Environmental aspects of tributyltin

The tributyltin species, the active ingredient in some antifouling paint formulations, is perhaps the most acutely toxic chemical to aquatic organisms ever deliberately introduced to water. It has been demonstrated to have an adverse effect on shellfish in France and England, and as a consequence the use of tributyltin-containing antifouling paints has been restricted in these countries. Other countries have banned the use of tributyltin-containing antifouling paints or are contemplating restrictions. This article reviews such environmental aspects of tributyltin as methods of analysis, toxicity, environmental occurrence, persistence and fate. Tributyltin concentrations in many locations may be high enough to cause chronic toxicity or harmful effects in some aquatic organisms, and in some locations the tributyltin concentrations may be high enough to be acutely toxic to some organisms. Biological degradation of tributyltin in water and sediment appears to be the most important factor limiting the persistence of tributyltin in aquatic environments. To some degree, then, the persistence of tributyltin in aquatic environments depends upon the nature of the ecosystem. Tributyltin exhibits low-to-medium persistence in water and moderate persistence in sediment. A summary is given of the regulatory status of tributyltin in some countries, and recommendations are made for further research.     

Imino-C-nucleoside synthesis: heteroaryl lithium carbanion additions to a carbohydrate cyclic imine and nitrone

Promotion by Lewis acid of the addition of some aryllithiums to a carbohydrate-based imine, which has allowed a more facile synthesis of some imino-C-nucleoside analogues, is described. Use of the corresponding nitrone does not assist in some cases, but lithiated acetonitrile adds to it efficiently to give a product from which further C-nucleoside analogues can be derived.     

Prediction and correlations of some delayed neutron precursor yields for certain actinide nuclides

In this paper some predictions about some delayed neutron precursor yields are presented. The predictions are applied for certain actinides with some special interest in the nuclear energy field. The predictions are based on correlations which might be related to the cluster structure of the nucleus.     

Determination of Gold Content in Geological Samples by Atomic Absorption Spectrometry Method Applied after Separation of Gold by Tellurium or MIBK

Research has been carried out for the application of AAS method to determine gold content in geological samples. These samples usually contain mainly metal sulfides and quartz. Gold usually occurs in the samples as native gold in free state or in joints of some other minerals. The gold grain size is usually below 0.01 mm to over 1 mm and the gold content varies from some ppb to some tens of g/t.     

四氢萘热解中间产物及其反应机理的进一步研究

在四氢萘热解实验中,我们曾注意到,某些热解产物如甲基茚(?)和正丁基苯有进一步的反应.对这些中间产物做热解实验,无疑将为更全面了解四氢萘热解反应机理提供新的信息.对四氢萘热解反应,我们曾提出了自由基反应机理,在四氢萘中加入一些自由基引发剂,将会为自由基反应机理的假设提供一些实验上的旁证.     

微量元素与老年性痴呆

阐明了几种微量元素在人体内某些部位的含量变化及其对神经系统产生的影响 ,以及与阿尔茨海默病 (老年性痴呆病 ,AD)临床症状的关系。研究表明 ,一些AD发病机制诸如突触及神经元的丢失、细胞内神经原的缠结和细胞外的老年斑等 ,与病人体内某些微量元素含量的异常密切相关 ,而且影响机制复杂 ,途径多样。探明微量元素的作用机制 ,对AD病的防治和诊断意义重大     

Improved addition of organolithium reagents to hindered and/or enolisable ketones

A study of the addition of some aryl- and alkyllithium derivatives to some hindered and/or enolisable ketones in different solvents (polar and apolar) and, in some cases, at different temperatures and reaction times, will be presented here. The reversibility of the addition of aryllithium to these specific ketones will be observed and discussed. This approach is then used to prepare new steroids as precursor for potentially interesting substituted testosterones.     

Tribo-electricity

Tribo-electrification is a process in which two bodies are contacted and separated with the result that each body becomes electrically charged. The connection between chemistry and charging is illustrated by describing, in some detail, contacting experiments between mercury and insulating organic materials after various chemical treatments of the organic surface. Introductions to selected topics are presented; principles for methods of measurment, some experimental results, an electroni model involving surface states for charging between a metal and an insulator, some factors limiting chargin, and some qualitative correltaions with the macroscopic compositions of the materials.     

Theoretical aspects of systems with competing interactions

This contribution from a non-theorist aims to give some introduction to the following theoretical papers as well as some of the points brought out in the oral discussion.     

Electrochemistry of porphyrins and related macrocycles

The electrochemistry of metallomacrocycles is known to depend on a variety of factors, some of which are related to the nature of the macrocycle, some to the central metal ion and some to the solution conditions. This present paper presents a brief overview of metalloporphyrin and metallocorrole redox reactivity while outlining the most important structural factors which influence the reversible half-wave potentials for oxidation or reduction of these complexes in non-aqueous media. Electronic Publication     

Riboflavin Interactions with Oxygen—A Survey from the Photochemical Perspective

In this short review we provide some insights to the main processes that riboflavin is involved in upon absorption of a photon. We describe riboflavin properties in its interactions with oxygen, comparing them to the properties of some other singlet oxygen sensitizers. Data are provided on riboflavin photosensitizing properties in vivo and in vitro, and its properties as an endogenous singlet oxygen sensitizer are discussed. We additionally report flavin catalytic role in organic synthesis and photochemical reactivity in solutions of riboflavin and some of its derivatives.     

