obtained as a difference between the reflection intensity of the pure subphase and the subphase covered by the floating film that is directly proportional to the absorbance of the floating thin film. (35)
The floating films were transferred to different solid supports (quartz and silicon dioxide) by means of the LS method, (36) the horizontal variation of the most known Langmuir–Blodgett technique. (37) For ellipsometer measurements and UV–visible characterization, four LS runs were deposited.
UV–visible spectroscopy was performed with a PerkinElmer 650 spectrophotometer, and an EP4 Accurion-modified nulling ellipsometer was used to monitor the optical activity of the LS films. The angle of the compensator element of the nulling ellipsometer, a λ/4 phase retarder, was set to 0°, and the polarizer was fixed first at 45° to obtain left-handed circularly polarized incident light and at −45° to obtain right-handed circularly polarized incident light. The circularly polarized light was incident directly on the LS films deposited on silicon slides, and a multi-wavelength source was used to investigate the visible range. This configuration was necessary for monitoring the optical activity of the transferred thin films because the optical density related to a LS film obtained by 4 LS runs appears to be too low to be characterized by circular dichroism. Unfortunately, the possibility to deposit a larger number of layers has to be excluded because when the number of LS runs increases, the optical absorption profile of the deposited film strongly changes the relative intensities of the syn-, anti-, and tweezer forms (Figure S2). This evidence prompted us to work with a very low number of LS layers in order to minimize the effect of stacking process on the detection mechanism.
Results and Discussion
ARTICLE SECTIONS
H2por-cubane-H2por molecules can adopt three different conformations called syn-, anti-, and tweezer (Figure 1). The three conformers are characterized by different positions of the maximum absorption of the Soret band that red-shifts from the closed (syn-) to the opened (anti-) form. (38)
Chloroform solutions of H2por-cubane-H2por were spread at the air/water interface by means of a gas tight syringe (150 μL) and, after the chloroform evaporation, the isotherm curve surface pressure vs area per molecule was recorded at a constant barrier speed of 5 mm min–1 (black line in Figure 2A). A long pseudo-gaseous phase is recorded, suggesting that the behavior of the molecules of the floating film is far enough from the ideal amphiphilic molecules forming the typical Langmuir floating films. (39) An abrupt slope change is recorded at approx. 250 Å2 molecule–1, and a further variation of curve profile is evident at approx. 15 mN m–1. Both variations are related to a new rearrangement of the molecules at the air–water interface (blue line, Figure 2A). The value of the limiting area per molecule calculated for the first slope change of the isotherm curve (approx. 250 Å2) agrees with the area occupied by a single 5,10,15,20-tetraphenylporphyrin; (40) hence, it is indicative of H2por-cubane-H2por in the syn-form. For further clarification, Brewster angle microscopy (BAM) was performed (Figure 3), and the results suggest that a nonhomogenous covering of the surface is obtained for the H2por-cubane-H2por floating film. Therefore, the extrapolated area per molecule value of 250 Å2 is not unequivocally connected to the syn- or anti-form of the bisporphyrin. The second branch of the isotherm curve gives a limiting area per molecule of approx. 112 Å2; this confirms the formation of a multilayered floating film. (38) Preliminary evidence of the selective interaction between H2por-cubane-H2por molecules and histidine enantiomers was readily evident by the Langmuir curves in red and black in Figure 2A, recorded for l- and d-enantiomers, respectively. The curve trend recorded for the H2por-cubane-H2por Langmuir layer spread on l-histidine containing aqueous subphase (10–4 M) is very similar to that one recorded in the case of an ultrapure water subphase, even though a higher value of surface pressure is reached (approx. 38 mN m–1 for the film floating on l-histidine containing subphase and about 32 mN m–1 for H2por-cubane-H2por on ultrapure water subphase). In the presence of the d-histidine containing subphase (10–4 M), the isotherm Langmuir curve appears drastically different from both the H2por-cubane-H2por layer spread on ultrapure water subphase and bisporphyrins Langmuir layer floating on 10–4 M l-histidine water solution. BAM images (Figure 3) confirm that floating films obtained on the three different subphases are morphologically different and that a nonuniform covering of the interface is obtained in the three Langmuir experiments.
Figure 2
Figure 2. (A) Comparison of the three isotherm curves’ surface pressure vs area per molecule recorded for a H2por-cubane-H2por Langmuir floating film on ultrapure water subphase (blue line), aqueous subphase containing l-histidine (10–4 M) (red line), and aqueous subphase containing d-histidine (10–4 M) (black line). (B) Reflection spectra of H2por-cubane-H2por floating film on ultrapure water subphase (blue line), aqueous subphase containing l-histidine (10–4 M) (red line), and aqueous subphase containing d-histidine (10–4 M) (black line). All the spectra were acquired at a surface pressure of 20 mN m–1.
Figure 3
Figure 3. Brewster Angle Microscopy carried out on H2por-cubane-H2por floating films spread on ultrapure water subphase (top line), on subphase containing l-histidine (10–4 M) (middle row) and, in lower line, on subphase containing d-histidine (10–4 M).
The chloroform solution of H2por-cubane-H2por at the air/water subphase showed a Soret band at 432 nm (Figures 2B and S3). The introduction of l-histidine at low surface pressure to the porphyrin floating layer did not alter the position of the Soret band, indicating that the H2por-cubane-H2por molecules exist in the tweezer form (Figure S4). With the increasing surface pressure, the Soret band intensity (ΔR) increased, and a shoulder appeared at 400 nm. The band at 400 nm corresponds to the closed (syn-) conformer of H2por-cubane-H2por. A further increase of the surface pressure by the barrier compression induced an enhancement of the intensity band at 400 nm and a new strong absorption band appeared at 445 nm, corresponding to the anti-conformer (Figure 2B). In the presence of d-histidine (Figure S5), the main absorption band is still located at 432 nm and the intensities of two signals at 400 and 445 nm do not substantially increase under the barrier action; hence, the tweezer conformation was retained. Overall, the reflection spectra demonstrated that two histidine enantiomers interact with the H2por-cubane-H2por molecules at the air/subphase interface and the interaction mechanisms are governed by the chiral form of the amino acid.
The floating films from water, l-histidine, and d-histidine subphases were transferred on a solid substrate using the LS method. The obtained thin solid films were characterized by means of UV–visible spectroscopy (Figure 4). The differences among the three LS layers are evident: the LS film deposited from the ultrapure water subphase showed a well-defined band at 425 nm; the thin film transferred using d-histidine containing subphase was characterized by a pronounced shoulder at 445 nm and a less intense one at 402 nm. In the case of the thin film obtained from the l-histidine subphase, an absorption band at 445 nm is dominated in the whole absorption spectrum, even though the bands at 425 and 400 nm are evident. Furthermore, the Q-bands at 521, 556, 594, and 650 nm are red-shifted for H2por-cubane-H2por LS films obtained from both l- and of d-histidine-containing subphase.
Figure 4
Figure 4. Visible spectra of LS films (4 runs) of H2por-cubane-H2por transferred from ultrapure water (blue line), aqueous subphase containing l-histidine (10–4 M) (red line), and aqueous subphase containing d-histidine (10–4 M) (black line).
The optical activity of the H2por-cubane-H2por LS films was investigated by means of an ellipsometer set to have left and right circularly polarized incident light. (41) In an EP4 nulling ellipsometer, the polarizer was set at 45° and the compensator at 0° to obtain a left-handed circularly polarized light; when the polarizer is fixed at −45° and the compensator at 0°, a right-handed circularly polarized is incident on the sample. This approach was used because it allows for the characterization of very thin solid films without any sample treatment. The results obtained using this approach are reported in Figure 5 for the case of LS films deposited from the water subphase (Figure 5A), from l-histidine subphase (Figure 5B), from d-histidine (Figure 5C), and from a histidine racemic solution (Figure 5D).
Figure 5
Figure 5. Ellipsometer measurements performed using left-handed circularly polarized light (in blue in all the images) and right-handed circularly polarized light (black lines). Four samples were investigated: (A) 4 runs of LS film transferred from ultrapure water subphase; (B) 4 runs of LS film transferred from water subphase containing l-histidine (10–4 M); (C) 4 runs of LS film transferred from water subphase containing d-histidine (10–4 M); and (D) 4 runs of LS film transferred from water subphase containing racemic solution of D and l-histidine (10–4 M).
Ellipsometer measurements suggest that the Langmuir film transferred onto the silicon substrate from the air/ultrapure water subphase is formed both by right-handed and by left-handed conformers. When right-handed light is used, a pronounced band at 425 nm appears, indicating the presence of the tweezer form, whereas the presence of left-handed light induces a shoulder at 440 nm, suggesting the presence of the anti-form of H2por-cubane-H2por (Figure 5A). These results further confirm the observation obtained from the visible spectra (Figure 4, line blue) and suggest that the tweezer and anti-forms are preferentially characterized by clockwise and anticlockwise chirality, respectively. Therefore, the tweezer arrangement is the predominant molecular structure at the air/ultrapure water subphase. The presence of l-histidine in the subphase during the transfer process considerably influences the aggregation state of the thin film’s molecules, as observed in Figure 4 and in Figure 5B. The features observed for the right-handed circularly polarized light show an intense and symmetric band at 425 nm; on the contrary, the left-handed circularly polarized light clearly evidences the band at 440 nm. This result suggests that the presence of l-histidine in the subphase influences the H2por-cubane-H2por Langmuir film deposition process. In particular, the formation of a chiral supramolecular adduct (porphyrin/l-amino acid) is favorable. This adduct is preserved during the deposition process and shows a preferential anti-clockwise chirality.
The opposite effect on the porphyrin aggregation is induced by the presence of d-histidine in the subphase (Figure 5C). The number of molecules that interact with the circularly polarized light in a left-handed way (anti-form) decreases, and the number of molecules in tweezer conformation (characterized by a clockwise chirality) increases. From the reflection spectra, it can be proposed that at the air/water interface, the porphyrin molecules are arranged in both the tweezer and anti-forms (Figure 6, image a). However, the tweezer form was found to be predominant at the air/water interface. Furthermore, the deposition procedure preferentially promotes the molecules to change to the tweezer form that shows a predominant clockwise chirality.
Figure 6
Figure 6. Schematic representation of the plausible interaction mechanisms that govern the configuration changes of H2Por-cubane-H2Por at the air/subphase interface (panel a) in the presence of d-histidine (panel b,c) and l-histidine (panel d). The behavior of each bisporphyrin conformer was considered depending on the analyte dissolved in the subphase.
When the interaction takes place between d-histidine and the tweezer porphyrin molecules, no relevant effect on the conformational arrangement can be observed. Furthermore, d-histidine can be accommodated in the bite of the tweezer conformer, promoting a stable binding among the amino acids’ carboxylic group and the amide groups on the two sides of the cubane. (31) The imidazole group of histidine can be trapped between the two macrocycles of the bisporphyrin in tweezer form (Figure 6b). The tweezer form, which presents clockwise chirality, is so stabilized by interaction with d-histidine molecules. On the other hand, when d-histidine interacts with the anti-form of H2por-cubane-H2por (anti clockwise chiral behavior), the COO– moiety of histidine can interact with the −NH group of the amide bond, while the histidine NH3+ interacts with the C═O of the amide group (Figure 6c). It is reasonable to propose that the imidazole ring of the dissolved amino acid overlaps with the π-cloud of the porphyrin macrocycle on the subphase interface. As reported for similar systems, a conformational change from the opened to the tweezer form of bisporphyrin derivatives can be promoted. (31,42)
When l-histidine is dissolved in the subphase, it can interact with both the anti- and tweezer forms (Figure 6d). The anti-form is stabilized by the simultaneous interaction with the imidazole and the carboxylic moieties of l-histidine, ensuring the presence of both the opened and the tweezer conformer during the deposition process. This mechanism preserves, contrary to the case of the D enantiomer of the amino acid, the presence of anti-clockwise conformers within the film. In the presence of a racemic histidine solution, ellipsometry suggests that the H2por-cubane-H2por molecules in Langmuir film are again arranged both as tweezer and anti-conformers with a preference for the former. This behavior can be explained considering that (i) the molecules in tweezer and anti-form interacting with d-histidine are stabilized in the tweezer form; (ii) the noninteracting bisporphyrin molecules are preferentially transferred in the tweezer form; (iii) the tweezer molecules interacting with l-histidine are stabilized again in the tweezer form; and (iv) the molecules arranged as anti-conformer that interact with l-histidine are immobilized on the solid support in the opened form (left-handed). It is worth noting that when the LS film is deposited on the solid substrate from air/ultrapure water subphase, the conformational changes induced by L and d-histidine fluxes are strongly attenuated (Figure S6) due to the larger energy needed to induce a conformational change in the immobilized molecules.
To corroborate the proposed rationale, H2por-cubane-H2por floating films were transferred from subphases containing different analytes. In particular, chiral aliphatic amino acids (l- and d-lysine) were used to investigate the role of the aromatic moiety in adduct formation. Additionally, the achiral and smallest amino acid glycine was used to investigate the effect of chirality and steric bulk on the adduct formation. When l- and d-lysine were dissolved in the subphase, no relevant changes were observed in the absorption spectra of LS films. This is the consequence of the absence of imidazole moiety in the lysine (Figure S7A). Similarly, glycine did not induce any changes in the absorption spectrum (Figure S7B). In contrast, the presence of histamine in the subphase strongly affected the absorption profile of the bisporphyrin LS film (Figure S7C). In this case, the opened bisporphyrin form is preserved during the deposition process, as for l-histidine, even though changes are smaller due to the absence of the amide moiety and the geometric arrangement of the analyte. This evidence confirms the crucial role of both the imidazole ring and −NH2 group in chiral detection. An aromatic amino acid without the imidazole moiety, phenylalanine, was used to clarify the role of imidazole. The effect of d-phenylalanine on the H2por-cubane-H2por molecules of the LS film is very similar to that one observed for d-histidine: the bisporphyrins are pushed to preferentially arrange in tweezer form. In contrast to the observations in the case of l-histidine, the effect of l-phenylalanine on the H2por-cubane-H2por conformational arrangement is almost negligible (Figure S7D). In this case, the Soret band is sharp and centered at 425 nm, indicating that only one form is preserved (the tweezer form). d-phenylalanine and l-phenylalanine have the same behavior. No chiral discrimination takes place.
According to the mechanism proposed in Figure 6, the imidazole group plays a fundamental role in the interaction with the imide group of the cubane bridge, inducing the stabilization of the opened form of the bisporphyrin molecules.
When the monometallated (Zn)por-cubane-H2por was used to detect histidine in the subphase, no conformational changes were observed in the presence of d- and l-enantiomers (Figure S8). The high affinity of the imidazole group toward the Zn(II) center promotes the mixing of porphyrin and histidine subphases. (43) This preferential mechanism inhibits the supramolecular adduct formation and also supports the interaction pathways described earlier (Figure S9).
Conclusions
ARTICLE SECTIONS
The chiral discrimination of d- and l-histidine was achieved by tuning the conformational switching of a cubane-bridged bisporphyrin (H2por-cubane-H2por). Spectroscopic investigations of Langmuir films allowed us to monitor the conformations adopted by the bisporphyrin molecules spread at the air/ultrapure water interface of a Langmuir trough. It was observed that the presence of l- and d-histidine in the subphase (10-4 M) greatly influences the floating film behavior. Reflection spectra of floating films in the presence of l-histidine showed the presence of an anti-conformation, whereas air/water and d-histidine subphase promoted the tweezer conformation. Chiral discrimination was preserved during the deposition process using the LS method. Ultrapure water was used as a subphase for the H2por-cubane-H2por LS film. The absorption spectrum of the film exhibited an absorption band at 425 nm, revealing the presence of the tweezer conformation. A similar absorption spectrum was obtained when the d-histidine subphase was introduced. In contrast, l-histidine promoted the formation of a predominant band at 440 nm, a characteristic of the anti-form of H2por-cubane-H2por. A rationale for the chiral selectivity and induced conformational changes was further confirmed by investigating the thin LS films under circularly polarized light. The presence of d-histidine increases the number of molecules that interact with the right-handed circularly polarized light; hence, fewer molecules interact with the left-handed polarized light. The very low number of LS layers did not allow for the use of circular dichroism as a characterization technique and an ad hoc modified ellipsometer was used. Furthermore, l-histidine promotes the stabilization of anti-conformer of the porphyrin molecules, which preferentially interact with left-handed polarized light. A variety of amino acids including glycine, lysine, histamine, and phenylalanine were used to investigate the effect of different functional groups involved in the interactions with H2por-cubane-H2por. We observed that a combined presence of the imidazole ring and NH2 groups plays a crucial in chiral discrimination and conformational switching. Overall, this work demonstrated that H2por-cubane-H2por can be used to determine the absolute configuration of l- and d-histidine.
Supporting Information
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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.langmuir.1c02377.
Chemical structure of H2por-cubane-H2por and (Zn)por-cubane-H2por, influence of the number of LS runs on the spectral profile of H2por-cubane-H2por, reflection spectra of the floating film of H2por-cubane-H2por spread at air/ultrapure water subphase acquired at different surface pressures, reflection spectra of the floating film of H2por-cubane-H2por spread at air/l-histidine aqueous subphase acquired at different surface pressures, reflection spectra of the floating film of H2por-cubane-H2por spread at air/d-histidine aqueous subphase acquired at different surface pressures, spectral variation induced by fluxing l- and d-histidine on 4 runs LS film of H2por-cubane-H2por transferred from ultrapure water subphase, effect on the H2por-cubane-H2por LS film absorption spectrum induced by different analytes dissolved in the subphase: (A) l and d-lysine, (B) glycine, (C) histamine, (D) l and d-phenylalanine, LS films of (Zn)por-cubane-H2por transferred from ultrapure water (blue line), from subphases containing l-histidine (10–4 M) and d-histidine (10–4 M), and schematic representation of the interaction among l and d-histidine with the floating molecules of (Zn)por-cubane-H2por (PDF)
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Author Information
ARTICLE SECTIONS
- Gabriele Giancane - Consorzio Interuniversitario Nazionale per la Scienza e, Tecnologia dei Materiali, INSTM, Via G. Giusti, 9, Firenze 50121, Italy; Department of Cultural Heritage, University of Salento, Via D. Birago, Lecce 73100, Italy;
https://orcid.org/0000-0001-5089-5429;
- Simona Bettini - Department of Biological and Environmental Sciences and Technologies, DISTEBA, University of Salento, Via per Arnesano, Lecce 73100, Italy; Consorzio Interuniversitario Nazionale per la Scienza e, Tecnologia dei Materiali, INSTM, Via G. Giusti, 9, Firenze 50121, Italy;https://orcid.org/0000-0002-5506-5413
- Ludovico Valli - Department of Biological and Environmental Sciences and Technologies, DISTEBA, University of Salento, Via per Arnesano, Lecce 73100, Italy; Consorzio Interuniversitario Nazionale per la Scienza e, Tecnologia dei Materiali, INSTM, Via G. Giusti, 9, Firenze 50121, Italy;https://orcid.org/0000-0002-6943-8647
The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.
