I. Configurational stability and redistribution equilibria in organomagnesium compounds. II. Redistribution equilibria in organocadmium compounds

I. CONFIGURATIONAL STABILITY AND REDISTRIBUTION EQUILIBRIA IN ORGANOMAGNESIUM COMPOUNDS

The dependence of the rate of inversion of a dialkylmagnesium compound on the solvent has been studied.

Examination of the temperature dependence of the nuclear magnetic resonance spectrum of 1-phenyl-2-propylmagnesium bromide in diethyl ether solution indicates that inversion of configuration at the methylene group of this Grignard reagent occurs with an approximate rate of 2 sec^-1 at room temperature. This is the first example of a rapid inversion rate in a secondary Grignard reagent.

The rates of exchange of alkyl groups between dineopentylmagnesium and di-s-butylmagnesium, bis-(2-methylbutyl)-magnesium and bis-(4, 4-dimethyl-2-pentyl)-magnesium respectively in diethyl ether solution were found to be fast on the nmr time scale. However, the alkyl group exchange rate was found to be slow in a diethyl ether solution of dineopentylmagnesium and bis-(2-methylbutyl)-magnesium containing N, N, N', N'-tetramethylethylenediamine. The unsymmetrical species neopentyl-2-methylbutyl-magnesium was observed at room temperature in the nmr spectrum of the solution containing the diamine.

II. REDISTRIBUTION EQUILIBRIA IN ORGANOCADMIUM COMPOUNDS

The exchange of methyl groups in dimethylcadmium has been studied by nuclear magnetic resonance spectroscopy. Activation parameters for the methyl group exchange have been measured for a neat sample and for a solution in tetrahydrofuran. The exchange is faster in the basic solvent tetrahydrofuran relative to the neat sample and in tetrahydrofuran solution is retarded by the solvating agent N, N, N’, N’-tetramethylethylenediamine and greatly increased by cadmium bromide. The addition of methanol to a solution of dimethylcadmium in tetrahydrofuran appears to have very little effect on the rate of exchange. The exchange was found to proceed with retention of configuration. The rate-limiting step for the exchange of methyl groups in a basic solvent appears to be the dissociation of coordinating solvent from dimethylcadmium.

The equilibrium between methylcadmium bromide, dimethylcadmium and cadmium bromide in tetrahydrofuran solution has also been studied. At room temperature the interconversion of the species is very fast on the nmr time scale but at -100° distinct absorptions for methylcadmium bromide and imethylcadmium are observed.

The species ethylmethylcadmium has been observed in the nmr spectrum.

The rate of exchange of vinyl groups in a solution of divinylcadmium in tetrahydrofuran has been found to be fast on the nmr time scale.

Toxicity of phenyl-mercuric lactate for fish

Phenyl-mercuric lactate is included in the pulp processing reagents by some paper mills to eliminate slime formation in the pulp. Small quantities of this chemical are added to the wet pulp in the beaters, particularly for the bactericidal action against Aerobacter aerogenes. Subsequently the mecurial is carried away in the wash waters. However, as the highly poisonous nature of many compounds of mercury is well known, questions have been raised concerning the pollution hazards created by phenyl-mercuric lactate in streams receiving effluents from mills using this substance.

Ferroelectric liquid crystal mixtures containing chiral ether and ester compounds with the 2-arylidene-p-menthan-3-one skeleton

Some 1R,4R-2-(4-phenylbenzylidene)-p-menthane-3-one derivatives containing the ether or ester linking group between benzene rings of the arylidene fragment have been studied as chiral dopants in ferroelectric liquid crystal systems based on the eutectic mixture (1:1) of two phenylbenzoate derivatives CmH2m+1OC6H4COOC6 H4OCnH2n+1 (n = 6; m = 8, 10). The ferroelectric properties of these compositions (spontaneous polarization, rotation viscosity, smectic tilt angle as well as quantitative characteristics of their concentration dependences) were compared with those for systems including chiral dopants containing no linking group. Ferroelectric parameters of the induced ferroelectric compositions studied have been shown to depend essentially on the presence of the linking group between benzene rings and its nature as well as on the number of the benzene rings in the rigid molecular core of the chiral dopants used. For all ferroelectric liquid crystal systems studied, the influence of the chiral dopants on the thermal stability of N*, SmA and SmC* mesophases has been quantified. The influence of the linking group nature in the dopant molecules on the characteristics of the systems studied is discussed taking into account results of the conformational analysis carried out by the semi-empirical AM1 and PM3 methods.

