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  • Wiley-Blackwell  (35,738)
  • American Physical Society  (21,688)
  • Oxford University Press  (10,148)
  • 1965-1969  (52,709)
  • 1935-1939  (14,865)
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  • 201
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 5 (1967), S. 243-249 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Block and random copolymers of γ-benzyl L-glutamate and glycine were studied by optical rotatory dispersion methods in order to ascertain the extent and stability of the α-helix formed by these polymers in appropriate solvent mixtures. Results indicate that when in solution such polymers do contain sections of α-helix. However, it appears that glycine does not readily fit into the α-helix which is largely due to the γ-benzyl L-glutamate segments. Further, there are indications that the helical sections in the random copolymers are due to the nonrandomness of the polymerization.
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  • 202
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is demonstrated that, poly(A + U) and poly(I + C) are both formed under low ionic strength conditions. Continuous variation studies indicate the formation of copper(II) complexes of poly A, poly C, and poly I, but not of poly U. Copper(II) in a 1:1 ratio to polynucleotide prevents the formation of poly(A + U) and brings about the dissociation of the poly (A + U) complex produced in the absence of the metal. Poly (I + C) is similarly dissociated by copper(II) ions. The addition of sufficient electrolyte reverses the copper(II) induced dissociation of poly(I + C). The effect of copper(II) on ordered synthetic polynucleotides is thus very similar to its effect on DNA.
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  • 203
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    Biopolymers 5 (1967), S. 259-271 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and some of the physical-chemical properties of tricopolymers of L-glutamic acid, L-lysine, and L-alanine are reported here. The molar ratios of the glutamyl: lysyl: alanyl residues were 1:1:X or 3:2:X, where the alanyl content X was increased in regular steps. The α-helix content calculated from the optical rotatory dispersion of the polypeptides is compared with a predicted helix content estimated from the composition of the polymers and the known behavior of the homopolypeptides at pH 3, 8, and 12. At pH 3 copolypeptides containing 20 mole-% or more alanine exhibit a helix content equal to the sum of their alanyl and glutamyl residue contents. At pH 8 the helix content equals the alanyl content when the latter was 40 mole-% or higher; at lower alanyl contents the electrostatic interaction between charged glutamyl and lysyl residues makes some contribution. At pH 12 the amount of helix observed is proportional to the mole ratio of alanine residues present in the polymer. The helix content of a tricopolymer containing 1:1:3 mole ratios of glutamyl: lysyl: alanyl residues was determined in solutions of lithium bromide and in urea solutions. Both reagents led to a decrease in helix content at pH 3 and 8 to a minimum of approximately 20% helix in 8M urea or 5.5M LiBr. The helix-random chain transition curves at pH 3 and 8 are parallel when the urea concentration is varied, but differ in shape when the lithium bromide concentration is varied at pH 3 and 8. The mode of action of these two “denaturing” reagents may thus be different. Heating the same tricopolypeptide at pH 3 or 8 from 5 to 80°C. also led to a helix-random chain transition centered at approximately 45°C.
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  • 204
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Potentiometric titration curves of the silver(I) complexes of cytidine, adenosine, and uridine show little uptake of base below pH 7, unlike the curve for silver(I)-guanosine, which shows extensive base uptake at neutral pH. This observation is correlated with spectrophotometric data showing little difference between the silver complex spectra of adenosine, cytidine, and uridine and the spectra of uncomplexed nucleosides, except at high pH, but showing a great difference between the silver complex spectra of guanosine and inosine and the corresponding uncomplexed nucleosides even at pH 6. Similar comparisons of the silver complexes of poly A, poly C, poly I, and poly U, both by potentiometric titration and by spectrophotometry, show that poly I behaves like guanosine and inosine as expected, differing from poly A and poly C. However, poly U behaves like poly I and thus does not resemble uridine in its complexing behavior. There is thus a dichotomy between poly A and poly C on the one hand in silver complexing phenomena, compared with poly U and poly I on the other. When silver(I) is added to systems containing zinc(II) and various polynucleotides, the same dichotomy is noted. Silver(I) inhibits the degradation by zinc(II) of all four polynucleotides, but the degradation of poly I and poly U is prevented virtually completely. Silver(I) alone has no degradative effect on RNA and inhibits, the zinc(II) degradation of RNA. Polynucleotide complexes in which silver(I) and zinc(II) are simultaneously bound to different positions on the macromolecules are postulated as intermediates in the inhibited degradation reactions.
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  • 205
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    Biopolymers 5 (1967), S. 325-326 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 206
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    Biopolymers 6 (1968), S. 1389-1389 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 207
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    New York : Wiley-Blackwell
    Biopolymers 6 (1968) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 208
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By using optical rotatory dispersion measurements, the helix content of poly Glu50Lys50 has been investigated and compared with that of poly Glu20Lys20Ala60 in aqueous solutions. Measurements were made at pH 3 and at pH 8 in various concentrations of lithium bromide. Various factors affecting helix stabilization are considered and their perturbation by lithium bromide is related to the shape of the observed transition curves. A residual helix content of 12% in 8M LiBr, based upon a b0 of +100 for a fully random conformation, was observed for poly Glu50Lys50 at pH 3 and 8. The loss of helix content of poly Glu50Lys50 as a function of temperature is also reported. ΔH is approximately -6.9 kcal./mole for the overall transition, compared to -6.5 kcal./mole for poly Glu20Lys20Ala60. The midpoint of the broad transition is near 40°C. at pH 3, but much lower, at -10 to 0°C., at pH 8. These results are discussed in terms of the stabilizing factors for the partial helix content of the polypeptides.
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  • 209
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    Biopolymers 6 (1968), S. 215-222 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The absorption spectrum of the aqueous solution of acridine orange (AO)-poly-(D-glutamic acid) (PDGA) complex at pH 4.5 (helix form) did not show any wavelength shift, but at pH 7.5 (coil form) changed to the absorption curve of the helix form by compression up to 4500 atm. The ionization degree of PDGA estimated from the electric conductivity of the aqueous solution of PDGA at 4500 atm. was a value of about 5.3%. The entropy of the helix formation of PDGA from the titration data at 1 atm. and 30°C. was negative -2.98 e.u. It will be concluded in this report that the volume change for coil to helix could be positive for PDGA and negative for AO-PDGA complexes.
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  • 210
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    Biopolymers 6 (1968), S. 223-242 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The optical rotatory dispersion, hypochromism, and proton magnetic resonance were measured for a number of dinucleoside phosphates in both dilute salt solutions and in 25.2% LiCl (which freezes below -70°C.) as a function of temperature. Two models for the “disordering” of dinucleoside phosphates: the two-state model and the oscillating dimer model, are used to analyze the data. Both models fit some of the data, but neither are completely satisfactory. Evidence is given for a dynamic structure of dinucleoside phosphates, in which the bases oscillate with respect to one another, remaining parallel to one another with no solvent in between, even at high temperatures. Implications of this model to the structures of single-strand sections of RNA's are discussed.
