Reactive molecular dynamics insight into the thermal decomposition mechanism of 2,6-Bis(picrylamino)-3,5-dinitropyridine

2,6-bis(picrylamino)-3,5-dinitropyridine(PYX)has excellent thermostability,which makes its thermal decomposition mechanism receive much attention.In this paper,the mechanism of PYX thermal decomposition was investigated thoroughly by the ReaxFF-lg force field combined with DFT-B3LYP(6-311++G)method.The detailed decomposition mechanism,small-molecule product evolution,and cluster evolution of PYX were mainly analyzed.In the initial stage of decomposition,the intramolecular hydrogen transfer reaction and the formation of dimerized clusters are earlier than the denitration reaction.With the progress of the reaction,one side of the bitter amino group is removed from the pyridine ring,and then the pyridine ring is cleaved.The final products produced in the thermal decomposition process are CO_(2),H_(2)O,N_(2),and H_(2).Among them,H_(2)O has the earliest generation time,and the reaction rate constant(k_(3))is the largest.Many clusters are formed during the decomposition of PYX,and the formation,aggregation,and decomposition of these clusters are strongly affected by temperature.At low temperatures(2500 K-2750 K),many clusters are formed.At high temperatures(2750 K-3250 K),the clusters aggregate to form larger clusters.At 3500 K,the large clusters decompose and become small.In the late stage of the reaction,H and N in the clusters escaped almost entirely,but more O was trapped in the clusters,which affected the auto-oxidation process of PYX.PYX's initial decomposition activation energy(E_(a))was calculated to be 126.58 kJ/mol.This work contributes to a theoretical understanding of PYX's entire thermal decomposition process.

Tree ecophysiology in the context of climate change

Forest structure and function strongly depend on and concurrently influence environmental conditions.Tree performance is generally governed by its genetics and environment;thus,recent hotspots in this field include tree genotype×environment,phenotype×environment,and functional trait×environment interactions.The editorial,review,and 22 original research articles in this Special Issue,"Tree ecophysiology in the context of climate change",highlight ecophysiological phenomena(e.g.,climate hormesis,seed germination,tree mortality),processes(e.g.,tree metabolism,photosynthate allocation,nutrient uptake and transport),indicators(e.g.,carbon sequestration,pollutants),measurements(e.g.,thermal time methods,soil quality indices,vegetation spectral index,and near-infrared leaf reflectance),and modeling(e.g.,climate correlations with tree growth,photo synthetic phenology,hydraulic strategies,OliveCan model)in the context of global climate change.Understanding forest-environment interactions from an ecophysiological perspective as climate changes provides insights into species fitness in suboptimal environments,species competition for limited resources,and phylogenetic divergence or convergence of species,and predicting species distributions.

Extraction of Natural Nanostructured Hydroxyapatite from Pacific Cod(Gadus macrocephalus)Bone with a Thermostable Collagenolytic Protease and Its ex vivo Intestinal Bioavailability

Natural nano-hydroxyapatite(HA)was extracted from Pacific cod(Gadus macrocephalus)bone with a thermostable col-lagenolytic protease in the present study.Conditions for the enzymatic reaction were optimized to be 60℃and pH 7.0,and a desir-able extraction efficiency was achieved by using the crude collagenolytic protease.Dynamic light scattering,transmission electron microscopy and energy-dispersive X-ray analysis revealed that nano-HA are anionic spherical(about 110nm)particles mainly com-prised of calcium and phosphorus at an approximate ratio of 5:3.As evaluated with the mouse ex vivo intestinal segments,the extracted nano-HA displayed comparable level of intestinal bioavailability to the positive control CaCl_(2).By treating with inhibitors(NaN3,ami-loride)and low temperature(4℃),clathrin-mediated endocytosis was assumed to involve the intestinal absorption of nano-HA.Over-all,the application of thermostable collagenolytic protease is proved to be a promising alternative method for nano-HA extraction from natural resource with improved ecological and biological value.

