Heterogeneous asymmetric reactions. 23. Enantioselective hydrogenation of ethyl pyruvate over cinchonine- and α-isocinchonine-modified platinum catalysts

The enantioselective hydrogenation of ethyl pyruvate to (S)-ethyl lactate over cinchonine- and -isocinchonine-modified Pt/Al₂O₃ catalysts was studied as a function of modifier concentration and reaction temperature. The maximum enantioselectivities obtained under the applied mild conditions were 89% ee using cinchonine (0.014 mmoldm^–3, 1 bar H₂, 23°C, 6% AcOH in toluene), and 76% ee in the case of -isocinchonine (0.14 mmoldm^–3, 1 bar H₂, –10°C, 6% AcOH in toluene). Since -isocinchonine of rigid structure exists only in anti-open conformation these data provide additional experimental evidence to support the former suggestion concerning the dominating role of anti-open conformation in these cinchona-modified enantioselective hydrogenations.     

X-ray diffraction study of anisotropy by the formation and decomposition of nickel hydride Part II: Decomposition kinetics

The role of the microstructure on the decomposition of -NiH formed as a result of the H cathodic charging of nickel was studied with the help of X-ray diffraction methods. This decomposition follows Kolmogorov-Avrami-Johnson-Mehl kinetics. The microstructural anisotropy induces anisotropy in the rate of phase transformation which is governed by the chemical reaction -NiHNi+H, i.e. it proceeds without diffusion limitations.     

Inhibition and nickel electrocrystallization

The electrocrystallization of Ni is known to be a highly inhibited process. This work gives some conclusions about the nature of the major inhibiting species. All of these species are formed in the catholyte because of the hydrogen codeposition. Depending on plating conditions, mainly pH and current density of metallic deposition, we observe a predominancy of a definite inhibitor which selectively promotes one mode of growth and leads to a deposit exhibiting definite structural properties. A careful structural investigation of Ni deposits obtained from a Watts solution, thanks to both X-ray diffractometry and electron-microscope techniques, leads us to distinguish a free mode of growth, which is characterized by [100] oriented deposits, from several inhibited modes such as 110, [210], 211 and 111. The two latter are stabilized by Ni(OH)₂ while the two former are respectively due to atomic and molecular forms of adsorbed hydrogen.     

Specific features of the phase transformations occurring during the sintering process of the beta-alumina based ceramics and their properties

Conclusions During the sintering process of beta-alumina obtained using the method of plasmochemical synthesis, the structural transformation occurs and it is accompanied by the separation of the excess Na₂O and the formation of an intergranular meltlike phase that is saturated with sodium and is characterized by high dielectric properties.The quantity of the meltlike phase and the magnitude of the /( + ) ratio determine the degree of stabilization (stability) and the final resistivity of the material and depend on the initial chemical composition and the heating rate maintained during the sintering process.It was shown that when the duration of residence of the material in the hot zone of the furnace is increased or when the specimens sintered maintaining high heating rates are subjected to additional heat treatment, one observes the occurrance of the reverse structural transformation that is characterized by an increase of the phase ratio /( + ) 1, a reduction in the quantity of the meltlike phase right up to its complete disappearance, and a decrease of the electrical resistivity of the material.In the materials having a large excess quantity of sodium oxide, the process of crystallization of the intergranular NaAlO₂ phase occurs simultaneously with the second phase transformation.The best ceramic and electrophysical parameters were obtained when sintering the material contained 7.9% Na₂O.Translated from Ogneupory, No. 3, pp. 13–18, March, 1990.     

Critical solution point and chain dimension of branched-polystyrene solutions

Summary Critical solution point and chain dimension were measured for branched polystyrene(BPS) in solution as a function of molecular weight(M) and compared with those for linear polystyrene(LPS). The critical concentration _c of BPS was quite different from that of LPS at a fixed M, but the same at a fixed overlap-concentration ^*, i.e., plots of _c vs. ^* fall on a single straight line for both BPS and LPS (gf_c ^*). Reduced critical temperature _c defined by gt_c=(–T_c)/ [T_c: critical temperature, : the -temperature] was related to _c as _{c c} ² for BPS, whereas _{c c} for LPS.     