Highly diastereoselective 1,4-addition of an organocuprate to methyl alpha-D-gluco-, alpha-D-manno-, or alpha-D-galactopyranosides tethering an alpha,beta-unsaturated ester. Novel asymmetric access to beta-C-substituted butanoic acids

The 1,4-addition of magnesium divinylcuprate prepared from vinylmagnesium bromide and cuprous bromide to some 4-O-crotonyl derivatives of methyl alpha-D-glucopyranoside proceeds with a high level of diastereochemical induction, providing the adduct in good-to-excellent yields. Other organocuprates also serve as effective carbon nucleophiles for the 1,4-addition. Removal of the carbohydrate moiety from each adduct afforded a variety of beta-C-substituted butanoic esters in remarkable enantiomeric excess. The 1,4-addition of the same cuprate to some methyl alpha-D-manno- or alpha-D-galactopyranosidic substrates in which a crotonyl group was incorporated, each at 3-OH, was also investigated. The reverse pi-facial attack of the cuprate was observed when some D-manno-type substrates were subjected to 1,4-addition conditions similar to those used for the D-gluco-type substrates. Furthermore, some D-galacto-type substrates provided 1,4-adducts with higher diastereoselectivities.     

苯并-15-冠-5取代的有机硅化合物的合成及其性能

我们提出了一条合成含有苯并-15-冠-5取代基的某些有机硅冠醚化合物的简易路线。通过Wittig反应合成的4'-乙烯基苯并-15-冠-5,经过双键上的硅氢加成反应,得到几种新型含有冠醚基团的有机硅烷或氯硅烷。后者可以进一步烷氧基化或者水解成冠醚取代的聚有机硅氧烷。此外,还测定了它们对碱金属离子的络合容量和作为相转移催化剂的能力。     

On the Compensation Effect at the Form of the Differential Conversion Function

From the general form of the rate equation under non-isothermal conditions, some relationships showing the existence of a compensation effect due to the change of the analytical form of the differential conversion function were derived. These relationships were checked for some simulated TG curves, as well as thermogravimetric data corresponding to the degradation of some polymers and to the decomposition of calcium carbonate. This revised version was published online in July 2006 with corrections to the Cover Date.     

Symmetries of deoxyribonucleic acid (DNA) and related molecules

The basic groups and some atomic groups in polynucleotide long-chains of deoxyribonucleic acid (DNA) and ribonucleic acid (RNA) have been used as the basic structural unit to analyze their molecular symmetry. The basic groups have been treated as the same structural unit in spite of the fact that they have very different intrinsic characteristics. In this paper, we developed bi-double-valued H- and P-representations to distinguish between the various structural units in DNA and RNA. We simulated their molecular symmetries based on our earlier work on the symmetry analysis of cylinder and torus carbon nanotubes. The symmetric and antisymmetric components of some gene segments with some transformations have been calculated in the bi-double-valued HP-representation space. By analyzing the genetic code table, we investigated the distributive features of codons in corresponding H- and P-representations. The results indicate that some characteristics of H- and P-representation carry messages of the corresponding genetic processes in DNA. In addition, we analyzed some topologic features and Möbius twists of torus groups for circular DNA.     

Detection of irradiation treatment of foods using DNA ‘comet assay’

Microgel electrophoresis of single cells (DNA comet assay) has been investigated to detect irradiation treatment of some food samples. These samples of fresh and frozen rainbow trout, red lentil, gram and sliced almonds were irradiated to 1 or 2 kGy using 10 MeV electron beam from a linear accelerator. Rainbow trout samples yielded good results with samples irradiated to 1 or 2 kGy showing fragmentation of DNA and, therefore, longer comets with no intact cells. Unirradiated samples showed shorter comets with a significant number of intact cells. For rainbow trout stored in a freezer for 11 days the irradiated samples can still be discerned by electrophoresis from unirradiated samples, however, the unirradiated trouts also showed some longer comets besides some intact cells. Radiation treatment of red lentils can also be detected by this method, i.e. no intact cells in 1 or 2 kGy irradiated samples and shorter comets and some intact cells in unirradiated samples. However, the results for gram and sliced almond samples were not satisfactory since some intact DNA cells were observed in irradiated samples as well. Probably, incomplete lysis has led to these deviating results.     

Recent Advances in Organic Reactions Catalyzed by Lanthanide(III) Complexes

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High-order averaging schemes with error bounds for thermodynamical properties calculations by molecular dynamics simulations

We introduce high-order formulas for the computation of statistical averages based on the long-time simulation of molecular dynamics trajectories. In some cases, this allows us to significantly improve the convergence rate of time averages toward ensemble averages. We provide some numerical examples that show the efficiency of our scheme. When trajectories are approximated using symplectic integration schemes (such as velocity Verlet), we give some error bounds that allow one to fix the parameters of the computation in order to reach a given desired accuracy in the most efficient manner.     

Synthesis and biological evaluation of structural variants of carbazoquinocin C

Some new structural variants of the alkaloid carbazoquinocin C were synthesized in a few steps with good to excellent yields. The key step comprises a cyclisation reaction of appropriate 2‐vinylindoles with oxalyl chloride. The carbazole‐3,4‐quinones are able to trap oxygen‐centred radicals. In some biological/biochemical assays some of these compounds exhibit extraordinary results including inhibition of cyclooxygenase‐1 and 5‐lipoxygenase in the μM‐range. Moreover some of the carbazoquinocin C‐variants inhibit significant oxidative damage of cellular DNA in nM‐range.