离子的极化和形变

离子的极化和形变是无机化学教学中的一对重要概念,这对概念可以用于解释化合物的结构及许多物理和化学性质.然而一些教科书在介绍这对概念时,大都把极化作用限于阳离子,把形变作用限于阴离子,而忽略了阴离子的极化作用和阳离子的形变作用.同时,在应用这对概念解释化合物结构和性质时,条理上也不十分清晰,甚至还出现自相矛盾的情况,使得...     

Kinetic evaporation and condensation rates and their coefficients

The origins and properties of evaporation and condensation coefficients are described, and results of their measurement are surveyed for water and liquid metals. Contrasts are drawn as to whether their values are likely to limit practical transfer rates at plane surfaces and on aerosols, and between evaporation and condensation. Existing theories which express condensation and evaporation rates in terms of the coefficients are described. Their failure to satisfy energy and momentum conservation as well as mass conservation at the interface is remedied by constructing a new theory which also starts with vapor molecules in Maxwell-Boltzmann distributions. The resulting rates are shown to be close to those predicted by more accurate theories in which the Boltzmann transport equation is solved.     

Photochromic,Thermochromic, and Fluorescent Spirooxazines and Naphthopyrans: A Spectrokinetic and Thermodynamic Study

The photochromic and thermochromic behavior of four commercially available Reversacol dyes are presented. The compounds studied belong to the class of spirooxazines and naphthopyrans, which are typically thermoreversible photochromic molecules. On stimulation with UV light, these compounds become colored and exhibit spectra which extend over the whole visible region. Increasing the temperature causes spontaneous coloration (thermochromism). Herein, absorption and fluorescence spectra, molar absorption coefficients of the colorless and colored forms, fluorescence and photochemical quantum yields, and kinetic parameters of thermal bleaching (rate constant, frequency factor, and activation energy) are determined in acetonitrile solution. The thermal ground‐state reaction is exhaustively described in terms of thermodynamic parameters (equilibrium constant, free energy, enthalpy, and entropy). Temperature effects on photochemical and thermal colorabilities are evaluated. The results indicate that the two spirooxazines are good photochromes below room temperature, whereas they are efficient thermochromic compounds above room temperature. Naphthopyrans are better photochromes but worse thermochromic compounds than spirooxazines.     

Cytotoxic and antioxidant marine prenylated quinones and hydroquinones

Covering: 1972 to 2011. This review covers the literature of prenylated quinone, hydroquinone and naphthoquinone marine natural products with reported cytotoxic and/or antioxidant properties. The structures, biological activity and, where applicable, the syntheses of 159 cytotoxic/antioxidant compounds, isolated from various marine organisms, are presented, while trends in the distribution of these cytotoxic metabolites, across the different marine phyla, are highlighted. Marine prenylated quinones, hydroquinones and naphthoquinones are of mixed polyketide and terpenoid biogenesis and recent biosynthetic studies of selected compounds are discussed.     

Lipidated ras and rab peptides and proteins--synthesis, structure, and function

Chemical biology can be defined as the study of biological phenomena from a chemical approach. Based on the analysis of relevant biological phenomena and their structural foundation, unsolved problems are identified and tackled through a combination of chemistry and biology. Thus, new synthetic methods and strategies are developed and employed for the construction of compounds that are used to investigate biological procedures. Solid-phase synthesis has emerged as the preferred method for the synthesis of lipidated peptides, which can be chemoselectively ligated to proteins of the Ras superfamily. The generated peptides and proteins have solved biological questions in the field of the Ras-superfamily GTPases that are not amendable to chemical or biological techniques alone.     

Capillary electrophoresis and electrochromatography of pesticides and metabolites

Synthetic pesticides are important chemicals since they are widely used to control many types of weeds, insects, and other pests in a wide variety of agricultural and nonagricultural settings. This review article is aimed at describing the recent progress made in capillary electrophoresis (CE) and capillary electrochromatography (CEC) of pesticides and metabolites. The various electrophoretic systems and detection schemes that were introduced during the period extending from the second half of 1999 to the first half of 2001 for the CE and CEC of pesticides are discussed. Also included in this review article are the various approaches for trace enrichment that are involved in the analysis of dilute pesticide samples.     

