Molecular relaxation processes in triatomic molecules. II. The N2–CO2 system

Translation–vibration (T–V) and vibration–vibration (V–V) energy transfer processes in the N₂–CO₂ system were investigated using classical trajectory techniques. Two empirical interaction potentials were employed. One is comprised of independent, atom–atom Morse-type functions operating between nonbonded atoms. The other included these atom–atom Morse functions plus Coulombic terms to account for the quadrupole–quadrupole intertion. Both interaction potentials led to similar T–V results. However, the result that CO₂(v₃) is excited ～10³ times more efficiently than N₂(v = 1) was obtained, which is at variance with existing analytical theories of T–V energy transfer employing purely repulsive short-range potentials. Different V–V energy transfer probabilities were obtained from the two interaction potentials. The most important finding is that only when electrostatic orientation effects are combined with short-range repulsive interactions is the near-resonant V–V transfer found to be the dominant energy transfer path. This interaction potential also crudely accounts for the negative temperature dependence observed for this near-resonant V–V transfer at low temperatures (300–1000°K).     

Kinetic study of the gas-phase reaction c-C5H8 + I2 ⇄ c-C5H6 + 2HI the heat of formation and the stabilization energy of the cyclopentenyl radical

The gas-phase dehydrogenation of cyclopentene to cyclopentadiene catalyzed by iodine in the range 178–283°C has been found to obey a rate law consistent with the slow rate-determining step, \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm I} + {\rm c} - {\rm C}_5 {\rm H}_8 \stackrel{4}{\rightarrow}{\rm HI} + {\rm c} - {\rm C}_5 {\rm H}_7 $\end{document}, log [k₄/(1 mole^?1 sec^?1)] = 10.25 ± 0.08 - (12.26 ± 0.18)/θ, where θ = 2.303 R T in kcal/mole. Surface effects are not important. This value of E₄ leads to a value of DH = 82.3 ± 1 kcal/mole and ΔH_f298 = 38.4 ± 1 kcal/mole. From difference in bond strengths in the alkane and the alkene, the allylic resonance stabilization in the cyclopentenyl radical is 12.6 ± 1.0 kcal/mole, in excellent agreement with the value for the butenyl radical. Arrhenius parameters for the other steps in the mechanism are evaluated. The low value of A₄ (compared with A₄ for cyclopentane) suggests a “tighter” transition state for H-atom abstraction from alkenes than from alkanes.     

Review of ferroelectric hydroxyapatite and its application to biomedicine*

ABSTRACT

Hydroxyapatite (HA) is a major component of bone in humans and animals. Until about 10 years ago, it was considered to have a centrosymmetric crystal structure and could not contribute to the well-known piezoelectric effect in bone. This review describes the theoretical and experimental studies that showed that HA does have a non-centrosymmetric structure. Recent experiments have shown that HA exhibits piezoelectricity, pyroelectricity, and ferroelectricity. It has been made in the form of thick films and as space-charge electrets. It has an important biomedical application as an implant for bone cell attachment and growth.     

Preparation and characterization of new glassy system As2P2S8-Ga2S3

Glasses having the composition (100 - x)As2P2S8-xGa2S3 with x ranging from 0 to 50% were investigated to determine the compositional effect on properties and local structure. The glass transition temperature (Tg) and the stability parameter against crystallization (Tx - Tg) increased with the addition of Ga2S3. The structure of these glasses was probed by Raman scattering, Fourier transform infrared (FT-IR) and 31P nuclear magnetic resonance. On the basis of the observed vibrations and the strength of the 31P-31P homonuclear magnetic dipolar coupling, two scenarios can be proposed for the structural evolution induced by the addition of Ga2S3. For x or= 30% we have depolymerization of the As2P2S8 units and the formation of a network of GaPS4 units with each PS 4/2 unit (Q4) species carrying a single positive formal charge.     