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  • 211
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    Biopolymers 6 (1968) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 212
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: If the collagen triple helix is so built as to have one set of NH ⃛ O hydrogen bonds of the type N3H3(A) ⃛ O2(B), then it is possible to have a linkage between N1H1(B) and O1(A) through the intermediary of a water molecule with an oxygen O1W leading to the formation of the hydrogen bonds N1(B) ⃛ O1W and O1W (A). In the same configuration, another water molecule with an oxygen O1W can link two earbonyl oxygens of chains A and B forming the hydrogen bonds O2W O1(A) and O2W O0 (B). The two water oxygens also become receptors at the same time for CH ⃛ O hydrogen bonds. Thus, the neighboring chains in the triple helix are held together by secondary valence bond linkages occurring regularly sit intervals of about 3 Å along the length of the protofibril. The additional water molecules occur on the periphery of the proto-fibril and will contribute their full share towards stabilizing the structure in the solid state. In solution, they will be disturbed by the medium unless they are protected by long side groups. It appears that this type of two-bonded structure, in which one NH ⃛ O bond is to a water molecule, can explain several observations on the stability and hydrogen exchange properties of collagen itself and related synthetic polypeptides. The nature of the water bonds and their strength are found to be better in the one-bonded structure proposed from Madras than in the one having the coordinates of Rich and Crick.
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  • 213
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    Biopolymers 6 (1968), S. 1659-1670 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The study of the structure of KBr-amylose begun by Senti and Witnauer has been extended by a three-dimensional crystallographic analysis and by stereochemical considerations. Location of Br- at (0.200, 0.200, 0.000) and K+ at (0.540, 0.540, 0.000) was obtained from the three-dimensional map of vector interactions. By using known parameters for the D-glucose residue and accurate space-filling models, an amylose helix was constructed to meet the fiber repeat spacing of 16.1 Å. The helix was determined to be left-handed, and the correct space group for KBr-amylose is P43 212. Placement of the helix in the unit cell resulted from structure factor calculations; minima in the grid of R values were checked with space-filling models to establish the final structure. Both ions are located in a waterlike environment. The oxygen atoms O(2), O(3), and O(4) from glucose residues on adjacent chains coordinate around K+.
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  • 214
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    Biopolymers 6 (1968), S. 1673-1689 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We present here a brief analysis of ultraviolet isotropic absorption and related circular dichroism of the n-π* and π-π* transitions for the peptide (amide) chromophore in the 185-240 mμ region. Investigations by ultraviolet absorption and circular dichroism techniques on natural amino acids with aromatic chromophores in their side chains are also reported. By taking into account both the peptide and aromatic transitions we discuss the conformational studies of proteins with aromatic side-chain effects. Our attention is largely focused on the optical rotatory dispersion and circular dichroism spectra of these proteins in the near ultraviolet region, where characteristic aromatic side-chain bands occur. The 185-240 mμ region is also discussed when evidence exists of overlapping Cotton effects of aromatic and peptide groups.
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  • 215
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Recent improvements in apparatus permit the examination of circular dichroism (CD) and optical rotatory dispersion (ORD) spectra to 185 mμ. In addition, new solvents which are transparent to 185 mμ have become available for synthetic polypeptides. The spectral region 185-250 mμ is extremely important for the amide (peptide) chromophore, because of the presence at these wavelengths of the n-π* and π-π* bands,1 and of another transition, the assignment of which remains unsettled.2
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  • 216
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    Biopolymers 6 (1968), S. 1491-1493 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 217
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    Biopolymers 6 (1968), S. 1391-1404 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method is reported for calculating the melting curve of a DNA molecule of random base sequence, including in the formalism the dependence of the free energy of base pair formation on the size of a denatured section. Some explicit results are shown for a “typical” base sequence, in particular the probability of helix formation at individual base pairs in several different regions of the molecule and the amount of melting from the end of the chain. Particular attention is drawn to the variation of local melting behavior from one region of the molecule to another. It is found that sections rich in AT melt at relatively low temperatures with a fairly broad transition curve, whereas regions rich in GC pairs melt at higher temperatures (as expected) with a very abrupt, local transition curve. To account qualitatively for the results one may divide melting into two kinds of processes: (a) the nucleation and growth of denatured regions, and (b) the merging together of two denatured sections at the expense of the intervening helix. The first of these processes dominates in the first stages of melting, and leads to rather broad local melting curves, whereas the second process predominates in the later stages, and occurs, in a particular part of the molecule, over a very narrow temperature range. It is estimated that the average length of a helix plus adjacent coil section at the midpoint of the transition is approximately 600 base pairs. Since transition curves which measure the local melting behavior reflect local compositions fluctuations, these curves contain information about the broad outlines of base sequence in the molecule. Some suggestions are made concerning experiments by which this potential information source could be exploited. In particular, it is pointed out that one might hope to map AT or GC rich regions at particular genetic loci in a biologically active DNA molecule. Values of the relevant parameters found earlier for the transition of homopolymers produce melting curves for a DNA of random base sequence which are in good agreement with the experimental transition curve for T2 phage DNA. Hence the present theoretical picture of the melting of polynucleotides is at least internally self-consistent.
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  • 218
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    Biopolymers 6 (1968), S. 1169-1175 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Studies have been made of the contraction of collagen fibers in acetone due to the action of LiBr. No contraction occurs unless a small amount of water is added; on further increase of the water concentration, the fibers relax. The first contraction is irreversible. The effect of water is discussed in terms of hydrate formation.
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  • 219
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    Biopolymers 6 (1968), S. 1177-1183 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Knowledge of the total particle volume and the specific volumes of the constituent polar and nonpolar amino acid residues of a globular protein may be used in suitable instances to estimate the size and shape, of the macromolecule. Use has been made of the data, which is available in the literature for phycocyanin from Plectonema calothricoidcs, to predict possible models for the monomer and hexamer forms of this protein. The monomer is well represented by a prolate ellipsoid with semiaxes of 45 and 17Å and an approximate molecular weight of (46000). The hexamer is envisaged as the aggregate of six such monomers, in juxtaposition, with their major axes parallel so as to form a closed ring structure of about 268000 molecular weight. These proposed models are consistent with the previously published electron micrographs and hydrodynamic properties of this protein.
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  • 220
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    Biopolymers 6 (1968), S. 1185-1200 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A computer program has been developed for calculating equilibrium centrifugation density distributions by direct integration of tabulated data, which eliminates curve fitting. Error calculations showed that a high accuracy is required for the measurement of the data needed a determine a density distribution either by computation or by direct measurements. In particular, the variation in drop size during the fractionation of the contents of a centrifuge tube have been investigated by computer simulation. A direct measurement of the drop size indicated that it may increase somewhat during collection. In addition, plots are presented of the dependence upon seven parameters of the centrifugation required to approach equilibrium to a desired degree (based on the formula of Van Holde and Baldwin).
