- Anomeric alkylations and acylations of unprotected mono- and disaccharides mediated by pyridoneimine in aqueous solutions
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A site-specific deprotonation followed by alkylations and acylations of sugar hemiacetals to the corresponding alkyl glycosides and acylated sugars in aqueous solutions is disclosed herein. Pyridoneimine as a new base is developed to mediate the deprotonation of readily available sugar hemiacetals and further reactions with alkylation and acylation agents.
- Dey, Kalyan,Jayaraman, Narayanaswamy
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supporting information
p. 2224 - 2227
(2022/02/17)
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- BORON CLUSTER-COUPLED COMPOUND
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To provide a novel boron-containing compound which increases intratumorous accumulation and tumor retention, and is efficiently taken into a tumor cell.SOLUTION: The present invention relates to a compound represented by formula (I) in the figure or a salt thereof. [In the formula, X represents a divalent to pentavalent organic group; Y represents a linker structure; R represents a monovalent group comprising boron clusters; and n represents 2, 3, 4 or 5.SELECTED DRAWING: None
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Paragraph 0169; 0174-0176
(2021/03/05)
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- 8-hydroxyquinoline glycoconjugates: Modifications in the linker structure and their effect on the cytotoxicity of the obtained compounds
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Small molecule nitrogen heterocycles are very important structures, widely used in the design of potential pharmaceuticals. Particularly, derivatives of 8-hydroxyquinoline (8-HQ) are successfully used to design promising anti-cancer agents. Conjugating 8-HQ derivatives with sugar derivatives, molecules with better bioavailability, selectivity, and solubility are obtained. In this study, 8-HQ derivatives were functionalized at the 8-OH position and connected with sugar derivatives (D-glucose or D-galactose) substituted with different groups at the anomeric position, using copper(I)-catalyzed 1,3-dipolar azide-alkyne cycloaddition (CuAAC). Glycoconjugates were tested for inhibition of the proliferation of cancer cell lines (HCT 116 and MCF-7) and inhibition of β-1,4-galactosyltransferase activity, which overexpression is associated with cancer progression. All glycoconjugates in protected form have a cytotoxic effect on cancer cells in the tested concentration range. The presence of additional amide groups in the linker structure improves the activity of glycoconjugates, probably due to the ability to chelate metal ions present in many types of cancers. The study of metal complexing properties confirmed that the obtained glycoconjugates are capable of chelating copper ions, which increases their anti-cancer potential.
- Krawczyk, Monika,Pastuch-Gawo?ek, Gabriela,Pluta, Aleksandra,Erfurt, Karol,Domiński, Adrian,Kurcok, Piotr
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- Synthesis and optical and electrochemical properties of glucose-cored ferrocenyl dendrimers
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Triazole-based ferrocenyl glycoconjugates 1, 2, and 3 were synthesized by regiospecific copper(I)-catalyzed azide–alkyne cycloaddition (CuAAC) of azidoferrocenyl derivatives with glucose pentaacetylide. Higher generation ferrocenyl glycoconjugates form the stable ferrocenium cation and exhibit increased light harvesting property as revealed from cyclic voltammogram studies and ultraviolet–visible spectrum respectively due to the presence of more ferrocenyl and triazolyl units than the lower generation dendrimer.
- Kannan, Ayyavoo,Anandhan, Ramasamy,Rajakumar, Perumal
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supporting information
p. 541 - 550
(2017/03/15)
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- NIR fluorescent DCPO glucose analogues and their application in cancer cell imaging
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Given the increased glucose uptake in cancer cells than normal cells, near-infrared (NIR) fluorescent glucose analogues have been previously synthesized and applied in cancer cell imaging. However, most NIR dyes usually have one or more charge in their structures, which may cause low cell membrane permeability and hamper their application in cell imaging. Here we report the synthesis and characterization of a series of DCPO-conjugated glucose analogues (N0-N4), which have no charge in their structures and have different lengths of the spacer arm. Experiments in different cancer cell lines showed the uptake of N0-N4 was dependent on the protein levels of GLUT-1. The distance between the dyes and glucose was adjusted by the length of PEG. Of these five glucose analogues, the length of the linker in N2 which contains a diethylene glycol was the most appropriate spacer arm, a longer or shorter linker exhibited reduced cellular uptake efficiency. Moreover, the uptake of DCPO-conjugated glucose analogues could be inhibited by phloretin, a GLUT-1 inhibitor or competitively inhibited by unlabeled d-glucose. Therefore, our study has reported a novel type of NIR-conjugated glucose analogues, whose cell permeability ensured the potential application for cancer cell bioimaging in the NIR region. We also demonstrated, for the first time, that the length of the linker between the dyes and glucose was also an important factor that will affect the delivery efficiency of the glucose analogues to cells.
