Ionophore-Based Titrimetric Detection of Alkali Metal Ions in SerumClick to copy article linkArticle link copied!
- Jingying ZhaiJingying ZhaiDepartment of Inorganic and Analytical Chemistry, University of Geneva, Quai Ernest-Ansermet 30, CH-1211 Geneva, SwitzerlandMore by Jingying Zhai
- Xiaojiang XieXiaojiang XieDepartment of Chemistry, Southern University of Science and Technology, Shenzhen, 518000, ChinaMore by Xiaojiang Xie
- Thomas CherubiniThomas CherubiniDepartment of Inorganic and Analytical Chemistry, University of Geneva, Quai Ernest-Ansermet 30, CH-1211 Geneva, SwitzerlandMore by Thomas Cherubini
- Eric Bakker*Eric Bakker*E-mail: [email protected]Department of Inorganic and Analytical Chemistry, University of Geneva, Quai Ernest-Ansermet 30, CH-1211 Geneva, SwitzerlandMore by Eric Bakker
Abstract
While the titrimetric assay is one of the most precise analytical techniques available, only a limited list of complexometric chelators is available, as many otherwise promising reagents are not water-soluble. Recent work demonstrated successful titrimetry with ion-exchanging polymeric nanospheres containing hydrophobic complexing agents, so-called ionophores, opening an exciting avenue in this field. However, this method was limited to ionophores of very high affinity to the analyte and exhibited a relatively limited titration capacity. To overcome these two limitations, we report here on solvent based titration reagents. This heterogeneous titration principle is based on the dissolution of all hydrophobic recognition components in a solvent such as dichloromethane (CH2Cl2) where the ionophores are shown to maintain a high affinity to the target ions. HSV (hue, saturation, value) analysis of the images captured with a digital camera provides a convenient and inexpensive way to determine the end point. This approach is combined with an automated titration setup. The titrations of the alkali metals K+, Na+, and Li+ in aqueous solution are successfully demonstrated. The potassium concentration in human serum without pretreatment was precisely and accurately determined as 4.38 mM ± 0.10 mM (automated titration), which compares favorably with atomic emission spectroscopy (4.47 mM ± 0.20 mM).
Experimental Section
Reagents
Preparation of Ionophore-Based Titration Reagents
Optical Titration
Instrumentation
Results and Discussion
Scheme 1
a(a) Before end point. (b) After end point.




Figure 1
Figure 1. Optical reverse titration curves (a, b, c) and corresponding absorption spectra (d, e, f) for K+, Na+, and Li+, respectively. Titrant: 10–2 M KCl or NaCl or LiCl. The dashed vertical lines indicate the expected end point. Buffer solution: 10–2 M Tris-HCl pH 7.0 for K+ titration; 10–2 M Tris-HCl pH 7.4 for Na+ and Li+ titration. Absorption spectra recorded at each titration point.
Figure 2
Figure 2. Response of the K+ (a), Na+ (b), and Li+ (c) selective reagents to various interfering ions, respectively. Buffer solution: (a)10–2 M Tris-HCl pH 7.0, (b,c) 10–2 M Tris-HCl pH 7.4. The horizontal distance between the calibration curve for primary ion and any interfering ions represents log K1.
Figure 3
Figure 3. Pictures of the K+ titration process after shaking (a) and after two phases separated (b) and the corresponding titration curves (c) and (d) based on the HSV analysis. The dashed vertical lines indicate the expected end points. Buffer solution: 10–2 M Tris-HCl pH 7.0.
Figure 4
Figure 4. Setup of the automated titration: (a) before titration, (b) after the end point. (c) Titration analysis for K+ based on the hue signals retrieved from the frames in the video. (d) Serum titration based on the hue signals retrieved from the frames in the video. Organic phase: K+ selective titration reagent. Aqueous phase: 10–2 M Tris-HCl pH 7.0 buffer solution. The volume of the added serum at the end point is Vserum = 73 μL.
Supporting Information
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acssensors.7b00165.
Detailed theoretical approach; additional results on optical reverse titration, experimental titration curve, and serum titration (PDF)
Automatic titration of potassium in human serum by using home-made setup (AVI)
Terms & Conditions
Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.
Acknowledgments
The authors thank the Swiss National Science Foundation (SNF) and the University of Geneva for financial support and Valentin Waeber for technical assistance in extracting color information from the movie frames. Jingying Zhai gratefully acknowledges support by the China Scholarship Council (CSC).
References
This article references 37 other publications.
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- 18Swain, B. Recovery and recycling of lithium: A review. Sep. Purif. Technol. 2017, 172, 388– 403, DOI: 10.1016/j.seppur.2016.08.031Google Scholar18https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhsVOiu7jO&md5=a13a324ed0f98f6cd0e5886e0b9c2acaRecovery and recycling of lithium: A reviewSwain, BasudevSeparation and Purification Technology (2017), 172 (), 388-403CODEN: SPUTFP; ISSN:1383-5866. (Elsevier B.V.)A review. Projected demands for lithium as LIB for the plug-in hybrid elec. (PHEV), elec. (EV) and hybrid elec. (HEV) vehicle in the recent future is huge and estd. to reach $221 billion by 2024. Currently, 35% of global lithium prodn. being used for LIBs and consumption for estd. LIB demand could be 66% (out of global lithium prodn.) by 2025. During last five (2011-2015) years, global lithium prodn. is almost const. At present, up to 3% of LIBs are recycled with the only focus of valuable metal recovery, but motivation on lithium recovery almost nonexistence. The global rate of lithium recycling is only < 1%. Considering the current global lithium prodn. with respect to projected demand, environment and regulation, green energy and energy security, cradle-to-cradle technol. management and circular economy of crit. metal and minimization of waste crime and maximization of the urban mining, recovery and recycling status of lithium should be well understood. In this review recovery of lithium from various resources such as different ores, clay, brine, seawater and recycling of battery by different technique are reviewed. Lithium recovery from various primary resources and its sepn. purifn. by different routes such as hydrometallurgy, pyro-metallurgy, chem. metallurgy, and bioleaching are discussed. Lithium recovery through chem. leaching, bioleaching, and floatation of different ores also thoroughly reviewed. The extn. of lithium from seawater by co-pptn. and extn., ion-exchange and sorption by using various org., inorg. and composite polymer sorbents has been discussed thoroughly. Although, several industries recovering lithium from primary resources, but lithium recovery from secondary resources almost non-existence. The non-existence of lithium recovery process from LIB or techno-economically inefficient process is a greater challenge for the projected lithium demand. As the cradle-to-grave technol. is a sustainability challenge, cradle-to-cradle technol. management could be achieved through efficient recycling. Hence, techno-economically feasible, environment-friendly and sustainable process needs to be developed and recommended. Considering technol. advantages of hydrometallurgy process like; smaller scale, minimal energy investment, minimal CO2 emission, and the plant can be designed based on available waste, lithium recovery by hydrometallurgy should be focused.
- 19Zhai, J.; Xie, X.; Bakker, E. Ionophore-based ion-exchange emulsions as novel class of complexometric titration reagents. Chem. Commun. 2014, 50, 12659– 12661, DOI: 10.1039/C4CC05754FGoogle Scholar19https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhsVyhtLzE&md5=bff9c778b3d99c918d05af744a5a6dccIonophore-based ion-exchange emulsions as novel class of complexometric titration reagentsZhai, Jingying; Xie, Xiaojiang; Bakker, EricChemical Communications (Cambridge, United Kingdom) (2014), 50 (84), 12659-12661CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)Complexometric titrns. rely on a drastic change of the pM value at the equivalence point with a water sol. chelator forming typically 1 : 1 complexes of high stability. The available chem. toolbox of suitable chelating compds. is unfortunately limited because many promising complexing agents are not water sol. The authors introduce here a novel class of complexometric titrn. reagents, a suspension of polymeric nanospheres whose hydrophobic core is doped with lipophilic ion-exchanger and a selective complexing agent (ionophore). The emulsified nanospheres behave from heterogeneous ion exchange equil. where the initial counterion of the ion-exchanger is readily displaced from the emulsion for the target ion that forms a stable complex in the nanosphere core. Two different examples are shown with Ca2+ and Pb2+ as target ions. The lack of protonatable groups on the calcium receptor allows one to perform Ca2+ titrn. without pH control.
- 20Zhai, J.; Xie, X.; Bakker, E. Ion-Selective optode nanospheres as heterogeneous indicator reagents in complexometric titrations. Anal. Chem. 2015, 87 (5), 2827– 2831, DOI: 10.1021/ac504213qGoogle Scholar20https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhsF2ntLc%253D&md5=d3fd26c25e61daa65ea0912b209ded20Ion-Selective Optode Nanospheres as Heterogeneous Indicator Reagents in Complexometric TitrationsZhai, Jingying; Xie, Xiaojiang; Bakker, EricAnalytical Chemistry (Washington, DC, United States) (2015), 87 (5), 2827-2831CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)Traditionally, optical titrns. of inorg. ions are based on a rapid and visible color change at the end point with water-sol. org. dyes as indicators. Adequate selectivity is required for both the indicator and the complexing agent, which is often limited. The authors present here alternative, heterogeneous ionophore-based ion-selective nanospheres as indicators and chelators for optical titrns. The indicating nanospheres rely on a weaker extn. of the analyte of interest by ion-exchange, owing to the addnl. incorporation of a lipophilic pH indicator in the nanosphere core. Ca2+ titrn. was demonstrated as a proof-of-concept. Both the chelating and the indicating nanospheres showed good selectivity and a wide working pH range.
