Boronic acid and guanidinium based synthetic receptors: new applications in differential sensing

textIn the field of supramolecular chemistry a common goal is to design a receptor that is highly selective for a targeted analyte. While this is a worthwhile goal, many of these synthetic receptors are less selective than their natural counterparts such as enzymes or antibodies. Many aspects of the work shown herein demonstrate that these less selective synthetic receptors are still useful chemosensors. Just as Nature utilizes differential receptors in our sense of taste and smell, synthetic sensor arrays can be developed to achieve similar results. Chapter 1 is an overview of the development of a sensor. It begins with the aspects of binding carboxylates and diols, specifically by guanidiniums and boronic acids. Next, signaling motifs of a sensor are discussed, leading to the advantages of using an indicator displacement assay. Finally, differential sensors are discussed, introducing the idea of incorporating non-selective synthetic sensors for the detection of multiple analytes with the use of pattern recognition. Chapter 2 discusses the use of non-selective synthetic receptors in a number of sensing schemes. First a receptor was used to bind a class of age related analytes found in scotch whiskies. A correlation was found between the age of the scotch and the sensing ensemble’s response to the beverage. In another sensing application, a high degree of selectivity was achieved by using two receptors and two indicators together in solution. Due to the differential response of the receptors to the indicators and the guests, the simultaneous quantification of tartrate and malate was achieved with the aid of pattern recognition. Finally, initial efforts were put forth for incorporating the receptor into a differential sensing array by immobilizing the receptor on a solid support. The selectivity of the receptor was investigated, showing that the receptor still had a higher affinity for tartrate over malate. Chapter 3 investigated the thermodynamics of guanidiniums and boronic acids binding carboxylates and diols, respectively. Four hosts were investigated with a variety of guests. The association constants were determined through UV/vis analysis, while the entropy and enthalpy were determined with isothermal titration calorimetry. The binding of boronic acids to more than just aliphatic diols was also investigated. Chapter 4 discussed the development of new sensor for catechol containing analytes. The sensor’s design is based on iron binding siderophores. The iron is both the binding site and the signaling motif for the sensor. Upon addition of catechol guests, a signal modulation did occur.Chemistry and BiochemistryChemistr

Specific interaction of citrate with bis(fluorophoric) bibrachial lariat aza-crown in comparison with the other components of the Krebs cycle

Clares Garcia, M. Paz, [email protected] ; Garcia-España Monsonis, Enrique, [email protected] ; Soriano Soto, Concepcion, [email protected] ; Tejero Toquero, Roberto, [email protected]

Chromogenic and fluorogenic chemosensors and reagents for anions. A comprehensive review of the year 2009

This critical review is focused on examples reported in the year 2009 dealing with the design of chromogenic and fluorogenic chemosensors or reagents for anions (264 references). © 2011 The Royal Society of Chemistry.Moragues Pons, ME.; Martínez Mañez, R.; Sancenón Galarza, F. (2011). Chromogenic and fluorogenic chemosensors and reagents for anions. A comprehensive review of the year 2009. Chemical Society Reviews. 