Formation of isomers of anionic hemiesters of sugars and carbonic acid in aqueous medium
•Hemiesters of carbonic acid and sugars are spontaneously formed in aqueous solutions.•Isomers are formed according to the reactivity of the hydroxy group.•Higher concentrations of carbonate are observed for sugars with a primary alcohol.•d-Glucopyranose 6-carbonate corresponds to 74% of the glucose...
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Veröffentlicht in: | Carbohydrate research 2016-06, Vol.428, p.18-22 |
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creator | dos Santos, Vagner B. Vidal, Denis T.R. Francisco, Kelliton J.M. Ducati, Lucas C. do Lago, Claudimir L. |
description | •Hemiesters of carbonic acid and sugars are spontaneously formed in aqueous solutions.•Isomers are formed according to the reactivity of the hydroxy group.•Higher concentrations of carbonate are observed for sugars with a primary alcohol.•d-Glucopyranose 6-carbonate corresponds to 74% of the glucose carbonate in water.
[Display omitted]
Hemiesters of carbonic acid can be freely formed in aqueous media containing HCO3−/CO2 and mono- or poly-hydroxy compounds. Herein, 13C NMR spectroscopy was used to identify isomers formed in aqueous solutions of glycerol (a prototype compound) and seven carbohydrates, as well as to estimate the equilibrium constant of formation (Keq). Although both isomers are formed, glycerol 1-carbonate corresponds to 90% of the product. While fructose and ribose form an indistinct mixture of isomers, the anomers of d-glucopyranose 6-carbonate correspond to 74% of the eight isomers of glucose carbonate that were detected. The values of Keq for the disaccharides sucrose (4.3) and maltose (4.2) are about twice the values for the monosaccharides glucose (2.0) and fructose (2.3). Ribose (Keq = 0.89)—the only sugar without a significant concentration of a species containing a –CH2OH group in an aqueous solution—resulted in the smallest Keq. On the basis of the Keq value and the concentrations of HCO3− and glucose in blood, one can anticipate a concentration of 2–4 µmol L–1 for glucose 6-carbonate, which corresponds to ca. of 10% of its phosphate counterpart (glucose 6-phosphate). |
doi_str_mv | 10.1016/j.carres.2016.04.007 |
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[Display omitted]
Hemiesters of carbonic acid can be freely formed in aqueous media containing HCO3−/CO2 and mono- or poly-hydroxy compounds. Herein, 13C NMR spectroscopy was used to identify isomers formed in aqueous solutions of glycerol (a prototype compound) and seven carbohydrates, as well as to estimate the equilibrium constant of formation (Keq). Although both isomers are formed, glycerol 1-carbonate corresponds to 90% of the product. While fructose and ribose form an indistinct mixture of isomers, the anomers of d-glucopyranose 6-carbonate correspond to 74% of the eight isomers of glucose carbonate that were detected. The values of Keq for the disaccharides sucrose (4.3) and maltose (4.2) are about twice the values for the monosaccharides glucose (2.0) and fructose (2.3). Ribose (Keq = 0.89)—the only sugar without a significant concentration of a species containing a –CH2OH group in an aqueous solution—resulted in the smallest Keq. On the basis of the Keq value and the concentrations of HCO3− and glucose in blood, one can anticipate a concentration of 2–4 µmol L–1 for glucose 6-carbonate, which corresponds to ca. of 10% of its phosphate counterpart (glucose 6-phosphate).</description><identifier>ISSN: 0008-6215</identifier><identifier>EISSN: 1873-426X</identifier><identifier>DOI: 10.1016/j.carres.2016.04.007</identifier><identifier>PMID: 27111726</identifier><language>eng</language><publisher>Netherlands: Elsevier Ltd</publisher><subject>Carbohydrates - chemistry ; Carbon-13 Magnetic Resonance Spectroscopy - methods ; Carbonic Acid - chemistry ; Esters - chemical synthesis ; Esters - chemistry ; Glycerol - chemistry ; Hemiester of carbonic acid ; Isomerism ; Isomers ; Molecular Structure ; Monoalkyl carbonate ; NMR spectroscopy ; Sugar carbonate ; Water - chemistry</subject><ispartof>Carbohydrate research, 2016-06, Vol.428, p.18-22</ispartof><rights>2016 Elsevier Ltd</rights><rights>Copyright © 2016 Elsevier Ltd. All rights reserved.