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  • Chemistry  (4,546)
  • General Chemistry  (1,245)
  • ddc:330
  • 2015-2019
  • 1960-1964  (4,546)
  • 1963  (4,546)
Collection
Publisher
Years
  • 2015-2019
  • 1960-1964  (4,546)
Year
  • 11
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 1 (1963), S. 209-229 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The inactivation of sRNA by reaction with formaldehyde has been reported as it occurs under various conditions giving differing amounts of secondary structure. The theory of inactivation of an active macromolecule by a chemical reaction is developed. Results obtained with a partially melted out secondary structure show that formaldehyde inactivates sRNA by a single reaction at any one of about ten sites, while reaction at other sites does not affect the activity of the sRNA. In the presence of Mg++ at neutral pH, a large proportion of the active molecules are completely protected against inactivation. From the correlation between the amount of secondary structure and the difficulty of inactivation, it is shown that at least a portion of the secondary structure of sRNA is essential to its amino acid acceptor ability. A comparison of results of various workers shows that formaldehyde does not alter RNA as drastically as other reagents and thus enables more discrimination between sites of reaction which are essential and those which are not essential to biochemical activity.
    Additional Material: 5 Ill.
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  • 12
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 1 (1963), S. 295-295 
    ISSN: 0006-3525
    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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  • 13
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Infrared absorption and x-ray diffraction measurements have been made of D,L-copoly-γ-benzylglutamate fibers (cast from dioxane solutions) with various D/L ratios and with various degrees of polymerization. It was found that each chain of these copolymers consists of a random coil portion and an α-helix portion and that the conformation of the latter is similar to the α-helix of pure poly-γ-benzyl-L-glutamate. It was also found that the fraction of the α-helix portion increases with the degree of polymerization of the copolymer. A simplified polymerization mechanism has been proposed for mixtures of D- and L-amino acid N-carboxyanhydrides. A model of the molecular conformation of the D,L-copolypeptide chains derived from this proposed polymerization mechanism is in good agreement with infrared, x-ray, and other measurements. Based on the results of these observations, we discuss the number of L- or D-residues linked in succession that is required for initiating the formation of an α-helix during the course of polymerization.
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  • 14
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly-L-proline I and II, polyphydroxy-L-proline II, polysarcosine, and collagen, as well as two model amides have been examined by far ultraviolet spectrophotometry. Absorption spectral data are presented. Neither in solution nor in oriented films of poly-L-proline I and II is there any indication of excition resonance splitting of the peptide absorption band. In collagen there is some, in the poly-L-prolines only minimal, hypochromicity. These observations, at least in poly-L-proline II, run counter to theory. Optical rotatory dispersion measurements in the ultraviolet indicate simple dispersion in collagen and poly-L-proline II down to at least 232 mμ. The Cotton effect (trough at 233 mμ) observed in α-helical polypeptides and proteins is absent. The implications of these findings are discussed.
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  • 15
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The helix - coil transition of poly-L-glutamic acid (PGA) in aqueous solutions was followed by volume changes, ΔV, and also differential refractive indices, Δn. The increase in ΔV or decrease in Δn upon mixing the sodium salt of PGA with dilute HCl gave three straight lines between pH 7 and 4, the two breaks corresponding to the transition zone observed by other physical methods. For the reaction: —COO- + H+ → —CO-OH, ΔV per mole of H+ bound was 11.4 and 11.1 ml. in 0.01 and 0.2M NaCl solutions, respectively. An additional conformational change of about 0.5-1 ml. per amino acid residue was observed for the reaction: coil → helix, after taking electrostatic interaction into consideration. This was probably due to the release of the water of hydration at the amide linkages when the polypeptide coil is converted into the α-helix, or even the occurrence of voids in the polypeptide chain as a result of imperfect packing of the atoms, although the origin of this volume change is still not fully understood at the present time. The volume changes as calculated from Δn by assuming a constant polarizability of the polymer was found to be higher for the association reaction than those mentioned above. On the other hand, the calculated ΔV for the transition was in fair agreement with those by direct measurements.
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  • 16
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dye-macromolecule complexes provide good models for the study of the effects of coupling between chromophores. In addition to modifications of the visible and UV absorption spectra of the dyes at small interchromophore distances, very efficient energy transfer has been demonstrated at longer distances. The probability of nonradiative transition increases with the number of excitation transfers so that an array of oscillators close to one another becomes nonfluorescent. The insertion of a dye molecule, acting as a trap for the excitation energy, in the highly ordered system of chromophores constituted by the purine and pyrimidine bases of native DNA has given results supporting the intercalation model of Lerman and providing an experimental approach to the problem of the path length of energy migration in the DNA molecule. The average excitation path length seems to be of the order of only ten base pairs, a result which can explain the lack of fluorescence of the DNA.
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  • 17
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 1 (1963), S. 473-495 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The sedimentation, diffusion, and osmotic behavior of poly-L-lysine hydrochloride is examined over a wide range of ionic strengths and in solutions which range in relative composition from a swamping excess of added salt (suppression of charge effect) to salt-free solutions (maximum effect). The charge effect is found to essentially obey the theoretical treatment proposed in Part I of this work. The frictional coefficient of the macroion in salt-free solutions is comparable to that of the fully stretched chain. In excess of salt the friction is appreciably smaller, its magnitude not varying greatly with ionic strength. The molecular weight is determined osmotically and also from diffusion-sedimentation, with the charge effect suppressed by addition of salt or eliminated through the use of non-ionized forms of the polymer; a reasonable agreement is obtained between the methods. The influence of small ions on sedimentation is also examined. The secondary salt effect is found to be much smaller than that predicted theoretically; on the other hand, the substitution of different counterions in the absence of secondary salt effect gives rise to changes of the expected magnitude.
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  • 18
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 1 (1963), S. 500-502 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 19
    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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  • 20
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It has been suggested previously that water is a nearly indifferent solvent for amylose on the basis that the exponent a of the Mark-Houwink equation is very nearly 0.50 and the second virial coefficient A2 is extremely small. It is shown that such solutions do not show the expected precipitation on cooling and the temperature coefficient of the intrinsic viscosity is small and negative. It is suggested that water is both an indifferent and a nearly athermal solvent for this polymer. Various lines of evidence suggest the polymer to exist as a very stiff coil in this and in other solvents. Variations in the intrinsic viscosity and radius of gyration in various solvents show the importance of skeletal effects in addition to the usual osmotic effects. Application of the Porod-Kratky wormlike coil model leads to unreasonably short persistence lengths if the contour length is based on a fully extended conformation but large and reasonable values of the order 40-70 A. if it is assumed that the basic conformation is the helical one observed in various amylose complexes in the crystalline state. As was previously known, the specific optical rotation decreases sharply in aqueous solutions above approximately pH 12. Accompanying this change in rotation there is first a decrease, then an increase in intrinsic viscosity. This later behavior is strikingly reminiscent of the known behavior of polyglutamic acid in the pH-dependent transition from helix to coil. It is concluded that the conformation is that of a stiff coil with essentially helical backbone contour in neutral solution, and the decrease in rotation and in intrinsic viscosity at high pH results from a partial breakdown of the helical structure with a concomitant increase in backbone flexibility. The increase in viscosity and radius of gyration in extreme alkaline solution is probably due to a polyelectrolyte expansion of the polymer coil. Some other miscellaneous observations which are in accord with this model are also pointed out.
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