Synthesis and pro-apoptotic activity of novel glycyrrhetinic acid derivatives

Triterpenoids are used for medicinal purposes in many countries. Some, such as oleanolic and glycyrrhetinic acids, are known to be anti-inflammatory and anticarcinogenic. However, the biological activities of these naturally occurring molecules against their particular targets are weak, so the synthesis of new synthetic analogues with enhanced potency is needed. By combining modifications to both the A and C rings of 18βH-glycyrrhetinic acid, the novel synthetic derivative methyl 2-cyano-3,12-dioxo-18βH-olean-9(11),1(2)-dien-30-oate was obtained. This derivative displays high antiproliferative activity in cancer cells, including a cell line with a multidrug-resistance phenotype. It causes cell death by inducing the intrinsic caspase-dependent apoptotic pathway.     

Regulation of Phosphatidic Acid Levels in <Emphasis Type="Italic">Trypanosoma cruzi</Emphasis>

Lipid kinases and phosphatases play essential roles in signal transduction processes involved in cytoskeletal rearrangement, membrane trafficking, and cellular differentiation. Phosphatidic acid (PtdOH) is an important mediator lipid in eukaryotic cells, but little is known regarding its regulation in the parasite Trypanosoma cruzi, an agent of Chagas disease. In order to clarify the relationship between PtdOH metabolism and developmental stages of T. cruzi, epimastigotes in culture were subjected to hyperosmotic stress (~1,000 mOsm/L), mimicking the environment in the rectum of vector triatomine bugs. These experimental conditions resulted in differentiation to an intermediate form between epimastigotes and trypomastigotes. Morphological changes of epimastigotes were correlated with an increase in PtdOH mass accomplished by increased enzyme activity of diacylglycerol kinase (DAGK, E.C. 2.7.1.107) and concomitant decreased activity of phosphatidate phosphatases type 1 and type 2 (PAP1, PAP2, E.C. 3.1.3.4). Our results indicate progressive increases of PtdOH levels during the differentiation process, and suggest that the regulation of PtdOH metabolism is an important mechanism in the transition from T. cruzi epimastigote to intermediate form.     

The Cost Evaluation of Advanced Oxidation Processes in Laboratory and Pilot-Scale Experiments

The present level of the development of water/wastewater treatment methods, including advanced oxidation processes, allows removal of pollutants of wide spectrum under no question. However, the overall process cost and, especially, associated energy consumption are of increased importance. The present review presents the energy cost calculations made for the pollutants removal reported in more than forty publications for over the last four decades. Phenol, glycols, methyl-tert-butyl ether (MTBE), aliphatic unsaturated compounds, humic acids and lignin were considered as water pollutants for economic evaluation of their removal. Two oxidation processes, ozonation and Fenton reaction, were chosen as water treatment methods.     

Synthesis of cross‐linked polyethylene oxide‐acetal macrocycles for solid superbase catalysts

A novel long‐chain divinyl ether of tris(diethyleneglycol)‐bisacetal, has been synthesized by electrophilic addition of one molecule of diethylene glycol to two molecules of divinyl ether of diethylene glycol (DVDEG) in the presence of CF₃COOH in quantitative yield. The monomer was cationically polymerized (BF₃·OEt₂, or complex LiBF₄·MeO(CH₂)₂OMe) and copolymerized with DVDEG to deliver solid polymers the yields being 80–100%. The polymers represent the cross‐linked polyether‐polyacetal structures comprising macrocycles. The polymers were treated with 3% solution of KOH or CsOH in methanol to afford solid superbase complexes of KOH (CsOH) with cross‐linked polyether‐polyacetal macrocyclic networks. Preliminary tests have shown the complexes to be active catalysts for ethynylation of acetones and prototropic isomerization of methyl propargyl ethers to allenyl methyl ethers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Experimental and modelling of supercritical oil extraction from rapeseeds and sunflower seeds

The supercritical oil extraction from oleaginous seeds (sunflower and rapeseeds) is presented here through experimental and modelling results. The experimental setup allows an accurate following of the mass of the oil extracted and to derive the experimental influences of pressure, temperature and supercritical CO₂ flowrate on the extraction curves. These parameters are very sensitive and highlight the necessity of precise optimisation of experimental conditions. In order to complete the behaviour of supercritical fluids extraction, an improved modelling is proposed. The modelling basic equations are based on others modelling published previously. In this work, the determination of several parameters comes from correlations and the other constants are fitted with all the experimental results. Thus the modelling is more representative and predictive as other ones. The modelling results present a good agreement with the experimental results, and hence it can be used for the dimensioning of some extraction autoclaves.     