- 21Zhai, J.; Xie, X.; Bakker, E. Anion-exchange nanospheres as titration reagents for anionic analytes. Anal. Chem. 2015, 87 (16), 8347– 8352, DOI: 10.1021/acs.analchem.5b01530Google Scholar21https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXht1Srs7nI&md5=0ec43e32dd1195dfdeb82ccddd6f856dAnion-Exchange Nanospheres as Titration Reagents for Anionic AnalytesZhai, Jingying; Xie, Xiaojiang; Bakker, EricAnalytical Chemistry (Washington, DC, United States) (2015), 87 (16), 8347-8352CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)The authors present here anion-exchange nanospheres as novel titrn. reagents for anions. The nanospheres contain a lipophilic cation for which the counterion is initially Cl-. Ion exchange takes place between Cl- in the nanospheres and a more lipophilic anion in the sample, such as ClO4- and NO3-. Consecutive titrn. in the same sample soln. for ClO4- and NO3- were demonstrated. As an application, the concn. of NO3- in spinach was successfully detd. using this method.
- 22Zhai, J.; Xie, X.; Bakker, E. Solvatochromic dyes as pH-independent indicators for ionophore nanosphere-based complexometric titrations. Anal. Chem. 2015, 87 (24), 12318– 12323, DOI: 10.1021/acs.analchem.5b03663Google Scholar22https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhvV2rurfF&md5=c0f81464743a05a563c56f9ab945a509Solvatochromic Dyes as pH-Independent Indicators for Ionophore Nanosphere-Based Complexometric TitrationsZhai, Jingying; Xie, Xiaojiang; Bakker, EricAnalytical Chemistry (Washington, DC, United States) (2015), 87 (24), 12318-12323CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)For half a century, complexometric titrns. of metal ions have been performed with water-sol. chelators and indicators that typically require careful pH control. Very recently, ion-selective nanosphere emulsions were introduced that exhibit ion-exchange properties and are doped with lipophilic ionophores originally developed for chem. ion sensors. They may serve as novel, highly selective and pH independent complexometric reagents. While ion optode emulsions have been demonstrated as useful indicators for such titrns., they exhibit a pH cross-response that unfortunately complicates the identification of the end point. Here, we present pH-independent optode nanospheres as indicators for complexometric titrns., with calcium as an initial example. The nanospheres incorporate an ionic solvatochromic dye (SD), ion exchanger and ionophore. The solvatochromic dye will be only expelled from the core of the nanosphere into the aq. soln. at the end point at which point it results in an optical signal change. The titrn. curves are demonstrated to be pH-independent and with sharper end points than with previously reported chromoionophore-based optical nanospheres as indicator. The calcium concn. in mineral water was successfully detd. using this method.
- 23Xie, X.; Bakker, E. Determination of effective stability constants of ion-carrier complexes in ion selective nanospheres with charged solvatochromic dyes. Anal. Chem. 2015, 87 (22), 11587– 11591, DOI: 10.1021/acs.analchem.5b03526Google Scholar23https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhslSqu7nM&md5=26ca37df84ea5dea56cf42af086ea0efDetermination of Effective Stability Constants of Ion-Carrier Complexes in Ion Selective Nanospheres with Charged Solvatochromic DyesXie, Xiaojiang; Bakker, EricAnalytical Chemistry (Washington, DC, United States) (2015), 87 (22), 11587-11591CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)Ionophores are widely used ion carriers in ion selective sensors. The effective stability const. (β) is a key phys. parameter providing valuable guidelines to the design of ionophores and carrier-based ion selective sensors. The β value of ion-carrier complex in plasticized poly(vinyl chloride) (PVC) membranes and solns. have been detd. in the past by various techniques, but most of them are difficult to implement at the nanoscale owing to the ultrasmall sample vol. A new methodol. based on charged solvatochromic dyes is introduced here for the first time to det. β values directly within ion selective nanospheres. Four ionophores with different selectivities toward Na+, K+, Ca2+, and H+, resp., are successfully characterized in nanospheres composed of triblock copolymer Pluronic F-127 and bis(2-ethylhexyl) sebacate. The values detd. in the nanospheres are smaller compared with those in plasticized PVC membranes, indicating a more polar nanosphere microenvironment and possible uneven distribution of the sensing components in the interfacial region.
- 24Leong, Y. K.; Lan, J. C.-W.; Loh, H.-S.; Ling, T. C.; Ooi, C. W.; Show, P. L. Thermoseparating aqueous two-phase systems: recent trends and mechanisms. J. Sep. Sci. 2016, 39 (4), 640– 647, DOI: 10.1002/jssc.201500667Google Scholar24https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhs1elsLrE&md5=f1851d057c12f19bbdd0977439183a09Thermoseparating aqueous two-phase systems: Recent trends and mechanismsLeong, Yoong Kit; Lan, John Chi-Wei; Loh, Hwei-San; Ling, Tau Chuan; Ooi, Chien Wei; Show, Pau LokeJournal of Separation Science (2016), 39 (4), 640-647CODEN: JSSCCJ; ISSN:1615-9314. (Wiley-VCH Verlag GmbH & Co. KGaA)A review. Having the benefits of being environmentally friendly, providing a mild environment for biosepn., and scalability, aq. two-phase systems (ATPSs) have increasingly caught the attention of industry and researchers for their application in the isolation and recovery of bioproducts. The limitations of conventional ATPSs give rise to the development of temp.-induced ATPSs that have distinctive thermosepg. properties and easy recyclability. This review starts with a brief introduction to thermosepg. ATPSs, including its history, unique characteristics and advantages, and lastly, key factors that influence partitioning. The underlying mechanism of temp.-induced ATPSs is covered together with a summary of recent applications. Thermosepg. ATPSs have been proven as a soln. to the demand for economically favorable and environmentally friendly industrial-scale bioextn. and purifn. techniques.
- 25Buschmann, H.-J.; Mutihac, L. Complexation, liquid-liquid extraction, and transport through a liquid membrane of protonated peptides using crown ethers. Anal. Chim. Acta 2002, 466, 101– 108, DOI: 10.1016/S0003-2670(02)00513-5Google ScholarThere is no corresponding record for this reference.
- 26Wang, J.; Su, D.; Wang, D.; Ding, S.; Huang, C.; Huang, H.; Hu, X.; Wang, Z.; Li, S. Selective extraction of americium(III) over europium(III) with the pyridylpyrazole based tetradentate ligands: experimental and theoretical study. Inorg. Chem. 2015, 54, 10648– 10655, DOI: 10.1021/acs.inorgchem.5b01452Google Scholar26https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhslyqu7%252FO&md5=8f93c23ed9d98dd6d71ad21814632df4Selective Extraction of Americium(III) over Europium(III) with the Pyridylpyrazole Based Tetradentate Ligands: Experimental and Theoretical StudyWang, Jieru; Su, Dongping; Wang, Dongqi; Ding, Songdong; Huang, Chao; Huang, Huang; Hu, Xiaoyang; Wang, Zhipeng; Li, ShimengInorganic Chemistry (2015), 54 (22), 10648-10655CODEN: INOCAJ; ISSN:0020-1669. (American Chemical Society)1,3-Bis[3-(2-pyridyl)pyrazol-1-yl]propane (Bippp) and 1,2-bis[3-(2-pyridyl)pyrazyl-1-methyl]benzene (Dbnpp), the pyridylpyrazole based tetradentate ligands, were synthesized and characterized by MS, NMR, and FT-IR. The solvent extn. and complexation behaviors of Am(III) and Eu(III) with the ligands were investigated exptl. and theor. In the presence of 2-bromohexanoic acid, the two ligands can effectively ext. Am(III) over Eu(III) and other rare earth(III) metals (RE(III)) in HNO3 soln. with the sepn. factors (SFAm/RE) ranging from 15 to 60. Slope analyses showed that both Am(III) and Eu(III) were extd. as monosolvated species, which agrees well with the results obsd. from X-ray crystallog. and MS analyses. The stability consts. (log K) obtained from UV-vis titrn. for Eu(III) complexes with Bippp and Dbnpp are 4.75 ± 0.03 and 4.45 ± 0.04, resp. Both UV-vis titrn. and solvent extn. studies indicated that Bippp had stronger affinity for Eu(III) than Dbnpp, which is confirmed by d. functional theory (DFT) calcns. DFT calcns. revealed that the AmL(NO3)3 (L = Bippp and Dbnpp) complexes are thermodynamically more stable in water than their Eu(III) analogs, which is caused by greater covalency of the Am-N than Eu-N bonds. Theor. studies gave an insight into the nature of the M(III)-ligand bonding interactions.
