In situ carburization of metallic molybdenum during catalytic reactions of carbon-containing gases

Supported molybdenum clusters were prepared by sublimation of Mo(CO)₆ onto dehy-droxylated alumina followed by decomposition in flowing dihydrogen at 970 K. These alumina-supported molybdenum clusters were found by XAFS to transform into Mo₂C if heated in a 20% methane/H₂ mixture at 950 K. For the hydrogenolysis ofn-butane at 510 K and CO-H₂ reactions at 570 K, both at atmospheric pressure, molybdenum and carburized molybdenum showed similar, but different for each reaction, turnover rates. The product distribution was the same for each reaction on Mo and Mo₂C. In both reactions, in situ XAFS data for fresh and used catalysts indicated that Mo clusters progressively transformed into Mo₂C under the reaction conditions     

Structure and functional complementation of engineered fragments from yeast phosphoglycerate kinase

Previous studies have shown that, although the isolated structuraldomains of yeast phosphoglycerate kinase recover a quasi-nativestructure in vitro as well as in vivo, they do not reassociatenor generate a functional enzyme. The aim of this work was firstto study the folding of complementary fragments different fromstructural domains and second to determine the requirementsfor their reassociation and functional complementation. Themethod used for producing rigorously defined fragments consistsof the introduction of a unique cysteinyl residue in the proteinfollowed by a specific cleavage by 5'5'-dithiobis(2-nitrobenzoate)/potassiumcyanide at this residue. Two pairs of complementary fragmentswere thus obtained, 1–96/97–415 and 1–248/249–415.The structure and stabilities of the different fragments werestudied. The short fragments, i.e. 1–96 and 249–415were found to contain some secondary structure, but to havea low stability. Each large fragment has a high structural contentand a stability close to that of the corresponding domain. Incontrast to that observed with the isolated domains, a weakbut significant complementation was observed for the two pairsof fragments; the pair of fragments 1–248/249–415recovered 8% of the activity of the native enzyme upon complementation.An independent refolding of the complementary fragments beforereassociation decreased the yield of complementation for thepair of fragments 1–96/97–415, but did not affectthe complementation for the other pair (1–248/249–415).From the present data and previous work on the isolated domains,it appears that the correct folding of the isolated fragmentsis not a prerequisite for their complementation.     

Synthesis, structure and catalytic properties of Fe-substituted barium hexaaluminates

A sol–gel method using Ba and Al isopropylates and iron nitrate has been used to synthesise barium hexaaluminate partially substituted with iron. After calcination under oxygen at 1200°C the -alumina structure was obtained. Formation of the mixed BaFe_xAl_12-xO₁₉ phase occurred for x=1–4. XRD measurements showed a good crystallinity of the structure and expansion of unit cell parameters due to the presence of larger Fe³⁺ ions substituting Al³⁺ ones in octahedral sites only. Mössbauer spectroscopy revealed that Fe³⁺ ions are present in four different octahedral sites slightly distorted. Catalytic activity in methane combustion showed that an optimum was obtained for solid containing 2 Fe ions per unit cell: the increase of the amount of introduced iron was counterbalanced by the decrease of specific surface area. Intrinsic activities have been calculated for the four solids in both the fresh and aged states. It is observed that increasing iron content increases relative activities in the same ratio as the populations of iron located in two sites as deduced from Mössbauer spectroscopy. It is then tentatively assumed that activity is attributed to octahedrally coordinated Fe³⁺ ions in some specific sites.     

Rate of adsorption to and desorption from a langmuir surface: The case of zero activation barrier to adsorption without dissociation

Many rate constants of elementary steps on single crystals have been measured. Their pre-exponential factors can now be compared to those calculated by transition state theory. Such a calculation is presented in this Letter with due attention to microscopic reversibility, standard states, and configurational entropy.     

Measurement of thermal conductivity of polymer melts by the line-source method

An apparatus has been developed for the measurement of thermal conductivity of polymer melts. Based on the transient “line source method,” it is ideally suited to these materials because measurements can be made quickly, before the onset of thermal degradation. Also, little or no sample preparation is required. A number of commercial polymers have been tested, including some glass-fiber filled composites.     