- Chen, Shiguang,Fang, Yanfen,Zhu, Qiwen,Zhang, Wanli,Zhang, Xiongwen,Lu, Wei
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p. 81894 - 81901
(2016/09/09)
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- NOVEL SOLANIDINE-DERIVED COMPOUNDS
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Novel solanidine-derived compounds, the synthesis method thereof and the uses of same in the fields of phytosanitary protection and health. In particular, the novel compounds have toxic and/or repellent properties in relation to aphids, as well as other properties.
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Paragraph 0067-0078
(2016/06/28)
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- Synthesis of Dense and Chiral Dendritic Polyols Using Glyconanosynthon Scaffolds
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Most classical dendrimers are frequently built-up from identical repeating units of low valency (usually AB2 monomers). This strategy necessitates several generations to achieve a large number of surface functionalities. In addition, these typical monomers are achiral. We propose herein the use of sugar derivatives consisting of several and varied functionalities with their own individual intrinsic chirality as both scaffolds/core as well as repeating units. This approach allows the construction of chiral, dense dendrimers with a large number of surface groups at low dendrimer generations. Perpropargylated β-D-glucopyranoside, serving as an A5 core, together with various derivatives, such as 2-azidoethyl tetra-O-allyl-β-D-glucopyranoside, serving as an AB4 repeating moiety, were utilized to construct chiral dendrimers using "click chemistry" (CuAAC reaction). These were further modified by thiol-ene and thiol-yne click reactions with alcohols to provide dendritic polyols. Molecular dynamic simulation supported the assumption that the resulting polyols have a dense structure
- Shiao, Tze Chieh,Rej, Rabindra,Rose, Mariécka,Pavan, Giovanni M.,Roy, René
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- Recognition of concanavalin a by cationic glucosylated liposomes
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The specificity of carbohydrate-lectin interaction has been reported as an attractive strategy for drug delivery in cancer therapy because of the high levels of lectins in several human malignancies. A novel cationic glucosylated amphiphile was therefore
- Mauceri, Alessandro,Borocci, Stefano,Galantini, Luciano,Giansanti, Luisa,Mancini, Giovanna,Martino, Antonio,Salvati Manni, Livia,Sperduto, Claudio
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p. 11301 - 11306
(2015/02/19)
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- Cell internalization of BODIPY-based fluorescent dyes bearing carbohydrate residues
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Red-absorbing BODIPY species have been prepared and their photophysical properties have been studied. The high fluorescence quantum yield of such compounds allowed us to study their cell internalization by fluorescence microscopy, using concentration as l
- Papalia, Teresa,Siracusano, Gabriel,Colao, Ivana,Barattucci, Anna,Aversa, Maria Chiara,Serroni, Scolastica,Zappalà, Gabriella,Campagna, Sebastiano,Sciortino, Maria Teresa,Puntoriero, Fausto,Bonaccorsi, Paola
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- 1,2-cis Alkyl glycosides: Straightforward glycosylation from unprotected 1-thioglycosyl donors
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A 1,2-cis-alkyl glycosidation protocol that makes use of unprotected phenyl 1-thioglycosyl donors is reported. Glycosylation of various functionalized alcohols was accomplished in moderate to high yield and selectivity to give the 1,2-cis-glycosides. In order to quickly develop optimum glycosylation conditions, an FIA (flow injection analysis)-ESI-TOF-MS method was developed that enabled rapid and quantitative evaluation of yield on small scale. This methodology, coupled with NMR spectroscopy, allowed for rapid evaluation of the overall reactions.
