Hydrolysis of Toxic Natural Glucosides Catalyzed by Cyclodextrin Dicyanohydrins

Bjerre, Jeannette; Nielsen, Erik H.; Bols, Mikael

doi:10.1002/ejoc.200700954

Cited by 25 publications

(14 citation statements)

References 34 publications

(30 reference statements)

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“…''MALDI'' used when instrument not specified. (Cirillo, et al, 2008) Benzoate methanolysis catalyzed by α-cyclosophorohexadecaose isolated from Xanthomonas oryzae TOF (DHB) Bradyrhizobial cyclic β-(1→3),(1→6)-glucans as chiral additives for enantiomeric separation of flavanones, by CE TOF (DHB) (Kwon, et al, 2007a) Cyclosophorohexadecaose and succinoglycan monomers as catalytic carbohydrates for the Strecker reaction TOF (DHB) (Lee, et al, 2007f) Hydrolysis of digoxin catalysed by cyclodextrin dicyanohydrins TOF (Bjerre, et al, 2008) Selective acetolysis of 6-deoxy-sugar oligosaccharide building blocks MALDI …”

Section: R-tof (Dhb)mentioning

confidence: 99%

Analysis of carbohydrates and glycoconjugates by matrix‐assisted laser desorption/ionization mass spectrometry: An update for 2007–2008

Harvey

2011

Mass Spectrometry Reviews

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This review is the fifth update of the original review, published in 1999, on the application of MALDI mass spectrometry to the analysis of carbohydrates and glycoconjugates and brings coverage of the literature to the end of 2008. The first section of the review covers fundamental studies, fragmentation of carbohydrate ions, use of derivatives and new software developments for analysis of carbohydrate spectra. Among newer areas of method development are glycan arrays, MALDI imaging and the use of ion mobility spectrometry. The second section of the review discusses applications of MALDI MS to the analysis of different types of carbohydrate. Specific compound classes that are covered include carbohydrate polymers from plants, N- and O-linked glycans from glycoproteins, biopharmaceuticals, glycated proteins, glycolipids, glycosides and various other natural products. There is a short section on the use of MALDI mass spectrometry for the study of enzymes involved in glycan processing and a section on the use of MALDI MS to monitor products of the chemical synthesis of carbohydrates with emphasis on carbohydrate-protein complexes and glycodendrimers. Corresponding analyses by electrospray ionization now appear to outnumber those performed by MALDI and the amount of literature makes a comprehensive review on this technique impractical. However, most of the work relating to sample preparation and glycan synthesis is equally relevant to electrospray and, consequently, those proposing analyses by electrospray should also find material in this review of interest.

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Section: R-tof (Dhb)mentioning

confidence: 99%

Analysis of carbohydrates and glycoconjugates by matrix‐assisted laser desorption/ionization mass spectrometry: An update for 2007–2008

Harvey

2011

Mass Spectrometry Reviews

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“…37 Similarly, functionalized synthetic cyclodextrins have been used in the hydrolysis of glycosides at physiological pH with sizeable rate accelerations over the background reaction. [38][39][40] The reactivity which has been achieved to date in synthetic molecular hosts exemplifies how simple and defined local environments are able to alter substrate reactivity.…”

Section: Introductionmentioning

confidence: 99%

Spin Equilibria in Monomeric Manganocenes: Solid-State Magnetic and EXAFS Studies

et al. 2009

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A water-soluble self-assembled supramolecular host molecule catalyzes the hydrolysis of orthoformates in basic solution. Comparison of the rate constants of the catalyzed and uncatalyzed reactions for hydrolysis displays rate accelerations of up to 3900 for tri-n-propyl orthoformate. Kinetic analysis shows that the mechanism of hydrolysis with the supramolecular host obeys the Michaelis-Menten model.Mechanistic studies, including 13 C-labeling experiments, revealed that the resting state of the catalytic system is the neutral substrate encapsulated in the host. Activation parameters for the k cat step of the reaction revealed that upon encapsulation in the assembly, the entropy of activation becomes more negative in contrast to the uncatalyzed reaction. Furthermore, solvent isotope effects reveal a normal k(H 2 O)/k(D 2 O) = 1.6, confirming that proton transfer is occurring in the transition state and is rate limiting in the catalyzed reaction. In comparison to the uncatalyzed reaction, which operates by an A-1 mechanism in which the decomposition of the protonated substrate is rate limiting, the encapsulated reaction proceeds through an A-S E 2 mechanism in which proton transfer from protonated water to the substrate is rate limiting.

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“…[15][16][17] The CD cyanohydrins are the most effective CD glycosidases yet crafted, and interestingly they have even mastered catalysis of a range of natural toxic glucosides. [18] We here present the latest developments in CD cyanohydrins, whose catalysis surpasses previously reported results, and novel findings for permethylated cyanohydrin-and carboxylate-CD artificial glycosidases.…”

mentioning

confidence: 63%

Substantial Spatial Flexibility and Hydrogen Bonding within the Catalysis Exerted by Cyclodextrin Artificial Glycosidases

Bjerre

Bols

2010

Eur J Org Chem

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Herein we report the synthesis of a novel 7A,7D‐dicyanohydrin‐β‐cyclodextrin that catalyzes the hydrolysis of aryl glycosides with up to 5500 times rate increase (kcat/kuncat), functioning as a glycosidase enzyme mimic. For all glycoside substrates tested at 50 mM phosphate buffer this catalysis is superior to previously reported results for 6A,6D‐dicyanohydrin cyclodextrin (CD) artificial glycosidases, i.e. analogues which have their catalytic group one carbon atom closer to the cyclodextrin cavity. This provides proof of substantial flexibility within the catalysis exerted by these CD chemzymes. A series of permethylated mono‐ and dicyanohydrin α‐ and β‐CDs were also synthesized, and these showed more modest catalytic rate enhancements of up to 110 times (10 % catalysis rate, relative to non‐methylated analogues), implying that the permethylation blocks or hampers catalytically important binding between the saccharide part of the substrate and the CD. For comparison, the permethylated 6A,6D‐dicarboxylic acid β‐CD was also synthesized and afforded 25 % activity (up to 250 times rate increase) relative to the nonpermethylated 6A,6D‐dicarboxylic acid β‐CD. This suggests that the catalytic effect of the polar interactions of the ionized carboxylate entity is less dependent on the substrate position. These findings afford new information on the scopes and boundaries for CD artificial glycosidase catalysis, and the spatial flexibility discovered fosters optimism for future advances and discoveries within the field of artificial enzymes.

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Hydrolysis of Toxic Natural Glucosides Catalyzed by Cyclodextrin Dicyanohydrins

Cited by 25 publications

References 34 publications

Analysis of carbohydrates and glycoconjugates by matrix‐assisted laser desorption/ionization mass spectrometry: An update for 2007–2008

Analysis of carbohydrates and glycoconjugates by matrix‐assisted laser desorption/ionization mass spectrometry: An update for 2007–2008

Spin Equilibria in Monomeric Manganocenes: Solid-State Magnetic and EXAFS Studies

Substantial Spatial Flexibility and Hydrogen Bonding within the Catalysis Exerted by Cyclodextrin Artificial Glycosidases

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