New chiral ether derivatives of 2-arylidene-p-menthane-3-ones as components of induced ferroelectric systems

New 2-arylidene-p-menthane-3-ones containing the ether bridging group in the arylidene fragment have been synthesized and studied as chiral dopants in ferroelectric liquid crystal mixtures. The ferroelectric properties of these compositions were compared with those for compositions including chiral dopants that do not contain any bridging group. The influence of bridging group and terminal alkyl substituent length in the dopant molecule on the ferroelectric parameters of systems studied is discussed. © 2001 OPA (Overseas Publishers Association) N.V. Published by license under the Gordon and Breach Science Publishers imprint, a member of the Taylor & Francis Group,.

Efficient synthesis and utilization of phenyl-substituted heteroaromatic carboxylic acids as aryl diketo acid isosteres in the design of novel HIV-1 integrase inhibitors

Three new types of aryl diketo acid (ADK) isosteres were designed by conversion of the biologically labile 1,3-diketo unit into heteroaromatic motif such as isoxazole, isothiazole, or 1H-pyrazole to improve the physicochemical property of ADK-based HIV-1

Roadmapping an emerging energy technology: An ex-ante examination of dimethyl ether development in China

Technology roadmapping has been used to strategise the development of energy technologies. However, there have been limited roadmapping applications that analyse the emergence of a new energy technology that then forms a new industry and propels broad-based low-carbon economic growth. This paper, therefore, attempts to develop a roadmapping framework by integrating the lifecycle analysis tool, in order to strategise the emergence of dimethyl ether, an alternative energy based on advanced engineering technologies such as carbon capture and storage. This paper compares two scenarios of dimethyl ether vs. diesel and finds that the superiority of dimethyl ether will not arise until 2030, when the complementary engineering technologies become available. This proposed framework can also be generalised to other clean energy industries, and we anticipate our paper will spark inspiration for roadmapping and strategising the 'right' technologies for the growth of Chinese energy industries. Copyright © 2012 Inderscience Enterprises Ltd.

Effects of tetrabrominated diphenyl ether and hexabromocyclododecanes in single and complex exposure to hepatoma HepG2 cells

This study was designed to determine cytotoxic effects of PBDE-47 and HBCDs individually or with a mixture of both compounds exposure to Hep G2 cells. The results showed PBDE-47 and HBCDs induced increase of nitric oxide synthase (NOS) activity, release of NO. dissipation of mitochondria membrane potential and cell apoptosis. Exposure to HBCDs induced ROS formation. Moreover, preincubation with PTIO (NO scavanger) and N-acetylcysteine (ROS scavanger) partially reversed cytotoxic effects of these compounds. The possible mechanism is that PBDE-47 and HBCDs could boost generation of NO and/or ROS, impact mitochondria, and result in start-ups of apoptosis program. Cells exposed to mixture of both compounds and each of them showed non-apoptotic rate significant difference, but the combination of them caused more adverse effects on cells. These results Suggest that PBDE-47 and HBCDs in single and complex exposure have the cytotoxic activity of anti-proliferation and induction of apoptosis in tumor cells in vitro. (C) 2008 Elsevier B.V. All rights reserved.