40(5):2593-2643. doi:10.1039/c0cs00015aS25932643405Schmidtchen, F. P., Gleich, A., & Schummer, A. (1989). Selective molecular hosts for anions. Pure and Applied Chemistry, 61(9), 1535-1546. doi:10.1351/pac198961091535Dietrich, B. (1993). Design of anion receptors: Applications. Pure and Applied Chemistry, 65(7), 1457-1464. doi:10.1351/pac199365071457Atwood, J. L., Holman, K. T., & Steed, J. W. (1996). Laying traps for elusive prey: recent advances in the non-covalent binding of anions. Chemical Communications, (12), 1401. doi:10.1039/cc9960001401Schmidtchen, F. P., & Berger, M. (1997). Artificial Organic Host Molecules for Anions. Chemical Reviews, 97(5), 1609-1646. doi:10.1021/cr9603845Antonisse, M. M. G., & Reinhoudt, D. N. (1998). Neutral anion receptors: design and application. Chemical Communications, (4), 443-448. doi:10.1039/a707529dGale, P. (2000). Anion coordination and anion-directed assembly: highlights from 1997 and 1998. Coordination Chemistry Reviews, 199(1), 181-233. doi:10.1016/s0010-8545(99)00149-6Gale, P. A. (2001). Anion receptor chemistry: highlights from 1999. Coordination Chemistry Reviews, 213(1), 79-128. doi:10.1016/s0010-8545(00)00364-7Gale, P. A. (2003). Anion and ion-pair receptor chemistry: highlights from 2000 and 2001. Coordination Chemistry Reviews, 240(1-2), 191-221. doi:10.1016/s0010-8545(02)00258-8Gale, P. A., & Quesada, R. (2006). Anion coordination and anion-templated assembly: Highlights from 2002 to 2004. Coordination Chemistry Reviews, 250(23-24), 3219-3244. doi:10.1016/j.ccr.2006.05.020Gale, P. A., García-Garrido, S. E., & Garric, J. (2008). Anion receptors based on organic frameworks: highlights from 2005 and 2006. Chem. Soc. Rev., 37(1), 151-190. doi:10.1039/b715825dCaltagirone, C., & Gale, P. A. (2009). Anion receptor chemistry: highlights from 2007. Chem. Soc. Rev., 38(2), 520-563. doi:10.1039/b806422aKubik, S. (2009). Amino acid containing anion receptors. Chem. Soc. Rev., 38(2), 585-605. doi:10.1039/b810531fSchmidtchen, F. P. (2005). Artificial Host Molecules for the Sensing of Anions. Anion Sensing, 1-29. doi:10.1007/b101160Schmidtchen, F. P. (2006). Reflections on the construction of anion receptors. Coordination Chemistry Reviews, 250(23-24), 2918-2928. doi:10.1016/j.ccr.2006.07.009Gale, P. A. (2006). Structural and Molecular Recognition Studies with Acyclic Anion Receptors†. Accounts of Chemical Research, 39(7), 465-475. doi:10.1021/ar040237qSessler, J. L., Camiolo, S., & Gale, P. A. (2003). Pyrrolic and polypyrrolic anion binding agents. Coordination Chemistry Reviews, 240(1-2), 17-55. doi:10.1016/s0010-8545(03)00023-7Bondy, C. R., & Loeb, S. J. (2003). Amide based receptors for anions. Coordination Chemistry Reviews, 240(1-2), 77-99. doi:10.1016/s0010-8545(02)00304-1Choi, K., & Hamilton, A. D. (2003). Macrocyclic anion receptors based on directed hydrogen bonding interactions. Coordination Chemistry Reviews, 240(1-2), 101-110. doi:10.1016/s0010-8545(02)00305-3Davis, A. P. (2006). Anion binding and transport by steroid-based receptors. Coordination Chemistry Reviews, 250(23-24), 2939-2951. doi:10.1016/j.ccr.2006.05.008Best, M. D., Tobey, S. L., & Anslyn, E. V. (2003). Abiotic guanidinium containing receptors for anionic species. Coordination Chemistry Reviews, 240(1-2), 3-15. doi:10.1016/s0010-8545(02)00256-4Llinares, J. M., Powell, D., & Bowman-James, K. (2003). Ammonium based anion receptors. Coordination Chemistry Reviews, 240(1-2), 57-75. doi:10.1016/s0010-8545(03)00019-5Schug, K. A., & Lindner, W. (2005). Noncovalent Binding between Guanidinium and Anionic Groups:  Focus on Biological- and Synthetic-Based Arginine/Guanidinium Interactions with Phosph[on]ate and Sulf[on]ate Residues. Chemical Reviews, 105(1), 67-114. doi:10.1021/cr040603jYoon, J., Kim, S. K., Singh, N. J., & Kim, K. S. (2006). Imidazolium receptors for the recognition of anions. Chemical Society Reviews, 35(4), 355. doi:10.1039/b513733kBlondeau, P., Segura, M., Pérez-Fernández, R., & de Mendoza, J. (2007). Molecular recognition of oxoanions based on guanidinium receptors. Chem. Soc. Rev., 36(2), 198-210. doi:10.1039/b603089kXu, Z., Kim, S. K., & Yoon, J. (2010). Revisit to imidazolium receptors for the recognition of anions: highlighted research