- 27Soares, R. R. G.; Silva, D. F. C.; Fernandes, P.; Azevedo, A. M.; Chu, V.; Conde, J. P.; Aires-Barros, M. R. Miniaturization of aqueous two-phase extraction for biological applications: from micro-tubes to microchannels. Biotechnol. J. 2016, 11, 1498, DOI: 10.1002/biot.201600356Google Scholar27https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhsFSjtLzP&md5=2f4993fe6126158151b504f16cd333bbMiniaturization of aqueous two-phase extraction for biological applications: From micro-tubes to microchannelsSoares, Ruben R. G.; Silva, Daniel F. C.; Fernandes, Pedro; Azevedo, Ana M.; Chu, Virginia; Conde, Joao P.; Aires-Barros, M. RaquelBiotechnology Journal (2016), 11 (12), 1498-1512CODEN: BJIOAM; ISSN:1860-6768. (Wiley-VCH Verlag GmbH & Co. KGaA)Aq. two-phase extn. (ATPE) is a biocompatible liq.-liq. (L-L) sepn. technique that has been under research for several decades towards the purifn. of biomols., ranging from small metabolites to large animal cells. More recently, with the emergence of rapid-prototyping techniques for fabrication of microfluidic structures with intricate designs, ATPE gained an expanded range of applications utilizing phys. phenomena occurring exclusively at the microscale. Today, research is being carried simultaneously in two different vol. ranges, mL-scale (microtubes) and nL-scale (microchannels). The objective of this review is to give insight into the state of the art at both microtube and microchannel-scale and to analyze whether miniaturization is currently a competing or divergent technol. in a field of applications including biosepn., bioanalytics, enhanced fermn. processes, catalysis, high-throughput screening and phys./chem. compartmentalization. From our perspective, both approaches are worthy of investigation and, depending on the application, it is likely that either (i) one of the approaches will eventually become obsolete in particular research areas such as purifn. at the preparative scale or high-throughput screening applications; or (ii) both approaches will function as complementing techniques within the bioanalytics field.
- 28Tang, S.; Zhang, H.; Lee, H. K. Advances in sample extraction. Anal. Chem. 2016, 88, 228– 249, DOI: 10.1021/acs.analchem.5b04040Google Scholar28https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhvFWrsLfN&md5=8845bcaaea2d5984bd537f8f25ef8a81Advances in Sample ExtractionTang, Sheng; Zhang, Hong; Lee, Hian KeeAnalytical Chemistry (Washington, DC, United States) (2016), 88 (1), 228-249CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)Analyte or sample extn. is the most basic, yet a very important and dominant feature of any sample prepn. technique which in general can also include other processes such as pretreatment, cleanup, analyte enrichment, and derivatization (or any other reaction such as complexation). The main aim of sample extn. is to clean up, isolate and conc. the analytes of interest in a matrix, while rendering them in a form that is compatible with the instrument used for the subsequent anal. For this purpose, two classical sample prepn. methods, liq.-liq. extn. (LLE) (since ∼1870) and solid-phase extn. (SPE) (com. available since 1978), were popular choices throughout the years. Based on solvent- and sorbent-based approaches, various microscale extn. methods were developed and widely used in the past 25 years, such as solid-phase microextn. (SPME), various implementations of liq.-phase microextn. (LPME) including single-drop microextn., dispersive solid-phase extn. (DSPE), stir-bar sorptive extn. (SBSE) and microextn. by packed sorbent (MEPS). However, the practice of modern sample prepn. continues to evolve to address some key challenges, e.g., the preference, or sometimes necessity, for lower sample vols., consideration of more complex sample matrixes, and need for more rapid anal. To address these challenges, in recent years, researchers were designing and developing newer and innovative extn. methods, which usually employ new materials to handle emerging chems. Whereas most review articles have focused on a specific sub-field of sample extn. (e.g., development of new materials as sorbents, or specific methodologies, for instance, liq.-phase extn.), it is equally important and instructive to cover more wide-ranging developments to portray the bigger picture of the latest and emerging trends in sample extn.
- 29Sviben, I.; Galić, N.; Tomišić, V.; Frkanec, L. Extraction and complexation of alkali and alkaline earth metal cations by lower-rim calix[4]arene diethylene glycol amide derivatives. New J. Chem. 2015, 39, 6099– 6107, DOI: 10.1039/C5NJ00805KGoogle ScholarThere is no corresponding record for this reference.
- 30Elçin, S.; Deligöz, H. Synthesis and metal extraction studies of a novel chromogenic 5,17-bisazocalix[4]arenes. J. Inclusion Phenom. Macrocyclic Chem. 2014, 80 (3), 337– 343, DOI: 10.1007/s10847-014-0408-4Google ScholarThere is no corresponding record for this reference.
- 31Nacham, O.; Clark, K. D.; Anderson, J. L. Extraction and purification of DNA from complex biological sample matrices using solid-phase microextraction coupled with real-time PCR. Anal. Chem. 2016, 88, 7813– 7820, DOI: 10.1021/acs.analchem.6b01861Google Scholar31https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhtFSjurzN&md5=dda054d7af72a021a8489a9453d5ec00Extraction and Purification of DNA from Complex Biological Sample Matrices Using Solid-Phase Microextraction Coupled with Real-Time PCRNacham, Omprakash; Clark, Kevin D.; Anderson, Jared L.Analytical Chemistry (Washington, DC, United States) (2016), 88 (15), 7813-7820CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)The detn. of extremely small quantities of DNA from complex biol. sample matrixes represents a significant bottleneck in nucleic acid anal. In this study, polymeric ionic liq. (PIL)-based solid-phase microextn. (SPME) was applied for the extn. and purifn. of DNA from crude bacterial cell lysate with subsequent quantification by real-time PCR (qPCR) anal. Using an on-fiber UV initiated polymn. technique, eight different PIL sorbent coatings were generated and their DNA extn. performance evaluated using qPCR. The PIL sorbent coating featuring halide anions and carboxylic acid groups in the cationic portion exhibited superior DNA extn. capabilities when compared to the other studied PILs and a com. polyacrylate SPME fiber. Electrostatic interactions as well as an ion-exchange mechanism were identified as the driving forces in DNA extn. by the PIL sorbents. The selectivity of the PIL sorbent coating for DNA was demonstrated in the presence of PCR inhibitors at high concn., where a quantifiable amt. of template DNA was extd. from aq. samples contg. CaCl2 and FeCl3. Furthermore, the PIL-based SPME method was successfully applied for the extn. of DNA from crude bacterial cell lysate spiked with 1 pg mL-1 template DNA without requiring the use of org. solvents or centrifugation steps. Following PIL-based SPME of DNA from a dil. cell lysate, the qPCR amplification efficiency was detd. to be 100.3%, demonstrating the feasibility of the developed method to ext. high purity DNA from complex sample matrixes.
- 32He, Q.; Zhang, Z.; Brewster, J. T.; Lynch, V. M.; Kim, S. K.; Sessler, J. L. Hemispherand-strapped calix[4]pyrrole: an ion-pair receptor for the recognition and extraction of lithium nitrite. J. Am. Chem. Soc. 2016, 138, 9779– 9782, DOI: 10.1021/jacs.6b05713Google Scholar32https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28Xht1SktLnN&md5=57ed662d1cbbf79dcdb063b3f58e7d42Hemispherand-Strapped Calix[4]pyrrole: An Ion-pair Receptor for the Recognition and Extraction of Lithium NitriteHe, Qing; Zhang, Zhan; Brewster, James T.; Lynch, Vincent M.; Kim, Sung Kuk; Sessler, Jonathan L.Journal of the American Chemical Society (2016), 138 (31), 9779-9782CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)The hemispherand-strapped calix[4]pyrrole (1) acts as an ion pair receptor that exhibits selectivity for Li salts. In org. media (CD2Cl2 and CD3OD, vol./vol., 9:1), receptor 1 binds LiCl with high preference relative to NaCl, KCl, and RbCl. DFT calcns. provided support for the obsd. selectivity. Single crystal structures of five different Li ion-pair complexes of 1 were obtained. In the case of LiCl, a single bridging H2O mol. between the Li cation and chloride anion was obsd., while tight contact ion pairs were obsd. in the case of the LiBr, LiI, LiNO3, and LiNO2 salts. Receptor 1 proved effective as an extractant for LiNO2 under both model solid-liq. and liq.-liq. extn. conditions.