Thermostability of Vane Absorber

Aim To improve the thermostability of vane absorbers while designing and manu- facturing. Methods Having considered the structural features of vane absorbers, measures that could reduce the force decay ratio of vane absorbers were discussed. A kind of practical auto temperature compensation apparatus, whose theoretical basis had been discussed, was designed. Results Compared to the prototype vane absorber, this kind of apparatus could decrease force decay ratio sharply. Thus, the thermostability of vane absorbers was improved greatly The accuracy of theoretical analysis and the effectiveness and feasibility of the apparatus was proved by actual testing Conclusion changing vane absorber's configuration, its performance is improved.

聚硫醚酮与聚苯硫醚的合成及热性能研究

聚硫醚酮;聚苯琉醚;合成;

Thermostability,mechanical and tribological behaviors of polyimide matrix composites interpenetrated with foamed copper

Polyimide matrix composites interpenetrated with foamed copper were prepared via pressure impregnation and vacuum immersion to focus on their thermostability, mechanical and tribological behaviors as sliding electrical contact materials. The results show that the interpenetrating phase composites（IPC） are very heat-resistant and exhibit higher hardness as well as bending strength, when compared with homologous polyimide matrix composites without foamed copper. Sliding electrical contact property of the materials is also remarkably improved, from the point of contact voltage drops. Moreover, it is believed that fatigue wear is the main mechanism involved, along with slight abrasive wear and oxidation wear. The better abrasive resistance of the IPC under different testing conditions was detected, which was mainly attributed to the successful hybrid of foamed copper and polyimide.

Purification and Characterization of a New Thermostable κ-CarrageenasefromtheMarineBacterium Pseudoalteromonas sp. QY203

A new extracellular κ-carrageenase, namely CgkP, 34.0 kDa in molecular weight, was purified from Pseudoalteromonas sp. QY203. CgkP showed relatively high activity at acidities ranging from pH6.0 to pH9.0 and temperatures ranging from 30℃ to 50℃ with the highest activity at 45℃ and pH7.2. Sodium chloride increased its activity markedly, and KC1 increased its activity slightly. The divalent and trivalent metal ions including Cu^2＋, Ni^2＋, Zn^2＋, Mn^2＋, Al^3＋ and Fe^3＋ significantly inhibited its activity, while Mg^2＋ did not. CgkP remained 70% of original activity after being incubated at 40℃ for 48h, and remained 80% of the activity after being incubated at 45℃ for 1 h. It exhibited endo-κ-carrageenase activity, mainly depolymerizing the κ-carrageenan into disaccharide and tetrasaccharide. CgkP was more thermostable than most of previously reported κ-carrageenases with a potential of being used in industry.

Sperm immobilization activity of Allium sativum L. and other plant extracts

<abstract>Aim: To identify possible spermicidal agents through screening a number of edible medicinal plants with antimicrobial activity. Methods: Initial screening was made on the basis of ram cauda epididymal sperm immobilization immediately after addition of extracts. The most potent extract was selected and was evaluated on both ram and human spermatozoa. To unravel its mode of action several sperm functional tests were carried out, namely viability of cells, hypo-osmotic swelling test for membrane integrity and assays of membrane-bound enzyme 5'-nucleotidase and acrosomal marker enzyme acrosin. Results: The crude aqueous extract of the bulb of Allium sativum L. showed the most promising results by instant immobilization of the ram epididymal sperm at 0.25 g/mL and human ejaculated sperm at 0.5 g/mL. Sperm immobilizing effects were irreversible and the factor of the extract responsible for immobilization was thermostable up to 90 癈. On boiling at 100 癈 for 10 minutes, this activity was markedly reduced. Moreover, this extract was able to cause aggregation of ram sperms into small clusters after 30 minutes of incubation at 37 癈. However this property was not found in human spermatozoa. More than 50 % reduction in sperm viability and hypo-osmotic swelling occurred in treated sperm as compared with the controls, indicating the possibility of plasma membrane disintegration which was further supported by the significant reduction in the activity of membrane bound 5'-nucleotidase and acrosomal acrosin. Conclusion: The crude aqueous extract of A. sativum bulb possesses spermicidal activity in vitro.

