Reactant adsorption in differential pulse polarography: Effects of adsorptive depletion of reactant,non-linear adsorption isotherms and uncompensated resistance

Digital simulation techniques are applied to the diagnosis of the ways in which the peak currents and wave shapes of differential pulse polarograms are affected by the adsorption of reactants or products. The changes in the polarograms introduced by the items mentioned in the title are examined and their magnitudes calculated and compared with experimental polarograms. Some implications of the results in analytical applications of differential pulse polarography are described.     

Laser micro-machining using near-field optics

Solid immersion lenses (SIL) facilitate high numerical aperture (NA) and consequent sub-wavelength diffraction limited focusing in near-field optics based systems. Such systems are in commercial and research use for various applications including near-field scanning optical microscopy, ultra-high-density magneto-optic data storage and near-field nanolithography. Here, we present a novel manufacturing method using SIL-based near-field optics for laser-induced patterning on silicon wafers. The near-field effect of SILs was investigated by using hemispherical lenses made of three different materials (BK7, Sapphire, LaSFN9) to superfocus an incident Q-switched, 532 nm Nd:YAG laser beam transmitted through a focusing objective. This optical arrangement achieved a laser-processed feature resolution near the diffraction limit in air. Results of experiments that were conducted at various processing conditions to investigate the effects of varying incident laser power (with peak pulse power less than 1 W), pulse width, number of pulses and size of SIL on processed feature size and resolution are presented. Experimental results are compared with numerical simulations using the simplified model.     

Dissolution kinetics of K-alum crystals as judged from the measurements of surface undersaturations

The normal dissolution rates, the slopes and the average velocities of dissolution steps of etch pits on the (111) face of a K-alum crystal, originating from dislocations with Burgers vector 110, were measured in relation to the surface undersaturations. From the mutual relations, it was shown that the dissolution was controlled by both diffusion and surface kinetic processes, although the contribution of the latter process was smaller than in the case of growth. It was also demonstrated that the normal dissolution rate was always larger than the growth rate. This is attributed to the fact that the slopes of growth hillocks are invariably smaller than those of etch pits.     

Generalized rational identities of subnormal subgroups of skew fields

Let be a skew field with infinite center such that , and let be a non-central subnormal subgroup of the multiplicative group of . Then there are no non-trivial generalized rational identities of . This generalizes a theorem proved by Makar-Limanov.

     

Polymerization mechanism of vinyl chloride with titanium tetrabutoxide–ethylaluminum sesquichloride catalyst and some physical properties of poly(vinyl chloride) prepared at low temperature

The mechanism of vinyl chloride polymerization by titanium tetrabutoxide–ethylaluminum sesquichloride catalyst system was investigated from the view of the stereoregularity of poly(vinyl chloride). The samples were prepared at a selected temperature in the range from 23 to ?78°C. The tactic triads, obtained from 220-MHz NMR spectra, show clearly the adequacy of Bernoullian statistics in describing the mechanism for stereochemical propagation. The chain propagation proceeds according to Bernoullian statistics with syndiotactic placements favored by 550 cal/mole. These results suggest that vinyl chloride polymerizes by a free-radical mechanism under the action of the present catalyst system.     

Z-selective synthesis of alpha,beta-unsaturated amides with triphenylsilylacetamides

With the purpose of developing a method of preparing Z-alpha,beta-unsaturated amides, the Peterson reaction of the (triphenylsilyl)acetamide Ph(3)SiCH(2)COX (1, X = NBn(2); 3, X = NMe(2)) with various aldehydes was examined. The reaction of aromatic aldehydes gave selectivities up to >97:3. It was found that the selectivity was a function of the electronic nature of the aromatic ring and higher Z selectivity was attained with electron-rich aldehydes. With aliphatic aldehydes selectivities up to 92:8 were achieved, and unlike with analogous phosphorus reagents, less sterically hindered aldehydes gave higher Z selectivity. Also, 3, which has a smaller amide group than 1, tended to give rise to higher selectivity. A comparison with the reaction of trimethylsilyl analogues revealed the significance of the phenyl substituents on the silyl group.     

Stereochemical regulation of polypropylenes prepared with various Ziegler-Natta catalysts

The 220-MHz proton magnetic resonance and infrared spectra of stereoregular polypropylenes polymerized with a number of Ziegler-Natta catalysts and isotactic polymers of low molecular weight obtained by thermal degradation of a highly isotactic polypropylene were measured in an attempt to obtain some information on the local regularity. The fraction of thermally degraded polymer soluble in diethyl ether shows stereorandomness (tactie sequence length is quite short), and the portion soluble in n-pentane has stereoblock character. The results so obtained provide strong evidence that racemic dyads of whole polymer consist of two models of racemic dyad isolated and racemic dyads in groups. The polymers prepared with vanadium catalyst systems show stereorandom character and these polymers have \documentclass{article}\pagestyle{empty}\begin{document}$\hbox{-\hskip-1pt-}\hskip-4pt({\rm CH}_2 \rlap{--} )$\end{document} groups formed by two propylene units in a tail-to-tail linkage. Syndiotactic polypropylene has head-to-head and tail-to-tail arrangements of two propylene units and this is the origin of randomness of syndiotacticity.     

The Effects of Serum on Cellular Uptake and Phototoxicity of Mono-L-Aspartyl Chlorin e6 (NPe6) In Vitro

Abstract— Previous reports showed that the photosensitizer mono- l -aspartyl chlorin e6 (NPe6) binds to serum proteins. However, the influence of this binding on the cellular uptake and photodynamic therapy (PDT) phototoxicity of NPe6 is still undefined. In this paper, we studied how serum in medium affected the P388 cellular uptake and PDT phototoxicity of NPe6 in vitro. This was assessed by (1) detection of the red shift (654 nm Q band peak of absorption) induced by protein binding NPe6; (2) detection of intracellular concentration of NPe6 by HPLC and (3) measurements of the cell survival ratio after PDT by MTT assay. The 654 nm Q band peak of NPe6 shifted to 665 nm after binding of NPe6 and serum proteins. The protein-bound NPe6 cannot be uptaken by cells, thus there was no PDT phototoxicity. Nevertheless, phototoxicity recovered when the concentration of NPe6 excessed the serum protein binding ability or there was free serum protein in the medium. These data suggested that the cellular uptake of NPe6 is inhibited by serum components in the medium, and that only free NPe6 is accumulated by P388 cells even during relatively long incubations. The cytotoxicity of PDT mainly depends on the free NPe6 level in the medium.     

The relative merits of 6π9C bishomoaromatic and 10π13C longicyclic stabilization

The behaviour of tricyclo[4.4.3.0^1,6] tridecapentaenyl and tricyclo[4.4.3.0^1,6]trideca- 2,4,11-trienyl cations under short- and long- life conditions is described.