Influence of nanoparticles and antioxidants on mechanical properties of titania/polydicyclopentadiene polyHIPEs: A statistical approach

Open porous Pickering poly(high internal phase emulsion) composites were prepared by ring opening metathesis polymerization of surface modified TiO₂ nanoparticle stabilized dicyclopentadiene (DCPD) high internal phase emulsions. Oxidation of the double bonds in the polyDCPD chains of the resulting materials was prevented using antioxidants. Oxidation dependent variation of mechanical properties was demonstrated by applying compression tests to the resulting composite materials periodically. Periodical measurements revealed significantly reduced brittleness in the case of antioxidant containing polyHIPE composites. Furthermore, it was determined that the initial compression moduli and the compressive strengths of the resulting materials were significantly improved by using antioxidants as compared to antioxidant free samples. Moreover, increasing nanoparticle amount was found to have a beneficial effect with the presence of antioxidants. The relationship between the compression modulus with nanoparticle loading and different types of antioxidants was revealed by developing model regression equations and graphs. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46913.     

Comparison of properties of acrylic–polyurethane hybrid emulsions prepared by batch and semibatch processes with monomer emulsion feed

Aqueous acrylic–polyurethane hybrid emulsions were prepared by batch and semibatch polymerization of acrylic monomer mixtures (butyl acrylate, methyl methacrylate and acrylic acid) in the presence of polyurethane dispersion. The acrylic component was introduced in the monomer emulsion feed. The weight ratio between acrylic and polyurethane components was varied to obtain different emulsion properties, microphase structure and mechanical film properties. Scanning electron microscopy, average particle size and molecular weight measurements were performed to characterize the latex systems. Mechanical properties were examined by measuring Koenig hardnesses of dried films. The average particle size increased with the acrylic/polyurethane ratio. Particles of larger than average size and, to some extent, higher than average molecular weights by batch process were formed. Koenig hardnesses decreased with increasing acrylic/polyurethane ratio. Properties of emulsions synthesized by semibatch processes were compared with the results reported for a different polyurethane dispersion. Copyright © 2003 Society of Chemical Industry     

Kinetics and modeling of the diffusion‐controlled diallyl terephthalate polymerization

Free radical polymerization kinetics of diallyl terephthalate in bulk was investigated in a wide temperature range from 50°C to 150°C with four different peroxide initiators. Conversion points were measured using Fourier Transform Infrared (FTIR) measurements. The initiator efficiencies and the initiator decomposition rate constants were evaluated from special experiments, applying the theory of dead end polymerization. In addition, the ratios between the degradative and the effective kinetic rate constants to propagation rate constants were obtained from molecular weight measurements at various initiator concentrations. The ratio of chemically controlled termination and propagation rate constant k/k_tc of the polymerization system was obtained using the initial rates of polymerization and the number average molecular weight data between 0.25 · 10^?3 and 15.7 · 10^?3 L mol^?1 s^?1. The glass transition temperature of the polymer, 191°C, was measured by the Alternating Differential Scanning Calorimetry (ADSC) technique. Computed conversions from the developed kinetic model were in good agreement with the conversion and molecular weight measured data. The values of diffusion controlled propagation and termination rate constants k_td0 and k_pd0 with clear and physical meaning were the only two parameters obtained from the developed kinetic model fitting. Polym. Eng. Sci. 44:2005–2018, 2004. © 2004 Society of Plastics Engineers.     

Pressure and temperature behavior of thermoplastic polymer melts during high‐pressure expansion injection molding

The development of expansion injection molding as new technology for producing thin plastic parts has raised questions about polymer melt behavior in the process of rapid high pressure compression and expansion. To investigate those phenomena, the new in‐line injection molding machine mounted measurement system has been developed. Measuring nozzle equipped with hydraulically driven closing bolts and contact fast response pressure and infrared temperature sensors enabled us to measure the compression and expansion of polymer melts at different starting conditions. Results presented for high impact polystyrene and polyamide show that polymer melt temperature rise is linearly dependent on compression pressure as well as it is dependent on compression speed. Comparable effect of temperature fall has been recorded during the polymer expansion, resulting in no noticeable loss of dissipation energy during this reversible process. Measurements have been compared with modified 2‐domain Tait equation of state. Curve fitting analysis to manufacturer's material data show that measurements fit well with the model, even at very high compression speeds. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Characterization of phenol–urea–formaldehyde resin by inline FTIR spectroscopy

