Properties of poly(ethylene terephthalate)–poly(ethylene naphthalene 2,6‐dicarboxylate) blends with montmorillonite clay

The production and properties of blends of poly(ethylene terephthalate) (PET) and poly(ethylene naphthalene 2,6‐dicarboxylate) (PEN) with three modified clays are reported. Octadecylammonium chloride and maleic anhydride (MAH) are used to modify the surface of the montmorillonite–Na⁺ clay particles (clay–Na⁺) to produce clay–C18 and clay–MAH, respectively, before they are mixed with the PET/PEN system. The transesterification degree, hydrophobicity and the effect of the clays on the mechanical, rheological and thermal properties are analysed. The PET–PEN/clay–C18 system does not show any improvements in the mechanical properties, which is attributed to poor exfoliation. On the other hand, in the PET–PEN/clay–MAH blends, the modified clay restricts crystallization of the matrix, as evidenced in the low value of the crystallization enthalpy. The process‐induced PET–PEN transesterification reaction is affected by the clay particles. Clay–C18 induces the largest proportion of naphthalate–ethylene–terephthalate (NET) blocks, as opposed to clay–Na⁺ which renders the lowest proportion. The clay readily incorporates in the bulk polymer, but receding contact‐angle measurements reveal a small influence of the particles on the surface properties of the sample. The clay–Na⁺ blend shows a predominant solid‐like behaviour, as evidenced by the magnitude of the storage modulus in the low‐frequency range, which reflects a high entanglement density and a substantial degree of polymer–particle interactions. Copyright © 2005 Society of Chemical Industry     

Comparison between the binding of chlorpheniramine maleate to poly(sodium 4-styrenesulfonate) and the binding to other polyelectrolytes

The interactions of the antihistaminic drug chlorpheniramine maleate (CPM) with the negatively charged polyelectrolytes poly(sodium 4-styrenesulfonate) (PSS) and poly(acrylic acid) (PAA) are studied by the washing method of the diafiltration technique at conditions simulating those of the small intestine such as pH 7.5 and 0.13 M NaCl. The results are compared with those already reported involving other pharmacologically important polyelectrolytes such as alginic acid (ALG), carboxymethylcellulose (CMC), and κ- and ι-carrageenan (κ- and ι-CAR). As in the case of ALG, CMC, and CAR, interactions of CPM with PAA appear to be electrostatic and are cleaved in the presence of 0.13 M NaCl. On the contrary, apart from electrostatic interactions, additional interactions are found with PSS and residual interactions are kept in the presence of 0.13 M NaCl, a fact that may be attributed to π-π interactions and hydrophobic forces. The effect of the addition of 4 M urea, branched poly(ethyleneimine) (BPEI), and poly(vinylpyrrolidone) (PVP) is also studied. The addition of urea 4 M or 0.001 M BPEI produces a decrease on the amounts of counterions bound to PSS at infinite elution, while the addition of PVP does not produce any change on the diafiltration profiles.     

Polymerization of ionic monomers in polar solvents: kinetics and mechanism of the free radical copolymerization of acrylamide/acrylic acid

A precise data set describing the kinetics of the free radical copolymerization of acrylamide/acrylic acid (AM/AA) in the range of low total monomer concentration as a function of the pH, total monomer concentration, initiator concentration, and comonomer ratio is presented. Strong impact on the reactivity ratios has been identified for the pH and total monomer concentration. Specifically, at constant total monomer concentration of 0.4 mol/l and T=313 K the reactivity ratio of AM increases from 0.54 at pH 1.8 to 3.04 at pH 12. Contrarily, the reactivity ratio of AA decreases from 1.48 to 0.32. The crossover occurs at pH≈4.2. Electrostatic effects due to the variation of the degree of ionization of AA are primarily suggested to influence the kinetics. When the total monomer concentration increases from 0.2 to 0.6 mol/l at constant pH=12, the reactivity ratios of AM and AA decrease from 4.01 to 2.13 and increase from 0.25 to 0.47, respectively. Reduction of electrostatic repulsion between the ionized monomer AA and partially charged growing polymer chain ends due to higher ionic strength at higher total monomer concentration serves as explanation of the effect. The precise data set is the prerequisite for a novel approach to calculate copolymer compositions in case of variable monomer reactivity.     

