Effects of molecular structure and environment on the photodimerization of substituted anthracenes

Photochemical and photophysical studies of a number of 9-substituted anthracene sandwich pairs in their corresponding photodimer crystal matrices have been carried out. Corresponding studies have also been made in methylcyclohexane matrices at 6 K. Photodimerization of the 9-methyl, 9-chloro and 9-cyano derivatives in the photodimer matrices occurs at 6 K with unit quantum yield. The presence of excimer fluorescence from sandwich pairs indicates the lack of a perfect topochemical orientation while activation processes, leading to photodimerization, involve molecular re-orientation from more stable ground state configurations which are achieved within the constraints imposed by the solvent or crystalline cage.     

Thermal stability of segmented polyurethanes

The thermal stabilities of two series of segmented polyurethane fibres have been compared with their chemical structure. The polyurethanes were synthesized from trimethylene diamine; 4, 4′ diphenylmethane di-isocyanate and two polyether based macrodi-isocyanates. Thermal stability was measured by thermogravimetric analysis and differential thermal analysis. By comparing the changes in weight loss and DTA peaks with chemical structure it has been found possible to separate soft segment from hard segment degradation.In the initial stages stability increases as soft segment concentration increases while the reverse is true in the later stages of degradation. The 100% soft segment polymer (polytetrahydrofuran) and the 100% hard segment polymer appear to behave anomalously. It is suggested that the hard segment has a stabilizing influence on the degradation of the soft segment. The results are discussed in the light of various theories of polyurethane degradation.     

Enantioselective Sulfoxidations Catalyzedby Horseradish Peroxidase, ManganesePeroxidase, and Myeloperoxidase

Summary.  Horseradish peroxidase (HRP), myeloperoxidase (MPO), and manganese peroxidase (MnP) have been shown to catalyze the asymmetric sulfoxidation of thioanisole. When H₂O₂ was added stepwise to MPO, a maximal yield of 78% was obtained at pH 5 (ee 23%), whereas an optimum in the enantiomeric excess (32%, (R)-sulfoxide) was found at pH 6 (60% yield). For MnP a yield of 18% and a high enantiomeric excess of 91% of the (S)-sulfoxide were obtained at pH 5 and a yield of 36% and an ee of 87% at pH 7.0. Optimization of the conversion catalyzed by horseradish peroxidase at pH 7.0 by controlled continuous addition of hydrogen peroxide during turnover and monitoring the presence of native enzyme as well as of intermediates I, II, and III led to the formation of the sulfoxide in high yield (100%) and moderate enantioselectivity (60%, (S)-sulfoxide). Received November 18, 1999. Accepted January 21, 2000     

Toward high-performance computational chemistry: I. Scalable Fock matrix construction algorithms

Several parallel algorithms for Fock matrix construction are described. The algorithms calculate only the unique integrals, distribute the Fock and density matrices over the processors of a massively parallel computer, use blocking techniques to construct the distributed data structures, and use clustering techniques on each processor to maximize data reuse. Algorithms based on both square and row-blocked distributions of the Fock and density matrices are described and evaluated. Variants of the algorithms are discussed that use either triple-sort or canonical ordering of integrals, and dynamic or static task clustering schemes. The algorithms are shown to adapt to screening, with communication volume scaling down with computation costs. Modeling techniques are used to characterize algorithm performance. Given the characteristics of existing massively parallel computers, all the algorithms are shown to be highly efficient for problems of moderate size. The algorithms using the row-blocked data distribution are the most efficient. © 1996 by John Wiley & Sons, Inc.     

Easily grafted polyurethanes with reactive main chain functional groups. Synthesis,characterization, and antithrombogenicity of poly(ethylene glycol)-grafted poly(urethanes)

A novel synthesis of poly(ethylene glycol) (PEG)-grafted poly(urethanes) (PURs) is described based on a precursor PUR containing free amino groups in the main chain. Three different poly(urethane) backbones were prepared: a homopoly(urethane) comprised of N-Bocdiethanolamine (BDA) and 4,4′-methylenebis(phenyl isocyanate) (MDI), a copoly(urethane) (COPUR) consisting of BDA, N-benzyldiethanolamine and MDI, and a poly(urethane urea) (PUU) that was prepared from BDA, MDI, and ethylenediamine as the chain extender. The M_n of these poly(urethanes) ranged from 32,000 to 72,000 g/mol. PEG (750, 1,900, and 5,000 g/mol) was grafted onto the boc-deprotected poly(urethanes) via the chloroformate. Films of the polymers were spin cast from dilute solutions, annealed, and the surfaces analyzed by goniometry. Water contact angle data indicates increasing PEG surface coverage of the poly(urethanes) with increasing PEG molecular weight. Reorientation of the polymer films is evidenced by contact angle hysteresis. Polymer thrombogenicity, which was studied using blood perfusion experiments, shows that COPUR-g-PEG5000 and PUU-g-PEG5000 exhibit very little platelet adhesion. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3441–3448, 1999     

The synthesis of Leishmania major phosphoglycan fragments

The triglycosyl monophosphate 1, heptaglycosyl triphosphates 2 and 3, and octaglycosyl triphosphate 4, which are fragments of the phosphoglycan part of Leishmania major lipo- and proteo-phosphoglycans have been prepared using di- and tri-saccharide H-phosphonates for construction of the phosphodiester bridges.