Translational energy disposal in molecular collisions: The transfer of momentum constraint

A Franck—Condon type argument, which requires the least transfer of momenta to the nuclei during a collision is outlined and applied to the analysis of translational energy disposal and its dependence on the initial translational energy. Using the maximal entropy procedure of information theory we are able to proceed directly from the assumed (model) constraint to the product state distribution.     

A thermochemical study of acid-base interactions in aqueous solutions of citric acid

The heat effects of interaction of a solution of citric acid with HNO₃ and KOH were measured calorimetrically at 298.15 K and ionic strengths of 0.5, 1.0, and 1.5 (KNO₃). The heat effects of acid dissociation were calculated using the universal HEAT program. The standard thermodynamic characteristics of step dissociation of citric acid were determined.     

The synthesis of diene and of vinyl copolymers containing predetermined quantities of polynuclear hydrocarbon or heterocyclic adducts—IV. Copolymers of butadiene or isoprene,anthracene and a linking agent

Evidence is given that, when solutions of diene monomers and anthracene in tetrahydrofuran are reacted with alkali metal and subsequently titrated with linking agents such as alkyl dihalides, copolymers are formed; they contain the 9,10-dihydroanthracene adduct and the diene in the same proportion as in the original solution. The structures of these copolymers have been elucidated by NMR spectroscopy and the mechanism of formation is discussed.     

Qy-excitation resonance Raman spectra of chlorophyll a and bacteriochlorophyll c/d aggregates. Effects of peripheral substituents on the low-frequency vibrational characteristics

Low-frequency (80-700 cm-1) Qy-excitation resonance Raman (RR) spectra are reported for thin-solid-film aggregates of several chlorophyll (Chl) a and bacteriochlorophyll (BChl) c/d pigments. The pigments include Chl a, pyrochlorophyll a (PChl a), methylpyrochloropyllide a (MPChl a), methylbacteriochloropyllide d (MBChl d), [E,M] BChl cS, [E,E] BChl cF, and [P,E] BChl cF. The BChl c/d's are the principal constituents of the chlorosomal light-harvesting apparatus of green photosynthetic bacteria. Together, the various Chl a's and BChl c/d's represent a series in which the peripheral substituent groups on the chlorin macrocycle are varied in systematic fashion. All of the Chl a and BChl c/d aggregates exhibit rich low-frequency vibrational patterns. In the case of the BChl c/d's, certain modes in the very low-frequency region (100-200 cm-1) experience exceptionally strong Raman intensity enhancements. The frequencies of these modes are qualitatively similar to those of oscillations observed in femtosecond optical experiments on chlorosomes. The RR data indicate that the low-frequency vibrations are best characterized as intramolecular out-of-plane deformations of the chlorin macrocycle rather than intermolecular modes. The coupling of the out-of-plane modes in turn implies that the Qy electronic transition(s) of the aggregate have out-of-plane character. The RR spectra of the BChl c/d's also reveal that the nature of the alkyl substituents at the 8 and 12 positions of the macrocycle plays an important role in determining the detailed features of the low-frequency vibrational patterns. The frequencies of the modes are particularly sensitive to larger substituent groups whose conformations may be more easily perturbed in the tightly packed aggregates. These factors also make aggregates of pigments containing larger substituents more susceptible to structural, electronic, and vibrational inhomgeneities. Collectively, the RR studies of the various pigments delineate the factors which influence the low-frequency vibrational characteristics of chlorosomal aggregates.     

Influence of medium on the kinetics of oxidation of iron(II) ion with t-butyl hydroperoxide