Electrochemical study of 7α,12,20-O-trimethyl-conacytone in acetonitrile

An electrochemical study of the electroreduction in anhydrous acetonitrile of 7α,12,20-O-trimethyl-conacytone, an abietane quinoid diterpene derivative from the natural product 7α-O-methyl-conacytone, showed two reduction signals. At the first reduction step, fast chemical reactions involving the loss of the methoxyl group located at C-7 with simultaneous regeneration of the quinoid moiety were observed. This electrogenerated quinone is reduced again, at the same potential used with the former quinone, resulting in a two-electron peak. These results were obtained by cyclic voltammetry and double-step chronoamperometry experiments. The electrolysis under methylating conditions of 7α-O-methyl-conacytone, at potential values of the second electron transfer, generates as major products, methoxy-hydroquinone, where the methoxy group at C-7 is lost, which is in agreement with the proposed mechanism. Therefore, the second reduction signal was attributed to the reduction of semiquinone intermediates by a mechanism not elucidated.     

Degradation of lincomycin in aqueous medium: Coupling of solar photocatalysis and membrane separation

The photocatalytic oxidation of a common antibiotic, the lincomycin was carried out in aqueous suspensions of polycrystalline TiO₂ Degussa P25 irradiated by sunlight. In order to improve the performance of the lincomycin degradation a hybrid system consisting of a solar photoreactor with the photocatalyst in suspension coupled with a membrane module, used to confine both photocatalyst and pollutants in the reaction environment, was tested.A preliminary study was carried out in order to determine some kinetics parameters of the drug photodegradation. The influence of initial substrate concentration on the lincomycin photooxidation rate was investigated. The photooxidation rate follows a pseudo-first order kinetics with respect to the lincomycin concentration under the used experimental conditions. The presence of the membrane reactor allows the catalyst separation and to operate in continuous mode as the membranes rejection for lincomycin and its oxidation products was quite high.     

Infrared absorption in Li-intercalated tungsten oxide

Thin films of amorphous and polycrystalline tungsten oxide were produced by reactive dc magnetron sputtering and nanocrystalline films were deposited by advanced gas evaporation. The films were submitted to electrochemical intercalation of Li ions before infrared reflectance measurements were carried out. For crystalline films, the reflectance in the wavelength region 10–30 μm increases upon intercalation, indicating an increasing free-electron contribution. On the other hand, all the films display an increased absorption at wavelengths less than 10 μm when intercalated. The thermal emittance could be varied from about 0.5 to 0.7–0.75 by intercalation in films with thicknesses in excess of 1 μm. Both absorption and interference contribute to the emittance contrast.     

Ivabradine Induces Cardiac Protection against Myocardial Infarction by Preventing Cyclophilin-A Secretion in Pigs under Coronary Ischemia/Reperfusion

In response to cardiac ischemia/reperfusion, proteolysis mediated by extracellular matrix metalloproteinase inducer (EMMPRIN) and its secreted ligand cyclophilin-A (CyPA) significantly contributes to cardiac injury and necrosis. Here, we aimed to investigate if, in addition to the effect on the funny current (I(f)), Ivabradine may also play a role against cardiac necrosis by reducing EMMPRIN/CyPA-mediated cardiac inflammation. In a porcine model of cardiac ischemia/reperfusion (IR), we found that administration of 0.3 mg/kg Ivabradine significantly improved cardiac function and reduced cardiac necrosis by day 7 after IR, detecting a significant increase in cardiac CyPA in the necrotic compared to the risk areas, which was inversely correlated with the levels of circulating CyPA detected in plasma samples from the same subjects. In testing whether Ivabradine may regulate the levels of CyPA, no changes in tissue CyPA were found in healthy pigs treated with 0.3 mg/kg Ivabradine, but interestingly, when analyzing the complex EMMPRIN/CyPA, rather high glycosylated EMMPRIN, which is required for EMMPRIN-mediated matrix metalloproteinase (MMP) activation and increased CyPA bonding to low-glycosylated forms of EMMPRIN were detected by day 7 after IR in pigs treated with Ivabradine. To study the mechanism by which Ivabradine may prevent secretion of CyPA, we first found that Ivabradine was time-dependent in inhibiting co-localization of CyPA with the granule exocytosis marker vesicle-associated membrane protein 1 (VAMP1). However, Ivabradine had no effect on mRNA expression nor in the proteasome and lysosome degradation of CyPA. In conclusion, our results point toward CyPA, its ligand EMMPRIN, and the complex CyPA/EMMPRIN as important targets of Ivabradine in cardiac protection against IR.     

