1, n-Triorganosilyl migrations in the rearrangements of silyl-substituted organolithium compounds

Under the agency of the potent lithiating agent, n-butyllithium in TMEDA, an array of organosilanes was found to undergo 1, n-silyl rearrangements via carbanionic intermediates. Unambiguous 1, 2-, 1, 3- and 1, 4-silyl shifts were uncovered in 1-trimethylsilyl-1, 1, 2-triphenylethane, 1, 1-bis(trimethylsilyl)-1-phenylalkanes and 1, 2-bis(trimethylsilyl)-1, 2-diphenylethane, respectively. Cross-over and competition experiments established that these rearrangements generally are intramolecular and occur with decreasing ease in the order, 1, 2 > 1, 3 > 1, 4. In other compounds, such as 1, 1-bis(trimethylsilyl)-1, 2-diphenylethane, 1, n-bis(trimethylsilyl)benzenes and triphenyl(trimethylsilyl)methane, competing 1, n-silyl shifts occurred. Attack of the organolithium intermediates on solvent and silicon—lithium exchange were significant side reactions in some instances. 1-Trimethylgermyl-1, 1, 2-triphenylgermane underwent no discernible rearrangement but rather gave the product expected from germanium—lithium exchange. By conducting time and competition studies, it was shown that lithiation is the product-determining step in these rearrangements and that dual pathways, namely 1, 3-versus consecutive 1, 2- 1, 4-pathways, are operative in certain rearrangements.     

Polyarylates. III. Kinetic studies of interfacial polycondensation

The kinetics of interfacial polycondensation of bisphenol A with isophthaloyl chloride and terephthaloyl chloride in dichloromethane with triethylbenzylammonium chloride (TEBAC) as the catalyst was investigated via measurements of bisphenolate concentration by UV. The reaction was found to be second order with respect to bisphenolate. The dependence of the rate constant on stirring speed, amount of TEBAC, and reaction temperature was studied. The rate constant was increased with an increase of stirring speed, quantity of TEBAC added, as well as the reaction temperature. The activation energy was found to be 7.7 kcal/mol at a stirring speed of 700 rpm in the presence of 0.160 of TEBAC. The role of TEBAC was found to be interesting. It did not alter the equilibrium (the partition coefficient remained the same in the presence of TEBAC), but it did enhance the transfer rate of bisphenolate.     

The roles of the rel+ gene and of 4-thiouridine in killing and photoprotection of Escherichia coli by near-ultraviolet radiation

Abstract— Photoprotection is a reduction in response to far-UV (190–300. nm) radiation in cells that have been previously exposed to longer wavelengths. It has been proposed that photoprotection operates by means of a growth delay that permits more time for dark repair. Growth delay in Escherichia coli utilizes 4-thiouridine (⁴Srd) in transfer RNA as a chromophore and it requires the rel⁺ gene, which exerts a stringent control upon RNA synthesis. Mutants that were either rel or ⁴Srd^? were isolated from E. coli B, utilizing a near-UV-induced growth-delay selection technique. The rel mutants, which undergo little growth delay after near-UV irradiation, show only 50% as much photoprotection as wild types, while ⁴Srd^? mutants show no photoprotection at all. Thus, photoprotection appears to utilize ⁴Srd as its sole chromophore in E. coli B and B/r, and no more than 50% of photoprotection in these strains can be a result of near-UV-induced growth delay.     

The Stabilities and Thermodynamic Properties of Manganese(II) and Nickel(II) Chelates of Trans-1,2-Diaminocyclohexane-N,N, N', N'-Tetraacetic Acid

The interaction between trans-1,2-diaminocyclohexane-N, N, N', N'-tetraacetic acid (H₁DCTA or H₄Z) and Mn(II) and Ni(II) ions has been investigated. The formation constants of the hydrogen chelates (MHZ^?), and of the normal chelates (MZ^2?), have been measured at 20, 30 and 40°C, and an ionic strength of 0.10 (KNO₃). The former was done by a titration technique and the latter by a mercury indicator electrode method. Enthalpy and entropy changes characterizing the formation of the normal chelates have been calculated at 25°C.     

High-performance liquid chromatographic determination of 18 alpha-glycyrrhetinic acid and 18 beta-glycyrrhetinic acid in rat plasma: application to pharmacokinetic study.

A high-performance liquid chromatographic method for the separation and determination of 18 alpha-glycyrrhetinic acid and 18 beta-glycyrrhetinic acid has been developed. Indomethacin was used as an internal standard. The drugs were separated on a reversed-phase column and detected by UV detection at a wavelength of 254 nm. Methanol-water-perchloric acid-ammonia (80:20:0.4:0.4, v/v) was used as the mobile phase at pH of 7.0-7.5. The detection limit of both compounds was 0.1 microgram/ml in rat plasma. The method was applied to pharmacokinetic studies of glycyrrhetinic acids in rats. The results suggest that the pharmacokinetics appeared to be non-linear in nature.     

