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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 13 (1974), S. 879-890 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Samples of epichlorohydrin crosslinked potato starch were prepared by using a high ratio of starch to water and alkali concentration below the gelatinization level. This yielded crosslinked samples that were partially crystalline, and where the number of crosslinks could be varied between 1 and 20 crosslinks per 100 anhydroglucose units. The degree of swelling varied regularly with degree of crosslinking, and the molecular weight between crosslinks Mc as derived from swelling data in a good swelling agent compared favorably with Mc derived from chemical analysis.From the heat of gelatinization of the crosslinked starches, as observed in a differential scanning calorimeter, for gelatinization in glycerol, water, and dimethylsulfoxide, a model for the gel state of the crosslinked starch is proposed. It is concluded that the entropy of melting is the determining factor in establishing the temperature of gelatinization.
    Additional Material: 4 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 301-319 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Five different glucomannan samples were recrystallized from dilute solution. Depending on the experimental conditions, the crystals obtained could be identified as corresponding to the mannan I (anhydrous precipitate of more or less regular lozenge-shaped crystals) or mannan II (hydrated gel-forming pseudo-fibrillar precipitate). High-molecular-weight material, low temperature of crystallization, or a polar crystallization medium favored the mannan II polymorph, whereas a low-molecular weight, a high temperature of crystallization, and a crystallization medium of low polarity yielded the mannan I polymorph. Since the base-plane unit-cell dimensions are fairly constant with respect to variation of glucose, it is likely that isomorphous replacement of mannose by glucose occurs in glucomannan crystallization; the data also indicate that perfection of the glucomannan crystals was reduced in specimens having a high glucose:mannose ratio. The oriented crystallization of glucomannan on cellulose microfibrils was also studied under conditions where the mannan I polymorph was obtained. This gave shish-kebab structures that were characterized.
    Additional Material: 10 Ill.
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  • 3
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly-β-hydroxybutyric acid has been isolated from two bacterial sources by two different procedures. Molecular weight and intrinsic viscosity for the two samples were vastly different. This was blamed on degradation occurring during polymer isolation. An optical rotatory dispersion curve for the high molecular weight sample showed a sharp increase in specific rotation at wavelengths less than 450mμ. From this fact and the reported optical activity of the monomer it is concluded that the polymer is stereo-regular. X-ray examination of the “native” and “regenerated” polymer yielded the same crystalline pattern. Electron diffraction and x-ray data on single crystals of the polymer indicate a fiber repeat of 5.9 A. The value can only be reconciled with some kind of helical conformation in the solid state.
    Additional Material: 8 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 11 (1972), S. 291-301 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Optial rotatory dispersion (ORD) and Circular dichroism (CD) spectra of several β-1,4 xylan and cellulose acetates and some of their oligomers were investigated. The CD spectra proved considerably superior in terms of information content and interpretability. Comparison of the xylan and cellulose acetate series which also included partially substited cellulose acetates showed that the sign of the CD of the C(6) acetyl was negative. Likewise, the combined contribution of C(1) and C(4) to their equatorially substituted acetyls was positive (with C(1) definitely Positive) and the combined contribution of C(2)eq and C(3)eq negative. The solution conformations of both polysaccharide acetates appeared to be random. The CD of White birch xylan acetate which is substituted on the average at every tenth residue with a 4-O-methyl glucuronic acid substituent, was sensitive to it. The xylan oligomer series also illustrated that CD may be used to determine the degree of polymerization of these oligomers up to about 20.
    Additional Material: 7 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 11 (1972), S. 1335-1344 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A structure is proposed for xylan hydrate as a result of investigations by x-ray fiber diffraction and computer-aided chain-packing methods. The unit-cell dimensions are a = b = 9.16 Å, c (fiber axis) = 14.85Å, γ = 120° and the proposed anti-parallel chain arrangement corresponds to a space group symmetry of P3221. Left-handed threefold screw helices are stabilized in this conformation by their interaction with chains of water molecules, so that a satisfactory hydrogen-bonding scheme is achieved. The proposed structure provides an explanation of the changes in the x-ray diagram with relative humidity and yields a very good structure factors agreement. An x-ray fiber diagram corresponding to a higher hydrate (xylan dihydrate) is presented. Comments are made on the possible role of xylan in nature and in technological processes.
    Additional Material: 4 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 18 (1979), S. 887-898 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preparation of lamellar single crystals of mannan[poly((1 → 4)-β-D-mannose)] is described. Electron diffractograms clearly identify the perpendicular orientation of the chain axis with respect to the lamellar surface. Since the degree of polymerization is 40 or less, no conclusion is made as to chain folding. The unit cell corresponds to the mannan I structure derived from x-ray fiber data on oriented algal mannan. The baseplane dimensions found were a = 7.22 Å and b = 8.92 Å, and the systematic absences observed confirm the proposed P212121 group. It was found that cellulose microfibrils from Valonia ventricosa and bacterial cellulose could serve as extended chain nuclei for inducing oriented crystallization of mannan on cellulose. This produces a shish-kebab type of morphology.
    Additional Material: 7 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Letters Edition 25 (1987), S. 139-140 
    ISSN: 0887-6258
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 11 (1972), S. 829-833 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 11 (1972), S. 79-94 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By means of x-ray fiber diffraction, it has been found that xylan diacetate crystallizes with two chains or four residues in a monoclinic cell (space group P21): a = 7.64, b = 12.44, c (fiber axis) = 10.31 Å, and γ = 85°. Pairs of residues are related by a twofold screw axis in the c direction. Based on the observed fiber repeat and chain symmetry, the probable conformation of a pair of xylose diacetate residues joined via a β-1,4′ linkage has been obtained by energy minimization methods. The conformations corresponding to a threefold screw axis and a twofold screw axis along the chain have been compared and the reason why xylan diacetate assumes a twofold screw axis seems to be due to intermolecular packing effects rather than intramolecular non-bonded interactions.
    Additional Material: 8 Ill.
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  • 10
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ultraviolet ORD and CD spectra of amylose, dextran, and mycodextran acetates and some of thier oligomers were recorded in trifluoroethanol solution in the 300-185nm wavelength range. Similarly, the spectra of amylose and dextran xanthates in water solution were obtained in the 400-200 nm range. In the amylose acetate series, the monomer and dimer both show a normal acetyl n → π* transition in CD, while the trimer and the polymer both exhibit an additional, shorter wavelength peak. The latter is presumed to arise from a helical conformation of the amylose chain. This interpretation is substantiated by a helix-coil type transition of the CD spectra of amylose triacetate at elevated temperatures and a reversion of the anomalous CD to the normal CD upon partial deacetylation. By contrast, neither dextran acetates nor mycodextran acetate exhibit any conformational effects. The CD of dextran acetates is quite sensitive to β-1,6 and branch linkages. The ORD and CD of amylose xanthate are complex, suggesting the presence of organized structure in solution. The dextran xanthate shows only a simple ORD spectrum and no observable CD.
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