Photochemical vapor deposition of amorphous silicon through 185 nm excitation of monosilane

Photochemical vapor deposition of a-Si films at a high rate using SiH₄ and a 185 nm low pressure mercury lamp is described. A maximum rate of 1 nm/sec was attained using the 185 nm lamp. This rate was about ten times higher than that using a 254 nm lamp. Assuming that there is no interaction between the effects of the two wavelengths, the deposition rate per light output power of 184.9 nm light is 160 times larger than that for 253.7 nm light. The absorption cross-section of the 184.9 nm light is ten times greater than that for the 253.7 nm light.     

A new strategy for the design of water-soluble synthetic receptors: specific recognition of DNA intercalators and diamines

Water-soluble zinc bisporphyrin receptors 1 and 2 having two Lewis acidic sites (zinc) in the hydrophobic environment consisting of alkyl chains and a bisporphyrin framework, and covered with hydrophilic exterior (twelve or eighteen carboxyl groups) were prepared. The receptors show high affinity for diamines and DNA intercalators in water where the binding constants K(a) are of the order of 10(7) and 10(8) M(-1), respectively. Diamines and DNA intercalators are bound to the receptor through different mechanisms. Diamines are bound through hydrophobic interactions and zinc-nitrogen interactions, while DNA intercalators are bound through hydrophobic interactions and charge-transfer interactions. Flexible alkyl chains can make van der Waals contact with guests and create a hydrophobic environment around the bound guest by an induced-fit-type mechanism. For the binding of DNA intercalators, the following features are noteworthy: 1). Binding constants are similar between the zinc porphyrins and zinc-free porphyrins; 2). the binding constant is larger for the guest having the lower LUMO; this indicates the important contribution of charge-transfer interactions to binding; 3). the hydrophobic and cationic nature of DNA intercalators is substantially important, and 4). higher ionic strength reduced the binding affinities; this shows a moderate contribution of electrostatic interactions. The conformational instability of the receptors also contributes to the tight binding: hydrophobic and electrostatic interactions cannot both be favorable at the same time in the guest-free receptor. Enthalpy-entropy compensation observed for the binding of diamines and DNA intercalators is characterized by a relatively small slope (alpha=0.74) and a large intercept (beta=7.75 kcal mol(-1)) in the DeltaH degrees versus TDeltaS degrees plot; this shows that a conformational change of receptors and a significant desolvation occur upon binding. The receptor can competitively bind to propidium iodide to deprive DNA of the intercalated propidium iodide. These features of water-soluble receptors consisting of a rigid framework and flexible side chains with a large solvent-accessible area are in contrast to highly preorganized rigid receptors, and they can provide useful guidelines for rational design of induced-fit artificial receptors in water.     

Complete memory of chirality upon photodecarboxylation of mesityl alkanoate to mesitylalkane: theoretical and experimental evidence for cheletropic decarboxylation via a spiro-lactonic transition state

The photodecarboxylation of chiral mesityl alkanoate to mesitylalkane has been studied experimentally/theoretically, and it has been found that the photodecarboxylation proceeds to give the product in > 99% enantiomeric excesses under a variety of conditions, indicating no involvement of any radical intermediates, but that the reaction proceeds through the concerted cheletropic extrusion of CO2 from the energetically less-favored s-cis conformation.     

Individual Cerebral Hemodynamic Response to Caffeine Was Related to Performance on a Newly Developed Stroop Color-Word Task

A modified Stroop color-word task has been developed to activate the prefrontal cortex as a cognitive task and it has been tried to clarify whether change in the cerebral hemodynamics after ingesting caffeine is associated with change in performance on the modified Stroop task in young male subjects. In this modified task, subjects were instructed to quickly select a colored disk on a computer screen in response to an instruction, i.e. “color” or “meaning”, presented simultaneously with one color word at each trial. The color of the presented color word was discordant with the meaning of the word. Relative changes in blood volume and oxygenation in the prefrontal association cortex were measured noninvasively using continuous-wave near-infrared spectroscopy. The results showed that caffeine ingestion decreased blood volume and oxygenated hemoglobin concentration in the brain during the modified Stroop task, and that the individual change in the latter was related to change in performance on the task following caffeine ingestion.     

THE ROLE OF DIOXYGEN SPECIES IN THE BASE- AND COBALT-CATALYZED OXYGENATION OF HINDERED PHENOLS

Abstract— The mechanisms by which 4-substituted 2,6-di- t -butylphenols are oxygenated by base- and Co(II) Schiff base complex-catalysis into o - or p -peroxyquinols and their Co(III) complexes, respectively, have been investigated. For the base-catalyzed oxygenation, a one-step ionic mechanism involving no radical species is suggested to be the most probable one. For the formation of the peroxycobalt(III) complexes, the following stoichiometry is concluded: ArOH + Co(II) + 5/4 O₂→ peroxycobalt(III) complex + 1/2 H₂O. A mechanism involving an electron transfer between the phenols and the Co(II)-O₂ complex followed by further electron transfer between the formed phenoxy radicals and the Co(II) complex to give the corresponding phenolate anions is proposed.     