This research was supported by the European Innovation Council through the FET-OPEN Project INITIO (grant agreement: 828779).
Acknowledgments
ARTICLE SECTIONS
The authors wish to thank Dr. Okano Shun for his support for the optimization of experimental device used in the ellipsometer measurements.
References
ARTICLE SECTIONS
This article references 43 other publications.
- 1Hembury, G. A.; Borovkov, V. V.; Inoue, Y. Chirality-Sensing Supramolecular Systems. Chemical Reviews; American Chemical Society January, 2008, 108, pp 1– 73. DOI: 10.1021/cr050005k .
- 2Kim, J. H.; Scialli, A. R. Thalidomide: The Tragedy of Birth Defects and the Effective Treatment of Disease. Toxicol. Sci. 2011, 122, 1– 6, DOI: 10.1093/toxsci/kfr088[Crossref], [PubMed], [CAS], Google Scholar2https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXpslSjs7Y%253D&md5=232e9769ad27e497c979bc8134d209d1Thalidomide: The Tragedy of Birth Defects and the Effective Treatment of DiseaseKim, James H.; Scialli, Anthony R.Toxicological Sciences (2011), 122 (1), 1-6CODEN: TOSCF2; ISSN:1096-0929. (Oxford University Press)A review. Thalidomide was a widely used drug in the late 1950s and early 1960s for the treatment of nausea in pregnant women. It became apparent in the 1960s that thalidomide treatment resulted in severe birth defects in thousands of children. Though the use of thalidomide was banned in most countries at that time, thalidomide proved to be a useful treatment for leprosy and later, multiple myeloma. In rural areas of the world that lack extensive medical surveillance initiatives, thalidomide treatment of pregnant women with leprosy has continued to cause malformations. Research on thalidomide mechanisms of action is leading to a better understanding of mol. targets. With an improved understanding of these mol. targets, safer drugs may be designed. The thalidomide tragedy marked a turning point in toxicity testing, as it prompted United States and international regulatory agencies to develop systematic toxicity testing protocols; the use of thalidomide as a tool in developmental biol. led to important discoveries in the biochem. pathways of limb development. In celebration of the Society of Toxicol.'s 50th Anniversary, which coincides with the 50th anniversary of the withdrawal of thalidomide from the market, it is appropriate to revisit the lessons learned from the thalidomide tragedy of the 1960s.
- 3Tokunaga, E.; Yamamoto, T.; Ito, E.; Shibata, N. Understanding the Thalidomide Chirality in Biological Processes by the Self-Disproportionation of Enantiomers. Sci. Rep. 2018, 8, 1– 7, DOI: 10.1038/s41598-018-35457-6[Crossref], [PubMed], [CAS], Google Scholar3https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXls1Cksrc%253D&md5=d56a5255f9df7de2219a761238b2c275Genome-wide association study of self-reported food reactions in Japanese identifies shrimp and peach specific loci in the HLA-DR/DQ gene regionKhor, Seik-Soon; Morino, Ryoko; Nakazono, Kazuyuki; Kamitsuji, Shigeo; Akita, Masanori; Kawajiri, Maiko; Yamasaki, Tatsuya; Kami, Azusa; Hoshi, Yuria; Tada, Asami; Ishikawa, Kenichi; Hine, Maaya; Kobayashi, Miki; Kurume, Nami; Kamatani, Naoyuki; Tokunaga, Katsushi; Johnson, Todd A.Scientific Reports (2018), 8 (1), 1-17CODEN: SRCEC3; ISSN:2045-2322. (Nature Research)Food allergy is an increasingly important health problem in the world. Several genome-wide assocn. studies (GWAS) focused on European ancestry samples have identified food allergy-specific loci in the HLA class II region. We conducted GWAS of self-reported reactivity with common foods using the data from 11011 Japanese women and identified shrimp and peach allergy-specific loci in the HLA-DR/DQ gene region tagged by rs74995702 (P = 6.30 × 10-17, OR = 1.91) and rs28359884 (P = 2.3 × 10-12, OR = 1.80), resp. After HLA imputation using a Japanese population-specific ref., the most strongly assocd. haplotype was HLA-DRB1*04:05-HLA-DQB1*04:01 for shrimp allergy (P = 3.92 × 10-19, OR = 1.99) and HLA-DRB1*09:01-HLA-DQB1*03:03 for peach allergy (P = 1.15 × 10-7, OR = 1.68). Addnl., both allergies' assocd. variants were eQTLs for several HLA genes, with HLA-DQA2 the single eQTL gene shared between the two traits. Our study suggests that allergy to certain foods may be related to genetic differences that tag both HLA alleles having particular epitope binding specificities as well as variants modulating expression of particular HLA genes. Investigating this further could increase our understanding of food allergy etiol. and potentially lead to better therapeutic strategies for allergen immunotherapies.
- 4Leung, D.; Kang, S. O.; Anslyn, E. V. Rapid Determination of Enantiomeric Excess: A Focus on Optical Approaches. Chem. Soc. Rev. 2012, 41, 448– 479, DOI: 10.1039/c1cs15135e[Crossref], [PubMed], [CAS], Google Scholar4https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXhsFKntrbF&md5=2df381154b10f72348dd423c045b6b17Rapid determination of enantiomeric excess: a focus on optical approachesLeung, Diana; Kang, Sung Ok; Anslyn, Eric V.Chemical Society Reviews (2012), 41 (1), 448-479CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)A review. High-throughput screening (HTS) methods are becoming increasingly essential in discovering chiral catalysts or auxiliaries for asym. transformations due to the advent of parallel synthesis and combinatorial chem. Both parallel synthesis and combinatorial chem. can lead to the exploration of a range of structural candidates and reaction conditions as a means to obtain the highest enantiomeric excess (ee) of a desired transformation. One current bottleneck in these approaches to asym. reactions is the detn. of ee, which led researchers to explore a wide range of HTS techniques. To be truly high-throughput, probably a technique that can analyze a thousand or more samples per day is needed. Many of the current approaches to this goal are based on optical methods because they allow for a rapid detn. of ee due to quick data collection and their parallel anal. capabilities. In this crit. review these techniques are reviewed with a discussion of their resp. advantages and drawbacks, and with a contrast to chromatog. methods (180 refs.).
- 5Gordon, A. H.; Martin, A. J. P.; Synge, R. L. M. Partition Chromatography in the Study of Protein Constituents. Biochem. J. 1943, 37, 79– 86, DOI: 10.1042/bj0370079[Crossref], [PubMed], [CAS], Google Scholar5https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaH2cXisFWgtg%253D%253D&md5=737913509d70b1b3326bd0ff6f01ec18Partition chromatography in the study of protein constituentsGordon, A. H.; Martin, A. J. P.; Synge, R. L. M.Biochemical Journal (1943), 37 (), 79-86CODEN: BIJOAK; ISSN:0264-6021.Correction. New compds. and compds. for which new data are given, referred to in C. A. 37, 5436.6, are: acetyl-l-valine, prepd. by resoln. of acetyl-dl-valine, m. 164°, [α]19D 4° (EtOH, c = 2); acetyl-dl-norvaline, m. 111.0-12.5° (may contain some isomer as impurity); N,N'-diacetyl-dl-lysine, m. 140-1°; acetyl-l-aspartic acid, sirup; acetyl-l-tryptophan, m. 185-6°, [α]21.5D 27.6° (H2O contg. 1 equiv. NaOH, c = 1), [α]19D 26.0° (EtOH, c = 1.1); acetylglycyl-dl-leucine, m. 176-7°; acetyl-dl-leucylglycine, dried over P2O5 in vacuo to remove Me2CO, m. 178°; acetyl-dl-leucyl-dl-leucine, m. 200°; acetylglycylglycine, m. 178-9°.
- 6Chela-Flores, J. The Origin of Chirality in Protein Amino Acids. Chirality 1994, 6, 165– 168, DOI: 10.1002/chir.530060302[Crossref], [CAS], Google Scholar6https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2cXksFOqsLo%253D&md5=4538008ecc2847014a171d7bbd094fd1The origin of chirality in protein amino acidsChela-Flores, JulianChirality (1994), 6 (3), 165-8CODEN: CHRLEP; ISSN:0899-0042.The origin of the chirality of protein amino acids is discussed from the point of view of a phase transition from a racemic mixt. into an optically pure state. It is assumed that Bose-Einstein condensation act as an amplification mechanism. The original theory is due to A. Salam (1991, 1992). A new role for the phase transition is suggested. Following M. Quack (1993), parity violations of two kinds (de facto and de lege symmetry breaking) are distinguished. While the Salam phase transition corresponds to parity violation of the second kind (de lege), the phase transition discussed in this work corresponds to parity violation of what may be called a third kind. This is suggested by recent exptl. phenomena which correlate chiral symmetry breaking and pattern formation (spontaneous symmetry breaking that separates an initial racemic mixt. into right- and left-handed space domains by means of a substrate). Tentative comments are given on the eventual design of possible expts. that may test this new hypothesis.
- 7Dalangin, R.; Kim, A.; Campbell, R. E. The Role of Amino Acids in Neurotransmission and Fluorescent Tools for Their Detection. Int. J. Mol. Sci. 2020, 21, 6197, DOI: 10.3390/ijms21176197[Crossref], [PubMed], [CAS], Google Scholar7https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXitVKqtbzO&md5=f3ddf494c65a37d051c70cf382e6dcb2The role of amino acids in neurotransmission and fluorescent tools for their detectionDalangin, Rochelin; Kim, Anna; Campbell, Robert E.International Journal of Molecular Sciences (2020), 21 (17), 6197CODEN: IJMCFK; ISSN:1422-0067. (MDPI AG)A review. Neurotransmission between neurons, which can occur over the span of a few milliseconds, relies on the controlled release of small mol. neurotransmitters, many of which are amino acids. Fluorescence imaging provides the necessary speed to follow these events and has emerged as a powerful technique for investigating neurotransmission. In this review, we highlight some of the roles of the 20 canonical amino acids, GABA and β-alanine in neurotransmission. We also discuss available fluorescence-based probes for amino acids that have been shown to be compatible for live cell imaging, namely those based on synthetic dyes, nanostructures (quantum dots and nanotubes), and genetically encoded components. We aim to provide tool developers with information that may guide future engineering efforts and tool users with information regarding existing indicators to facilitate studies of amino acid dynamics.
- 8Wu, G. Functional Amino Acids in Growth, Reproduction, and Health. Adv. Nutr. 2010, 1, 31– 37, DOI: 10.3945/an.110.1008[Crossref], [PubMed], [CAS], Google Scholar8https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXpsF2lur8%253D&md5=9c7209ab9f41539f6e2b6b16586dca81Functional amino acids in growth, reproduction, and healthWu, GuoyaoAdvances in Nutrition (2010), 1 (1), 31-37CODEN: ANDUAW; ISSN:2156-5376. (American Society for Nutrition)A review. Amino acids (AA) were traditionally classified as nutritionally essential or nonessential for animals and humans based on nitrogen balance or growth. A key element of this classification is that all nonessential AA (NEAA) were assumed to be synthesized adequately in the body as substrates to meet the needs for protein synthesis. Unfortunately, regulatory roles for AA in nutrition and metab. have long been ignored. Such conceptual limitations were not recognized until recent seminal findings that dietary glutamine is necessary for intestinal mucosal integrity and dietary arginine is required for max. neonatal growth and embryonic survival. Some of the traditionally classified NEAA (e.g. glutamine, glutamate, and arginine) play important roles in regulating gene expression, cell signaling, antioxidative responses, and immunity. Addnl., glutamate, glutamine, and aspartate are major metabolic fuels for the small intestine and they, along with glycine, regulate neurol. function. Among essential AA (EAA), much emphasis has been placed on leucine (which activates mammalian target of rapamycin to stimulate protein synthesis and inhibit proteolysis) and tryptophan (which modulates neurol. and immunol. functions through multiple metabolites, including serotonin and melatonin). A growing body of literature leads to a new concept of functional AA, which are defined as those AA that regulate key metabolic pathways to improve health, survival, growth, development, lactation, and reprodn. of organisms. Both NEAA and EAA should be considered in the classic "ideal protein" concept or formulation of balanced diets to maximize protein accretion and optimize health in animals and humans.
- 9Kubota, T.; Kobayashi, T.; Nunoura, T.; Maruyama, F.; Deguchi, S. Enantioselective Utilization of D-Amino Acids by Deep-Sea Microorganisms. Front. Microbiol. 2016, 7, 511, DOI: 10.3389/fmicb.2016.00511[Crossref], [PubMed], [CAS], Google Scholar9https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BC28bms1Ggsw%253D%253D&md5=086d671b6e098ccb0db9fd10f8a57ab9Enantioselective Utilization of D-Amino Acids by Deep-Sea MicroorganismsKubota Takaaki; Kobayashi Tohru; Nunoura Takuro; Deguchi Shigeru; Maruyama FumitoFrontiers in microbiology (2016), 7 (), 511 ISSN:1664-302X.Microorganisms that utilize various D-amino acids (DAAs) were successfully isolated from deep-sea sediments. The isolates were phylogenetically assigned to Alphaproteobacteria, Gammmaproteobacteria, and Bacilli. Some of the isolates exhibited high enantioselective degradation activities to various DAAs. In particular, the Alphaproteobacteria Nautella sp. strain A04V exhibited robust growth in minimal medium supplemented with D-Val as a sole carbon and nitrogen source, whereas its growth was poor on minimal medium supplemented with L-Val instead of D-Val. Its growth was facilitated most when racemic mixtures of valine were used. In contrast, the Nautella strains isolated from shallow-sea grew only with L-Val. No significant differences were found among the strains in the genome sequences including genes possibly related to DAA metabolisms.
- 10Lam, H.; Oh, D.-C.; Cava, F.; Takacs, C. N.; Clardy, J.; De Pedro, M. A.; Waldor, M. K. D-Amino Acids Govern Stationary Phase Cell Wall Remodeling in Bacteria. Science 80 2009, 325, 1552– 1555, DOI: 10.1126/science.1178123[Crossref], [PubMed], [CAS], Google Scholar10https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXhtFanurrE&md5=600d0c84c5b973564cced8fe2c9df734D-Amino acids govern stationary phase cell wall remodeling in bacteriaLam, Hubert; Oh, Dong-Chan; Cava, Felipe; Takacs, Constantin N.; Clardy, Jon; de Pedro, Miguel A.; Waldor, Matthew K.Science (Washington, DC, United States) (2009), 325 (5947), 1552-1555CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)In all known organisms, amino acids are predominantly thought to be synthesized and used as their L-enantiomers. Here, the authors found that bacteria produce diverse D-amino acids as well, which accumulate at millimolar concns. in supernatants of stationary phase cultures. In Vibrio cholerae, a dedicated racemase produced D-Met and D-Leu, whereas Bacillus subtilis generated D-Tyr and D-Phe. These unusual D-amino acids appear to modulate synthesis of peptidoglycan, a strong and elastic polymer that serves as the stress-bearing component of the bacterial cell wall. D-Amino acids influenced peptidoglycan compn., amt., and strength, both by means of their incorporation into the polymer and by regulating enzymes that synthesize and modify it. Thus, synthesis of D-amino acids may be a common strategy for bacteria to adapt to changing environmental conditions.
- 11Holeček, M. Histidine in Health and Disease: Metabolism, Physiological Importance, and Use as a Supplement. Nutrients 2020, 12, 848, DOI: 10.3390/nu12030848[Crossref], [PubMed], [CAS], Google Scholar11https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhvVeitrjM&md5=013dc87d4e2f2341492908bfed5c7c8fHistidine in health and disease: metabolism, physiological importance, and use as a supplementHolecek, MilanNutrients (2020), 12 (3), 848CODEN: NUTRHU; ISSN:2072-6643. (MDPI AG)A review. L-histidine (HIS) is an essential amino acid with unique roles in proton buffering, metal ion chelation, scavenging of reactive oxygen and nitrogen species, erythropoiesis, and the histaminergic system. Several HIS-rich proteins (e.g., haemoproteins, HIS-rich glycoproteins, histatins, HIS-rich calcium-binding protein, and filaggrin), HIS-contg. dipeptides (particularly carnosine), and methyland sulfur-contg. derivs. of HIS (3-methylhistidine, 1-methylhistidine, and ergothioneine) have specific functions. The unique chem. properties and physiol. functions are the basis of the theor. rationale to suggest HIS supplementation in a wide range of conditions. Several decades of experience have confirmed the effectiveness of HIS as a component of solns. used for organ preservation and myocardial protection in cardiac surgery. Further studies are needed to elucidate the effects of HIS supplementation on neurol. disorders, atopic dermatitis, metabolic syndrome, diabetes, uremic anemia, ulcers, inflammatory bowel diseases,malignancies, andmuscle performance during strenuous exercise. Signs of toxicity, mutagenic activity, and allergic reactions or peptic ulcers have not been reported, although HIS is a histamine precursor. Of concern should be findings of hepatic enlargement and increases in ammonia and glutamine and of decrease in branched-chain amino acids (valine, leucine, and isoleucine) in blood plasma indicating that HIS supplementation is inappropriate in patients with liver disease.
- 12McCall, K. A.; Huang, C.-c.; Fierke, C. A. Function and Mechanism of Zinc Metalloenzymes. Journal of Nutrition; American Institute of Nutrition, 2000; Vol. 130.
- 13Wade, A. M.; Tucker, H. N. Antioxidant Characteristics of L-Histidine. Journal of Nutritional Biochemistry; Elsevier June, 1998, 9, pp 308– 315. DOI: 10.1016/S0955-2863(98)00022-9 .
