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A zein-degrading protease (ZDP) from Zea mays was heterologously expressed using Pichia pastoris and its characteristics and effects on enzymatic hydrolysis of corn starch were investigated in the current study. The optimal temperature and pH for ZDP activity was 40 °C and pH 5.0, respectively. The ZDP exhibited a degree of thermal stability and was repressed by some metal ions (5 mM) including Zn2+, Mg2+, Cu2+, Mn2+, Ni2+, K+, and Ca2+, especially Mn2+ and Cu2+, which caused near complete inhibition. Dithiothreitol and β-mercaptoethanol (5 mM) could tremendously increase the ZDP activity by 102.1% and 60.7%, respectively. The ZDP could not tolerate organic solvents such as ethanol, acetone, and dimethyl sulphoxide. The ZDP could efficiently degrade the pure commercial zein and the native zein in the corn, increase the leaching of corn soluble sugars, destroy the cross-linked starch-zein structure, and release the starch granules, consequently increasing the α-amylase hydrolysis of corn starch. The recombinant ZDP might be useful to improve the utilization of corn.

A study was carried out to produce a fusion protein (Swo-Xyn) using the Trichoderma reesei swollenin and Lentinula edodes xylanase and to investigate its characteristics and application in degrading soybean straw. In parallel, L. edodes xylanase (Xyn) alone was used as a control protein in application tests. The Swo-Xyn was recombined, expressed and produced by Pichia pastoris and had the maximum activity at 40 °C and pH 3.0 using xylan as substrate. The Swo-Xyn exhibited preferential hydrolysis of Xylan. The Swo-Xyn had slight low Km value (23.90 vs. 25.36 mg/ml) but significantly low Vmax value (162.4 vs. 227.2 μmol/mg·min) and specific activity (18.82 vs. 38.97 U/mg) relative to the Xyn. The Swo-Xyn activity was enhanced by Zn2+ in dose dependent manners with the peak activity at 30 mM of Zn2+. The Swo-Xyn could tolerate 15% of methanol, ethanol, aceton, and DMSO with >60% residual activity. The Swo-Xyn had the greater tolerance to SDS, EDTA, 2-ME than the Xyn and could be activated by DTT, Triton X-100, and Tween 20. Compared with the Xyn, the hydrolysis and sequent cellulose enzymolysis of soybean straw could be better improved by the Swo-Xyn. The Swo-Xyn should be more useful for improving the utilization of soybean straw.

An experiment was conducted to determine the characteristics of recombinant endoglucanase and its effects on rape straw silage. The endoglucanase from Lentinula edodes (LeCel12A) was produced in Pichia pastoris and shown maximum activity at 40 °C and pH 3.0. The LeCel12A exhibited preferential hydrolysis of carboxymethylcellulose. The activity of LeCel12A could be enhanced by MnCl2 in dose-dependent manners. Trp22 was a key amino acid affecting LeCel12A activity. The LeCel12A enhanced the hydrolysis of rape straw, rice straw, wheat straw, and corn straw. Supplemental LeCel12A increased lactic acid concentration and reduced lignocellulosic content of the rape straw silage. Though an increase in the saccharification efficiency of LeCel12A-treated rape straw silage was observed when the fibrolytic enzyme loading of hydrolysis system was enough, supplemental LeCel12A did not dramatically enhance the saccharification of rape straw silage in the current study. This study demonstrates that LeCel12A may be useful for improving the utilization of rape straw silage as an additive, but its supplemental dose, cost benefit, and consequent application possibility in biofuel production require careful consideration and further investigation.

An experiment was conducted to determine the effects of recombinant cellobiohydrolase on the hydrolysis and in vitro rumen microbial fermentation of agricultural straws including rice straw, wheat straw, and corn straw. The cellobiohydrolase from Lentinula edodes (LeCel7A) was produced in Pichia pastoris. The optimal temperature and pH for LeCel7A were 60 °C and 5.0, respectively. The recombinant protein enhanced the hydrolysis of three straws. During in vitro rumen fermentation of three straws, the fiber digestibility, concentration of acetate and total volatile fatty acids, and fermentation liquid microbial protein were increased by LeCel7A. High throughput sequencing and real-time PCR data showed that the effects of LeCel7A on ruminal microbial community depended on the fermentation substrates. The relative abundances of Prevotellaceae_UCG_003 and Saccharofermentans were increased by LeCel7A regardless of agricultural straws. With rice straw, LeCel7A increased the relative abundances of Desulfovibrio, Ruminococcaceae and its some genus. With wheat straw, LeCel7A increased the relative abundances of Succiniclasticum, Ruminococcus flavefaciens, and Ruminococcus albus. With corn straw, Succiniclasticum, Christensenellaceae_R_7_group and Desulfovibrio were increased by LeCel7A. This study demonstrates that LeCel7A could enhance the hydrolysis and in vitro ruminal fermentation of agricultural straws, showing the potential of LeCel7A for improving the utilization of agricultural straws in ruminants.