Growth of single-walled carbon nanotubes with controlled diameters and lengths by an aerosol method

On the basis of combined study of the transmission electron microscopy, scanning electron microscopy, Raman spectroscopy and ultraviolet–visible–near infrared absorption spectroscopy, the properties of the single-walled carbon nanotubes (SWCNTs), synthesized by aerosol (floating catalyst) chemical vapor deposition method by ferrocene vapor decomposition in the presence of carbon monoxide, are studied in details. The results show that increasing the temperature gives rise to the formation of high quality and large diameter SWCNTs. By monitoring the water-cooled probe position, both the bundle length and the diameter of the SWCNTs are effectively tuned due to the variation of the residence time and temperature profile in the reactor. An introduction of a small amount of CO₂ suppresses the growth of small diameter nanotubes and enlarges the mean diameter of SWCNT samples. The mean diameter of SWCNTs could be easily altered in a broad range from 1.1 to 1.9 nm during growth, which is essential for the SWCNT applications in optical and electronic devices.     

Phosphorus‐containing soybean‐oil copolymers: Cross‐metathesis of fatty acid derivatives as an alternative to phosphorus‐containing reactive flame retardants

Two different approaches to the creation of phosphorus‐containing soybean‐oil copolymers were investigated. First, two phosphorus‐containing styrene (ST) derivatives, diphenyl styryl phosphine oxide and dimethyl‐p‐vinylbenzylphosphonate (STP2), where tested as comonomers in the cationic copolymerization of soybean oil (SOY), ST, and divinylbenzene (DVB), to obtain heterogeneous systems in all cases. To overcome this drawback, the cross‐metathesis reaction of methyl 10‐undecenoate and STP2 was carried out to link the phosphorus moiety to the vegetable‐oil derivative. This second approach permitted the synthesis of a new reactive phosphorus‐containing plant‐oil derivative, which was incorporated into the soybean oil, ST, and DVB system. The cationic copolymerization was investigated, and the structure, thermal stability, and mechanical and flame‐retardant properties of the resulting copolymers were studied. Thermosets with moderate glass‐transition temperatures were obtained; this showed that the cross‐metathesis reaction is a convenient way to produce oil‐compatible monomers able to undergo homogeneous polymerization reactions. The resulting thermosets with 1% phosphorus had limiting oxygen index values about 24.0; this indicated an improvement in the fire‐retardant properties of the soybean‐oil‐based copolymers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Diaminofuroxan: Synthetic Approaches and Computer‐Aided Study of Thermodynamic Stability

Different approaches to synthesize diaminofuroxan are presented herein. Mathematical and quantum chemical methods were used to study the possible reasons for failures in the syntheses of diaminofuroxan. Additionally, structural isomers of this compound were generated. With the help of the results of quantum chemical calculations at levels of DFT B3LYP 6‐31G(d) and MP2 6‐31G(d), screening of the most stable isomeric forms in the gaseous phase and in water was performed. It was shown that diaminofuroxan is not the thermodynamically most stable isomer among its structural analogues.     

Renewable polybenzoxazines based in diphenolic acid

The reaction of mixtures of renewable diphenolic acid (DPA) and its methylesterbenzoxazine derivative (MDP-Bz) has been studied. The DPA was introduced to lower the high temperature needed to complete the curing of the pure benzoxazine. In this way, samples with different DPA/MDP-Bz ratio (0, 2, 5, 10 and 25% of DPA) were investigated. Moreover, high performance flame retardant thermosetting resins with phosphorus were prepared through the mixture of MDP-Bz and a DPA-phosphazene derivative (DPA-PPZ). The curing behavior of these materials was studied by differential scanning calorimetry (DSC). Finally, the properties of the materials were evaluated by termogravimetric analysis (TGA), dynamic mechanical analysis (DMTA), tensile measurements, limiting oxygen index (LOI) and UL-94 Burn Test.     

Styrene-butadiene branched star-shaped asphalt modifiers: Synthesis and mechanical characterization

Abstract

The synthesis and the corresponding characterization of styrene-butadiene (SB), branched, star-shaped copolymers was investigated as part of a research project on asphalt modification using polymers with precise molecular structures. The method of anionic polymerization was followed to prepare samples of block copolymers of SB, a synthesis method that controls chain-architecture, molecular weight distribution, monomer distribution, and the average molecular weight. The research studies are the synthesis of block copolymers including linear, three- and four-arms constructs, depending on the coupling agent used. The techniques of nuclear magnetic resonance (1NMR), differential scanning calorimetry (DSC), gel permeation chromatography (GPC), and rheology were carried out to characterize the copolymers. From the results of the 1NMR, DSC, and GPC analyses, all star-shaped copolymers investigated showed a similar block copolymer composition. Furthermore, the rheological behavior of one of the synthesized star-shaped copolymers was nearly the same as a four-branched commercial copolymer. Rheologically, the four-arm block copolymer sample had the largest storage modulus (G′) among the branched copolymers synthetized, indicating that such architecture produces a highly structured material. In regard to polymer-modified asphalt formulations, the three-branched copolymer architecture yielded better elastic behavior than the four-branch version. In summary, the findings of this investigation provide new insight about a polymer system that may offer advantages in industrial asphalt paving applications.