- Meng, Bo,Zhu, Zhenqian,Baker, David C.
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p. 5182 - 5191
(2014/07/08)
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- Protection-free synthesis of alkyl glycosides under hydrogenolytic conditions
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A convenient protection-free synthetic route for the preparation of alkyl glycosides has been developed. The alcoholysis of one-step preparable glycosyl donors, 4,6-dibenzyloxy-1,3,5-triazin-2-yl (DBT) glycosides, under hydrogenolytic conditions gave the corresponding glycosides in good yields without the addition of any acid promoters. The method could be successfully applied to the glycosylation of an acidlabile oligosaccharide.
- Ishihara, Masaki,Takagi, Yuka,Li, Gefei,Noguchi, Masato,Shoda, Shin-Ichiro
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supporting information
p. 1235 - 1237
(2013/10/22)
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- Real-time evaluation of binding mechanisms in multivalent interactions: A surface plasmon resonance kinetic approach
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Multivalency is a key, ubiquitous phenomenon in nature characterized by a complex combination of binding mechanisms, with special relevance in carbohydrate-lectin recognition. Herein we introduce an original surface plasmon resonance kinetic approach to analyze multivalent interactions that has been validated with dendrimers as monodisperse multivalent analytes binding to lectin clusters. The method, based on the analysis of early association and late dissociation phases of the sensorgrams provides robust information of the glycoconjugate binding efficiency and real-time structural data of the binding events under the complex scenario of the glyco-cluster effect. Notably, it reveals the dynamic nature of the interaction and offers experimental evidence on the contribution of binding mechanisms.
- Munoz, Eva Maria,Correa, Juan,Riguera, Ricardo,Fernandez-Megia, Eduardo
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supporting information
p. 5966 - 5969
(2013/05/22)
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- Synthesis and anticancer activity of glucosylated podophyllotoxin derivatives linked via 4β-triazole rings
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A series of 4β-triazole-linked glucose podophyllotoxin conjugates have been designed and synthesized by employing a click chemistry approach. All the compounds were evaluated for their anticancer activity against a panel of five human cancer cell lines (HL-60, SMMC-7721, A-549, MCF-7, SW480) using MTT assays. Most of these triazole derivatives have good anticancer activity. Among them, compound 35 showed the highest potency against all five cancer cell lines tested, with IC50 values ranging from 0.59 to 2.90 μM, which is significantly more active than the drug etoposide currently in clinical use. Structure-activity relationship analysis reveals that the acyl substitution on the glucose residue, the length of oligoethylene glycol linker, and the 4'-demethylation of podophyllotoxin scaffold can significantly affect the potency of the anticancer activity. Most notably, derivatives with a perbutyrylated glucose residue show much higher activity than their counterparts with either a free glucose or a peracetylated glucose residue.
- Zi, Cheng-Ting,Xu, Feng-Qing,Li, Gen-Tao,Li, Yan,Ding, Zhong-Tao,Zhou, Jun,Jiang, Zi-Hua,Hu, Jiang-Miao
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p. 13992 - 14012
(2014/01/06)
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- Towards biodegradable elastomers: Green synthesis of carbohydrate functionalized styrene-butadiene-styrene copolymer by click chemistry
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Random attachment of sugar molecules to synthetic polymers is an important strategy to induce biodegradability in these polymers. The present study successfully employs "click" chemistry to introduce low levels of sugar molecules onto styrene-butadiene-styrene (SBS) copolymer, a widely used commodity polymer which is not biodegradable. Spectral, morphological and thermal studies of the modified polymers were carried out to show the dramatic changes in the properties of these modified polymers. Thermal stability of glucose linked SBS had onset of degradation at 428 °C, down from 478 °C observed for SBS. Morphology studied by WAXRD and SEM showed destructuring of the polymer domains of SBS, which is beneficial for biodegradation of these polymers. Previous studies showed that sugars anchored by hydrolysable ester groups onto polystyrene were biodegradable; current studies show that sugars anchored by unhydrolyzable C-C bonds on the butadiene component of SBS copolymer are also significantly biodegradable.