during 2006–2009. Chemical Society Reviews, 39(5), 1457. doi:10.1039/b918937hGarcía-España, E., Díaz, P., Llinares, J. M., & Bianchi, A. (2006). Anion coordination chemistry in aqueous solution of polyammonium receptors. Coordination Chemistry Reviews, 250(23-24), 2952-2986. doi:10.1016/j.ccr.2006.05.018Schmuck, C. (2006). How to improve guanidinium cations for oxoanion binding in aqueous solution? Coordination Chemistry Reviews, 250(23-24), 3053-3067. doi:10.1016/j.ccr.2006.04.001Amendola, V. (2001). Anion recognition by dimetallic cryptates. Coordination Chemistry Reviews, 219-221, 821-837. doi:10.1016/s0010-8545(01)00368-xBeer, P. D., & Hayes, E. J. (2003). Transition metal and organometallic anion complexation agents. Coordination Chemistry Reviews, 240(1-2), 167-189. doi:10.1016/s0010-8545(02)00303-xSteed, J. W. (2009). Coordination and organometallic compounds as anion receptors and sensors. Chem. Soc. Rev., 38(2), 506-519. doi:10.1039/b810364jO’Neil, E. J., & Smith, B. D. (2006). Anion recognition using dimetallic coordination complexes. Coordination Chemistry Reviews, 250(23-24), 3068-3080. doi:10.1016/j.ccr.2006.04.006Rice, C. R. (2006). Metal-assembled anion receptors. Coordination Chemistry Reviews, 250(23-24), 3190-3199. doi:10.1016/j.ccr.2006.05.017Amendola, V., & Fabbrizzi, L. (2009). Anion receptors that contain metals as structural units. Chem. Commun., (5), 513-531. doi:10.1039/b808264mMartínez-Máñez, R., & Sancenón, F. (2003). Fluorogenic and Chromogenic Chemosensors and Reagents for Anions. Chemical Reviews, 103(11), 4419-4476. doi:10.1021/cr010421eKatayev, E. A., Ustynyuk, Y. A., & Sessler, J. L. (2006). Receptors for tetrahedral oxyanions. Coordination Chemistry Reviews, 250(23-24), 3004-3037. doi:10.1016/j.ccr.2006.04.013Suksai, C., & Tuntulani, T. (2003). Chromogenic anion sensors. Chemical Society Reviews, 32(4), 192. doi:10.1039/b209598jKim, S. K., Lee, D. H., Hong, J.-I., & Yoon, J. (2009). Chemosensors for Pyrophosphate. Accounts of Chemical Research, 42(1), 23-31. doi:10.1021/ar800003fBeer, P. (2000). Electrochemical and optical sensing of anions by transition metal based receptors. Coordination Chemistry Reviews, 205(1), 131-155. doi:10.1016/s0010-8545(00)00237-xBeer, P. D. (1996). Anion selective recognition and optical/electrochemical sensing by novel transition-metal receptor systems. Chemical Communications, (6), 689. doi:10.1039/cc9960000689De Silva, A. P., Gunaratne, H. Q. N., Gunnlaugsson, T., Huxley, A. J. M., McCoy, C. P., Rademacher, J. T., & Rice, T. E. (1997). Signaling Recognition Events with Fluorescent Sensors and Switches. Chemical Reviews, 97(5), 1515-1566. doi:10.1021/cr960386pGunnlaugsson, T., Glynn, M., Tocci (née Hussey), G. M., Kruger, P. E., & Pfeffer, F. M. (2006). Anion recognition and sensing in organic and aqueous media using luminescent and colorimetric sensors. Coordination Chemistry Reviews, 250(23-24), 3094-3117. doi:10.1016/j.ccr.2006.08.017Amendola, V., Esteban-Gómez, D., Fabbrizzi, L., & Licchelli, M. (2006). What Anions Do to N−H-Containing Receptors. Accounts of Chemical Research, 39(5), 343-353. doi:10.1021/ar050195lGunnlaugsson, T., Ali, H. D. P., Glynn, M., Kruger, P. E., Hussey, G. M., Pfeffer, F. M., … Tierney, J. (2005). Fluorescent Photoinduced Electron Transfer (PET) Sensors for Anions; From Design to Potential Application. Journal of Fluorescence, 15(3), 287-299. doi:10.1007/s10895-005-2627-yWiskur, S. L., Ait-Haddou, H., Lavigne, J. J., & Anslyn, E. V. (2001). Teaching Old Indicators New Tricks. Accounts of Chemical Research, 34(12), 963-972. doi:10.1021/ar9600796Nguyen, B. T., & Anslyn, E. V. (2006). Indicator–displacement assays. Coordination Chemistry Reviews, 250(23-24), 3118-3127. doi:10.1016/j.ccr.2006.04.009Xu, Z., Chen, X., Kim, H. N., & Yoon, J. (2010). Sensors for the optical detection ofcyanide ion. Chem. Soc. Rev., 39(1), 127-137. doi:10.1039/b907368jMartínez-Máñez, R., & Sancenón, F. (2005). New Advances in Fluorogenic Anion Chemosensors. Journal of Fluorescence, 15(3), 267-285. doi:10.1007/s10895-005-2626-zHijji, Y. M., Barare, B., Kennedy, A. P., & Butcher, R. (2009). Synthesis and photophysical characterization of a Schiff base as anion sensor. Sensors and Actuators B: Chemical, 136(2), 297-302. doi:10.1016/j.snb.2008.11.045Zhang, Y.