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  • 221
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    Biopolymers 6 (1968), S. 1515-1518 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 222
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    Biopolymers 6 (1968), S. 1218-1223 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 223
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    Biopolymers 6 (1968) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 224
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    Biopolymers 6 (1968), S. 1201-1211 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper reports a calculation of the angular dependence of light scattering from wormlike chains with excluded volume effects. The Daniels distribution function, modified for excluded volume effects, is used to compute averages for scattering elements separated by contour lengths which are long with respect to the persistence length of the chain. An expansion in terms of exactly known moments of the distribution for the wormlike coil without excluded volume is used for short contour lengths. The results are applied to scattering from calf thymus (M = 18.1 × 106) and T7 (M = 25.4 × 106) DNA. It is demonstrated that the same values of excluded volume parameter (ε = 0.11) and statistical segment length (1/λ′ = 900 Å) which explain the sedimentation and viscosity behavior of DNA also account satisfactorily for the scattering behavior. Molecular weights and root-mean-square radii estimated by extrapolation from scattering data obtained in the angular region from 10° to 25° will be 5-10% too large for DNA of molecular weight 20 × 106-30 × 106.
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  • 225
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    Biopolymers 6 (1968), S. 1225-1253 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No Abstract
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  • 226
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using potential energy formulas for variation of bond angles and for ω-distortion, the conformation of minimum energy for the cisform of the petide unit has been worked out. This agrees very well with the corresponding set of atoms in the crystal structure of Leu-Pro-Gly and the dimensions of a standard cispeptide unit are given based on these. The conformational (φ,Ψ) map for a cispeptide unit has been worked out from contact criteria, both for a pair of linked units as well as for-helices having constant (φ,Ψ). The small allowed region of the helical map contains the conformation experimentally observed for poly-L-proline I.
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  • 227
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    Biopolymers 6 (1968), S. 1279-1296 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Phosphorescence and fluorescence from the dye in complexes of DNA with 9-amino-acridine and acridine orange in a glycerol-H2O glass have been measured at 77°K. The dependence of the p/fratio for 9-aminoacridine on the exciting wavelength demonstrates triplet-triplet energy transfer from DNA to dye. The result provides evidence for π electron overlap between the dye and the bases of native DNA. The observation that the magnitude of the enhancement in ultraviolet-excited dye phosphorescence increases with the base to dye ratio indicates triplet delocalization in the polymer. Preliminary flash experiments provide evidence that this delocalization is not limited by slow diffusion of the triplet exciton. The inability to detect transfer on denaturation of the DNA illustrates the sensitivity of triplet-triplet energy transfer to the conformation of the macromolecular complex.
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  • 228
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    Biopolymers 6 (1968), S. 1297-1309 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ratio of the intrinsic viscosities of the linear and circular forms of λ DNA, [η]L/[η]c, has been measured as a function of ionic strength in the range [Na+] = 0.6. M-0.03MCorrections were made for the presence of uncyclizable linear contaminant in circular preparations. By combining data in the literature on the ionic strength dependence of linear DNA of various molecular weights with that obtained here, it was possible to determine the expansion parameter εL as a function of [Na+]. εL is defined by the relation 〈L2〉 = b2N1+εL, where 〈L1〉 is the mean-square end-to-end distance of a chain of N segments of length b. The empirical relation εL = 0.05 - 0.11 log [Na+] for native NaDNA at 25°C is found. When εL = 0, [η]L/[η]c extrapolates to 1.6, in good agreement with the theoretical prediction of 1.55. As εL increases, [η]L/[η]c increases, in agreement with a theory of Bloomfield and Zimm.
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  • 229
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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  • 230
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    Biopolymers 6 (1968), S. 1778-1778 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 231
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    Biopolymers 7 (1969) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 232
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    Biopolymers 7 (1969), S. 1-3 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
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  • 233
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    Biopolymers 7 (1969), S. 5-19 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The osmotic pressure equation for nonideal, associating systems of the type nA +mB ⇄ AnBm, has been derived, by using the assumption yAnBm/yAnyBm = 1. This treatment can also be applied to related associations such as nA + mB ⇄ AB + AB2 + A2B + …. From osmotic pressure experiments on the pure reactants it is possible to obtain the molecular weights (MA and MB) of the reactants and also the virial coefficients (BAA and BBB) of the reactants. The osmotic pressure of a nonreacting mixture of A and B can be calculated from these measurements. It can be used along with osmotic pressure measurements on equilibrium mixtures of A and B to obtain expressions containing the equilibrium constant (or constants) and the cross-virial coefficients (BAB and BBA). Several procedures are described for the evaluation of the equilibrium constant (or constants) and the BAB or BBA terms. It appears that this procedure is a general one which is applicable to associations of the type nA + mB ⇄ AB + A2B + AB2 + …. By correcting for nonideal behavior, one should then be able to apply it to any method available for analyzing ideal associations of the types considered here. In addition it is possible, subject to certain restrictions, to analyze associations of the type 3A + B ⇄ A2 + AB.
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  • 234
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    Biopolymers 7 (1969), S. 39-58 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method has been developed for characterizing at, submicrogram levels the heterogeneity of histones from purified nuclei. The histones are eluted with a smooth concentration gradient from nuclei trapped in polyacrylamide-gel threads and are collected in a micro fraction collector suitable for volumes in the 10-100 μl range. The gradient and fraction collection systems are governed by cam driven syringes. Samples obtained are subjected to electrophoresis in a starch-gel system and the gels are stained with a highly sensitive stain specific for guanidinium groups. Seven major and a similar number of minor components are demonstrated in the histones. The method of differential elution of trapped macromolecules is suitable for use with systems other than nuclei and histones.
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  • 235
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: A method is presented for the treatment of distribution functions obtained by ultra-centrifugal sedimentation velocity experiments on the plasma lipoproteins, so that adequate corrections can he made for the effects of diffusion and concentration dependence of the sedimentation coefficient. The method involves the use of modified equations derived from those presented in 1952 by Gosting for the transform from g* (S) to g(S) distributions. The evaluation of the molecular parameters of lipoprotein density and size, from a set of g(Si°) distribution functions obtained in solvents of varying density, is also outlined. Preparations of the β-lipoprotein of human plasma are found to follow a bivariate normal distribution that requires evaluation of five parameters, x̄1, σ1, x̄2, σ2and p. The first two represent the mean and standard deviation of the lipoprotein density, the third and fourth the same quantities for the size, expressed as ft “logarithmic diameter parameter”, and the final value is a measure of the correlation between these two variables.
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  • 236
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    Biopolymers 7 (1969), S. 133-133 
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 237
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    Biopolymers 7 (1969) 
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 238
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    Biopolymers 7 (1969), S. 155-171 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: High-resolution nuclear magnetic resonance spectra at 100 MHz and 220 MHz have been obtained on two samples of poly-L-alanine of differing molecular weights (2500 and 42 500) in the chloroform-trifluoroacetic acid system under various conditions of solvent composition, temperature, and polypeptide concentration. Separate helix and random coil peaks are observed for the α-CH and peptide NH backbone proton resonances, thereby permitting the determination of helix content. This observation of separate peaks demonstrates that the lifetimes of the helix and random coil portions of poly-L-alanine have lower limits of about 10-1 sec. It is suggested that solvent-peptide versus peptide-peptide hydrogen bond competition, coupled with a destabilizing effect of the trifluoroacetic acid on the helix, is responsible for the helix-random coil transformation.