Characterization of glucoamylase immobilized on celite

Immobilization of glucoamylase (EC 3.2.1.3) on Celite R649 bio-catalyst carrier for hydrolysis of maltose and maltodextrin has been investigated in both packed bed and recirculated batch reactors. The kinetics parameters on the hydrolysis of maltose were estimated from the packed bed reactor. It is found that this immobilized enzyme is as efficient as the soluble enzyme in catalyzing hydrolysis of maltose. However, it is less efficient than the soluble enzyme in hydrolyzing 30% (w/v) maltodextrin, giving a maximum dextrose equivalent (DE) value of 96.0% instead of 98.2%.     

Efficient total synthesis of pulchellalactam,a CD45 protein tyrosine phosphatase inhibitor

A new approach to a CD45 protein tyrosine phosphatase inhibitor, pulchellalactam, is described. The key step of the sequence involves addition and elimination of an enolic lactam in a single step and 70% yield, employing an organocuprate reagent. The resulting alpha,beta-unsaturated lactam could be condensed with isobutyraldehyde to produce Z-pulchellalactam or converted into siloxypyrrole, which was subjected to the BF(3) x Et(2)O-promoted coupling reaction with isobutyraldehyde to afford E-pulchellalactam after E1-cB elimination and TFA deprotection. This first total synthesis afforded Z-pulchellalactam in six steps and 32% overall yield from Boc-glycine. The same sequence of reactions could also be applied to the liquid- or solid-phase synthesis of trifunctionalized pulchellalactam derivatives.     

Vertically well aligned P-doped ZnO nanowires synthesized on ZnO-Ga/glass templates

Vertically well aligned P-doped ZnO nanowires were prepared on ZnO-Ga/glass templates at 550 degrees C by reactive evaporation without metal catalysts and the nanowires were found to be single crystalline with the würtzite structure, oriented in the c-axis direction; the P-doping shortened the physical lengths of the ZnO nanowires without changing their diameter, and furthermore, the introduction of P atoms resulted in a much weaker and broader ZnO band edge emission.     

Effects of gamma irradiation on the yields of volatile extracts of Angelica gigas Nakai

The study was carried out to determine the effects of gamma irradiation on the volatile flavor components including essential oils, of Angelica gigas Nakai. The volatile organic compounds from non- and irradiated A. gigas Nakai at doses of 1, 3, 5, 10 and 20 kGy were extracted by a simultaneous steam distillation and extraction (SDE) method and identified by GC/MS analysis. A total of 116 compounds were identified and quantified from non- and irradiated A. gigas Nakai. The major volatile compounds were identified 2,4,6-trimethyl heptane, α-pinene, camphene, α-limonene, β-eudesmol, α-murrolene and sphatulenol. Among these compounds, the amount of essential oils in non-irradiated sample were 77.13%, and the irradiated samples at doses of 1, 3, 5, 10 and 20 kGy were 84.98%, 83.70%, 83.94%, 82.84% and 82.58%, respectively. Oxygenated terpenes such as β-eudesmol, α-eudesmol, and verbenone were increased after irradiation but did not correlate with the irradiation dose. The yields of active substances such as essential oil were increased after irradiation; however, the yields of essential oils and the irradiation dose were not correlated. Thus, the profile of composition volatiles of A. gigas Nakai did not change with irradiation.     

Cooled internal reflection element for infrared chemical sensing of volatile to semi-volatile organic compounds in the headspace of aqueous solutions

In this study, the cooling effect was applied to an evanescent wave type infrared (IR) chemical sensing method to effectively trap volatile organic compounds (VOCs), which have been absorbed in the hydrophobic film coated around the internal reflection element (IRE). The detection of VOCs in aqueous solutions was taken in the headspace of the aqueous solution. This method eliminates the long-term instability of hydrophobic film soaked in an aqueous solution and the potential spectral interference caused by the matrix of the aqueous solution. Thermal energy has been applied to the aqueous solution to assist in the evaporation of VOCs out of the aqueous matrix. By applying a cooling system to the IRE, the excess thermal energy can be removed leading to more stable IR signals. After examination of organic compounds with vapour pressure (P_v) ranging from 0.017 to 150 Torr, significant differences were found between IR signals from cooled and un-cooled systems. Because the thermal conductivity of the IRE used in IR detection is typically low; the efficiency in removing the thermal energy is limited. By heating the aqueous solutions to different temperatures, the IR signals showed that the sample temperature was limited to around 80 °C. The IR signal determination results for five different volatility organic compounds indicated that the optimal heating temperature was not necessary to match with the volatilities of organic compounds in cooling system. The linear regression coefficient (R²) of the standard curve for sample concentrations in the range 5-200 μg ml⁻¹ was generally higher than 0.991 and the detection limit was around a few hundred ng ml⁻¹, which was two to three times lower than that of un-cooled system.