-M., Lin, Q., Wei, T.-B., Wang, D.-D., Yao, H., & Wang, Y.-L. (2009). Simple colorimetric sensors with high selectivity for acetate and chloride in aqueous solution. Sensors and Actuators B: Chemical, 137(2), 447-455. doi:10.1016/j.snb.2009.01.015Anzenbacher, P., Nishiyabu, R., & Palacios, M. A. (2006). N-confused calix[4]pyrroles. Coordination Chemistry Reviews, 250(23-24), 2929-2938. doi:10.1016/j.ccr.2006.09.001Anzenbacher,, P., Try, A. C., Miyaji, H., Jursíková, K., Lynch, V. M., Marquez, M., & Sessler, J. L. (2000). Fluorinated Calix[4]pyrrole and Dipyrrolylquinoxaline:  Neutral Anion Receptors with Augmented Affinities and Enhanced Selectivities. Journal of the American Chemical Society, 122(42), 10268-10272. doi:10.1021/ja002112wBlack, C. B., Andrioletti, B., Try, A. C., Ruiperez, C., & Sessler, J. L. (1999). Dipyrrolylquinoxalines:  Efficient Sensors for Fluoride Anion in Organic Solution. Journal of the American Chemical Society, 121(44), 10438-10439. doi:10.1021/ja992579aMizuno, T., Wei, W.-H., Eller, L. R., & Sessler, J. L. (2002). Phenanthroline Complexes Bearing Fused Dipyrrolylquinoxaline Anion Recognition Sites:  Efficient Fluoride Anion Receptors. Journal of the American Chemical Society, 124(7), 1134-1135. doi:10.1021/ja017298tMaeda, H., & Kusunose, Y. (2005). Dipyrrolyldiketone Difluoroboron Complexes: Novel Anion Sensors With C-H⋅⋅⋅X− Interactions. Chemistry - A European Journal, 11(19), 5661-5666. doi:10.1002/chem.200500627Ghosh, T., Maiya, B. G., & Samanta, A. (2006). A colorimetric chemosensor for both fluoride and transition metal ions based on dipyrrolyl derivative. Dalton Transactions, (6), 795. doi:10.1039/b510469fAldakov, D., & Anzenbacher, P. (2004). Sensing of Aqueous Phosphates by Polymers with Dual Modes of Signal Transduction. Journal of the American Chemical Society, 126(15), 4752-4753. doi:10.1021/ja039934oSessler, J. L., Cho, D.-G., & Lynch, V. (2006). Diindolylquinoxalines:  Effective Indole-Based Receptors for Phosphate Anion. Journal of the American Chemical Society, 128(51), 16518-16519. doi:10.1021/ja067720bChauhan, S. M. S., Bisht, T., & Garg, B. (2009). 1-Arylazo-5,5-dimethyl dipyrromethanes: Versatile chromogenic probes for anions. Sensors and Actuators B: Chemical, 141(1), 116-123. doi:10.1016/j.snb.2009.06.013Liu, W.-X., Yang, R., Li, A.-F., Li, Z., Gao, Y.-F., Luo, X.-X., … Jiang, Y.-B. (2009). N-(Acetamido)thiourea based simple neutral hydrogen-bonding receptors for anions. Organic & Biomolecular Chemistry, 7(19), 4021. doi:10.1039/b910255hBabu, J. N., Bhalla, V., Kumar, M., Puri, R. K., & Mahajan, R. K. (2009). Chloride ion recognition using thiourea/urea based receptors incorporated into 1,3-disubstituted calix[4]arenes. New Journal of Chemistry, 33(3), 675. doi:10.1039/b816610bBoiocchi, M., Fabbrizzi, L., Garolfi, M., Licchelli, M., Mosca, L., & Zanini, C. (2009). Templated Synthesis of Copper(II) Azacyclam Complexes Using Urea as a Locking Fragment and Their Metal-Enhanced Binding Tendencies towards Anions. Chemistry - A European Journal, 15(42), 11288-11297. doi:10.1002/chem.200901364Lin, Y.-S., Tu, G.-M., Lin, C.-Y., Chang, Y.-T., & Yen, Y.-P. (2009). Colorimetric anion chemosensors based on anthraquinone: naked-eye detection of isomeric dicarboxylate and tricarboxylate anions. New Journal of Chemistry, 33(4), 860. doi:10.1039/b811172cQing, G.-Y., Sun, T.-L., Wang, F., He, Y.-B., & Yang, X. (2009). Chromogenic Chemosensors forN-Acetylaspartate Based on Chiral Ferrocene-Bearing Thiourea Derivatives. European Journal of Organic Chemistry, 2009(6), 841-849. doi:10.1002/ejoc.200800961Lu, Q.