- 14Pichili, V. B. R.; Rao, K. V. R.; Jayakumar, A. R.; Norenberg, M. D. Inhibition of Glutamine Transport into Mitochondria Protects Astrocytes from Ammonia Toxicity. Glia 2007, 55, 801– 809, DOI: 10.1002/glia.20499[Crossref], [PubMed], [CAS], Google Scholar14https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BD2s3jtVWksw%253D%253D&md5=6b3ef324df010931c3e364f47c14a2d9Inhibition of glutamine transport into mitochondria protects astrocytes from ammonia toxicityPichili V B R; Rao K V Rama; Jayakumar A R; Norenberg M DGlia (2007), 55 (8), 801-9 ISSN:0894-1491.Hepatic encephalopathy (HE) is a major neurological complication that occurs in the setting of severe liver failure. Ammonia is a key neurotoxin implicated in this condition, and astrocytes are the principal neural cells histopathologically and functionally affected. Although the mechanism by which ammonia causes astrocyte dysfunction is incompletely understood, glutamine, a by-product of ammonia metabolism, has been strongly implicated in many of the deleterious effects of ammonia on astrocytes. Inhibiting mitochondrial glutamine hydrolysis in astrocytes mitigates many of the toxic effects of ammonia, suggesting the involvement of mitochondrial glutamine metabolism in the mechanism of ammonia neurotoxicity. To determine whether mitochondriaare indeed the organelle where glutamine exerts its toxic effects, we examined the effect of L-histidine, an inhibitor of mitochondrial glutamine transport, on ammonia-mediated astrocyte defects. Treatment of cultured astrocytes with L-histidine completely blocked or significantly attenuated ammonia-induced reactive oxygen species production, cell swelling, mitochondrial permeability transition, and loss of ATP. These findings implicate mitochondrial glutamine transport in the mechanism of ammonia neurotoxicity.
- 15Cho, E. S.; Anderson, H. L.; Wixom, R. L.; Hanson, K. C.; Krause, G. F. Long-Term Effects of Low Histidine Intake on Men. J. Nutr. 1984, 114, 369– 384, DOI: 10.1093/jn/114.2.369[Crossref], [PubMed], [CAS], Google Scholar15https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL2cXhtF2kur8%253D&md5=5d3a13bb26bc68f3c20881b08f26e886Long-term effects of low histidine intake on menCho, Ei Soon; Anderson, Helen L.; Wixom, Robert L.; Hanson, Kenneth C.; Krause, Gary F.Journal of Nutrition (1984), 114 (2), 369-84CODEN: JONUAI; ISSN:0022-3166.The purpose of this 85-day study was to investigate the long-term effects of histidine [71-00-1] depletion on N utilization in young adult men. A low N (6.3 g/day), low histidine (10 mg/day) amino acid diet was fed to 7 men for 8 wk. The mean N balance became neg. after 8 wk. Free histidine in postabsorptive plasma and 24-h urine decreased during the 1st 2 wks of the depletion and remained low and const. for the remaining 6 wk. Hb concn. decreased somewhat, and serum Fe concn. increased during histidine depletion. Lean body mass, urinary Nτ-methylhistidine [332-80-9] and total creatinine [60-27-5] did not change. On addn. of histidine to the low histidine diet for 2 wk, N retention became pos. plasma and urinary histidine returned to initial values, serum Fe fell, and Hb concn. slowly increased. These parameters remained unchanged in 2 control men fed the same diet supplemented with histidine (1.05 g/day) for 8 wk. Histidine may be indispensable for young men consuming a low N diet.
- 16Abe, H.; Dobson, G. P.; Hoeger, U.; Parkhouse, W. S. Role of Histidine-Related Compounds to Intracellular Buffering in Fish Skeletal Muscle. Am. J. Physiol.: Regul., Integr. Comp. Physiol. 1985, 249, R449– R454, DOI: 10.1152/ajpregu.1985.249.4.r449
- 17Hisatsune, T.; Kaneko, J.; Kurashige, H.; Cao, Y.; Satsu, H.; Totsuka, M.; Katakura, Y.; Imabayashi, E.; Matsuda, H. Effect of Anserine/Carnosine Supplementation on Verbal Episodic Memory in Elderly People. J. Alzheimer’s Dis. 2015, 50, 149– 159, DOI: 10.3233/JAD-150767
- 18Tan, S. P.; Brown, S. B.; Griffiths, C.; Weller, R.; Gibbs, N. K. Feeding Filaggrin: Effects of l-Histidine Supplementation in Atopic Dermatitis. Clin., Cosmet. Invest. Dermatol. 2017, 10, 403– 411, DOI: 10.2147/CCID.S146760[Crossref], [PubMed], [CAS], Google Scholar18https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXkt1ehtr4%253D&md5=bb4d91e221abcc5587873cadc8cbc173Feeding filaggrin: effects of l-histidine supplementation in atopic dermatitisTan, Siao Pei; Brown, Simon B.; Griffiths, Christopher EM; Weller, Richard B.; Gibbs, Neil K.Clinical, Cosmetic and Investigational Dermatology (2017), 10 (), 403-411CODEN: CCIDCL; ISSN:1178-7015. (Dove Medical Press Ltd.)Atopic dermatitis (AD), also known as eczema, is one of the most common chronic skin conditions worldwide, affecting up to 16% of children and 10% of adults. It is incurable and has significant psychosocial and economic impacts on the affected individuals. AD etiol. has been linked to deficiencies in the skin barrier protein, filaggrin. In mammalian skin, l-histidine is rapidly incorporated into filaggrin. Subsequent filaggrin proteolysis releases l-histidine as an important natural moisturizing factor (NMF). In vitro studies were conducted to investigate the influence of l-histidine on filaggrin processing and barrier function in human skin-equiv. models. Our further aim was to examine the effects of daily oral l-histidine supplementation on disease severity in adult AD patients. We conducted a randomized, double-blind, placebo-controlled, crossover, nutritional supplementation pilot study to explore the effects of oral l-histidine in adult AD patients (n = 24). In vitro studies demonstrated that l-histidine significantly increased both filaggrin formation and skin barrier function (P<0.01, resp.). Data from the clin. study indicated that once daily oral l-histidine significantly reduced (P<0.003) AD disease severity by 34% (physician assessment using the SCORingAD tool) and 39% (patient self-assessment using the Patient Oriented Eczema Measure tool) after 4 wk of treatment. No improvement was noted with the placebo (P>0.32). The clin. effect of oral l-histidine in AD was similar to that of mid-potency topical corticosteroids and combined with its safety profile suggests that it may be a safe, nonsteroidal approach suitable for long-term use in skin conditions that are assocd. with filaggrin deficits such as AD.
- 19Babizhayev, M. A.; Guiotto, A.; Kasus-Jacobi, A. N-Acetylcarnosine and Histidyl-Hydrazide Are Potent Agents for Multitargeted Ophthalmic Therapy of Senile Cataracts and Diabetic Ocular Complications. J. Drug Targeting 2009, 17, 36– 63, DOI: 10.1080/10611860802438736[Crossref], [PubMed], [CAS], Google Scholar19https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXhsFarsrvI&md5=ad309c1393f1f9ddb3b10a123bc15ff9N-Acetylcarnosine and histidyl-hydrazide are potent agents for multitargeted ophthalmic therapy of senile cataracts and diabetic ocular complicationsBabizhayev, Mark A.; Guiotto, Andrea; Kasus-Jacobi, AnneJournal of Drug Targeting (2009), 17 (1), 36-63CODEN: JDTAEH; ISSN:1061-186X. (Informa Healthcare)Aims: In human diabetes, the deleterious effects of chronic hyperglycemia are the result of excessive nonenzymic modification of proteins and phospholipids by glucose and its byproducts leading to the formation of irreversible oxidized, arom., and fluorescent ligands known as advanced glycation end products. This glycation process has been assocd. with deleterious health effects. The present invention provides the potent inhibitors of protein glycation and AGEs formation, which are particularly advantageous for eyedrop delivery in the prevention and treatment of diabetes- and age-related pathologies. Main Methods and Key findings: We proposed a deglycation system involving removal, by transglycation of sugar or aldehyde moieties from the Schiff bases by ophthalmic aldehyde scavenger l-carnosine derived from its ocular bioactivating sustained release prodrug 1% N-acetylcarnosine (NAC) lubricant eyedrops contg. a mucoadhesive cellulose compd. combined with corneal absorption promoters in drug delivery system. Carnosine analogs bearing the histidyl-hydrazide moiety were synthesized and patented in ophthalmic formulations with NAC bioactivating prodrug to moderate the enzymic hydrolysis of a dipeptide by carnosinase (inhibited by a nonhydrolyzable substrate analog so that this keeps steadier levels of the drug active principle in the aq. humor). Leucyl-histidylhydrazide peptidomimetic demonstrated the transglycation activity more pronounced than l-carnosine accounting for the ability of either mol. to reverse pre-existing, glycation-induced, crosslinking, and checking the nonenzymic glycation cascade in the ophthalmic pathologies. The ophthalmic drug N-acetylcarnosine eye drop formulation with sustained time- release and increased absorption of L-carnosine in the aq. humor (a prolonged ED) showed follow-up treatment efficacy for age-related cataracts for enrolled patients into the randomized double blind placebo controlled crossover clin. trial, and in over 50250 various cohort patients, was demonstrated to have an efficacy, safety and good tolerability for prevention and treatment of visual impairment in the older population data base. Significance: The bioactivating antioxidant NAC and histidyl-hydrazide are potent agents with the pleiotropic effects for ophthalmic therapy of senile cataracts and diabetic ocular complications.
- 20Hu, H.; Emerson, J.; Aronson, A. I. Factors Involved in the Germination and Inactivation of Bacillus Anthracis Spores in Murine Primary Macrophages. FEMS Microbiol. Lett. 2007, 272, 245– 250, DOI: 10.1111/j.1574-6968.2007.00766.x[Crossref], [PubMed], [CAS], Google Scholar20https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2sXnslyhtrs%253D&md5=affa28952f3f2923dada4c4a2a8fed0fFactors involved in the germination and inactivation of Bacillus anthracis spores in murine primary macrophagesHu, Haijing; Emerson, James; Aronson, Arthur I.FEMS Microbiology Letters (2007), 272 (2), 245-250CODEN: FMLED7; ISSN:0378-1097. (Blackwell Publishing Ltd.)Since macrophages have been implicated in inhalation anthrax either for defense and/or as enablers for spore trafficking, their function has been further defined. Spores were efficiently taken up by primary mouse bone marrow-derived macrophages even in the absence of serum but a minimal amt. was required for spore germination and subsequent inactivation. With 10% fetal bovine serum (FBS) virtually all of the spores germinated but when the concn. of FBS was lowered to 1.0% or less, or when 10% horse serum replaced FBS, only 50% of the spores were inactivated within 1 h with no subsequent loss. Chloramphenicol, which blocks spore outgrowth but not germination, did not inhibit spore killing in macrophages. Based on complete inhibition of germination by D-alanine plus D-histidine, it is likely that only two of the several Bacillus anthracis germination systems are involved within macrophages. D-Histidine inhibits the gerH system previously implicated in germination within macrophages. D-Alanine is likely to block the gerX system since disruption of the gerXA gene resulted in little germination within 4 h in macrophages. Macrophages provide a major line of defense against infection by efficiently sequestering spores and in the presence of minimal nutrients effectively killing those that germinate before outgrowth.
- 21Friedman, M.; Levin, C. E. Nutritional and Medicinal Aspects of D-Amino Acids. Amino Acids. Amino Acids 2012, 42, 1553– 1582, DOI: 10.1007/s00726-011-0915-1[Crossref], [PubMed], [CAS], Google Scholar21https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XlsFertLg%253D&md5=bdc310ce8ea5c066d88adac4f19b31f3Nutritional and medicinal aspects of D-amino acidsFriedman, Mendel; Levin, Carol E.Amino Acids (2012), 42 (5), 1553-1582CODEN: AACIE6; ISSN:0939-4451. (SpringerWienNewYork)A review. This paper reviews and interprets a method for detg. the nutritional value of D-amino acids, d-peptides, and amino acid derivs. using a growth assay in mice fed a synthetic all-amino acid diet. A large no. of expts. were carried out in which a molar equivalent of the test compd. replaced a nutritionally essential amino acid such as L-lysine (L-Lys), L-methionine (L-Met), L-phenylalanine (L-Phe), and L-tryptophan (L-Trp) as well as the semi-essential amino acids L-cysteine (L-Cys) and L-tyrosine (L-Tyr). The results show wide-ranging variations in the biol. utilization of test substances. The method is generally applicable to the detn. of the biol. utilization and safety of any amino acid deriv. as a potential nutritional source of the corresponding l-amino acid. Because the organism is forced to use the D-amino acid or amino acid deriv. as the sole source of the essential or semi-essential amino acid being replaced, and because a free amino acid diet allows better control of compn., the use of all-amino-acid diets for such detns. may be preferable to protein-based diets. Also covered are brief summaries of the widely scattered literature on dietary and pharmacol. aspects of 27 individual D-amino acids, D-peptides, and isomeric amino acid derivs. and suggested research needs in each of these areas. The described results provide a valuable record and resource for further progress on the multifaceted aspects of D-amino acids in food and biol. samples.
- 22Mason, S. F. The Development of Concepts of Chiral Discrimination. Chirality 1989, 1, 183– 191, DOI: 10.1002/chir.530010302[Crossref], [PubMed], [CAS], Google Scholar22https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK3cXmvVeg&md5=f397ef943ba1128e2895c6127e412b7eThe development of concepts of chiral discriminationMason, Stephen F.Chirality (1989), 1 (3), 183-91CODEN: CHRLEP; ISSN:0899-0042.A review with 43 refs.
- 23Jeong, Y.; Kim, H. W.; Ku, J.; Seo, J. Breakdown of Chiral Recognition of Amino Acids in Reduced Dimensions. Sci. Rep. 2020, 10, 16166, DOI: 10.1038/s41598-020-73300-z[Crossref], [PubMed], [CAS], Google Scholar23https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhvFyqsLfO&md5=e92c07dfd8ae9ee1bb9663746f204541Breakdown of chiral recognition of amino acids in reduced dimensionsJeong, Yongchan; Kim, Hyo Won; Ku, JiYeon; Seo, JungpilScientific Reports (2020), 10 (1), 16166CODEN: SRCEC3; ISSN:2045-2322. (Nature Research)The homochirality of amino acids in living organisms is one of the great mysteries in the phenomena of life. To understand the chiral recognition of amino acids, we have used scanning tunnelling microscopy to investigate the self-assembly of mols. of the amino acid tryptophan (Trp) on Au(111). Earlier expts. showed only homochiral configurations in the self-assembly of amino acids, despite using a mixt. of the two opposite enantiomers. In our study, we demonstrate that heterochiral configurations can be favored energetically when L- and D-Trp mols. are mixed to form self-assembly on the Au surface. Using d. functional theory calcns., we show that the indole side chain strongly interacts with the Au surface, which reduces the system effectively to two-dimension, with chiral recognition disabled. Our study provides important insight into the recognition of the chirality of amino acid mols. in life.
- 24Berthod, A. Chiral Recognition Mechanisms. Anal. Chem. 2006, 78, 2093– 2099, DOI: 10.1021/ac0693823[ACS Full Text
], [CAS], Google Scholar24https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BD28zns1Gqtw%253D%253D&md5=615a0b44aff34c67df159b0c260941e3Chiral recognition mechanismsBerthod AlainAnalytical chemistry (2006), 78 (7), 2093-9 ISSN:0003-2700.There is no expanded citation for this reference. - 25Randazzo, R.; Gaeta, M.; Gangemi, C.; Fragalà, M.; Purrello, R.; D’Urso, A. Chiral Recognition of L- and D- Amino Acid by Porphyrin Supramolecular Aggregates. Molecules 2018, 24, 84, DOI: 10.3390/molecules24010084
- 26Bettini, S.; Syrgiannis, Z.; Ottolini, M.; Bonfrate, V.; Giancane, G.; Valli, L.; Prato, M. Supramolecular Chiral Discrimination of D-Phenylalanine Amino Acid Based on a Perylene Bisimide Derivative. Front. Bioeng. Biotechnol. 2020, 8, 160, DOI: 10.3389/fbioe.2020.00160[Crossref], [PubMed], [CAS], Google Scholar26https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BB383lslCmtQ%253D%253D&md5=b3f418edad5065ac576335e9eca7a2c1Supramolecular Chiral Discrimination of D-Phenylalanine Amino Acid Based on a Perylene Bisimide DerivativeBettini Simona; Ottolini Michela; Bettini Simona; Giancane Gabriele; Valli Ludovico; Syrgiannis Zois; Syrgiannis Zois; Prato Maurizio; Bonfrate Valentina; Valli Ludovico; Giancane Gabriele; Prato Maurizio; Prato MaurizioFrontiers in bioengineering and biotechnology (2020), 8 (), 160 ISSN:2296-4185.The interaction between homochiral substituted perylene bisimide (PBI) molecule and the D enantiomer of phenylalanine amino acid was monitored. Spectroscopic transitions of PBI derivative in aqueous solution in the visible range were used to evaluate the presence of D-phenylalanine. UV-visible, fluorescence, FT-IR, and AFM characterizations showed that D-phenylalanine induces significant variations in the chiral perylene derivative aggregation state and the mechanism is enantioselective as a consequence of the 3D analyte structure. The interaction mechanism was further investigated in presence of interfering amino acid (D-serine and D-histidine) confirming that both chemical structure and its 3D structure play a crucial role for the amino acid discrimination. A D-phenylalanine fluorescence sensor based on perylene was proposed. A limit of detection (LOD) of 64.2 ± 0.38 nM was calculated in the range 10(-7)-10(-5) M and of 1.53 ± 0.89 μM was obtained in the range 10(-5) and 10(-3) M.