An experiment was conducted to determine the effects of swollenin on the enzymatic hydrolysis and in vitro rumen microbial fermentation of agricultural straws. The swollenin from Trichoderma reesei was produced in Pichia pastoris in current study. The recombinant protein caused an obvious disruption on filter paper and slight increase in reducing sugars release when treating xylan, Avicel, rice straw, wheat straw, and corn straw. Simultaneous incubation of swollenin with fibrolytic enzyme resulted in a significant synergistic activity on disruption of filter paper and hydrolysis of above-mentioned substrates. During in vitro rumen fermentation of three straw diets, the dry matter digestibility, acetate production, microbial protein synthesis, and fibrolytic bacterial population were increased by swollenin. This study demonstrates that swollenin could enhance the enzymatic hydrolysis and in vitro ruminal fermentation of agricultural straws, showing the potential of swollenin for improving the utilization of agricultural straws in ruminants.

Ferroelectric glass–ceramics, with a basic composition 90 wt.% (Ba0.65Sr0.35)TiO3−10 wt.% (B2O3−nSiO2) (n = 0.5, 1, 3, 5) were synthesized by the sol–gel method and their phase development and dielectric properties were investigated by differential thermal analysis, x-ray diffraction, field emission scanning electron microscopy, dielectric temperature curves and impedance spectroscopy. From the differential thermal analysis, glass transition and crystallization behavior can be observed. From the x-ray diffraction study, two crystalline phases (Ba,Sr)TiO3 and Ba2TiSi2O8 were formed over the entire composition range of the glass–ceramics. In addition, the main crystal phase has undergone a transformation from (Ba,Sr)TiO3 to Ba2TiSi2O8 with the increase of n. A typical structure in which the crystal phase was surrounded by a glassy matrix has been observed in the scanning electron microscope images. As a result of temperature dependent dielectric property measurements, the dielectric constant increased obviously with the increase of n from 0.5 to 1. Further increasing n led to a reduction of the dielectric constant, which is in coincidence with the variation of the intensity of (Ba,Sr)TiO3 phase with n. According to the impedance spectroscopy analysis and the activation energy calculation, the relaxation peak in both Z″ and M″ data should be attributed to the crystal–glass interface, and the change of conduction mechanism with the increase of SiO2/B2O3 ratio may be attributed to the corresponding transition of the main crystal phase.

The effect of thermal annealing atmosphere on dielectric properties of barium strontium titanate glass ceramics was investigated by impedance analysis and thermally stimulated depolarization current measurement. As a result of impedance analysis, the resistances of both air-annealed and O2-annealed glass ceramic samples were found to be two orders of magnitude higher than that of the as-sintered samples. This annealing atmosphere induced change in electrical properties can be ascribed to the variation in oxygen vacancy concentration. From the thermally stimulated depolarization current measurement, the annealing atmosphere dependence of current density was found for the annealed samples. It was shown that the reduction in oxygen vacancy concentration lowers the ac conductivity and defect dipole concentration.

The sintering of barium strontium titanate glass–ceramics in nitrogen modified their dielectric properties significantly compared to the sintering in air. The experimental results demonstrate that the glass–ceramics sintered at low temperatures contain a major phase Ba2TiSi2O8 (BTS), known as fresnoite. The fresnoite phase disappeared and the barium strontium titanate perovskite phase became the major phase when the sintering temperature was increased. In addition, the microstructure observation showed that both the proportion of crystal phase and the crystal size increase obviously with the increase of sintering temperature. Most importantly, impedance spectroscopy has been employed to study the electrical responses arising from the glass and the crystal phases in the glass–ceramics sintered at low temperatures and high temperatures. The magnitudes of impedance and modulus changed significantly for the glass–ceramics sintered at the two temperature ranges. The activation energy calculated from the complex impedance, complex modulus and dc conductivity suggests that the dielectric relaxation for the glass phase and the glass–crystal interface may be attributed to the motion of the dipole associated with oxygen vacancy. And for the barium strontium titanate perovskite glass–ceramics, the motion of the electrons from the second ionization of oxygen vacancies leads to dc electrical conduction. The mechanism for the giant dielectric properties of the glass–ceramics sintered at high temperatures in nitrogen is discussed.