Phenol–urea–formaldehyde (PUF) resins were synthesized by a two‐step polymerization process. The first step was the synthesis of 2,4,6‐trimethylolphenol (TMeP) from phenol and formaldehyde, under alkaline conditions. In the second step PUF resins were synthesized by the reaction of TMeP with urea, under acidic and alkaline conditions. The influence of temperature on the synthesis of TMeP was investigated. The molar ratio between TMeP and urea was varied to study the composition effect on the second step of the PUF synthesis and final product properties. Synthesis of TMeP and PUF resins were monitored by inline FTIR‐ATR system. Analytical methods, such as differential scanning calorimetry, nuclear magnetic resonance, thermogravimetric analysis, and infrared spectroscopy were used for characterization of TMeP and PUF resins. Obtained PUF resins were cured and tested on flexural strength. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

The occurrence and characterisation of phenolic compounds in Camelina sativa seed, cake and oil

In this study, the antioxidant activities of Camelina sativa methanolic extracts were evaluated by different chemical assays: reducing power, 2,2-diphenyl-1-picrylhydrazyl (DPPH·) assay, the β-carotene bleaching method and the metal chelating activity assay. An LC-MS profiling method was used for a comprehensive study of the phenolic compounds and their representation in camelina seeds, cake and oil. For this purpose, 4-vinyl derivatives of hydroxycinnamic acids were synthesized by thermal decarboxylation of the corresponding phenolic acids and sinapine was isolated from kale (Brassica oleracea) applying a new method and confirmed by NMR. The results revealed that besides the total phenolic content and antioxidant activity, seeds and cake also possess a similar phenolic profile. In addition to sinapine and 4-vinyl derivatives, other antioxidants were successfully identified: ellagic acid, protocatechuic acid, p-hydroxybenzoic acid, sinapic acid, salicylic acid, catechin, rutin, quercetin and quercetin glucoside. Since after oil pressing most of the phenolic compounds remain in the seed residues, only a few compounds were identified in the oil. Camelina cake was found to have the best reducing power and radical scavenging activity, whereas camelina oil, with a relatively low phenolic content, exhibited the highest iron-chelating capacity and the best inhibitory action against β-carotene discolouration in an emulsified system.     

A Tryptophan ‘Gate’ in the CRISPR-Cas3 Nuclease Controls ssDNA Entry into the Nuclease Site,That When Removed Results in Nuclease Hyperactivity

Cas3 is a ssDNA-targeting nuclease-helicase essential for class 1 prokaryotic CRISPR immunity systems, which has been utilized for genome editing in human cells. Cas3-DNA crystal structures show that ssDNA follows a pathway from helicase domains into a HD-nuclease active site, requiring protein conformational flexibility during DNA translocation. In genetic studies, we had noted that the efficacy of Cas3 in CRISPR immunity was drastically reduced when temperature was increased from 30 °C to 37 °C, caused by an unknown mechanism. Here, using E. coli Cas3 proteins, we show that reduced nuclease activity at higher temperature corresponds with measurable changes in protein structure. This effect of temperature on Cas3 was alleviated by changing a single highly conserved tryptophan residue (Trp-406) into an alanine. This Cas3^W406A protein is a hyperactive nuclease that functions independently from temperature and from the interference effector module Cascade. Trp-406 is situated at the interface of Cas3 HD and RecA1 domains that is important for maneuvering DNA into the nuclease active site. Molecular dynamics simulations based on the experimental data showed temperature-induced changes in positioning of Trp-406 that either blocked or cleared the ssDNA pathway. We propose that Trp-406 forms a ‘gate’ for controlling Cas3 nuclease activity via access of ssDNA to the nuclease active site. The effect of temperature in these experiments may indicate allosteric control of Cas3 nuclease activity caused by changes in protein conformations. The hyperactive Cas3^W406A protein may offer improved Cas3-based genetic editing in human cells.     

Comparison of isolation methods for the determination of buckwheat volatile compounds

Five different isolation techniques were combined with gas chromatographic–mass spectrometric determination of aroma compounds from buckwheat: dynamic headspace (DHS) with cryotrapping or sorbent trapping, solid-phase microextraction (SPME), headspace sorptive extraction (HSSE), solvent extraction (SE) and simultaneous distillation–extraction (SDE). Optimisation of each technique is presented, as well as comparison of the chemical profiles obtained by them. Solvent extraction with methanol resulted in the isolation of rather polar and less volatile compounds and was deemed least suitable for the odour-active compounds. Only SPME with DVB/CAR/PDMS fibre was suitable for the isolation of highly volatile compounds in a wider polarity range. DHS extracted the smallest number of compounds, but with the comparable chemical profile as obtained by SDE, which was chosen as the most suitable technique to obtain the aroma compounds of cooked buckwheat. The applied isolation techniques are complementary in their ability to extract a representative aroma profile of buckwheat.