Acid dissociation constants of uridine-5′-diphosphate compounds determined by 31phosphorus nuclear magnetic resonance spectroscopy and internal pH referencing
[Display omitted] ► The first reported phosphate and imide pKa values of UDP-GlcNAc and UDP-S-GlcNAc. ► New role for the monosaccharide in the imide pKa of uridine-5′-phosphate compounds. ► UDP-S-GlcNAc and UDP-GlcNAc have the same phosphate pKa, unlike thioyl analogs. ► The 31P chemical shift of in...
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► The first reported phosphate and imide pKa values of UDP-GlcNAc and UDP-S-GlcNAc. ► New role for the monosaccharide in the imide pKa of uridine-5′-phosphate compounds. ► UDP-S-GlcNAc and UDP-GlcNAc have the same phosphate pKa, unlike thioyl analogs. ► The 31P chemical shift of inorganic phosphate is a viable internal pH reference. ► Stability of the external 31P chemical shift reference is essential.
The acid dissociation constant (pKa) of small, biological molecules is an important physical property used for investigating enzyme mechanisms and inhibitor design. For phosphorus-containing molecules, the 31P nuclear magnetic resonance (NMR) chemical shift is sensitive to the local chemical environment, particularly to changes in the electronic state of the molecule. Taking advantage of this property, we present a 31P NMR approach that uses inorganic phosphate buffer as an internal pH reference to determine the pKa values of the imide and second diphosphate of uridine-5′-diphosphate compounds, including the first reported values for UDP-GlcNAc and UDP-S-GlcNAc. New methods for using inorganic phosphate buffer as an internal pH reference, involving mathematical correction factors and careful control of the chemical shift reference sample, are illustrated. A comparison of the newly determined imide and diphosphate pKa values of UDP, UDP-GlcNAc, and UDP-S-GlcNAc with other nucleotide phosphate and thio-analogs reveals the significance of the monosaccharide and sulfur position on the pKa values. |
doi_str_mv | 10.1016/j.aca.2012.08.052 |
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► The first reported phosphate and imide pKa values of UDP-GlcNAc and UDP-S-GlcNAc. ► New role for the monosaccharide in the imide pKa of uridine-5′-phosphate compounds. ► UDP-S-GlcNAc and UDP-GlcNAc have the same phosphate pKa, unlike thioyl analogs. ► The 31P chemical shift of inorganic phosphate is a viable internal pH reference. ► Stability of the external 31P chemical shift reference is essential.
The acid dissociation constant (pKa) of small, biological molecules is an important physical property used for investigating enzyme mechanisms and inhibitor design. For phosphorus-containing molecules, the 31P nuclear magnetic resonance (NMR) chemical shift is sensitive to the local chemical environment, particularly to changes in the electronic state of the molecule. Taking advantage of this property, we present a 31P NMR approach that uses inorganic phosphate buffer as an internal pH reference to determine the pKa values of the imide and second diphosphate of uridine-5′-diphosphate compounds, including the first reported values for UDP-GlcNAc and UDP-S-GlcNAc. New methods for using inorganic phosphate buffer as an internal pH reference, involving mathematical correction factors and careful control of the chemical shift reference sample, are illustrated. A comparison of the newly determined imide and diphosphate pKa values of UDP, UDP-GlcNAc, and UDP-S-GlcNAc with other nucleotide phosphate and thio-analogs reveals the significance of the monosaccharide and sulfur position on the pKa values.</description><identifier>ISSN: 0003-2670</identifier><identifier>EISSN: 1873-4324</identifier><identifier>DOI: 10.1016/j.aca.2012.08.052</identifier><identifier>PMID: 23036468</identifier><language>eng</language><publisher>Netherlands: Elsevier B.V</publisher><subject>31Phosphorus ; Acid dissociation ; Acids - chemistry ; Hydrogen-Ion Concentration ; Kinetics ; Magnetic Resonance Spectroscopy ; Nuclear magnetic resonance ; pH reference ; Phosphorus - chemistry ; Thio-analog ; Uridine 5′-diphosphate-N-acetylglucosamine ; Uridine Diphosphate - chemistry ; Uridine Diphosphate N-Acetylglucosamine - chemistry</subject><ispartof>Analytica chimica acta, 2012-10, Vol.749, p.63-69</ispartof><rights>2012 Elsevier B.V.