Studies concerning charged nickel hydroxide electrodes IV. Reversible potentials in LiOH,NaOH, RbOH and CsOH

The variation of reversible potential E_r with log a_moh and has been studied for several nickel hydroxide/oxyhydroxide couples in various alkali hydroxides. Both activated and deactivated -phase couples show only a small dependence ofE _r with log_moh (or where known) in LiOH, NaOH, RbOH and CsOH electrolytes. The change in MOH content on oxidation/reduction is found to be about 0.1 mol MOH per two-electron transfer and is the same as found previously in KOH. These results confirm that the bulk oxidized -phase lattice is devoid of alkali cation although a small quantity may be adsorbed by the surface. On the other hand both activated and deactivated /-phase couples show a marked dependence of 0.45 mol MOH per two-electron transfer in LiOH, NaOH and RbOH (at concentrations > 0.5 m), also in good agreement with earlier data for KOH. On the basis of these results a general stoichiometry can be inferred for the -phase, namely M_0.32NiO₂ · 0.7H₂O where M=Li⁺, Na⁺, K⁺ or Rb⁺. Measurements imply that the Cs⁺ ion or the Rb⁺ ion at low concentration (<0.5 m) do not enter the interlayer structure of the -phase. This behaviour is thought to be related to the low Rb-O and Cs-O bond strengths afforded by the -phase structure.     

Variable‐temperature IR spectroscopic studies of CO adsorbed on Na‐ZSM‐5 and Na‐Y zeolites

CO interacts with extraframework alkali metal cations (M⁺=) of zeolites to form both M⁺CO and M⁺OC species. By using variabletemperature FTIR spectroscopy, these Cbonded and Obonded species were found to be in a temperaturedependent equilibrium. For the same cation, the difference in interaction energy depends upon the zeolite framework. Thus, for the equilibrium process ZNa⁺=CO ZNa⁺OC, where Z represents the zeolite framework, H ⁰ was found to take the values 3.8 and 2.4 kJ mol^– for CO/NaZSM5 and CO/NaY, respectively. The Cbonded species show always the highest cation–CO interaction energy.     

Convective Regime of Filtration Combustion of Energetic Materials in a Cocurrent Flow of Their Combustion Products

The convective regime of filtration combustion of energetic materials in a cocurrent flow of their combustion products is studied using a model with extremely simplified kinetics and heat transfer, which shows instability of the process. It is shown that the more accurate twotemperature model describes a steadystate regime. In this regime, the gas temperature on the hot boundary of the heating zone is well below the combustion temperature, and the solidphase temperature is well below the temperature proposed in recent studies on this topic. It is pointed out that the twotemperature approach is unjustified and intragranular nonisothermicity must be taken into account for convective regimes. It is shown that the threetemperature model, which takes into account this effect, does not give a stable steadystate solution.     

Model Detonation of Solid Explosives by the Homogeneous Mechanism

A twophase detonation model of solid porous explosives, which takes into account the compression of solidstate particles and the presence of a solid component in detonation products, is developed. The homogeneous detonation mechanism based on the Arrheniustype reaction is studied. Detonation is initiated by the region of highpressure and hightemperature gases modeling the detonator explosion. A numerical experiment confirms that there exists an initiationpressure limit below which no homogeneous mechanism of detonation is active. The detonation wave has the leading front in which the explosive is precompacted and the gas in the porous volume is compressed up to a pressure of 100 GPa without any significant change in particle density. Then the gas compresses the particles themselves up to the pressure and temperature of the thermal explosion. As a result, the leading front is followed (after a certain delay) by a narrow reaction zone where detonation products are formed with a further increase in pressure.     

Nucleation and growth kinetics of Ag7NO11 on a platinum single crystal electrode

The process of electrochemical deposition of Ag₇NO₁₁ on a platinum single crystal anode from 5M AgNO₃ is investigated. The nucleation and growth rates are measured at different constant overpotentials. The orientation of the Ag₇NO₁₁ crystals with respect to the substrate surface is determined in the case of deposition on glassy carbon and on the 100, 111 and 110 faces of a platinum single crystal.     