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c362t-b9ef12361dbe76578c8c82d3023afe1053374438743bb988bb6b998bdf8a3af83</citedby><cites>FETCH-LOGICAL-c362t-b9ef12361dbe76578c8c82d3023afe1053374438743bb988bb6b998bdf8a3af83</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktohtml>$$Uhttps://dx.doi.org/10.1016/j.carres.2016.04.007$$EHTML$$P50$$Gelsevier$$H</linktohtml><link.rule.ids>314,780,784,3550,27924,27925,45995</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/27111726$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>dos Santos, Vagner B.</creatorcontrib><creatorcontrib>Vidal, Denis T.R.</creatorcontrib><creatorcontrib>Francisco, Kelliton J.M.</creatorcontrib><creatorcontrib>Ducati, Lucas C.</creatorcontrib><creatorcontrib>do Lago, Claudimir L.</creatorcontrib><title>Formation of isomers of anionic hemiesters of sugars and carbonic acid in aqueous medium</title><title>Carbohydrate research</title><addtitle>Carbohydr Res</addtitle><description>•Hemiesters of carbonic acid and sugars are spontaneously formed in aqueous solutions.•Isomers are formed according to the reactivity of the hydroxy group.•Higher concentrations of carbonate are observed for sugars with a primary alcohol.•d-Glucopyranose 6-carbonate corresponds to 74% of the glucose carbonate in water.
[Display omitted]
Hemiesters of carbonic acid can be freely formed in aqueous media containing HCO3−/CO2 and mono- or poly-hydroxy compounds. Herein, 13C NMR spectroscopy was used to identify isomers formed in aqueous solutions of glycerol (a prototype compound) and seven carbohydrates, as well as to estimate the equilibrium constant of formation (Keq). Although both isomers are formed, glycerol 1-carbonate corresponds to 90% of the product. While fructose and ribose form an indistinct mixture of isomers, the anomers of d-glucopyranose 6-carbonate correspond to 74% of the eight isomers of glucose carbonate that were detected. The values of Keq for the disaccharides sucrose (4.3) and maltose (4.2) are about twice the values for the monosaccharides glucose (2.0) and fructose (2.3). Ribose (Keq = 0.89)—the only sugar without a significant concentration of a species containing a –CH2OH group in an aqueous solution—resulted in the smallest Keq. On the basis of the Keq value and the concentrations of HCO3− and glucose in blood, one can anticipate a concentration of 2–4 µmol L–1 for glucose 6-carbonate, which corresponds to ca. of 10% of its phosphate counterpart (glucose 6-phosphate).</description><subject>Carbohydrates - chemistry</subject><subject>Carbon-13 Magnetic Resonance Spectroscopy - methods</subject><subject>Carbonic Acid - chemistry</subject><subject>Esters - chemical synthesis</subject><subject>Esters - chemistry</subject><subject>Glycerol - chemistry</subject><subject>Hemiester of carbonic acid</subject><subject>Isomerism</subject><subject>Isomers</subject><subject>Molecular Structure</subject><subject>Monoalkyl carbonate</subject><subject>NMR spectroscopy</subject><subject>Sugar carbonate</subject><subject>Water - chemistry</subject><issn>0008-6215</issn><issn>1873-426X</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2016</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNp9kE1LxDAQhoMo7rr6D0R69NKajzYfF0EWV4UFLwp7C0maapZtsyat4L83tatHySEzwzPzzrwAXCJYIIjozbYwKgQbC5yyApYFhOwIzBFnJC8x3RyDOYSQ5xSjagbOYtymFFJGT8EMM4QQw3QONisfWtU732W-yVz0rQ1xDFWXas5k77Z1NvaHahzeVIpUV2dJXf8Qyrg6c12mPgbrh5i1tnZDew5OGrWL9uLwL8Dr6v5l-Zivnx-elnfr3BCK-1wL2yBMKKq1ZbRi3KSHawIxUY1FsCKElSXhrCRaC861ploIruuGq0RwsgDX09x98GmB2MvWRWN3O9WN20jEBBS4EqJMaDmhJvgYg23kPrhWhS-JoBw9lVs5eSpHTyUsZfI0tV0dFAadbvtr-jUxAbcTYNOdn84GGY2znUk-BGt6WXv3v8I3NQeKKA</recordid><startdate>20160616</startdate><enddate>20160616</enddate><creator>dos Santos, Vagner B.</creator><creator>Vidal, Denis T.R.</creator><creator>Francisco, Kelliton J.M.</creator><creator>Ducati, Lucas C.</creator><creator>do Lago, Claudimir L.