Sequence distribution of partially hydrolyzed poly(vinyl acetate)

Copolymers of vinyl acetate and vinyl alcohol were studied by differential thermal analysis. The melting points of the copolymers are not a simple function of the composition, but depend on the method of preparation of the copolymers. Partial saponification of poly(vinyl acetate) with sodium hydroxide leads to high melting, ordered copolymers, while reacetylation of poly(vinyl alcohol) leads to low melting, random copolymers. Catalytic alcoholysis of PVAc yields copolymers intermediate in melting point and order. The results are treated by assuming that equal melting points indicate similar sequence length distributions of crystallizable units.     

DETECTION OF DNA-PSORALEN PHOTOADDUCTS in situ

Abstract— An immunological method, with the use of specific immune serum, has been developed for detection of 8-methoxypsoralen (8-MOP) photoadducts to DNA, formed in situ in cell nuclei, after combined treatment with 8MOP and UV-A irradiation (Zarçbska et al. , 1978). Lymphocytes fixed on slides or in suspension, and cryostat sections of different mammalian tissues, served as antigenic substrate, after treatment with 8-MOP and UV-A in vitro. Specific fluorescence in these substrates was detected in the nuclei after treatment with 30 ˜ 140 kJ/m² UV-A in the presence of 0.1-0.3 μg/cm² 8-MOP. PHA-stimulated-lymphocytes appeared to be the most sensitive substrate.
However, hairless mice treated with high doses of UV-A in vivo , 70 ˜ 360 kJ/m² did not reveal a specific fluorescence of epidermal nuclei, unless a high local concentration of 8-MOP was attained.
The apparent discrepancy in the level of photoadduct detection between the in vitro and in vivo treated specimens was explained by the low number of DNA-8-MOP-photoadducts formed in vivo under these experimental conditions. The relevance of these findings to the role of DNA-8-MOP-photoadducts formed during PUVA photochemotherapy is discussed.     

ON QUOTIENTS OF BRAID GROUPS

ABSTRACT.

Let G be the group ?[t, t ^?1] x ?. By studying the action of the braid group B_n on the set Gⁿ , we obtain representations of B_n into a wreath product of the symmetric group and the general linear group over ?[t, t ^?1]. This in particular recovers the Burau representation of the braid group. Furthermore, some quotients of the braid group are obtained by using the representations found.     

Mononuclear N3S(thioether)-ligated copper(II) methoxide complexes: synthesis,characterization, and hydrolytic reactivity

Mononuclear copper(II) methoxide complexes supported by N(3)S(thioether) chelate ligands having two internal hydrogen bond donors have been prepared, comprehensively characterized, and evaluated for hydrolytic reactivity.     

Characterization of partially transesterified poly(beta-hydroxyalkanoate)s using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) was used for the characterization of a partially transesterified poly(beta-hydroxyalkanoate), PHA, polymer produced by the bacterial strain Alcaligenes eutrophus using saponified vegetable oils as the sole carbon sources. The transesterification was carried out separately under acidic and basic conditions to obtain PHA oligomers weighing less than 10 kDa. The intact oligomers were detected in their cationized [M + Na](+) and [M + K](+) forms by MALDI-TOFMS. A composition analysis, using the MALDI-TOF spectra, indicate that the oligomers obtained via acid catalysis were terminated with a methyl 3-hydroxybutyrate end group, and those obtained by base catalysis had a methyl crotonate (olefinic) termination. In addition to HB (hydroxy butyrate), the oligomers were found to contain a small percentage of HV (hydroxy valerate). This was independently confirmed using gas chromatography/mass spectrometry (GC/MS). In comparison, the analysis of a commercial PHA polymer, transesterified under identical conditions, only showed the presence of HB, i.e. a pure PHB homopolymer. Copyright 1999 John Wiley & Sons, Ltd.     

Visual-field displacements in human beings evoked by accoustical transients.

Sixty-two of 133 subjects reported visual-field displacements when they were exposed to intense (125 dB SPL) repetitive audiofrequency transients. This phenomenon was investigated in three experiments. Frequency (100-5000 Hz) was varied in experiment I; repetition rate (0.5/s--6.0/s) was varied in experiment II; acoustical transient onset/offset time (0.2--25 ms) was examined in experiment III. The results of these three experiments indicated that the largest proportion of displacement reports and the largest perceived motion magnitudes followed stimulation in the 500- to 1000-Hz frequency range at repetition rates of about 1/s. Response differences as a function of onset/offset time were erratic. The pattern of results obtained in this study, in conjunction with the results of previous investigations of acoustical vestibular stimulation, suggests that the visual-field displacments resulted from stimulation of the receptors of the vestibular system. These experiments may account for discrepancies in reports of infrasound-evoked eye movements. Finally, it is suggested that intense sound exposure may damage the vestibular receptors with or without concomitant damage to the auditory portion of the membranous labyrinth.     

More efficient Brownian dynamics algorithms

We examine the relative efficiencies of three- algorithms for performing Brownian Dynamics simulations without many-body hydrodynamics. We compare the conventional Brownian Dynamics algorithm of Ermak (CBD), Smart Monte Carlo (SMC) which incorporates Boltzmann sampling into essentially a CBD procedure, and the Stochastic Runge Kutta (SRK) method. We show, using the repulsive potential φ(r) = ε(σ/r) ⁿ , where n = 36 and 72, that the SRK algorithm gives the most accurate short-time dynamics for the mean-square displacements. The SRK algorithm static and dynamical properties converge better with a reducing time step to the exact values, than those generated by the CBD algorithm; giving efficiency gains typically of a factor of 3–4. Both CBD and SMC have the incorrect sign for the first correction term to the mean square displacement in a time step, whereas the SRK algorithm gives essentially the exact solution to order Δt ², where Δt is the simulation time step. In fact, these correction terms are almost equal and opposite in sign. Expressions for these terms were derived in terms of the average interaction energy per particle. The force, shear and bulk stress autocorrelation functions were calculated. The average energy per particle and time correlation functions at short time have values in excess of the exact values, while the corresponding quantities for SRK are below this. This difference in behaviour can be traced back to the extent of compliance of the particle trajectories with the exact expansion of the Smoluchowski equation. The accuracy, at a given value of the time step, of the stochastic algorithms can significantly depend on the form of the interaction potential between particles. It is also demonstrated that the long time limits of various correlation functions are fairly insensitive to a particular scheme (SRK or CBD) used in the simulations. All the correlation functions have a stretched exponential region at intermediate to long times, and the values of the exponents on density and force law steepness have been determined.     

Mononuclear nitrogen/sulfur-ligated cobalt(II) methoxide complexes: structural, EPR, paramagnetic 1H NMR, and electrochemical investigations

The first examples of mononuclear nitrogen/sulfur-ligated Co(II) alkoxide complexes, species of relevance to a reactive intermediate observed for Co(II)-substituted liver alcohol dehydrogenase, have been isolated and characterized by multiple methods including X-ray crystallography, EPR, paramagnetic (1)H NMR, and cyclic voltammetry.