The oxidation of iron(II) with tert-butyl hydroperoxide was investigated in the absence of oxygen in water, methanol, and the dichloromethane—methanol solvent mixture (φ_r = 2:1). The oxidation rate depends on solvent polarity; measured in the presence of SCN⁻ at constant 0.8 mmol dm⁻³ HCl, the rate constant increases with the polarity decrease passing from water and methanol to the dichloromethane—methanol solvent mixture. Further, in non-aqueous solutions at this acid concentration the rate constant was higher than the rate constant in the presence of Cl⁻ only. The oxidation rate measured in the [FeCl]²⁺ complex in dichloromethane—methanol was slow in acidic medium and increased by decreasing the acid concentration. Approaching the physiological pH conditions the rate constant attained the value of an order of magnitude of 10³ dm³ mol⁻¹ s⁻¹, while very little alteration of stoichiometry of the oxidation reaction was observed. The rate constant measured in the presence of Cl⁻ strongly depends on electrolyte concentration at concentrations less than 0.5 mmol dm⁻³ HCl, both in MeOH and the solvent mixture. Based on these results, a possible mechanism of the influence of solvent, acidity, and ligand type on the rate constant is discussed. We assume that the oxidation proceeds by an inner-sphere mechanism considering that the breakdown of the successor inner-sphere complex forming reactive alkoxyl radicals is probably the rate-limiting step. Presented at the 20th International Conference on the Coordination and Bioinorganic Chemistry organized by the Slovak Chemical Society, Slovak University of Technology, Comenius University, and the Slovak Academy of Sciences, Smolenice Castle, 5–10 June 2005.     

Ovine luteinizing hormone. VI. Analysis of the misclassification errors in the separation of intrapituitary isohormones by chromatofocusing.

Luteinizing hormone (LH) in extracts of the ovine (o) anterior pituitary gland elutes as eight or more distinct peaks when analyzed by chromatofocusing on pH 10.5-7 gradients [Keel et al., Biol. Reprod., 36 (1987) 1102]. In order to examine the efficacy of this approach to identify the distinct charge isomers of oLH, a pool of pituitary extracts was de-salted by flow dialysis and chromatofocused on a pH 10.5-7 gradient. The immunoreactive oLH eluted in nine distinct peaks which were coded with letters beginning with the most basic form. The fractions corresponding to each peak were pooled, dialyzed and lyophilized. Each peak was then re-chromatofocused on a pH 10.5-7 gradient except for the immunoreactive oLH eluting in peak A' because of the small amount present in this peak. Each peak, except for F and H, also consisted of a small percentage of immunoreactive oLH associated with adjacent peaks. This was plausible because chromatofocusing does not generally yield baseline resolution of peaks. Peak H eluted in a broad manner and was contaminated with significant amounts of isohormones F, G and Z. In contrast, peaks B, E, F, G and Z almost completely eluted in the anticipated regions. Thus, it appears that analysis of oLH charge isomers by chromatofocusing yields minimal misclassification errors and that the misclassification errors observed are associated with molecular forms which comprise a relatively small percentage of the oLH in pituitary extracts.     

Isolement du prestegane B à partir de Steganotaenia araliacea hochst., premier lignane bis-(meta-hydroxy-benzyl)-butanolide d'origine végétale. - Isolement et synthèse en une étape du diméthylmatairésinol-

Prestegane B -the first higher plant occured dibenzyl butanolide lignan with two $\text{meta}$-phenols- and its dimethylether were isolated from $\text{S.araliacea}$ and the structure determinations were performed with the aid of high resolution NMR and Mass fragmentation for the former, and with 2-D J resolved ¹H NMR studies and synthesis for the latter.     

Nivyaside — A new glycoside fromLeucanthemum vulgare

From the ligulate flowers ofLeucanthemum vulgare Lam. growing on the territory of the Georgian SSR a new glycoside has been isolated which has been called nivyaside and has the structure 8-(1-α-D-glucopyranosyl-5-deoxyquercit-5-yl)-4′,5,7-trihydroxyflavone.     

The determination of molybdenum and tungsten by high resolution spectrometry of alpha-induced prompt photon emission

A simple, rapid and non-destructive method is described for determining molybdenum and tungsten in steels over the concentration range 0.07 to about 20% by mass. The method uses high resolution spectrometry of the low energy gamma-rays induced by 5 MeV alpha-particle beams. The precision for molybdenum is 2.7% and for tungsten is 0.55% using respectively the 204 and 100.1 keV gamma-rays. Results obtained by Ge(Li) and intrinsic germanium detectors are compared. The extent of interference from other elements is discussed.