Precise Synthesis and Thin Film Self-Assembly of PLLA-b-PS Bottlebrush Block Copolymers

The ability of bottlebrush block copolymers (BBCPs) to self-assemble into ordered large periodic structures could greatly expand the scope of photonic and membrane technologies. In this paper, we describe a two-step synthesis of poly(l-lactide)-b-polystyrene (PLLA-b-PS) BBCPs and their rapid thin-film self-assembly. PLLA chains were grown from exo-5-norbornene-2-methanol via ring-opening polymerization (ROP) of l-lactide to produce norbornene-terminated PLLA. Norbonene-terminated PS was prepared using anionic polymerization followed by a termination reaction with exo-5-norbornene-2-carbonyl chloride. PLLA-b-PS BBCPs were prepared from these two norbornenyl macromonomers by a one-pot sequential ring opening metathesis polymerization (ROMP). PLLA-b-PS BBCPs thin-films exhibited cylindrical and lamellar morphologies depending on the relative block volume fractions, with domain sizes of 46–58 nm and periodicities of 70–102 nm. Additionally, nanoporous templates were produced by the selective etching of PLLA blocks from ordered structures. The findings described in this work provide further insight into the controlled synthesis of BBCPs leading to various possible morphologies for applications requiring large periodicities. Moreover, the rapid thin film patterning strategy demonstrated (>5 min) highlights the advantages of using PLLA-b-PS BBCP materials beyond their linear BCP analogues in terms of both dimensions achievable and reduced processing time.     

Simple and efficient cleavage reaction of the boc group in heterocyclic compounds

Dedicated to the memory of Pr. Ladjama Daif A series of chiral cyclosulfamides have been synthesized by alkaline cyclisation starting from N‐benzoylamino acids (Ala, Val, Leu, Phe) derivatives and chlorosulfonyl isocyanate. A simplified and regioselective deprotection of the cyclic compounds (cyclosulfamides) containing the tert‐butyloxycarbonyl group (Boc) has been achieved in good yield by fusion under reduced pressure.     

DTA and X-ray diffraction investigations of laser-irradiated CeO2 powders

The TG and DTA curves and diffractograms of powdered CeO₂ samples irradiated with a CO₂ laser beam with powers of 0.41–1.39 kW/cm² are presented. The laser treatment induced structural changes and probably generation of a metastable phase. X-ray diffraction coupled with thermal analysis was used to establish the structural modifications in the irradiated samples after heating.     

Oxidative deamination of benzylamine by electrogenerated quinonoid systems as mimics of amine oxidoreductases cofactors

The reactions of a new type of quinonoid system with benzylamine have been investigated in methanol in order to mimic the reactions occurring in the course of the enzymatic oxidation of amines by quinone cofactors. Under strictly anaerobic conditions, unstable quinonoid species 1(ox)()-4(ox)() have been selectively electrogenerated using anodic-controlled potential electrolysis. Thus, we have demonstrated that 3,4-quinone 1(ox)() is incapable of deaminating benzylamine, while 3,4-iminoquinone species 3(ox)() and 4(ox)() act as efficient catalysts for the autorecycling oxidation of benzylamine: the reaction efficiency reached 64 turnovers. Additional mechanistic investigations reveal that the oxidation of benzylamine by our quinonoid model cofactors proceeds unambiguously via a transamination mechanism, as suggested for many enzymatic systems.     

Thermal studies of pre-formulates of metronidazole obtained by spray drying technique

Compatibility studies between active drugs and excipients are substantial in the pharmaceutical technology. The objective of the present work was to develop pre-formulated mixtures of metronidazole (MT) obtained by spray drying (SPDR) and their thermoanalytical characterization. Dynamic and isothermal TG, conventional DSC and DSC coupled to a photovisual system were used. DSC experiments with both techniques confirmed the homogeneity of the conventional and pre-formulated mixtures. The TG data made possible the comparison the thermal stability of the different mixtures. Similar thermal stabilities were found of the conventional and pre-formulated mixtures, with slower particles sizes of MT.     