</rights><rights>Copyright © 2012 Elsevier B.V. All rights reserved.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c2318-672b26934d96ecfd1d2211f221ca86427be455c4f10f16a6cb7a7e639ab6c9d73</citedby><cites>FETCH-LOGICAL-c2318-672b26934d96ecfd1d2211f221ca86427be455c4f10f16a6cb7a7e639ab6c9d73</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktohtml>$$Uhttps://dx.doi.org/10.1016/j.aca.2012.08.052$$EHTML$$P50$$Gelsevier$$H</linktohtml><link.rule.ids>314,780,784,3550,27924,27925,45995</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/23036468$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Jancan, Igor</creatorcontrib><creatorcontrib>Macnaughtan, Megan A.</creatorcontrib><title>Acid dissociation constants of uridine-5′-diphosphate compounds determined by 31phosphorus nuclear magnetic resonance spectroscopy and internal pH referencing</title><title>Analytica chimica acta</title><addtitle>Anal Chim Acta</addtitle><description>[Display omitted]
► The first reported phosphate and imide pKa values of UDP-GlcNAc and UDP-S-GlcNAc. ► New role for the monosaccharide in the imide pKa of uridine-5′-phosphate compounds. ► UDP-S-GlcNAc and UDP-GlcNAc have the same phosphate pKa, unlike thioyl analogs. ► The 31P chemical shift of inorganic phosphate is a viable internal pH reference. ► Stability of the external 31P chemical shift reference is essential.
The acid dissociation constant (pKa) of small, biological molecules is an important physical property used for investigating enzyme mechanisms and inhibitor design. For phosphorus-containing molecules, the 31P nuclear magnetic resonance (NMR) chemical shift is sensitive to the local chemical environment, particularly to changes in the electronic state of the molecule. Taking advantage of this property, we present a 31P NMR approach that uses inorganic phosphate buffer as an internal pH reference to determine the pKa values of the imide and second diphosphate of uridine-5′-diphosphate compounds, including the first reported values for UDP-GlcNAc and UDP-S-GlcNAc. New methods for using inorganic phosphate buffer as an internal pH reference, involving mathematical correction factors and careful control of the chemical shift reference sample, are illustrated. A comparison of the newly determined imide and diphosphate pKa values of UDP, UDP-GlcNAc, and UDP-S-GlcNAc with other nucleotide phosphate and thio-analogs reveals the significance of the monosaccharide and sulfur position on the pKa values.</description><subject>31Phosphorus</subject><subject>Acid dissociation</subject><subject>Acids - chemistry</subject><subject>Hydrogen-Ion Concentration</subject><subject>Kinetics</subject><subject>Magnetic Resonance Spectroscopy</subject><subject>Nuclear magnetic resonance</subject><subject>pH reference</subject><subject>Phosphorus - chemistry</subject><subject>Thio-analog</subject><subject>Uridine 5′-diphosphate-N-acetylglucosamine</subject><subject>Uridine Diphosphate - chemistry</subject><subject>Uridine Diphosphate N-Acetylglucosamine - chemistry</subject><issn>0003-2670</issn><issn>1873-4324</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2012</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNqFkU1u1TAURi0Eoq-FBTBBHjJJ8N9zHDGqKqBIlZjA2HKub1o_JXawE6Q3YyldA0tiJbh6hSFMbFk695Pvdwh5xVnLGddvD60D1wrGRctMy_biCdlx08lGSaGekh1jTDZCd-yMnJdyqE_BmXpOzoRkUittduT-EoKnPpSSILg1pEghxbK6uBaaRrrl4EPEZv_rx8_Gh-UuleXOrVipeUlb9IV6XDHPFfJ0OFLJT0zKW6FxgwldprO7jbgGoBlLii4C0rIgrDkVSMuRuuhpiDUmuoku1xUbMWOEEG9fkGejmwq-fLwvyNcP779cXTc3nz9-urq8aUBIbhrdiUHoXirfa4TRcy8E52M9wBmtRDeg2u9BjZyNXDsNQ-c61LJ3g4bed_KCvDnlLjl927Csdg4FcJpcxLQVy3nHjdG8V_9HWf2HMbxnFeUnFOqqpa5llxxml48Vsg8O7cFWh_bBoWXGVod15vVj_DbM6P9O_JFWgXcnAGsf3wNmWyDUttCHXEu1PoV_xP8GLJqwrg</recordid><startdate>20121024</startdate><enddate>20121024</enddate><creator>Jancan, Igor</creator><creator>Macnaughtan, Megan A.