{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,19]],"date-time":"2026-03-19T03:21:05Z","timestamp":1773890465648,"version":"3.50.1"},"reference-count":37,"publisher":"MDPI AG","issue":"3","license":[{"start":{"date-parts":[[2010,3,23]],"date-time":"2010-03-23T00:00:00Z","timestamp":1269302400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/3.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Sensors"],"abstract":"<jats:p>The complexing properties of p-sulfonatocalix[n]arenes (n = 4: S[4], n = 6: S[6], and n = 8: S[8]) for rhodamine 800 (Rh800) and indocyanine green (ICG) were examined to develop a near-infrared (NIR) fluorescence detection method for acetylcholine (ACh). We found that Rh800 (as a cation) forms an inclusion complex with S[n], while ICG (as a twitter ion) have no binding ability for S[n]. The binding ability of Rh800 to S[n] decreased in the order of S[8] &gt; S[6] &gt;&gt; S[4]. By the formation of the complex between Rh800 and S[8], fluorescence intensity of the Rh800 was significantly decreased. From the fluorescence titration of Rh800 by S[8], stoichiometry of the Rh800-S[8] complex was determined to be 1:1 with a dissociation constant of 2.2 mM in PBS. The addition of ACh to the aqueous solution of the Rh800-S[8] complex caused a fluorescence increase of Rh800, resulting from a competitive replacement of Rh800 by ACh in the complex. From the fluorescence change by the competitive fluorophore replacement, stoichiometry of the Rh800-ACh complex was found to be 1:1 with a dissociation constant of 1.7 mM. The effects of other neurotransmitters on the fluorescence spectra of the Rh800-S[8] complex were examined for dopamine, GABA, glycine, and L-asparatic acid. Among the neurotransmitters examined, fluorescence response of the Rh800-S[8] complex was highly specific to ACh. Rh800-S[8] complexes can be used as a NIR fluorescent probe for the detection of ACh (5 \u00d7 10-4\u221210-3 M) in PBS buffer (pH = 7.2).<\/jats:p>","DOI":"10.3390\/s100302438","type":"journal-article","created":{"date-parts":[[2010,3,23]],"date-time":"2010-03-23T11:50:56Z","timestamp":1269345056000},"page":"2438-2449","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":44,"title":["Near-Infrared Fluorescence Detection of Acetylcholine in Aqueous Solution Using a Complex of Rhodamine 800 and p-Sulfonato-calix[8]arene"],"prefix":"10.3390","volume":"10","author":[{"given":"Takashi","family":"Jin","sequence":"first","affiliation":[{"name":"WPI Immunology Frontier Research Center, Osaka University, Yamada-oka, 1-3, Suita, Osaka 565-0871, Japan"}]}],"member":"1968","published-online":{"date-parts":[[2010,3,23]]},"reference":[{"key":"ref_1","unstructured":"Purves, D., Augustine, G.J., Fritzpatrick, D., Hall, W.C., LaMantia, A.-S., MaNamara, J.O., and White, L.E. (2008). NeuroScienec, Sinauer. Chapter 6."},{"key":"ref_2","unstructured":"Albert, B., Johnson, A., Lewis, J., Laff, M., Roberts, K., and Walter, P. (2008). Molecular Biology of the Cell, Garland Science. [5th ed]. Chapter 15."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"335","DOI":"10.1016\/S0021-9673(00)81992-5","article-title":"Determination of picomole amounts of choline and acetylcholine in blood by gas chromatography-mass spectrometry equipped with a newly improved pyrolyzer","volume":"239","author":"Honda","year":"1982","journal-title":"J. Chromatogr. A"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"50","DOI":"10.1016\/0003-2697(86)90059-X","article-title":"High-performance liquid chromatography followed by chemiluminescence detection of acetylcholine and choline utilizing immobilized enzymes","volume":"153","author":"Honda","year":"1986","journal-title":"Anal. Biochem"},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"221","DOI":"10.1016\/0003-2697(89)90299-6","article-title":"Determination of acetylcholine and choline by flow injection with immobilized enzymes and fluorometric or luminometric detection","volume":"170","author":"Ricny","year":"1989","journal-title":"Anal. Biochem"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"249","DOI":"10.1016\/S0021-9258(18)56740-5","article-title":"The reaction of acetylcholine and other carboxylic acid derivatives with hydroxylamine, and its analytical application","volume":"180","author":"Hestrin","year":"1949","journal-title":"J. Biol. Chem."