- 33Qin, Y.; Mi, Y.; Bakker, E. Determination of complex formation constants of 18 neutral alkali and alkaline earth metal ionophores in poly(vinyl chloride) sensing membranes plasticized with bis(2-ethylhexyl)sebacate and o-nitrophenyloctylether. Anal. Chim. Acta 2000, 421, 207– 220, DOI: 10.1016/S0003-2670(00)01038-2Google Scholar33https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3cXmtF2mu74%253D&md5=dda619a357a6d0dd2345f8c18c891e0cDetermination of complex formation constants of 18 neutral alkali and alkaline earth metal ionophores in poly(vinyl chloride) sensing membranes plasticized with bis(2-ethylhexyl)sebacate and o-nitrophenyloctyletherQin, Y.; Mi, Y.; Bakker, E.Analytica Chimica Acta (2000), 421 (2), 207-220CODEN: ACACAM; ISSN:0003-2670. (Elsevier Science B.V.)A segmented sandwich membrane method is used to det. complex formation consts. of 18 elec. neutral ionophores in situ in solvent polymeric sensing membranes. These ionophores are commonly used in potentiometric and optical sensors, and knowledge of such binding information is important for ionophore and sensor design. In this method, two membrane segments are fused together, with only one contg. the ionophore, to give a concn.-polarized sandwich membrane. Unlike other approaches, this method does not require the use of a ref. ion in the sample and/or a 2nd ionophore in the membrane, and is typically pH insensitive. The following ionophores responsive for the common cations lithium, sodium, potassium, magnesium and calcium are characterized and discussed: valinomycin, BME-44, bis[(benzo-15-crown-5)-4'-ylmethyl]pimelate, ETH 157, ETH 2120, bis[(12-crown-4)methyl]dodecylmethylmalonate, 4-tert-butylcalix [4] arene tetraacetic acid tetra-Et ester, ETH 149, ETH 1644, ETH 1810, 6,6-dibenzyl-14-crown-4, N,N,N',N',N'',N''-hexacyclohexyl-4,4',4''-propylidyne tris(3-oxabutyramide), ETH 1117, ETH 4030, ETH 1001, ETH 129, ETH 5234, and A23187. The logarithmic complex formation consts. range from 4.4 to 29 and compare well to published data for ionophores that were characterized earlier. From the obsd. complex formation consts., max. possible selectivities are calcd. that would be expected if interfering ions show no binding affinity to the ionophore, and the values are compared with exptl. findings. Each ionophore is characterized in poly(vinyl chloride) membranes plasticized either with a polar (NPOE) or a nonpolar plasticizer (DOS). Membranes based on NPOE always show larger complex formation consts. of the embedded ionophore.
- 34Bakker, E.; Willer, M.; Lerchi, M.; Seiler, K.; Pretsch, E. Determination of complex formation constants of neutral cation-selective ionophores in solvent polymeric membranes. Anal. Chem. 1994, 66, 516– 521, DOI: 10.1021/ac00076a016Google Scholar34https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2cXltFyktrs%253D&md5=742e06bb5ef87bf8a1ec418235447ba6Determination of complex formation constants of neutral cation-selective ionophores in solvent polymeric membranesBakker, Eric; Willer, Michael; Lerchi, Markus; Seiler, Kurt; Pretsch, ErnoeAnalytical Chemistry (1994), 66 (4), 516-21CODEN: ANCHAM; ISSN:0003-2700.Formal complex formation consts. between lipophilic ligands and cations have been detd. within the solvent polymeric membrane phase. The method is based on spectrophotometric measurements on a 1-2-μm thin membrane phase (optode) contg. a H+-selective chromoionophore. Ion exchange equil. between the membrane and the aq. phase are traced for membranes with and without ionophore. A theor. discussion is given as well as exptl. results with the ionophores valinomycin and BME-44 (for K+), ETH 4120 (for Na+), ETH 1001 and ETH 129 (for Ca2+), and ETH 7025 (for Mg2+). Complexes with various stoichiometries are formed for the Mg2+ and Ca2+ complexes of ETH 7025, which make the realization of a selective magnesium optode with this ionophore not possible. With this novel method, the key parameters detg. the performance of ionophore-based ion-selective optodes and electrodes become directly accessible.
- 35Bakker, E. Selectivity comparison of neutral carrier-based ion-selective optical and potentiometric sensing schemes. Anal. Chim. Acta 1997, 350, 329– 340, DOI: 10.1016/S0003-2670(97)00218-3Google ScholarThere is no corresponding record for this reference.
- 36Wang, X.; Qin, Y.; Meyerhoff, M. E. Paper-based plasticizer-free sodium ion-selective sensor with camera phone as a detector. Chem. Commun. 2015, 51, 15176– 15179, DOI: 10.1039/C5CC06770GGoogle Scholar36https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhsVSnsL3J&md5=c18275a7e7a8e27d201ea5e59d8d0660Paper-based plasticizer-free sodium ion-selective sensor with camera phone as a detectorWang, Xuewei; Qin, Yu; Meyerhoff, Mark E.Chemical Communications (Cambridge, United Kingdom) (2015), 51 (82), 15176-15179CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)An ionophore-based ion-selective optode platform on paper is described for the 1st time with a sodium optode as the example. Cellulose paper is an excellent substrate for adsorption of the required chromoionophore, ionophore, and ion-exchanger species. These adsorbed components form a hydrophobic phase that enables heterogeneous optical ion sensing in the absence of any plasticizer or org. polymer phase.
- 37Cantrell, K.; Erenas, M. M.; Orbe-Payá, I. d.; Capitán-Vallvey, L. F. Use of the hue parameter of the hue, saturation, value color space as a quantitative analytical parameter for bitonal optical sensors. Anal. Chem. 2010, 82 (2), 531– 542, DOI: 10.1021/ac901753cGoogle Scholar37https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXhsFGkurvI&md5=9573668c8ffbfeb623151ad29f8e82baUse of the Hue Parameter of the Hue, Saturation, Value Color Space As a Quantitative Analytical Parameter for Bitonal Optical SensorsCantrell, K.; Erenas, M. M.; de Orbe-Paya, I.; Capitan-Vallvey, L. F.Analytical Chemistry (Washington, DC, United States) (2010), 82 (2), 531-542CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)The hue or H component of the hue, satn., value (HSV) color space was studied as a quant. anal. parameter for bitonal optical sensors. The robust nature of this parameter provides superior precision for the measurement of sensors which change colors with the speciation of some indicator mol. This parameter was compared to red, green, blue (RGB) intensity and RGB absorbance along with differences and ratios of both intensity and absorbance and is 2 to 3 times superior. The H value maintains this superior precision with variations in indicator concn., membrane thickness, detector spectral responsivity, and illumination. Because this parameter is stable, simple to calc., easily obtained from com. devices such as scanners and digital cameras, continuous over the entire color gamut, and bound between values of 0 and 1, it shows great promise for use in a variety of sensing applications including imaging, automated anal., pharmaceutical sensing, lab-on-a-chip devices, and quality control applications.
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Abstract
Scheme 1
Scheme 1. Working Principle of the Solvent Based Titration Reagentsaa(a) Before end point. (b) After end point.
Figure 1
Figure 1. Optical reverse titration curves (a, b, c) and corresponding absorption spectra (d, e, f) for K+, Na+, and Li+, respectively. Titrant: 10–2 M KCl or NaCl or LiCl. The dashed vertical lines indicate the expected end point. Buffer solution: 10–2 M Tris-HCl pH 7.0 for K+ titration; 10–2 M Tris-HCl pH 7.4 for Na+ and Li+ titration. Absorption spectra recorded at each titration point.
Figure 2
Figure 2. Response of the K+ (a), Na+ (b), and Li+ (c) selective reagents to various interfering ions, respectively. Buffer solution: (a)10–2 M Tris-HCl pH 7.0, (b,c) 10–2 M Tris-HCl pH 7.4. The horizontal distance between the calibration curve for primary ion and any interfering ions represents log K1.
Figure 3
Figure 3. Pictures of the K+ titration process after shaking (a) and after two phases separated (b) and the corresponding titration curves (c) and (d) based on the HSV analysis. The dashed vertical lines indicate the expected end points. Buffer solution: 10–2 M Tris-HCl pH 7.0.
Figure 4
Figure 4. Setup of the automated titration: (a) before titration, (b) after the end point. (c) Titration analysis for K+ based on the hue signals retrieved from the frames in the video. (d) Serum titration based on the hue signals retrieved from the frames in the video. Organic phase: K+ selective titration reagent. Aqueous phase: 10–2 M Tris-HCl pH 7.0 buffer solution. The volume of the added serum at the end point is Vserum = 73 μL.
References
This article references 37 other publications.
