Gas-phase hydroformylation of propylene on Ru/SiO2 catalysts

Ru/SiO₂ catalysts prepared by reduction of supported RuCl₃·xH₂O are active in gas-phase hydroformylation of propylene at low pressure (ca. 0.3 MPa) of H₂+CO+C₃H₆ mixtured and show unexpectedly high selectivity towards unbranched oxo-products. Data concerning the effect of electronic state and dispersity of Ru on their catalytic behavior have been obtained.

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Ru/SiO₂, RuCl₃·xH₂O, (0,3 ) - . .

     

Ultraviolet bands of Na2 and K2

The ultraviolet spectra of Na₂ and K₂ molecules have been investigated. These studies were made in absorption in the second order of a 3.4 m Ebert Spectrograph with a reciprocal dispersion of 2.6 Å/mm. A number of new bands in the spectra of both the molecules not previously reported have been observed. Computer methods have been used to calculate the term values and to evaluate molecular constants.     

Highly oxygenated triterpenes from the roots of Atropa acuminata

Two new oleanane triterpenes; 2alpha,3alpha,24-trihydroxyolean-12-ene-28,30-dioic acid ([structure: see text]) and 2alpha,3alpha,24,28-tetrahydroxyolean-12-ene ([structure: see text]) have been isolated from the roots of Atropa acuminata. Anti-oxidant p-hydroxyphenethyl trans-ferulate ([structure: see text]), beta-sitosterol-3-O-beta-D-glucopyranoside ([structure: see text]) and oleanolic acid ([structure: see text]) have also been reported for the first time from this species. The structures were determined by spectroscopic studies including 2D-NMR.     

Ruthenium(II) complexes with mono and ditertiary arsines and phosphines and their reaction with small molecules

Dichlorotetrakis(dimethylsulphoxide)ruthenium(II) reacts with AsPh₃ AsMePh₂, AsMe₂Ph and SbPh₃ in ethanolic hydrochloric acid solution to yield the complexes RuCl₂(DMSO)₂(AsPh₃)₂, RuCl₂(DMSO) L₂ (L = AsMePh₂, AsMe₂Ph, SbPh₃) respectively. The treatment of ruthenium(II) blue solution with AsMePh₂, AsMe₂Ph and SbPh₃ in alcohol resulted in the formation of the complexes; RuCl₂L₃ (L = AsMePh₂, AsMe₂Ph and SbPh₂), respectively. The reaction of RuCl₂(DMSO)₄ with the bidentate ligands 1,2 bis (diphenylarsino)methane (DPAM), 1,2 bis(diphenylarsino)ethane (DPAE) and 1,2 bis (diphenylphosphino)methane (DPPM). 1,2 bis(diphenylphosphino)ethane (DPPE), in ethanol gave the complexes RuCl₂(DPAM)₂, RuCl₂(DPAE)₂, RuCl₂ (DPPM)₂ RuCl₂(DPPE)₂, respectively. The complexes thus obtained undergo reaction with carbon monoxide, hydrogen, molecular nitrogen and nitric oxide to yield a variety of mixed ligand complexes.     

Kinetics and mechanism of ruthenium(III) and ruthenium(III)-EDTA catalyzed oxidation of cyclohexanol by molecular oxygen

The kinetics of the oxidation of cyclohexanol by molecular O₂ catalyzed by Ru(III) and Ru(III)-EDTA complexes has been investigated by oxygen absorption method in the pH range 1.75–3.00 at 30°C (=0.1M KNO₃) in a 11 ethanol-water medium. In both cases the reaction was found to be first order with respect to substrate and catalyst concentration. The rate was found to decrease with the decrease of pH in case of Ru(III)-EDTA complex. Ethanol is not oxidized under the reaction conditions. A possible mechanism for the catalytic oxidation of cyclohexanol is proposed.

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O₂, Ru(III) Ru(III)-EDTA, pH 1,75–3,00 30°C (=0,1M KNO₃) - (11). . pH Ru(III)-EDTA. . .