Study of the β — α solid-solid transition of isotactic polypropylene by synchrotron radiation

Synopsis The transformation of the -modification into -modification in isotactic polypropylene was investigated by WAXS, DSC and dilatometric methods. The temperature and time dependent WAXS spectra were made by using high-intensity synchrotron radiation. The - transformation was followed by short time exposures. The transformation of the -modification was found to act toward the increase in the total crystallinity.     

Synthesis and polymerization of 2-(β-N-3′-halogencarbazolylethyl)-2-oxazolines

Summary The synthesis of three novel oxazoline monomers,all of which contain 3-halogen substituted carbazolyl groups [i.e., 2-(-N-3 chlorocarbazolylethyl)-2-oxazoline, 2-(-N-3 bromocarbazolylethyl)-2-oxazoline and 2-(-N-3 iodocarbazolylethyl)-2-oxazoline]and their polymerization is described.     

Preparation of Linear π-Conjugated Coordination Polymers Having Ruthenium(II) Complex in the Main Chain

Soluble -conjugated coordination polymers having a ruthenium(II) complex in the main chain were prepared from a soluble metal complex monomer and a bridging ligand via coordination. Refluxing of an ethanol-water suspension containing (4,4-dinonyl-2,2-bipyridyl)Ru(III) with 2,3-bis(2-pyridyl)pyrazine gave the coordination polymer. The resulting polymer was soluble in common organic solvents. The structure was confirmed by uv/vis spectra and gpc analysis.     

Crystal structure and morphology of electrodeposited zinc-iron binary alloys

Deposits of zinc-iron alloy have been prepared galvanostatically from a sulphate bath and the crystal structure has been determined by X-ray diffraction and transmission electron microscopy measurements. The electrodeposited zinc-iron alloys have metastable structures and the individual phases coexist over wide composition ranges. The phases are identified as (10073 at % zinc), (8748 at % zinc), ₁(7862 at % zinc) and (620 at % zinc). Thec andc/a in the h.c.p. lattice of the -phase decrease continuously with decrease of zinc concentrations, and the latter changes from 1.86 to 1.60 (a andc are the lattice constants of the -phase in the direction of thea- andc-axes, respectively). The -phase particles exhibit a hexagonal plate-like morphology which is thin in the direction of thec-axis. The morphology of the electrodeposits changes from plate-like to pyramidal shape when fine -phase particles (100 nm) start to form surrounding the -phase platelets, and then to lenticular or granular in the /₁ duplex region. The -phase forms in the low zinc concentration region and changes the electrodeposits to a fine cuboidal morphology.     

II-I phase transformation of melt-crystallized oriented lamellae of polybutene-1 by shear deformation

Summary Modification II-I transformation of polybutene-1 was investigated on oriented lamellae, which were melt-crystallized in the temperature gradient. WAXS photograph of as-grown specimen showed prefered orientation of [110] to the lamellar axis, and after transformation it showed twelve point pattern due to dual orientation of hexagonal lattice. By shear deformation parallel or perpendicular to lamellar axis, WAXS photograph showed the appearance of six point pattern due to single orientation of hexagonal lattice, and also the enhancement of transformation rate. These were explained by the growth of hexagonal nuclei formed by the slip in the tetragonal crystal.     

The effects of antimony and glue on zinc electrowinning from Kidd Creek electrolyte

The individual and combined effects of antimony and glue on zinc deposition current efficiency and polarization and on the morphology and orientation of 6h zinc deposits electrowon at 500 A m^–2 and 38° C from Kidd Creek zinc electrolyte were determined. Glue increased zinc deposition polarization, reduced the deposit grain size, changed the preferred deposit orientation from basal to intermediate, but decreased the current efficiency. At concentrations above 0.02 mgl^–1, antimony had a strong depolarizing effect on zinc deposition resulting in a basal deposit orientation and very low current efficiency. Certain combinations of antimony and glue, however, optimized zinc deposition current efficiency and consistently gave an intermediate 114 112 103 102 101 preferred deposit orientation. A correlation was observed between the current efficiency (CE) and the nucleation overpotential (NOP) for zinc deposition such that the CE was a maximum when the NOP of the initial cell electrolyte was 120–130 mV and when the NOP of the final cell electrolyte was 100–110 mV.     