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- 4Zhang, S.; Zhang, R.; Ma, B.; Qiu, J.; Li, J.; Sang, Y.; Liu, W.; Liu, H. Specific detection of potassium ion in serum by a modified G-Quadruplex method. RSC Adv. 2016, 6, 41999– 42007, DOI: 10.1039/C6RA04046B4https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XmsF2gs7s%253D&md5=58406e10f76fbc7f981c88032d40759dSpecific detection of potassium ion in serum by a modified G-quadruplex methodZhang, Shan; Zhang, Ruibin; Ma, Baojin; Qiu, Jichuan; Li, Jianhua; Sang, Yuanhua; Liu, Wei; Liu, HongRSC Advances (2016), 6 (48), 41999-42007CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)Potassium ion (K+) plays a central role in several fundamental physiol. processes. Detection of the K+ concn. is an essential diagnostic tool for various medical diseases. However, most com. detection methods are complex and expensive, which are not easily implemented in community hospitals or at home, in this study, we present a simple fluorescent K+ detection system based on the formation of G-quadruplex between K+ and dual-labeled thrombin aptamer oligonucleotide deriv. (5prime-FAM-TTTTTTAGGTTGGTGTGGTTGG-TAMRA-3prime). Furthermore, based on this method, highly sensitive and selective detection of K+ in actual serum was realized by using EDTA as chelating agent to avoid the interference of Ca2+ and Mg2+ at physiol. concns. Thus, this study paves the road toward the design and manuf. of portable potassium ions sensors based on fluorescence.
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- 9Moody, G. J.; Saad, B. B.; Thomas, J. D. R. Studies on bis(crown ether)-based ion-selective electrodes for the potentiometric determination of sodium and potassium in serum. Analyst 1989, 114, 15– 20, DOI: 10.1039/an98914000159https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL1MXhtlWms7Y%253D&md5=97e4d2ac5a1626abc2f35d46ef1f7321Studies on bis(crown ether)-based ion-selective electrodes for the potentiometric determination of sodium and potassium in serumMoody, G. J.; Saad, Bahruddin B.; Thomas, J. D. R.Analyst (Cambridge, United Kingdom) (1989), 114 (1), 15-20CODEN: ANALAO; ISSN:0003-2654.Bis(crown ether)-based ion-selective electrodes for sodium and potassium are described, based on the bis[(12-crown-4)-2-ylmethyl]-2-dodecyl-2-methyl malonate sensor (I) for sodium and the bis[(benzo-15-crown-5)-15-ylmethyl] pimelate sensor (II) for potassium. The best results were obtained when the sensors were used in assocn. with 2-nitrophenyl octyl ether as plasticizing solvent mediator and potassium tetrakis(4-chlorophenyl)borate as anion excluder in poly(vinyl chloride) matrixes. Electrode slopes were near-Nernstian, with detection limits of <10-5M. The electrode features are compared with those of a sodium glass membrane electrode, for sensor I, and with a valinomycin-based potassium electrode, for sensor II. The electrodes are also discussed in relation to others reported for sensors I and II and are shown to be superior. However, although the electrodes described offer promising alternatives to glass electrodes for sodium and valinomycin electrodes for potassium, data for sodium and potassium measurements in blood serum indicate a need for further research to improve the correlation with flame photometric measurements.
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- 12Roy, N.; Nath, S.; Dutta, A.; Mondal, P.; Paul, P. C.; Singh, T. S. A highly efficient and selective coumarin based fluorescent probe for colorimetric detection of Fe3+ and fluorescence dual sensing of Zn2+ and Cu2+. RSC Adv. 2016, 6, 63837– 63847, DOI: 10.1039/C6RA12217E12https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhtVOnt73K&md5=15d60db896cd86de84884bae4025ac55A highly efficient and selective coumarin based fluorescent probe for colorimetric detection of Fe3+ and fluorescence dual sensing of Zn2+ and Cu2+Roy, Nayan; Nath, Surjatapa; Dutta, Abhijit; Mondal, Paritosh; Paul, Pradip C.; Singh, T. SanjoyRSC Advances (2016), 6 (68), 63837-63847CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)A new coumarin based Schiff-base chemosensor, (E)-7-(((8-hydroxyquinoline-2-yl)methylene)amino)-4-(trifluoromethyl)-2H-chromen-2-one (H12L) was designed and synthesized. This chemosensor was evaluated as a colorimetric sensor for Fe3+ and fluorescence "turn on-off" response to Zn2+ and Cu2+ using steady-state absorption and fluorescence spectroscopy. In the presence of Fe3+ and Zn2+, the absorption intensity as well as the fluorescence emission intensity increases drastically compared to other surveyed metal ions, with a distinct color change which provides naked eye detection. However, in the presence of Cu2+, it also exhibits quenching of fluorescence emission intensity which may be due to the paramagnetic nature of Cu2+ ions. The stoichiometric ratio and binding const. were calcd. using the Benesi-Hildebrand relation and Job's plot analyses, giving 1 : 1 stoichiometry. The interaction and binding nature of H12L with Zn2+ ions was further confirmed by 1H NMR titrn. assay and ESI-mass spectral anal. The reversibility of H12L was also studied using EDTA as a chelating ligand. Moreover, H12L exhibits two INHIBIT logic gates with two different chem. inputs (i) Zn2+ (IN1) and Cu2+ (IN2) and (ii) Zn2+ (IN1) and EDTA (IN2) and the emission as output. Again, an IMPLICATION logic gate is obtained with Cu2+ and EDTA as chem. inputs and emission as the output mode. Both H12L and metal-complexes were optimized using d. functional theory and vibrational frequency calcns. confirm that both are at local min. on the potential energy surfaces. The corresponding energy difference between the HOMOs and LUMOs of H12L, Zn-complex and Cu-complex are found to be 2.11, 0.81 and 0.17 eV, resp.
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- 14Bian, X.; Lockless, S. W. Preparation to minimize buffer mismatch in isothermal titration calorimetry experiments. Anal. Chem. 2016, 88 (10), 5549– 5553, DOI: 10.1021/acs.analchem.6b0131914https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28Xmt12msb0%253D&md5=87a3bee6d02164f8fe8d15499339fa79Preparation To Minimize Buffer Mismatch in Isothermal Titration Calorimetry ExperimentsBian, Xuelin; Lockless, Steve W.Analytical Chemistry (Washington, DC, United States) (2016), 88 (10), 5549-5553CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)There is a growing need to study ligand binding to proteins in native or complex soln. using isothermal titrn. calorimetry (ITC). For example, it is desirable to measure ligand binding to membrane proteins in more native lipid-like environments such as bicelles, where ligands can access both sides of the membrane in a homogeneous environment. A crit. step to obtain high signal-to-noise is matching the reaction chamber soln. to the ligand soln., typically through a final dialysis or gel filtration step. However, to obtain reproducible bicelles, the lipid concns. must be carefully controlled which eliminates the use of dialysis that can disrupt these parameters. Here, we report and validate a rapid prepn. ITC (RP-ITC) approach to measure ligand binding without the need for a dialysis step. This general approach is used to quantify ion binding to a K+ channel embedded in bicelles and can be applied to complex, less defined systems.
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- 17Männel-Croisé, C.; Meister, C.; Zelder, F. ″Naked-Eye″ screening of metal-based chemosensors for biologically important anions. Inorg. Chem. 2010, 49 (22), 10220– 10222, DOI: 10.1021/ic1015115There is no corresponding record for this reference.
- 18Swain, B. Recovery and recycling of lithium: A review. Sep. Purif. Technol. 2017, 172, 388– 403, DOI: 10.1016/j.seppur.2016.08.03118https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhsVOiu7jO&md5=a13a324ed0f98f6cd0e5886e0b9c2acaRecovery and recycling of lithium: A reviewSwain, BasudevSeparation and Purification Technology (2017), 172 (), 388-403CODEN: SPUTFP; ISSN:1383-5866. (Elsevier B.V.)A review. Projected demands for lithium as LIB for the plug-in hybrid elec. (PHEV), elec. (EV) and hybrid elec. (HEV) vehicle in the recent future is huge and estd. to reach $221 billion by 2024. Currently, 35% of global lithium prodn. being used for LIBs and consumption for estd. LIB demand could be 66% (out of global lithium prodn.) by 2025. During last five (2011-2015) years, global lithium prodn. is almost const. At present, up to 3% of LIBs are recycled with the only focus of valuable metal recovery, but motivation on lithium recovery almost nonexistence. The global rate of lithium recycling is only < 1%. Considering the current global lithium prodn. with respect to projected demand, environment and regulation, green energy and energy security, cradle-to-cradle technol. management and circular economy of crit. metal and minimization of waste crime and maximization of the urban mining, recovery and recycling status of lithium should be well understood. In this review recovery of lithium from various resources such as different ores, clay, brine, seawater and recycling of battery by different technique are reviewed. Lithium recovery from various primary resources and its sepn. purifn. by different routes such as hydrometallurgy, pyro-metallurgy, chem. metallurgy, and bioleaching are discussed. Lithium recovery through chem. leaching, bioleaching, and floatation of different ores also thoroughly reviewed. The extn. of lithium from seawater by co-pptn. and extn., ion-exchange and sorption by using various org., inorg. and composite polymer sorbents has been discussed thoroughly. Although, several industries recovering lithium from primary resources, but lithium recovery from secondary resources almost non-existence. The non-existence of lithium recovery process from LIB or techno-economically inefficient process is a greater challenge for the projected lithium demand. As the cradle-to-grave technol. is a sustainability challenge, cradle-to-cradle technol. management could be achieved through efficient recycling. Hence, techno-economically feasible, environment-friendly and sustainable process needs to be developed and recommended. Considering technol. advantages of hydrometallurgy process like; smaller scale, minimal energy investment, minimal CO2 emission, and the plant can be designed based on available waste, lithium recovery by hydrometallurgy should be focused.