Allelopathic interactions between Potamogelon maackianus and Microcystis aeruginosa

The allelopathic interactions between Potamogeton maackianus and toxic cyanobacteria (Microcystis aeruginosa) were studied. P maackianus inhibited the growth of M. aeruginosa, both in a coexistence culture system and in exudates experimental culture system. M. aeruginosa also showed effects on the secondary metabolic biosynthesis and secreting behavior of P maackianus. The main lipophilic components of the hexane extracts and the exudates from the macrophyte were analyzed through GC-MS determination. The lipophilic components of the hexane extracts and the exudates from P. maackianus were influenced by M. aeruginosa or their released chemicals. Comparing the lipophilic constituents of the hexane extracts with those in the exudates, the results showed that weak polar compounds contained in the macrophytes can be secreted into the surrounding water. Many compounds, such as N-phenyl-2-naphthalenamine and isopropyl myristate, were detected both in the hexane extracts and the exudates. The changes of lipophilic components in the hexane extracts would be a response to the stress of toxic cyanobacteria or their released toxins. Those changes of exudates, especially the increased content of N-phenyl-2-naphthalenamine, might also be an induced defensive behavior mediated by the released toxins from M aeruginosa. The study results about reciprocal allelopathic responses between macrophytes and cyanobacteria can help in the management of eutrophic waters, and is also important information concerning strategies for recovering eutrophic waters.

Apoptosis induction on human hepatoma cells Hep G2 of decabrominated diphenyl ether (PBDE-209)

Polybrominated diphenyl ethers (PBDEs) are an important class of halogenated organic brominated flame retardants. Because of their presence in abiotic and biotic environments widely and their structural similarity to polychlorinated biphenyls (PCBs), concern has been raised on their possible adverse health effects to humans. This study was designed to determine the anti-proliferative, apoptotic properties of decabrominated diphenyl ether (PBDE-209), using a human hepatoma Hep G2 line as a model system. Hep G2 cells were cultured in the presence of PBDE-209 at various concentrations (1.0-100.0 mu mol/L) for 72 h and the percentage of cell viability was evaluated by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT) assay. The results showed that PBDE-209 inhibited the cells viability in time and concentration-dependent characteristics at concentrations (10.0-100.0 mu mol/L). We found that anti-proliferative effect of PBDE-209 was associated with apoptosis on Hep G2 cells by determinations of morphological changes, cell cycle and apoptosis. Mechanism study showed that PBDE-209 could increase the generation of intracellular reactive oxygen species (ROS) concentration-dependently. Antioxidant N-acetylcyteine partially inhibited the increase of ROS. The mechanism for its hepatoma-inhibitory effects was the induction of cellular apoptosis through ROS generation. In addition, activity of lactate dehydrogenase (LDH) release increased when the cells incubated with PBDE-209 at various concentrations and times. These results suggested that PBDE-209 had the toxicity activity of anti-proliferation and induction of apoptosis in tumor cells in vitro. (c) 2007 Elsevier Ireland Ltd. All rights reserved.

Analysis of estrogens in environmental waters using polymer monolith in-polyether ether ketone tube solid-phase microextraction combined with high-performance liquid chromatography

A simple, rapid and sensitive on-line method for simultaneous determination of four endocrine disruptors (17 beta-estradiol, estriol, bisphenol A and 17 alpha-ethinylestradiol) in environmental waters was developed by coupling in-tube solid-phase microextraction (SPME) to high-performance liquid chromatography (HPLC) with fluorescence detection (FLD). A poly(acrylamide-vinylpyridine-NAP-methylene bisacrylamide) monolith, synthesized inside a polyether ether ketone (PEEK) tube, was selected as the extraction medium. To achieve optimum extraction performance, several parameters were investigated, including extraction flow-rate, extraction time, and pH value, inorganic salt and organic solvent content of the sample matrix. By simply filtered with nylon membrane filter and adjusting the pH of samples to 6.0 with phosphoric acid, the sample solution then could be directly injected into the device for extraction. Low detection limits (S/N = 3) and quantification limits (S/N = 10) of the proposed method were achieved in the range of 0.006-0.10 ng/mL and 0.02-0.35 ng/mL from spiked lake waters, respectively. The calibration curves of four endocrine disruptors showed good linearity ranging from quantification limits to 50 ng/mL with a linear coefficient R-2 value above 0.9913. Good method reproducibility was also found by intra- and inter-day precisions, yielding the RSDs less than 12 and 9.8%, respectively. Finally, the proposed method was successfully applied to the determination of these compounds in several environmental waters. (c) 2006 Elsevier B.V. All rights reserved.