Neue 1,5-benzodiazepinderivate

The 1,5-benzodiazepines 1,6 add benzoylphenylketene ( 3 ) across the azomethine bond to produce the 1,3-oxazino[3,2-a]-1,5-benzodiazepines 4,5,7. In 6a azo coupling occurs at the exocyclic methyl group leading to the formation of 10 , while diazo group transfer takes place at the cyclic methylene group to afford 11. The latter compounds react with 3 without loss of the diazo nitrogen, yielding the diazo-oxazinobenzodiazepine 12 ; whereas, by interaction with phenyl isocyanate, the pyrazolo[4,3-b]-1,5-benzodiazepine 14 is formed.     

Sucrose-Branched Polymer Synthesized by Protease from Bacillus Subtilis

Summary: Vinyl sugar ester, 1′-O-vinyladipoyl-sucrose, was synthesized using sucrose and DVA (divinyl adipate) in organic medium (dimethylformamide), catalyzed by protease from Bacillus subtilis. Several reaction conditions were examined by means of qualitative analysis (TLC). The monomer obtained has undergone chemical polymerization with potassium persulfate and hydrogen peroxide to produce an amphiphilic polymer having sugar branches. The monomer was characterized by ¹³C-NMR and FTIR spectra. The IR analysis confirmed the synthesis of the poly (1′-O-vinyladipoyl-sucrose).     

Effect of Clay/Diamond and Clay/Carbon Nanosystems on Structure-Properties Relationships of iPP

The effect of the addition of two combined fillers, smectite clay and diamond and smectite clay and carbon nanoparticles, on structure, morphology, isothermal and non isothermal crystallization behaviour, tensile and thermal properties of isotactic polypropylene (iPP) has been investigated by using several techniques: wide angle X-ray diffraction, optical and scanning electron microscopy, thermogravimetry, differential scanning calorimetry and tensile techniques. It was found that nanoparticles of diamond and carbon favour the nucleation of the β-form of iPP crystal, whereas the clay nanolayers do not have any influence on the crystal structure of iPP. The thermal stability of iPP/(clay+diamond) and iPP/(clay+carbon) is improved with respect to neat iPP, whereas no influence is detected when only clay is added to iPP. At the given crystallization conditions, the overall crystallization peak of iPP/(clay+diamond) almost exactly overlaps the crystallization peak of neat iPP, whereas in the case of iPP/clay and iPP/(clay+carbon) the maximum of the crystallization peaks is shifted to higher temperature. The spherulite growth rate, G values do not differ from one another. The iPP/(clay+carbon) system shows ductile behavior. The other systems show brittle behavior with failure before necking. These results were related with the very high percentage of beta phase present in the samples of iPP/(clay+carbon).     

Solution Properties of Partially Hydrolysed Polyacrylamide and Chitosan Mixed Solutions

Summary: In this paper, the properties of a partially hydrolysed polyacrylamide with a low charge density and chitosan mixtures were evaluated in an aqueous acid solution. The formation of a soluble complex was followed by conductometry and potentiometry, and the stoichiometry at the titration endpoint was investigated as a function of the polyanion added. The influence of salts on the titration endpoint and on the rheological behavior of the mixed solutions was also studied. The mixture of equal concentration of both polymers, in the absence of salt, presented synergy, with a significant viscosity increase. Nevertheless, in the presence of salts, this mixture presented minimum viscosity. These results were discussed as a function of the polymers structural features and the environment used in the study.     

Probing Molybdenum Active Sites during In Situ Photoreduction of the Mo6+/SiO2 Catalyst

The photoreduction of the Mo⁶⁺/SiO₂ system with CO was investigated in situ, employing a recently developed experimental setup allowing for the acquisition of transmission FT-IR spectra under simultaneous UV irradiation. Carbon monoxide, besides acting as a reducing agent in such processes, is also a useful probe molecule able to detect coordinatively unsaturated sites exposed on the surface. The unprecedented quality of the spectroscopic data, obtained as a function of the reduction time, allowed us to better rationalize the different mechanisms previously proposed for the photoreduction process. These results, coupled with UV-Vis spectroscopic data, shed light on the oxidation state and surface structure of supported molybdenum species, which are key active sites for several important reactions, such as selective oxidation, polymerization, hydrodesulfurization, epoxidation and olefin metathesis.     

New hybrids of clozapine and haloperidol and their isosteric analogues: synthesis,X-ray crystallography,conformational analysis and preliminary pharmacological evaluation

