Degradation kinetics of PVC plasticized with different plasticizers under isothermal conditions

The aim of the present work is to elucidate the degradation kinetics of polyvinyl chloride (PVC) plasticized with some phthalate and nonphthalate plasticizers. A PVC thermomat instrument was utilized to maintain the isothermal degradation conditions at 140 and 160°C, and to suppress the oxidative degradation by means of nitrogen flow. The conductivity measurements were performed to follow hydrogen chloride (HCl) gas which is released upon PVC degradation and trapped in water. Dehydrochlorination of plasticized PVC films occurred with activation energies of about 23–160 and 26–117 kJ mol^?1 and the isokinetic temperatures, at which the dehydrochlorination rate constants of all p‐PVC films would have the same value, were found to be 171 and 128°C for initial and linear regions of dehydrochlorination curve, respectively. Plasticizer incorporation contributes to the stability of the films particularly after the consumption of stabilizer due to the dehydrochlorination. Influence of temperature rise by 20°C on the degradation rate constant is the lowest for DINCH having p‐PVC films as 0.36 and 0.42% increment at the initial region and linear region, respectively. On the other hand, DOTP reveals greater stability than the others do since the compensation ratio of the PVC film having DOTP is greater than the other films. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41579.     

Swelling kinetics,mechanical properties,and release characteristics of chitosan‐based semi‐IPN hydrogels

Two series of pH‐sensitive semi‐interpenetrating network hydrogels (semi‐IPN) based on chitosan (CS) natural polymer and acrylamide (AAm) and/or N‐hydroxymethyl acrylamide (HMA) monomers by varying the monomer and CS ratios were synthesized by free radical chain polymerization. 5‐Fluorouracil (5‐FU), a model anticancer drug, has been added to the feed composition before the polymerization. The characterization of gels indicated that the drug is molecularly dispersed in the polymer matrix. The swelling kinetics of drug‐loaded gels have decreased with increased HMA content at 37°C in both distilled water and buffer solutions with a pH of 2.1 or 7.4. Elastic modulus of the gels increased with the increase in HMA content and higher CS concentration enhanced the elastic modulus positively. Moreover, cumulative release percentages of the gels for 5‐FU were ca. 10% higher in pH 2.1 than those in pH 7.4 media. It was determined that they can be suitable for the use in both gastric and colon environments. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41886.     

高效液相色谱法同时测定化妆品中的7种香豆素

基于香豆素类化合物在化妆品中的使用情况及其对人体健康的危害,采用C18色谱柱作为分析柱,通过优化试验条件建立了一种可准确、简便测定化妆品中多种香豆素类化合物的高效液相色谱法。试验结果表明,7种香豆素类化合物的保留时间和峰面积的相对标准偏差分别小于0.1%和2%,且检出限均低于40μg/L;通过样品加标试验,得到7种目标化合物的回收率为80%~94%。所建立方法具有快速、简便、准确、灵敏的特点,是测定化妆品中多种香豆素类化合物的有效方法。     

Histone Methylation Marks on Circulating Nucleosomes as Novel Blood-Based Biomarker in Colorectal Cancer

Circulating nucleic acids (CNAs) are under investigation as a liquid biopsy in cancer as potential non-invasive biomarkers, as stable structure in circulation nucleosomes could be valuable sources for detection of cancer-specific alterations in histone modifications. Our interest is in histone methylation marks with a focus on colorectal cancer, one of the leading cancers respective the incidence and mortality. Our previous work included the analysis of trimethylations of lysine 9 on histone 3 (H3K9me3) and of lysine 20 on histone 4 (H4K20me3) by chromatin immuno- precipitation-related PCR in circulating nucleosomes. Here we asked whether global immunologic measurement of histone marks in circulation could be a suitable approach to show their potential as biomarkers. In addition to H3K9me3 and H4K20me3 we also measured H3K27me3 in plasma samples from CRC patients (n = 63) and cancer free individuals (n = 40) by ELISA-based methylation assays. Our results show that of three marks, the amounts of H3K27me3 (p = 0.04) and H4K20me3 (p < 0.001) were significantly lower in CRC patients than in healthy controls. For H3K9me3 similar amounts were measured in both groups. Areas under the curve (AUC) in receiver operating characteristic (ROC) curves indicating the power of CRC detection were 0.620 for H3K27me3, 0.715 for H4K20me3 and 0.769 for the combination of both markers. In conclusion, findings of this preliminary study reveal the potential of blood-based detection of CRC by quantification of histone methylation marks and the additive effect of the marker combination.     