- 27Stefanelli, M.; Mandoj, F.; Magna, G.; Lettieri, R.; Venanzi, M.; Paolesse, R.; Monti, D. The Self-Aggregation of Porphyrins with Multiple Chiral Centers in Organic/Aqueous Media: The Case of Sugar- and Steroid-Porphyrin Conjugates. Molecules 2020, 25, 4544, DOI: 10.3390/molecules25194544[Crossref], [CAS], Google Scholar27https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXitVOlsLrN&md5=9540667a3285cf47c22d01bdadf88394The self-aggregation of porphyrins with multiple chiral centers in organic/aqueous media: the case of sugar- and steroid-porphyrin conjugatesStefanelli, Manuela; Mandoj, Federica; Magna, Gabriele; Lettieri, Raffaella; Venanzi, Mariano; Paolesse, Roberto; Monti, DonatoMolecules (2020), 25 (19), 4544CODEN: MOLEFW; ISSN:1420-3049. (MDPI AG)A review. An overview of the solvent-driven aggregation of a series of chiral porphyrin derivs. studied by optical methods (UV/Vis, fluorescence, CD and RLS spectroscopies) is herein reported. The investigated porphyrins are characterized by the presence in the meso-positions of glycol-, steroidal- and glucosteroidal moieties, conferring amphiphilicity and soly. in aq. media to the primarily hydrophobic porphyrin platform. Aggregation of the macrocycles is driven by a change in bulk solvent compn., forming architectures with supramol. chirality, steered by the stereogenic centers on the porphyrin peripheral positions. The aggregation behavior and chiroptical properties of the final aggregated species strongly depend on the no. and stereogenicity of the ancillary groups that dictate the mutual spatial arrangement of the porphyrin chromophores and their further organization in larger structures, usually detectable by different microscopies, such as AFM and SEM. Kinetic studies are fundamental to understand the aggregation mechanism, which is frequently found to be dependent on the substrate concn. Addnl., Mol. Mechanics calcns. can give insights into the intimate nature of the driving forces governing the self-assembly process. The crit. use of these combined methods can shed light on the overall self-assembly process of chirally-functionalized macrocycles, with important implications on the development of chiral porphyrin-based materials.
- 28Torsi, L.; Farinola, G. M.; Marinelli, F.; Tanese, M. C.; Omar, O. H.; Valli, L.; Babudri, F.; Palmisano, F.; Zambonin, P. G.; Naso, F. A Sensitivity-Enhanced Field-Effect Chiralsensor. Nat. Mater. 2008, 7, 412– 417, DOI: 10.1038/nmat2167[Crossref], [PubMed], [CAS], Google Scholar28https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXltVGktbk%253D&md5=afad3322d7b8f222ea49ff468636f2a2A sensitivity-enhanced field-effect chiral sensorTorsi, Luisa; Farinola, Gianluca M.; Marinelli, Francesco; Tanese, M. Cristina; Omar, Omar Hassan; Valli, Ludovico; Babudri, Francesco; Palmisano, Francesco; Zambonin, P. Giorgio; Naso, FrancescoNature Materials (2008), 7 (5), 412-417CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)Org. thin-film transistor sensors were recently attracting the attention of the plastic electronics community for their potential exploitation in novel sensing platforms. Specificity and sensitivity are however still open issues: in this respect chiral discrimination-being a scientific and technol. achievement in itself-is indeed one of the most challenging sensor bench-tests. So far, conducting-polymer solid-state chiral detection was carried out at part-per-thousand concn. levels. Here, a novel chiral bilayer org. thin-film transistor gas sensor-comprising an outermost layer with built-in enantioselective properties-is demonstrated to show field-effect amplified sensitivity that enables differential detection of optical isomers in the tens-of-parts-per-million concn. range. The ad-hoc-designed org. semiconductor endowed with chiral side groups, the bilayer structure and the thin-film transistor transducer provide a significant step forward in the development of a high-performance and versatile sensing platform compatible with flexible org. electronic technologies.
- 29Bhyrappa, P.; Borovkov, V. V.; Inoue, Y. Supramolecular Chirogenesis in Bis-Porphyrins: Interaction with Chiral Acids and Application for the Absolute Configuration Assignment. Org. Lett. 2007, 9, 433– 435, DOI: 10.1021/ol062776w[ACS Full Text], [CAS], Google Scholar29https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2sXhvVCnsA%253D%253D&md5=71458f6200b379a21194d5564b83cdf9Supramolecular Chirogenesis in Bis-porphyrins: Interaction with Chiral Acids and Application for the Absolute Configuration AssignmentBhyrappa, Puttaiah; Borovkov, Victor V.; Inoue, YoshihisaOrganic Letters (2007), 9 (3), 433-435CODEN: ORLEF7; ISSN:1523-7060. (American Chemical Society)A new supramol. chirogenic system on the basis of bis(free base porphyrin) and various enantiopure acids, which can be effectively applied for chirality sensing purposes, is reported. The temp. and solvent are found to be key factors controlling the chirality transfer process in these assemblies.
- 30Battersby, A. R. Tetrapyrroles: The Pigments of Life. Natural Product Reports. Nat. Prod. Rep. 2000, 17, 507– 526, DOI: 10.1039/b002635m[Crossref], [PubMed], [CAS], Google Scholar30https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3cXotFWhtrw%253D&md5=e3b5dff991443310ca31d6dffe93815bTetrapyrroles: the pigments of lifeBattersby, Alan R.Natural Product Reports (2000), 17 (6), 507-526CODEN: NPRRDF; ISSN:0265-0568. (Royal Society of Chemistry)Review with 106 refs. on the title compds. is presented.
- 31Giancane, G.; Borovkov, V.; Inoue, Y.; Conoci, S.; Valli, L. Syn-Anti Conformation Switching of a Bis-Porphyrin Derivative at the Air-Water Interface and in the Solid State as an Effective Tool for Chemical Sensing. Soft Matter 2013, 9, 2302– 2307, DOI: 10.1039/c2sm27141a[Crossref], [CAS], Google Scholar31https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhsVCmsL4%253D&md5=fa54e83413ef027a096702afe5fac9c7Syn-anti conformation switching of a bis-porphyrin derivative at the air-water interface and in the solid state as an effective tool for chemical sensingGiancane, Gabriele; Borovkov, Victor; Inoue, Yoshihisa; Conoci, Sabrina; Valli, LudovicoSoft Matter (2013), 9 (7), 2302-2307CODEN: SMOABF; ISSN:1744-683X. (Royal Society of Chemistry)A Langmuir film of bis(zinc octaethylporphyrin) (ZnPP) was characterized at the air-water interface and its syn-anti conformation switching induced upon addn. of arom. amines was studied by IR and UV-visible reflection spectroscopic methods. The highly specific interaction of ZnPP with arom. amines was maintained even after the floating film was transferred onto solid supports by the Langmuir-Schaefer (LS) technique, enabling the authors to selectively sense arom. amines at concns. ≥20 ppb. Also, LS ZnPP active layer selectivity was evaluated in the presence of aliph. amines.
- 32Grover, N.; Locke, G. M.; Flanagan, K. J.; Beh, M. H. R.; Thompson, A.; Senge, M. O. Bridging and Conformational Control of Porphyrin Units through Non-Traditional Rigid Scaffolds. Chem.─Eur. J. 2020, 26, 2405– 2416, DOI: 10.1002/chem.201904199[Crossref], [PubMed], [CAS], Google Scholar32https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXht1Gqs78%253D&md5=99a03c22b01ea27d660f53c41f891581Bridging and Conformational Control of Porphyrin Units through Non-Traditional Rigid ScaffoldsGrover, Nitika; Locke, Gemma M.; Flanagan, Keith J.; Beh, Michael H. R.; Thompson, Alison; Senge, Mathias O.Chemistry - A European Journal (2020), 26 (11), 2405-2416CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)Connecting two porphyrin units in a rigid linear fashion, without any undesired electron delocalization or communication between the chromophores, remains a synthetic challenge. Herein, a broad library of functionally diverse multi-porphyrin arrays that incorporate the non-traditional rigid linker groups cubane and bicyclo[1.1.1]pentane (BCP) is described. A robust, reliable, and versatile synthetic procedure was employed to access porphyrin-cubane/BCP-porphyrin arrays, representing the largest non-polymeric structures available for cubane/BCP derivs. These reactions demonstrate considerable substrate scope, from utilization of small Ph moieties to large porphyrin rings, with varying lengths and different angles. To control conformational flexibility, amide bonds were introduced between the bridgehead carbon of BCP/cubane and the porphyrin rings. Through varying the orientation of the substituents around the amide bond of cubane/BCP, different intermol. interactions were identified through single crystal X-ray anal. These studies revealed non-covalent interactions that are the first-of-their-kind including a unique iodine-oxygen interaction between cubane units. These supramol. architectures indicate the possibility to mimic a protein structure due to the sp3 rigid scaffolds (BCP or cubane) that exhibit the essential conformational space for protein function while simultaneously providing amide bonds for mol. recognition.
- 33Buccolieri, A.; Bettini, S.; Salvatore, L.; Baldassarre, F.; Ciccarella, G.; Giancane, G. Sub-Nanomolar Detection of Biogenic Amines by SERS Effect Induced by Hairy Janus Silver Nanoparticles. Sens. Actuators, B 2018, 267, 265– 271, DOI: 10.1016/j.snb.2018.04.028[Crossref], [CAS], Google Scholar33https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXns1eqtLc%253D&md5=05441031b0fdf2389558e6c6fe1ea779Sub-nanomolar detection of biogenic amines by SERS effect induced by hairy Janus silver nanoparticlesBuccolieri, A.; Bettini, S.; Salvatore, L.; Baldassarre, F.; Ciccarella, G.; Giancane, G.Sensors and Actuators, B: Chemical (2018), 267 (), 265-271CODEN: SABCEB; ISSN:0925-4005. (Elsevier B.V.)Surface enhanced Raman scattering (SERS) is largely used as a transduction method for analytes detection in liq. and vapor phase. In particular, SERS effect was promoted by a plethora of different metal and semiconducting nanoparticles (NPs) and silver and gold nanoparticles appear particularly suitable for this application. Nevertheless, silver nanoparticles intrinsic propensity to aggregate in large clusters reduces the possibility to use naked nanoparticles in SERS applications, for this reason they are usually functionalized with org. mols. This approach inhibits the aggregation process but, on the other hand, reduces the surficial area of the NPs able to interact with the analyte mols. In the present work, we propose a simple method to obtain surficial anisotropic Janus silver nanoparticles: octadecylamine was used to stabilize the nanoparticles and to promote the deposition of the silver nanoparticles on a solid substrate. The AgNPs/octadecylamine nanostructures showed the typical "hairy" Janus morphol. and a strong SERS effect was obsd. when two biogenic amines, i. e. 2-phenylethylamine and tyramine, were fluxed on the solid film. SERS phenomenon was studied as a function both of the chem. structure of the fluxed amine and of the distance between the arom. moiety and the nanoparticle allowing to propose the AgNPs/octadecylamine Janus nanoparticles as an active layer for the detection of phenylethylamine and tyramine in picomolar concn.
- 34Hoenig, D.; Moebius, D. Direct Visualization of Monolayers at the Air-Water Interface by Brewster Angle Microscopy. J. Phys. Chem. 1991, 95, 4590– 4592, DOI: 10.1021/j100165a003[ACS Full Text], [CAS], Google Scholar34https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK3MXktFKjs7s%253D&md5=86998e589d88b0e87a81e1aa0eaecc51Direct visualization of monolayers at the air-water interface by Brewster angle microscopyHoenig, Dirk; Moebius, DietmarJournal of Physical Chemistry (1991), 95 (12), 4590-2CODEN: JPCHAX; ISSN:0022-3654.No light is reflected from the air-water interface under Brewster angle incidence if p-polarized light is used. With const. angle of incidence, the formation of a monolayer on the water surface modifies the Brewster angle condition, and light reflection is obsd. Reflectivity-area isotherms of arachidic acid monolayers on pure water and on aq. solns. of different pH have been measured. Areas of different brightness due to different mol. d. and/or refractive index in the monolayer were recorded with a video system as microg. pictures. This Brewster angle microscopy can also detect monolayer inhomogeneities and reversible formation of solid-phase domains upon compression of monolayers of DMPE.
- 35Bettini, S.; Valli, L.; Santino, A.; Martinelli, C.; Farinola, G. M.; Cardone, A.; Sgobba, V.; Giancane, G. Spectroscopic Investigations, Characterization and Chemical Sensor Application of Composite Langmuir-Schäfer Films of Anthocyanins and Oligophenylenevinylene Derivatives. Dyes Pigm. 2012, 94, 156, DOI: 10.1016/j.dyepig.2011.12.010[Crossref], [CAS], Google Scholar35https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XhslChu7o%253D&md5=d0a3b09b7da18904b919ac04abc8f243Spectroscopic investigations, characterization and chemical sensor application of composite Langmuir-Schaefer films of anthocyanins and oligophenylenevinylene derivativesBettini, S.; Valli, L.; Santino, A.; Martinelli, C.; Farinola, G. M.; Cardone, A.; Sgobba, V.; Giancane, G.Dyes and Pigments (2012), 94 (1), 156-162CODEN: DYPIDX; ISSN:0143-7208. (Elsevier Ltd.)Anthocyanins, extd. from grape skin (Vitis vinifera), were dissolved in ultrapure aq. subphase and an oligophenylenevinylene deriv. was spread on the subphase surface. Such oligomer was chosen as anionic counterpart of hydrosol. anthocyanins in order to perform a Langmuir-Schaefer film of the dyad. Interface interactions between oligophenylenevinylene deriv. and anthocyanins were studied by Brewster angle microscopy and reflection spectroscopy. Addnl., the oligomer exhibits a chem. structure able to ensure an enhancement of the stability under UV-visible irradiations of the film of the dyad without any variation of the natural pigment absorption in the visible range. The visible spectra of cast anthocyanins film and Langmuir-Schaefer oligomer/anthocyanins film after exposure to 254 nm irradn. showed a remarkable increase of the film stability, probably due to the screening effect of the oligomer. Preliminary test of a Langmuir-Schaefer film of oligophenylenevinylene deriv./anthocyanins as a herbicide sensor showed that sensing is completely reversible, stable and repeatable.
- 36Bettini, S.; Pagano, R.; Bonfrate, V.; Maglie, E.; Manno, D.; Serra, A.; Valli, L.; Giancane, G. Promising Piezoelectric Properties of New ZnO@Octadecylamine Adduct. J. Phys. Chem. C 2015, 119, 20143– 20149, DOI: 10.1021/acs.jpcc.5b06013[ACS Full Text], [CAS], Google Scholar36https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXht12ksLjN&md5=61d3c63b1773ab1e36565d151394e2ecPromising Piezoelectric Properties of New ZnO@Octadecylamine AdductBettini, Simona; Pagano, Rosanna; Bonfrate, Valentina; Maglie, Emanuela; Manno, Daniela; Serra, Antonio; Valli, Ludovico; Giancane, GabrieleJournal of Physical Chemistry C (2015), 119 (34), 20143-20149CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)A supramol. adduct formed by the interaction among octadecylamine (ODA) and zinc oxide nanostructures was promoted. A stable dispersion of the ZnO@ODA adduct was obtained and characterized by TGA and IR and Raman spectroscopy. Then, the supramol. adduct was spread at the air/water interface of a Langmuir trough. The presence of octadecylamine gave amphiphilic features to the ZnO@ODA adduct that was transferred from the air/water interface to solid substrates by Langmuir-Schaefer (LS) method. The transferred film was characterized by tunnel electron microscopy that highlighted rectangular well-shaped structures assembled by nanostructure of ZnO arranged in an ODA matrix. Piezoelec. feature of large LS film (1 cm2) was tested and a very promising response was obsd. as a consequence of the application of a pressure of 1 kPa.
- 37Ariga, K. Don’t Forget Langmuir-Blodgett Films 2020: Interfacial Nanoarchitectonics with Molecules, Materials, and Living Objects. Langmuir 2020, 36, 7158– 7180, American Chemical Society July DOI: 10.1021/acs.langmuir.0c01044[ACS Full Text], [CAS], Google Scholar37https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhtV2ks7nN&md5=00dc60be618f9358edc8a70e8f939da4Don't Forget Langmuir-Blodgett Films 2020: Interfacial Nanoarchitectonics with Molecules, Materials, and Living ObjectsAriga, KatsuhikoLangmuir (2020), 36 (26), 7158-7180CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)A review. Designing interfacial structures with nanoscale (or mol.) components is one of the important tasks in the nanoarchitectonics concept. In particular, the Langmuir-Blodgett (LB) method can become a promising and powerful strategy in interfacial nanoarchitectonics. From this viewpoint, the status of LB films in 2020 will be discussed in this feature article. After one section on the basics of interfacial nanoarchitectonics with the LB technique, various recent research examples of LB films are introduced according to classifications of (i) growing research, (ii) emerging research, and (iii) future research. In recent LB research, various materials other than traditional lipids and typical amphiphiles can be used as film components of the LB techniques. Two-dimensional materials, supramol. structures such as metal org. frameworks, and biomaterials such as DNA origami pieces are capable of working as functional components in the LB assemblies. Possible working areas of the LB methods would cover emerging demands, including energy, environmental, and biomedical applications with a wide range of functional materials. In addn., forefront research such as mol. manipulation and cell fate control is conducted in LB-related interfacial science. The LB technique is a traditional and well-develop methodol. for mol. films with a ca. 100 yr history. However, there is plenty of room at the interfaces, as shown in LB research examples described in this feature article. It is hoped that the continuous development of the science and technol. of the LB method make this technique an unforgettable methodol.
- 38Buccolieri, A.; Hasan, M.; Bettini, S.; Bonfrate, V.; Salvatore, L.; Santino, A.; Borovkov, V.; Giancane, G. Ethane-Bridged Bisporphyrin Conformational Changes As an Effective Analytical Tool for Nonenzymatic Detection of Urea in the Physiological Range. Anal. Chem. 2018, 90, 6952– 6958, DOI: 10.1021/acs.analchem.8b01230[ACS Full Text], [CAS], Google Scholar38https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXptVeqtL4%253D&md5=eb1275537f1bbbbaf18c365bc71bf7faEthane-Bridged Bisporphyrin Conformational Changes As an Effective Analytical Tool for Nonenzymatic Detection of Urea in the Physiological RangeBuccolieri, Alessandro; Hasan, Mohammed; Bettini, Simona; Bonfrate, Valentina; Salvatore, Luca; Santino, Angelo; Borovkov, Victor; Giancane, GabrieleAnalytical Chemistry (Washington, DC, United States) (2018), 90 (11), 6952-6958CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)Conformational switching induced in ethane-bridged bisporphyrins was used as a sensitive transduction method for revealing the presence of urea dissolved in water via nonenzymic approach. Bisporphyrins were deposited on solid quartz slides by means of the spin-coating method. Mol. conformations of Zn and Ni monometalated bis-porphyrins were influenced by water solvated urea mols. and their fluorescence emission was modulated by the urea concn. Absorption, fluorescence and Raman spectroscopies allowed the identification of supramol. processes, which are responsible for host-guest interaction between the active layers and urea mols. A high selectivity of the sensing mechanism was highlighted upon testing the spectroscopic responses of bis-porphyrin films to citrulline and glutamine used as interfering agents. Addnl., potential applicability was demonstrated by quantifying the urea concn. in real physiol. samples proposing this new approach as a valuable alternative anal. procedure to the traditionally used enzymic methods.