Schizophrenia is a debilitating mental disorder which affects approximately 1% of the world’s population. Clozapine is an atypical antipsychotic showing unmatched effectiveness in the control of treatment-resistant schizophrenia. Unlike typical antipsychotics, clozapine does not induce extrapyramidal side effects (EPS), tardive dyskinesia or elevate prolactin levels. However, clozapine can induce a potentially fatal blood disorder, agranulocytosis, in 1–2% of patients, severely limiting its clinical use. The model for antipsychotic activity under investigation is based on obtaining a clozapine-like profile with preferential dopamine D₄ and serotonin 5-HT_2A receptor affinity. Profiled herein are three unique members of a series of prospective antipsychotic agents. Compound (I) originated from the structural hybridization of the commercial therapeutics, clozapine and haloperidol, whilst compounds (II) and (III) possess an alternative tricyclic nucleus derived from JL13; a clozapine-like atypical antipsychotic developed by Liégeois et al. These compounds have been synthesized and characterized by means of elemental analysis, IR, ¹H and ¹³C-NMR spectroscopy, MS and X-ray diffraction. Compound (I) crystallizes in space group P(?1) with a = 10.5032(1), b = 10.6261(2), c = 12.6214(3) Å, α = 81.432(1)°, β = 83.292(1)°, γ = 61.604(1)°, Z = 2, V = 1223.62(4) Å³, C₂₈H₂₉ClN₄O, M _r = 473.00, D _c = 1.284 Mg/m³, μ = 0.185 mm^?1, F(000) = 500, R = 0.0506 and wR = 0.1304. Compound (II) crystallizes in the monoclinic space group P2₁/c with a = 10.8212(2), b = 9.3592(2), c = 22.9494(5) Å, β = 106.471(1)°, Z = 4, V = 2228.88(8) Å³, C₂₅H₂₅ClN₄O₂, M _r = 448.94, D _c = 1.338 Mg/m³, μ = 0.202 mm^?1, F(000) = 944, R = 0.0529 and wR = 0.1129. Compound (III) crystallizes in the monoclinic space group P2₁/c with a = 10.5174(2), b = 9.3112(2), c = 24.2949(5) Å, β = 98.666(1)°, Z = 4, V = 2352.03(8) Å³, C₂₅H₂₄Cl₂N₄O₂, M _r = 483.38, D _c = 1.365 Mg/m³, μ = 0.306 mm^?1, F(000) = 1008, R = 0.0478 and wR = 0.1067. The solid state conformations of (I), (II) and (III) exhibit the characteristic V-shaped buckled nature of the respective dibenzodiazepine and pyridobenzoxazepine nuclei with the central seven-membered heterocycle in a boat conformation. The molecules of (I) form a head-to-tail dimeric motif stabilized by hydrogen bonding. The results of a conformational analysis of compounds (I)–(III) investigating the effect of environment (in vacuo and aqueous solution) are presented. These analogues were tested for in vitro affinity for the dopamine D₄ and serotonin 5-HT_2A receptors and their comparative receptor binding profiles to clozapine and JL13 are reported.     

Interaction of small amounts of bovine serum albumin with phospholipid monolayers investigated by surface pressure and atomic force microscopy

The influence of small amounts of bovine serum albumin (BSA) (nM concentration) on the lateral organization of phospholipid monolayers at the air-water interface and transferred onto solid substrates as one-layer Langmuir-Blodgett (LB) films was investigated. The kinetics of adsorption of BSA onto the phospholipid monolayers was monitored with surface pressure isotherms in a Langmuir trough, for the zwitterionic dipalmitoylphosphatidyl ethanolamine (N,N-dimethyl-PE) and the anionic dimyristoylphosphatidic acid (DMPA). A monolayer of N,N-dimethyl-PE or DMPA incorporating BSA was transferred onto a solid substrate using the Langmuir-Blodgett technique. Atomic force microscopy (AFM) images of one-layer LB films displayed protein-phospholipid domains, whose morphology was characterized using dynamic scaling theories to calculate roughness exponents. For DMPA-BSA films the surface is characteristic of self-affine fractals, which may be described with the Kardar-Parisi-Zhang (KPZ) equation. On the other hand, for N,N-dimethyl-PE-BSA films, the results indicate a relatively flat surface within the globule. The height profile and the number and size of globules varied with the type of phospholipid. The overall results, from kinetics of adsorption on Langmuir monolayers and surface morphology in LB films, could be interpreted in terms of the higher affinity of BSA to the anionic DMPA than to the zwitterionic N,N-dimethyl-PE. Furthermore, the effects from such small amounts of BSA in the monolayer point to a cooperative response of DMPA and N,N-dimethyl-PE monolayers to the protein.     

Cross‐linking emulsion copolymerization of butyl acrylate with diallyl maleate

The emulsion copolymerization of butyl acrylate (BA) with a trifunctional cross‐linker, diallyl maleate (DAM), was investigated. The effect of the monomer feeding time and the amount of cross‐linker on the microstructural properties (branching, cross‐linking, gel formation, and sol MWD) of the seeded semicontinuous emulsion copolymerization of BA with DAM was investigated. It was found that the gel content was not significantly affected by increasing feeding time, but the level of quaternary carbons (an indication of the branching density) increased. On the other hand, increasing the amount of DAM in the feed composition caused gel content, level of quaternary carbons, and the cross‐linking density to increase. Interestingly, the level of quaternary carbons and the cross‐linking density sharply increased during the cooking period. The molecular weight of the sol decreased as DAM increased in the feed. In addition, the effect of process type, batch versus semibatch, was also considered and important differences in the level of quaternary carbons, cross‐linking, and gel content were found. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4684–4694, 2005     

Fluorescent cyclodextrins bearing metal binding sites and their use for chemo- and enantioselective sensing of amino acid derivatives

Ditopic receptors based on cyclodextrins bearing a metal binding site were used as enantioselective fluorescence sensors, which were able to generate different responses in the presence of d- or l-amino acids. The performances of the selectors as a function of their structure were evaluated, and the same analysis was extended to other analytes. In this work, this approach is used for the enantiomers of a series of amino acid derivatives and in particular of 2-aminocaprolactam. The results showed that the ability of these sensors to perform enantiomeric analysis can be extended to other analytes of interest in organic synthesis such as amino acid amides and α-aminolactams.