Thermal properties of pressure sintered alumina–graphene composites

Journal of Thermal Analysis and Calorimetry - The work concerns the alumina–graphene materials sintered by two different pressure methods. The different particle sizes of graphene were used....     

Roles of rhenium diimine complexes as metal‐ion probes and photosensitizers in functional polyurethanes

Polyurethanes incorporated with rhenium diimine complexes were synthesized. The polymers exhibited interesting morphologies and solution properties. Results from gel permeation chromatography suggested the formation of polymer aggregates in solutions. The polymers could act as probes for metal ions. The addition of metal ions to polymer solutions led to significant changes in the electronic absorption properties of the polymer solutions. This was attributed to the interactions between the polyether moieties and metal ions. The metal complexes could also act as efficient photosensitizers. After doping with charge‐transport viologens, the photoconductivity of the polymers was greatly enhanced. The experimental quantum efficiency was simulated with Onsager's theory. The thermalization distances and the primary yields were typically 12–14 Å and 10^?3, respectively. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1708–1715, 2003     

Effect of the fibre-forming material structure and silica nanoparticles

The paper discusses the thermal properties of alginate fibres made from alginic acid or sodium alginate and from alginates substituted with divalent metal ions during the fibre-forming stage. Alginate fibres with an addition of silica nanoparticles have also been examined. The selection of fibre-forming parameters was intended to obtain the best either sorption or strength properties depending on the specific fibre application. Thermal curves of the fibres under investigations obtained by under air atmosphere and differential scanning calorimetry (DSC) under neutral gas atmosphere have been interpreted from the view of physical and chemical changes in the fibre-forming material. Based on thermogravimetric curves, the fibre thermal stability indices have been determined. It has been found that the addition of silica nanoparticles exerts a positive influence on the thermal properties of the examined fibres.     

Determination of traces of cobalt in the presence of nioxime and cetyltrimethylammonium bromide by adsorptive stripping voltammetry

A sensitive method of Co(II) determination by adsorptive stripping voltammetry is presented. The method exploits the enhancement of cobalt peak current observed in the system Co(II)-nioxime-cetyltrimethylammonium bromide-piperazine-N,N′-bis(2-ethanesulfonic acid). The calibration plot for an accumulation time of 60 s is linear from 5 × 10⁻¹¹ to 3 × 10⁻⁹ mol L⁻¹. The relative standard deviation is 3.8% for Co(II) determination at concentration 1 × 10⁻⁹ mol L⁻¹. The detection limit is 1.7 × 10⁻¹¹ mol L⁻¹. The validation of the method is performed by the analyses of certified reference materials and comparing the result of Co(II) determination in river water sample by the proposed method with those obtained by ET AAS. The main advantage of this new system is the micro-trace Co(II) determination by adsorptive stripping voltammetry, as compared to those described before, a low concentration of the supporting electrolyte used, and so commercially available reagents without additional purification can be used.     

A novel synthesis of racemic and enantiomeric forms of prostaglandin B1 methyl ester

3-(Dimethoxyphosphorylmethyl)cyclopent-2-enone was converted into (+/-)-prostaglandin B1 methyl ester in two steps involving regioselective alkylation at C(2) with methyl 7-iodoheptanoate and subsequent Horner-Wittig reaction with dimer of 2-hydroxyheptanal (42% overall yield). The use of (R)- and (S)-2-(tert-butyldimethylsilyloxy)heptanal for the Horner olefination reaction gave, after deprotection of the hydroxy group, the enantiopure forms of the title compound in 28% overall yield.     

