Hydrogenolysis of cycloalkanes on a tantalum hydride complex supported on silica and insight into the deactivation pathway by the combined use of 1D solid-state NMR and EXAFS spectroscopies

Hydrogenolysis of cyclic alkanes is catalysed by [(triple bond)SiO)(2)Ta-H] (1) at 160 degrees C and leads to lower alkanes and cyclic alkanes including cyclopentane. The turnover number is correlated with the number of carbon atoms of the cyclic alkanes, and therefore while cycloheptane is readily transformed, cyclopentane does not give any product (<1 %). The mechanism of ring contraction probably involves carbene de-insertion as a key carbon-carbon bond-cleavage step. The reluctance of cyclopentane to undergo hydrogenolysis was further studied: under the reaction conditions cyclopentane reacts with 1 to give the corresponding cyclopentyl derivative [(triple bond)SiO)(2)Ta-C(5)H(9)] (13), which evolves towards cyclopentadienyl derivative [(triple bond)SiO)(2)Ta(C(5)H(5))] (14) according to both solid-state NMR and EXAFS spectroscopies. This latter complex is inactive in the hydrogenolysis of alkanes, and therefore the formation of cyclopentane in the hydrogenolysis of various cyclic alkanes is probably responsible for the de-activation of the catalyst by formation of cyclopentadienyl complexes.     

Calibration and determination of volatile fatty acids in waste leachates by gas chromatography

Low-level radioactive waste leachates were analyzed for volatile fatty acids by gas chromatography as part of the continuing waste management program at the Chalk River Laboratories. An existing method was optimized whereby carboxylic acids were detected at the mg/1 level with a precision of 5% or better for C₂---C₇ acids and an accuracy of 3% or better for acetic acid. Parameters such as sample handling, calibration and accuracy are discussed.     

Correlation between the chromatographic poperties of silica phenyl packing materials and the retention behaviour of methylated β-cyclodextrins

Summary The chromatographic properties of five columns packed with phenyl-bonded phases were characterized by an approach based on Tanaka's method for column to column comparisons in order to develop an LC analysis of partially methylated β-cyclodextrins. The retention behaviour of β-cyclodextrin, heptakis(2,6-di-O-methyl)-β-cyclodextrin and heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin was examined in order to evaluate the different interactions between phenyl stationary phase and this family of compound. Chromatograms show that the residual silanol activity of the packing materials plays a beneficial role in the partially methylated β-cyclodextrins separation process. It is concluded that knowledge of the interactions involved allows one to make a reasoned choice of the stationary phase in order to obtain the best possible analysis of three different commercial samples of partially methylated β-cyclodextrins.     

Structure-Lipophilicity Relationships of Neutral and Protonated β-Blockers,Part I,Intra- and Intermolecular Effects in Isotropic Solvent Systems

The objectives of this study were to validate new experimental techniques used to measure the log P of protonated drugs, and to investigate the inter- and intramolecular forces influencing the partitioning behavior of β-blockers in isotropic biphasic solvent systems. The lipophilicity parameters of a number of β-blockers were measured by two-phase titration, centrifugal partition chromatography (CPC), and cyclic voltammetry (CV) in one or more of the following solvent systems: octanol/water, 1,2-dichloroethane/water, and dibutyl ether/water. CV proved to be a promising technique for measuring the lipophilicity of protonated β-blockers. Derived parameters such as Δlog P (difference between log P in two different solvent systems, a parameter valid for a given solute in a given electrical form) and diff (difference between log P of two different electrical forms of a given solute, in the same system) yielded insights into inter- and intramolecular interactions characteristic of β-blockers. The relevance of these parameters in structure-permeation relationships is explored.     

Structure-Property Relationships in the Basicity and Lipophilicity of Arylalkylamine Oxides

Homologous N,N-dimethyl-phenylalkylamine oxides and N,N-dimethyl-diphenylalkylamine oxides were prepared. Their basicity and lipophilicity (octan-1-ol/H₂O) were compared to those of the parent amines. In contrast to the amines, the basicity of all N,N-dimethyl-arylalkylamine oxides showed very limited pK_a variations (range 4.65 – 5.01) with increasing chain length and number of Ph groups. The N-oxides in their neutral form had a log P^N value lower by 2.77±0.34 (n=9) units than that of the parent amine. The log P^C of the cationic N,N-dimethyl-diphenylalkylamines was lower than that of their neutral form, with a decrement diff(log P^N−C) that increased from 3.25 to 4.21 in the homologous series. Unexpectedly, the decrement diff(log P^N−C) for the N-oxides was much smaller than for the tertiary amines, being 0.23 for the aliphatic N,N-dimethyl-pentylamine oxide, 0.47±0.13 for the phenylalkylamine oxides, and 0.80±0.07 for the diphenylalkylamine oxides. In fact, the protonated N-oxides had log P^C values that were quite comparable to those of the protonated parent amines. Because of the differences in basicity, the difference in distribution coefficients at physiological pH (log D^7.4) between a tertiary arylalkylamine and its N-oxide was 0.82±0.66 (n=9). The pharmacokinetic implication is that N-oxygenation may have a smaller effect on the urinary excretion of tertiary amines than usually assumed.     

Generalized Motzkin Theorems of the Alternative and Vector Optimization Problems

In this paper, we introduce a definition of generalized convexlike functions (preconvexlike functions). Then, under the weakened convexity, we study vector optimization problems in Hausdorff topological linear spaces. We establish some generalized Motzkin theorems of the alternative. By use of these theorems of the alternative, we obtain some Lagrangian multiplier theorems. A saddle-point theorem and a scalarization theorem are also derived.Communicated by F. GiannessiThe author thank Ginndomenico Mastrocni for helpful and useful comments.     

An Experimental Investigation of Second Harmonic Generation in a Cyclotron and Upper Hybrid Resonant Plasma

An experiment is described in which an electromagnetic wave (extraordinary mode) is propagated across a magnetized plasma and second harmonic generation is detected. The generation of the plasma and the second harmonic wave is associated with resonant conditions of electron cyclotron resonance and upper hybrid resonance. By adjusting the intensity of axial magnetic field, the second harmonic generation can be made solely due to the electron cyclotron resonance, the upper hybrid resonance or both. The experiment is qualitatively in agreement with previous similar experiments and can be explained in terms of the spatial variations of the magnetic field intensity and the electron number density. A technique for diagnosing peak number density is developed from the observed second harmonic power characteristics.     

Blind deconvolution of audio-frequency signals using the self-deconvolving data restoration algorithm

A signal processing algorithm has been developed in which a filter function is extracted from degraded data through mathematical operations. The filter function can be used to restore much of the degraded content of the data through use of a deconvolution process. The operation can be performed without prior knowledge of the detection system, a technique known as blind deconvolution. The extraction process, designated self-deconvolving data reconstruction algorithm, is applied here to audio-frequency signals showing significant qualitative improvement. Degradation arising from the process of electronic recording and reproduction is significantly reduced.     

Blind data restoration with an extracted filter function

A method for performing blind deconvolutions on degraded images and data has been developed. The technique uses a power law relation applied to the Fourier transform of the degraded data to extract a filter function. This filter function closely resembles the point-spread function of the system and can be used to restore and enhance higher-frequency content. The process is noniterative and requires only that the point-spread function be space invariant and the transfer function be real. The algorithm has been validated by direct comparisons by use of a pseudoinverse filter with known transfer functions.