若干含多硫基的配合物的合成方法及结构特征

本文综述了近年来我们合成的十二种多硫基的配合物，这些配合物含有Ｓ＾２－２，Ｓ＾２－４，Ｓ＾２－５，Ｓ＾２－６，Ｓ＾２－７等多硫革配体，总结了这些配合物中的金属配位构型，比较了各种多硫基的Ｓ－Ｓ键长及有关键角，归纳了配合物外光谱，并阐述了其中几个配合物与ＮＨ２ＮＨ２的反应性能。     

Liquid crystalline block copolymers by sequential cationic or promoted cationic and free-radical polymerizations

The scope for the study of the synthesis and properties of liquid crystalline (LC) block copolymers is briefly outlined. While there are many approaches to the synthesis of LC block copolymers, the use of azo macroinitiators is very versatile and allows one to produce diverse block copolymer architectures. Azo macroinitiators are prepared by cationic or promoted cationic polymerization of tetrahydrofuran (1) or cyclohexene oxide (2), and are then used to initiate the free-radical polymerization of various methacrylates 3,4 or acrylates 5–9 containing mesogenic azobenzene or biphenyl units thereby yielding block copolymers. The AB or ABA block copolymers are microphase-separated and form smectic and/or nematic mesophases similar to the respective LC homopolymers.     

Synthesis of Defective Phospholipids

Phospholipids have been synthesized that possess a normal 16-carbon chain plus a "defective" chain only 8 or 12 carbons long and terminated with methoxyl, hydroxyl, or carboxyl groups. In addition, dimeric phospholipids have been prepared in which two phospholipid units are joined at position-1 with chains of 22 or 32 carbons while unconnected chains at position-2 are, once again, short and functionalized. These phospholipids are potentially useful for constructing membranes that contain cavities or irregularities and, therefore, are capable of serving as self-assembled host systems in which drugs and other guest molecules are retained and, perhaps, eventually released.     

Solvent-free Knoevenagel condensations and Michael additions in the solid state and in the melt with quantitative yield

Numerous Knoevenagel condensations of solid or liquid aromatic aldehydes are performed with four barbituric acids, Meldrum's acid, dimedone, cyanoacetamide, malodinitrile and methyl cyanoacetate in stoichiometric mixtures of the solids or of stoichiometric melts. The product yields are quantitative in 23 reported cases and the products do not require purifying workup. Therefore, these reactions are truly solvent-free, atom economic and sustainable and no wastes are produced. They are highly superior to less productive so-called ‘solvent-free’ techniques using solid supports and microwave irradiation that require solvents for removal of the support or reagents or side products. Similarly, the solution reactions generally requiring catalysts suffer from low yields and purifying workup. The new techniques provide numerous common electron-poor alkenes very easily. These are valuable building blocks for example in Michael additions. Also the latter can be quantitatively obtained in stoichiometric melts in the absence of any auxiliaries or microwave irradiation and this is demonstrated with stable and rearranging/cyclizing Michael adducts using dimedone. The quantitative yields are most easily obtained if the products are formed in the solid-state or if they crystallize directly from the melt at the reaction temperature.     

Referee analysis of precious metal sweeps and related materials

Sweeps samples are often complex mixtures containing from trace amounts to 20% of one or more precious metals distributed in matrices consisting of widely varying mixtures of base metals or their oxides. Three collection procedures are described that are suitable for the isolation of precious metals from base substances. One is based on direct fusion of the sample (high-grade sweeps) with sodium peroxide, and the others on collection of the precious metals by fire-assay techniques using either nickel sulphide or silver. The precious metals are then determined either gravimetrically or by atomic-absorption or plasma-emission spectrometry.     

Electrogenerated Base-Promoted Synthesis of Dithiocarbamate Acid Esters and 3-(N-Substituted-amino)-2-cyanodithiocrotonates from Primary or Secondary Amines and Carbon Disulfide

Electrogenerated cyanomethyl anion promotes the reaction between primary or secondary amines, carbon disulfide, and alkyl or benzyl halide. Secondary amines are converted to alkyl or benzyl dithiocarbamates, whereas primary amines give N-substituted alkyl or benzyl 3-amino-2-cyanodithiocrotonates. The mechanisms are discussed.     