- 19Zhai, J.; Xie, X.; Bakker, E. Ionophore-based ion-exchange emulsions as novel class of complexometric titration reagents. Chem. Commun. 2014, 50, 12659– 12661, DOI: 10.1039/C4CC05754F19https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhsVyhtLzE&md5=bff9c778b3d99c918d05af744a5a6dccIonophore-based ion-exchange emulsions as novel class of complexometric titration reagentsZhai, Jingying; Xie, Xiaojiang; Bakker, EricChemical Communications (Cambridge, United Kingdom) (2014), 50 (84), 12659-12661CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)Complexometric titrns. rely on a drastic change of the pM value at the equivalence point with a water sol. chelator forming typically 1 : 1 complexes of high stability. The available chem. toolbox of suitable chelating compds. is unfortunately limited because many promising complexing agents are not water sol. The authors introduce here a novel class of complexometric titrn. reagents, a suspension of polymeric nanospheres whose hydrophobic core is doped with lipophilic ion-exchanger and a selective complexing agent (ionophore). The emulsified nanospheres behave from heterogeneous ion exchange equil. where the initial counterion of the ion-exchanger is readily displaced from the emulsion for the target ion that forms a stable complex in the nanosphere core. Two different examples are shown with Ca2+ and Pb2+ as target ions. The lack of protonatable groups on the calcium receptor allows one to perform Ca2+ titrn. without pH control.
- 20Zhai, J.; Xie, X.; Bakker, E. Ion-Selective optode nanospheres as heterogeneous indicator reagents in complexometric titrations. Anal. Chem. 2015, 87 (5), 2827– 2831, DOI: 10.1021/ac504213q20https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhsF2ntLc%253D&md5=d3fd26c25e61daa65ea0912b209ded20Ion-Selective Optode Nanospheres as Heterogeneous Indicator Reagents in Complexometric TitrationsZhai, Jingying; Xie, Xiaojiang; Bakker, EricAnalytical Chemistry (Washington, DC, United States) (2015), 87 (5), 2827-2831CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)Traditionally, optical titrns. of inorg. ions are based on a rapid and visible color change at the end point with water-sol. org. dyes as indicators. Adequate selectivity is required for both the indicator and the complexing agent, which is often limited. The authors present here alternative, heterogeneous ionophore-based ion-selective nanospheres as indicators and chelators for optical titrns. The indicating nanospheres rely on a weaker extn. of the analyte of interest by ion-exchange, owing to the addnl. incorporation of a lipophilic pH indicator in the nanosphere core. Ca2+ titrn. was demonstrated as a proof-of-concept. Both the chelating and the indicating nanospheres showed good selectivity and a wide working pH range.
- 21Zhai, J.; Xie, X.; Bakker, E. Anion-exchange nanospheres as titration reagents for anionic analytes. Anal. Chem. 2015, 87 (16), 8347– 8352, DOI: 10.1021/acs.analchem.5b0153021https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXht1Srs7nI&md5=0ec43e32dd1195dfdeb82ccddd6f856dAnion-Exchange Nanospheres as Titration Reagents for Anionic AnalytesZhai, Jingying; Xie, Xiaojiang; Bakker, EricAnalytical Chemistry (Washington, DC, United States) (2015), 87 (16), 8347-8352CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)The authors present here anion-exchange nanospheres as novel titrn. reagents for anions. The nanospheres contain a lipophilic cation for which the counterion is initially Cl-. Ion exchange takes place between Cl- in the nanospheres and a more lipophilic anion in the sample, such as ClO4- and NO3-. Consecutive titrn. in the same sample soln. for ClO4- and NO3- were demonstrated. As an application, the concn. of NO3- in spinach was successfully detd. using this method.
- 22Zhai, J.; Xie, X.; Bakker, E. Solvatochromic dyes as pH-independent indicators for ionophore nanosphere-based complexometric titrations. Anal. Chem. 2015, 87 (24), 12318– 12323, DOI: 10.1021/acs.analchem.5b0366322https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhvV2rurfF&md5=c0f81464743a05a563c56f9ab945a509Solvatochromic Dyes as pH-Independent Indicators for Ionophore Nanosphere-Based Complexometric TitrationsZhai, Jingying; Xie, Xiaojiang; Bakker, EricAnalytical Chemistry (Washington, DC, United States) (2015), 87 (24), 12318-12323CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)For half a century, complexometric titrns. of metal ions have been performed with water-sol. chelators and indicators that typically require careful pH control. Very recently, ion-selective nanosphere emulsions were introduced that exhibit ion-exchange properties and are doped with lipophilic ionophores originally developed for chem. ion sensors. They may serve as novel, highly selective and pH independent complexometric reagents. While ion optode emulsions have been demonstrated as useful indicators for such titrns., they exhibit a pH cross-response that unfortunately complicates the identification of the end point. Here, we present pH-independent optode nanospheres as indicators for complexometric titrns., with calcium as an initial example. The nanospheres incorporate an ionic solvatochromic dye (SD), ion exchanger and ionophore. The solvatochromic dye will be only expelled from the core of the nanosphere into the aq. soln. at the end point at which point it results in an optical signal change. The titrn. curves are demonstrated to be pH-independent and with sharper end points than with previously reported chromoionophore-based optical nanospheres as indicator. The calcium concn. in mineral water was successfully detd. using this method.
- 23Xie, X.; Bakker, E. Determination of effective stability constants of ion-carrier complexes in ion selective nanospheres with charged solvatochromic dyes. Anal. Chem. 2015, 87 (22), 11587– 11591, DOI: 10.1021/acs.analchem.5b0352623https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhslSqu7nM&md5=26ca37df84ea5dea56cf42af086ea0efDetermination of Effective Stability Constants of Ion-Carrier Complexes in Ion Selective Nanospheres with Charged Solvatochromic DyesXie, Xiaojiang; Bakker, EricAnalytical Chemistry (Washington, DC, United States) (2015), 87 (22), 11587-11591CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)Ionophores are widely used ion carriers in ion selective sensors. The effective stability const. (β) is a key phys. parameter providing valuable guidelines to the design of ionophores and carrier-based ion selective sensors. The β value of ion-carrier complex in plasticized poly(vinyl chloride) (PVC) membranes and solns. have been detd. in the past by various techniques, but most of them are difficult to implement at the nanoscale owing to the ultrasmall sample vol. A new methodol. based on charged solvatochromic dyes is introduced here for the first time to det. β values directly within ion selective nanospheres. Four ionophores with different selectivities toward Na+, K+, Ca2+, and H+, resp., are successfully characterized in nanospheres composed of triblock copolymer Pluronic F-127 and bis(2-ethylhexyl) sebacate. The values detd. in the nanospheres are smaller compared with those in plasticized PVC membranes, indicating a more polar nanosphere microenvironment and possible uneven distribution of the sensing components in the interfacial region.
- 24Leong, Y. K.; Lan, J. C.-W.; Loh, H.-S.; Ling, T. C.; Ooi, C. W.; Show, P. L. Thermoseparating aqueous two-phase systems: recent trends and mechanisms. J. Sep. Sci. 2016, 39 (4), 640– 647, DOI: 10.1002/jssc.20150066724https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhs1elsLrE&md5=f1851d057c12f19bbdd0977439183a09Thermoseparating aqueous two-phase systems: Recent trends and mechanismsLeong, Yoong Kit; Lan, John Chi-Wei; Loh, Hwei-San; Ling, Tau Chuan; Ooi, Chien Wei; Show, Pau LokeJournal of Separation Science (2016), 39 (4), 640-647CODEN: JSSCCJ; ISSN:1615-9314. (Wiley-VCH Verlag GmbH & Co. KGaA)A review. Having the benefits of being environmentally friendly, providing a mild environment for biosepn., and scalability, aq. two-phase systems (ATPSs) have increasingly caught the attention of industry and researchers for their application in the isolation and recovery of bioproducts. The limitations of conventional ATPSs give rise to the development of temp.-induced ATPSs that have distinctive thermosepg. properties and easy recyclability. This review starts with a brief introduction to thermosepg. ATPSs, including its history, unique characteristics and advantages, and lastly, key factors that influence partitioning. The underlying mechanism of temp.-induced ATPSs is covered together with a summary of recent applications. Thermosepg. ATPSs have been proven as a soln. to the demand for economically favorable and environmentally friendly industrial-scale bioextn. and purifn. techniques.
- 25Buschmann, H.-J.; Mutihac, L. Complexation, liquid-liquid extraction, and transport through a liquid membrane of protonated peptides using crown ethers. Anal. Chim. Acta 2002, 466, 101– 108, DOI: 10.1016/S0003-2670(02)00513-5There is no corresponding record for this reference.
