Direct Electrochemistry with Nitrate Reductase in Chitosan Films

Stable films made from chitosan (CS) on pyrolytic graphite electrode (PGE) gave direct electrochemistry for incorporated enzyme nitrate reductase (NR).Cyclic voltammetry of CS/NR films showed a pair of well-defined and nearly reversible redox peaks at about-0.430 V vs.SCE at pH 7.0 phosphate buffers.     

Products in the Reactions of Trialkyl Phosphites with α-Halogeno-acetophenones in Alcoholic Media

Abstract

α-Hydroxyphosphonates are formed, in addition to vinyl phosphates and dehalogenated ketones, in the reactions of trimethyl phosphite (in methanol) or triethyl phosphite (in ethanol) with variously substituted α-chloro, α-bromo, and α,α,-dichloro-acetophenones. Tri-isopropyl phosphite in propan-2-ol gives only the vinyl phosphate. Ketophosphonates are not detectable amongst the reaction products under the conditions used. Trends in product composition can be correlated with the leaving ability of halogen, substituent effects, structure of the phosphite, and reaction temperature. Reactant ratios may also influence the product composition. The reactions of trimethyl phosphite in methanol with 4-nitro-α-chloroacetophenone, or α,α-dichloroacetophenones yield the dehalogenated α-hydrogxyphosphonates in addition. In the case of the 4-nitro derivative, this product cannot be accounted for by reaction of the phosphite with dehalogenated ketone (4-nitroacetophenone). Dehalogenation of the first-formed α-hydroxyphosphonate was, however, shown to occur under reaction conditions and appears to require the removal of positive chlorine, followed by protonation. Reactions of the α,α-dichloroacetophenones were similar to those of the α-chloroacetophenones, giving the corresponding chlorovinyl phosphate, α,α-dichloro-α-hydroxyphosphonate, and monodehalogenated ketone(i.e. α-chloroacetophenone); the latter was not however detected as it reacted further with excess phosphite to give the expected products as described above. Possible mechanisms for the various reactions are discussed. The ¹H and ¹³C nmr spectra of the α-hydroxy-phosphonates show magnetic non-equivalence of the two alkoxy groups, attributed to restricted rotation about the P-C bond as a result of intramolecular hydrogen-bonding.     

Interaction Study of Guest with Host in Clathrate Hydrate

Lattice dynamical simulations of noble gas hydrate structuresⅠandⅡhave been performed. Potential energies were investigated to study the influence of guest species on the stability of the hydrate structure.Results show that when the diameter of inclusion molecules is between 3(?)and 4.2(?),such as Ar and Kr,the critical role of the 5~(12)cage in the stabilization of hydrates becomes effective.For Xe hydrates SⅠand SⅡ,with the help of lattice dynamical calcnlations,the modes attributions are identified directly.We proposed the resonant effect of the fingerprint frequency at about 7 meV and 10 meV which arise from the coupling of Xe molecules in the 5~(12)cage with the host lattice.     

Stable σH-adducts in reactions of ferrocenyllithium with azines

Stable σ^H-adducts as intermediates of the nucleophilic substitution of hydrogen in 3-(2-pyridyl)-1,2,4-triazines were obtained for the first time using ferrocenyllithium as a nucleophilic reagent. The three-dimensional structures of the reaction products were established based on the X-ray diffraction study of 1-[4-ethyl-6-phenyl-3-(2-pyridyl)-5(H)-1,2,4-triazin-5-yl]ferrocene.     

Interaction of Polyelectrolyte with Fluorocarbon Surfactant in Aqueous Solution

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Electrochemical CO2 reduction with power generation in SOFCs with Cu-added LSCF–GDC cathode

Solid oxide fuel cell (SOFC) unit was constructed with Ni–GDC (gadolinia-doped ceria) as the anode, YSZ as the electrolyte, and Cu-added La_0.58Sr_0.4Co_0.2Fe_0.8O_3–δ–GDC as the cathode. Electrochemical CO₂ reduction occurs. The CO formation rate, the CO₂ conversion and the generated current density increase with increasing CO₂ concentration and temperature. The CO₂ conversion rate equals exactly the CO formation rate. No carbon deposition occurs. The activation energy is 2.72 kcal mol^?1. The electrochemical CO₂ reduction (dissociation) can have much lower activation barrier than the catalytic one. Simultaneous CO₂ reduction with power generation in SOFCs can be feasible.     

