Home About us Contact
|
Home About us Contact | ||
|
|
||
Molecular Relaxation (molecular + relaxation)
Selected AbstractsMolecular relaxation and metalloenzyme active site modelingINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 4-5 2002James W. Whittaker Abstract Metalloenzymes represent a broad class of important biomolecules containing an essential metal ion cofactor in their catalytic active sites, forming biologic metal complexes that perform a wide range of important functions: activation of small molecules (O2, N2, H2, CO), atom transfer chemistry, and the control of oxidation equivalents. The structures of many metalloenzyme active sites have been defined by X-ray crystallography, revealing transition metal ions in unique low-symmetry environments. These bioinorganic complexes present significant challenges for computational studies aimed at going beyond crystal structures to develop a detailed understanding of the catalytic mechanisms. Considerable progress has been made in the theoretical characterization of these sites in recent years, supported by the availability of efficient computational tools, in particular density functional methods. However, the ultimate success of a theoretical model depends on a number of factors independent of the specific computational method used, including the quality of the initial structural data, the identification of important environmental perturbations and constraints, and experimental validation of theoretical predictions. We explore these issues in detail and illustrate the effects of molecular relaxation in calculations of two metalloenzymes, manganese superoxide dismutase and galactose oxidase. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002 [source] Dielectric relaxation and crystallization of ultraviscous melt and glassy states of aspirin, ibuprofen, progesterone, and quinidineJOURNAL OF PHARMACEUTICAL SCIENCES, Issue 5 2007G.P. Johari Abstract Molecular relaxation in ultraviscous melt and glassy states of aspirin, ibuprofen, progesterone, and quinidine has been studied by dielectric spectroscopy. The asymmetric relaxation spectra is characterized by the Kohlrausch distribution parameter of 0.46,±,0.02 for aspirin to 0.67,±,0.02 for progesterone. The dielectric relaxation time varies with the temperature, T, according to the Vogel,Fulcher,Tammann Equation, log10(,0),=,AVFT,+,[BVFT/(T,,,T0)], where AVFT, BVFT, and T0 are empirical constants. The extrapolated ,0 at calorimetric glass-softening temperature is close to the value expected. The equilibrium permittivity, ,0, is lowest for ibuprofen which indicates an antiparallel orientation of dipoles in its liquid's hydrogen-bonded structure. A decrease in ,0 with time shows that ultraviscous aspirin, progesterone, and quinidine begin to cold-crystallize at a relatively lower temperature than ibuprofen. ,0 of the cold-crystallized phases are, 4.7 for aspirin at 290 K, 2.55 for ibuprofen at 287 K, 2.6 for progesterone at 320 K, and 3.2 for quinidine at 375 K. It is argued that hydrogen-bonding, the Kohlrausch parameter, extent of localized motions and the long-range diffusion times all determine the physical and chemical stability of an amorphous pharmaceutical during storage. © 2007 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 96: 1159,1175, 2007 [source] Molecular relaxation and metalloenzyme active site modelingINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 4-5 2002James W. Whittaker Abstract Metalloenzymes represent a broad class of important biomolecules containing an essential metal ion cofactor in their catalytic active sites, forming biologic metal complexes that perform a wide range of important functions: activation of small molecules (O2, N2, H2, CO), atom transfer chemistry, and the control of oxidation equivalents. The structures of many metalloenzyme active sites have been defined by X-ray crystallography, revealing transition metal ions in unique low-symmetry environments. These bioinorganic complexes present significant challenges for computational studies aimed at going beyond crystal structures to develop a detailed understanding of the catalytic mechanisms. Considerable progress has been made in the theoretical characterization of these sites in recent years, supported by the availability of efficient computational tools, in particular density functional methods. However, the ultimate success of a theoretical model depends on a number of factors independent of the specific computational method used, including the quality of the initial structural data, the identification of important environmental perturbations and constraints, and experimental validation of theoretical predictions. We explore these issues in detail and illustrate the effects of molecular relaxation in calculations of two metalloenzymes, manganese superoxide dismutase and galactose oxidase. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002 [source] Effect of molecular relaxation of acrylic elastomers on impact toughening of polybutylene terephthlateJOURNAL OF APPLIED POLYMER SCIENCE, Issue 4 2007Nafih Mekhilef Abstract In this study, we examined the performance of two core-shell acrylic-based impact modifiers (AIM) prepared by emulsion polymerization. The rubber core was prepared from ethyl hexyl acrylate (EHA) and n -octyl acrylate (n -OA). In such as process, the particle size and particle-size distribution of the modifiers were precisely controlled, so that performance differences observed in polybutylene terephthlate (PBT), used as matrix resin, could only be interpreted in terms of the nature of the elastomeric component of the modifiers. When isolated, the rubber core of the modifiers showed identical glass transition temperatures (Tg) by differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) despite the fact that they were made from two different acrylic monomers. Temperature-frequency superposition principle inferred from the classical WLF equation showed that the rubber components exhibit the same Tg at all frequencies including at the time scale at which mechanical impact typically occurs. However, significant differences in low temperature impact performance measured at ,30°C using notched Izod impact test according to ASTM D 256 were obtained even though their rubber components had identical Tg. Such differences were attributed to the dynamic relaxation behavior of the rubber components and identified as inherent properties of the elastomers due to the structure of the monomers' repeat units. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007 [source] Ionic and excited species in irradiated poly(dimethylsiloxane) doped with pyreneJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 23 2004M. Szadkowska-Nicze Abstract The influence of temperature (77,230 K) on the fate of pyrene (Py) radical ions and Py excited states in irradiated poly(dimethylsiloxane) (PDMS) doped with Py is described. At 77 K, the Py radical ions seem to be stable, whereas the Py excited states [fluorescence (, = 395 nm) and phosphorescence (, = 575,650 nm)] are generated via tunneling charge transfer. In the range of the glass-transition temperature (Tg = 152,153 K), the Py radical ions start to decay, taking part in a recombination process and leading to the Py monomer and Py excimer fluorescence (, = 475 nm). The wavelength-selected radiothermoluminescence (WS RTL) observed at approximately 395, 475, and 600 nm has helped us to identify the Tg range (152,153 K). The absorption maximum at approximately 404 nm, found in the temperature range under consideration, is thought to represent PyH,, cyclohexadienyl-type radicals produced as a result of the reaction of Py,, with protonated PDMS macromolecules. With the initial-rise method of evaluating the activation energy (Ea) with the WS RTL peaks observed in the Tg range, Ea values of 123,151 kJ mol,1 have been found. Such high Ea values can be explained by the contribution of energy connected to the molecular relaxation of the matrix in the Tg range. The well-known Williams,Landel,Ferry equation, with universal constants C1 = 17.4 and C2 = 12.7, has been successfully applied to the interpretation of old pulse-radiolysis/viscosity data found for crosslinked PDMS doped with Py. The mechanisms involved in these phenomena are discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6125,6133, 2004 [source] Network density control in epoxy,silica hybrids by selective silane functionalization of precursorsADVANCES IN POLYMER TECHNOLOGY, Issue 2 2005Luca Prezzi Abstract Following previous work on the compatibilization of organic,inorganic hybrids through coupling reactions with the precursor components, the present study evaluates the relative efficiency of different types of coupling agents on the morphology and properties of epoxy,silica hybrids. In particular, this investigation compares the effects of introducing trialkoxysilane functional groups at the chain end (using amine- and mercapto-silanes) with similar types grafted in the middle of the chain of the constituent resin (using an isocyanate silane). The use of coupling agents with a basic character (amine silane type) brings about the formation of denser networks in both constituent phases of the resulting epoxy,silica hybrid, which is manifest through a large increase in the Tg and a more extensive suppression of the molecular relaxations within the glass transition regions. Increasing the number of alkoxysilane functional groups at the chain end, with the use of a bis-aminosilane, has a relatively minor effect on the morphology and dynamic mechanical spectra of the resulting epoxy,silica hybrids. It was also found that while the incorporation of small amounts of a high molecular weight epoxy resin causes considerable plasticization of the organic phase, much larger amounts of organic (aliphatic) co-agent within the siloxane phase are required to deteriorate those properties that are related to the inorganic character of the hybrid material. © 2005 Wiley Periodicals, Inc. Adv Polym Techn 24:91,102, 2005; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/adv.20033 [source] | |||||||||||||