Aldol condensations over reconstructed Mg-Al hydrotalcites: structure-activity relationships related to the rehydration method

Two different rehydration procedures in the liquid or gas phase have been applied to reconstruct mixed oxides derived from calcined hydrotalcite-like materials to be used as catalysts for aldol condensation reactions. The as-synthesized hydrotalcite, its decomposition product, as well as the reconstructed solids upon rehydration were characterized by XRD, N(2) adsorption, He pycnometry, FTIR, SEM, TEM, (27)Al MAS-NMR and CO(2)-TPD (TPD=temperature-programmed desorption). Compared to the Mg-Al mixed oxide rehydrated in the gas phase (HT-rg), that rehydrated in the liquid phase (HT-rl) exhibits a superior catalytic performance with respect to the aldol condensation of citral with ketones to yield pseudoionones and in the self-aldolization of acetone. The textural properties of HT-rl and HT-rg differ strongly and determine the catalytic behavior. A memory effect led to a higher degree of reconstruction of the lamellar structure when the mixed oxide was rehydrated in the gas phase rather than in the liquid phase, although liquid-phase rehydration under fast stirring produced a surface area that was 26 times greater. This contrasts to typical statements in the literature claiming a higher degree of reconstruction in the presence of large amounts of water in the medium. CO(2)-TPD shows that the number of OH(-) groups and their nature are very similar in HT-rg and HT-rl, and cannot explain the markedly different catalytic behavior. Accordingly, only a small fraction of the available basic sites in the rehydrated samples is active in liquid-phase aldol condensations. Our results support the model in which only basic sites near the edges of the hydrotalcite platelets are partaking in aldol reactions. Based on this, reconstructed materials with small crystallites (produced by exfoliation during mechanical stirring), that is, possessing a high external surface area, are beneficial in the reactions compared to larger crystals with a high degree of intraplatelet porosity.     

Production of antitumoral retamycin during fed-batch fermentations of Streptomyces olindensis

Fed-batch runs were performed in order to correlate the production of retamycin, an anthracycline antibiotic produced by Streptomyces olindensis in submerged cultures, with the specific growth rate. Maximum retamycin production was achieved with an exponential feed rate, controlling the specific growth rate at a low value (0.03 h-1, about 10% of the maximum specific growth rate). Control of the specific growth rate at higher values (0.10 and 0.17 h-1) caused a decrease in antibiotic production. Morphology, assessed by image analysis, was shown to be highly relevant in this process. Cell growth mainly in the form of clumps (90% clumps and 10% free filaments) led to better results than growth as clumps (75%) and free filaments (25%).     

Studies of the reaction of substituted 1,2-dithiole-3-thiones and -3-ones with sodium cyanide in acetonitrile

The reactions of substituted 1,2-dithiole-3-thiones and -3-ones with sodium cyanide, in acetonitrile, afford convenient routes to indolizine, pyrrolo[1,2-a]pyrazine and 4H-1,3-thiazin-4-one species.     

Preliminary characterization of anhydrous ethanol used in Brazil as automotive fuel

This work reports preliminary studies on the characterisation of anhydrous ethanol (AEA) used as an automotive fuel mixed with gasoline in Porto Alegre (South Brazil). Pre-concentration of the impurities contained in 1000 ml of AEA was carried on through solid-phase extraction using XAD4 resin. The main compounds in the extract were identified by means of spectral data from the library of the equipment. The concentrate was then fractionated using a preparative liquid chromatographic column filled with activated silica gel and the elution procedure was carried out with, n-hexane, n-hexane-benzene (1:1, v/v) and dichloromethane. Prior to analysis by GC-MS, each fraction was reduced to 1 ml with a gentle stream of nitrogen. Saturated linear hydrocarbons and aromatic hydrocarbons eluted in the first fraction and oxygenated compounds such as aldehydes. ketones and alcohols, eluted in the second one. were the main compounds detected in the sample.