Thermal analysis graphite intercalation compounds with dichlorides of some d-elements: A.S. Skoropanov,G.S. Petrov,A.A. Vecher,Yu.N. Novikov and M.E. Vol'pin,Thermochim. Acta, 90 (1985) 339-342

Kinetic and thermodynamic aspects of the axial base dissociation of solid Co(salen) (X-py) complexes, X = H (1), 3-Me (2), 4-Me (3), 3,4-Me₂ (4), 3,5-Me₂ (5), 3-NH₂ (6), 3-Cl (7), 3-CN (8), 4-CN (9), have been investigated by means of TG-DSC and isothermal weight-loss measurements. These adducts endothermically dissociate the axial base giving rise to the oxygen-active Co(salen) complex. The axial base dissociation reactions fit the contracting disc equation and the kinetic compensation effect is observed for all the adducts excepting Adducts 4–6. For the remaining adducts the kinetic and thermodynamic stabilities of the Co-(X-py) bond are found to increase linearly with increasing Hammett's substitution constants of X except for Adducts 3 and 9. These results are discussed in terms of the σ and π interactions between cobalt(II) and substituted pyridine. Factors dominating the kinetic bond stability are briefly discussed.     

First example of chiral N-heterocyclic carbenes as catalysts for kinetic resolution

Chiral N-heterocyclic carbenes, which are derived from C2-symmetric 1,3-bis(1-arylethyl)imidazolium salts, catalyze enantioselective acylation of racemic secondary alcohols.     

Absolute stereochemistry of citrinadins a and B from marine-derived fungus

[Structure: see text]. Citrinadin A (2) is a pentacyclic indolinone alkaloid isolated from the cultured broth of a fungus, Penicillium citrinum, which was separated from a marine red alga. The absolute stereochemistry of the pentacyclic core in 2 and its new congener, citrinadin B (1), was elucidated by analysis of the ROESY spectrum for the chlorohydrin derivative (3) of 1 as well as comparison of the electronic circular dichroism (ECD) spectra for 1 and 2 with those of known spirooxiindole alkaloids. On the other hand, the absolute configuration at C-21 bearing an epoxide ring was assigned as S by comparison of the vibrational circular dichroism (VCD) spectra of 1 with those of model compounds 2S- and 2R-2,3-epoxy-3,3-dimethyl-1-phenylpropan-1-one (4a and 4b, respectively).     

Thick Silicate Film by an Interfacial Polymerization

A thick silica gel film, corresponding to the glass film of 10–20 micron in thickness, has been formed at the interface between two immiscible liquids, hexane and water, using E-40, a partially polymerized silicon alkoxide, as the precursor. The film formation was possible using both acid- and base-catalyzed water, but was greatly dependent on the type of catalyst. Only the trace of a film was observed for the system catalyzed with a strong electrolyte such as HCl, HNO₃ or NaOH, while a gel film, corresponding to the glass film of several to 10 micron in thickness was formed with a weak electrolyte such as ammonia, organic acid like acetic acid, citric acid, etc., of similar pH value. The direct introduction of organic base catalyst like triethylamine in hexane was much more effective than the use of ammonia water, suggesting that the polymerization of E-40 to form a gel film takes place in the organic phase, where water molecules, as well as undissociated ammonia or organic acids, can diffuse in.     

A frequency response model in multiquantum well lasers with unequilibrium carrier transport

A carrier transport model to explain the high-frequency response in high-speed MQW lasers is described. The ambipolar approximation, which is unsuitable for dealing with the high-speed carrier dynamics in MQW structures, was not adopted for small-signal analysis. The carrier transport effect can be characterized by four time constants: the electron transport time, _bmn; the hole transport time, _bmp; the electron escape time, _wbn; and the hole escape time, _wbp. The frequency response was interpreted as the sum of the constant response term due to the fast electron current and the roll-off term due to the slow hole transport time. The ratio of the electron contribution to the total response was proportional to the ratio of electron contribution to the total differential gain, , and reciprocally proportional to _n0 = 1 + _bmn/_wbn. The value of was calculated to be about 0.5 for typical MQW lasers. The roll-off frequency is mainly determined by . The ratio _p0 = 1 + _bmp/_wbp affects the resonant frequency and the damping rate in the high-bias condition.     

High output power operation of 1.3-μm strained MQW lasers with low threshold currents at high temperature

We have investigated the temperature dependencies of the slope efficiency and the threshold current for strained multiquantum well (MQW) lasers as a parameter of the well number. Smaller well numbers mean larger temperature dependencies of the slope efficiency and the threshold current, while larger well numbers mean larger internal loss and broadening of the photoluminescence linewidth of the MQW structure. Furthermore, the change in the slope efficiency with temperature change is related to the change in internal loss. In this work, the 1.3-m strained MQW laser with a compressive strain of 1.0% and 7 wells shows the highest output power of 6.8 mW for an injection current of 50 mA and the lowest threshold current of 5.5 mA at 85°C, and the lowest variation in output power of 2.0 dB from 25–85°C at injection current of 50 mA.     

Preparation and electrochemical polymerization of new multifunctional pyrrolethiolate-stabilized gold and palladium nanoparticles

New pyrrolylalkanethiolate-stabilized gold and palladium nanoparticles have been prepared: electrochemical polymerization of their metal nanoparticles and their TEMPO-derivatized metal nanoparticles gave the remarkably stable poly(pyrrole metal nanoparticle) films on metal electrodes.     

Total synthesis of merrilactone A

Merrilactone A (1) has been shown to possess neurotrophic activity and thus is expected to hold therapeutic potential in the treatment of neurodegeneration diseases. In this paper, we report the total synthesis of (+/-)-1, employing, as key steps, a novel desymmetrization protocol of meso-diketone to construct the core cis-bicyclo[3.3.0]octyl system of 1 (3 --> 2) and a radical cyclization to install the highly congested C9-quaternary carbon (16 --> 17).     

Hole Burning and Fluorescence Spectra of Sol-Gel Derived Sm2+-Doped Glasses

Sm2+-doped glasses in the system of Al2O3-SiO2 were prepared by sol-gel processing of metal alkoxides and reacting with H2 gas at 800°C. The hole burning properties of these glasses were investigated. The holes were burned in the 7F0 5D0 line of the Sm2+ ions using a DCM dye laser at 77 K. The hole depth increased with increasing the laser irradiation time, reaching up to 15% of the total intensity within a few hundred seconds. The hole width was 3 cm–1 full width at half maximum. Fluorescence line narrowing spectra of the 5D0 7 F1 transition were analyzed to study the local structure surrounding the Sm2+ ion. It is concluded that the Sm2+ ions are closely coordinated with nine oxygens of the AlO6 group in aluminosilicate glasses and that the addition of Al3+ ions into glass induces an increase in the coordination number of the Sm2+.