- Singh, Rakesh,Varma
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experimental part
p. 348 - 356
(2012/04/10)
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- Synthesis and biological evaluation of a library of glycoporphyrin compounds
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A library of glycosylated porphyrins (glycoporphyrins) was prepared and the compounds were evaluated for their photodynamic therapy (PDT) activity against the oesophageal squamous-cell carcinoma cell line OE21 in vitro. A synthetic methodology was develop
- Daly, Robin,Vaz, Gisela,Davies, Anthony M.,Senge, Mathias O.,Scanlan, Eoin M.
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supporting information
p. 14671 - 14679
(2013/01/15)
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- 'Click' synthesis of triazole-based spirostan saponin analogs
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Novel analogs of spirostan saponins in which the glycosidic bond has been replaced by a triazole linkage are described. For this, a direct oligosaccharide-steroid conjugation approach based on the CuI- catalyzed azide-alkyne 1,3-dipolar cycload
- Pérez-Labrada, Karell,Brouard, Ignacio,Morera, Cercis,Estévez, Francisco,Bermejo, Jaime,Rivera, Daniel G.
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experimental part
p. 7713 - 7727
(2011/10/13)
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- Efficient glycosylation of unprotected sugars using sulfamic acid: A mild eco-friendly catalyst
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Sulfamic acid, a mild and environmentally benign catalyst has been successfully used in the Fischer glycosylation of unprotected sugars for the preparation alkyl glycosides. A diverse range of aliphatic alcohols have been used to prepare a series of alkyl glycosides in good to excellent yield.
- Guchhait, Goutam,Misra, Anup Kumar
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experimental part
p. 52 - 57
(2012/01/15)
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- Expanding the application scope of glycosidases using click chemistry
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Glycosidase-mediated glycosylation of alkynyl alcohols and azide-containing alcohols was followed by a click reaction, affording various types of triazole glycosides. The activities of triazole glycosides detected in subsequent bioassays show that this procedure is a feasible approach to the development of anti-fungal drugs.
- Lu, Wen-Ya,Sun, Xing-Wen,Zhu, Chen,Xu, Jian-He,Lin, Guo-Qiang
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experimental part
p. 750 - 757
(2010/09/14)
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- Ionic liquid promoted atom economic glycosylation under Lewis acid catalysis
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Straightforward glycosylation of various alcohols with unprotected and non-activated monosaccharides were performed under scandium triflate catalysis. Rate and yield of glycosylation were highly improved when using 1-butyl-3-methylimidazolium trifluoromethanesulfonate as a green solvent. This ionic liquid was allowed to be recycled at least three times without loss of activity. The possibility of drastically reducing the amounts of catalyst (down to 1 mol%) and aglycone (down to 1 equiv) when performing the reaction in ionic liquid opens new perspectives in O-glycosylation, as a direct coupling between an aglycone and free sugars.
- Auge, Jacques,Sizun, Gwenaelle
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scheme or table
p. 1179 - 1183
(2010/05/02)
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- Efficient synthesis of "star-like" surfactants via "click chemistry" [3+2] copper (I)-catalyzed cycloaddition
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We report an efficient synthesis of tetra- and hexa-substituted carbohydrate-coated compounds, which we have named "star-like" surfactants, starting from either α-methylglucose or myo-inositol as a central core. The synthesis explores a new approach to su
- Neto, Virginie,Granet, Robert,Mackenzie, Grahame,Krausz, Pierre
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p. 231 - 237
(2008/12/20)
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- Design, synthesis, and biological testing of 4β-[(4-substituted)-1,2, 3-triazol-1-yl]podophyllotoxin analogues as antitumor agents
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A series of 4β-[(4-substituted)-1,2,3-triazol-1-yl]podophyllotoxin analogues have been synthesized with high regio-selectivity by employing copper(I)-catalyzed 1,3-dipolar cycloaddition of 1-O-propargyl monosaccharides with C4β-azido podophyllotoxin and C4β-azido-4′-O-demethyl podophyllotoxin. All the compounds were evaluated for their anticancer activity against a panel of six human cancer cell lines. Among these, 4′-O-demethyl podophyllotoxin congeners are showing promising anticancer activity mainly against HCT-15 (colon) and DU-145 (prostate) cells.