- 26Wang, J.; Su, D.; Wang, D.; Ding, S.; Huang, C.; Huang, H.; Hu, X.; Wang, Z.; Li, S. Selective extraction of americium(III) over europium(III) with the pyridylpyrazole based tetradentate ligands: experimental and theoretical study. Inorg. Chem. 2015, 54, 10648– 10655, DOI: 10.1021/acs.inorgchem.5b0145226https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhslyqu7%252FO&md5=8f93c23ed9d98dd6d71ad21814632df4Selective Extraction of Americium(III) over Europium(III) with the Pyridylpyrazole Based Tetradentate Ligands: Experimental and Theoretical StudyWang, Jieru; Su, Dongping; Wang, Dongqi; Ding, Songdong; Huang, Chao; Huang, Huang; Hu, Xiaoyang; Wang, Zhipeng; Li, ShimengInorganic Chemistry (2015), 54 (22), 10648-10655CODEN: INOCAJ; ISSN:0020-1669. (American Chemical Society)1,3-Bis[3-(2-pyridyl)pyrazol-1-yl]propane (Bippp) and 1,2-bis[3-(2-pyridyl)pyrazyl-1-methyl]benzene (Dbnpp), the pyridylpyrazole based tetradentate ligands, were synthesized and characterized by MS, NMR, and FT-IR. The solvent extn. and complexation behaviors of Am(III) and Eu(III) with the ligands were investigated exptl. and theor. In the presence of 2-bromohexanoic acid, the two ligands can effectively ext. Am(III) over Eu(III) and other rare earth(III) metals (RE(III)) in HNO3 soln. with the sepn. factors (SFAm/RE) ranging from 15 to 60. Slope analyses showed that both Am(III) and Eu(III) were extd. as monosolvated species, which agrees well with the results obsd. from X-ray crystallog. and MS analyses. The stability consts. (log K) obtained from UV-vis titrn. for Eu(III) complexes with Bippp and Dbnpp are 4.75 ± 0.03 and 4.45 ± 0.04, resp. Both UV-vis titrn. and solvent extn. studies indicated that Bippp had stronger affinity for Eu(III) than Dbnpp, which is confirmed by d. functional theory (DFT) calcns. DFT calcns. revealed that the AmL(NO3)3 (L = Bippp and Dbnpp) complexes are thermodynamically more stable in water than their Eu(III) analogs, which is caused by greater covalency of the Am-N than Eu-N bonds. Theor. studies gave an insight into the nature of the M(III)-ligand bonding interactions.
- 27Soares, R. R. G.; Silva, D. F. C.; Fernandes, P.; Azevedo, A. M.; Chu, V.; Conde, J. P.; Aires-Barros, M. R. Miniaturization of aqueous two-phase extraction for biological applications: from micro-tubes to microchannels. Biotechnol. J. 2016, 11, 1498, DOI: 10.1002/biot.20160035627https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhsFSjtLzP&md5=2f4993fe6126158151b504f16cd333bbMiniaturization of aqueous two-phase extraction for biological applications: From micro-tubes to microchannelsSoares, Ruben R. G.; Silva, Daniel F. C.; Fernandes, Pedro; Azevedo, Ana M.; Chu, Virginia; Conde, Joao P.; Aires-Barros, M. RaquelBiotechnology Journal (2016), 11 (12), 1498-1512CODEN: BJIOAM; ISSN:1860-6768. (Wiley-VCH Verlag GmbH & Co. KGaA)Aq. two-phase extn. (ATPE) is a biocompatible liq.-liq. (L-L) sepn. technique that has been under research for several decades towards the purifn. of biomols., ranging from small metabolites to large animal cells. More recently, with the emergence of rapid-prototyping techniques for fabrication of microfluidic structures with intricate designs, ATPE gained an expanded range of applications utilizing phys. phenomena occurring exclusively at the microscale. Today, research is being carried simultaneously in two different vol. ranges, mL-scale (microtubes) and nL-scale (microchannels). The objective of this review is to give insight into the state of the art at both microtube and microchannel-scale and to analyze whether miniaturization is currently a competing or divergent technol. in a field of applications including biosepn., bioanalytics, enhanced fermn. processes, catalysis, high-throughput screening and phys./chem. compartmentalization. From our perspective, both approaches are worthy of investigation and, depending on the application, it is likely that either (i) one of the approaches will eventually become obsolete in particular research areas such as purifn. at the preparative scale or high-throughput screening applications; or (ii) both approaches will function as complementing techniques within the bioanalytics field.
- 28Tang, S.; Zhang, H.; Lee, H. K. Advances in sample extraction. Anal. Chem. 2016, 88, 228– 249, DOI: 10.1021/acs.analchem.5b0404028https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhvFWrsLfN&md5=8845bcaaea2d5984bd537f8f25ef8a81Advances in Sample ExtractionTang, Sheng; Zhang, Hong; Lee, Hian KeeAnalytical Chemistry (Washington, DC, United States) (2016), 88 (1), 228-249CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)Analyte or sample extn. is the most basic, yet a very important and dominant feature of any sample prepn. technique which in general can also include other processes such as pretreatment, cleanup, analyte enrichment, and derivatization (or any other reaction such as complexation). The main aim of sample extn. is to clean up, isolate and conc. the analytes of interest in a matrix, while rendering them in a form that is compatible with the instrument used for the subsequent anal. For this purpose, two classical sample prepn. methods, liq.-liq. extn. (LLE) (since ∼1870) and solid-phase extn. (SPE) (com. available since 1978), were popular choices throughout the years. Based on solvent- and sorbent-based approaches, various microscale extn. methods were developed and widely used in the past 25 years, such as solid-phase microextn. (SPME), various implementations of liq.-phase microextn. (LPME) including single-drop microextn., dispersive solid-phase extn. (DSPE), stir-bar sorptive extn. (SBSE) and microextn. by packed sorbent (MEPS). However, the practice of modern sample prepn. continues to evolve to address some key challenges, e.g., the preference, or sometimes necessity, for lower sample vols., consideration of more complex sample matrixes, and need for more rapid anal. To address these challenges, in recent years, researchers were designing and developing newer and innovative extn. methods, which usually employ new materials to handle emerging chems. Whereas most review articles have focused on a specific sub-field of sample extn. (e.g., development of new materials as sorbents, or specific methodologies, for instance, liq.-phase extn.), it is equally important and instructive to cover more wide-ranging developments to portray the bigger picture of the latest and emerging trends in sample extn.
- 29Sviben, I.; Galić, N.; Tomišić, V.; Frkanec, L. Extraction and complexation of alkali and alkaline earth metal cations by lower-rim calix[4]arene diethylene glycol amide derivatives. New J. Chem. 2015, 39, 6099– 6107, DOI: 10.1039/C5NJ00805KThere is no corresponding record for this reference.
- 30Elçin, S.; Deligöz, H. Synthesis and metal extraction studies of a novel chromogenic 5,17-bisazocalix[4]arenes. J. Inclusion Phenom. Macrocyclic Chem. 2014, 80 (3), 337– 343, DOI: 10.1007/s10847-014-0408-4There is no corresponding record for this reference.
- 31Nacham, O.; Clark, K. D.; Anderson, J. L. Extraction and purification of DNA from complex biological sample matrices using solid-phase microextraction coupled with real-time PCR. Anal. Chem. 2016, 88, 7813– 7820, DOI: 10.1021/acs.analchem.6b0186131https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhtFSjurzN&md5=dda054d7af72a021a8489a9453d5ec00Extraction and Purification of DNA from Complex Biological Sample Matrices Using Solid-Phase Microextraction Coupled with Real-Time PCRNacham, Omprakash; Clark, Kevin D.; Anderson, Jared L.Analytical Chemistry (Washington, DC, United States) (2016), 88 (15), 7813-7820CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)The detn. of extremely small quantities of DNA from complex biol. sample matrixes represents a significant bottleneck in nucleic acid anal. In this study, polymeric ionic liq. (PIL)-based solid-phase microextn. (SPME) was applied for the extn. and purifn. of DNA from crude bacterial cell lysate with subsequent quantification by real-time PCR (qPCR) anal. Using an on-fiber UV initiated polymn. technique, eight different PIL sorbent coatings were generated and their DNA extn. performance evaluated using qPCR. The PIL sorbent coating featuring halide anions and carboxylic acid groups in the cationic portion exhibited superior DNA extn. capabilities when compared to the other studied PILs and a com. polyacrylate SPME fiber. Electrostatic interactions as well as an ion-exchange mechanism were identified as the driving forces in DNA extn. by the PIL sorbents. The selectivity of the PIL sorbent coating for DNA was demonstrated in the presence of PCR inhibitors at high concn., where a quantifiable amt. of template DNA was extd. from aq. samples contg. CaCl2 and FeCl3. Furthermore, the PIL-based SPME method was successfully applied for the extn. of DNA from crude bacterial cell lysate spiked with 1 pg mL-1 template DNA without requiring the use of org. solvents or centrifugation steps. Following PIL-based SPME of DNA from a dil. cell lysate, the qPCR amplification efficiency was detd. to be 100.3%, demonstrating the feasibility of the developed method to ext. high purity DNA from complex sample matrixes.