Thiyl radical interaction with pyrimidine C5-C6 double bond

Addition and elimination interaction of thiyl radicals with the C5-C6 double bond in pyrimidines was studied by the pulse radiolysis technique in aqueous solution with the use of different monitoring systems. For this purpose, p-thiocresol, cysteamine hydrochloride, and mercaptoethanol were used. The rate constants of addition and elimination of thiyl radicals were determined by applying the modified version of ACUCHEM (computer program for modeling complex reaction systems). Aliphatic thiyl radicals add to the pyrimidine C5-C6 double bond with k = 1.0-3.0 x 10(7) dm3 mol(-1) s(-1), whereas elimination takes place with k = 0.7-2.0 x 10(5) s(-1). Quantum chemical calculations at the B3LYP/6-31G(d)/PCM level show that the addition should occur at the C6 position of the pyrimidine ring and that the energy of interaction between thiyl radicals and the pyrimidine double bond C5-C6 is low.     

Asymmetry of electron transmission through monolayers of helical polyalanine adsorbed on gold surfaces

Polyalanine derivatives containing cysteamine linker R-(Ala)14NH-(CH2)2-SH, where R is ferrocenecarbonyl or hydrogen, were synthesized and then used to form self-assembled monolayers on gold. The tilt angles and the packing density of the molecules within monolayer assemblies were determined by FTIR spectroscopy and scanning tunneling microscopy, respectively. Electrochemical properties of monolayer-modified electrodes were studied using cyclic voltammetry and impedance spectroscopy. Measurements of electron-transfer rates using electrochemical techniques and scanning tunneling spectroscopy revealed asymmetry dependent on the applied voltage. It is suggested that the observed electron-transfer behavior is connected with the electric field generated by the molecular dipole of the polyalanine helix.     

Austausch von Chlorisotopen am Phosphoratom, 1. Mitt.: Dialkylchlorthiophosphate

Zusammenfassung An den Modellverbindungen Dialkylchlorthiophosphat (RO)₂P(S)Cl (R=Me, Et, n-Pr) und Diphenylchlorthiophosphat (PhO)₂P(S)Cl wurde der Austausch Chlorid—Radiochlorid am Thiophosphorylzentrum untersucht. Die bimolekularen Geschwindigkeitskonstanten, die Aktivierungsenergien und Aktivierungsentropien wurden berechnet. Der Einfluß von Substituenten auf bimolekulare Substitutionsreaktionen am vierfach koordinierten Phosphoratom wurde diskutiert.

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Chlorine isotopic exchange at phosphorus atoms, I.: Chloridothiophosphates

The chloride—radiochloride ion exchange at the thiophosphoryl centre has been studied using dialkylchloridothiophosphates (RO)₂P(S)Cl (R=Me, Et, n-Pr) and diphenylphosphorochloridothionate, (PhO)₂P(S)Cl, as model compounds. The bimolecular rate constants, energies and entropies of activation have been calculated. Effects of the substituents in the bimolecular displacement reaction on four-coordinated phosphorus atom have been discussed.

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Improvement in the synthesis of metallophthalocyanines using microwave irradiation

A successful application of microwave irradiation, in which phthalocyanines were synthesized under solventless conditions from 1,2-phthalonitrile or phthalic anhydride and urea in the presence of metal templates is described. It was found that in comparison with conventional heating, the microwave process is a very useful alternative for cyclotetramerization processes because of reduction of the reaction time, better yield, and easy-to-perform procedure.     

Improved selectivity and detection limit of the carbonate-selective electrode

The properties of the carbonate neutral carrier 4-( n-hexadecyl)-3-nitro-1-trifluoroacetylbenzene were compared with those of a similar carrier, without a nitro group, studied previously. In spite of differences in the Hammett constant of the carbonyl group responsible for interaction with the analyte, the analytical characteristics of both carriers, measured under the same conditions, were comparable. Special care was taken to avoid the presence of an excessive carbon dioxide level in the diffusion layer at the membrane-solution interface. The internal reference solution was prepared without carbonate components; the external solution was protected from contact with atmospheric carbon dioxide. Under such conditions the detection limit of both electrodes was extended to 10(-11 )mol L(-1), and the selectivity towards salicylate, chloride, and acetate was significantly improved.