Study of the compositional heterogeneity of ethylene/1–hexene copolymers produced over supported catalysts of different composition

Separation into narrow MWD fractions (liquid–liquid fractionation) and preparative TREF (temperature rising elution fractionation) with subsequent analysis of fractions by GPC, FTIR, and ¹³C NMR spectroscopy were used to study the comonomer distribution of ethylene/1–hexene copolymers produced over highly active supported titanium‐ and vanadium‐magnesium catalysts (TMC and VMC) and a supported zirconocene catalyst. These catalysts produce PE with different MWD: M_w/M_n values vary from 2.9 for zirconocene catalyst, 4.0 for TMC, and 15 for VMC. 1‐Hexene increases polydispersity to 25 for copolymer produced over VMC and hardly affects MWD of the copolymer produced over TMC and zirconocene catalysts. The most broad short chain branching distribution (SCBD) was found for ethylene/1–hexene copolymers produced over TMC. VMC and supported zirconocene catalyst produce copolymers with uniform profile of SCB content vs. molecular weight in spite of great differences in M_w/M_n values (22 and 2.5 respectively). TREF data showed that majority of copolymer produced over supported zirconocene catalyst was eluted at 70–90°C (about 85 wt %). In the case of VMC copolymer's fractions were eluted in the broad temperature interval (40–100°C). Accordingly, TREF data indicate a more homogeneous SCBD in copolymer, produced over supported zirconocene catalyst. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Copolymerization of ethylene with α-olefins over supported titanium–magnesium catalysts. II. Comonomer as a chain transfer agent

The data on the effect of comonomer (propylene and 1-hexene) on molecular weight (M_w), molecular weight distribution (MWD), and content of terminal double bonds were obtained for ethylene/α-olefin copolymers produced over a supported titanium–magnesium catalyst (TMC) upon polymerization in the absence of hydrogen. The experimental data on the effect of comonomer concentration on M_w of polymers were used to calculate the ratios between the effective rate constants of chain transfer with monomer and the propagation rate constant. It was shown that the effective rate constant of chain transfer with monomers increases in the row of monomers: ethylene < 1-hexene < propylene. Meanwhile, the data on the effect of copolymers on content of terminal double bonds of various types demonstrate that different reactions of chain transfer with comonomer may simultaneously occur during copolymerization. It results in simultaneous formation of terminal vinylidene and trans-vinylene bonds. Therefore, the calculated rate constants of chain transfer with comonomer are complex values, which include the rate constants of chain transfer with comonomer occurring via different mechanisms. The data on MWD, short chain branching (SCB) and terminal double bonds content of different types were obtained by molecular weight fractionation of copolymers followed by the analysis of narrow fractions. The analysis of the data on MWDs of SCB and terminal double bonds shows that active sites of the TMC are considerably heterogeneous with respect to the rates of different chain transfer reactions with monomers. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Polymers of intrinsic microporosity (PIMs) substituted with methyl tetrazole

A polymer of intrinsic microporosity (PIM-1) containing nitrile groups was reacted by [2 + 3] cycloaddition reaction to give a polymer substituted with tetrazole groups (TZ-PIM), and then was further methylated to give a new PIM substituted with methyl tetrazole groups (MTZ-PIM). In contrast to TZ-PIMs, the MTZ-PIMs had distinctly improved solubility characteristics, enabling a more detailed investigation of the degree of conversion for the cycloaddition reaction and the structures of TZ-PIMs, which showed the presence of two kinds of tetrazole rings. Compared with PIM-1, the MTZ-PIM showed higher gas permselectivity with a corresponding decrease in gas permeability for pure gas pairs such as O₂/N₂ and CO₂/N₂, and for mixed gases, such as CO₂/N₂. Data for selectivity coupled with high gas permeability is close to the Robeson 2008 upper-bound performance limit for the O₂/N₂ and CO₂/N₂ pure gas pairs, and exceeds the upper-bound for the CO₂/N₂ mixed gas pair.     