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  • 239
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    Biopolymers 7 (1969), S. 135-153 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The combination of an agarose gel (Bio-Gel A) and a dioxane-water (1:1) solvent system allowed the fractionation, on a preparative scale, of a very polydisperse, non-derivatized lignin preparation (enzymatically liberated lignin prepared from sweetgum sapwood with Lenzites trabea). Three fractions differing markedly in molecular weight were obtained. A gel of crosslinked alkylated dextran (Sephadex LH-20) with the same solvent system allowed division of the lowest molecular weight fraction into two fractions. These materials were characterized by measurements of intrinsic viscosity and number-average molecular weights in dimethylformamide and dioxane-water. It was established that the two highest molecular weight fractions were associated in an average trimeric form in dioxane-water (1:1) as compared to the form (considered to be molecular) that occurred in dimethylformamide. Molecular size distributions and eluant volumes of the fractions were determined with a Sephadex G-100-formamide system, the latter being one of the most powerful nonaqueous solvents for lignin. Adsorption effects were known to be absent in this case, and the lignin molecules were considered to be unassociated in formamide. The four fractions were distinguishable with the formamide-G-100 system, thus indicating that the original fractionation was based on molecular size. The enzymatically liberated lignin contained molecules that comprised a continuum of molecular weights from approximately monomeric to molecules that were at the limit of the solvating power of dioxane-water (1:1) and dimethylformamide. Limited physicochemical data were consistent with a compact, approximately spherically symmetric shape of the lignin in solution.
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  • 240
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    Biopolymers 7 (1969), S. 189-197 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A comparison has been made of the intrachain potential energy of an infinite straight α-helix of poly-L-alanine with that of the distorted form adopted in a coiled coil conformation. The energy terms included were the van der Waal's, electrostatic, hydrogen-bond, and the rotational potential terms. The results indicate that the potential energies of the structures investigated are almost the same, and so a transformation from one state to another may occur without significant changes in potential energy. Particular care has been taken to ensure that the electrostatic and van der Waal's interaction terms are fully convergent. The values obtained for the α-helix were compared with those already published, and some significant differences were found.
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  • 241
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    Topics: Chemistry and Pharmacology
    Notes: Ultraviolet optical rotatory dispersion curves of mucopolysaccharides exhibit particular Cotton effects in the spectral region of the n-π and π-π amide transitions. Two general patterns emerge: (1) enhancement of negative rotation and of the first negative Cotton effect (troughs 217-220 mμ) and (2) relative dominance of the positive Cotton effect in the π-π transition region (peak ∼198 mμ). Groups (1) and (2) can be correlated with a structural difference in the linkages of the amino sugars: (1) occurs with polymers containing 3-1-linked glycosamino sugars and (2) with glycosamino moieties linked 4-1 by either α- or β-glycosidie bonds. Measurements of the circular dichroic absorption bands support the qualitative conclusions from optical rotation. All mucopolysaccharides exhibit a first, negative band centered at 208-211 mμ, while only those in group (2) show, in addition, a positive band centered at 189-192 mμ. A suggested unifying model considers that difference in kind and/or degree of preferred geometry of the amide groups obtains from two forms of secondary order: (1) having a linear hydrogen bond from the N (acceptor) to the (C2)O - H of the preceding uronic acid and (2) having a linear hydrogen bond from the N (acceptor) to the (C2 or 3) O - H of the following sugar. The hydrogen bonds would have similar strength but opposite directions in two systems towards the nonreducing end (1) or towards the reducing end (2)], closing eight-membered rings
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  • 242
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    Biopolymers 7 (1969), S. 99-106 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The myosin molecule was extracted from the smooth muscle parts of horse esophagus and purified by ammonium sulfate fractionation. The schlieren pattern of the sedimentation velocity run showed a very sharp single peak of.5.9. S (s20,w). Molecular weight of the protein was measured by means of the Archibald and sedimentation equilibrium methods, both in 0.5M KCI buffered by 1/150 M phosphate at pH 7.5 and at 5°C. The values obtained were 6.25 × 105 and 5.81 × 105respectively, for the two methods. The second virial coefficients were 1.1 × 104 and 1.2 × 10-4 ml/g. Denatured smooth muscle myosin was prepared in a solution of 5M guanidine HC1 containing 0.4 M KC1 and 0.2 M β-mercaptoet hanol buffered at pH 8.0. The weight-average molecular weight of the denatured smooth muscle myosin was 2.24 × 105 and the second virial coefficient was 7.6 × 10-4 ml/g. The values described above are in good agreement with those reported for rabbit skeletal myosin with ammonium sulfate fractionation. The molecular dimension of the molecule is estimated as the value for an axial ratio of 100, assuming a rigid rod molecular model for this molecule, both the thermodynamical and hydrodynamical treatment being in a good agreement with this estimation.
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    Biopolymers 7 (1969) 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Biopolymers 7 (1969), S. 433-434 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: No. Abstract
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  • 245
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    Notes: The enthalpy change accompanying the double helix-coil transition of polyriboadenylic acid (poly A) in aqueous solution has been measured optically and calorimetrically in the pH range 5.7-4.5. The course of this cooperative transition was followed optically by measuring changes in ultraviolet absorption as a function of temperature at different pH values, and calorimetrically by determining the heat capacity of the solution through the transition region. From the latter measurements, the enthalpy of transition was calculated. It is shown, that ΔH is dependent on pH as it is expected from the influence of protonation of the double helix of poly A.
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  • 246
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    Biopolymers 7 (1969), S. 453-458 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The interaction between ionizable carboxyl groups and the conformation of poly-(glutamic acid) (PGA) in aqueous solution were investigated by the mechanical method. The dynamic rigidity of the PGA solution has a maximum value at the pH corresponding to about 50% neutralization point. This may be due to establishing of a maximum attractive force by proton/charge fluctuation between ionizable carboxyl groups at that pH. The dynamic viscosity has a sharp change in the region of pH 5.5-6.5. It is suggested that this behavior is due to the helix-coil transition.
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  • 247
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    Biopolymers 7 (1969), S. 447-452 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: By use of D2O we found that the shortening of the longitudinal proton relaxation time which occurs in the investigated aqueous yeast DNA solutions (≦ 2.4% with 2% protein) was not based on a hydration effect, but was caused by magnetic impurities only. An estimate shows that the mobility of the hydrated water molecules is reduced by less than two orders of magnitude in comparison with the free water molecules.
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    Biopolymers 7 (1969), S. 435-445 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A general approach to the determination of relative stability of any pair of con-formational states of biological macromolecules or their complexes (in particular, to the determination of relative stability of native and disordered states of the macromolecule) has been suggested. For determining the free energy difference of the two states under the conditions when one of them is considerably more advantageous than the other, it is necessary for the macromolecule to be influenced by the transforming agent which levels free energies of both the conformational states, and to determine the external parameter derivative of the free energy difference in the region of the conformational transition induced by the change in this parameter. If the character of the dependence of this derivative on the external parameter (temperature, solvent composition, etc.) is known, then this allows the determination of the free energy difference of the two states under the conditions considered, even including conditions far from the transition region. The value of the derivative of the free energy difference in the transition region in many cases can be measured directly (in particular, when using calorimetry), while in cases when a direct measurement of the derivative is impossible, it can often he estimated experimentally from the steepness of the conformational transition. The methods of this estimation and also a possible character of the change of the considered derivative during variation of the external parameter are considered for the case when the transforming agent is one of the components of the solvent and, consequently, the derivative of the free energy difference is equal to the difference of number of molecules of this component hound with the macromolecule in two conformational states.