</creator><general>Elsevier Ltd</general><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20160616</creationdate><title>Formation of isomers of anionic hemiesters of sugars and carbonic acid in aqueous medium</title><author>dos Santos, Vagner B. ; Vidal, Denis T.R. ; Francisco, Kelliton J.M. ; Ducati, Lucas C. ; do Lago, Claudimir L.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c362t-b9ef12361dbe76578c8c82d3023afe1053374438743bb988bb6b998bdf8a3af83</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2016</creationdate><topic>Carbohydrates - chemistry</topic><topic>Carbon-13 Magnetic Resonance Spectroscopy - methods</topic><topic>Carbonic Acid - chemistry</topic><topic>Esters - chemical synthesis</topic><topic>Esters - chemistry</topic><topic>Glycerol - chemistry</topic><topic>Hemiester of carbonic acid</topic><topic>Isomerism</topic><topic>Isomers</topic><topic>Molecular Structure</topic><topic>Monoalkyl carbonate</topic><topic>NMR spectroscopy</topic><topic>Sugar carbonate</topic><topic>Water - chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>dos Santos, Vagner B.</creatorcontrib><creatorcontrib>Vidal, Denis T.R.</creatorcontrib><creatorcontrib>Francisco, Kelliton J.M.</creatorcontrib><creatorcontrib>Ducati, Lucas C.</creatorcontrib><creatorcontrib>do Lago, Claudimir L.</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Carbohydrate research</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>dos Santos, Vagner B.</au><au>Vidal, Denis T.R.</au><au>Francisco, Kelliton J.M.</au><au>Ducati, Lucas C.</au><au>do Lago, Claudimir L.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Formation of isomers of anionic hemiesters of sugars and carbonic acid in aqueous medium</atitle><jtitle>Carbohydrate research</jtitle><addtitle>Carbohydr Res</addtitle><date>2016-06-16</date><risdate>2016</risdate><volume>428</volume><spage>18</spage><epage>22</epage><pages>18-22</pages><issn>0008-6215</issn><eissn>1873-426X</eissn><abstract>•Hemiesters of carbonic acid and sugars are spontaneously formed in aqueous solutions.•Isomers are formed according to the reactivity of the hydroxy group.•Higher concentrations of carbonate are observed for sugars with a primary alcohol.•d-Glucopyranose 6-carbonate corresponds to 74% of the glucose carbonate in water.
[Display omitted]
Hemiesters of carbonic acid can be freely formed in aqueous media containing HCO3−/CO2 and mono- or poly-hydroxy compounds. Herein, 13C NMR spectroscopy was used to identify isomers formed in aqueous solutions of glycerol (a prototype compound) and seven carbohydrates, as well as to estimate the equilibrium constant of formation (Keq). Although both isomers are formed, glycerol 1-carbonate corresponds to 90% of the product. While fructose and ribose form an indistinct mixture of isomers, the anomers of d-glucopyranose 6-carbonate correspond to 74% of the eight isomers of glucose carbonate that were detected. The values of Keq for the disaccharides sucrose (4.3) and maltose (4.2) are about twice the values for the monosaccharides glucose (2.0) and fructose (2.3). Ribose (Keq = 0.89)—the only sugar without a significant concentration of a species containing a –CH2OH group in an aqueous solution—resulted in the smallest Keq. On the basis of the Keq value and the concentrations of HCO3− and glucose in blood, one can anticipate a concentration of 2–4 µmol L–1 for glucose 6-carbonate, which corresponds to ca. of 10% of its phosphate counterpart (glucose 6-phosphate).</abstract><cop>Netherlands</cop><pub>Elsevier Ltd</pub><pmid>27111726</pmid><doi>10.1016/j.carres.2016.04.007</doi><tpages>5</tpages></addata></record> |
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subjects | Carbohydrates - chemistry Carbon-13 Magnetic Resonance Spectroscopy - methods Carbonic Acid - chemistry Esters - chemical synthesis Esters - chemistry Glycerol - chemistry Hemiester of carbonic acid Isomerism Isomers Molecular Structure Monoalkyl carbonate NMR spectroscopy Sugar carbonate Water - chemistry |
title | Formation of isomers of anionic hemiesters of sugars and carbonic acid in aqueous medium |
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