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NMR study of the rotational dynamics of linear homopolysaccharides in dilute solutions as a function of linkage position and stereochemistry
Variable temperature and magnetic field dependent 13C NMR relaxation measurements ( T 1, T 2, and NOE) were carried out on a series of linear homopolysaccharides: α-(1→3)- d-glucan, β-(1→3)- d-glucan in Me 2SO- d 6, and α-(1→6)- d-glucan in D 2O and Me 2SO- d 6 dilute solutions. The relaxation data...
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Published in: | Carbohydrate research 1999, Vol.315 (1), p.16-34 |
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container_title | Carbohydrate research |
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creator | Tylianakis, Manolis Spyros, Apostolos Dais, Photis Taravel, Francois R. Perico, Angelo |
description | Variable temperature and magnetic field dependent
13C NMR relaxation measurements (
T
1,
T
2, and NOE) were carried out on a series of linear homopolysaccharides: α-(1→3)-
d-glucan, β-(1→3)-
d-glucan in Me
2SO-
d
6, and α-(1→6)-
d-glucan in D
2O and Me
2SO-
d
6 dilute solutions. The relaxation data of the backbone carbons were analyzed quantitatively by using a variety of theoretical unimodal and bimodal time-correlation functions in an attempt to describe the main carbohydrate chain dynamics as a function of linkage position and stereochemistry. Among these, the time-correlation function developed by Dejean, Laupretre, and Monnerie (DLM) offered the best quantitative description of the segmental motion of the carbohydrate chains. The internal rotation of the hydroxymethyl groups about the exocyclic C-5–C-6 bonds superimposed on segmental motion has been described as a diffusion process of restricted amplitude. Comparison of the dynamics of polysaccharides has been extended to include amylose and inulin studied previously. On the basis of the calculated correlation times for segmental motion, the flexibility of the carbohydrate chains decreases from inulin and dextran following the order; inulin>dextran>α-(1→3)-
d-glucan>β-(1→3)-
d-glucan∼amylose, whereas the rate and the amplitude of the internal rotation of the hydroxymethyl groups about the exocyclic C-5–C-6 bonds showed that the restriction of the hydroxymethyl internal rotation decreases from inulin to amylose following the order; inulin>α-(1→3)-
d-glucan∼β-(1→3)-
d-glucan>amylose. Solvent effects on segmental dynamics and the temperature–frequency superposition of the relaxation data of the three polysaccharides have been discussed as well. |
doi_str_mv | 10.1016/S0008-6215(98)00263-8 |
format | article |
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13C NMR relaxation measurements (
T
1,
T
2, and NOE) were carried out on a series of linear homopolysaccharides: α-(1→3)-
d-glucan, β-(1→3)-
d-glucan in Me
2SO-
d
6, and α-(1→6)-
d-glucan in D
2O and Me
2SO-
d
6 dilute solutions. The relaxation data of the backbone carbons were analyzed quantitatively by using a variety of theoretical unimodal and bimodal time-correlation functions in an attempt to describe the main carbohydrate chain dynamics as a function of linkage position and stereochemistry. Among these, the time-correlation function developed by Dejean, Laupretre, and Monnerie (DLM) offered the best quantitative description of the segmental motion of the carbohydrate chains. The internal rotation of the hydroxymethyl groups about the exocyclic C-5–C-6 bonds superimposed on segmental motion has been described as a diffusion process of restricted amplitude. Comparison of the dynamics of polysaccharides has been extended to include amylose and inulin studied previously. On the basis of the calculated correlation times for segmental motion, the flexibility of the carbohydrate chains decreases from inulin and dextran following the order; inulin>dextran>α-(1→3)-
d-glucan>β-(1→3)-
d-glucan∼amylose, whereas the rate and the amplitude of the internal rotation of the hydroxymethyl groups about the exocyclic C-5–C-6 bonds showed that the restriction of the hydroxymethyl internal rotation decreases from inulin to amylose following the order; inulin>α-(1→3)-
d-glucan∼β-(1→3)-