Structural variations in amphiphiles: Discoidal multivalent cations

Fourteen cationic multipolar amphiphiles have been synthesized with pyridinium or trimethylammonium head groups. The hydrophobic cores are planar ring systems (benzene or triphenylene) to which two, three, four, or six decylene or undecylene alkyl chains are attached by ester linkages. The hydrophilic head groups are bound to the outer ends of the alkyl chains.The aggregation of the molecules in water into micelles and lyotropic liquid crystals has been studied. Hexagonal phases are preferred to lamellar phases by these amphiphiles and in more dilute solutions some of these multipolar amphiphiles form cylindrical micelles.     

Analysis of Organic Acids in Physiological Fluids by High Performance Liquid Chromatography

Abstract

Most organic acids in physiological fluids are carboxylic acids or their glycine or glucuronide conjugates. Also included are hydroxyl compounds, such as phenols or cresols. By definition, compounds with a primary amino group, detectable by conventional amino acid analysers, are excluded. Organic acids are produced continuously in the body as intermediates in the metabolism of amino acids, carbohydrates and fats, and of drugs and food additives. They do not accumulate in the body, since they are rapidly converted to non-acidic end products or excreted as water soluble metabolites i n urine. However, if they are produced in excess, or if their metabolism is prevented by an inherited enzyme defect, concentrations increase in the tissues, blood and urine. Examples of excessive production are during fasting ketosis, in which acetoacetic and 3-hydroxybutyric acids and a range of dicarboxylic acids derived from breakdown of fatty acids accumulate, and lactic acidosis, secondary to hypoxia, when increases in lactic, pyruvic and 2-hydroxybutyric acids are common.     

Nanoclusters of Silicon and Germanium

Synthetic routes for the preparation of Si or Ge nanoclusters as gaseous species, colloids, supported composites, or as unsupported powders are reviewed along with selected characterization data. The optical properties of these and related materials, such as porous Si, are summarized with particular emphasis on photo- or electroluminescence phenomena. Research opportunities related to Si and Ge cluster chemistry are suggested.     

Inorganic functional materials: optimization of properties by structural and compositional control

A review is given of the strategies used to dope inorganic solids and the consequences for properties such as ionic and electronic conductivity. Doping mechanisms involve either substitution of foreign ions onto lattice sites, creation of vacancies on either cation or anion sites, or population of normally empty interstitial sites by either anions or cations. Mechanisms for charge compensation associated with aliovalent doping are reviewed and examples are given in the fields of solid state ionics and high-temperature superconductivity. The strategies used for targeting materials with new properties are reviewed, including a surprising number of cases where startling new properties are encountered in well-known materials. Specific examples discussed include MgB2 superconductor, Na beta-alumina sodium ion conductor, Ca12Al14O33 oxide ion conductor, LiCoMnO4 lithium battery cathode, doped Li4SiO4 tunable lithium ion conductor, and La-doped BaTiO3 ferroelectric, which can be either semiconducting or insulating. Examples are also given of a curious observation that extraordinary properties are often encountered in materials that are on the edge of stability, either structurally or compositionally or at the crossover between different property types.     

Bestimmung des Wirkstoffrückstandes auf Weintrauben,in Traubenmost und in Wein nach Anwendung von SCLEX (ORT 8890 F,Dichlozolin)

The methods are examined and corrected with standard substances. Rubidium is determined with sodium tetraphenyloboron, while the iron, nickel and cobalt contents are titrated cerimetrically or complexometrically or measured photometrically, respectively. Fluorine is separated as fluorosilicic acid and determined with silver oxide. The relative errors are for the photometric cobalt analysis about 5%, or the other methods up to 1%.     

