Emulsion copolymerization of vinyl acetate-ethylene in high pressure reactor-characterization by inline FTIR spectroscopy

The objective of this research was to investigate the effect of temperature, pressure, initiator concentration and agitation rate, in ethylene-vinyl acetate emulsion copolymerization, on copolymer composition. The inline React-IR ATR system was used to monitor the reaction as well as to determine residual free vinyl acetate. Pressure, temperature and agitation rate have great influence on mass transfer of ethylene monomer to the reaction sites. The vinyl acetate was introduced in semi-batch mode as well as ethylene since the copolymerization was carried out under a constant pressure of ethylene. The higher temperature results in lower content of ethylene incorporated in copolymer. Increase of pressure has a direct effect on the ethylene content in the copolymers through increasing solubilization of ethylene monomer which in turn increases ethylene content in the copolymers. Copolymers of up to 15 wt.% of ethylene content have been synthesized at an ethylene pressure of 30 bar and a temperature of 75 °C. Analytical methods, such as differential scanning calorimetry, nuclear magnetic resonance, thermogravimetric analysis, and infrared spectroscopy were used for characterization of copolymers.     

Identification of Oxidative Stress Related Proteins as Biomarkers for Lung Cancer and Chronic Obstructive Pulmonary Disease in Bronchoalveolar Lavage

Lung cancer (LC) and chronic obstructive pulmonary disease (COPD) commonly coexist in smokers, and the presence of COPD increases the risk of developing LC. Cigarette smoke causes oxidative stress and an inflammatory response in lung cells, which in turn may be involved in COPD and lung cancer development. The aim of this study was to identify differential proteomic profiles related to oxidative stress response that were potentially involved in these two pathological entities. Protein content was assessed in the bronchoalveolar lavage (BAL) of 60 patients classified in four groups: COPD, COPD and LC, LC, and control (neither COPD nor LC). Proteins were separated into spots by two dimensional polyacrylamide gel electrophoresis (2D-PAGE) and examined by matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOF/TOF). A total of 16 oxidative stress regulatory proteins were differentially expressed in BAL samples from LC and/or COPD patients as compared with the control group. A distinct proteomic reactive oxygen species (ROS) protein signature emerged that characterized lung cancer and COPD. In conclusion, our findings highlight the role of the oxidative stress response proteins in the pathogenic pathways of both diseases, and provide new candidate biomarkers and predictive tools for LC and COPD diagnosis.     

Multi‐phosphorylation of the Intrinsically Disordered Unique Domain of c‐Src Studied by In‐Cell and Real‐Time NMR Spectroscopy

Intrinsically disordered regions (IDRs) are preferred sites for post‐translational modifications essential for regulating protein function. The enhanced local mobility of IDRs facilitates their observation by NMR spectroscopy in vivo. Phosphorylation events can occur at multiple sites and respond dynamically to changes in kinase–phosphatase networks. Here we used real‐time NMR spectroscopy to study the effect of kinases and phosphatases present in Xenopus oocytes and egg extracts on the phosphorylation state of the “unique domain” of c‐Src. We followed the phosphorylation of S17 in oocytes, and of S17, S69, and S75 in egg extracts by NMR spectroscopy, MS, and western blotting. Addition of specific kinase inhibitors showed that S75 and S69 are phosphorylated by CDKs (cyclin‐dependent kinases) differently from Cdk1. Moreover, although PKA (cAMP‐dependent protein kinase) can phosphorylate S17 in vitro, this was not the major S17 kinase in egg extracts. Changes in PKA activity affected the phosphorylation levels of CDK‐dependent sites, thus suggesting indirect effects of kinase–phosphatase networks. This study provides a proof‐of‐concept of the use of real‐time in vivo NMR spectroscopy to characterize kinase/phosphatase effects on intrinsically disordered regulatory domains.     