Study on polybenzoxazinone membrane in pervaporation processes

Poly(benz‐3,1‐oxazinone‐4) was prepared by thermal cyclization of its hydrolytically stable precursor polyamic acid. Both polymer and its precursor were investigated as membrane materials. Thermogravimetric analysis and contact angle measurements were carried out for characterization of peculiarity of membrane compositions and analysis of membrane surface. Pervaporation of water–isopropanol mixture was studied in the wide range of feed composition. To interpret the pervaporation transport properties of the membranes, swelling experiments were performed, kinetic curves of sorption and desorption were plotted, and basic sorption and diffusion parameters were analyzed. It was established that poly(benz‐3,1‐oxazinone‐4) membrane is extremely effective in dehydration of water–isopropanol mixture and shows high separation factor. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4024–4031, 2013     

Signaling Role of Mitochondrial Enzymes and Ultrastructure in the Formation of Molecular Mechanisms of Adaptation to Hypoxia

This study was the first comprehensive investigation of the dependence of mitochondrial enzyme response (catalytic subunits of mitochondrial complexes (MC) I-V, including NDUFV2, SDHA, Cyt b, COX1 and ATP5A) and mitochondrial ultrastructure in the rat cerebral cortex (CC) on the severity and duration of in vivo hypoxic exposures. The role of individual animal’s resistance to hypoxia was also studied. The respiratory chain (RC) was shown to respond to changes in environmental [O₂] as follows: (a) differential reaction of mitochondrial enzymes, which depends on the severity of the hypoxic exposure and which indicates changes in the content and catalytic properties of mitochondrial enzymes, both during acute and multiple exposures; and (b) ultrastructural changes in mitochondria, which reflect various degrees of mitochondrial energization. Within a specific range of reduced O₂ concentrations, activation of the MC II is a compensatory response supporting the RC electron transport function. In this process, MC I develops new kinetic properties, and its function recovers in hypoxia by reprograming the RC substrate site. Therefore, the mitochondrial RC performs as an in vivo molecular oxygen sensor. Substantial differences between responses of rats with high and low resistance to hypoxia were determined.     

Mechanisms linking socioeconomic status to smoking cessation: A structural equation modeling approach.

Objective: Although there has been a socioeconomic gradient in smoking prevalence, cessation, and disease burden for decades, these disparities have become even more pronounced over time. The aim of the current study was to develop and test a conceptual model of the mechanisms linking socioeconomic status (SES) to smoking cessation. Design: The conceptual model was evaluated using a latent variable modeling approach in a sample of 424 smokers seeking treatment (34% African American; 33% Latino; 33% White). Hypothesized mechanisms included social support, neighborhood disadvantage, negative affect/stress, agency, and craving. Main Outcome Measure: The primary outcome was Week 4 smoking status. Results: As was hypothesized, SES had significant direct and indirect effects on cessation. Specifically, neighborhood disadvantage, social support, negative affect/stress, and agency mediated the relation between SES and smoking cessation. A multiple group analysis indicated that the model was a good fit across racial/ethnic groups. Conclusion: The present study yielded one of the more comprehensive models illuminating the specific mechanisms that link SES and smoking cessation. Policy, community, and individual-level interventions that target low SES smokers and address the specific pathways identified in the current model could potentially attenuate the impact of SES on cessation. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

The Effects of Sperm and Seminal Fluid of Immunized Male Mice on In Vitro Fertilization and Surrogate Mother–Embryo Interaction

The latest vaccination campaign has actualized the potential impact of antigenic stimuli on reproductive functions. To address this, we mimicked vaccination’s effects by administering keyhole limpet hemocyanin (KLH ) to CD1 male mice and used their sperm for in vitro fertilization (IVF). Two-cell embryos after IVF with spermatozoa from control (C) or KLH-treated (Im) male mice were transferred to surrogate mothers mated with vasectomized control (C) or KLH-treated (Im) male mice, resulting in four experimental groups: C–C, Im–C, C–Im, and Im–Im. The pre-implantation losses were significantly lower in the Im–C group than in the C–Im group. At the same time, the resorption rates reduced markedly in the C–Im compared to the Im–C group. Embryo and placenta weights were significantly higher in the Im–Im group. Although the GM-CSF levels were lower in the amniotic fluid of the gestating surrogate mothers in the Im–Im group, they were strongly correlated with embryo mass. The number–size trade-off was only significant in the Im–Im group. This suggests a positive, cooperative effect of spermatozoa and seminal fluid from immune-primed males on embryo growth and the optimal distribution of surrogate mother maternal resources despite the negative impact of males’ antigenic challenge on the IVF success rate.     