- Reddy, Pitta B.,Paul, David V.,Agrawal, Satyam K.,Saxena, Ajit K.,Kumar, Halmuthur M. S.,Qazi, Ghulam N.
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body text
p. 126 - 131
(2009/04/04)
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- Click multivalent neoglycoconjugates as synthetic activators in cell adhesion and stimulation of monocyte/machrophage cell lines
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The efficient synthesis of fluorescent and non-fluorescent multivalent neoglycoconjugates is described by means of the Cu(i) catalyzed azide-alkyne 1,3-dipolar cycloaddition ("click-chemistry"). A well-defined glycopolymer, glycocyclodextrin or glycocluster architecture displaying galactose or lactose epitopes has been chosen. Cellular assays using U-937 and RAW 264.7 monocyte/macrophage cells showed that these glycocompounds have the capability to act as synthetic activators mimicking the lipopolysaccharide (LPS) effects. Thus, the click compounds promote cell adhesion and stimulation of monocytes, measured as an increase in the amount of TNFα, facilitating their differentiation to macrophages. The Royal Society of Chemistry.
- Ortega-Munoz, Mariano,Morales-Sanfrutos, Julia,Perez-Balderas, Francisco,Hernandez-Mateo, Fernando,Giron-Gonzalez, Ma Dolores,Sevillano-Tripero, Natalia,Salto-Gonzalez, Rafael,Santoyo-Gonzalez, Francisco
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p. 2291 - 2301
(2008/09/16)
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- Study of metal and acid catalysed deprotection of propargyl ethers of alcohols via their allenyl ethers
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A new method for the deprotection of prop-2-ynyl ethers 1b-9b is described. Isomerisation of 1b-9b to O-allenyl ethers 1d-9d and deprotection by reaction with Hg(OCOCF3)2, aq.HCl, aq.CF3CO2H and best by use of a catalytic amount of OsO4 is described to obtain the alcohols 1a-9a in good yield. Application of this method for the deprotection of prop-2-enyl ethers 7c,8c,10c-13c via their corresponding prop-1-enyl ethers 7e,8e,10e-13e to obtain the corresponding alcohols 7a,8a,10a-13a is also described.
- Mereyala, Hari Babu,Gurrala, Srinivas Reddy,Mohan, S. Krishna
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p. 11331 - 11342
(2007/10/03)
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- Design, development and utility of glycosyl donors bearing an acetoxymethoxy leaving group
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Novel glycosyl donors 2d, 4d and 6d bearing an 'acetoxy methoxy' leaving group have been prepared and their utility is shown by coupling them with alcohols A-G to obtain di- and trisaccharides by use of BF3-Et2O as a promoter.
- Mereyala, Hari Babu,Gurrala, Srinivas Reddy
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p. 863 - 864
(2007/10/03)
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- Enzymatic Derivatization of Saccharides and Their Chemical Polymerization
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The enzymatic synthesis of sugar-based acetylene and ethylene derivatives as precursors to hydrophilic polymers is described.Propargyl and allyl alcohols have been used as glycosyl acceptors in the transglycosylation reactions of glycosidases with various disaccharides including lactose, maltose, and cellobiose.Reaction of propargyl and allyl alcohols with lactose catalyzed by β-galactosidase resulted in the formation of propargyl-β-D-galalactopyranoside and allyl-β-D-galactopyranoside in 42 and 13percent yields, respectively.Polymerization of propargyl-β-D-galactopyranoside with AlBr3 in ethanol resulted in the formation of oligomeric poly(acetylenic) species (Mw = 1,300).Free radical polymerization of allyl-β-D-galactopyranoside in DMF or water resulted in poly(ethylenic) species with Mw > 30,000.The combined enzymatic and chemical reactions inherent in these syntheses provide a unique approach in the preparation of hydrophilic polymers containing sugars and their derivatives.
- Blinkovsky, Alexander M.,Dordick, Jonathan S.
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p. 1221 - 1228
(2007/10/02)
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