Antifungal polyoxygenated fatty acids fromAeollanthus parvifolius

Two polyoxygenated fatty acids with antifungal activity have been isolated from aerial parts ofAeollanthus parvifolius (Labiatae) using bioassay-guided isolation procedures. Spectroscopic analysis was used to identify the compounds as (Z)-4,9-diacetoxy-6,7-epoxy-5-hydroxy-8-oxododeca-2-enoic acid and (Z)-4,6,7,9-tetraacetoxy-5-hydroxy-8-oxododeca-2-enoic acid. Both of these compounds inhibited spore germination ofCladosporium cucumerinum. Minimum inhibitory doses were 1 µg and 5 µg, respectively, but only the former inhibited germination ofAspergillus niger at a dose of 5 µg. Neither compound exhibited antibacterial activity. (Z)-4,9-Diacetoxy-6,7-epoxy-5-hydroxy-8-oxododeca-2-enoic acid reduced the hyphal growth ofPythium ultimum. The mode of action was not resolved but did not involve either the disruption of the cell wall membrane or the inhibition of extracellular enzymes. Application of (Z)-4,6,7,9-tetraacetoxy-5-hydroxy-8-oxododeca-2-enoic acid to seedling plants did not give any protection against fungal attack, and indeed the compound appeared to be phytotoxic.     

Copolymerization of 2-phenoxy-1,3,2-dioxaphosphorinanes with α-keto acids involving deoxygenation of the keto oxygen atom: deoxy-copolymerization

Summary The copolymerization of 2-phenoxy-1,3,2-dioxaphosphorinanes (4) with -keto acids (2) took place at room temperature without added catalyst to produce copolymers (5). The copolymer 5 is composed of phosphoric acid triester unit (5 ) and of -hydroxy-carboxylic acid ester unit (5 ). Unit 5 is an alternating unit of monomers 4 and 2 whereas unit 5 is formed by deoxygenating 2 by 4. 5 can be taken as copolymers of units 5 and 5 , the formation of the latter involving a deoxygenation process (Deoxy-Copolymerization). The ratio of 5 /5 (m-value in 5) increased in the order of unsubstituted (4a)-, 5,5-dimethyl (4b)-, and 5-t-butyl (4c)-phosphorinane systems. The reaction mechanism is also discussed.Dedicated to the 65th birthday of Professor G. Manecke     

Oviposition deterrent from eggs ofCallosobruchus maculatus: Spacing mechanism or artifact?

Females ofCallosobruchus maculatus (F.) avoid ovipositing on host seeds already bearing conspecific eggs, and thus distribute eggs evenly among seeds. This behavior was presumed to be mediated by an ether-soluble oviposition marker that is deposited with the egg and can be extracted from egg-laden artificial hosts (glass beads). Ablation experiments revealed that the true factors promoting an even dispersion of eggs were perceived by the maxillary and labial palpi. In contrast, receptors on the antennae were largely responsible for avoidance of seeds treated with oviposition marker. Taken together, these results suggest that a careful distinction should be drawn between factors that promote spacing of eggs under natural conditions and general oviposition deterrents that may be isolated from both sexes.     

Textural and structural studies on nickel hydroxide electrodes. II. Turbostratic nickel (II) hydroxide submitted to electrochemical redox cycling

The textural and structural modifications involved in electrochemical redox cycling of turbostratic nickel (II) hydroxide has been investigated using X-ray diffraction and electron microscopy methods. It was found that during the first cycles, different phenomena compete: redox reactions which occur in the solid state, and ageing reactions via the solution. For the first galvanostatic charge performed at the C/5 rate in 4.5 N KOH, the direct oxidation of (II) to (III) and the ageing of (II) to (II) via the solution followed by the oxidation to (III) are in competition. The study of the discharge mechanism shows that the direct reduction (III)(II) is parallel to the reduction (III)(II) and the ageing of the turbostratic hydroxide via the solution. After the first cycle it was established that the alpha-generated (II) active phase consisted of a mixture of two kinds of particles, the oxidation of which follows two paths: (II)/(III) for the thicker particles and for the thinner (II)/(III), but these latter (II) particles aged via the solution by Oswald ripening and the (II)/(III) couples swung to (II)/(III).