A Li2O-ZnO-SiO2 (LZS) glass system was modified with CuO, and its phase development, microstructure evolution, crystallization kinetics and thermal expansion properties were investigated as a function of heat treatment temperature. As a result of the X-ray diffraction study and microstructure observation, lithium zinc silicate formed as the first crystalline phase with increasing heat treatment temperature. Silica polymorph developed as minor crystalline phase at higher temperatures. From the X-ray diffraction patterns, CuO addition led to a decrease in both the crystallization temperature of lithium zinc silicate phase and the volume fraction of quartz phase. According to the crystallization kinetics, the crystallization activation energy for lithium zinc silicates is almost equal to the diffusion activation energy of Zn2+ in glass, it suggests that the diffusion of network modifier Zn2+ dominates the crystallization of lithium zinc silicates. Additionally, CuO addition caused the transition of Zn2+ from network modifiers to network formers. From the thermal expansion coefficient measurements, two abrupt changes in slope of the thermal expansion curves were observed and attributed to the phase transitions of cristobalite and lithium zinc silicate, respectively. Comparison of the thermal expansion coefficient of two types of glass-ceramics revealed that CuO addition in the LZS system can partly inhibit the formation of cristobalite at high temperatures.

The depolarization process of glass-added barium titanate (BaTiO3) ceramics with two different glass concentrations was investigated using a thermally stimulated depolarization current (TSDC) technique. The TSDC spectra of the glass-added BaTiO3 ceramics show three peaks. The first sharp peak near the Curie temperature is due to pyroelectric current associated with ferroelectric-paraelectric phase transition. The middle temperature peak at about 200°C showed no dependence on the depolarization current peak position in the polarization field, and the activation energies of this peak were between 0.43 eV and 0.55 eV, which are attributed to the behavior of defect dipoles related to oxygen vacancies within the BaTiO3 grains. Moreover, the high temperature peak at around 300°C indicated that the depolarization current peak position depends on the polarization temperature and decreases with increasing polarization field. The activation energy of this high temperature peak was between 0.78 eV and 0.98 eV, which is similar to the activation energy for the motion of oxygen vacancies in perovskite oxides. The high temperature peak could be attributed to the migration of oxygen vacancies across grain boundaries. In this work we developed a model in which oxygen vacancies that originated from the defect within grains migrated from the anode to the cathode and some were trapped at the grain boundaries. It is presented here and successfully interprets the appearance and behavior of these peaks.

The influences of sintering temperature and holding time on porosity and shrinkage of glass tubes have been studied by optical microscope. It is evident that there exists three stages for the sintering process of glass. At the first stage, both increasing temperature and prolonging the holding time contribute to lowering the porosity and to intensifying the shrinkage greatly. At the second stage, the glass further densifies and the voids among particles become smaller and less. Finally, at the third stage the shrinkage rate almost keeps unchanged to sintering temperature and holding time.

The effect of lanthanum concentration on dielectric relaxation behavior in lead zirconate stannate titanate antiferroelectric ceramics was investigated by X-ray diffraction technique, dielectric spectroscopy, Sawyer–Tower polarization methods, and thermally stimulated depolarization current (TSDC) measurements. The tetragonal phase was found to be stabilized from the rhombohedral phase by lanthanum substitution. As the lanthanum content was increased, the dielectric constant decreased gradually over the measuring temperature range. As a result of polarization–electric field hysteresis loops, the maximum polarization decreased and the switching field increased with the increase of lanthanum content. Investigations of TSDC measurements revealed that the peak is due to space-charge polarization. It is suggested to be associated with the relaxation of oxygen vacancies.

