SynopsisThe conformational change of Li-DNA in water/ethanol mixtures is followed by the change in the CD spectrum in solutions containing various percentages of ethanol in the range from 0 to 95%. Two main transitions can be distinguished. The first occurs in the range from 0 to 70% and is represented by a large reduction of the intensity of the positive CD band around 275 nm, which is apparently related to a small change in the number of base pairs per turn. Secondly, at higher percentages of ethanol (> 80%) a conformational change is detected, which is expressed as a reduction of the 245-nm negative CD intensity. According to x-ray difiaction experiments of fibers of Li-DNA, the C-form is attained in 95% ethanol, while at 70% ethanol a B-like structure is observed. The CD experiments reported here also show that for DNA in solution the dependence on percentage of ethanol is composed of two main transition regions. The C-form would then be adopted at high (-958) ethanol percentage. The 670% transition, although strongly expressed in optical CD experiments, has to be related to relatively small structural changes within the B-family of DNA structures, which probably induce an enhanced contribution of n --t n* transitions to the CD spectrum.
Strong electric fields have been applied to dielectric polymer films to study field-induced mechanical stresses. For voltages near breakdown the mechanical forces are sufficient to cause localized deformation in some polymer films. Considerable field enhancement can occur at the deformation sites, leading to reduced nominal dielectric strength for the samples. Experimental evidence for electromechanical deformation is presented as a possible explanation for the poor agreement between the observed dielectric strength and that predicted theoretically.
SynopsisThe CD and absorption (OD) spectra of single-stranded nucleic acids in complex with the helix-destabilizing protein of either bacteriophage T4 (GP32) or bacteriophage fd (GP5) show similar and unusual features for all polynucleotides investigated. The change in the CD spectra between 310 and 240 nm is in all cases characterized by a considerable decrease in the positive band, while the negative band (if present) remains relatively intense. These changes are different from those due to temperature or solvent denaturation and, moreover, cannot be induced by the binding of simple oligopeptides. Absorption measurements show that all polynucleotides remain hypochromic in the complex. Both CD and OD spectra point to a specific and probably similar conformation in complex for all polynucleotides with substantial interactions between the bases. The spectral properties are almost temperature independent (0-40°C). Therefore, we conclude that the conformation must be regular and rigid. To investigate the relation between these optical properties and the specific polynucleotide structure, CD and OD spectra were calculated for an adenine hexamer over a wide range of the conformational parameters. It appears that the calculated CD intensity is not very sensitive to an increase in the axial increment and that many different conformations can give rise to more or less similar CD spectra. However, simulation of the very nonconservative experimental CD spectrum of the poly(rA)-GP32 complex requires that the conformation satisfies two criteria: (1) a considerable tilt of the bases (< -10") in combination with (2) a small rotation per base (=ZOO) andor a position of the bases close to the helix axis (dx = 0 A). Such conformations can also explain the observed hyperchromism upon binding of GP32 to poly(rA)/(dA). Very similar structural characteristics also account for the optical properties of the complexes with GP5. These are discussed as an alternative to the structure suggested by Alma-Zeestraten for poly(dA) in the complex [N. C. M. Alma-Zeestraten (1982) Doctoral thesis Catholic University, Nijmegen, The Netherlands]. The secondary structure proposed in this work can be reconciled with the overall dimensions of the complex, assuming that the polynucleotide helix is further organized in a superhelix.
Eight transitions in the Eu I-spectrum connecting the ground state with configuration 4f 7 6S 2 with states of the configuration 4f 7 6s 6p were studied with high resolution laseratomic-beam spectroscopy. CW dye lasers operating in the wavelength regions 435--470nm and 560-630nm were used for this study. New data for the hyperfine structure in lS3Eu were obtained as well as new and more accurate values for the isotope shifts between lSlEu and 153Eu. The existing data for the hyperfine structure in ~SlEu were reproduced with an exception for the level z~'P>2 .
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