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    Biopolymers 7 (1969), S. 459-474 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Wool-water systems, at water contents above a threshold value of 22.7 g of water per 100 g of wool keratin, yielded curves of specific heat against temperature showing peaks that are ascribed to the fusion of the absorbed water. Integral and incremental heats of fusion were obtained. Integral heats increase as the square of the water content above the threshold, and incremental heats follow a linear relationship. The incremental heat reaches a value of 55 cal/absorbed water, at the saturation water content, at 0°C of 33.9 g of water per 100 g of keratin. The state of the absorbed water is discussed. Clustering of water molecules takes place only above the threshold water content.
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    Biopolymers 8 (1969), S. 173-179 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The laser-excited Raman spectra have been obtained of poly-L-proline in the solid and aqueous solution. In the solid state, the Raman spectra are of the form II which is the left-handed helical form with the peptide bonds in the trans configuration. Dissolution of this form in water produced only minor changes in the Raman spectra. The differences in frequencies produced by dissolving the polymer are associated with vibrational modes of the pyrrolidine ring as indicated by comparison with the Raman spectrum of L-proline. The similarity of the Raman spectra dictates that, the conformations of poly-L-proline chain are similar in the solid and aqueous solution.
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    Biopolymers 8 (1969), S. 181-185 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: A comparative study on sonicated calf thymus DNA was made by using electron microscopy and sedimentation methods. The length distribution, established by electron microscopy by using Kleinschmidt's technique, is related to the sedimentation curve obtained with the same solution. The relation permits a determination of the sedimentation constant corresponding to a given length up to 8000 Å and vice versa.
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    Biopolymers 8 (1969), S. 199-216 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The π-electron polarizability of conjugated base molecules such as uracil and adenine are calculated semiempirically by using molecular orbital theories. The Hüekel method and the self-consistent-field (SCF) theory are used in the present calculation. The theoretical values obtained by the Hüekel method are consistently larger than the experimental results. The values obtained by the SCF theory are in good agreement with observed values. It is clearly demonstrated that the SCF method is better than the Hükel method for the calculation of polarizability. The polarizability of the adenine-uracil pair is calculated as the sum of the polarizabilities of adenine and uracil and also calculated by solving the eigenvalue problem for the A-U pair as an entity. The second method gives considerably larger polarizability than the first method. Discussions are presented and it is demonstrated that the second method is the correct way to calculate the polarizability of the A-U pair.
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  • 253
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    Topics: Chemistry and Pharmacology
    Notes: The reversibility of the thermal denaturation of a low-sulfur fraction of solubilized wool keratin (SCMKA) has been studied under a variety of conditions of time, protein concentration, and pH. Two types of irreversibility for the transition have been encountered. One of these is associated with an aggregation of the protein on denaturation to give a product which may contain elements of a β conformation. This type of irreversibility is favored by high protein concentration, and the original conformation may in fact be regained if the aggregated structure is broken down by a solvent such as 8M urea and the urea subsequently removed by dialysis. The other type of irreversibility appears to be due to racemization of the protein. It does not seem to be dependent on protein concentration and is apparent only at temperatures beyond the actual transition range (∼40-65°C) at pH values below 11, At pH 12, however, racemization appears to proceed slowly even at 4°C. The thermal transition at pH 9 and pH 10 has been shown to be multistage in nature. Over the pH range 9-12 there is a progressive decrease in thermal stability with increase of pH. Addition of NaCl at pH 10 leads to an increase in thermal stability of the molecule.
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    Biopolymers 8 (1969), S. 217-235 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: We report studies of the optical properties of the proflavine-DNA complex, using absorbance and circular dichroism spectroscopy. From comparison of the absorption spectra of proflavine complexed with calf thymus and T2 DNA, we conclude that stacking of the dyes external to the double helix is comparatively much weaker with T2 DXA, probably because of its glucosylation. Several sources are found for the circular dichroism induced in proflavine when it is complexed with DNA. There is a relatively weak circular dichroism induced when the dye is infinitely dilute on the DNA lattice; this presumably arises from the environmental asymmetry of the binding site. Stronger circular dichroism effects are induced by interaction of intercalated and stacked dyes; studies with T2 DNA, for which stacking seems to be blocked, permit a tentative resolution of effects due to the two modes of binding. One recurring theme of these studies is the observation that the optical properties are quite dependent on environment. The most dramatic example is a strong variation with salt concentration of the amplitude of the circular dichroism induced in the isolated (intercalated) monomer by the surrounding DNA. This suggests that the structure of the intercalated complex is quite sensitive to external conditions.
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  • 255
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    Topics: Chemistry and Pharmacology
    Notes: The binding of n-butanol, benzyl alcohol, and trifluoroethanol to polyproline I (all peptide bonds in cis configuration) and II (all peptide bonds in trans configuration) has been demonstrated. It was found by infrared spectroscopy that hydrogen bonds are formed between the CO groups of the polymer and the OH groups of the alcohols. Their strength increases from n-butanol via benzyl alcohol to trifluoroethanol. The binding of benzyl alcohol could also be followed by optical rotatory dispersion due to the fact that the electronic transitions of the benzyl ring are rendered optically active by the binding to the polymer.
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    Biopolymers 8 (1969), S. 259-274 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The statistical mechanics of the effect of a small number of randomly occurring defects on the melting of a polypeptide chain is developed by using a perturbation of Boltzmann factors technique. The method is illustrated by an example where a second-component impurity contributes more to the energy of the hydrogen-bonded superstructure of the polypeptide chain than does the dominant amino acid residue, resulting in the overall destabilization of the helical conformation.
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    Biopolymers 8 (1969), S. 275-287 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: Biological membranes consist mainly of lipids and proteins. At present, the structure of the lipid phase appears to be established, but hypotheses on the molecular organization of the protein are difficult to support. Thus the deformation behavior of whole human erythrocyte ghosts, ghosts after the selective removal of lipids and ghosts stripped of lipids as well as nonlipid components have been examined in the hope of securing indirect information on the organization of the protein. It has been found that large localized deformations result in partial membrane failure and long uniformly wide fibrils, frequently in excess of 3000 Å, are drawn across the rupture. These data are interpreted in terms of currently favored membrane models and the possibility of a fibrous membrane framework consisting predominantly of protein is reviewed. The behavior of the membrane in its various stages of extraction is compared and contrasted to that of synthetic polymer films of known organization.
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    Biopolymers 8 (1969), S. 247-257 
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    Topics: Chemistry and Pharmacology
    Notes: The thermally induced conformational changes of poly-N5-(3-hydroxypropyl)-L-glutamine in water and in methanol-water (3:7 v/v) have been analyzed in terms of the Lifson-Roig theory. The transitions in both solvents can be described by using v = 0.017. The thermodynamic parameters for the random coil-to-helix transition of one amino acid residue at room temperature were found to be: in water, ΔH = - 130 cal/mole and ΔS = - 0.45 e.u.; in methanol-water (3:7 v/v), ΔH = - 170 cal mole and ΔS = - 0.45 e.u. The size distribution of helical segments is broad, and the results of numerical calculations are presented for three degrees of polymerization (DP = 100, 300, and 750).
