Ab initio MO Calculations of benzene + TCNE and naphthalene + TCNE complexes with STO-3G π-split basis set

Ab initio SCF MO calculations have been carried out on benzene + TCNE (tetracyanoethylene) and naphthalene + TCNE complexes with the STO -3G, STO -3G π-split (STO -3G for π orbitals and a split basis for π orbitals), and 4–31G basis sets. The interaction energy, gross charges, dipole moment, and the electron density in the middle plane of the complexes have also been evaluated. The STO -3G π-split basis set is appropriate for the calculation of large π–π stacking complexes from two points of view, production of reliable results and ease of computations. The approximation scheme based on the semiorthogonalized orgitals is revealed to be very efficient to save CPU time and storage in such calculations. The stable conformation and the charge-transfer interaction of the two complexes are discussed on the basis of the calculated quantities.     

A concept for controlling singlet oxygen (1 Delta g) yields using nitroxide radicals: phthalocyaninatosilicon covalently linked to nitroxide radicals

In this study, we have investigated the singlet oxygen ((1)Delta(g)) generation mechanism using phthalocyaninatosilicon (SiPc) covalently linked to nitroxide radicals (NRs), and we succeeded in increasing the singlet oxygen quantum yield (Phi(Delta)) by linking the NRs. This originates from both an increase in the triplet quantum yield and excited-state lifetimes long enough to utilize photochemical reactions. Because the electron exchange interactions with paramagnetic species were known to result only in very fast excited-state relaxation, leading to a decrease in photochemical reaction yields, this increase in Phi(Delta) is an unusual and precious example for increasing photochemical reaction yields by electron exchange interactions with paramagnetic species. In addition, our experiments and theoretical analyses show that the spin-selective energy transfer rate constant is not influenced by linking the NRs and can be evaluated by the product of spin-statistical factors and matrix elements between the initial and final states.     

Modern synthetic methods for fluorine-substituted target molecules

Fluorine has come to be recognized as a key element in materials science: in heat-transfer agents, liquid crystals, dyes, surfactants, plastics, elastomers, membranes, and other materials. Furthermore, many fluorine-containing biologically active agents are finding applications as pharmaceuticals and agrochemicals. Progress in synthetic fluorine chemistry has been critical to the development of these fields and has led to the invention of many novel fluorinated molecules as future drugs and materials. As a result of the electronic effects of fluorine substituents, fluorinated substrates and reagents often exhibit unusual and unique chemical properties, which often make them incompatible with established synthetic methods. Thus, the problem of how to control the unusual properties of compounds with fluorine substituents deserves much attention, so as to promote the design of facile, efficient, and environmentally benign methods for the synthesis of valuable organofluorine targets.     

Simultaneous discrimination of diastereotopic groups and faces: the first example in intramolecular [3+2] and [2+2+1] cycloaddition reactions

To explore a novel concept for controlling diastereoselectivity, systematic studies on the sense and degree of diastereotopic groups and face selections in intramolecular [3 + 2] (nitrile oxide and nitrone) and [2 + 2 + 1] (Pauson-Khand) cycloadditions have been conducted. Optically pure methyl (S)-3,4-O-isopropylidene-3,4-dihydroxybutanoate (5) and methyl (S)-2,3-O-isopropylidene-2,3-dihydroxypropanoate (6) were converted to substrate aldehydes (1-4) that bear geminal allyl groups and four types of controllers with the intention of imparting a stereochemical bias to the allylic groups and their faces. The controllers involve 1,2-bis(tert-butyldimethylsiloxy), 1,3-bis(tert-butyldimethylsiloxy), 1,2-acetonide, and 1,3-acetonide groups, which are referred to as 1,2-(TBDMSO)(2), 1,3-(TBDMSO)(2), 1,3-dioxolane, and 1,3-dioxane, respectively. Twelve runs of cycloaddition reactions as combinations between the three types of reactions and the four types of substrates were performed to provide bicyclo[4.3.0] or -[3.3.0] adducts of synthetic importance in which isoxazolidine, isoxazoline, or cyclopentenone segments were fused. For every case, high levels of diastereoselectivity have been achieved: >99% (in eight cases), 82%, and 76% for the discrimination of diastereotopic groups and 68-->99% for the discrimination of diastereotopic faces. On the basis of the absolute structures of the cycloadducts, plausible stereochemical models are proposed.     