-S., Dong, L., Zhang, J., Li, J., Jiang, L., Huang, Y., … Yu, X.-Q. (2009). Imidazolium-Functionalized BINOL as a Multifunctional Receptor for Chromogenic and Chiral Anion Recognition. Organic Letters, 11(3), 669-672. doi:10.1021/ol8027303Bao, X., Yu, J., & Zhou, Y. (2009). Selective colorimetric sensing for F− by a cleft-shaped anion receptor containing amide and hydroxyl as recognition units. Sensors and Actuators B: Chemical, 140(2), 467-472. doi:10.1016/j.snb.2009.04.056Bhardwaj, V. K., Hundal, M. S., & Hundal, G. (2009). A tripodal receptor bearing catechol groups for the chromogenic sensing of F− ions via frozen proton transfer. Tetrahedron, 65(41), 8556-8562. doi:10.1016/j.tet.2009.08.023Caltagirone, C., Mulas, A., Isaia, F., Lippolis, V., Gale, P. A., & Light, M. E. (2009). Metal-induced pre-organisation for anion recognition in a neutral platinum-containing receptor. Chemical Communications, (41), 6279. doi:10.1039/b912942aShiraishi, Y., Maehara, H., Sugii, T., Wang, D., & Hirai, T. (2009). A BODIPY–indole conjugate as a colorimetric and fluorometric probe for selective fluoride anion detection. Tetrahedron Letters, 50(29), 4293-4296. doi:10.1016/j.tetlet.2009.05.018Shiraishi, Y., Maehara, H., & Hirai, T. (2009). Indole-azadiene conjugate as a colorimetric and fluorometric probe for selective fluoride ion sensing. Organic & Biomolecular Chemistry, 7(10), 2072. doi:10.1039/b821466bBhosale, S. V., Bhosale, S. V., Kalyankar, M. B., & Langford, S. J. (2009). A Core-Substituted Naphthalene Diimide Fluoride Sensor. Organic Letters, 11(23), 5418-5421. doi:10.1021/ol9022722Lin, Z., Chen, H. C., Sun, S.-S., Hsu, C.-P., & Chow, T. J. (2009). Bifunctional maleimide dyes as selective anion sensors. Tetrahedron, 65(27), 5216-5221. doi:10.1016/j.tet.2009.04.090Yoo, J., Kim, M.-S., Hong, S.-J., Sessler, J. L., & Lee, C.-H. (2009). Selective Sensing of Anions with Calix[4]pyrroles Strapped with Chromogenic Dipyrrolylquinoxalines. The Journal of Organic Chemistry, 74(3), 1065-1069. doi:10.1021/jo802059cShang, X.-F., Li, J., Lin, H., Jiang, P., Cai, Z.-S., & Lin, H.-K. (2009). Anion recognition and sensing of ruthenium(ii) and cobalt(ii) sulfonamido complexes. Dalton Transactions, (12), 2096. doi:10.1039/b804445gDydio, P., Zieliński, T., & Jurczak, J. (2009). Bishydrazide Derivatives of Isoindoline as Simple Anion Receptors. The Journal of Organic Chemistry, 74(4), 1525-1530. doi:10.1021/jo802288uZimmermann-Dimer, L. M., Reis, D. C., Machado, C., & Machado, V. G. (2009). Chromogenic anionic chemosensors based on protonated merocyanine solvatochromic dyes in trichloromethane and in trichloromethane–water biphasic system. Tetrahedron, 65(21), 4239-4248. doi:10.1016/j.tet.2009.03.049Goswami, S., Hazra, A., Chakrabarty, R., & Fun, H.-K. (2009). Recognition of Carboxylate Anions and Carboxylic Acids by Selenium-Based New Chromogenic Fluorescent Sensor: A Remarkable Fluorescence Enhancement of Hindered Carboxylates. Organic Letters, 11(19), 4350-4353. doi:10.1021/ol901737sBarnard, A., Dickson, S. J., Paterson, M. J., Todd, A. M., & Steed, J. W. (2009). Enantioselective lactate binding by chiral tripodal anion hosts derived from amino acids. Organic & Biomolecular Chemistry, 7(8), 1554. doi:10.1039/b817889eHung, C.-Y., Singh, A. S., Chen, C.-W., Wen, Y.-S., & Sun, S.