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    Biopolymers 8 (1969), S. 289-292 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Biopolymers 8 (1969), S. 293-295 
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    Biopolymers 8 (1969), S. 297-299 
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    Topics: Chemistry and Pharmacology
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    Biopolymers 8 (1969), S. 303-304 
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    Biopolymers 8 (1969), S. 301-301 
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    Biopolymers 8 (1969), S. 304-304 
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    Biopolymers 8 (1969) 
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    Biopolymers 6 (1968), S. 731-765 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A detailed comparison of the various models used in the literature to calculate the melting curve of DNA molecules is made. It is shown that basically all the models are identical. The form developed earlier by the authors has been extended to include the dependence of the correlation parameter on the type and the orientation of the nearest neighbor bonds. A rather exhaustive theoretical study of the metling curves for the synthetic polydeoxyribose copolymers is made. A comparison of these results with the suggested experimental results obtained will enable us to decide on a reliable model which could be used to determine the melting curve if the sequence of the bonds is given. A preliminary discussion of a very general model which we will call a “bubble model” is given.
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    Biopolymers 6 (1968), S. 771-773 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Biopolymers 7 (1969), S. 595-610 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cyclic dipeptide, L-alanylglycyl anhydride, has been studied by optical rotatory dispersion; both L-alanylglycyl anhydride and the lactam, L-3-aminopyrrolidin-2-one, have been studied by circular dichroism. In hydroxylic solvents the circular dichroism spectra of 3-aminopyrrolidin-2-one can be attributed to an n-π* transition near 220 mμ and a π-π* transition near 190 mμ. In these solvents the optical activity of L-alanylglycyl anhydride can be explained as being due to contributions of n-π* transitions and a split π-π* transition. In acetonitrile, however, the circular dichroism spectrum of 3-aminopyrrolidin-2-one shows an additional apparent minimum near 200 mμ. The CD spectrum of the dipeptide is also quite distinctive in this solvent. The possible nature of the band at 200 mμ and the implications of these findings are discussed.
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    Biopolymers 7 (1969), S. 619-623 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Biopolymers 7 (1969) 
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 271
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    Biopolymers 7 (1969), S. 627-648 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The flow birefringence, extinction angles, and intrinsic viscosity have been determined at low velocity gradients for a complex of T2 bacteriophage DNA and methylated serum albumin prepared in dilute solution to a stoichiometry of approximately 90 proteins per DNA molecule. Comparative data upon equivalent solutions of pure uncomplexed T2 DNA are also presented, and these data are completely in accord with the results of previous study. The experimental data are interpreted in terms of current dynamical theory and indicate that the complex has an essentially linear chain structure, consisting of approximately two DNA molecules, which is hydrodynamically indistinguishable from the pure DNA and that extensive internal or intramolecular binding in the complex does not occur. Although interpretation of the results is hampered by an apparent moderate degree of polydispersity in the complex preparations and by relatively large shear extrapolations, the data for both DNA and the complex are substantially in accord with dynamical theory for a nondraining bead subchain model having high kinetic segmental rigidity.
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    Biopolymers 7 (1969), S. 649-658 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Far-infrared spectra in the region from 700 to 60 cm-1 have been measured for the α-helix structures of poly(L-α-amino-n-butyric acid), poly-L-norvaline, poly-L-norleucine, and poly-L-leucine and for the β-form structures of poly(L-α-amino-n-butyric acid), poly-L-valine, poly(DL-amino-n-butyric acid), poly-DL-norvaline, and poly-DL-norleucine. The changes of the spectra on N-deuteration have been measured in the region between 700 and 400 cm-1. It is concluded that, the α-helix has characteristic bauds near 690, 650, 610, 380, 150, and 100 cm-1, and that the β-form has characteristic bands near 700, 240, and 120 cm-1. The main-chain vibrations in the region from 600 to 200 cm-1 are strongly coupled with the side-chain deformation vibrations.
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    Biopolymers 7 (1969), S. 681-693 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Single-strand breaks (ssb) in opposite strands of DNA can be sufficiently near that a double-strand break (dsb) results. A theory is presented by which the maximum number h of base pairs which cannot prevent double-strand breakage can be determined from the rates of production of ssb and dsb. The assumptions required to derive the necessary equations as well as the range of validity of the equations are discussed in detail. In the experiments ssb and dsb were produced by x-irradiation in buffers which do not eliminate indirect effects and were measured by analytical ultracentrifugation. Values of h have been determined in low and high ionic strength and in low ionic strength over a range of temperatures. The values, 2.64 and 15.8, were obtained for high and low ionic strength, respectively.
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    Biopolymers 7 (1969), S. 695-705 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The nature of a specific association between acriflavine and cellular DNA was investigated by subjecting the DNA of intact cells to denaturation, ultraviolet radiation, and base analog substitution. The predictable modifications of DNA structure were then correlated with the quantitative alterations in dye adsorption by the cells. It was concluded that, under experimental conditions of limited dye availability, the bonding of dye was restricted to sites of highest bonding affinity. These were shown to be situated between adjacent thymine molecules on a single strand of DNA. The 5-methyl groups of thymine may endow the bond with its specificity.
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    Biopolymers 7 (1969), S. 659-670 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The theory of polyelectrolyte solution of Alexandrowicz: and Katchalsky is used to calculate the electrostatic potential of single stranded polynucleotides for different ionic strength. We have considered the potential of double stranded DNA as the superposition of the different potentials produced by each chain, provided the average distance between the strands is higher than an ionic strength-dependent parameter b. For ionic strength lower than 5 × 10-2M, the assumption is no longer valid, and a cylindrical model with a uniform charge density must be used. The continuity between the two models was tested, and thus we can calculate the electrical potential at the vicinity of a phosphate group in the whole range of ionic-strength where the double helix is stable. It was therefore possible to determine the theoretical number of ions bound electrostatically to DNA and we found an increase of ion binding with a decrease of ionic strength. Such a model was further applied to the change of specific volume in different salt solutions. Comparison is made with recent pycnometric data on Na- and Cs- salts of DNA. Agreement is good in the case of Cs+, but for Na+, cation binding is likely to be accompanied by a change of the hydration of DNA, which depends on ionic strength. With the same model we can see easily the ion-trapping properties of DNA which play an important role in any formation of complex between heavy ions and bases.
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    Biopolymers 7 (1969), S. 671-680 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Preferential adsorption of cations occurs in the solvated shell surrounding polyanions, especially polynucleotides and nucleic acids. The solvation parameter Γ is determined from sedimentation coefficients which are considered as pienometric determinations of the specific volume of the sample. By comparing two identical concentrations (0.1M) of monovalent salts, NaCl and CsCl, and using the model of DNA described in the preceding paper, one can relate the ratio SCs/SNa to solvation parameters ΓCs, and ΓNa.On the other hand, Γ can be related to the difference of energy W, between cation and water, to be extracted from the solution and placed in the vicinity of the polyanion. One finds generally a preferential solvation of the polarizable caesium ion by means of London-van der Waals interactions with bases. With reasonable assumptions, an estimate of W can be made, and the predicted value of Γ can be compared to the experimental one. An average of six sites is found around each base in a single-stranded polymer, but-only one in the double-stranded structure. The amount of secondary structure can thus be estimated from the simple measurement of the ratio of two sediment constants.