     

Neutron induced radiography in the determination of boron in drinking water

Neutron induced radiography has been applied to the determination of boron concentrations in drinking water, collected from natural springs of Reshian and Muzaffarabad areas of Azad Kashmir, Pakistan, using CR-39 etched track detectors. The technique is based upon the simultaneous irradiation with thermal neutrons of a sample of unknown concentration and a standard of known boron concentration, fixed on a track detector. The subsequent counting of alpha and ⁷Li tracks in the detector resulting from the ¹⁰B(n,)⁷Li nuclear reaction is done after chemical etching. Boron concentration in the sample is determined by comparing ⁷Li and alpha-particle track density with that of a standard of known boron concentration. Boron concentrations in drinking water samples from Muzaffarabad and Reshian area of Azad Kashmir have been found to vary from (0.054±0.001) mg/l to (0.250±0.004) mg/l with an average of (0.16±0.002) mg/l. The observed concentration of boron in drinking water has been found to be less than the provisional Maximum Acceptable Concentration level (0.4 mg//l) of WHO. The drinking water from the reported area has been found to be within safe limits as far as boron related health hazards are concerned.This revised version was published online in November 2005 with corrections to the Cover Date.     

Factors affecting propagating fronts of addition polymerization: Velocity,front curvature,temperatue profile,conversion, and molecular weight distribution

Several properties of propagating fronts of addition polymerization were studied. A power function could be fit to the velocity dependence on initiator concentration, but not with the exponents predicted by current models or in agreement with other published work. Bubbles from the volatile by-products of initiator decomposition were found to affect the front velocity and curvature. The front velocity for triethylene glycol dimethacrylate polymerization was found to depend linearly on temperature over a moderate range. The conversion of methacrylic acid in fronts varied greatly with initiator type and concentration. Benzoyl peroxide produced much lower conversion than t-butyl peroxide, but fronts with tBPO propagated slower. A dual initiator system of BPO and tBPO produced rapidly propagating fronts with good conversion but the contribution of each initiator to the velocity was not additive. The possibility of chain branching was considered. The apparent molecular weight distributions were very broad, often trimodal, and found to depend on initiator type and concentration as well as the tube diameter. The temperature profiles were measured and found to be very sharp for BPO and broader for tBPO but both had front temperatures in excess of 200°C, indicating a high ceiling temperature. © 1995 John Wiley & Sons, Inc.     

Excitation-energy migration in self-assembled cyclic zinc(II)-porphyrin arrays: a close mimicry of a natural light-harvesting system

The excitation-energy-hopping (EEH) times within two-dimensional cyclic zinc(II)-porphyrin arrays 5 and 6, which were prepared by intermolecular coordination and ring-closing metathesis reaction of olefins, were deduced by modeling the EEH process based on the anisotropy depolarization as well as the exciton-exciton annihilation dynamics. Assuming the number of energy-hopping sites N = 5 and 6, the two different experimental observables, that is, anisotropy depolarization and exciton-excition annihilation times, consistently give the EEH times of 8.0 +/- 0.5 and 5.3 +/- 0.6 ps through the 1,3-phenylene linkages of 5 and 6, respectively. Accordingly, the self-assembled cyclic porphyrin arrays have proven to be well-defined two-dimensional models for natural light-harvesting complexes.     

Fast folding of a four-helical bundle protein

The FK506-FKBP12 binding-domain of the kinase FRAP (FRB) forms a classic up-down four-helical bundle. The folding pathway of this protein has been investigated using a combination of equilibrium and kinetic studies. The native state of the protein is stable with respect to the unfolded state by some 7 kcal mol(-1) at pH 6.0, 10 degrees C. A kinetic analysis of unfolding and refolding rate constants as a function of chemical denaturant concentration suggests that an intermediate state may be populated during folding at low concentrations of denaturant. The presence of this intermediate state is confirmed by refolding experiments performed in the presence of the hydrophobic dye 8-anilinonaphthalene-1 sulfonate (ANS). ANS binds to the partially folded intermediate state populated during the folding of FRB and undergoes a large change in fluorescence that can be detected using stopped-flow techniques. Analysis of the kinetic data suggests that the intermediate state is compact and it may even be a misfolded species that has to partially unfold before it can reach the transition state. Folding and unfolding rate constants in water are approximately 150-200 s(-1) and 0.005-0.06 s(-1), respectively, at neutral pH and 10 degrees C. The folding of FRB is somewhat slower than for other all-helical proteins, probably as a consequence of the formation of a metastable intermediate state. The folding rate constant in the absence of any populated intermediate can be estimated to be 8800 s(-1). Despite the presence of an intermediate state, which effectively slows folding, the protein still folds rapidly with a half-life of 5 ms at 10 degrees C. The dependence of the rate constants on denaturant concentration indicates that the transition state for folding is compact with some 80% of the surface area exposed in the unfolded state buried in the transition state. Data presented for FRB is compared with kinetic data obtained for other all-helical proteins.