-S. (2009). Colorimetric and luminescent sensing of F− anion through strong anion–π interaction inside the π-acidic cavity of a pyridyl-triazine bridged trinuclear Re(i)–tricarbonyl diimine complex. Chemical Communications, (12), 1511. doi:10.1039/b820234fMetzger, A., & Anslyn, E. V. (1998). A Chemosensor for Citrate in Beverages. Angewandte Chemie International Edition, 37(5), 649-652. doi:10.1002/(sici)1521-3773(19980316)37:53.0.co;2-hNiikura, K., Metzger, A., & Anslyn, E. V. (1998). Chemosensor Ensemble with Selectivity for Inositol-Trisphosphate. Journal of the American Chemical Society, 120(33), 8533-8534. doi:10.1021/ja980990cAït-Haddou, H., Wiskur, S. L., Lynch, V. M., & Anslyn, E. V. (2001). Achieving Large Color Changes in Response to the Presence of Amino Acids:  A Molecular Sensing Ensemble with Selectivity for Aspartate. Journal of the American Chemical Society, 123(45), 11296-11297. doi:10.1021/ja011905vWiskur, S. L., & Anslyn, E. V. (2001). Using a Synthetic Receptor to Create an Optical-Sensing Ensemble for a Class of Analytes:  A Colorimetric Assay for the Aging of Scotch. Journal of the American Chemical Society, 123(41), 10109-10110. doi:10.1021/ja011800sZhong, Z., & Anslyn, E. V. (2002). A Colorimetric Sensing Ensemble for Heparin. Journal of the American Chemical Society, 124(31), 9014-9015. doi:10.1021/ja020505kLavigne, J. J., & Anslyn, E. V. (1999). Teaching Old Indicators New Tricks: A Colorimetric Chemosensing Ensemble for Tartrate/Malate in Beverages. Angewandte Chemie International Edition, 38(24), 3666-3669. doi:10.1002/(sici)1521-3773(19991216)38:243.0.co;2-eWiskur, S. L., Floriano, P. N., Anslyn, E. V., & McDevitt, J. T. (2003). A Multicomponent Sensing Ensemble in Solution: Differentiation between Structurally Similar Analytes. Angewandte Chemie International Edition, 42(18), 2070-2072. doi:10.1002/anie.200351058Fabbrizzi, L., Marcotte, N., Stomeo, F., & Taglietti, A. (2002). Pyrophosphate Detection in Water by Fluorescence Competition Assays: Inducing Selectivity through the Choice of the Indicator. Angewandte Chemie International Edition, 41(20), 3811-3814. doi:10.1002/1521-3773(20021018)41:203.0.co;2-wHortalá, M. A., Fabbrizzi, L., Marcotte, N., Stomeo, F., & Taglietti, A. (2003). Designing the Selectivity of the Fluorescent Detection of Amino Acids:  A Chemosensing Ensemble for Histidine. Journal of the American Chemical Society, 125(1), 20-21. doi:10.1021/ja027110lFabbrizzi, L., Leone, A., & Taglietti, A. (2001). A Chemosensing Ensemble for Selective Carbonate Detection in Water Based on Metal-Ligand Interactions. Angewandte Chemie International Edition, 40(16), 3066-3069. doi:10.1002/1521-3773(20010817)40:163.0.co;2-0Kim, S. Y., & Hong, J.-I. (2009). Dual signal (color change and fluorescence ON–OFF) ensemble system based on bis(Dpa-CuII) complex for detection of PPi in water. Tetrahedron Letters, 50(17), 1951-1953. doi:10.1016/j.tetlet.2009.02.036Khatua, S., Kim, K., Kang, J., Huh, J. O., Hong, C. S., & Churchill, D. G. (2009). Synthesis, Structure, Magnetic Properties and Aqueous Optical Citrate Detection of Chiral Dinuclear CuIIComplexes. European Journal of Inorganic Chemistry, 2009(22), 3266-3274. doi:10.1002/ejic.200900357Wright, A. T., & Anslyn, E. V. (2006). Differential receptor arrays and assays for solution-based molecular recognition. Chem. Soc. Rev., 35(1), 14-28. doi:10.1039/b505518kKitamura, M., Shabbir, S. H., & Anslyn, E. V. (2009). Guidelines for Pattern Recognition Using Differential Receptors and Indicator Displacement Assays. The Journal of Organic Chemistry, 74(12), 4479-4489. doi:10.1021/jo900433jZhang, T., Edwards, N. Y., Bonizzoni, M., & Anslyn, E. V. (2009). The Use of Differential Receptors to Pattern Peptide Phosphorylation. Journal of the American Chemical Society, 131(33), 11976-11984. doi:10.1021/ja9041675Zhang, D. (2009). Highly selective colorimetric detection of cysteine and homocysteine in water through a direct displacement approach. Inorganic Chemistry Communications, 12(12), 1255-1258. doi:10.1016/j.inoche.2009.09.035Li, S., Zhou, Y., Yu, C., Chen, F., & Xu, J. (2009). Switching the ligand-exchange reactivities of chloro-bridged cyclopalladated azobenzenes for the colorimetric sensing of thiocyanate. New Journal of Chemistry, 33(7), 1462. doi:10.1039/b903752gMännel-Croisé, C., & Zelder, F. (2009). Side Chains of Cobalt Corrinoids Control the Sensitivity and Selectivity in the Colorimetric Detection of Cyanide. Inorganic Chemistry, 48(4), 1272-1274. doi:10.1021/ic900053hMullen, K. M., Davis, J. J., & Beer, P. D. (2009). Anion induced displacement studies in naphthalene diimide containing interpenetrated and interlocked structures. New Journal of Chemistry, 33(4), 769. doi:10.1039/b819322cSancenón, F., Martínez-Máñez, R., Miranda, M. A., Seguí, M.