</creator><general>Elsevier B.V</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><scope>7ST</scope><scope>C1K</scope><scope>SOI</scope></search><sort><creationdate>20121024</creationdate><title>Acid dissociation constants of uridine-5′-diphosphate compounds determined by 31phosphorus nuclear magnetic resonance spectroscopy and internal pH referencing</title><author>Jancan, Igor ; Macnaughtan, Megan A.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c2318-672b26934d96ecfd1d2211f221ca86427be455c4f10f16a6cb7a7e639ab6c9d73</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2012</creationdate><topic>31Phosphorus</topic><topic>Acid dissociation</topic><topic>Acids - chemistry</topic><topic>Hydrogen-Ion Concentration</topic><topic>Kinetics</topic><topic>Magnetic Resonance Spectroscopy</topic><topic>Nuclear magnetic resonance</topic><topic>pH reference</topic><topic>Phosphorus - chemistry</topic><topic>Thio-analog</topic><topic>Uridine 5′-diphosphate-N-acetylglucosamine</topic><topic>Uridine Diphosphate - chemistry</topic><topic>Uridine Diphosphate N-Acetylglucosamine - chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Jancan, Igor</creatorcontrib><creatorcontrib>Macnaughtan, Megan A.</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><collection>Environment Abstracts</collection><collection>Environmental Sciences and Pollution Management</collection><collection>Environment Abstracts</collection><jtitle>Analytica chimica acta</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Jancan, Igor</au><au>Macnaughtan, Megan A.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Acid dissociation constants of uridine-5′-diphosphate compounds determined by 31phosphorus nuclear magnetic resonance spectroscopy and internal pH referencing</atitle><jtitle>Analytica chimica acta</jtitle><addtitle>Anal Chim Acta</addtitle><date>2012-10-24</date><risdate>2012</risdate><volume>749</volume><spage>63</spage><epage>69</epage><pages>63-69</pages><issn>0003-2670</issn><eissn>1873-4324</eissn><abstract>[Display omitted]
► The first reported phosphate and imide pKa values of UDP-GlcNAc and UDP-S-GlcNAc. ► New role for the monosaccharide in the imide pKa of uridine-5′-phosphate compounds. ► UDP-S-GlcNAc and UDP-GlcNAc have the same phosphate pKa, unlike thioyl analogs. ► The 31P chemical shift of inorganic phosphate is a viable internal pH reference. ► Stability of the external 31P chemical shift reference is essential.
The acid dissociation constant (pKa) of small, biological molecules is an important physical property used for investigating enzyme mechanisms and inhibitor design. For phosphorus-containing molecules, the 31P nuclear magnetic resonance (NMR) chemical shift is sensitive to the local chemical environment, particularly to changes in the electronic state of the molecule. Taking advantage of this property, we present a 31P NMR approach that uses inorganic phosphate buffer as an internal pH reference to determine the pKa values of the imide and second diphosphate of uridine-5′-diphosphate compounds, including the first reported values for UDP-GlcNAc and UDP-S-GlcNAc. New methods for using inorganic phosphate buffer as an internal pH reference, involving mathematical correction factors and careful control of the chemical shift reference sample, are illustrated. A comparison of the newly determined imide and diphosphate pKa values of UDP, UDP-GlcNAc, and UDP-S-GlcNAc with other nucleotide phosphate and thio-analogs reveals the significance of the monosaccharide and sulfur position on the pKa values.</abstract><cop>Netherlands</cop><pub>Elsevier B.V</pub><pmid>23036468</pmid><doi>10.1016/j.aca.2012.08.052</doi><tpages>7</tpages></addata></record> |
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subjects | 31Phosphorus Acid dissociation Acids - chemistry Hydrogen-Ion Concentration Kinetics Magnetic Resonance Spectroscopy Nuclear magnetic resonance pH reference Phosphorus - chemistry Thio-analog Uridine 5′-diphosphate-N-acetylglucosamine Uridine Diphosphate - chemistry Uridine Diphosphate N-Acetylglucosamine - chemistry |
title | Acid dissociation constants of uridine-5′-diphosphate compounds determined by 31phosphorus nuclear magnetic resonance spectroscopy and internal pH referencing |
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