d-glucan>amylose. Solvent effects on segmental dynamics and the temperature–frequency superposition of the relaxation data of the three polysaccharides have been discussed as well.</description><identifier>ISSN: 0008-6215</identifier><identifier>EISSN: 1873-426X</identifier><identifier>EISSN: 0008-6215</identifier><identifier>DOI: 10.1016/S0008-6215(98)00263-8</identifier><language>eng</language><publisher>Elsevier Ltd</publisher><subject>Dynamics ; molecular conformation ; NMR-relaxation ; nuclear magnetic resonance spectroscopy ; Polysaccharides ; Time-correlation functions</subject><ispartof>Carbohydrate research, 1999, Vol.315 (1), p.16-34</ispartof><rights>1999 Elsevier Science Ltd</rights><rights>Distributed under a Creative Commons Attribution 4.0 International License</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c365t-1b779c944daef1729ba1994ddaf079712d7ab41a612ddfd439c78ed27b5bebb33</citedby><cites>FETCH-LOGICAL-c365t-1b779c944daef1729ba1994ddaf079712d7ab41a612ddfd439c78ed27b5bebb33</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>230,314,780,784,885,4024,27923,27924,27925</link.rule.ids><backlink>$$Uhttps://hal.science/hal-00309798$$DView record in HAL$$Hfree_for_read</backlink></links><search><creatorcontrib>Tylianakis, Manolis</creatorcontrib><creatorcontrib>Spyros, Apostolos</creatorcontrib><creatorcontrib>Dais, Photis</creatorcontrib><creatorcontrib>Taravel, Francois R.</creatorcontrib><creatorcontrib>Perico, Angelo</creatorcontrib><title>NMR study of the rotational dynamics of linear homopolysaccharides in dilute solutions as a function of linkage position and stereochemistry</title><title>Carbohydrate research</title><description>Variable temperature and magnetic field dependent
13C NMR relaxation measurements (
T
1,
T
2, and NOE) were carried out on a series of linear homopolysaccharides: α-(1→3)-
d-glucan, β-(1→3)-
d-glucan in Me
2SO-
d
6, and α-(1→6)-
d-glucan in D
2O and Me
2SO-
d
6 dilute solutions. The relaxation data of the backbone carbons were analyzed quantitatively by using a variety of theoretical unimodal and bimodal time-correlation functions in an attempt to describe the main carbohydrate chain dynamics as a function of linkage position and stereochemistry. Among these, the time-correlation function developed by Dejean, Laupretre, and Monnerie (DLM) offered the best quantitative description of the segmental motion of the carbohydrate chains. The internal rotation of the hydroxymethyl groups about the exocyclic C-5–C-6 bonds superimposed on segmental motion has been described as a diffusion process of restricted amplitude. Comparison of the dynamics of polysaccharides has been extended to include amylose and inulin studied previously. On the basis of the calculated correlation times for segmental motion, the flexibility of the carbohydrate chains decreases from inulin and dextran following the order; inulin>dextran>α-(1→3)-
d-glucan>β-(1→3)-
d-glucan∼amylose, whereas the rate and the amplitude of the internal rotation of the hydroxymethyl groups about the exocyclic C-5–C-6 bonds showed that the restriction of the hydroxymethyl internal rotation decreases from inulin to amylose following the order; inulin>α-(1→3)-
d-glucan∼β-(1→3)-
d-glucan>amylose. Solvent effects on segmental dynamics and the temperature–frequency superposition of the relaxation data of the three polysaccharides have been discussed as well.</description><subject>Dynamics</subject><subject>molecular conformation</subject><subject>NMR-relaxation</subject><subject>nuclear magnetic resonance spectroscopy</subject><subject>Polysaccharides</subject><subject>Time-correlation functions</subject><issn>0008-6215</issn><issn>1873-426X</issn><issn>0008-6215</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1999</creationdate><recordtype>article</recordtype><recordid>eNqFkM9q3DAQxkVoIdu0j1CiY3NwKsl_ZJ1KCEk2sG0g20BvYiyNY6Vea5G8C36HPnTk3ZBrQTCamd83w3yEfOXskjNefV8zxuqsErz8puoLxkSVZ_UJWfBa5lkhqj8fyOIdOSWfYnxJKatktSD_fv18pHHc2Yn6lo4d0uBHGJ0foKd2GmDjTJxbvRsQAu38xm99P0UwpoPgLEbqBmpdvxuRRp9C0kYK6dF2N5g5fdP_hWekWx_doQaDTYsxoDcdblwcw_SZfGyhj_jlLZ6Rp9ub39fLbPVwd399tcpMXpVjxhsplVFFYQFbLoVqgCtVWAstk0pyYSU0BYcq_Wxri1wZWaMVsikbbJo8PyMXx7kd9Hob3AbCpD04vbxa6bnGWM6UVPWeJ7Y8sib4GAO27wLO9Gy_PtivZ2-1qvXBfl0n3flR14LX8Bxc1E9rwXjOhGKFKMpE_DgSmE7dOww6GoeDQesCmlFb7_6z4xUy_pl1</recordid><startdate>1999</startdate><enddate>1999</enddate><creator>Tylianakis, Manolis</creator><creator>Spyros, Apostolos</creator><creator>Dais, Photis</creator><creator>Taravel, Francois R.