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"695","DOI":"10.1111\/j.1471-4159.1969.tb06447.x","article-title":"A technique for the study of acetylcholine turnover in mouse brain in vivo","volume":"16","author":"Schuberth","year":"1969","journal-title":"J. Neurochem"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"1479","DOI":"10.1016\/0006-2952(69)90262-7","article-title":"An enzyme assay for acetylcholine","volume":"18","author":"Feigenson","year":"1969","journal-title":"Biochem. Pharmacol"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"79","DOI":"10.1016\/j.aca.2004.03.019","article-title":"Acetylcholineesterase sensors based on gold electrodes modified with dendrimer and polyaniline A comparative research","volume":"514","author":"Snejdarkova","year":"2004","journal-title":"Anal. Chem. Acta"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"633","DOI":"10.1016\/j.bios.2006.01.020","article-title":"Nano nickel oxide\/nickel incorporated nickel composite coating for sensing and estimation of acetylcholine","volume":"22","author":"Shibli","year":"2006","journal-title":"Biosens. Bioelectron"},{"key":"ref_11","doi-asserted-by":"crossref","unstructured":"Lakowicz, J.R. (2006). Principles of Fluorescence Spectroscopy, Springer. [3rd ed.]. Chapter 23.","DOI":"10.1007\/978-0-387-46312-4"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"316","DOI":"10.1038\/86684","article-title":"A clearer vision for in vivo imaging","volume":"19","author":"Weissleder","year":"2001","journal-title":"Nat. Biotechnol"},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"200","DOI":"10.1117\/12.231370","article-title":"Dependence of tissue optical properties on solute-induced changes in refractive index and osmolarity","volume":"1","author":"Liu","year":"1996","journal-title":"J. Biomed. Opt"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"50","DOI":"10.1162\/153535003765276282","article-title":"Selection of quantum dot wavelengths for biomedical assays and imaging","volume":"2","author":"Lim","year":"2003","journal-title":"Mol. Imaging"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"7214","DOI":"10.1021\/ja00229a046","article-title":"NMR determination of association constants for calixarene complexes. Evidence for the formation of a 1:2 complex with calix[8]arene","volume":"110","author":"Shinkai","year":"1988","journal-title":"J. Am. Chem. Soc"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"9053","DOI":"10.1021\/ja00181a004","article-title":"NMR and crystallographic studies of a p-sulfonatocalix[4]arene-guest complex","volume":"112","author":"Shinkai","year":"1990","journal-title":"J. Am. Chem. Soc"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"419","DOI":"10.1039\/a909847j","article-title":"Entropic origin of the sulfonate groups\u2019 electrostatic assistance in the complexation of quaternary ammonium cations by water soluble calix[4]arenes","volume":"2","author":"Arena","year":"2000","journal-title":"J. Chem. Soc. Perkin Trans"},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"645","DOI":"10.1039\/b411883a","article-title":"Recognition of quaternary ammonium cations by calix[4]arene derivatives supported on gold nanoparticles","volume":"5","author":"Aruduini","year":"2005","journal-title":"Chem. Commun"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"132","DOI":"10.1016\/j.tca.2005.12.025","article-title":"Thermodynamics of interactions between organic ammonium ions and sulfonatocalixarenes","volume":"443","author":"Wang","year":"2006","journal-title":"Thermoch. Acta"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"97","DOI":"10.1080\/10610279508029480","article-title":"Binding of acetylcholine and other quaternary ammonium cations by sulfonated calixarenes. Crystal structure of a [choline-tetrasulfonated calix[4]arene] complex","volume":"5","author":"Lehn","year":"1995","journal-title":"Supramol. Chem"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"755","DOI":"10.1021\/ja951488k","article-title":"Reinvestigation of calixarene-based artificial-signaling acetylcholine receptors useful in neutral aqueous (water-methanol) solution","volume":"118","author":"Koh","year":"1996","journal-title":"J. Am. Chem. Soc"},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"322","DOI":"10.1002\/cjoc.20020200406","article-title":"Interaction of sulfonated calix[n]arenes