Complexes of β-cyclodextrin with chloronitrobenzenes and with solvents in water + organic solvent mixtures

Inclusion complexes of chloronitrobenzenes with -cyclodextrin in aqueous 0.1 M phosphate buffer solutions containing various concentrations of ethanol, dimethylsulfoxide, dimethylformamide, acetone and acetonitrile have been studied by a polarographic method. The diffusion coefficients and the stability constants of the corresponding complexes have been determined. Using an equation derived by us which takes account of the change in the cyclodextrin concentration due to the simultaneous complexation of the solvent, both stability constants have been calculated. The influence of solvent on the stability constant of chloronitrobenzenes is discussed     

Purification of RhIFN- in Bacteria Bodies with Acetic Acid-Water as Mobile Phase in RPLC

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Small Peptides Catalyzed Direct Aldol Reactions of Aldehydes with Hydroxyacetone with Regiocontrol in Aqueous Media

Very recently, we[1] found that L-proline amides and dipeptides acted as efficient catalysts for the asymmetric direct aldol reaction. We report here that L-proline-based peptides 1～5 can catalyze the aldol reactions of hydroxyacetone with aldehydes 6 in aqueous media, to give 1,4-diols (7), the disfavored products with either aldolase or L-proline. Both peptides 3 and 4 give good results.     

Thermodynamic Complexation of Dopamine with Zinc(II) in Media with Different Dielectric Constants

The complexation of zinc(II) with dopamine has been investigated by spectrophotometric measurements in mixed solvent system at an ionic strength of 0.2 mol•dm－3 sodium chloride, employed at at (15±0.1), (25±0.1), (35±0.1) ℃ at inin a pH range of ca. 6 to ca. 7 with a high ratio of ligand to metal. The effect of solvent systems on protonation and complexation are was was discussed. Linear relationships are werewere observed by plotting lg K versus 1/D, where K and D show stability and dielectric constants, respectively.     

Estimation of the intrinsic stresses in α-alumina in relation with its elaboration mode

The specific signatures of α-Al₂O₃ by Fourier transform infrared (FTIR) spectroscopy were investigated to estimate the intrinsic stress in this compound according to its elaboration mode. Thus, α-alumina was prepared either by calcination of boehmite or gibbsite and also generated by oxidation of a metallic FeCrAl alloy. FTIR results were mainly supported by X-ray diffraction (XRD) patterns that allowed to determine the crystallite size and the strain in the various alpha aluminas. Moreover, the infrared peak at 378.7 cm⁻¹ was used as a reference for stress free α-alumina and the shift of this peak allowed to estimate intrinsic stresses, which were related to the morphology and to the specific surface area of aluminas according to their elaboration mode. These interpretations were confirmed by results obtained by cathodoluminescence experiments.     

Synthesis of New Multibranch Chromophores with Strong Light-emitting in Solution and in PMMA Film

Three new chromophores with triphenylamine as molecular focal point bearing one,two, or three 4-(n-butyloxystyryl) group(s) at the periphery respectively, (named as T1, T2, and T3) have been synthesized and characterized. It is interesting to find that the fluorescence quantum yield increases from T1 (0.489), to T3 (0.535), and to T2 (0.628) in cyclohexane, meanwhile the lifetime for T3 is shorter than T1 and T2, which is an important characteristic for applications in light emitting diode. Also PMMA (polymethyl methacrylate) film doped with T3 gives stronger fluorescence than T1, and T2. Cyclic voltammetry showed that T3 exhibited lowest oxidation potential of-0.52 V vs SCE, suggesting its better hole-transport property.     

Living with multiple standards – QA in a multidisciplinary laboratory

 The paper describes the experiences of a medium-sized analytical laboratory in implementing and developing a quality system compliant with several standards. The effect of the laboratory's changing role and work pattern on the quality system are considered. The laboratory costs are explored. The laboratory's particular experiences are shown to be consistent with recent market research in the United Kingdom. Some of the factors a laboratory needs to consider in formulating a quality strategy are described, including the possibility of joint assessments. Also, possible courses of development of the standards themselves are suggested. These developments could simplify the existing situation where laboratories are forced into a quality approach based on multiple standards and assessment. Received: 1 October 1998 · Accepted: 26 January 1999     

Complexation of β-cyclodextrin with carborane derivatives in aqueous solution

β-Cyclodextrin formed the most robust complexes with o-carboranols 1b and 1c in aqueous solution, and the association constants estimated from NMR titration studies indicated K_a >1 × 10⁶ M⁻¹ and K_a = 6 × 10⁵ M⁻¹, respectively.     

Stability of Mefenamic Acid in the Inclusion Complex with β-Cyclodextrin in the Solid Phase

The inclusion complex of mefenamic acid with -cyclodextrin was obtained by the method of coprecipitation from diethyl ether. The product was identified by the thermogravimetric and X-ray methods. The complex stability constants were determined by the potentiometric method. The effect of -CD on the solubility and stability of mefenamic acid was analysed.     

First electronic transitions in compounds with the perimeter π-system

In the Pariser-Parr-Pople approximation, an analysis has been made of the first -electron transitions in neutral and charged [N]annulenes with a closed shell. The influence of the ratio of numbers of -electrons and atoms in the annulene on the spectrum of the annulene has been examined critically. A similarity of the spectra of [N]annulenes and polymethine dyes has been noted.Deceased.Institute of Organic Chemistry, Academy of Sciences of the Ukrainian SSR, Kiev. Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 27, No. 4, pp. 493–499, July–August, 1991. Original article submitted February 8, 1988.     

The Phenomenon of Mutual Media in Polypyrole with Electroactive Ions

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