- 39Capistran, B. A.; Blanchard, G. J. Effects of Cu(II) on the Formation and Orientation of an Arachidic Acid Langmuir-Blodgett Film. Langmuir 2019, 35, 3346– 3353, DOI: 10.1021/acs.langmuir.9b00022[ACS Full Text], [CAS], Google Scholar39https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXivVOnsb4%253D&md5=c38c32e5a9c4b5d3b68f8d05e9dc757fEffects of Cu(II) on the Formation and Orientation of an Arachidic Acid Langmuir-Blodgett FilmCapistran, Briana A.; Blanchard, G. J.Langmuir (2019), 35 (9), 3346-3353CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)The influence of the copper (II) ion on the formation, morphol., and organization of an arachidic acid monolayer was investigated using Langmuir-Blodgett (LB) monolayers, π-A isotherms and Brewster angle microscopy (BAM). Our findings indicate that a Cu2+-complexed LB film exhibits order that depends on the subphase pH, analogous to other metal ions. The metal ion facilitates formation of solid-phase films at surface pressures as low at 5 mN/m. The films exhibit a rigid, ordered phase, evidenced by the absence of a collapse point and an increase in surface pressure rather than the typical sharp decrease in surface pressure indicative of film failure. The role of amphiphile ionic charge vs. pH (i.e., the extent of arachidic acid protonation) plays a role in the obsd. absence of collapse and the ability of the films to maintain order and cohesion at high surface pressures (ca. 65 mN/m). Addnl., film thickness data suggest that the incorporation of Cu2+ ions induces a change in orientation of the aliph. chains of the amphiphiles, and that amphiphile soly. in the subphase may play a role in the obsd. film behavior at low surface areas and high pH.
- 40Nurhayati; Suendo, V.; Alni, A.; Nugroho, A. A.; Majima, Y.; Lee, S.; Nugraha, Y. P.; Uekusa, H. Revealing the Real Size of a Porphyrin Molecule with Quantum Confinement Probing via Temperature-Dependent Photoluminescence Spectroscopy. J. Phys. Chem. A 2020, 124, 2672– 2682, DOI: 10.1021/acs.jpca.0c00665[ACS Full Text], [CAS], Google Scholar40https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXkslWrtb8%253D&md5=e65eef8b4a3a69840f5878c4a0dafd7aRevealing the Real Size of a Porphyrin Molecule with Quantum Confinement Probing via Temperature-Dependent Photoluminescence SpectroscopyNurhayati; Suendo, Veinardi; Alni, Anita; Nugroho, Agustinus A.; Majima, Yutaka; Lee, Seungjoo; Nugraha, Yuda Prasetya; Uekusa, HidehiroJournal of Physical Chemistry A (2020), 124 (13), 2672-2682CODEN: JPCAFH; ISSN:1089-5639. (American Chemical Society)The confinement energy of electrons in an arom. mol. was studied by indirect and direct methods, namely, temp.-dependent photoluminescence (TDPL) spectroscopy and scanning tunneling microscopy (STM). We obsd. a decrease in the tetraphenylporphyrin (H2TPP) PL intensity with increasing temp. The increase in temp. provides kinetic energy for the electrons to overcome the confinement energy barrier, making recombination via nonradiative pathways more favorable. The results of fitting the integrated TDPL intensity with a modified Arrhenius equation suggest two confinement energy values. We propose that these energy values are related to the size of the delocalized electron cloud along the plane and thickness of the H2TPP ring. These values quant. express an abstr. form of the size of the arom. ring system. These results are in good agreement with the topog. images of single H2TPP mols. and monolayer H2TPP obtained by a direct probing method using STM. These results are also supported by the porphyrin ring orientation relative to the excited crystal face during the TDPL measurements.
- 41Bass, M. Handbook of Optics; McGraw-Hill Education, 2010.Google ScholarThere is no corresponding record for this reference.
- 42Colombelli, A.; Manera, M. G.; Borovkov, V.; Giancane, G.; Valli, L.; Rella, R. Enhanced Sensing Properties of Cobalt Bis-Porphyrin Derivative Thin Films by a Magneto-Plasmonic-Opto-Chemical Sensor. Sens. Actuators, B 2017, 246, 1039– 1048, DOI: 10.1016/j.snb.2017.01.192[Crossref], [CAS], Google Scholar42https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXjvFamsr8%253D&md5=659005cca1d7ca5589b9c963f37ef52bEnhanced sensing properties of cobalt bis-porphyrin derivative thin films by a magneto-plasmonic-opto-chemical sensorColombelli, A.; Manera, M. G.; Borovkov, V.; Giancane, G.; Valli, L.; Rella, R.Sensors and Actuators, B: Chemical (2017), 246 (), 1039-1048CODEN: SABCEB; ISSN:0925-4005. (Elsevier B.V.)This work reports on the spectroscopic properties and gas sensing performances of cobalt bis-porphyrin deriv. ((Co-H)Por2) in a thin films form obtained by Langmuir-Schafer (LS) method towards Volatile Org. Compds. (VOCs) and an oxidizing gas in a Magneto-Optical Surface Plasmon Resonance (MO-SPR) configuration. In particular the optical and spectroscopic properties of (Co-H)Por2 multilayers deposited onto proper Au/Co/Au magneto-plasmonic (MP) transducers were inspected in dry air conditions and after exposure to different analyte gas concns. The mol. organization of these thin films deposited by Langmuir-Schafer technique has been investigated and a comparison between the MOSPR exptl. data and simulation has been also reported. In order to validate our exptl. results and obtain further insight into the phys. mechanism of interaction between the organometallic mols. and magneto plasmonic nanostructured systems, numerical simulations based on Finite Element Method (FEM) techniques, have been performed. The optical and magneto-optical properties of these hybrid systems have been theor. analyzed to confirm the exptl. outcomes. Finally, a peculiar sensitivity of the MOSPR sensing probe in respect to investigated analytes has been recorded.
- 43Bettini, S.; Pagano, R.; Borovkov, V.; Giancane, G.; Valli, L. The Role of the Central Metal Ion of Ethane-Bridged Bis-Porphyrins in Histidine Sensing. J. Colloid Interface Sci. 2019, 533, 762– 770, DOI: 10.1016/j.jcis.2018.08.116[Crossref], [PubMed], [CAS], Google Scholar43https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhs1Oltb7I&md5=f5cf6f81320465b4002eda27d597ae7dThe role of the central metal ion of ethane-bridged bis-porphyrins in histidine sensingBettini, Simona; Pagano, Rosanna; Borovkov, Victor; Giancane, Gabriele; Valli, LudovicoJournal of Colloid and Interface Science (2019), 533 (), 762-770CODEN: JCISA5; ISSN:0021-9797. (Elsevier B.V.)Ethane-bridged bis-porphyrin derivs. are reported for the selective detection of various analytes in sensing applications. The central metal ion is able to rule specific mol. arrangements upon analyte binding. Three bis-porphyrin compds.: a free base (metal free), Ni complex, and Cu complex, have been tested for histidine detection in aq. media. Histidine is involved in various biol. processes, including such deadly disease as lung cancer. The conformational changes of bis-porphyrins, induced by histidine binding, can be detected by monitoring the Soret band position. The spectroscopic characterization, at the air-water subphase interface, indicates that, in the presence of histidine, the Ni and Cu metalated derivs. undergo conformational changes. This behavior was confirmed when these two derivs. were deposited onto the solid support by Langmuir-Schaefer (LS) technique. A prototypal Surface Plasmon Resonance (SPR) detection system for histidine based on these two porphyrin LS films was developed. The Cu substituted compd. based SPR system allows the histidine sensing down to nanomolar concn. Furthermore, a SPR response of the Ni bis-porphyrin shows a semilogarithmic dependence on the histidine concn. up to 10-6 M proposing the use of these two porphyrins in a sensor array for the monitoring of histidine levels in plasma.
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- Gabriele Giancane, Rosanna Pagano, Mario Luigi Naitana, Gabriele Magna, Manuela Stefanelli, Donato Monti, Roberto Paolesse, Simona Bettini, Ludovico Valli. Proline Enantiomers Discrimination by (L)-Prolinated Porphyrin Derivative Langmuir–Schaefer Films: Proof of Concept for Chiral Sensing Applications. Chemosensors 2022, 10 (8) , 331. https://doi.org/10.3390/chemosensors10080331
Abstract
Figure 1
Figure 1. Chemical structure of the cubane-bridged bisporphyrin (H2por-cubane-H2por) and schematic representation of the possible configurations adopted by the H2por-cubane-H2por. (A) Syn-form, (B) tweezer configuration, and (C) anti-form.
Figure 2
Figure 2. (A) Comparison of the three isotherm curves’ surface pressure vs area per molecule recorded for a H2por-cubane-H2por Langmuir floating film on ultrapure water subphase (blue line), aqueous subphase containing l-histidine (10–4 M) (red line), and aqueous subphase containing d-histidine (10–4 M) (black line). (B) Reflection spectra of H2por-cubane-H2por floating film on ultrapure water subphase (blue line), aqueous subphase containing l-histidine (10–4 M) (red line), and aqueous subphase containing d-histidine (10–4 M) (black line). All the spectra were acquired at a surface pressure of 20 mN m–1.
Figure 3
Figure 3. Brewster Angle Microscopy carried out on H2por-cubane-H2por floating films spread on ultrapure water subphase (top line), on subphase containing l-histidine (10–4 M) (middle row) and, in lower line, on subphase containing d-histidine (10–4 M).
Figure 4
Figure 4. Visible spectra of LS films (4 runs) of H2por-cubane-H2por transferred from ultrapure water (blue line), aqueous subphase containing l-histidine (10–4 M) (red line), and aqueous subphase containing d-histidine (10–4 M) (black line).
Figure 5
Figure 5. Ellipsometer measurements performed using left-handed circularly polarized light (in blue in all the images) and right-handed circularly polarized light (black lines). Four samples were investigated: (A) 4 runs of LS film transferred from ultrapure water subphase; (B) 4 runs of LS film transferred from water subphase containing l-histidine (10–4 M); (C) 4 runs of LS film transferred from water subphase containing d-histidine (10–4 M); and (D) 4 runs of LS film transferred from water subphase containing racemic solution of D and l-histidine (10–4 M).
Figure 6
Figure 6. Schematic representation of the plausible interaction mechanisms that govern the configuration changes of H2Por-cubane-H2Por at the air/subphase interface (panel a) in the presence of d-histidine (panel b,c) and l-histidine (panel d). The behavior of each bisporphyrin conformer was considered depending on the analyte dissolved in the subphase.
References
ARTICLE SECTIONSThis article references 43 other publications.
- 1Hembury, G. A.; Borovkov, V. V.; Inoue, Y. Chirality-Sensing Supramolecular Systems. Chemical Reviews; American Chemical Society January, 2008, 108, pp 1– 73. DOI: 10.1021/cr050005k .
- 2Kim, J. H.; Scialli, A. R. Thalidomide: The Tragedy of Birth Defects and the Effective Treatment of Disease. Toxicol. Sci. 2011, 122, 1– 6, DOI: 10.1093/toxsci/kfr088[Crossref], [PubMed], [CAS], Google Scholar2https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXpslSjs7Y%253D&md5=232e9769ad27e497c979bc8134d209d1Thalidomide: The Tragedy of Birth Defects and the Effective Treatment of DiseaseKim, James H.; Scialli, Anthony R.Toxicological Sciences (2011), 122 (1), 1-6CODEN: TOSCF2; ISSN:1096-0929. (Oxford University Press)A review. Thalidomide was a widely used drug in the late 1950s and early 1960s for the treatment of nausea in pregnant women. It became apparent in the 1960s that thalidomide treatment resulted in severe birth defects in thousands of children. Though the use of thalidomide was banned in most countries at that time, thalidomide proved to be a useful treatment for leprosy and later, multiple myeloma. In rural areas of the world that lack extensive medical surveillance initiatives, thalidomide treatment of pregnant women with leprosy has continued to cause malformations. Research on thalidomide mechanisms of action is leading to a better understanding of mol. targets. With an improved understanding of these mol. targets, safer drugs may be designed. The thalidomide tragedy marked a turning point in toxicity testing, as it prompted United States and international regulatory agencies to develop systematic toxicity testing protocols; the use of thalidomide as a tool in developmental biol. led to important discoveries in the biochem. pathways of limb development. In celebration of the Society of Toxicol.'s 50th Anniversary, which coincides with the 50th anniversary of the withdrawal of thalidomide from the market, it is appropriate to revisit the lessons learned from the thalidomide tragedy of the 1960s.
- 3Tokunaga, E.; Yamamoto, T.; Ito, E.; Shibata, N. Understanding the Thalidomide Chirality in Biological Processes by the Self-Disproportionation of Enantiomers. Sci. Rep. 2018, 8, 1– 7, DOI: 10.1038/s41598-018-35457-6[Crossref], [PubMed], [CAS], Google Scholar3https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXls1Cksrc%253D&md5=d56a5255f9df7de2219a761238b2c275Genome-wide association study of self-reported food reactions in Japanese identifies shrimp and peach specific loci in the HLA-DR/DQ gene regionKhor, Seik-Soon; Morino, Ryoko; Nakazono, Kazuyuki; Kamitsuji, Shigeo; Akita, Masanori; Kawajiri, Maiko; Yamasaki, Tatsuya; Kami, Azusa; Hoshi, Yuria; Tada, Asami; Ishikawa, Kenichi; Hine, Maaya; Kobayashi, Miki; Kurume, Nami; Kamatani, Naoyuki; Tokunaga, Katsushi; Johnson, Todd A.Scientific Reports (2018), 8 (1), 1-17CODEN: SRCEC3; ISSN:2045-2322. (Nature Research)Food allergy is an increasingly important health problem in the world. Several genome-wide assocn. studies (GWAS) focused on European ancestry samples have identified food allergy-specific loci in the HLA class II region. We conducted GWAS of self-reported reactivity with common foods using the data from 11011 Japanese women and identified shrimp and peach allergy-specific loci in the HLA-DR/DQ gene region tagged by rs74995702 (P = 6.30 × 10-17, OR = 1.91) and rs28359884 (P = 2.3 × 10-12, OR = 1.80), resp. After HLA imputation using a Japanese population-specific ref., the most strongly assocd. haplotype was HLA-DRB1*04:05-HLA-DQB1*04:01 for shrimp allergy (P = 3.92 × 10-19, OR = 1.99) and HLA-DRB1*09:01-HLA-DQB1*03:03 for peach allergy (P = 1.15 × 10-7, OR = 1.68). Addnl., both allergies' assocd. variants were eQTLs for several HLA genes, with HLA-DQA2 the single eQTL gene shared between the two traits. Our study suggests that allergy to certain foods may be related to genetic differences that tag both HLA alleles having particular epitope binding specificities as well as variants modulating expression of particular HLA genes. Investigating this further could increase our understanding of food allergy etiol. and potentially lead to better therapeutic strategies for allergen immunotherapies.
- 4Leung, D.; Kang, S. O.; Anslyn, E. V. Rapid Determination of Enantiomeric Excess: A Focus on Optical Approaches. Chem. Soc. Rev. 2012, 41, 448– 479, DOI: 10.1039/c1cs15135e[Crossref], [PubMed], [CAS], Google Scholar4https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXhsFKntrbF&md5=2df381154b10f72348dd423c045b6b17Rapid determination of enantiomeric excess: a focus on optical approachesLeung, Diana; Kang, Sung Ok; Anslyn, Eric V.Chemical Society Reviews (2012), 41 (1), 448-479CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)A review. High-throughput screening (HTS) methods are becoming increasingly essential in discovering chiral catalysts or auxiliaries for asym. transformations due to the advent of parallel synthesis and combinatorial chem. Both parallel synthesis and combinatorial chem. can lead to the exploration of a range of structural candidates and reaction conditions as a means to obtain the highest enantiomeric excess (ee) of a desired transformation. One current bottleneck in these approaches to asym. reactions is the detn. of ee, which led researchers to explore a wide range of HTS techniques. To be truly high-throughput, probably a technique that can analyze a thousand or more samples per day is needed. Many of the current approaches to this goal are based on optical methods because they allow for a rapid detn. of ee due to quick data collection and their parallel anal. capabilities. In this crit. review these techniques are reviewed with a discussion of their resp. advantages and drawbacks, and with a contrast to chromatog. methods (180 refs.).
- 5Gordon, A. H.; Martin, A. J. P.; Synge, R. L. M. Partition Chromatography in the Study of Protein Constituents. Biochem. J. 1943, 37, 79– 86, DOI: 10.1042/bj0370079[Crossref], [PubMed], [CAS], Google Scholar5https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaH2cXisFWgtg%253D%253D&md5=737913509d70b1b3326bd0ff6f01ec18Partition chromatography in the study of protein constituentsGordon, A. H.; Martin, A. J. P.; Synge, R. L. M.Biochemical Journal (1943), 37 (), 79-86CODEN: BIJOAK; ISSN:0264-6021.Correction. New compds. and compds. for which new data are given, referred to in C. A. 37, 5436.6, are: acetyl-l-valine, prepd. by resoln. of acetyl-dl-valine, m. 164°, [α]19D 4° (EtOH, c = 2); acetyl-dl-norvaline, m. 111.0-12.5° (may contain some isomer as impurity); N,N'-diacetyl-dl-lysine, m. 140-1°; acetyl-l-aspartic acid, sirup; acetyl-l-tryptophan, m. 185-6°, [α]21.5D 27.6° (H2O contg. 1 equiv. NaOH, c = 1), [α]19D 26.0° (EtOH, c = 1.1); acetylglycyl-dl-leucine, m. 176-7°; acetyl-dl-leucylglycine, dried over P2O5 in vacuo to remove Me2CO, m. 178°; acetyl-dl-leucyl-dl-leucine, m. 200°; acetylglycylglycine, m. 178-9°.
- 6Chela-Flores, J. The Origin of Chirality in Protein Amino Acids. Chirality 1994, 6, 165– 168, DOI: 10.1002/chir.530060302[Crossref], [CAS], Google Scholar6https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2cXksFOqsLo%253D&md5=4538008ecc2847014a171d7bbd094fd1The origin of chirality in protein amino acidsChela-Flores, JulianChirality (1994), 6 (3), 165-8CODEN: CHRLEP; ISSN:0899-0042.The origin of the chirality of protein amino acids is discussed from the point of view of a phase transition from a racemic mixt. into an optically pure state. It is assumed that Bose-Einstein condensation act as an amplification mechanism. The original theory is due to A. Salam (1991, 1992). A new role for the phase transition is suggested. Following M. Quack (1993), parity violations of two kinds (de facto and de lege symmetry breaking) are distinguished. While the Salam phase transition corresponds to parity violation of the second kind (de lege), the phase transition discussed in this work corresponds to parity violation of what may be called a third kind. This is suggested by recent exptl. phenomena which correlate chiral symmetry breaking and pattern formation (spontaneous symmetry breaking that separates an initial racemic mixt. into right- and left-handed space domains by means of a substrate). Tentative comments are given on the eventual design of possible expts. that may test this new hypothesis.
