Pyrolysis study of hydrophobic tholins By TG-MS, TG, DTA and DSC methods

This study presents the thermogravimetry (TG) of hydrophobic tholins, obtained from different simulation experiments of prebiotic synthesis carried out in a CH₄/N₂/H₂ atmosphere with spark discharge activation of aqueous aerosols and liquid water. Differential thermal analysis and differential scanning calorimetry were also used to evaluate the thermal behaviour of these complex organic compounds that could play an important role in prebiotic chemistry. A coupled thermogravimetry-mass spectrometry system allowed us to analyse the principal volatile thermal decomposition and fragmentation products of the hydrophobic tholins under dynamic conditions and an inert atmosphere. During their thermal degradation, which occurs in two stages, a wide variety of hydrocarbon products including methane, vinyl monomers (such as ethylene and propylene), acetylene, oligomers, and some other unknown compounds are found. Besides, a thermally stable structure is present (graphitic structure) in these particular organic substances. Finally, data collected from TG experiments in an oxidative atmosphere showed significant differences at temperatures above 240 °C. According to these results, the different techniques of thermal analysis here applied have proved to be an adequate methodology for the study and characterization of these complex systems, structures of which remain controversial even in these days.     

Capillary electrophoretic separation of serum proteins of workers occupationally exposed to heavy metals

Metallurgy processes are associated with many hazardous and toxic factors, including heavy metals. Exposure to heavy metals can cause damage to different organs, which can be observed through variation in the concentration of proteins in serum. The aim of this study was to evaluate the changes in a serum protein profile of copper smelters exposed to As, Cd and Pb ions, and xenobiotics present in tobacco smoke. A 2.3-fold higher Pb concentration in the blood and a 2.8-fold greater As concentration have been observed in the urine of non-smoking smelters compared to a control group. In the blood of smoking smelters, Cd concentration was 2-fold higher than in non-smoking ones. Serum proteins were separated by capillary electrophoresis, and in the group of non-smoking smelters, a higher amount of α₁-globulins was observed. In the group of smoking smelters, fewer α₁-globulins were noted. Furthermore, a greater amount of α₂-globulins in the serum of smoking and non-smoking workers in relation to the control group was revealed. A positive correlation between the concentration of Cd in the blood and the content of a fraction containing α₁- and α₂-globulins was revealed. Urine Cd concentration was found to be negatively associated with the α₁- and α₂-globulins fraction. Observed abnormalities in the proteins profiles of smelters can be important markers when assessing exposure to heavy metals and in the early diagnosis of diseases caused by them.     

ADSORPTION OF METAL IONS ON STEARIC ACID-NONADECANE PARTICLES IN AQUEOUS SOLUTION

The adsorption of metal ions at the stearic acid/electrolyte and nnonadccane-stearic acid mixture/electrolyte interface was investigated by means of the potentiometric titration, zeta potential and adsorption measurements. It was found that the studied colloidal suspensions exhibited an adsorption affinity towards multivalent metal ions. The adsorption of Ca²⁺, Cd²⁺ and Al³⁺ ions caused a strong decrease of surface charge density and zeta potential values in this systems. The adsorption reactions occur by way of cation exchange with protons from two surface carboxyl groups. Al high metal concentrations, in adsorption reactions there are involved also carboxyl groups from the subsurface layer. On the basis of the adsorption data, the cation surface complexation constants were calculated by Shindler's method.     

Drop Size Distribution Bimodality and Its Effect on O/W Emulsion Viscosity

The research work on why and how distribution bimodality tends to reduce the viscosity of a particulate suspension is reviewed. The transfer of the corresponding concepts to emulsions requires some statistical tools, and becomes particularly easy with probability scale plotting which is reviewed. Viscosity reduction can be attained for different kinds of fine and coarse emulsion associations. The results are shown to depend on the characteristics of the base emulsions as well as on the way they are mixed.     

New Heterocyclic Analogues of Anthracycline Antibiotics

ABSTRACT

Synthetic approaches to anthracycline antibiotic analogues in which the nitrogen atom of the carbohydrate portion is incorporated into a 1, 2, 3-triazolyl moiety were investigated. By using methyl 6-azido-2, 6-dideoxy-β-D--arabino-hexopyranoside and methyl 6-azido-2, 3, 6-tricdeoxy--α-L-arabino-hexopyranoside, the corresponding glycosides (16 a, b - 18 a, b) of carminomycinone and daunomycinone were prepared. The desired heterocyclic system was developed directly with the C-3′ and C-6′ azido anthracyclines by means of a cycloaddition process to give 7-0-[6′-(4, 5--dicarboethoxy-l, 2, 3-triazolyl)-2′, 6′-dideoxy-β-D-arabino--hexopyranosyl]-carminomycinone (23) and -daunomycinone (22), and 3′-(4, 5-dicarboethoxy - l, 2, 3-triazolyl)-4′ -epi-daunomycin (24).     

Artificial neural networks for quantification in unresolved capillary electrophoresis peaks

The application of the combination of experimental design (ED) and artificial neural networks (ANNs) for the quantification of overlapped peaks in capillary zone electrophoresis is described. When the total separation cannot be achieved by separation techniques, the use of ED-ANN can be a suitable approach. The unstability of EOF causes peak shift that has to be corrected in order to apply ED-ANN methods. In this work, normalization procedure of electropherograms with consequent application of ANNs for quantification purpose was developed. Both, spectra and electropherograms can be used as multivariate data. In general, both kinds of data were found to be suitable for unresolved peaks quantification by ED-ANN approach.     

Tandem RCM-Pauson-Khand reaction for access to tricycles in one step

Starting from conveniently designed dienynes complexed to cobalt, a tandem RCM-intramolecular Pauson-Khand reaction yields tricyclic compounds. The methodology allows the synthesis of 6,5,5 and 7,5,5 systems.     

Synthesis and structure of [(Sn(mu-PCy))3(Na x PMDETA)2], containing an electron-deficient [(Sn(mu-PCy))3]2- dianion

The reaction of CyPHNa with Sn(NMe2)2 in the presence of PMDETA (= (Me2NCH2CH2)2NMe) gives the title compound [(Sn(mu-PCy))3(Na x PMDETA)2] (1), containing an electron-deficient [(Sn(mu-PCy))]3(2-) dianion with a novel two-electron, three centre (2e-3c) bonding arrangement.     

ITQ-12: a new microporous silica polymorph potentially useful for light hydrocarbon separations

The new synthetic form of microporous crystalline silica, denoted as ITQ-12, shows a high potential for the separation of propane and propene from its mixtures.     

THE α-OXIDASE SYSTEM OF YOUNG PEA LEAVES (Pisum sativum) AS GENERATOR OF ELECTRONICALLY EXCITED STATES. EXCITATION IN THE DARK UNDER NATURAL CONDITIONS

Abstract. The aerobic oxidation of saturated long chain fatty acids to the lower aldehyde and CO₂ catalyzed by the α-oxidase system of young leaves from germinating Pisum sativum results in concomitant excitation of the chloroplasts or/and fractions present in the α-oxidase preparation. The excitation is attested to by both chlorophyll emission and Hill activity. This is the first case of photobiochemistry without light within a natural system.