5-[4-(1-Hydroxyethyl)phenyl]-10,15,20-triphenylporphyrin as a probe of the transition-state conformation in hydrolase-catalyzed enantioselective transesterifications

5-[4-(1-Hydroxyethyl)phenyl]-10,15,20-triphenylporphyrin (1a) and zinc porphyrin 1b were designed and synthesized to experimentally examine the validity of the transition-state model previously proposed for the lipase-catalyzed kinetic resolution of secondary alcohols. The lipases from Pseudomonas cepacia (lipase PS), Candida antarctica (CHIRAZYME L-2), Rhizomucor miehei (CHIRAZYME L-9), and Pseudomonas aeruginosa (lipase LIP) exhibited excellent enantioselectivity (E >100 at 30 degrees C). Subtilisin Carlsberg from Bacillus licheniformis (ChiroCLEC-BL) also showed high enantioselectivity for 1a (E = 140 at 30 degrees C), and the thermodynamic parameters were determined: DeltaDeltaH = -6.8 +/- 0.8 kcal mol(-1), DeltaDeltaS = -13 +/- 3 cal mol(-1) K(-1). Lipases and subtilisin showed R- and S-preference for 1, respectively. The mechanisms underlying the experimental observations are explained in terms of the transition-state models. The large secondary alcohol 1 is a powerful tool for investigating the conformation of the transition state of the enzyme-catalyzed reactions. The fact that 1 was resolved with high enantioselectivity strongly suggests that the gauche conformation, but not the anti conformation, is taken in the transition state, in agreement with the transition-state models involving the stereoelectronic effect.     

Micelle structures in aqueous solutions of glucose-based surfactants having an isoprenoid-type hydrophobic chain

Surfactant self-diffusion coefficients have been measured on a binary system of 1-O-beta-3,7-dimethyloctyl-D-maltopyranoside (beta-Mal(2)(Ger))/water and a mixed surfactant system of beta-Mal(2)(Ger)/1-O-beta-3,7-dimethyloctyl-D-glucopyranoside (beta-Glc(Ger))/water at 25 degrees C. For comparison, measurements have also been made on 1-O-beta-decyl-D-maltopyranoside (beta-Mal(2)C(10))/water and beta-Mal(2)C(10)/1-O-beta-decyl-D-glucopyranoside (beta-GlcC(10))/water. The hydrodynamic radius of beta-Mal(2)(Ger) micelles obtained from the micellar diffusion coefficient is around 3 nm and nearly equal to that of beta-GlcC(10) micelles within experimental error. In the mixed surfactant systems, the hydrodynamic radii for both systems increase with increasing X(G) (the mole fraction of beta-Glc(Ger) or beta-GlcC(10) in the total mixed solute) above X(G) congruent with 0.4 when the total surfactant concentration is kept constant at 2 wt%. The R(H) of beta-Glc(Ger)/Mal(2)(Ger) micelles increases more rapidly than beta-GlcC(10)/beta-Mal(2)C(10) micelles, and then phase separation occurs at X(G) congruent with 0.65. On the other hand, the R(H) of beta-GlcC(10)/beta-Mal(2)C(10) micelles continues to increase until the phase separation occurs at X(G) congruent with 0.92. Measurements have also been performed as a function of total surfactant concentration at constant X(G) (=0.6). The CMC of the beta-Glc(Ger)/Mal(2)(Ger) system is larger than that of the beta-GlcC(10)/beta-Mal(2)C(10) system as expected from the results of the pure surfactant systems published previously. The R(H) increases with increasing total surfactant concentration for both systems. At higher concentrations, the R(H) of beta-Glc(Ger)/Mal(2)(Ger) micelles increases more rapidly than beta-GlcC(10)/beta-Mal(2)C(10) micelles. These results can be explained by the fact that the geranyl and decyl chains have the same volume but different chain lengths.     

A new microbial electrode for BOD estimation

A new microbial electrode using immobilizedClostridium butyricum was prepared for biochemical oxygen demand (BOD) estimation of wastewaters. The current of the electrode was decreased with time until a steady state was reached. The steady state current was in all cases attained within 30-40 min at 37°C, and the maximum current output was obtained at 37°C and pH between 6.2 and 7.0. A linear relationship was obtained between the steady state current and BOD. The steady state current values were reproducible within ±7% of the relative error. The BOD of industrial wastewaters can be estimated by using the microbial electrode. Relative error of the BOD estimation of industrial wastewaters was within ± 10%. The current output of the microbial electrode was almost constant for 30 days.