Selectivity in epoxidation: acyclic diastereo- and enantio-selection with peroxide mediated by titanium(iv) and with peracid

New diastereoselective epoxidation on the olefin 1 with TBHP mediated by Ti(IV) is described to give the epoxide 2 which has reverse orientation of the one, 3 with MCPBA. Ti-mediation was ineffective on the olefin 4, on which MCPBA worked in high selectivity. Example of kinetic resolution is also described on 1b under Katsuki-Sharpless condition.     

Synthesis and nucleophilic substitutions of 3-alkyl-5-chloroisoxazoles

A 3-alkyl-5-chloroisoxazole synthesis is described based on the cycloaddition of nitrile oxides to 1,1-dichloroethylene, an inexpensive dipolarophile. Substitution of the chloride in these adducts by various nucleophiles is also described.     

Hydrocolloid gels of polysaccharides and proteins

Recent developments from 1997 to 2000 in hydrocolloid gels which consist of dispersed phase (polysaccharide or protein) and dispersing medium (water) are reviewed in the present paper. Gels and gelling processes of polysaccharides such as gellan gum, methylcellulose, xyloglucan, curdlan, konjac glucomannan and starch are described. Fluid gels and galactomannan gels prepared by freeze-thaw cycling are also described. Effects of pH and ionic strength on the gelation of proteins such as casein and β-lactoglobulin are described. Fractal treatment is introduced to study the structure–property relationship for globular protein gels. Gels formed by different hydrocolloids are also described briefly.     

Analysis of natural corticosteroids in adrenal extracts and in biological fluids by high-performance liquid chromatography

A liquid chromatographic procedure is described for the analysis of the principal natural corticosteroids in extracts of adrenal glands. Microparticulate silicic acid columns and gradients of methanol in chloroform are used: conditions are described for the quantitative analysis of the single principal steroidal components of adrenal extracts for pharmaceutical use and of adrenal extracts of rats. In the last case, the use of a 5-micron silica column with the appropriate gradient allows the determination of corticosterone and of 18-hydroxydeoxycorticosterone, which were identified by means of mass spectrometry on their eluates. A single analysis can be performed on the extract of 15 mg of rat adrenal tissue. For the last type of analysis, isocratic conditions on a 10-micron LiChrosorb Diol column are also described. The application of the gradient elution procedure to the analysis of steroidal compounds in human plasma is also described.     

Comparison between experimental and theoretical scales of electrophilicity in benzhydryl cations

The theoretical electrophilicity pattern of a series of benzhydryl cations as described in terms of a model based on global reactivity indexes is compared with an experimental scale recently proposed by Mayr et al. [J. Am. Chem. Soc. 2001, 123, 9500]. A good correlation between both theoretical and experimental quantities is found. The effect of chemical substitution on the electrophilic power of these charged electrophiles may also be assessed as local responses at the active site, in terms of a global contribution described by changes in global electrophilicity with reference to the dianisylcarbenium ion, and a local contribution described by the variations in electrophilic Fukui function at that site.     

The application of microchemical methods to radiochemical analysis : Part III. Solvent extraction of diethyldithiocarbamates and the radiochemical separation and purification of cobalt,nickel, palladium,silver and cadmium

The advantages of solvent extraction of diethyldithiocarbamatcs in radiochcmical separations are discussed. The development of a procedure for the separation and purification of cobalt and nickel from mixtures containing fission products is described; diethyldithiocarbamate extraction is used extensively. A scheme incorporating this procedure is also described whereby the fission products palladium, cadmium and silver are also determined on the same sample.     

Gravimetric and spectrophotometric determination of hexafluoroantimonate with tetraphenylarsonium chloride, nitron and ferroin

Two methods are described for the gravimetric determination of the hexafluoroantimonate anion with tetraphenylarsonium chloride and nitron as precipitants. In addition, a spectrophotometric method for this anion with ferroin as reagent is described. Hydrolysis of the anion is avoided by using stock solutions of KSbF(6) in N,N-dimethylformanude and adding these directly to concentrated aqueous solutions of the analytical reagent. Interference studies are included on a number of anions.     

Protein–polysaccharide complexes and coacervates

Recent advances on protein–polysaccharide electrostatic complex and coacervates' formation, structure and properties are presented. The first section emphasises on the thermodynamics of complexes formation, the contribution of enthalpic and entropic effects is specifically discussed. Then, their structure is described at different length scales and recent findings on the phase-ordering dynamics of complex and coacervates formation are covered. Finally, the most relevant functional properties of protein–polysaccharide complexes and coacervates for food applications are described.     

Cation and anion fluorescent and electrochemical sensors derived from 4,4′-substituted biphenyl

Five new fluorescent macrocyclic ligands derived from biphenyl are described. These new compounds can be used in cation and anion recognition and sensing. Their fluorescent and electrochemical properties are studied and the influence of the biphenyl conformation on these properties is considered. The X-ray single crystal structure of one of the described ligands has been determined.     