Water sorption on and water diffusion in chitin and chitosan

The kinetics of the sorption of water vapor on powders of crab-shell chitin and chitosan are studied via the methods of static sorption, thermography, and X-ray structural analysis. Sorption isotherms are obtained in the range of humidity from 10 to 95%. S-Shaped water-sorption isotherms observed for all chitin and chitosan samples are approximated via superpositioning of Langmuir and Flory-Huggins isotherms. The water-polysaccharide interaction parameters and the maximum sorption capacities of water located in chitin and chitosan are determined. The cluster integral is calculated, and the moisture values corresponding to water-cluster formation are determined. The water-diffusion coefficients are determined, and the effective activation energies of water diffusion are estimated: 70 kJ/mol in chitosan and 60 kJ/mol in chitin. The data on the concentration dependences of the coefficients of diffusion of water in the powdered chitin and chitosan are summarized.     

Capillary electrophoresis and electrochromatography of pesticides and metabolites

Synthetic pesticides are important chemicals since they are widely used to control many types of weeds, insects and other pests in a wide variety of agricultural and nonagricultural settings. This review article is aimed at describing the recent progress made in capillary electrophoresis (CE) and capillary electrochromatography (CEC) of pesticides and their metabolites. The various electrophoretic systems and detection schemes that have been introduced so far for the CE and CEC of pesticides are discussed. Also included in this review article are the various approaches for trace enrichment that are involved in the analysis of dilute pesticide samples.     

Aspartic and glutamic acids polymers: preparation and applications in medicinal chemistry and pharmaceutics

The methods of the fabrication of polymers based on aspartic and glutamic acids as monomers are reviewed. The methods are perspective from the viewpoint of green chemistry and economics. Actual tendencies existing in the application of the polymers in medicinal chemistry and pharmaceutics are also considered. The results of using mentioned polymers of amino acids to obtain stable nanosized enzymatic complex drugs, based on organophosphate hydrolase and possessing both antibacterial and antineurotoxic action are presented. The drugs are effective destructors of N-acyl homoserine lactones, playing the role of signaling molecules for the quorum response of gram-negative bacteria. These enzymatic-polymer complexes in combination with well-known antibiotics reduce antimicrobial doses inhibiting growth of the pathogens.     

Synthesis and electrooptical properties of triphenylamine- and oxadiazole-containing polymers

Soluble aromatic polyimides and copolyimides are synthesized on the basis of 4,4′-diaminotriphenylamine and oxadiazole-containing diamines. Poly(ester oxadiazoles) are prepared from acid dichlorides or oxadiazole-containing acid dihydrazides. The optical, electrochemical, and thermal properties of the polymers are investigated. It is shown that oxadiazole-containing polyimides and poly(ester oxadiazoles) are able to transfer electrons, while triphenylamine-containing polyimides and copolyimides can transfer holes and electrons.     

基因传感技术及目前存在的问题和发展对策

对最近几年报道的比较有特色的光学、压电、电化学等基因(DNA)传感器方面的研究工作进行介绍,并就目前基因传感器研究中存在的问题进行了分析讨论,提出了相应的发展对策.     

Hydrogenation and hydrocarbonation and etching of single-walled carbon nanotubes

We present a systematic experimental investigation of the reactions between hydrogen plasma and single-walled carbon nanotubes (SWNTs) at various temperatures. Microscopy, infrared (IR) and Raman spectroscopy, and electrical transport measurements are carried out to investigate the properties of SWNTs after hydrogenation. Structural deformations, drastically reduced electrical conductance, and an increased semiconducting nature of SWNTs upon sidewall hydrogenation are observed. These changes are reversible upon thermal annealing at 500 degrees C via dehydrogenation. Harsh plasma or high temperature reactions lead to etching of nanotubes likely via hydrocarbonation. Smaller SWNTs are markedly less stable against hydrocarbonation than larger tubes. The results are fundamental and may have implications to basic and practical applications including hydrogen storage, sensing, band gap engineering for novel electronics, and new methods of manipulation, functionalization, and etching of nanotubes.     