Nonseparable closed vector subspaces of separable topological vector spaces

In 1983 P. Domański investigated the question: For which separable topological vector spaces E, does the separable space Open image in new window have a nonseparable closed vector subspace, where \(\hbox {c}\) is the cardinality of the continuum? He provided a partial answer, proving that every separable topological vector space whose completion is not q-minimal (in particular, every separable infinite-dimensional Banach space) E has this property. Using a result of S.A. Saxon, we show that for a separable locally convex space (lcs) E, the product space Open image in new window has a nonseparable closed vector subspace if and only if E does not have the weak topology. On the other hand, we prove that every metrizable vector subspace of the product of any number of separable Hausdorff lcs is separable. We show however that for the classical Michael line \(\mathbb M\) the space of all continuous real-valued functions on \(\mathbb M\) endowed with the pointwise convergence topology, \(C_p(\mathbb M)\) contains a nonseparable closed vector subspace while \(C_p(\mathbb M)\) is separable.     

Positional assignment of differentially substituted bisaminoacylated pdCpAs

The synthesis and NMR analysis of a 2'-O-alanyl, 3'-O-[1-(13)C]valyl-pdCpA derivative has permitted the definitive assignment of the positions of acylation of tandemly activated pdCpAs, and the bisaminoacylated transfer RNAs derived therefrom.     

Silk layering as studied with neutron reflectivity

Neutron reflectivity (NR) measurements of ultrathin surface films (below 30 nm) composed of Bombyx mori silk fibroin protein in combination with atomic force microscopy and ellipsometry were used to reveal the internal structural organization in both dry and swollen states. Reconstituted aqueous silk solution deposited on a silicon substrate using the spin-assisted layer-by-layer (SA-LbL) technique resulted in a monolayer silk film composed of random nanofibrils with constant scattering length density (SLD). However, a vertically segregated ordering with two different regions has been observed in dry, thicker, seven-layer SA-LbL silk films. The vertical segregation of silk multilayer films indicates the presence of a different secondary structure of silk in direct contact with the silicon oxide surface (first 6 nm). The layered structure can be attributed to interfacial β-sheet crystallization and the formation of well-developed nanofibrillar nanoporous morphology for the initially deposited silk surface layers with the preservation of less dense, random coil secondary structure for the layers that follow. This segregated structure of solid silk films defines their complex nonuniform behavior in the D(2)O environment with thicker silk films undergoing delamination during swelling. For a silk monolayer with an initial thickness of 6 nm, we observed the increase in the effective thickness by 60% combined with surprising decrease in density. Considering the nanoporous morphology of the hydrophobic silk layer, we suggested that the apparent increase in its thickness in liquid environment is caused by the air nanobubble trapping phenomenon at the liquid-solid interface.     

The Use of PAMAM Dendrimers as a Platform for Laccase Immobilization: Kinetic Characterization of the Enzyme

The kinetic behavior of the enzyme laccase in solution and immobilized onto carbon platforms using poly(amido amine) (PAMAM) dendrimers has been investigated. The results with the immobilized enzymes have demonstrated that almost ten times more enzyme on the carbon support is required for satisfactory kinetic rates to be achieved. Furthermore, the study as a function of the substrate concentration revealed that the kinetic behavior of the enzyme in solution fits the Michaelis?CMenten model. However, when the enzyme is immobilized onto the carbon surface, the catalyzed reaction follows a particular kinetic behavior with apparent positive cooperativity. The highest activity with laccase (in solution or immobilized) is achieved around pH?4.5, and the substrate conversion rate clearly diminishes with rising pH. The optimum temperature lies around 60?°C. The enzyme displays good catalytic activity in a wide range of pH and temperature values. The stability tests evidenced that there is no appreciable reduction in the enzymatic activity after immobilization within the first 30?days. Taking into account both the kinetic and stability tests, one can infer that the use of PAMAM dendrimers seems to be a very attractive approach for the immobilization of enzymes, as well as a feasible and useful methodology for the anchoring of enzymes with potential application in many biotechnological areas.     

Tunable intramolecular multicenter H-bonding interactions in first-row metal complexes bearing bidentate redox-active ligands

Abstract

In this research article, we report the synthesis and structural characterization of a family of first-row metal complexes bearing redox-active ligands with tunable H-bonding donors. We observed that these coordination complexes can adopt three different geometries and that they are stabilized by intramolecular multicenter H-bonding interactions, which are systematically modified by changing the metal ion (Co, Ni, Cu, Zn), the ligand scaffold (variations in the diamine and ureanyl substituents used) and the solvent of crystallization.