Structural Study of the Partially Disordered Full‐Length δ Subunit of RNA Polymerase from Bacillus subtilis

The partially disordered δ subunit of RNA polymerase was studied by various NMR techniques. The structure of the well‐folded N‐terminal domain was determined based on inter‐proton distances in NOESY spectra. The obtained structural model was compared to the previously determined structure of a truncated construct (lacking the C‐terminal domain). Only marginal differences were identified, thus indicating that the first structural model was not significantly compromised by the absence of the C‐terminal domain. Various ¹⁵N relaxation experiments were employed to describe the flexibility of both domains. The relaxation data revealed that the C‐terminal domain is more flexible, but its flexibility is not uniform. By using paramagnetic labels, transient contacts of the C‐terminal tail with the N‐terminal domain and with itself were identified. A propensity of the C‐terminal domain to form β‐type structures was obtained by chemical shift analysis. Comparison with the paramagnetic relaxation enhancement indicated a well‐balanced interplay of repulsive and attractive electrostatic interactions governing the conformational behavior of the C‐terminal domain. The results showed that the δ subunit consists of a well‐ordered N‐terminal domain and a flexible C‐terminal domain that exhibits a complex hierarchy of partial ordering.     

Preparation and characterization of ethylene‐vinyl acetate nanocomposites: enhanced flame retardant

Ethylene‐vinyl acetate (EVA) nanocomposites with enhanced flame retardance were prepared by the sol–gel process in the melt. Two EVAs with different vinyl acetate (VA) contents and aluminium isopropoxide were used as organic and inorganic phases. The nanocomposites were prepared in a batch mixer under constant processing conditions and were analysed by several characterization techniques. Aluminium isopropoxide presented low activation energy, which allows the synthesis of the nanoparticles without a post step treatment. The reaction mechanism is proposed. Nanocomposites with smaller and well dispersed metal nanoparticles were produced with an EVA with higher VA content. EVA nanocomposites achieve the requirements for 94 V‐0 classification. © 2013 Society of Chemical Industry     

Mechanochemical and Low‐Temperature Synthesis of Nanocrystalline Fluorohydroxyapatite/Fluorapatite

Low‐temperature synthesis of fluorapatite/fluorohydroxyapatite with precursor mixture previously mechanochemically treated is described in this article. Ethylene vinylacetate/versatate copolymer as a surface active substance was mechanically treated to obtain a core‐shell system with strongly controlled grain size. Despite usual behavior of mechanically activated systems, only an amorphous phase formed from precursor ions present in the mixture composed of β‐Ca₂P₂O₇, CaCO₃, CaF₂, and unreacted Ca(OH)₂ was obtained during milling for 5 min to 8 h. The mixture contained depots of labile F^? ions conserved in micelles cages, which are useful for teeth protection from carries. For transformation of these amorphous phases into fluorapatite, an additional low thermal treatment was necessary. The mechanism of the precursor mixture transformation into fluorapatite during milling and thermal treatment was investigated using FTIR spectroscopy and X‐ray diffraction. The morphology and size distribution of the obtained powders was studied using SEM and TEM.     

Dewetting and Adsorption in Homopolymer Films Containing Triblock Copolymers: Role of Chain Architecture and Anchoring Block Molar Fraction

Triblock copolymer additives are found to stabilize thin-film dewetting of B-type homopolymers with degree of polymerization (DOP) P deposited on silicon oxide. The triblock copolymers’ architectures are ABA and BAB, where A and B represent anchoring and nonadsorbing blocks with DOP's N _A and N _B, respectively. Upon adding 1 vol.% of the ABA additive, dewetting is only observed for anchoring block molar fractions, f _A, below 4%. Dewetting is arrested in films containing 1 vol.% ABA, BAB, or AB that have similar values of f _A ～ 8%, showing that chain architecture is not the only indicator of a successful additive. Compared with films containing diblock copolymers, the interfacial excess, z*, of triblock copolymers at the melt/substrate interface is relatively small as measured by low-energy forward-recoil spectrometry. Because adsorbed copolymers can reduce the capillary driving force for dewetting and participate in entanglements with matrix chains, the higher coverage and grafting density observed for diblock copolymers suggests that diblocks are more effective than triblocks in improving thin-film stability.