Al2O3-coated 3-N-propylpyridinium chloride silsesquioxane polymer film: preparation and electrochemical property study of adsorbed cobalt tetrasulfophthalocyanine

Porous Al2O3 presenting a specific surface area of SBET = 105 m2 g(-1) was coated with 3-N-propylpyridinium chloride silsesquioxane polymer. The ion exchange capacity of this polymer grafted onto an Al2O3 surface, resulting in a material designated as AlSiPy(+)Cl-, was 1.09 mmol g(-1). Furthermore, a cobalt(II) tetrasulfophthalocyanine anionic complex was immobilized on the chemically modified surface by an ion exchange reaction with a yield of 40 micromol g(-1) (the surface density of the electroactive species is 3.80 x 10(-11) mol cm(-2)). The electrochemical properties of the material obtained, AlSiPy/CoTsPc, were tested for the catalytic oxidation of oxalic acid at 0.77 V vs SCE in 1.0 mol l(-1) KCl solution. Furthermore, a chronoamperometric technique was used with the electrode to test its potential use as a sensor for oxalic acid. The electrode response to oxalic acid concentrations between 1.0 and 3.5 mmol l(-1) was linear with an estimated detection limit of 0.5 mmol l(-1). The charge transfer resistance of the material, measured using the electrochemical impedance spectroscopy technique, was 43 Omega cm2.     

Trifluoromethyl‐Radical‐Mediated Carbonylation of Alkanes Leading to Ethynyl Ketones

The carbonylation of alkanes 1 under radical‐reaction conditions was examined by using ethynyl triflone A as the unimolecular chain‐transfer (UMCT) reagent. Good to moderate yields of ethynyl ketones 2 were prepared by means of this three‐component coupling reaction. Higher CO pressures as well as lower concentrations of triflone A improved the efficiency of the reaction over the direct addition, the latter leading to alkylated ethynes 3 . In contrast to the reaction with A , the reaction of cyclohexane ( 1a ) with allyl triflone B (= ethyl 2‐methylene‐3‐[(trifluoromethyl)sulfonyl]propanoate) in the presence of CO gave a mixture of carbonylation products, including 8a formed from two molecules each of cyclohexane, CO, and allyl triflone B .     

Analytical application and spectrophotometric study of the scandium-indoferron complex

A new spectrophotometric method for microgram amounts of scandium with indoferron is described. The molar absorptivity is 960 l.mole⁻¹.mm⁻¹ at 600 nm. Uranium and the rare earths do not interfere, if present in amounts less than 50 μg. Scandium in silicate rocks can be determined by the procedure after separation of the scandium by a three-stage ion-exchange Chromatographic technique. The acid dissociation constants of indoferron and conditional formation constants of the 1:2 complex have been determined spectrophotometrically.     

A new biomaterial,hen egg shell membrane,to eliminate heavy metal ion from their dilute waste solution

The egg shell membrane (ESM) is an intricate lattice network of stable and water-insoluble fibers with high surface area. ESM accumulates and eliminates various heavy metal ions from dilute aqueous solution with high affinity and in short contact time, depending on pH and characteristics of the individual ion. Under certain conditions, the level of precious ions, Au, Pt, and Pd accumulation approaches 55, 25, and 22% of dry wt of ESM, respectively. Also uranium uptake 30% of that of ESM. Experiments suggested that ESM is promising to use for the purpose of removal/recovery of metals and water pollution control.     

Staggered polarization of vertex models withU_q (\widehat{sl(}n))-Symmetry

In this paper we give an explicit formula for level 1 vertex operators related to as operators on the Fock spaces. We derive also their commutation relations. As an application we calculate with the vector representation of , thereby extending the recent work on the staggered polarization of the XXZ-model.