Poly(β-malic acid) : a new polymeric drug-carrier

Summary Poly(-malic acid) is a new synthetic functional polyester of the poly(-hydroxy-acid)-type whose properties are investigated in regard to possible uses as bioresorbable polyvalent drug-carrier. Degradation of polymer chains in 0.15 N phosphate buffer at pH=7.5 is monitored by aqueous GPC on SEPHADEX gels and by enzymatic titration of ultimate degradation products. It is shown that the rate of degradation obeys first order kinetics at the begining and that poly(-malic acid) degrades to malic acid at last.Presented at the 26th IUPAC Microsymposium on Macromolecules: Polymers in Medicine and Biology, Prague, July 9–12, 1984     

Glass fiber-filled thermoplastics. I. Wall and processing effects on rheological properties

A systematic study of wall effects on the shear viscosity of short glass fiber-filled polypropylene and polystyrene is presented. The dependence of these effects on capillary radius, shear rate, temperature, and polymer matrix is examined. The “true” viscosity curves of these materials (free from wall effects) can be obtained by an extrapolation procedure. Breakage of glass fibers in the high shear-rate processes of extrusion and injection molding lead to an appreciable reduction of the viscosity of these materials and is probably the more important effect to take into account in these processes.     

Ionization of Acetylacetone in Me2SO—Water Mixtures. Reactivity—Selectivity Principle or Principle of Imperfect Synchronization?

Rate constants for the reversible deprotonation of acetylacetone were measured in carboxylate and amine buffers in water and in 50%, 90% and 95% Me₂SO at 20°C. The Brønsted plot for the carboxylate ions is curved in the Me₂SO—water mixtures, but straight in water. The curvature is in the direction predicted by the Reactivity—Selectivity Principle (RSP). However, the Brønsted plot for the reaction with primary amines is straight in all solvents. This suggests that the curvature observerd with the carboxylate ions is caused by loss of solvation of the base; this loss of solvation is ahead of bond formation in the transition state rather than being a manifestation of the RSP. (Note that all Brønsted plots are based on pK_a values measured in the respective solvents.) The intrinsic rate constant (k₀) for proton transfer increases with the addition of Me₂SO, and more so with the carboxylate buffers than with the amines. This increase in k₀ is attributed to delayed solvation of the developing enolate ion in the transition state; with the carboxylate buffers, an additional factor is the early loss of solvation of the base. The various solvation effects observed in this study can all be understood in the context of the Principle of Imperfect Synchronization (PIS).     

High‐Temperature Neutron Diffraction,Raman Spectroscopy,and First‐Principles Calculations of Ti3SnC2 and Ti2SnC

Herein, we report—for the first time—on the additive‐free bulk synthesis of Ti₃SnC₂. A detailed experimental study of the structure of the latter together with a secondary phase, Ti₂SnC, is presented through the use of X‐ray diffraction (XRD), and high‐resolution transmission microscopy (HRTEM). A previous sample of Ti₃SnC₂, made using Fe as an additive and Ti₂SnC as a secondary phase, was studied by high‐temperature neutron diffraction (HTND) and XRD. The room‐temperature crystallographic parameters of the two MAX phases in the two samples are quite similar. Based on Rietveld analysis of the HTND data, the average linear thermal expansion coefficients of Ti₃SnC₂ in the a and c directions were found to be 8.5 (2)·10^?6 K^?1 and 8.9 (1)·10^?6 K^?1, respectively. The respective values for the Ti₂SnC phase are 10.1 (3)·10^?6 K^?1 and 10.8 (6)·10^?6 K^?1. Unlike other MAX phases, the atomic displacement parameters of the Sn atoms in Ti₃SnC₂ are comparable to those of the Ti and C atoms. When the predictions of the atomic displacement parameters obtained from density functional theory are compared to the experimental results, good quantitative agreement is found for the Sn atoms. In the case of the Ti and C atoms, the agreement is more qualitative. We also used first principles to calculate the elastic properties of both Ti₂SnC and Ti₃SnC₂ and their Raman active modes. The latter are compared to experiment and the agreement was found to be good.