- 32He, Q.; Zhang, Z.; Brewster, J. T.; Lynch, V. M.; Kim, S. K.; Sessler, J. L. Hemispherand-strapped calix[4]pyrrole: an ion-pair receptor for the recognition and extraction of lithium nitrite. J. Am. Chem. Soc. 2016, 138, 9779– 9782, DOI: 10.1021/jacs.6b0571332https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28Xht1SktLnN&md5=57ed662d1cbbf79dcdb063b3f58e7d42Hemispherand-Strapped Calix[4]pyrrole: An Ion-pair Receptor for the Recognition and Extraction of Lithium NitriteHe, Qing; Zhang, Zhan; Brewster, James T.; Lynch, Vincent M.; Kim, Sung Kuk; Sessler, Jonathan L.Journal of the American Chemical Society (2016), 138 (31), 9779-9782CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)The hemispherand-strapped calix[4]pyrrole (1) acts as an ion pair receptor that exhibits selectivity for Li salts. In org. media (CD2Cl2 and CD3OD, vol./vol., 9:1), receptor 1 binds LiCl with high preference relative to NaCl, KCl, and RbCl. DFT calcns. provided support for the obsd. selectivity. Single crystal structures of five different Li ion-pair complexes of 1 were obtained. In the case of LiCl, a single bridging H2O mol. between the Li cation and chloride anion was obsd., while tight contact ion pairs were obsd. in the case of the LiBr, LiI, LiNO3, and LiNO2 salts. Receptor 1 proved effective as an extractant for LiNO2 under both model solid-liq. and liq.-liq. extn. conditions.
- 33Qin, Y.; Mi, Y.; Bakker, E. Determination of complex formation constants of 18 neutral alkali and alkaline earth metal ionophores in poly(vinyl chloride) sensing membranes plasticized with bis(2-ethylhexyl)sebacate and o-nitrophenyloctylether. Anal. Chim. Acta 2000, 421, 207– 220, DOI: 10.1016/S0003-2670(00)01038-233https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3cXmtF2mu74%253D&md5=dda619a357a6d0dd2345f8c18c891e0cDetermination of complex formation constants of 18 neutral alkali and alkaline earth metal ionophores in poly(vinyl chloride) sensing membranes plasticized with bis(2-ethylhexyl)sebacate and o-nitrophenyloctyletherQin, Y.; Mi, Y.; Bakker, E.Analytica Chimica Acta (2000), 421 (2), 207-220CODEN: ACACAM; ISSN:0003-2670. (Elsevier Science B.V.)A segmented sandwich membrane method is used to det. complex formation consts. of 18 elec. neutral ionophores in situ in solvent polymeric sensing membranes. These ionophores are commonly used in potentiometric and optical sensors, and knowledge of such binding information is important for ionophore and sensor design. In this method, two membrane segments are fused together, with only one contg. the ionophore, to give a concn.-polarized sandwich membrane. Unlike other approaches, this method does not require the use of a ref. ion in the sample and/or a 2nd ionophore in the membrane, and is typically pH insensitive. The following ionophores responsive for the common cations lithium, sodium, potassium, magnesium and calcium are characterized and discussed: valinomycin, BME-44, bis[(benzo-15-crown-5)-4'-ylmethyl]pimelate, ETH 157, ETH 2120, bis[(12-crown-4)methyl]dodecylmethylmalonate, 4-tert-butylcalix [4] arene tetraacetic acid tetra-Et ester, ETH 149, ETH 1644, ETH 1810, 6,6-dibenzyl-14-crown-4, N,N,N',N',N'',N''-hexacyclohexyl-4,4',4''-propylidyne tris(3-oxabutyramide), ETH 1117, ETH 4030, ETH 1001, ETH 129, ETH 5234, and A23187. The logarithmic complex formation consts. range from 4.4 to 29 and compare well to published data for ionophores that were characterized earlier. From the obsd. complex formation consts., max. possible selectivities are calcd. that would be expected if interfering ions show no binding affinity to the ionophore, and the values are compared with exptl. findings. Each ionophore is characterized in poly(vinyl chloride) membranes plasticized either with a polar (NPOE) or a nonpolar plasticizer (DOS). Membranes based on NPOE always show larger complex formation consts. of the embedded ionophore.
- 34Bakker, E.; Willer, M.; Lerchi, M.; Seiler, K.; Pretsch, E. Determination of complex formation constants of neutral cation-selective ionophores in solvent polymeric membranes. Anal. Chem. 1994, 66, 516– 521, DOI: 10.1021/ac00076a01634https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2cXltFyktrs%253D&md5=742e06bb5ef87bf8a1ec418235447ba6Determination of complex formation constants of neutral cation-selective ionophores in solvent polymeric membranesBakker, Eric; Willer, Michael; Lerchi, Markus; Seiler, Kurt; Pretsch, ErnoeAnalytical Chemistry (1994), 66 (4), 516-21CODEN: ANCHAM; ISSN:0003-2700.Formal complex formation consts. between lipophilic ligands and cations have been detd. within the solvent polymeric membrane phase. The method is based on spectrophotometric measurements on a 1-2-μm thin membrane phase (optode) contg. a H+-selective chromoionophore. Ion exchange equil. between the membrane and the aq. phase are traced for membranes with and without ionophore. A theor. discussion is given as well as exptl. results with the ionophores valinomycin and BME-44 (for K+), ETH 4120 (for Na+), ETH 1001 and ETH 129 (for Ca2+), and ETH 7025 (for Mg2+). Complexes with various stoichiometries are formed for the Mg2+ and Ca2+ complexes of ETH 7025, which make the realization of a selective magnesium optode with this ionophore not possible. With this novel method, the key parameters detg. the performance of ionophore-based ion-selective optodes and electrodes become directly accessible.
- 35Bakker, E. Selectivity comparison of neutral carrier-based ion-selective optical and potentiometric sensing schemes. Anal. Chim. Acta 1997, 350, 329– 340, DOI: 10.1016/S0003-2670(97)00218-3There is no corresponding record for this reference.
- 36Wang, X.; Qin, Y.; Meyerhoff, M. E. Paper-based plasticizer-free sodium ion-selective sensor with camera phone as a detector. Chem. Commun. 2015, 51, 15176– 15179, DOI: 10.1039/C5CC06770G36https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhsVSnsL3J&md5=c18275a7e7a8e27d201ea5e59d8d0660Paper-based plasticizer-free sodium ion-selective sensor with camera phone as a detectorWang, Xuewei; Qin, Yu; Meyerhoff, Mark E.Chemical Communications (Cambridge, United Kingdom) (2015), 51 (82), 15176-15179CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)An ionophore-based ion-selective optode platform on paper is described for the 1st time with a sodium optode as the example. Cellulose paper is an excellent substrate for adsorption of the required chromoionophore, ionophore, and ion-exchanger species. These adsorbed components form a hydrophobic phase that enables heterogeneous optical ion sensing in the absence of any plasticizer or org. polymer phase.
- 37Cantrell, K.; Erenas, M. M.; Orbe-Payá, I. d.; Capitán-Vallvey, L. F. Use of the hue parameter of the hue, saturation, value color space as a quantitative analytical parameter for bitonal optical sensors. Anal. Chem. 2010, 82 (2), 531– 542, DOI: 10.1021/ac901753c37https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXhsFGkurvI&md5=9573668c8ffbfeb623151ad29f8e82baUse of the Hue Parameter of the Hue, Saturation, Value Color Space As a Quantitative Analytical Parameter for Bitonal Optical SensorsCantrell, K.; Erenas, M. M.; de Orbe-Paya, I.; Capitan-Vallvey, L. F.Analytical Chemistry (Washington, DC, United States) (2010), 82 (2), 531-542CODEN: ANCHAM; ISSN:0003-2700. (American Chemical Society)The hue or H component of the hue, satn., value (HSV) color space was studied as a quant. anal. parameter for bitonal optical sensors. The robust nature of this parameter provides superior precision for the measurement of sensors which change colors with the speciation of some indicator mol. This parameter was compared to red, green, blue (RGB) intensity and RGB absorbance along with differences and ratios of both intensity and absorbance and is 2 to 3 times superior. The H value maintains this superior precision with variations in indicator concn., membrane thickness, detector spectral responsivity, and illumination. Because this parameter is stable, simple to calc., easily obtained from com. devices such as scanners and digital cameras, continuous over the entire color gamut, and bound between values of 0 and 1, it shows great promise for use in a variety of sensing applications including imaging, automated anal., pharmaceutical sensing, lab-on-a-chip devices, and quality control applications.
Supporting Information
Supporting Information
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acssensors.7b00165.
Detailed theoretical approach; additional results on optical reverse titration, experimental titration curve, and serum titration (PDF)
Automatic titration of potassium in human serum by using home-made setup (AVI)
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