-J., & Soto, J. (2003). Towards the Development of Colorimetric Probes to Discriminate between Isomeric Dicarboxylates. Angewandte Chemie International Edition, 42(6), 647-650. doi:10.1002/anie.200390178Jiménez, D., Martínez-Máñez, R., Sancenón, F., Ros-Lis, J. V., Benito, A., & Soto, J. (2003). A New Chromo-chemodosimeter Selective for Sulfide Anion. Journal of the American Chemical Society, 125(30), 9000-9001. doi:10.1021/ja0347336Solé, S., & Gabbaï, F. P. (2004). A bidentate borane as colorimetric fluoride ion sensor. Chem. Commun., (11), 1284-1285. doi:10.1039/b403596hWang, W., Escobedo, J. O., Lawrence, C. M., & Strongin, R. M. (2004). Direct Detection of Homocysteine. Journal of the American Chemical Society, 126(11), 3400-3401. doi:10.1021/ja0318838Zhang, M., Yu, M., Li, F., Zhu, M., Li, M., Gao, Y., … Huang, C. (2007). A Highly Selective Fluorescence Turn-on Sensor for Cysteine/Homocysteine and Its Application in Bioimaging. Journal of the American Chemical Society, 129(34), 10322-10323. doi:10.1021/ja073140iCho, D.-G., Kim, J. H., & Sessler, J. L. (20

Intelligent Chiral Sensing Based on Supramolecular and Interfacial Concepts

Of the known intelligently-operating systems, the majority can undoubtedly be classed as being of biological origin. One of the notable differences between biological and artificial systems is the important fact that biological materials consist mostly of chiral molecules. While most biochemical processes routinely discriminate chiral molecules, differentiation between chiral molecules in artificial systems is currently one of the challenging subjects in the field of molecular recognition. Therefore, one of the important challenges for intelligent man-made sensors is to prepare a sensing system that can discriminate chiral molecules. Because intermolecular interactions and detection at surfaces are respectively parts of supramolecular chemistry and interfacial science, chiral sensing based on supramolecular and interfacial concepts is a significant topic. In this review, we briefly summarize recent advances in these fields, including supramolecular hosts for color detection on chiral sensing, indicator-displacement assays, kinetic resolution in supramolecular reactions with analyses by mass spectrometry, use of chiral shape-defined polymers, such as dynamic helical polymers, molecular imprinting, thin films on surfaces of devices such as QCM, functional electrodes, FET, and SPR, the combined technique of magnetic resonance imaging and immunoassay, and chiral detection using scanning tunneling microscopy and cantilever technology. In addition, we will discuss novel concepts in recent research including the use of achiral reagents for chiral sensing with NMR, and mechanical control of chiral sensing. The importance of integration of chiral sensing systems with rapidly developing nanotechnology and nanomaterials is also emphasized

The mechanisms of boronate ester formation and fluorescent turn-on in ortho-aminomethylphenylboronic acids

ortho-Aminomethylphenylboronic acids are used in receptors for carbohydrates and various other compounds containing vicinal diols. The presence of the o-aminomethyl group enhances the affinity towards diols at neutral pH, and the manner in which this group plays this role has been a topic of debate. Further, the aminomethyl group is believed to be involved in the turn-on of the emission properties of appended fluorophores upon diol binding. In this treatise, a uniform picture emerges for the role of this group: it primarily acts as an electron-withdrawing group that lowers the pK(a) of the neighbouring boronic acid thereby facilitating diol binding at neutral pH. The amine appears to play no role in the modulation of the fluorescence of appended fluorophores in the protic-solvent-inserted form of the boronic acid/boronate ester. Instead, fluorescence turn-on can be consistently tied to vibrational-coupled excited-state relaxation (a loose-bolt effect). Overall, this Review unifies and discusses the existing data as of 2019 whilst also highlighting why o-aminomethyl groups are so widely used, and the role they play in carbohydrate sensing using phenylboronic acids