Thermostable ethanol tolerant xylanase from a cold-adapted marine species Acinetobacter johnsonii

A xylanase-producing bacterium, isolated from deep sea sediments, was identified as the cold-adapted marine species Acinetobacter Johnsonii. A cold-adapted marine species Acinetobacter Johnsonii could grow at 4 ℃. The optimum temperature and pH of xylanase from a cold-adapted marine species Acinetobacter Johnsonii were 55 ℃ and pH 6.0. Xylanase from a cold-adapted marine species Acinetobacter Johnsonii remained at 80% activity after incubation for 1 h at 65 ℃. The xylanase activity was 1.2-fold higher in 4% ethanol solution than in ethanol free solution. Gibbs free energy of denaturation, ΔG, was higher in 4% ethanol solution than in ethanol free solution. Thermostable ethanol tolerant xylanase was valuable for bioethanol production by simultaneous saccharification and fermentation process with xylan as a carbon source.

Purification and Characterization of a Novel Thermostable Chitinase from Thermomyces lanuginosus SY2 and Cloning of Its Encoding Gene

A novel thermostable extracellular chitinase was purified from the culture filtrate of Thermomyces lanuginosus SY2 by using diethylaminoethyl Sepharose chromatography and Phenyl-Sepharose chromatography. The molecular size of the purified chitinase was estimated to be 48 kDa by sodium dodecyl sulfate-polyacrylamide gel electrophoresis. The chitinase exhibited optimum catalytic activity at pH 4.5 and 55℃. The enzyme was stable at 50℃, and its half-life time at 65℃ was 25 rain. The thermostable chitinase was obtained with 60% of the full activity, when it was incubated in the buffer （pH 2.5）. The enzyme showed the unique properties for thermostability and pH stability since it was one of the most thermostable chitinases so far isolated in fungi. Ca^2＋, Ba^2＋, Na^＋, and K^＋ enhanced the enzyme activity, whereas Fe^2＋, Ag^＋, Hg^2＋, and ethylene diamine tetraacetic acid caused obvious inhibition. The N-terminal amino acids were AQGYLSVQYFVNWAI. Degenerate primers based on the N-terminal sequences of purified chitinase and a cDNA fragment encoding the chitinase gene were obtained through reverse transcriptase-polymerase chain reaction amplication. The RACE was used to generate full-length cDNA clones. The cDNA of chit contained an open reading frame of 1 326 bp encoding 442 amino acids. The gene chit has been registered in GenBank with accession number DQ092332. The alignment results of putative amino acid sequence showed the lower similarity to other chitinases in family-18 except for the catalytic domain containing two conserved motifs related with catalytic activity of chitinase.

A versatile nano-TiO_(2) decorated gel separator with derived multi-scale nanofibers towards dendrite-blocking and polysulfide-inhibiting lithium-metal batteries

In this study,a versatile fluorine-bearing gel membrane with multi-scale nanofibers was rationally designed and synthesized via facile one-step blend electrospinning of nano-titanium dioxide(TiO_(2))particles and fluorinated poly-m-phenyleneisophthalamide(PMIA)polymer solution.The prepared multiscale TiO_(2)-assisted gel separator presented relatively high porosity,small aperture,giving rise to superior affinity to electrolyte and sufficient active sites to accelerate lithium ions migration.Meanwhile,the asfabricated multifunctional GPE also rendered outstanding heat-resistance and well-distributed lithiumions flux,and the mutual overlaps between the coarse fibers and the fine fibers within the multi-scale nanofiber membrane provided a strong skeleton support,which in turn laid a solid footing stone for high-security and dendrite-proof batteries.Particularly,the nano-TiO_(2) particles within PMIA membrane acted as"gatekeepers",which can not only resist the growth of lithium dendrites,but also intercept the dissolved polysulfide on cathode side.Based on these merits,the gel PMIA-based lithium cobalt(LCO)/lithium battery obtained the remarkably improved rate capability and cycle performances on account of superior ionic conductivity,steady anodic stability window and weakened polarization behavior.Meanwhile,the resultant lithium-sulfur cell also delivered the outstanding cycling stability with the aid of the greatly prevented"shuttle effect"of dissolved lithium polysulfides based on the physical trapping and chemical binding of the prepared GPE to polysulfides species.This work proved that the addition of functional inorganic nanoparticles similar with TiO_(2) in multi-scale gel PMIA membrane can enhance the lithium ions transport capability,resist the growth of lithium dendrites as well as inhibit the shuttle effect of polysulfides,which would prompt a great development for dendrite-blocking and polysulfideinhibiting lithium-metal cells.