Insoluble Vascular Amyloid Deposits Trigger Disruption of the Neurovascular Unit in Alzheimer’s Disease Brains

Alzheimer’s disease (AD) is a neurodegenerative disease, characterized histopathologically by intra-neuronal tau-related lesions and by the accumulation of amyloid β-peptide (Aβ) in the brain parenchyma and around cerebral blood vessels. According to the vascular hypothesis of AD, an alteration in the neurovascular unit (NVU) could lead to Aβ vascular accumulation and promote neuronal dysfunction, accelerating neurodegeneration and dementia. To date, the effects of insoluble vascular Aβ deposits on the NVU and the blood–brain barrier (BBB) are unknown. In this study, we analyze different Aβ species and their association with the cells that make up the NVU. We evaluated post-mortem AD brain tissue. Multiple immunofluorescence assays were performed against different species of Aβ and the main elements that constitute the NVU. Our results showed that there are insoluble vascular deposits of both full-length and truncated Aβ species. Besides, insoluble aggregates are associated with a decrease in the phenotype of the cellular components that constitute the NVU and with BBB disruption. This approach could help identify new therapeutic targets against key molecules and receptors in the NVU that can prevent the accumulation of vascular fibrillar Aβ in AD.     

Microencapsulated Bifidobacterium bifidum and Lactobacillus gasseri in Combination with Quercetin Inhibit Colorectal Cancer Development in ApcMin/+ Mice

Recent studies have suggested that flavonoids such as quercetin and probiotics such as Bifidobacterium bifidum (Bf) and Lactobacillus gasseri (Lg) could play a relevant role in inhibiting colon cancer cell growth. Our study investigated the role of dietary supplementation with microencapsulated probiotics (Bf and Lg) along with quercetin in the development of mouse colorectal cancer (CRC). Methods: Adenomatous polyposis coli/multiple intestinal neoplasia (Apc^Min/+) mice were fed a standard diet or the same diet supplemented with microencapsulated probiotics (Bf and Lg strains, 10⁷ CFU/100 g food) or both probiotics strains plus microencapsulated quercetin (15 mg/100 g food) for 73 days. Changes in body and organ weights, energy metabolism, intestinal microbiota, and colon tissue were determined. The expression of genes related to the Wnt pathway was also analyzed in colon samples. Results: Dietary supplementation with microencapsulated probiotics or microencapsulated probiotics plus quercetin reduced body weight loss and intestinal bleeding in Apc^Min/+ mice. An improvement in energy expenditure was observed after 8 weeks but not after 10 weeks of treatment. A supplemented diet with microencapsulated Bf and Lg reduced the number of aberrant crypt foci (ACF) and adenomas by 45% and 60%, respectively, whereas the supplementation with Bf, Lg and quercetin decreased the number of ACF and adenomas by 57% and 80%, respectively. Microencapsulated Bf and Lg in combination with quercetin could exert inhibition of the canonical Wnt/β-catenin signaling pathway in the colon of Apc^Min/+ mice Conclusions: The administration of microencapsulated Bf and Lg, individually or in combination with quercetin, inhibits the CRC development in Apc^Min/+ mice.     

Modelling the effects of human papillomavirus in cervical cells

Worldwide, cervical cancer is the second most common cancer in women, after breast cancer. The prevalence of this malignant disease is estimated at 1.4 million cases worldwide, causing about 290,000 deaths and 500,000 new cases per year, of which 80% correspond to women living in developing countries. In this work we propose a family of ordered models for basal cells of the cervix corresponding to different stages ranging from normal cells to the formation of precancerous lesions. We analyse the first member of the family analytically and for the second member we developed a non-standard numerical method in order to extract some biological information.