Alternating Copolymers of Cyclopenta[2,1‐b;3,4‐b′]dithiophene and Thieno[3,4‐c]pyrrole‐4,6‐dione for High‐Performance Polymer Solar Cells

A series of alternating copolymers of cyclopenta[2,1‐b;3,4‐b′]dithiophene (CPDT) and thieno[3,4‐c]pyrrole‐4,6‐dione (TPD) have been prepared and characterized for polymer solar cell (PSC) applications. Different alkyl side chains, including butyl (Bu), hexyl (He), octyl (Oc), and 2‐ethylhexyl (EH), are introduced to the TPD unit in order to adjust the packing of the polymer chain in the solid state, while the hexyl side chain on the CPDT unit remains unchanged to simplify discussion. The polymers in this series have a simple main chain structure and can be synthesized easily, have a narrow band gap and a broad light absorption. The different alkyl chains on the TPD unit not only significantly influence the solubility and chain packing, but also fine tune the energy levels of the polymers. The polymers with Oc or EH group have lower HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) energy levels, resulting higher open circuit voltages (V_oc) of the PSC devices. Power conversion efficiencies (PCEs) up to 5.5% and 6.4% are obtained from the devices of the Oc substituted polymer (PCPDTTPD‐Oc) with PC₆₁BM and PC₇₁BM, respectively. This side chain effect on the PSC performance is related to the formation of a fine bulk heterojunction structure of polymer and PCBM domains, as observed with atomic force microscopy.     

Promising antifungal effect of some Euro-Asiatic plants against dangerous pathogenic and toxinogenic fungi

BACKGROUND: Increasing evidence of fungicide‐resistant toxinogenic and pathogenic fungal species is obvious. Looking for new possibilities of antifungal treatment or sources of antifungal substances is a major problem. Some medicinal plants exert strong antifungal properties and could be conveniently used as a promising alternative source for presently problematic antifungal treatment in many areas with respect to their natural origin. Methanol extracts of 46 medicinal plants from the Eurasian area were used in a screening assay for antifungal activity in this study. The growth inhibitory effect was tested against six significant pathogenic and toxinogenic fungal species: Fusarium oxysporum, F. verticillioides, Penicillium expansum, P. brevicompactum, Aspergillus flavus and A. fumigatus. RESULTS: For 14 plant species, the possibility of using them as natural fungicides was indicated. The extract from Grindelia camporum showed significant activity against all target fungal species. The most sensitive target fungus was the toxinogenic and human pathogenic species A. fumigatus. CONCLUSION: This study has identified 14 extracts of medicinal plants with a potential use as an antifungal treatment in various areas. One of them showed promising efficiency against all selected significant pathogenic and toxinogenic fungal species. Copyright © 2010 Society of Chemical Industry     

Melissa officinalis: Composition,Pharmacological Effects and Derived Release Systems—A Review

Melissa officinalis is a medicinal plant rich in biologically active compounds which is used worldwide for its therapeutic effects. Chemical studies on its composition have shown that it contains mainly flavonoids, terpenoids, phenolic acids, tannins, and essential oil. The main active constituents of Melissa officinalis are volatile compounds (geranial, neral, citronellal and geraniol), triterpenes (ursolic acid and oleanolic acid), phenolic acids (rosmarinic acid, caffeic acid and chlorogenic acid), and flavonoids (quercetin, rhamnocitrin, and luteolin). According to the biological studies, the essential oil and extracts of Melissa officinalis have active compounds that determine many pharmacological effects with potential medical uses. A new field of research has led to the development of controlled release systems with active substances from plants. Therefore, the essential oil or extract of Melissa officinalis has become a major target to be incorporated into various controlled release systems which allow a sustained delivery.