Synthesis,characterization,and thermostability of bis(2,2,6,6-tetramethyl-3,5-heptanedionato)copper(Ⅱ)

Owing to the adaptability to large scale processing,excellent composition control and film uniformity,the metal-organic chemical vapor deposition（MOCVD） technique is a promising process for high-temperature superconductor YBa;Cu;O;（YBCO） preparation.In this technique,the evaporation characteristics and thermostability of adopted precursors in whole process will decide the quality and reproducible results of YBCO film.In the present report,bis（2,2,6,6-tetramethyl-3,5-heptanedionato）copper（II）(Cu（TMHD）;) was synthesized by the interaction of copper acetate hydrate with TMHD in methanol solution,and its structure was identified by FTIR,1 H NMR,and EI-MS spectroscopy.Subsequently,thermal property and the kinetics of decomposition were systematically investigated by nonisothermal thermogravimetric analysis methods（TGA） at different heating rates in streams of N;,and the average apparent activation energy of evaporation process was evaluated by the Ozawa,Kissinger,and Friedman methods.The possible conversion function was estimated through the Coats-Redfern method to characterize the evaporation patterns and followed a phase boundary reaction mechanism by the contracting area equation with average activation energy of 85.1 kJ·mol;.

Effects of the Composition of Electrodeposited Fe-Ni-P Alloy on the Thermostability and Magnetic Properties

The magnetic properties, structure defects of electrodeposited Fe-Ni-P alloys with various compositions and the thermostability at amorphous state have been studied by DSC, positron annihilation and electronic integrating instrument methods. The results show that the thermostability of amorphous Fe-Ni-P alloys increases with Fe content. Emergence and recrystallization of stable phases defer as the P content of the coating increases. The minimum H-c, B-r and P-h occur at 9.4 P (wt pet) content. Maximum H-c, B-r and P-h occur at the weight ratio of Fe to Ni equaling to 1/9.

Enhancement of the thermostability of β-1,3-1,4-glucanase by directed evolution

In order to improve the thermostability of β- 1,3-1,4-glucanase, evolutionary molecular engineering was used to evolve the β-1,3-1,4-glucanase from Bacillus subtilis ZJF-1A5. The process involves random mutation by error-prone PCR and DNA shuffling followed by screening on the filter-based assay. Two mutants, EGsl and EGs2, were found to have four and five amino acid substitutions, respectively. These substitutions resulted in an increase in melting temperature from Tm=62.5℃ for the wild-type enzyme to Tm=65.5℃ for the mutant EGsl and 67.5℃ for the mutant EGs2. However, the two mutated enzymes had opposite approaches to produce reducing sugar from lichenin with either much higher （28%） for the former or much lower （21.6%） for the latter in comparison with their parental enzymes. The results demonstrate that directed evolution is an effective approach to improve the thermostability of a mesophilic enzyme.