- 7Dalangin, R.; Kim, A.; Campbell, R. E. The Role of Amino Acids in Neurotransmission and Fluorescent Tools for Their Detection. Int. J. Mol. Sci. 2020, 21, 6197, DOI: 10.3390/ijms21176197[Crossref], [PubMed], [CAS], Google Scholar7https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXitVKqtbzO&md5=f3ddf494c65a37d051c70cf382e6dcb2The role of amino acids in neurotransmission and fluorescent tools for their detectionDalangin, Rochelin; Kim, Anna; Campbell, Robert E.International Journal of Molecular Sciences (2020), 21 (17), 6197CODEN: IJMCFK; ISSN:1422-0067. (MDPI AG)A review. Neurotransmission between neurons, which can occur over the span of a few milliseconds, relies on the controlled release of small mol. neurotransmitters, many of which are amino acids. Fluorescence imaging provides the necessary speed to follow these events and has emerged as a powerful technique for investigating neurotransmission. In this review, we highlight some of the roles of the 20 canonical amino acids, GABA and β-alanine in neurotransmission. We also discuss available fluorescence-based probes for amino acids that have been shown to be compatible for live cell imaging, namely those based on synthetic dyes, nanostructures (quantum dots and nanotubes), and genetically encoded components. We aim to provide tool developers with information that may guide future engineering efforts and tool users with information regarding existing indicators to facilitate studies of amino acid dynamics.
- 8Wu, G. Functional Amino Acids in Growth, Reproduction, and Health. Adv. Nutr. 2010, 1, 31– 37, DOI: 10.3945/an.110.1008[Crossref], [PubMed], [CAS], Google Scholar8https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXpsF2lur8%253D&md5=9c7209ab9f41539f6e2b6b16586dca81Functional amino acids in growth, reproduction, and healthWu, GuoyaoAdvances in Nutrition (2010), 1 (1), 31-37CODEN: ANDUAW; ISSN:2156-5376. (American Society for Nutrition)A review. Amino acids (AA) were traditionally classified as nutritionally essential or nonessential for animals and humans based on nitrogen balance or growth. A key element of this classification is that all nonessential AA (NEAA) were assumed to be synthesized adequately in the body as substrates to meet the needs for protein synthesis. Unfortunately, regulatory roles for AA in nutrition and metab. have long been ignored. Such conceptual limitations were not recognized until recent seminal findings that dietary glutamine is necessary for intestinal mucosal integrity and dietary arginine is required for max. neonatal growth and embryonic survival. Some of the traditionally classified NEAA (e.g. glutamine, glutamate, and arginine) play important roles in regulating gene expression, cell signaling, antioxidative responses, and immunity. Addnl., glutamate, glutamine, and aspartate are major metabolic fuels for the small intestine and they, along with glycine, regulate neurol. function. Among essential AA (EAA), much emphasis has been placed on leucine (which activates mammalian target of rapamycin to stimulate protein synthesis and inhibit proteolysis) and tryptophan (which modulates neurol. and immunol. functions through multiple metabolites, including serotonin and melatonin). A growing body of literature leads to a new concept of functional AA, which are defined as those AA that regulate key metabolic pathways to improve health, survival, growth, development, lactation, and reprodn. of organisms. Both NEAA and EAA should be considered in the classic "ideal protein" concept or formulation of balanced diets to maximize protein accretion and optimize health in animals and humans.
- 9Kubota, T.; Kobayashi, T.; Nunoura, T.; Maruyama, F.; Deguchi, S. Enantioselective Utilization of D-Amino Acids by Deep-Sea Microorganisms. Front. Microbiol. 2016, 7, 511, DOI: 10.3389/fmicb.2016.00511[Crossref], [PubMed], [CAS], Google Scholar9https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BC28bms1Ggsw%253D%253D&md5=086d671b6e098ccb0db9fd10f8a57ab9Enantioselective Utilization of D-Amino Acids by Deep-Sea MicroorganismsKubota Takaaki; Kobayashi Tohru; Nunoura Takuro; Deguchi Shigeru; Maruyama FumitoFrontiers in microbiology (2016), 7 (), 511 ISSN:1664-302X.Microorganisms that utilize various D-amino acids (DAAs) were successfully isolated from deep-sea sediments. The isolates were phylogenetically assigned to Alphaproteobacteria, Gammmaproteobacteria, and Bacilli. Some of the isolates exhibited high enantioselective degradation activities to various DAAs. In particular, the Alphaproteobacteria Nautella sp. strain A04V exhibited robust growth in minimal medium supplemented with D-Val as a sole carbon and nitrogen source, whereas its growth was poor on minimal medium supplemented with L-Val instead of D-Val. Its growth was facilitated most when racemic mixtures of valine were used. In contrast, the Nautella strains isolated from shallow-sea grew only with L-Val. No significant differences were found among the strains in the genome sequences including genes possibly related to DAA metabolisms.
- 10Lam, H.; Oh, D.-C.; Cava, F.; Takacs, C. N.; Clardy, J.; De Pedro, M. A.; Waldor, M. K. D-Amino Acids Govern Stationary Phase Cell Wall Remodeling in Bacteria. Science 80 2009, 325, 1552– 1555, DOI: 10.1126/science.1178123[Crossref], [PubMed], [CAS], Google Scholar10https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXhtFanurrE&md5=600d0c84c5b973564cced8fe2c9df734D-Amino acids govern stationary phase cell wall remodeling in bacteriaLam, Hubert; Oh, Dong-Chan; Cava, Felipe; Takacs, Constantin N.; Clardy, Jon; de Pedro, Miguel A.; Waldor, Matthew K.Science (Washington, DC, United States) (2009), 325 (5947), 1552-1555CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)In all known organisms, amino acids are predominantly thought to be synthesized and used as their L-enantiomers. Here, the authors found that bacteria produce diverse D-amino acids as well, which accumulate at millimolar concns. in supernatants of stationary phase cultures. In Vibrio cholerae, a dedicated racemase produced D-Met and D-Leu, whereas Bacillus subtilis generated D-Tyr and D-Phe. These unusual D-amino acids appear to modulate synthesis of peptidoglycan, a strong and elastic polymer that serves as the stress-bearing component of the bacterial cell wall. D-Amino acids influenced peptidoglycan compn., amt., and strength, both by means of their incorporation into the polymer and by regulating enzymes that synthesize and modify it. Thus, synthesis of D-amino acids may be a common strategy for bacteria to adapt to changing environmental conditions.
- 11Holeček, M. Histidine in Health and Disease: Metabolism, Physiological Importance, and Use as a Supplement. Nutrients 2020, 12, 848, DOI: 10.3390/nu12030848[Crossref], [PubMed], [CAS], Google Scholar11https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhvVeitrjM&md5=013dc87d4e2f2341492908bfed5c7c8fHistidine in health and disease: metabolism, physiological importance, and use as a supplementHolecek, MilanNutrients (2020), 12 (3), 848CODEN: NUTRHU; ISSN:2072-6643. (MDPI AG)A review. L-histidine (HIS) is an essential amino acid with unique roles in proton buffering, metal ion chelation, scavenging of reactive oxygen and nitrogen species, erythropoiesis, and the histaminergic system. Several HIS-rich proteins (e.g., haemoproteins, HIS-rich glycoproteins, histatins, HIS-rich calcium-binding protein, and filaggrin), HIS-contg. dipeptides (particularly carnosine), and methyland sulfur-contg. derivs. of HIS (3-methylhistidine, 1-methylhistidine, and ergothioneine) have specific functions. The unique chem. properties and physiol. functions are the basis of the theor. rationale to suggest HIS supplementation in a wide range of conditions. Several decades of experience have confirmed the effectiveness of HIS as a component of solns. used for organ preservation and myocardial protection in cardiac surgery. Further studies are needed to elucidate the effects of HIS supplementation on neurol. disorders, atopic dermatitis, metabolic syndrome, diabetes, uremic anemia, ulcers, inflammatory bowel diseases,malignancies, andmuscle performance during strenuous exercise. Signs of toxicity, mutagenic activity, and allergic reactions or peptic ulcers have not been reported, although HIS is a histamine precursor. Of concern should be findings of hepatic enlargement and increases in ammonia and glutamine and of decrease in branched-chain amino acids (valine, leucine, and isoleucine) in blood plasma indicating that HIS supplementation is inappropriate in patients with liver disease.
- 12McCall, K. A.; Huang, C.-c.; Fierke, C. A. Function and Mechanism of Zinc Metalloenzymes. Journal of Nutrition; American Institute of Nutrition, 2000; Vol. 130.
- 13Wade, A. M.; Tucker, H. N. Antioxidant Characteristics of L-Histidine. Journal of Nutritional Biochemistry; Elsevier June, 1998, 9, pp 308– 315. DOI: 10.1016/S0955-2863(98)00022-9 .
- 14Pichili, V. B. R.; Rao, K. V. R.; Jayakumar, A. R.; Norenberg, M. D. Inhibition of Glutamine Transport into Mitochondria Protects Astrocytes from Ammonia Toxicity. Glia 2007, 55, 801– 809, DOI: 10.1002/glia.20499[Crossref], [PubMed], [CAS], Google Scholar14https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BD2s3jtVWksw%253D%253D&md5=6b3ef324df010931c3e364f47c14a2d9Inhibition of glutamine transport into mitochondria protects astrocytes from ammonia toxicityPichili V B R; Rao K V Rama; Jayakumar A R; Norenberg M DGlia (2007), 55 (8), 801-9 ISSN:0894-1491.Hepatic encephalopathy (HE) is a major neurological complication that occurs in the setting of severe liver failure. Ammonia is a key neurotoxin implicated in this condition, and astrocytes are the principal neural cells histopathologically and functionally affected. Although the mechanism by which ammonia causes astrocyte dysfunction is incompletely understood, glutamine, a by-product of ammonia metabolism, has been strongly implicated in many of the deleterious effects of ammonia on astrocytes. Inhibiting mitochondrial glutamine hydrolysis in astrocytes mitigates many of the toxic effects of ammonia, suggesting the involvement of mitochondrial glutamine metabolism in the mechanism of ammonia neurotoxicity. To determine whether mitochondriaare indeed the organelle where glutamine exerts its toxic effects, we examined the effect of L-histidine, an inhibitor of mitochondrial glutamine transport, on ammonia-mediated astrocyte defects. Treatment of cultured astrocytes with L-histidine completely blocked or significantly attenuated ammonia-induced reactive oxygen species production, cell swelling, mitochondrial permeability transition, and loss of ATP. These findings implicate mitochondrial glutamine transport in the mechanism of ammonia neurotoxicity.
- 15Cho, E. S.; Anderson, H. L.; Wixom, R. L.; Hanson, K. C.; Krause, G. F. Long-Term Effects of Low Histidine Intake on Men. J. Nutr. 1984, 114, 369– 384, DOI: 10.1093/jn/114.2.369[Crossref], [PubMed], [CAS], Google Scholar15https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL2cXhtF2kur8%253D&md5=5d3a13bb26bc68f3c20881b08f26e886Long-term effects of low histidine intake on menCho, Ei Soon; Anderson, Helen L.; Wixom, Robert L.; Hanson, Kenneth C.; Krause, Gary F.Journal of Nutrition (1984), 114 (2), 369-84CODEN: JONUAI; ISSN:0022-3166.The purpose of this 85-day study was to investigate the long-term effects of histidine [71-00-1] depletion on N utilization in young adult men. A low N (6.3 g/day), low histidine (10 mg/day) amino acid diet was fed to 7 men for 8 wk. The mean N balance became neg. after 8 wk. Free histidine in postabsorptive plasma and 24-h urine decreased during the 1st 2 wks of the depletion and remained low and const. for the remaining 6 wk. Hb concn. decreased somewhat, and serum Fe concn. increased during histidine depletion. Lean body mass, urinary Nτ-methylhistidine [332-80-9] and total creatinine [60-27-5] did not change. On addn. of histidine to the low histidine diet for 2 wk, N retention became pos. plasma and urinary histidine returned to initial values, serum Fe fell, and Hb concn. slowly increased. These parameters remained unchanged in 2 control men fed the same diet supplemented with histidine (1.05 g/day) for 8 wk. Histidine may be indispensable for young men consuming a low N diet.
- 16Abe, H.; Dobson, G. P.; Hoeger, U.; Parkhouse, W. S. Role of Histidine-Related Compounds to Intracellular Buffering in Fish Skeletal Muscle. Am. J. Physiol.: Regul., Integr. Comp. Physiol. 1985, 249, R449– R454, DOI: 10.1152/ajpregu.1985.249.4.r449
- 17Hisatsune, T.; Kaneko, J.; Kurashige, H.; Cao, Y.; Satsu, H.; Totsuka, M.; Katakura, Y.; Imabayashi, E.; Matsuda, H. Effect of Anserine/Carnosine Supplementation on Verbal Episodic Memory in Elderly People. J. Alzheimer’s Dis. 2015, 50, 149– 159, DOI: 10.3233/JAD-150767
- 18Tan, S. P.; Brown, S. B.; Griffiths, C.; Weller, R.; Gibbs, N. K. Feeding Filaggrin: Effects of l-Histidine Supplementation in Atopic Dermatitis. Clin., Cosmet. Invest. Dermatol. 2017, 10, 403– 411, DOI: 10.2147/CCID.S146760[Crossref], [PubMed], [CAS], Google Scholar18https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXkt1ehtr4%253D&md5=bb4d91e221abcc5587873cadc8cbc173Feeding filaggrin: effects of l-histidine supplementation in atopic dermatitisTan, Siao Pei; Brown, Simon B.; Griffiths, Christopher EM; Weller, Richard B.; Gibbs, Neil K.Clinical, Cosmetic and Investigational Dermatology (2017), 10 (), 403-411CODEN: CCIDCL; ISSN:1178-7015. (Dove Medical Press Ltd.)Atopic dermatitis (AD), also known as eczema, is one of the most common chronic skin conditions worldwide, affecting up to 16% of children and 10% of adults. It is incurable and has significant psychosocial and economic impacts on the affected individuals. AD etiol. has been linked to deficiencies in the skin barrier protein, filaggrin. In mammalian skin, l-histidine is rapidly incorporated into filaggrin. Subsequent filaggrin proteolysis releases l-histidine as an important natural moisturizing factor (NMF). In vitro studies were conducted to investigate the influence of l-histidine on filaggrin processing and barrier function in human skin-equiv. models. Our further aim was to examine the effects of daily oral l-histidine supplementation on disease severity in adult AD patients. We conducted a randomized, double-blind, placebo-controlled, crossover, nutritional supplementation pilot study to explore the effects of oral l-histidine in adult AD patients (n = 24). In vitro studies demonstrated that l-histidine significantly increased both filaggrin formation and skin barrier function (P<0.01, resp.). Data from the clin. study indicated that once daily oral l-histidine significantly reduced (P<0.003) AD disease severity by 34% (physician assessment using the SCORingAD tool) and 39% (patient self-assessment using the Patient Oriented Eczema Measure tool) after 4 wk of treatment. No improvement was noted with the placebo (P>0.32). The clin. effect of oral l-histidine in AD was similar to that of mid-potency topical corticosteroids and combined with its safety profile suggests that it may be a safe, nonsteroidal approach suitable for long-term use in skin conditions that are assocd. with filaggrin deficits such as AD.
- 19Babizhayev, M. A.; Guiotto, A.; Kasus-Jacobi, A. N-Acetylcarnosine and Histidyl-Hydrazide Are Potent Agents for Multitargeted Ophthalmic Therapy of Senile Cataracts and Diabetic Ocular Complications. J. Drug Targeting 2009, 17, 36– 63, DOI: 10.1080/10611860802438736[Crossref], [PubMed], [CAS], Google Scholar19https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXhsFarsrvI&md5=ad309c1393f1f9ddb3b10a123bc15ff9N-Acetylcarnosine and histidyl-hydrazide are potent agents for multitargeted ophthalmic therapy of senile cataracts and diabetic ocular complicationsBabizhayev, Mark A.; Guiotto, Andrea; Kasus-Jacobi, AnneJournal of Drug Targeting (2009), 17 (1), 36-63CODEN: JDTAEH; ISSN:1061-186X. (Informa Healthcare)Aims: In human diabetes, the deleterious effects of chronic hyperglycemia are the result of excessive nonenzymic modification of proteins and phospholipids by glucose and its byproducts leading to the formation of irreversible oxidized, arom., and fluorescent ligands known as advanced glycation end products. This glycation process has been assocd. with deleterious health effects. The present invention provides the potent inhibitors of protein glycation and AGEs formation, which are particularly advantageous for eyedrop delivery in the prevention and treatment of diabetes- and age-related pathologies. Main Methods and Key findings: We proposed a deglycation system involving removal, by transglycation of sugar or aldehyde moieties from the Schiff bases by ophthalmic aldehyde scavenger l-carnosine derived from its ocular bioactivating sustained release prodrug 1% N-acetylcarnosine (NAC) lubricant eyedrops contg. a mucoadhesive cellulose compd. combined with corneal absorption promoters in drug delivery system. Carnosine analogs bearing the histidyl-hydrazide moiety were synthesized and patented in ophthalmic formulations with NAC bioactivating prodrug to moderate the enzymic hydrolysis of a dipeptide by carnosinase (inhibited by a nonhydrolyzable substrate analog so that this keeps steadier levels of the drug active principle in the aq. humor). Leucyl-histidylhydrazide peptidomimetic demonstrated the transglycation activity more pronounced than l-carnosine accounting for the ability of either mol. to reverse pre-existing, glycation-induced, crosslinking, and checking the nonenzymic glycation cascade in the ophthalmic pathologies. The ophthalmic drug N-acetylcarnosine eye drop formulation with sustained time- release and increased absorption of L-carnosine in the aq. humor (a prolonged ED) showed follow-up treatment efficacy for age-related cataracts for enrolled patients into the randomized double blind placebo controlled crossover clin. trial, and in over 50250 various cohort patients, was demonstrated to have an efficacy, safety and good tolerability for prevention and treatment of visual impairment in the older population data base. Significance: The bioactivating antioxidant NAC and histidyl-hydrazide are potent agents with the pleiotropic effects for ophthalmic therapy of senile cataracts and diabetic ocular complications.
