Mass spectrometry of heterocyclic compounds—III. Electron-impact-induced fragmentation of 1,2-benzisothiazole and some 3-substituted derivatives

The mass spectra of fifteen 1,2-benzisothiazoles are reported; their fragmentation patterns have been investigated by labelling experiments, high resolution mass measurements and defocused metastable ion detection. The parent compound of the series, 1,2-benzisothiazole, eliminates HCN after partial inter-ring hydrogen scrambling. The extent of scrambling has been determined for normal daughter ions produced at different electron beam energies and also for metastable daughter ions, and is compared with the data reported for benzothiazole. Some 3-substituted derivatives show unusual fragmentation patterns. The mechanisms of these processes are under further investigation.     

Binary mixtures based on polycaprolactone and cellulose derivatives

Pyrolytic process has a promising potential for the environmentally friendly upgrading of lignocellulosic and plastic waste. Thermogravimetry and pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS) were used to get information about the reactive decomposition of PCL in binary mixtures with microcrystalline cellulose (MC) or sisal fibres (SF). Preliminary thermogravimetric investigation showed that biomass is thermally degraded at lower temperatures than PCL and this process has a predominant influence on the thermal behaviour of the mixtures. Discrepancies between the experimental and predicted TG/DTG profiles were considered as a measurement of the extent of interactions occurring on co-pyrolysis. It was found that reactivity of PCL was slightly increased in PCL-SF binary mixtures. Evolution of acidic products from cellulose and hemicelluloses decomposition may promote PCL degradation in binary mixtures with SF. It seems that the co-pyrolysis process could have potential for the environmentally friendly transformation of biocomposites.     

Pyrylium-containing polymers as sensory materials for the colorimetric sensing of cyanide in water

A sensory polymeric material for the colorimetric sensing of cyanide in water has been developed based on the reactivity of this anion with the pyrylium cation.     

Preliminary study on dual fluorescence behavior of porphyrin

It is well known that porphyrin derivatives play a key role in the primary process of photo-synthesis[1], in which porphyrins directly absorb the sunlight or indirectly acquire excitation en-ergy from light-harvesting antenna system to reach their excited state, and then donate electrons to quinone acceptors to yield a series of charge-separated species. In general, only first singlet ex-cited state of porphyrins is involved in energy transfer process[2]. However, highly excited state (S2 stat…     

西印度蔗螟聚集信息素次要组份合成方法的改进

2-甲基-4-庚醇和2-甲基-4-辛醇是西印度蔗螟(Metamasiushemipterus)聚集信息素的次要组份，本文以天然产物(S)-亮氨酸为原料合成出了2-甲基-4-庚醇及2-甲基-4-辛醇的所有对映异构体，其关键步骤是由(2S)-4-甲基-1,2-戊二醇合成出(2S)和(2R)-4-甲基-1,2-环氧戊烷两种重要中间体，目标产物光学纯度可达95%以上。     

Studies on the refolding of the reduced-denatured insulin with size exclusion chromatography

The refolding of the reduced-denatured insulin from bovine pancreas was investigated with the size exclusion chromatography (SEC). It was shown that the reduced-denatured insulin originally denatured with 7.0 mol L^?1 guanidine hydrochloride (GuHCI) or 8.0 mol L^?1 urea could not be refolded with a non-oxidized mobile phase. Although the oxidized and reduced glutathione (GSSG and GSH) were employed in the oxidized mobile phase, the reduced-denatured insulin still could not be renatured. However, in the presence of 2.0 mol L^t-1 urea in the oxidized mobile phase employed, the reduced-denatured insulin can be refolded with SEC, and the aggregation of denatured insulin can be diminished by urea. In addition, the disulfide exchange of reduced-denatured insulin also can be accelerated with GSSG/GSH in the oxidized mobile phase. The three disulfide bridges of insulin were formed correctly and the reduced-unfolded insulin can be renatured completely. The results were further tested with reversed-phase liquid chromatography (RPLC) and hydrophobic interaction chromatography (HIC).     