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    Chemie in unserer Zeit 3 (1969), S. 163-170 
    ISSN: 0009-2851
    Keywords: Chemistry ; Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Berichte der deutschen chemischen Gesellschaft 98 (1965), S. 36-45 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2.3-Dihydro-thionaphthenon-(3)-1.1-dioxid (III), für das eine ergiebige Synthese beschrieben wird, bildet mit p-Tosylazid das Hydrazon VIII. Beim Erwärmen in stark polaren, „basischen“ Lösungsmitteln wie Äthylenglykol, Dimethylformamid oder Dimethylsulfoxid entkuppelt VIII zu dem α-Diazo-β-keto-sulfon IX und III. Einige Verkochungs- und Azo-Kupplungsreaktionen von IX mit trans-fixierten β-Diketonen zu Azoverbindungen werden beschrieben.
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    Berichte der deutschen chemischen Gesellschaft 98 (1965), S. 111-113 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die cyclische Dimerisierung von F3CSNCO und die quantitative Hydrolyse des Dimeren zu N.N′-Bis-trifluormethylsulfenyl-harnstoff und Kohlendioxid werden untersucht. Die daraus gefolgerte Struktur eines Bis-trifluormethylsulfenyl-uretidin-dions steht im Einklang mit dem IR- sowie dem 19F-NMR-Spektrum.
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    Berichte der deutschen chemischen Gesellschaft 98 (1965), S. 131-139 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tetraalkylharnstoffe zeigen einen starken katalytischen Effekt bei der Umsetzung von 1.3-Dimethyl-barbitursäure mit Phosgen. Die Struktur der erhaltenen Verbindungen wird aufgeklärt.
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    Berichte der deutschen chemischen Gesellschaft 98 (1965), S. 175-185 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Metallierung des Di-benzol-chroms(0) mit Amylnatrium konnte zu einer präparativen Methode für die Darstellung substituierter Di-benzol-chrom-Verbindungen ausgebaut werden. Es wurden die Abfangreaktionen mit CO2, CH2O, CH3CHO, C6H5CHO und (C6H5)2CO untersucht. Aus dem Gemisch der verschiedenen Substitutionsprodukte konnten jeweils die Monosubstitutionsprodukte isoliert werden. Die Konstitutionen der Verbindungen wurden durch gaschromatographische Untersuchung der abgespaltenen Aromaten ermittelt. Die Carboxylatgruppen konnten mit Dimethylsulfat verestert, die primären und sekundären Alkohole dehydriert werden. Mit den Carbonyl-Verbindungen wurden LiAlH4-Reduktionen und Grignard-Additionen durchgeführt. Sowohl der Effekt des Di-benzol-chrom-Restes auf die Reaktionen der organischen Seitenkette als auch der Einfluß der Substituenten auf den komplexen Molekülteil werden diskutiert. Im Falle der Carbonsäureester wurden auch die Di-, Tri-und Tetrasubstitutionsprodukte gefaßt und strukturell gesichert.
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    Berichte der deutschen chemischen Gesellschaft 98 (1965), S. 208-221 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Das sarkomerzeugende, heptacyclische Peropyren (IX) wurde aus dem Benzpyrenderivat IVb in einer Vierstufenreaktion synthetisiert. Ein Zwischenprodukt dieser Synthese ließ sich in das Methyl-naphthopyren XI überführen.
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    Berichte der deutschen chemischen Gesellschaft 98 (1965), S. 290-297 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Durch Umsetzung von Cl2O oder Ozon mit überschüssigem TiBr4 entsteht TiOBr2 in Form tiefgelber Kristalle. Analog entsteht SnOBr2 aus SnBr4 als farbloser, röntgenamorpher Festkörper. Die Eigenschaften und IR-Spektren werden mitgeteilt. Mit POX3 (X = Cl, Br) entstehen die Additionsverbindungen TiOBr2.2 POX3, mit Pyridin die Addukte TiOBr2.2 1/2 Pyridin und SnOBr2.1 1/2 Pyridin.
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    Berichte der deutschen chemischen Gesellschaft 98 (1965), S. 321-322 
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    Keywords: Chemistry ; Inorganic Chemistry
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    Topics: Chemistry and Pharmacology
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    Notes: Einige ω-Formylamino-acetophenone wurden mit Natriumborhydrid zu 2-Formylamino-1-phenyl-äthanolen-(1) reduziert, diese mit Phosphoroxychlorid in Pyridin behandelt. Es resultierten die entsprechenden β-Chlor-β-phenyl-äthylisonitrile. Nur in zwei Fällen entstanden durch HCl-Eliminierung Styrylisonitrile. Unter Anwendung der gewonnenen Erfahrungen gelang es, N.N′-Diformyl-1.2-bis-[4-methoxy-benzoyl]-äthylendiamin in das α.β-ungesättigte 1.2-Di-isonitril Xanthocillin-dimethyläther umzuwandeln und damit die analytisch ermittelte Struktur des Antibiotikums durch eine übersichtliche Synthese zu bestätigen.
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    Berichte der deutschen chemischen Gesellschaft 98 (1965), S. 235-240 
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Organopentafluorosilicate gestatten die Darstellung von Organoquecksilberverbindungen, wie z. B. CH3HgCl und (CH3)2Hg, aus anorganischen Quecksilbersalzen, da sie in wäßriger und alkoholischer Lösung als Organylierungsmittel zu wirken vermögen. An Stelle der Organopentafluorosilicate können vor allem in Gegenwart von Flußsäure auch die Organotrifluorsilane selbst eingesetzt werden.
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    Berichte der deutschen chemischen Gesellschaft 98 (1965), S. 259-273 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Umsetzung von in 4-Stellung alkyl- oder arylsubstituierten Thiosemicarbaziden mit α-Chlor-acetessigester in Äthanol führt unter Entschwefelung zu in der Aminogruppe substituierten 3-Amino-5-methyl-4-äthoxycarbonyl-pyrazolen. In saurer Lösung dagegen bilden sich 3-Amino-4-methyl-5-äthoxycarbonyl-thiazolon-(2)-alkylimide. Eine Ausnahme macht das 4-Phenyl-thiosemicarbazid, aus dem auch in saurer Lösung das Pyrazol-Derivat entsteht. Andererseits können durch Blockierung des N1-Atoms in den Thiosemicarbaziden die in 3-Stellung substituierten 4-Methyl-5-äthoxycarbonyl-thiazolon-(2)-hydrazone dargestellt werden.