Stable spirocyclic Meisenheimer complexes

Meisenheimer complexes are important intermediates in Nucleophilic Aromatic Substitution Reactions (S(N)Ar). They are formed by the addition of electron rich species to polynitro aromatic compounds or aromatic compounds with strong electron withdrawing groups. It is possible to distinguish two types of Meisenheimer or sigma-complexes, the sigma(H)-complex or sigma(X)-complex (also named ipso), depending on the aromatic ring position attacked by the nucleophile (a non-substituted or substituted one, respectively). Special examples of sigma(X)- or ipso-complexes are formed through intermediate spiro adducts, via intramolecular SNAr. Some of these spirocyclic Meisenheimer complexes, a type of sigma(X)-complex, are exceptionally stable in solution and/or as solids. They can be isolated and characterized using X-ray, and various spectroscopic techniques such as NMR, UV-Vis, IR, and fluorescence. A few of these stable spirocyclic Meisenheimer complexes are zwitterionic and exhibit interesting photophysical and redox properties. We will review recent advances, synthesis and potential applications of these stable spirocyclic Meisenheimer complexes.     

Structures and properties of functional metal selenites and tellurites

Metal selenites and tellurites are a class of very important compounds. In this paper, the structures and properties of metal selenites or tellurites combining with transition-metal (TM) ions with the d (0) electronic configuration or tetrahedral MO 4 building blocks of post-transition main-group elements were reviewed. Most compounds in the alkali or alkaline-earth-d (0) TM-Se (IV) (or Te (IV))-O systems exhibit extended anionic architectures composed of distorted octahedra of (d (0)) TM cations and tellurite or selenite groups. The distortion of the octahedron is always away from the lone-pair cation, and some of them exhibit excellent second-order nonlinear optical properties due to the adductive effects of two types of bond polarizations. Because of the high coordination number of Ln (III) ions, most of compounds in the Ln-d (0) TM-Se (IV) (or Te (IV))-O systems are not second-harmonic-generation active; however, they are able to emit strong luminescence in the visible or near-IR region; also in most cases, the d (0) TM cations are in tetrahedral geometry and are well separated from selenite or tellurite groups. It is also interesting to note that the selenite group is normally "isolated", whereas the TeO x ( x = 3-5) can be polymerized into a variety of discrete polynuclear anionic clusters or extended architectures via Te-O-Te bridges.     

An integration method of enzyme analysis

The application of an integration method of kinetic analysis to first-order and second-order reactions is discussed with particular emphasis on enzyme analyses. Transducer signals or concentrations of products or substrates are integrated for a Fixed time and the net integral of the increased or decreased signal or concentration is related to the initial substrate or enzyme concentration. Equations are developed describing the dependence of the integrals on enzyme and substrate concentrations for first- and second-order reactions, and examples are presented illustrating different cases. The application of this method to complicated enzymatic systems is discussed.     

Improvement in the Pharmacological Profile of Copper Biological Active Complexes by Their Incorporation into Organic or Inorganic Matrix

Every year, more Cu(II) complexes are proven to be biologically active species, but very few are developed as drugs or entered in clinical trials. This is due to their poor water solubility and lipophilicity, low stability as well as in vivo inactivation. The possibility to improve their pharmacological and/or oral administration profile by incorporation into inorganic or organic matrix was studied. Most of them are either physically encapsulated or conjugated to the matrix via a moiety able to coordinate Cu(II). As a result, a large variety of species were developed as delivery carriers. The organic carriers include liposomes, synthetic or natural polymers or dendrimers, while the inorganic ones are based on carbon nanotubes, hydrotalcite and silica. Some hybrid organic-inorganic materials based on alginate-carbonate, gold-PEG and magnetic mesoporous silica-Schiff base were also developed for this purpose.     