Preparation and application of cellular and nanoporous carbides

A tutorial review on cellular as well as nanoporous carbides covering their structure, synthesis and potential applications. Especially new carbide materials with a hierarchical pore structure are in focus. As a central theme silicon carbide based materials are picked out, but also titanium, tungsten and boron carbides, as well as carbide-derived carbons, are part of this review.     

Luminescence characteristics of dibenzofuran and several polychlorinated dibenzofurans and dibenzo-p-dioxins

The room-temperature fluorescence (RTP), low-temperature phosphorescence (LTP) and room-temperature phosphorescence (RTP) characteristics of dibenzofuran and several polychlorinated dibenzofurans and dibenzo-p-dioxins are presented and are shown to be suitable for the determination of these compounds. The limits of detection are as low as 0.02, 0.2 and 0.7 for RTF, LTP and RTP, respectively. The relative standard deviations are between 1 and 4% for RTP.     

Heparin and heparan sulfate: structure and function

This review covers the structure and function of heparin and heparan sulfate glycosaminoglycans. Their chemical structures are discussed, including recently developed methods for sequencing picomole to nanomole quantities of heparin- and heparan sulfate-derived oligosaccharides. The biosynthesis of heparin and heparan sulfate is reviewed as it relates to their diverse and varied structures, and their biological activities and functions are discussed. The literature up to August 2001 is reviewed, and 208 references are cited.     

Cucurbitacins and cucurbitane glycosides: structures and biological activities

The natural cucurbitacins constitute a group of triterpenoid substances which are well-known for their bitterness and toxicity. Structurally, they are characterized by the tetracyclic cucurbitane nucleus skeleton, namely, 19-(10-->9beta)-abeo-10alpha-lanost-5-ene (also known as 9beta-methyl-19-norlanosta-5-ene), with a variety of oxygen substitutions at different positions. According to the characteristics of their structures, cucurbitacins are divided into twelve categories. The biological effects of the cucurbitacins are also covered.     

Enzyme fingerprints of activity,and stereo- and enantioselectivity from fluorogenic and chromogenic substrate arrays

A series of stereochemically and structurally diverse fluorogenic and chromogenic substrates for hydrolytic enzymes has been synthesized and used to characterize enzyme activity profiles of esterases, lipases, proteases, peptidases, phosphatases, and epoxide hydrolases. The substrates used are particularly resilient to nonspecific reactions due to their mechanism of activation. The activities recorded with the individual substrates are therefore remarkably reproducible, and enable us to use the overall pattern of activity as a specific fingerprint for the enzyme sample. Fingerprints of activity, and enantio- and stereoselectivity are displayed as arrays of color-scale squares that are easily analyzed visually. Such fingerprints might be useful for quality control, enzyme discovery, and possibly for addressing the issue of functional convergence in enzymes.     

Synthesis and properties of blocked Di- and polyisocyanates

Tricresol-blocked di- and polyisocyanates (BDPs) of variable structure are synthesized, and their main physicochemical and technological properties are defined. They have lower melting points and thermal dissociation (deblocking) temperatures than do the known BDPs based on ε-caprolactam, oximes, and secondary amines.. The new blocked isocyanates are tested as latent curing agents for polyurethane varnish compositions of electroinsulating assignment.     

Inhomogeneity and microscopic structure in liquids and glasses

Our recent works on solutions of chemically different substances are reviewed. The emphasis is placed on the tendency of nano-scale heterogeneous phase separation in homogeneous solutions, which influences the bulk properties of the systems. Examples are alkali metal–ammonia solutions, AgI–alkylammonium iodide mixtures, and sodium borate glasses containing Ag or Bi fine particles. The correlations of the inhomogeneity and stability of solutions are discussed.     

The infrared spectra and structure of acetamide and acrylamide

The far-IR vapour phase spectra of acetamide and acrylamide are reported and several transitions in the amido “inversion” vibration are identified. The potential energy curves governing the vibration are deduced from the experimental data and are found to have a single broad minimum for both molecules, implying that the amido hydrogens are copianar with the N-CO atoms, but that the resistance to their out of plane displacement is small. The band contours found in the mid-IR spectrum of acrylamide suggest that the cis orientation of the two double bonds about the C-C single bond is favoured over the trans orientation; indeed no evidence of the latter has been found.