Emulsifier‐free cationic latexes based on vinylbenzyl chloride and 2‐(dimethylamino)ethyl methacrylate with adjusted hydrophilic–hydrophobic properties

Functional emulsifier‐free cationic latexes based on styrenic monomer vinylbenzyl chloride (VBC) and acrylic monomer 2‐(dimethylamino)ethyl methacrylate (DMA) were successfully prepared with dual quaternary ammonium ions (36–63 mol %) on both monomer moieties in two‐stages. First, [2‐(methacryloyloxy)ethyl]dimethylhexadecylammonium bromide monomer (DMA(C₁₆)), prepared via quaternization of DMA with 1‐bromohexadecane, was utilized as a comonomer (5–20%) as well as a surfactant in the emulsion polymerization of VBC. Next, the quaternization of chloromethyl groups in the VBC moiety in latex particles with trimethylamine and N,N‐dimethylhexadecylamine created a second type of quaternized sites on the latex particles. The percentages of the quaternary ammonium ions of the first‐stage latexes (P[VBC‐DMA(C₁₆‐x)]) and the second‐stage latexes (P[VBC(R)‐DMA(C₁₆‐x)]) were determined using bromide and chloride ion‐selective electrodes. The particles were characterized with a scanning electron microscope, Zetasizer, measuring water contact angles of their pellets. The polymer structure and the alkyl group length in their quaternary ammonium ions played an important role on the sizes, zeta potentials and hydrophilic–hydrophobic balances of the latexes. The water contact angles of the pellets of the latex particles varied from 50.3 to 109.6° depending on both the polymer structure and the alkyl group length. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42775.     

Detailed Structure–Function Correlations of Bacillus subtilis Acetolactate Synthase

Isobutanol is deemed to be a next‐generation biofuel and a renewable platform chemical. 1 Non‐natural biosynthetic pathways for isobutanol production have been implemented in cell‐based and in vitro systems with Bacillus subtilis acetolactate synthase (AlsS) as key biocatalyst. 2 – 6 AlsS catalyzes the condensation of two pyruvate molecules to acetolactate with thiamine diphosphate and Mg²⁺ as cofactors. AlsS also catalyzes the conversion of 2‐ketoisovalerate into isobutyraldehyde, the immediate precursor of isobutanol. Our phylogenetic analysis suggests that the ALS enzyme family forms a distinct subgroup of ThDP‐dependent enzymes. To unravel catalytically relevant structure‐function relationships, we solved the AlsS crystal structure at 2.3 Å in the presence of ThDP, Mg²⁺ and in a transition state with a 2‐lactyl moiety bound to ThDP. We supplemented our structural data by point mutations in the active site to identify catalytically important residues.     

Advanced Mutasynthesis Studies on the Natural α‐Pyrone Antibiotic Myxopyronin from Myxococcus fulvus

Myxopyronin is a natural α‐pyrone antibiotic from the soil bacterium Myxococcus fulvus Mx f50. Myxopyronin inhibits bacterial RNA polymerase (RNAP) by binding to a part of the enzyme not targeted by the clinically used rifamycins. This mode of action makes myxopyronins promising molecules for the development of novel broad‐spectrum antibacterials. We describe the derivatization of myxopyronins by an advanced mutasynthesis approach as a first step towards this goal. Site‐directed mutagenesis of the biosynthetic machinery was used to block myxopyronin biosynthesis at different stages. The resulting mutants were fed with diverse precursors that mimic the biosynthetic intermediates to restore production. Mutasynthon incorporation and production of novel myxopyronin derivatives were analyzed by HPLC‐MS/MS. This work sets the stage for accessing numerous myxopyronin derivatives, thus significantly expanding the chemical space of f α‐pyrone antibiotics.