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タイトル
Conformational, Dimensional, and Hydrodynamic Properties of Amylose Tris(n-butylcarbamate) in Tetrahydrofuran, Methanol, and Their Mixtures
著者
Terao, Ken
Terao, Ken
Murashima, Maiko
Murashima, Maiko
Sano, Yuichi
Sano, Yuichi
Arakawa, Shota
Arakawa, Shota
Kitamura, Shinichi
Kitamura, Shinichi
Norisuye, Takashi
Norisuye, Takashi
内容
This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in Macromolecules, copyright © American Chemical Society after peer review. To access the final edited and published work see https://doi.org/10.1021/ma902200z.
抄録
Twelve amylose tris(n-butylcarbamate) (ATBC) samples ranging in weight-average molecular weight from 1.7 × 104 to 1.7 × 106 have been prepared and studied by light and small-angle X-ray scattering, sedimentation equilibrium, viscosity, infrared absorption (IR), and optical rotation in methanol (MeOH), tetrahydrofuran (THF), and their mixtures at 25 °C (or 20−25 °C for IR). Data for the mean-square radius of gyration, the particle scattering function, and the intrinsic viscosity are analyzed on the basis of the wormlike chain to yield h (contour length per residue) = 0.32 nm and λ−1 (Kuhn’s segment length) = 11 nm in MeOH and h = 0.26 nm and λ−1 = 75 nm in THF. The high stiffness in THF indicated by λ−1 = 75 nm is most likely due to the intramolecular hydrogen bonding (between C═O and NH groups of ATBC) observed as the splitting amide I band in the IR spectra. Furthermore, the h value in this solvent is considerably smaller than the helix pitches per residue of 0.37−0.40 nm for amylose triesters in the crystalline state and those of 0.32−0.42 nm for semiflexible amylose tris(phenylcarbamate) in various solvents (λ−1 = 15−24 nm), indicating that the ATBC chain forms a tightly wound helix in THF. As the number of intramolecular hydrogen bonds decreases, i.e., as the MeOH content increases in THF−MeOH mixed solvents, λ−1 decreases while h increases. These relationships are successfully explained by a two-state model in which each chain consists of randomly distributed semiflexible (loosely helical) and rodlike (rigid helical) sequences. The resultant h values for the rodlike and semiflexible portions are 0.25−0.26 and 0.32 nm, respectively.
公開者
American Chemical Society
掲載誌名
Macromolecules
巻
43
号
2
開始ページ
1061
終了ページ
1068
刊行年月
2009-10-28
ISSN
00249297
15205835
NCID
AA0071963X
DOI
info:doi/10.1021/ma902200z
URL
http://hdl.handle.net/11094/77669
権利情報
Copyright © 2009 American Chemical Society
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英語
カテゴリ
学術雑誌論文 Journal Article
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DCTERMS.bibliographicCitation
Inorganic Chemistry.52(24) P.14368-P.14375
DC.title
Conformational, Dimensional, and Hydrodynamic Properties of Amylose Tris(n-butylcarbamate) in Tetrahydrofuran, Methanol, and Their Mixtures
DC.creator
Terao, Ken
Murashima, Maiko
Sano, Yuichi
Arakawa, Shota
Kitamura, Shinichi
Norisuye, Takashi
DC.publisher
American Chemical Society
DC.language" scheme="DCTERMS.RFC1766
英語
DCTERMS.issued" scheme="DCTERMS.W3CDTF
2009-10-28
DC.identifier
info:doi/10.1021/ma902200z
DC.identifier" scheme="DCTERMS.URI
http://hdl.handle.net/11094/77669
DC.description
This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in Macromolecules, copyright © American Chemical Society after peer review. To access the final edited and published work see https://doi.org/10.1021/ma902200z.
DCTERMS.abstract
Twelve amylose tris(n-butylcarbamate) (ATBC) samples ranging in weight-average molecular weight from 1.7 × 104 to 1.7 × 106 have been prepared and studied by light and small-angle X-ray scattering, sedimentation equilibrium, viscosity, infrared absorption (IR), and optical rotation in methanol (MeOH), tetrahydrofuran (THF), and their mixtures at 25 °C (or 20−25 °C for IR). Data for the mean-square radius of gyration, the particle scattering function, and the intrinsic viscosity are analyzed on the basis of the wormlike chain to yield h (contour length per residue) = 0.32 nm and λ−1 (Kuhn’s segment length) = 11 nm in MeOH and h = 0.26 nm and λ−1 = 75 nm in THF. The high stiffness in THF indicated by λ−1 = 75 nm is most likely due to the intramolecular hydrogen bonding (between C═O and NH groups of ATBC) observed as the splitting amide I band in the IR spectra. Furthermore, the h value in this solvent is considerably smaller than the helix pitches per residue of 0.37−0.40 nm for amylose triesters in the crystalline state and those of 0.32−0.42 nm for semiflexible amylose tris(phenylcarbamate) in various solvents (λ−1 = 15−24 nm), indicating that the ATBC chain forms a tightly wound helix in THF. As the number of intramolecular hydrogen bonds decreases, i.e., as the MeOH content increases in THF−MeOH mixed solvents, λ−1 decreases while h increases. These relationships are successfully explained by a two-state model in which each chain consists of randomly distributed semiflexible (loosely helical) and rodlike (rigid helical) sequences. The resultant h values for the rodlike and semiflexible portions are 0.25−0.26 and 0.32 nm, respectively.
DC.rights
Copyright © 2009 American Chemical Society
citation_title
Conformational, Dimensional, and Hydrodynamic Properties of Amylose Tris(n-butylcarbamate) in Tetrahydrofuran, Methanol, and Their Mixtures
citation_author
Terao, Ken
Murashima, Maiko
Sano, Yuichi
Arakawa, Shota
Kitamura, Shinichi
Norisuye, Takashi
citation_publisher
American Chemical Society
citation_language
英語
citation_date
2009-10-28
citation_journal_title
Macromolecules
citation_volume
43
citation_issue
2
citation_firstpage
1061
citation_lastpage
1068
citation_issn
00249297
15205835
citation_doi
info:doi/10.1021/ma902200z
citation_public_url
http://hdl.handle.net/11094/77669