Competitive adsorption and desorption of a bi-solute mixture: effect of activated carbon type

This study aims to clarify the effects of carbon activation type and physical form on the extent of adsorption capacity and desorption capacity of a bi-solute mixture of phenol and 2-chlorophenol (2-CP). For this purpose, two different PACs; thermally activated Norit SA4 and chemically activated Norit CA1, and their granular countertypes with similar physical characteristics, thermally activated Norit PKDA and chemically activated Norit CAgran, were used. The thermally activated carbons were better adsorbers for phenol and 2-CP compared with chemically activated carbons, but adsorption was more reversible in the latter case. 2-CP was adsorbed preferentially by each type of activated carbon, but adsorption of phenol was strongly suppressed in the presence of 2-CP. The simplified ideal adsorbed solution (SIAS) model underestimated the 2-CP loadings and overestimated the phenol loadings. However, the improved and modified forms of the SIAS model could better predict the competitive adsorption. The type of carbon activation was decisive in the application of these models. For each activated carbon type, phenol was desorbed more readily in the bi-solute case, but desorption of 2-CP was less compared with single-solute. This was attributed to higher energies of 2-CP adsorption.     

Influence of the preparation procedure on the properties of polyaniline based magnetic composites

A versatile process for the preparation of composite films consisting of magnetite (Fe₃O₄) nanoparticles embedded in a polyaniline (PANI) matrix is reported. Spectroscopic properties of polyaniline matrix (PANI-EB), polyaniline protonated with camphor sulfonic acid (PANI-CSA_0.5) PANI-ES and PANI/Fe₃O₄-CSA_0.5 composites were studied, both in the state of the solutions of m-cresol and in thin films processed from the same solvents. The results of these studies indicate that m-cresol can be used for PANI/Fe₃O₄ composite preparation. Such films show both reasonably high electrical conductivity and magnetic permeability. A controlled application of a magnetic field during the casting process resulted in the formation of the materials with an unusual combination of magnetic and transport properties. The obtained films show the behavior that can be explained by the presence of both ferromagnetic and paramagnetic phases. The superparamagnetic contribution, if any, is very small. Application of the external magnetic field during fabrication of the composites stimulates creation of the aggregates of magnetic particles which, although keeps conductivity at a relatively high level, leads to a small decrease of the conductivity value.     

Microwave-assisted synthesis of bipyrazolyls and pyrazolyl-substituted pyrimidines

We describe the preparation of 1,4′-bipyrazolyls and 4-pyrazolylpyrimidines by the reaction of 2-pyrazolyl-3-dimethylamino acrylate and acrylonitrile with double nucleophilic reagents such as hydrazines, urea and guanidine. Reactions were performed under microwave irradiation in 5-60 min. This is a useful procedure for the preparation of valuable compounds with applications in medicinal and coordination chemistry.     

Interactions of diethylenetriaminepentaacetic acid (dtpa) and triethylenetetraaminehexaacetic acid (ttha) with major components of natural waters

The binding ability of diethylene triamine pentaacetate (dtpa(5-)) and triethylene tetraamine hexaacetate (ttha(6-)) ligands towards major components, H(+), Na(+), Mg(2+) and Ca(2+), of natural waters was studied in both single and mixed ionic media at different ionic strengths and at T=25 degrees C. Some measurements, performed in Mg(2+)-Ca(2+) mixtures, allowed us to find the formation of new mixed species MgCa(dtpa), MgCa(ttha) and MgCaH(ttha), here reported for the first time. All the complexes formed in the various systems were characterized in terms of both stoichiometry and stability, and an attempt was made to find general rules for the stability of mixed metal complexes in comparison with that of simple species. To obtain quantitative information on the complexing ability of dtpa and ttha in seawater, measurements have been carried out in artificial seawater ionic medium (Na(+), K(+), Ca(2+), Mg(2+), Cl(-) and SO(4)(2-)). Calculations, performed by considering the salt mixture as single salt BA, allowed us to find some quite stable B(i)H(j)L species. Under the natural seawater conditions [S(salinity)=35], we found for the most important species logbeta( B(dtpa))=9.64 and. Literature data comparison is also reported.