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    Berichte der deutschen chemischen Gesellschaft 98 (1965), S. 280-289 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: SnCl4 und ClF reagieren bei 80° in guter Ausbeute zu SnF2Cl2, einem farblosen, hygroskopischen, kristallinen Pulver. Mit überschüssigem Chlornitrat bildet sich daraus quantitativ Zinndifluoriddinitrat, SnF2(ONO2)2. Beide Verbindungen besitzen nach dem IR-Spektrum Tetraedersymmetrie (C2v). Die ONO2-Gruppen sind weitgehend homöopolar gebunden und gegeneinander verdrillt. Durch thermischen Abbau von SnF2(ONO2)2 erhält man bei 250° kubisch kristallisierendes, polymeres SnOF2 (a = 8.89 Å, Z = 12). Das IR-Spektrum des SnOF2 läßt sich in erster Näherung nach der Symmetrie Oh mit sechsfach koordiniertem Zinn zuordnen.
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    Berichte der deutschen chemischen Gesellschaft 98 (1965), S. 307-310 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mit perfluorierten Carbonsäureanhydriden geht Natrium-tricarbonylnitrosylferrat im Gegensatz zu anderen Na-Carbonylmetallaten keine Reaktion ein, mit den betreffenden Perfluorcarbonsäuren selbst bilden sich jedoch bei Anwesenheit von Triphenylphosphin stabile Acylverbindungen gemäß (Rf = CF3 und C2F5): \documentclass{article}\pagestyle{empty}\begin{document}$${\rm Na[Fe}\langle {\rm CO}\rangle _{\rm 3} \langle {\rm NO}\rangle] + 2{\rm R}_{\rm f} {\rm CO}_{\rm 2} {\rm H + 2P(C}_{\rm 6} {\rm H}_{\rm 5} {\rm)}_{\rm 3} \to {\rm R}_{\rm f} {\rm CO}_{\rm 2} {\rm N}_{\rm a} + {\rm H}_{\rm 2} {\rm O + R}_{\rm f} {\rm COF}_{\rm e} ({\rm CO})\langle {\rm NO}\rangle ({\rm P(C}_{\rm 6} {\rm H}_{\rm 5})_3)_2 $$\end{document} Mit höheren Perfluorcarbonsäuren oder schwächeren Liganden wie As(C6H5)3 (L) entsteht keine derartige Acylverbindung, sondern es bilden sich unter Disproportionierung Derivate von Eisennitrosylcarbonyl Fe(NO)2L2.  -  Bei der Umsetzung des Natrium-tricarbonylnitrosylferrats mit Trifluoressigsäure und dem im Vergleich zum Triphenylphosphin stärker basischen Tricyclohexylphosphin entsteht das Phosphoniumsalz [HP(C6H11)3][Fe(CO)3(NO)].
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    Berichte der deutschen chemischen Gesellschaft 98 (1965), S. 548-551 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Für ein Flavon aus Lepidophyllum quadrangulare L. (Polycladin) wurde von G. B. MARINI-BETTÒLO und Mitarbb. die Struktur des 5.4′-Dihydroxy-3.6.7.3′-tetramethoxy-flavons (I) aufgestellt. Wir synthetisierten die Verbindung aus dem 2′-Hydroxy-3.4′.5′.6′-tetramethoxy-4-benzyloxy-chalkon durch ALGAR-FLYNN-OYAMADA-OXYDATION, vollständige Methylierung, Entbenzylierung und partielle Entmethylierung. Da das synthetische Produkt in allen chemischen und physikalischen Eigenschaften von dem natürlichen verschieden war, konnten wir die für das Polycladin aufgestellte Struktur nicht bestätigen.
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    Berichte der deutschen chemischen Gesellschaft 98 (1965), S. 516-519 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Beim Behandeln von 7anti-Jod-3endo-methyl-bicyclo[2.2.1]heptanol-(3exo)-carbonsäure-(2endo) (II) mit Natronlauge und Wasserdampf entsteht unter Hydrolyse, Ringöffnung und Decarboxylierung 1-Acetonyl-cyclopenten-(2) (III).
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    Berichte der deutschen chemischen Gesellschaft 98 (1965), S. 533-537 
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die milde Acidolyse von Fichtenholz mit 2-proz. Essigsäure bei 100° ergibt in geringer Ausbeute drei „dimere“ Phenole, die sich chromatographisch sehr ähnlich verhalten. Eines davon ist der Guajacylglycerin-β-coniferyläther (I), der nach katalytischer Hydrierung in einen kristallinen Dinitrophenyläther übergeführt wird.
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    Berichte der deutschen chemischen Gesellschaft 98 (1965), S. 540-547 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aus Hydrazinen und α-Isocyanato-fettsäure-äthylestern wurden Dipeptid-Analoge vom α-Semicarbazino-(4)-fettsäure-Typ dargestellt. Diese wurden mit verschiedenen, aus Carbonsäurehydraziden  -  besonders Benzyloxycarbonyl(Z)-aminosäurehydraziden  -  und Phosgen erhaltenen 2-substituierten 1.3.4-Oxdiazolonen-(5) zu „Aza“-Tri-bzw.-Tetrapeptiden umgesetzt. Mit Wasser bildeten 2-[α-(Z-Amino)-alkyl]-1.3.4-oxdiazolone-(5) symmetrische ω.ω′-Bis-[α-(Z-amino)-acyl]-carbohydrazide.
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    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Vereinigung von α.β-ungesättigten Ketonen mit 3.4-Dihydro-isochinolinen verläuft sowohl in saurem als auch basischem Medium über Imoniumverbindungen vom Typ III. Der Ringschluß zu IV wird durch Säuren und Basen katalysiert.
    Additional Material: 2 Ill.
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  • 296
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    Berichte der deutschen chemischen Gesellschaft 98 (1965), S. 588-592 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Ultraviolettspektren der Carbazole X - XIII stimmen hinsichtlich der Lage ihrerα- und β-Banden mit den Spektren der analogen Kohlenwasserstoffe (Phene) überein. Die bei den Phenen auftretende Lageabhängigkeit der para-Bande von der Symmetrie der Verbindungen wird bei den Carbazolen nicht beobachtet. Die Synthese des 2.3-Benzo-naphtho[2″.3″:6.7]carbazols (XII), ausgehend vom 2.3-Benzo-carbazol, wird beschrieben.
    Additional Material: 4 Ill.
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  • 297
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    Berichte der deutschen chemischen Gesellschaft 98 (1965), S. 604-612 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Synthese von 3-, 6- und 17-Alkyliden-Steroiden durch Wittig-Reaktion wird beschrieben und der sterische Verlauf der Reaktion an Hand der Ergebnisse diskutiert.
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  • 298
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 98 (1965), S. 617-622 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Es wird über eine neue Darstellungsmethode der Diäthylester der Arylsulfonylamidophosphorsäuren berichtet, der Reaktionsmechanismus geklärt und die Struktur dieser Verbindungsklasse ermittelt.
    Additional Material: 4 Tab.
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  • 299
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    Berichte der deutschen chemischen Gesellschaft 98 (1965), S. 634-637 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die PMR-Spektren der Methyl-aryl-stannane ArnSn(CH3)4-n mit Ar = Phenyl, p-Tolyl, Mesityl, 3.4.5-Trimethyl-phenyl und n = 1,2,3 werden mitgeteilt und diskutiert. Sie zeigen eine Spin-Spin-Kopplung der ortho- und meta-ständigen Ringprotonen mit den magnetisch aktiven Zinnisotopen.
    Additional Material: 2 Tab.
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  • 300
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 98 (1965) 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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