- 20Hu, H.; Emerson, J.; Aronson, A. I. Factors Involved in the Germination and Inactivation of Bacillus Anthracis Spores in Murine Primary Macrophages. FEMS Microbiol. Lett. 2007, 272, 245– 250, DOI: 10.1111/j.1574-6968.2007.00766.x[Crossref], [PubMed], [CAS], Google Scholar20https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2sXnslyhtrs%253D&md5=affa28952f3f2923dada4c4a2a8fed0fFactors involved in the germination and inactivation of Bacillus anthracis spores in murine primary macrophagesHu, Haijing; Emerson, James; Aronson, Arthur I.FEMS Microbiology Letters (2007), 272 (2), 245-250CODEN: FMLED7; ISSN:0378-1097. (Blackwell Publishing Ltd.)Since macrophages have been implicated in inhalation anthrax either for defense and/or as enablers for spore trafficking, their function has been further defined. Spores were efficiently taken up by primary mouse bone marrow-derived macrophages even in the absence of serum but a minimal amt. was required for spore germination and subsequent inactivation. With 10% fetal bovine serum (FBS) virtually all of the spores germinated but when the concn. of FBS was lowered to 1.0% or less, or when 10% horse serum replaced FBS, only 50% of the spores were inactivated within 1 h with no subsequent loss. Chloramphenicol, which blocks spore outgrowth but not germination, did not inhibit spore killing in macrophages. Based on complete inhibition of germination by D-alanine plus D-histidine, it is likely that only two of the several Bacillus anthracis germination systems are involved within macrophages. D-Histidine inhibits the gerH system previously implicated in germination within macrophages. D-Alanine is likely to block the gerX system since disruption of the gerXA gene resulted in little germination within 4 h in macrophages. Macrophages provide a major line of defense against infection by efficiently sequestering spores and in the presence of minimal nutrients effectively killing those that germinate before outgrowth.
- 21Friedman, M.; Levin, C. E. Nutritional and Medicinal Aspects of D-Amino Acids. Amino Acids. Amino Acids 2012, 42, 1553– 1582, DOI: 10.1007/s00726-011-0915-1[Crossref], [PubMed], [CAS], Google Scholar21https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XlsFertLg%253D&md5=bdc310ce8ea5c066d88adac4f19b31f3Nutritional and medicinal aspects of D-amino acidsFriedman, Mendel; Levin, Carol E.Amino Acids (2012), 42 (5), 1553-1582CODEN: AACIE6; ISSN:0939-4451. (SpringerWienNewYork)A review. This paper reviews and interprets a method for detg. the nutritional value of D-amino acids, d-peptides, and amino acid derivs. using a growth assay in mice fed a synthetic all-amino acid diet. A large no. of expts. were carried out in which a molar equivalent of the test compd. replaced a nutritionally essential amino acid such as L-lysine (L-Lys), L-methionine (L-Met), L-phenylalanine (L-Phe), and L-tryptophan (L-Trp) as well as the semi-essential amino acids L-cysteine (L-Cys) and L-tyrosine (L-Tyr). The results show wide-ranging variations in the biol. utilization of test substances. The method is generally applicable to the detn. of the biol. utilization and safety of any amino acid deriv. as a potential nutritional source of the corresponding l-amino acid. Because the organism is forced to use the D-amino acid or amino acid deriv. as the sole source of the essential or semi-essential amino acid being replaced, and because a free amino acid diet allows better control of compn., the use of all-amino-acid diets for such detns. may be preferable to protein-based diets. Also covered are brief summaries of the widely scattered literature on dietary and pharmacol. aspects of 27 individual D-amino acids, D-peptides, and isomeric amino acid derivs. and suggested research needs in each of these areas. The described results provide a valuable record and resource for further progress on the multifaceted aspects of D-amino acids in food and biol. samples.
- 22Mason, S. F. The Development of Concepts of Chiral Discrimination. Chirality 1989, 1, 183– 191, DOI: 10.1002/chir.530010302[Crossref], [PubMed], [CAS], Google Scholar22https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK3cXmvVeg&md5=f397ef943ba1128e2895c6127e412b7eThe development of concepts of chiral discriminationMason, Stephen F.Chirality (1989), 1 (3), 183-91CODEN: CHRLEP; ISSN:0899-0042.A review with 43 refs.
- 23Jeong, Y.; Kim, H. W.; Ku, J.; Seo, J. Breakdown of Chiral Recognition of Amino Acids in Reduced Dimensions. Sci. Rep. 2020, 10, 16166, DOI: 10.1038/s41598-020-73300-z[Crossref], [PubMed], [CAS], Google Scholar23https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhvFyqsLfO&md5=e92c07dfd8ae9ee1bb9663746f204541Breakdown of chiral recognition of amino acids in reduced dimensionsJeong, Yongchan; Kim, Hyo Won; Ku, JiYeon; Seo, JungpilScientific Reports (2020), 10 (1), 16166CODEN: SRCEC3; ISSN:2045-2322. (Nature Research)The homochirality of amino acids in living organisms is one of the great mysteries in the phenomena of life. To understand the chiral recognition of amino acids, we have used scanning tunnelling microscopy to investigate the self-assembly of mols. of the amino acid tryptophan (Trp) on Au(111). Earlier expts. showed only homochiral configurations in the self-assembly of amino acids, despite using a mixt. of the two opposite enantiomers. In our study, we demonstrate that heterochiral configurations can be favored energetically when L- and D-Trp mols. are mixed to form self-assembly on the Au surface. Using d. functional theory calcns., we show that the indole side chain strongly interacts with the Au surface, which reduces the system effectively to two-dimension, with chiral recognition disabled. Our study provides important insight into the recognition of the chirality of amino acid mols. in life.
- 24Berthod, A. Chiral Recognition Mechanisms. Anal. Chem. 2006, 78, 2093– 2099, DOI: 10.1021/ac0693823[ACS Full Text], [CAS], Google Scholar24https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BD28zns1Gqtw%253D%253D&md5=615a0b44aff34c67df159b0c260941e3Chiral recognition mechanismsBerthod AlainAnalytical chemistry (2006), 78 (7), 2093-9 ISSN:0003-2700.There is no expanded citation for this reference.
- 25Randazzo, R.; Gaeta, M.; Gangemi, C.; Fragalà, M.; Purrello, R.; D’Urso, A. Chiral Recognition of L- and D- Amino Acid by Porphyrin Supramolecular Aggregates. Molecules 2018, 24, 84, DOI: 10.3390/molecules24010084
- 26Bettini, S.; Syrgiannis, Z.; Ottolini, M.; Bonfrate, V.; Giancane, G.; Valli, L.; Prato, M. Supramolecular Chiral Discrimination of D-Phenylalanine Amino Acid Based on a Perylene Bisimide Derivative. Front. Bioeng. Biotechnol. 2020, 8, 160, DOI: 10.3389/fbioe.2020.00160[Crossref], [PubMed], [CAS], Google Scholar26https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BB383lslCmtQ%253D%253D&md5=b3f418edad5065ac576335e9eca7a2c1Supramolecular Chiral Discrimination of D-Phenylalanine Amino Acid Based on a Perylene Bisimide DerivativeBettini Simona; Ottolini Michela; Bettini Simona; Giancane Gabriele; Valli Ludovico; Syrgiannis Zois; Syrgiannis Zois; Prato Maurizio; Bonfrate Valentina; Valli Ludovico; Giancane Gabriele; Prato Maurizio; Prato MaurizioFrontiers in bioengineering and biotechnology (2020), 8 (), 160 ISSN:2296-4185.The interaction between homochiral substituted perylene bisimide (PBI) molecule and the D enantiomer of phenylalanine amino acid was monitored. Spectroscopic transitions of PBI derivative in aqueous solution in the visible range were used to evaluate the presence of D-phenylalanine. UV-visible, fluorescence, FT-IR, and AFM characterizations showed that D-phenylalanine induces significant variations in the chiral perylene derivative aggregation state and the mechanism is enantioselective as a consequence of the 3D analyte structure. The interaction mechanism was further investigated in presence of interfering amino acid (D-serine and D-histidine) confirming that both chemical structure and its 3D structure play a crucial role for the amino acid discrimination. A D-phenylalanine fluorescence sensor based on perylene was proposed. A limit of detection (LOD) of 64.2 ± 0.38 nM was calculated in the range 10(-7)-10(-5) M and of 1.53 ± 0.89 μM was obtained in the range 10(-5) and 10(-3) M.
- 27Stefanelli, M.; Mandoj, F.; Magna, G.; Lettieri, R.; Venanzi, M.; Paolesse, R.; Monti, D. The Self-Aggregation of Porphyrins with Multiple Chiral Centers in Organic/Aqueous Media: The Case of Sugar- and Steroid-Porphyrin Conjugates. Molecules 2020, 25, 4544, DOI: 10.3390/molecules25194544[Crossref], [CAS], Google Scholar27https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXitVOlsLrN&md5=9540667a3285cf47c22d01bdadf88394The self-aggregation of porphyrins with multiple chiral centers in organic/aqueous media: the case of sugar- and steroid-porphyrin conjugatesStefanelli, Manuela; Mandoj, Federica; Magna, Gabriele; Lettieri, Raffaella; Venanzi, Mariano; Paolesse, Roberto; Monti, DonatoMolecules (2020), 25 (19), 4544CODEN: MOLEFW; ISSN:1420-3049. (MDPI AG)A review. An overview of the solvent-driven aggregation of a series of chiral porphyrin derivs. studied by optical methods (UV/Vis, fluorescence, CD and RLS spectroscopies) is herein reported. The investigated porphyrins are characterized by the presence in the meso-positions of glycol-, steroidal- and glucosteroidal moieties, conferring amphiphilicity and soly. in aq. media to the primarily hydrophobic porphyrin platform. Aggregation of the macrocycles is driven by a change in bulk solvent compn., forming architectures with supramol. chirality, steered by the stereogenic centers on the porphyrin peripheral positions. The aggregation behavior and chiroptical properties of the final aggregated species strongly depend on the no. and stereogenicity of the ancillary groups that dictate the mutual spatial arrangement of the porphyrin chromophores and their further organization in larger structures, usually detectable by different microscopies, such as AFM and SEM. Kinetic studies are fundamental to understand the aggregation mechanism, which is frequently found to be dependent on the substrate concn. Addnl., Mol. Mechanics calcns. can give insights into the intimate nature of the driving forces governing the self-assembly process. The crit. use of these combined methods can shed light on the overall self-assembly process of chirally-functionalized macrocycles, with important implications on the development of chiral porphyrin-based materials.
- 28Torsi, L.; Farinola, G. M.; Marinelli, F.; Tanese, M. C.; Omar, O. H.; Valli, L.; Babudri, F.; Palmisano, F.; Zambonin, P. G.; Naso, F. A Sensitivity-Enhanced Field-Effect Chiralsensor. Nat. Mater. 2008, 7, 412– 417, DOI: 10.1038/nmat2167[Crossref], [PubMed], [CAS], Google Scholar28https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXltVGktbk%253D&md5=afad3322d7b8f222ea49ff468636f2a2A sensitivity-enhanced field-effect chiral sensorTorsi, Luisa; Farinola, Gianluca M.; Marinelli, Francesco; Tanese, M. Cristina; Omar, Omar Hassan; Valli, Ludovico; Babudri, Francesco; Palmisano, Francesco; Zambonin, P. Giorgio; Naso, FrancescoNature Materials (2008), 7 (5), 412-417CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)Org. thin-film transistor sensors were recently attracting the attention of the plastic electronics community for their potential exploitation in novel sensing platforms. Specificity and sensitivity are however still open issues: in this respect chiral discrimination-being a scientific and technol. achievement in itself-is indeed one of the most challenging sensor bench-tests. So far, conducting-polymer solid-state chiral detection was carried out at part-per-thousand concn. levels. Here, a novel chiral bilayer org. thin-film transistor gas sensor-comprising an outermost layer with built-in enantioselective properties-is demonstrated to show field-effect amplified sensitivity that enables differential detection of optical isomers in the tens-of-parts-per-million concn. range. The ad-hoc-designed org. semiconductor endowed with chiral side groups, the bilayer structure and the thin-film transistor transducer provide a significant step forward in the development of a high-performance and versatile sensing platform compatible with flexible org. electronic technologies.
- 29Bhyrappa, P.; Borovkov, V. V.; Inoue, Y. Supramolecular Chirogenesis in Bis-Porphyrins: Interaction with Chiral Acids and Application for the Absolute Configuration Assignment. Org. Lett. 2007, 9, 433– 435, DOI: 10.1021/ol062776w[ACS Full Text], [CAS], Google Scholar29https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2sXhvVCnsA%253D%253D&md5=71458f6200b379a21194d5564b83cdf9Supramolecular Chirogenesis in Bis-porphyrins: Interaction with Chiral Acids and Application for the Absolute Configuration AssignmentBhyrappa, Puttaiah; Borovkov, Victor V.; Inoue, YoshihisaOrganic Letters (2007), 9 (3), 433-435CODEN: ORLEF7; ISSN:1523-7060. (American Chemical Society)A new supramol. chirogenic system on the basis of bis(free base porphyrin) and various enantiopure acids, which can be effectively applied for chirality sensing purposes, is reported. The temp. and solvent are found to be key factors controlling the chirality transfer process in these assemblies.
- 30Battersby, A. R. Tetrapyrroles: The Pigments of Life. Natural Product Reports. Nat. Prod. Rep. 2000, 17, 507– 526, DOI: 10.1039/b002635m[Crossref], [PubMed], [CAS], Google Scholar30https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3cXotFWhtrw%253D&md5=e3b5dff991443310ca31d6dffe93815bTetrapyrroles: the pigments of lifeBattersby, Alan R.Natural Product Reports (2000), 17 (6), 507-526CODEN: NPRRDF; ISSN:0265-0568. (Royal Society of Chemistry)Review with 106 refs. on the title compds. is presented.
- 31Giancane, G.; Borovkov, V.; Inoue, Y.; Conoci, S.; Valli, L. Syn-Anti Conformation Switching of a Bis-Porphyrin Derivative at the Air-Water Interface and in the Solid State as an Effective Tool for Chemical Sensing. Soft Matter 2013, 9, 2302– 2307, DOI: 10.1039/c2sm27141a[Crossref], [CAS], Google Scholar31https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhsVCmsL4%253D&md5=fa54e83413ef027a096702afe5fac9c7Syn-anti conformation switching of a bis-porphyrin derivative at the air-water interface and in the solid state as an effective tool for chemical sensingGiancane, Gabriele; Borovkov, Victor; Inoue, Yoshihisa; Conoci, Sabrina; Valli, LudovicoSoft Matter (2013), 9 (7), 2302-2307CODEN: SMOABF; ISSN:1744-683X. (Royal Society of Chemistry)A Langmuir film of bis(zinc octaethylporphyrin) (ZnPP) was characterized at the air-water interface and its syn-anti conformation switching induced upon addn. of arom. amines was studied by IR and UV-visible reflection spectroscopic methods. The highly specific interaction of ZnPP with arom. amines was maintained even after the floating film was transferred onto solid supports by the Langmuir-Schaefer (LS) technique, enabling the authors to selectively sense arom. amines at concns. ≥20 ppb. Also, LS ZnPP active layer selectivity was evaluated in the presence of aliph. amines.
- 32Grover, N.; Locke, G. M.; Flanagan, K. J.; Beh, M. H. R.; Thompson, A.; Senge, M. O. Bridging and Conformational Control of Porphyrin Units through Non-Traditional Rigid Scaffolds. Chem.─Eur. J. 2020, 26, 2405– 2416, DOI: 10.1002/chem.201904199[Crossref], [PubMed], [CAS], Google Scholar32https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXht1Gqs78%253D&md5=99a03c22b01ea27d660f53c41f891581Bridging and Conformational Control of Porphyrin Units through Non-Traditional Rigid ScaffoldsGrover, Nitika; Locke, Gemma M.; Flanagan, Keith J.; Beh, Michael H. R.; Thompson, Alison; Senge, Mathias O.Chemistry - A European Journal (2020), 26 (11), 2405-2416CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)Connecting two porphyrin units in a rigid linear fashion, without any undesired electron delocalization or communication between the chromophores, remains a synthetic challenge. Herein, a broad library of functionally diverse multi-porphyrin arrays that incorporate the non-traditional rigid linker groups cubane and bicyclo[1.1.1]pentane (BCP) is described. A robust, reliable, and versatile synthetic procedure was employed to access porphyrin-cubane/BCP-porphyrin arrays, representing the largest non-polymeric structures available for cubane/BCP derivs. These reactions demonstrate considerable substrate scope, from utilization of small Ph moieties to large porphyrin rings, with varying lengths and different angles. To control conformational flexibility, amide bonds were introduced between the bridgehead carbon of BCP/cubane and the porphyrin rings. Through varying the orientation of the substituents around the amide bond of cubane/BCP, different intermol. interactions were identified through single crystal X-ray anal. These studies revealed non-covalent interactions that are the first-of-their-kind including a unique iodine-oxygen interaction between cubane units. These supramol. architectures indicate the possibility to mimic a protein structure due to the sp3 rigid scaffolds (BCP or cubane) that exhibit the essential conformational space for protein function while simultaneously providing amide bonds for mol. recognition.
