2012
DOI: 10.1021/ja306159t
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Main-Chain Optically Active Riboflavin Polymer for Asymmetric Catalysis and Its Vapochromic Behavior

Abstract: A novel optically active polymer consisting of riboflavin units as the main chain (poly-1) was prepared from naturally occurring riboflavin (vitamin B(2)) in three steps. The riboflavin residues of poly-1 were converted to 5-ethylriboflavinium cations (giving poly-2), which could be reversibly transformed into the corresponding 4a-hydroxyriboflavins (giving poly-2OH) through hydroxylation/dehydroxylation reactions. This reversible structural change was accompanied by a visible color change along with significa… Show more

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Cited by 93 publications
(75 citation statements)
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“…Recently, polymers possessing riboflavin moieties [10] and coordination polymers with multinuclear copper cluster [11], for examples, have been reported to exhibit vapochromic luminescence.…”
Section: Introductionmentioning
confidence: 99%
“…Recently, polymers possessing riboflavin moieties [10] and coordination polymers with multinuclear copper cluster [11], for examples, have been reported to exhibit vapochromic luminescence.…”
Section: Introductionmentioning
confidence: 99%
“…[12][13][14][15] Riboflavin (vitamin B2) is an important unit of cofactors of biologically-active flavoenzymes 16 and provides a variety of functions, such as catalytic and redox activities and a photoluminescent ability. Hence the readily-available natural riboflavin consisting of a diverse functional heterocyclic isoalloxazine ring together with an optically-active ribityl group and its derivatives have been considered as a promising class of novel asymmetric organocatalysts 17,18 and chiral materials for sensing 19 and separating enantiomers, but successful examples for the use as a CSP are still rare except for one precedent by Gil-Av et al; 20 they found that natural riboflavin had a high chiral recognition ability toward carbohelicenes ( [7] to [14]helicene) when coated on silica gel as a CSP for HPLC using a mixture of n-hexane and CH2Cl2 as the eluent. Recently, Papadimitrakopoulos and coworkers have also demonstrated that the flavin mononucleotide (FMN), a phosphorylated analog of riboflavin, self-assembled and wrapped around single-walled carbon nanotubes (SWCNTs) in a chirality and handedness selective way and enriched the lefthanded helical SWCNTs.…”
Section: Introductionmentioning
confidence: 99%
“…In fact, we recently prepared the first optically-active riboflavin-containing polymer with the fully acetylated riboflavin as the main-chain, which enantioselectively catalyzed the asymmetric oxidation of sulfides whose enantioselectivity was much higher than that catalyzed by the corresponding riboflavin monomer 18 and also detected the chirality of chiral primary and secondary amine vapors in the solid state. 19 We believe that such riboflavin-based optically-active polymers will show a better chiral recognition ability than the present riboflavin-based CSPs because such polymers may form a preferred-handed helical structure 18,34,35 and the research along this line is now in progress in our laboratory.…”
mentioning
confidence: 99%
“…However, the cationic poly-1 and its 4a-amine-adduct (poly-1 N) are totally nonfluorescent, therefore, the fluorogenic detection of amine vapors using poly-1 that may have a potential advantage over the colorimetric detection for its higher sensitivity and lower detection limit was impossible in spite of the inherent fluorescence property of riboflavin. [13,14] In order to develop a fluorogenic sensor for amine vapors using the nonfluorescent poly-1, we took advantage of the fluorescence quenching capability of poly-1 toward fluorescent riboflavins, such as tetraacetyl riboflavin (RF). Here we show a novel turn-on fluorogenic sensory system composed of a nonfluorescent protonated RF (RFH) and poly-1 immobilized in a poly(vinyl chloride) (PVC) film as a fluorophore precursor and a specific amine receptor, respectively, which exclusively convert to the corresponding fluorescent RF and nonfluorescent poly-1 N with a nonquenching capacity, respectively, upon exposure to primary and secondary amine vapors, thereby allowing the selective fluorogenic detection of primary and secondary amines.…”
mentioning
confidence: 99%
“…[13] The optically active cationic poly-1 exhibited a unique asymmetric organocatalytic activity for the oxidation of sulfides in solution along with a reversible colorimetric response to primary and secondary amine vapors due to the formation of the corresponding 4a-amine-adducts (poly-1 N) in the film, thereby enabling direct visual detection of primary and secondary amine vapors ( Figure 1). However, the cationic poly-1 and its 4a-amine-adduct (poly-1 N) are totally nonfluorescent, therefore, the fluorogenic detection of amine vapors using poly-1 that may have a potential advantage over the colorimetric detection for its higher sensitivity and lower detection limit was impossible in spite of the inherent fluorescence property of riboflavin.…”
mentioning
confidence: 99%