We studied microstructure, surface morphology, and domain structure of (Ba 0.75 ,Sr 0.25 )TiO 3 based glass-ceramics with different amount of Mn additive (from 0 to 0.5%) prepared from melted and quenched mixed powders using several microscopic methods. The as-quenched sample was annealed and subjected to a controlled crystallization in air for 2h at temperatures 850 and 950?C. It was shown that the addition of the Mn up to 0.5% had no impact on morphology and domain structure. The dendrite structure was revealed in the samples crystallized at 850?C. The geometry of the clusters was analysed in terms of fractal approach. The faceted grains with size about 150 nm were found in ceramics annealed at 950?C. Individual grains demonstrated non-uniform piezoresponse, which could be attributed to existence of domain structure. © 2018 Institute of Physics Publishing. All rights reserved. The equipment of the Ural Centre for Shared Use “Modern Nanotechnology” Ural Federal University was used. The research was made possible by Russian Foundation for Basic Research (grant 18-52-53032) and state task of Ministry of education and science of the Russian Federation (No. 3.4993.2017/6.7). The work was supported partially by Government of the Russian Federation (act 211, agreement 02.A03.21.0006). et al.;NT-MDT Spectrum Instruments;Ostec-ArtTool Ltd.;Promenergolab LLC;Russian Foundation for Basic Research;Taylor and Francis Group

The interfacial reaction and crystallization mechanism were evaluated in terms of the effect of pre-oxidation condition on the glass-to-metal sealing. The moderate oxidation of the alloy resulted in the formation of magnetite as the main crystalline phase in the oxide scale. The microstructural observation demonstrated that the glass-to-metal joint can be divided into four regions: the bulk metal region, the Fe depleted region, the transition region and the bulk glass region. However, higher oxidation degree of the alloy resulted in a thicker diffusion zone. The results show that the dissolution of oxide scale in glass inhibits the formation of fresnoite and enhances the formation of orthoclase. The crystallization mechanism of these two precipitate phases was discussed based on the dissolution of magnetite.

Barium strontium titanate glass-ceramics with different La2O3 contents (0, 0.5, 1.0, and 1.5 mol. %) were prepared by the melt-quenching technique. The phase developments, microstructures, and impedance behavior of these glass-ceramics have been investigated as a function of La2O3 content. By the X-ray diffraction study, a gradual change with increasing La2O3 content was observed. X-ray photoelectron spectroscopy indicated that the oxygen vacancy concentration decreases with the increase of La2O3 content. Lanthanum substitution resulted in an initial increase and then a decrease in the value of dielectric constant. From impedance spectroscopy, there are two electrical responses occurring: a low frequency response, which is related to the crystal-glass interface, and a high frequency response corresponding to the crystal phase. The low frequency peak shifts to lower frequencies and the high frequency peak shifts to higher frequencies with increasing lanthanum content. Both the temperature sensitivity of impedance and the value of ac conductivity decrease with the increase of La2O3 content.Barium strontium titanate glass-ceramics with different La2O3 contents (0, 0.5, 1.0, and 1.5 mol. %) were prepared by the melt-quenching technique. The phase developments, microstructures, and impedance behavior of these glass-ceramics have been investigated as a function of La2O3 content. By the X-ray diffraction study, a gradual change with increasing La2O3 content was observed. X-ray photoelectron spectroscopy indicated that the oxygen vacancy concentration decreases with the increase of La2O3 content. Lanthanum substitution resulted in an initial increase and then a decrease in the value of dielectric constant. From impedance spectroscopy, there are two electrical responses occurring: a low frequency response, which is related to the crystal-glass interface, and a high frequency response corresponding to the crystal phase. The low frequency peak shifts to lower frequencies and the high frequency peak shifts to higher frequencies with increasing lanthanum content. Both the temperature sensitivity of im...

Thermally stimulated depolarization current (TSDC) and highly accelerated lifetime testing studies of (Pb0.925-xLa0.05Bax)(Zr0.52Sn0.39Ti0.09)O3 (PLBZST) antiferroelectric ceramics have been performed for three compositions with different barium contents. These studies have revealed that barium substitution increases the failure time and improves the resistance degradation behavior. As a result of the variations of peak current intensity and peak temperature with different polarization temperatures in the TSDC curves, three successive relaxation peaks with different origins have been found to occur: a low-temperature defect dipole peak, an intermediate-temperature in-grain oxygen vacancy migration peak, and a high-temperature transgranular oxygen vacancy migration peak. These results demonstrate that the improved resistance degradation process with the increase of barium substitution is related to the decrease in oxygen vacancy concentration.