with rhodamine B and its application to determine acetylcholine in a real neutral aqueous medium","volume":"20","author":"Zhang","year":"2002","journal-title":"Chin. J. Chem"},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"195","DOI":"10.1023\/A:1024506714332","article-title":"A new fluorometric method for the detection of the neurotransmitter acetylcholine in water using a dansylcholine complex with p-sulfonated calix[8]arene","volume":"45","author":"Jin","year":"2003","journal-title":"J. Inclusion Phenom. Macrocyclic Chem"},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"132","DOI":"10.1016\/j.tca.2005.12.025","article-title":"Thermodynamics of interactions between organic ammonium ions and sulfonatocalixarenes","volume":"443","author":"Wang","year":"2006","journal-title":"Thermoch. Acta"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"237","DOI":"10.1002\/adfm.200500219","article-title":"Fluorescence regenerations as a signaling principle for choline and carnitine binding: a refined supramolecular sensor system based on a fluorescent azoalkane","volume":"16","author":"Bakirci","year":"2006","journal-title":"Adv. Funct. Mater"},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"2580","DOI":"10.1021\/la703010z","article-title":"Acetylcholine detection at micromolar concentrations with the use of an artificial receptor-based fluorescence switch","volume":"24","author":"Korbakov","year":"2008","journal-title":"Langmuir"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"6777","DOI":"10.3390\/s8106777","article-title":"Interfacial recognition of acetylcholine by an amphiphilc p-sulfonatocalix[8]arene derivative incorporated into dimyristoyl phosphatidylcholine vesicles","volume":"8","author":"Jin","year":"2008","journal-title":"Sensors"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"57","DOI":"10.1016\/0030-4018(90)90506-O","article-title":"A cw rhodamine 800 dye laser passively mode-locked with neocyanine","volume":"80","author":"Rizvi","year":"1990","journal-title":"Opt. Commun"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"014009(1)","DOI":"10.1117\/1.2159449","article-title":"Interaction of a mitochondrial membrane potential-sensitive dye, rhodamine 800, with rat mitochondria, cells, and perfused hearts","volume":"11","author":"Jilkina","year":"2006","journal-title":"J. biomed. Opt"},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"159","DOI":"10.1088\/0031-9155\/23\/1\/017","article-title":"Fluorescence properties of indocyanine green as related to angiography","volume":"23","author":"Benson","year":"1978","journal-title":"Phys. Med. Biol"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"2090","DOI":"10.1002\/jps.10470","article-title":"Degradation kinetics of indocyanine green in aqueous solution","volume":"92","author":"Saxena","year":"2003","journal-title":"J. Pharm. Sci"},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"438","DOI":"10.1016\/j.jphotochem.2008.09.008","article-title":"Fluorescence lifetime properties of near-infrared cyanine dyes in relation to their structures","volume":"200","author":"Lee","year":"2008","journal-title":"J. Photochem. Photobiol. A: Chem"},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"142","DOI":"10.1006\/abio.2000.4486","article-title":"Fluorescence properties of rhodamine 800 in whole blood and plazma","volume":"279","author":"Abugo","year":"2000","journal-title":"Anal. Biochem"},{"key":"ref_34","doi-asserted-by":"crossref","unstructured":"Lakowicz, J.R. (2006). Principles of Fluorescence Spectroscopy, Springer. [3rd ed]. Chapter 8.","DOI":"10.1007\/978-0-387-46312-4"},{"key":"ref_35","unstructured":"Purves, D., Augustine, G.J., Fritzpatrick, D., Hall, W.C., LaMantia, A.-S., MaNamara, J.O., and White, L.E. (2008). NeuroScienec, Sinauer. Chapter 6."},{"key":"ref_36","unstructured":"Purves, D., Augustine, G.J., Fritzpatrick, D., Hall, W.C., LaMantia, A.-S., MaNamara, J.O., and White, L.E. (2008). NeuroScienec, Sinauer. Chapter 6."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"727","DOI":"10.1111\/j.2042-7158.1987.tb06977.x","article-title":"An HPLC assay procedure of sensitivity and stability for measurement of acetylcholine and choline in neuronal tissue","volume":"39","author":"Barnes","year":"1987","journal-title":"J. Pharm. 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