Spectrophotometric determination of traces of lead with bromopyrogallol red and cetyltrimethylammonium or cetylpyridinium bromide

A method is described based on the sensitizing effect of cetyltrimethylammonium or cetylpyridinium bromide on the lead-Bromopyrogallol Red colour reaction. The reaction is instantaneous and the colour remains stable for over 120 hr in the presence of Triton X-100. Both colour systems obey Beer's law up to 5.5 ppm of lead. Methods are described for dealing with interferences.     

Estimating tissue permeability and other bioelectrical parameters using membrane voltage and short-circuit current

Evaluating the acute toxic effects of drugs or toxins is based mainly on studies which require the use of light microscopy. Recently, the effects of such substances on biological membranes, such as the nasal membrane, has been studied using the traditional Ussing chambers, which make it possible to study the transepithelial flux of drugs across membranes and to measure some bioelectrical parameters. A model is described, with which the changes in the membrane permeability, for sodium, potassium and chlorine, can be calculated directly, based on values obtained from the Ussing chamber system. Also, an experiment is described for evaluating the toxic effects of the cholera toxin B subunit, by measuring these changes in isolated rabbit nasal mucosa.     

Quantitative analysis of disulfiram and its metabolites in human blood by gas-liquid chromatography.

A simple method is described that permits the direct quantitative determination of carbon disulphide, free diethyldithiocarbamate and disulphides derived from disulfiram in 1 ml of a patient's blood. It is based on a gas chromatographic determination of carbon disulphide produced from diethyldithiocarbamate and disulfiram using the head-space technique and a flame-photometric detector. The method is compared with a recently described spectrophotometric method.     

The determination of parathion vapour and dust in the atmosphere

A sensitive method is described for the dctermination of parathion in air The air sample is drawn through filter paper or cellulose powder, winch traps both particles and vapour, and the parathion is reduced without heating by means of a zinc-copper couple in acid solution, followed by dia/otisation of the amimo derivative and coupling to give an azo dye An alternative procedure la described in winch the parathion is trapped on cellulose powder containing zinc dust, from which the reduced derivative is directly cluted     

The Binding of Cu(II) and Zn(II) Ions by Heparin

Abstract

A method is described for measuring the ion binding capacity of heparin. The method is based on the separation of the zinc or copper complex of heparin by gel permeation. It was found that the number of the cation per average molecule of heparin depends on the pH and on the initial concentration of metal cation in solution. The absorption spectrum of heparin-Cu complex is described. The molar absorptivity of this complex is determined, as is the complex formation constant.     

Design and operation of microelectrochemical gates and integrated circuits

Here we report a simple design philosophy, based on the principles of bipolar electrochemistry, for the operation of microelectrochemical integrated circuits. The inputs for these systems are simple voltage sources, but because they do not require much power they could be activated by chemical or biological reactions. Device output is an optical signal arising from electrogenerated chemiluminescence. Individual microelectrochemical logic gates are described first, and then multiple logic circuits are integrated into a single microfluidic channel to yield an integrated circuit that can perform parallel logic functions. AND, OR, NOR, and NAND gates are described. Eventually, systems such as those described here could provide on-chip data processing functions for lab-on-a-chip devices.     

Microdetermination of arsenic(III) and osmium(VIII) through osmium-thiourea reaction

Osmium-thioureau reaction is slow under conditions described in earlier methods. In the present study it has been observed that arsenic(III) catalyzed the reaction. Based on this, qualitative and quantitative methods are described for the determination of both osmium and arsenic. Interference study of 30 ions showed they do not interfere.     

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.     

A new and practical five-carbon component for metal-catalyzed

Described herein is an efficient preparative scale synthesis of 1-(2-methyoxyethoxy)-1-vinylcyclopropane and the investigation of the utility of this reagent as a new five-carbon component in metal-catalyzed [5 + 2] cycloadditions. A new cycloaddition procedure is also described that proceeds up to 12-fold faster and with 10-fold less catalyst than previously described, providing cycloheptenones in many cases in minutes and in isolated yields of 75-97%. The procedure is readily conducted on a small or large scale (up to 100 mmol thus far).     

DNA-templated assembly of nanoscale wires and protein-functionalized nanogap contacts

The use of DNA to template the assembly of nanoscale wires and protein-functionalized nanogap contacts is described: Specifically, the use of DNA to template the assembly of gold nanowires between conventionally patterned gold contacts on a silicon wafer substrate. Also described is the use of DNA to template the assembly of protein-functionalized nanogap gold contacts on a silicon wafer substrate. Of particular significance is the finding that suitably modified gold nanoparticles recognize and bind selectively the protein-functionalized nanogap and are localized there.     

Remote measurements of ozone concentration and aerosols in the Arctic stratosphere

Summary A LIDAR instrument for measurements of the ozone concentration and of aerosols in the middle atmosphere is briefly described. Data sets for ozone and aerosols, obtained at Spitsbergen during winter and early spring in 1989 and 1990, are presented. The Arctic ozone layer was found to be strongly influenced by atmospheric dynamics; a dramatic ozone depletion was not observed. Polar stratospheric clouds were detected in each winter, their dependence on the ambient atmospheric temperature is described.