Bloodstream-To-Eye Infections Are Facilitated by Outer Blood-Retinal Barrier Dysfunction

This work was funded by National Institutes of Health (NIH; http://www.nih.gov) Grants R01EY024140 and R21EY022466 (to M.C.C.) and R01EY019494 (to M.H.E.). Our research is also funded in part by NIH Core Grant P30EY021725 (to Robert E. Anderson, OUHSC) and an unrestricted grant from Research to Prevent Blindness Inc. (http://www.rpbusa.org) to the Dean A. McGee Eye Institute. The funders had no role in study design, data collection and analysis, decision to publish, or preparation of the manuscript.We thank Bolanle Adebayo (Cameron University, Lawton OK), Craig Land (Oklahoma State University, Stillwater OK), Nathan Jia (Oklahoma Christian University, Edmond OK), Kobbe Wiafe (Oklahoma School of Science and Mathematics, Oklahoma City OK), and Amanda Roehrkasse and Madhu Parkunan (OUHSC) for intellectual discussions and technical assistance. The authors also acknowledge thank Nanette Wheatley, Dr. Feng Li, and Mark Dittmar (OUHSC Live Animal Imaging Core, P30EY021725) for their invaluable technical assistance.This work was presented in part at the 2014 Association for Research in Vision and Ophthalmology Annual Conference in Orlando FL.The blood-retinal barrier (BRB) functions to maintain the immune privilege of the eye, which is necessary for normal vision. The outer BRB is formed by tightly-associated retinal pigment epithelial (RPE) cells which limit transport within the retinal environment, maintaining retinal function and viability. Retinal microvascular complications and RPE dysfunction resulting from diabetes and diabetic retinopathy cause permeability changes in the BRB that compromise barrier function. Diabetes is the major predisposing condition underlying endogenous bacterial endophthalmitis (EBE), a blinding intraocular infection resulting from bacterial invasion of the eye from the bloodstream. However, significant numbers of EBE cases occur in non-diabetics. In this work, we hypothesized that dysfunction of the outer BRB may be associated with EBE development. To disrupt the RPE component of the outer BRB in vivo, sodium iodate (NaIO3) was administered to C57BL/6J mice. NaIO3-treated and untreated mice were intravenously injected with 108 colony forming units (cfu) of Staphylococcus aureus or Klebsiella pneumoniae. At 4 and 6 days postinfection, EBE was observed in NaIO3-treated mice after infection with K. pneumoniae and S. aureus, although the incidence was higher following S. aureus infection. Invasion of the eye was observed in control mice following S. aureus infection, but not in control mice following K. pneumoniae infection. Immunohistochemistry and FITC-dextran conjugate transmigration assays of human RPE barriers after infection with an exoprotein-deficient agr/sar mutant of S. aureus suggested that S. aureus exoproteins may be required for the loss of the tight junction protein, ZO-1, and for permeability of this in vitro barrier. Our results support the clinical findings that for both pathogens, complications which result in BRB permeability increase the likelihood of bacterial transmigration from the bloodstream into the eye. For S. aureus, however, BRB permeability is not required for the development of EBE, but toxin production may facilitate EBE pathogenesis.Yeshttp://www.plosone.org/static/editorial#pee