- 33Buccolieri, A.; Bettini, S.; Salvatore, L.; Baldassarre, F.; Ciccarella, G.; Giancane, G. Sub-Nanomolar Detection of Biogenic Amines by SERS Effect Induced by Hairy Janus Silver Nanoparticles. Sens. Actuators, B 2018, 267, 265– 271, DOI: 10.1016/j.snb.2018.04.028[Crossref], [CAS], Google Scholar33https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXns1eqtLc%253D&md5=05441031b0fdf2389558e6c6fe1ea779Sub-nanomolar detection of biogenic amines by SERS effect induced by hairy Janus silver nanoparticlesBuccolieri, A.; Bettini, S.; Salvatore, L.; Baldassarre, F.; Ciccarella, G.; Giancane, G.Sensors and Actuators, B: Chemical (2018), 267 (), 265-271CODEN: SABCEB; ISSN:0925-4005. (Elsevier B.V.)Surface enhanced Raman scattering (SERS) is largely used as a transduction method for analytes detection in liq. and vapor phase. In particular, SERS effect was promoted by a plethora of different metal and semiconducting nanoparticles (NPs) and silver and gold nanoparticles appear particularly suitable for this application. Nevertheless, silver nanoparticles intrinsic propensity to aggregate in large clusters reduces the possibility to use naked nanoparticles in SERS applications, for this reason they are usually functionalized with org. mols. This approach inhibits the aggregation process but, on the other hand, reduces the surficial area of the NPs able to interact with the analyte mols. In the present work, we propose a simple method to obtain surficial anisotropic Janus silver nanoparticles: octadecylamine was used to stabilize the nanoparticles and to promote the deposition of the silver nanoparticles on a solid substrate. The AgNPs/octadecylamine nanostructures showed the typical "hairy" Janus morphol. and a strong SERS effect was obsd. when two biogenic amines, i. e. 2-phenylethylamine and tyramine, were fluxed on the solid film. SERS phenomenon was studied as a function both of the chem. structure of the fluxed amine and of the distance between the arom. moiety and the nanoparticle allowing to propose the AgNPs/octadecylamine Janus nanoparticles as an active layer for the detection of phenylethylamine and tyramine in picomolar concn.
- 34Hoenig, D.; Moebius, D. Direct Visualization of Monolayers at the Air-Water Interface by Brewster Angle Microscopy. J. Phys. Chem. 1991, 95, 4590– 4592, DOI: 10.1021/j100165a003[ACS Full Text], [CAS], Google Scholar34https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK3MXktFKjs7s%253D&md5=86998e589d88b0e87a81e1aa0eaecc51Direct visualization of monolayers at the air-water interface by Brewster angle microscopyHoenig, Dirk; Moebius, DietmarJournal of Physical Chemistry (1991), 95 (12), 4590-2CODEN: JPCHAX; ISSN:0022-3654.No light is reflected from the air-water interface under Brewster angle incidence if p-polarized light is used. With const. angle of incidence, the formation of a monolayer on the water surface modifies the Brewster angle condition, and light reflection is obsd. Reflectivity-area isotherms of arachidic acid monolayers on pure water and on aq. solns. of different pH have been measured. Areas of different brightness due to different mol. d. and/or refractive index in the monolayer were recorded with a video system as microg. pictures. This Brewster angle microscopy can also detect monolayer inhomogeneities and reversible formation of solid-phase domains upon compression of monolayers of DMPE.
- 35Bettini, S.; Valli, L.; Santino, A.; Martinelli, C.; Farinola, G. M.; Cardone, A.; Sgobba, V.; Giancane, G. Spectroscopic Investigations, Characterization and Chemical Sensor Application of Composite Langmuir-Schäfer Films of Anthocyanins and Oligophenylenevinylene Derivatives. Dyes Pigm. 2012, 94, 156, DOI: 10.1016/j.dyepig.2011.12.010[Crossref], [CAS], Google Scholar35https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XhslChu7o%253D&md5=d0a3b09b7da18904b919ac04abc8f243Spectroscopic investigations, characterization and chemical sensor application of composite Langmuir-Schaefer films of anthocyanins and oligophenylenevinylene derivativesBettini, S.; Valli, L.; Santino, A.; Martinelli, C.; Farinola, G. M.; Cardone, A.; Sgobba, V.; Giancane, G.Dyes and Pigments (2012), 94 (1), 156-162CODEN: DYPIDX; ISSN:0143-7208. (Elsevier Ltd.)Anthocyanins, extd. from grape skin (Vitis vinifera), were dissolved in ultrapure aq. subphase and an oligophenylenevinylene deriv. was spread on the subphase surface. Such oligomer was chosen as anionic counterpart of hydrosol. anthocyanins in order to perform a Langmuir-Schaefer film of the dyad. Interface interactions between oligophenylenevinylene deriv. and anthocyanins were studied by Brewster angle microscopy and reflection spectroscopy. Addnl., the oligomer exhibits a chem. structure able to ensure an enhancement of the stability under UV-visible irradiations of the film of the dyad without any variation of the natural pigment absorption in the visible range. The visible spectra of cast anthocyanins film and Langmuir-Schaefer oligomer/anthocyanins film after exposure to 254 nm irradn. showed a remarkable increase of the film stability, probably due to the screening effect of the oligomer. Preliminary test of a Langmuir-Schaefer film of oligophenylenevinylene deriv./anthocyanins as a herbicide sensor showed that sensing is completely reversible, stable and repeatable.
- 36Bettini, S.; Pagano, R.; Bonfrate, V.; Maglie, E.; Manno, D.; Serra, A.; Valli, L.; Giancane, G. Promising Piezoelectric Properties of New ZnO@Octadecylamine Adduct. J. Phys. Chem. C 2015, 119, 20143– 20149, DOI: 10.1021/acs.jpcc.5b06013[ACS Full Text], [CAS], Google Scholar36https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXht12ksLjN&md5=61d3c63b1773ab1e36565d151394e2ecPromising Piezoelectric Properties of New ZnO@Octadecylamine AdductBettini, Simona; Pagano, Rosanna; Bonfrate, Valentina; Maglie, Emanuela; Manno, Daniela; Serra, Antonio; Valli, Ludovico; Giancane, GabrieleJournal of Physical Chemistry C (2015), 119 (34), 20143-20149CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)A supramol. adduct formed by the interaction among octadecylamine (ODA) and zinc oxide nanostructures was promoted. A stable dispersion of the ZnO@ODA adduct was obtained and characterized by TGA and IR and Raman spectroscopy. Then, the supramol. adduct was spread at the air/water interface of a Langmuir trough. The presence of octadecylamine gave amphiphilic features to the ZnO@ODA adduct that was transferred from the air/water interface to solid substrates by Langmuir-Schaefer (LS) method. The transferred film was characterized by tunnel electron microscopy that highlighted rectangular well-shaped structures assembled by nanostructure of ZnO arranged in an ODA matrix. Piezoelec. feature of large LS film (1 cm2) was tested and a very promising response was obsd. as a consequence of the application of a pressure of 1 kPa.
- 37Ariga, K. Don’t Forget Langmuir-Blodgett Films 2020: Interfacial Nanoarchitectonics with Molecules, Materials, and Living Objects. Langmuir 2020, 36, 7158– 7180, American Chemical Society July DOI: 10.1021/acs.langmuir.0c01044[ACS Full Text], [CAS], Google Scholar37https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhtV2ks7nN&md5=00dc60be618f9358edc8a70e8f939da4Don't Forget Langmuir-Blodgett Films 2020: Interfacial Nanoarchitectonics with Molecules, Materials, and Living ObjectsAriga, KatsuhikoLangmuir (2020), 36 (26), 7158-7180CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)A review. Designing interfacial structures with nanoscale (or mol.) components is one of the important tasks in the nanoarchitectonics concept. In particular, the Langmuir-Blodgett (LB) method can become a promising and powerful strategy in interfacial nanoarchitectonics. From this viewpoint, the status of LB films in 2020 will be discussed in this feature article. After one section on the basics of interfacial nanoarchitectonics with the LB technique, various recent research examples of LB films are introduced according to classifications of (i) growing research, (ii) emerging research, and (iii) future research. In recent LB research, various materials other than traditional lipids and typical amphiphiles can be used as film components of the LB techniques. Two-dimensional materials, supramol. structures such as metal org. frameworks, and biomaterials such as DNA origami pieces are capable of working as functional components in the LB assemblies. Possible working areas of the LB methods would cover emerging demands, including energy, environmental, and biomedical applications with a wide range of functional materials. In addn., forefront research such as mol. manipulation and cell fate control is conducted in LB-related interfacial science. The LB technique is a traditional and well-develop methodol. for mol. films with a ca. 100 yr history. However, there is plenty of room at the interfaces, as shown in LB research examples described in this feature article. It is hoped that the continuous development of the science and technol. of the LB method make this technique an unforgettable methodol.
- 38Buccolieri, A.; Hasan, M.; Bettini, S.; Bonfrate, V.; Salvatore, L.; Santino, A.; Borovkov, V.; Giancane, G. Ethane-Bridged Bisporphyrin Conformational Changes As an Effective Analytical Tool for Nonenzymatic Detection of Urea in the Physiological Range. Anal. Chem. 2018, 90, 6952– 6958, DOI: 10.1021/acs.analchem.8b01230[ACS Full Text], [CAS], Google Scholar38https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXptVeqtL4%253D&md5=eb1275537f1bbbbaf18c365bc71bf7faEthane-Bridged Bisporphyrin Conformational Changes As an Effective Analytical Tool for Nonenzymatic Detection of Urea in the Physiological RangeBuccolieri, Alessandro; Hasan, Mohammed; Bettini, Simona; Bonfrate, Valentina; Salvatore, Luca; Santino, Angelo; Borovkov, Victor; Giancane, GabrieleAnalytical Chemistry (Washington, DC, United States) (2018), 90 (11), 6952-6958CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)Conformational switching induced in ethane-bridged bisporphyrins was used as a sensitive transduction method for revealing the presence of urea dissolved in water via nonenzymic approach. Bisporphyrins were deposited on solid quartz slides by means of the spin-coating method. Mol. conformations of Zn and Ni monometalated bis-porphyrins were influenced by water solvated urea mols. and their fluorescence emission was modulated by the urea concn. Absorption, fluorescence and Raman spectroscopies allowed the identification of supramol. processes, which are responsible for host-guest interaction between the active layers and urea mols. A high selectivity of the sensing mechanism was highlighted upon testing the spectroscopic responses of bis-porphyrin films to citrulline and glutamine used as interfering agents. Addnl., potential applicability was demonstrated by quantifying the urea concn. in real physiol. samples proposing this new approach as a valuable alternative anal. procedure to the traditionally used enzymic methods.
- 39Capistran, B. A.; Blanchard, G. J. Effects of Cu(II) on the Formation and Orientation of an Arachidic Acid Langmuir-Blodgett Film. Langmuir 2019, 35, 3346– 3353, DOI: 10.1021/acs.langmuir.9b00022[ACS Full Text], [CAS], Google Scholar39https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXivVOnsb4%253D&md5=c38c32e5a9c4b5d3b68f8d05e9dc757fEffects of Cu(II) on the Formation and Orientation of an Arachidic Acid Langmuir-Blodgett FilmCapistran, Briana A.; Blanchard, G. J.Langmuir (2019), 35 (9), 3346-3353CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)The influence of the copper (II) ion on the formation, morphol., and organization of an arachidic acid monolayer was investigated using Langmuir-Blodgett (LB) monolayers, π-A isotherms and Brewster angle microscopy (BAM). Our findings indicate that a Cu2+-complexed LB film exhibits order that depends on the subphase pH, analogous to other metal ions. The metal ion facilitates formation of solid-phase films at surface pressures as low at 5 mN/m. The films exhibit a rigid, ordered phase, evidenced by the absence of a collapse point and an increase in surface pressure rather than the typical sharp decrease in surface pressure indicative of film failure. The role of amphiphile ionic charge vs. pH (i.e., the extent of arachidic acid protonation) plays a role in the obsd. absence of collapse and the ability of the films to maintain order and cohesion at high surface pressures (ca. 65 mN/m). Addnl., film thickness data suggest that the incorporation of Cu2+ ions induces a change in orientation of the aliph. chains of the amphiphiles, and that amphiphile soly. in the subphase may play a role in the obsd. film behavior at low surface areas and high pH.
- 40Nurhayati; Suendo, V.; Alni, A.; Nugroho, A. A.; Majima, Y.; Lee, S.; Nugraha, Y. P.; Uekusa, H. Revealing the Real Size of a Porphyrin Molecule with Quantum Confinement Probing via Temperature-Dependent Photoluminescence Spectroscopy. J. Phys. Chem. A 2020, 124, 2672– 2682, DOI: 10.1021/acs.jpca.0c00665[ACS Full Text], [CAS], Google Scholar40https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXkslWrtb8%253D&md5=e65eef8b4a3a69840f5878c4a0dafd7aRevealing the Real Size of a Porphyrin Molecule with Quantum Confinement Probing via Temperature-Dependent Photoluminescence SpectroscopyNurhayati; Suendo, Veinardi; Alni, Anita; Nugroho, Agustinus A.; Majima, Yutaka; Lee, Seungjoo; Nugraha, Yuda Prasetya; Uekusa, HidehiroJournal of Physical Chemistry A (2020), 124 (13), 2672-2682CODEN: JPCAFH; ISSN:1089-5639. (American Chemical Society)The confinement energy of electrons in an arom. mol. was studied by indirect and direct methods, namely, temp.-dependent photoluminescence (TDPL) spectroscopy and scanning tunneling microscopy (STM). We obsd. a decrease in the tetraphenylporphyrin (H2TPP) PL intensity with increasing temp. The increase in temp. provides kinetic energy for the electrons to overcome the confinement energy barrier, making recombination via nonradiative pathways more favorable. The results of fitting the integrated TDPL intensity with a modified Arrhenius equation suggest two confinement energy values. We propose that these energy values are related to the size of the delocalized electron cloud along the plane and thickness of the H2TPP ring. These values quant. express an abstr. form of the size of the arom. ring system. These results are in good agreement with the topog. images of single H2TPP mols. and monolayer H2TPP obtained by a direct probing method using STM. These results are also supported by the porphyrin ring orientation relative to the excited crystal face during the TDPL measurements.
- 41Bass, M. Handbook of Optics; McGraw-Hill Education, 2010.Google ScholarThere is no corresponding record for this reference.
- 42Colombelli, A.; Manera, M. G.; Borovkov, V.; Giancane, G.; Valli, L.; Rella, R. Enhanced Sensing Properties of Cobalt Bis-Porphyrin Derivative Thin Films by a Magneto-Plasmonic-Opto-Chemical Sensor. Sens. Actuators, B 2017, 246, 1039– 1048, DOI: 10.1016/j.snb.2017.01.192[Crossref], [CAS], Google Scholar42https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXjvFamsr8%253D&md5=659005cca1d7ca5589b9c963f37ef52bEnhanced sensing properties of cobalt bis-porphyrin derivative thin films by a magneto-plasmonic-opto-chemical sensorColombelli, A.; Manera, M. G.; Borovkov, V.; Giancane, G.; Valli, L.; Rella, R.Sensors and Actuators, B: Chemical (2017), 246 (), 1039-1048CODEN: SABCEB; ISSN:0925-4005. (Elsevier B.V.)This work reports on the spectroscopic properties and gas sensing performances of cobalt bis-porphyrin deriv. ((Co-H)Por2) in a thin films form obtained by Langmuir-Schafer (LS) method towards Volatile Org. Compds. (VOCs) and an oxidizing gas in a Magneto-Optical Surface Plasmon Resonance (MO-SPR) configuration. In particular the optical and spectroscopic properties of (Co-H)Por2 multilayers deposited onto proper Au/Co/Au magneto-plasmonic (MP) transducers were inspected in dry air conditions and after exposure to different analyte gas concns. The mol. organization of these thin films deposited by Langmuir-Schafer technique has been investigated and a comparison between the MOSPR exptl. data and simulation has been also reported. In order to validate our exptl. results and obtain further insight into the phys. mechanism of interaction between the organometallic mols. and magneto plasmonic nanostructured systems, numerical simulations based on Finite Element Method (FEM) techniques, have been performed. The optical and magneto-optical properties of these hybrid systems have been theor. analyzed to confirm the exptl. outcomes. Finally, a peculiar sensitivity of the MOSPR sensing probe in respect to investigated analytes has been recorded.
- 43Bettini, S.; Pagano, R.; Borovkov, V.; Giancane, G.; Valli, L. The Role of the Central Metal Ion of Ethane-Bridged Bis-Porphyrins in Histidine Sensing. J. Colloid Interface Sci. 2019, 533, 762– 770, DOI: 10.1016/j.jcis.2018.08.116[Crossref], [PubMed], [CAS], Google Scholar43https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhs1Oltb7I&md5=f5cf6f81320465b4002eda27d597ae7dThe role of the central metal ion of ethane-bridged bis-porphyrins in histidine sensingBettini, Simona; Pagano, Rosanna; Borovkov, Victor; Giancane, Gabriele; Valli, LudovicoJournal of Colloid and Interface Science (2019), 533 (), 762-770CODEN: JCISA5; ISSN:0021-9797. (Elsevier B.V.)Ethane-bridged bis-porphyrin derivs. are reported for the selective detection of various analytes in sensing applications. The central metal ion is able to rule specific mol. arrangements upon analyte binding. Three bis-porphyrin compds.: a free base (metal free), Ni complex, and Cu complex, have been tested for histidine detection in aq. media. Histidine is involved in various biol. processes, including such deadly disease as lung cancer. The conformational changes of bis-porphyrins, induced by histidine binding, can be detected by monitoring the Soret band position. The spectroscopic characterization, at the air-water subphase interface, indicates that, in the presence of histidine, the Ni and Cu metalated derivs. undergo conformational changes. This behavior was confirmed when these two derivs. were deposited onto the solid support by Langmuir-Schaefer (LS) technique. A prototypal Surface Plasmon Resonance (SPR) detection system for histidine based on these two porphyrin LS films was developed. The Cu substituted compd. based SPR system allows the histidine sensing down to nanomolar concn. Furthermore, a SPR response of the Ni bis-porphyrin shows a semilogarithmic dependence on the histidine concn. up to 10-6 M proposing the use of these two porphyrins in a sensor array for the monitoring of histidine levels in plasma.
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ARTICLE SECTIONSThe Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.langmuir.1c02377.
Chemical structure of H2por-cubane-H2por and (Zn)por-cubane-H2por, influence of the number of LS runs on the spectral profile of H2por-cubane-H2por, reflection spectra of the floating film of H2por-cubane-H2por spread at air/ultrapure water subphase acquired at different surface pressures, reflection spectra of the floating film of H2por-cubane-H2por spread at air/l-histidine aqueous subphase acquired at different surface pressures, reflection spectra of the floating film of H2por-cubane-H2por spread at air/d-histidine aqueous subphase acquired at different surface pressures, spectral variation induced by fluxing l- and d-histidine on 4 runs LS film of H2por-cubane-H2por transferred from ultrapure water subphase, effect on the H2por-cubane-H2por LS film absorption spectrum induced by different analytes dissolved in the subphase: (A) l and d-lysine, (B) glycine, (C) histamine, (D) l and d-phenylalanine, LS films of (Zn)por-cubane-H2por transferred from ultrapure water (blue line), from subphases containing l-histidine (10–4 M) and d-histidine (10–4 M), and schematic representation of the interaction among l and d-histidine with the floating molecules of (Zn)por-cubane-H2por (PDF)
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