The Nano-threading of Polymers

When guest polymers are threaded by host cyclodextrins (CDs) to form crystalline inclusion compounds (ICs), the included polymer chains are highly extended and separated from neighboring chains. This is a consequence of the stacking of the cyclic oligosaccharides, α-, β-, or γ-CD containing 6, 7, or 8 glucose units, respectively, which produces continuous narrow channels (~0.5–1.0 nm diameters), where the guest polymers are included and confined. Observations that illuminate several important aspects of the nano-threading of polymers to form polymer-CD-ICs are described. These include (i) the competitive CD threading of polymers with different chemical structures and molecular weights from their solutions containing suspended solid or dissolved CDs, (ii) the threading and insertion of undiluted liquid polymers into solid CDs, and (iii) suspension of polymer A or B-CD-IC crystals in a solution of polymer B or A and observation of the transfer of polymer B or A from solution to displace polymer A or B and form polymer B or A-CD-ICs, without dissolution of the CD-ICs. In addition, we report observations of polyolefins adsorbed on zeolites, where we believe the adsorbed polyolefin chains are actually threaded and absorbed into the interiors of the zeolite nano-pores, rather than adsorbed on the zeolite surfaces. All of the above observations were made to assist in answering the question “Why do randomly-coiling polymer chains in solution or the melt become threaded or thread into the nano-pores of dissolved or solid CDs and solid zeolites, where they are highly extended and segregated from other polymer chains?” Though still not fully able to answer this question, we are able to assess the importance of several factors that have been previously suggested to be important in the formation of CD-ICs with both polymer and small-molecule guests and to the nano-threading of polymers in general. In particular, the value in observations of the inclusion of guest polymers, as well as small-molecule guests, into solid CDs suspended in their solutions and in neat guest liquids were made apparent, because interactions between host CDs, between CDs and solvents, and between quests and solvents, which complicate and make understanding the formation of polymer-CD-ICs difficult, are either eliminated or can be independently varied in these experiments.     

Accuracy in standards preparation for neutron activation analysis

Errors in preparing standards, especially multielemental standards, are extremely important if accurate results are desired from neutron activation analysis (NAA). It is often convenient to prepare standards for NAA from single or multi-element solutions which are then deposited onto (or into) a suitable matrix, such as filter paper or quartz vials. There are many potential sources of error in preparing single-element standards including: impurities and non-stoichiometric composition of the element or compound used to prepare the standard solutions; evaporative losses of solvent; inaccuracy of calibration, and imprecision of the pipettes used; moisture content of elements or compounds used; contamination from reagents, equipment, laboratory environment, or final matrix of the standard; instability of standard solutions (i.e., to losses via precipitation or adsorption), and losses of volatile elements during dissolution and/or irradiation. Additional sources of error in preparing multielement standards includes: instability of mixed, multielement solutions, and cross-contamination of one element by the addition of a second element. Procedures previously used by the author at NIST to prepare multielement standards with concentrations accurate to about one percent are described. Additional techniques needed to prepare multielement standards with accuracies better than 1 percent will be discussed.     

Rich chemistry of nitroso compounds

Nitrosobenzene or nitrosopyridine are found to be attractive electrophiles in catalytic enantioselective carbon-nitrogen and/or carbon-oxygen bond forming reactions. In the presence of designer Lewis or Br?nsted acid catalysts, catalytic enantioselective O- and N-nitroso aldol reaction or nitroso Diels-Alder reaction proceed smoothly. The scope and limitation of new catalytic processes are described.     

三苯基锗不饱和烃基膦酸衍生物的合成和性质

随着倍半锗氧类化合物的合成及应用研究的日益广泛,含Ge_O键的烃基锗衍生物的合成及应用也逐渐引起了人们的关注.1984年,Lukevics等[1]合成了具有抗癌活性的介吗川类化合物,1990年Kakimoto等[2]报道了具有杀菌活性的环状烃基羧酸的合成与应用.     

Determination of thiamine by high-performance liquid chromatography

High-performance liquid chromatographic methods for the determination of thiamine (vitamin B1) in foodstuffs or biological tissues and fluids are outlined and discussed. The methods are often similar and interchangeable, sample extraction and clean up procedures being the major difference. Most of the methods use either ultraviolet or fluorescence detection. Fluorescence detection requires either precolumn or postcolumn oxidation of thiamine to thiochrome. A number of methods are recommended and problems with standardization are emphasized.