</creator><creator>Perico, Angelo</creator><general>Elsevier Ltd</general><general>Elsevier</general><scope>FBQ</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>1XC</scope></search><sort><creationdate>1999</creationdate><title>NMR study of the rotational dynamics of linear homopolysaccharides in dilute solutions as a function of linkage position and stereochemistry</title><author>Tylianakis, Manolis ; Spyros, Apostolos ; Dais, Photis ; Taravel, Francois R. ; Perico, Angelo</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c365t-1b779c944daef1729ba1994ddaf079712d7ab41a612ddfd439c78ed27b5bebb33</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1999</creationdate><topic>Dynamics</topic><topic>molecular conformation</topic><topic>NMR-relaxation</topic><topic>nuclear magnetic resonance spectroscopy</topic><topic>Polysaccharides</topic><topic>Time-correlation functions</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Tylianakis, Manolis</creatorcontrib><creatorcontrib>Spyros, Apostolos</creatorcontrib><creatorcontrib>Dais, Photis</creatorcontrib><creatorcontrib>Taravel, Francois R.</creatorcontrib><creatorcontrib>Perico, Angelo</creatorcontrib><collection>AGRIS</collection><collection>CrossRef</collection><collection>Hyper Article en Ligne (HAL)</collection><jtitle>Carbohydrate research</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Tylianakis, Manolis</au><au>Spyros, Apostolos</au><au>Dais, Photis</au><au>Taravel, Francois R.</au><au>Perico, Angelo</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>NMR study of the rotational dynamics of linear homopolysaccharides in dilute solutions as a function of linkage position and stereochemistry</atitle><jtitle>Carbohydrate research</jtitle><date>1999</date><risdate>1999</risdate><volume>315</volume><issue>1</issue><spage>16</spage><epage>34</epage><pages>16-34</pages><issn>0008-6215</issn><eissn>1873-426X</eissn><eissn>0008-6215</eissn><abstract>Variable temperature and magnetic field dependent
13C NMR relaxation measurements (
T
1,
T
2, and NOE) were carried out on a series of linear homopolysaccharides: α-(1→3)-
d-glucan, β-(1→3)-
d-glucan in Me
2SO-
d
6, and α-(1→6)-
d-glucan in D
2O and Me
2SO-
d
6 dilute solutions. The relaxation data of the backbone carbons were analyzed quantitatively by using a variety of theoretical unimodal and bimodal time-correlation functions in an attempt to describe the main carbohydrate chain dynamics as a function of linkage position and stereochemistry. Among these, the time-correlation function developed by Dejean, Laupretre, and Monnerie (DLM) offered the best quantitative description of the segmental motion of the carbohydrate chains. The internal rotation of the hydroxymethyl groups about the exocyclic C-5–C-6 bonds superimposed on segmental motion has been described as a diffusion process of restricted amplitude. Comparison of the dynamics of polysaccharides has been extended to include amylose and inulin studied previously. On the basis of the calculated correlation times for segmental motion, the flexibility of the carbohydrate chains decreases from inulin and dextran following the order; inulin>dextran>α-(1→3)-
d-glucan>β-(1→3)-
d-glucan∼amylose, whereas the rate and the amplitude of the internal rotation of the hydroxymethyl groups about the exocyclic C-5–C-6 bonds showed that the restriction of the hydroxymethyl internal rotation decreases from inulin to amylose following the order; inulin>α-(1→3)-
d-glucan∼β-(1→3)-
d-glucan>amylose. Solvent effects on segmental dynamics and the temperature–frequency superposition of the relaxation data of the three polysaccharides have been discussed as well.</abstract><pub>Elsevier Ltd</pub><doi>10.1016/S0008-6215(98)00263-8</doi><tpages>19</tpages></addata></record> |
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source | ScienceDirect Journals |
subjects | Dynamics molecular conformation NMR-relaxation nuclear magnetic resonance spectroscopy Polysaccharides Time-correlation functions |
title | NMR study of the rotational dynamics of linear homopolysaccharides in dilute solutions as a function of linkage position and stereochemistry |
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