Thermostable Broad Band Polarizing PVA-Film: Theoretical and Experimental Investigations

In the present work, for the first time on the basis ofpoly （vinyl alcohol） （PVA）, 2- （4-dimethylaminostyryl）-l-ethylquinolinium iodide （quinaldine red （QR）） and trisodium （4E）-5-oxo- 1-（4-sulfonatophenyl）-4-[（4-sulfonatophenyl）hydrazono]-3 pyrazolecarboxylate （tartrazine （T））, thermostable polarizing film in a wide range of spectra （λmax=394-511 nm） with polarization efficiency （PE） = 98% in absorption maximum and stretching degree （Rs） = 3.5 was developed. The basic spectral-polarization parameters （polarization efficiency and transmittance） of oriented colored PVA-films were measured and discussed. During the work it was found that oriented PVA-films are the phenomenon of anisotropy of thermal conductivity （λ｜/λ⊥）. It is a very important parameter for the development of thermostable PVA-polarizing films. For the first time quantum-chemical calculations using density functional theory （DFT） approach for structural analysis and electronic spectrum of the QR were carried out via the B3LYP/dgdzvp and TDB3LYP/dgdzvp methods. Interpretation of absorption strips in visible region of spectrum was also reported. The excitation energies, electronic transitions and oscillator strengths for the studied structures have also been calculated （B3LYP/dgdzvp）. The NBO analysis and Mulliken atomic charges of the QR were carried out.

Discovery and Characterization of a Thermostable Esterase from an Oil Reservoir Metagenome

With the aim of identifying novel thermostable esterases, comprehensive sequence databases and cloned fosmid libraries of metagenomes derived from an offshore oil reservoir on the Norwegian Continental Shelf were screened for enzyme candidates using both sequence-and function-based screening. From several candidates identified in both approaches, one enzyme discovered by the functional approach was verified as a novel esterase and subjected to a deeper characterization. The enzyme was successfully over-produced in Escherichia coli and was shown to be thermostable up to 90°C, with the highest esterase activity on short-chain ester substrates and with tolerance to solvents and metal ions. The fact that the thermostable enzyme was solely found by functional screening of the oil reservoir metagenomes illustrates the importance of this approach as a complement to purely sequence-based screening, in which the enzyme candidate was not detected. In addition, this example indicates the large potential of deep-sub-surface oil reservoir metagenomes as a source of novel, thermostable enzymes of potential relevance for industrial applications.

在5L自控发酵罐内热稳定β淀粉酶的发酵

在５Ｌ自控发酵罐内热稳定β淀粉酶的发酵周蓓芸郑幼霞（中国科学院上海植物生理研究所上海２０００３２）β淀粉酶是一种外切型淀粉水解酶，它从淀粉的非还原性末端依此水解α１４葡萄糖苷键，产生β构型的麦牙糖，在食品、医药工业上有很大用途，但目前工业上...

Correlation between Structure and Thermal Properties of N-vinyl-3-alkylimidazolium Magnetic Ionic Liquids

Influence of structural variations of N-vinylimidazolium tetrahalogenidoferrate(III) magnetic ionic liquids(MILs) on thermal properties was investigated. Using Gaussian09/B3 PW91/6-311 G(2d, p) density functional methods, the microstructure of the MILs were analyzed. With differential scanning calorimeter(DSC) and thermogravimetric analysis(TGA), the thermal properties of the MILs were performed. The results showed that the interaction energies of ion pairs decreased, the crystallization temperature increased first and then decreased, and the surfusion first decreased and then increased with the elongation of the alkyl chain length on cation;with the increase of Br atom, the interaction energies of ion pairs increased;the interaction energies of ion pairs increased in the MILs with the same cation or anion, the nature of polarity of MILs increased and the melting point rose;as the cation or anion in MILs had a smaller size, it could have the solidsolid transition temperature. The results indicated that the decomposition temperature with the same type of MILs increased with the interaction energies of ion pairs. The interaction energy of ion pairs can be used to illuminate the correlation between the thermal properties and the structure of MILs. ILs possesses the properties of macromolecular.

Characterization of Ser73 in Arabidopsis thaliana Glutathione S-transferase zeta class

Glutathione S-transferases （GSTs） are ubiquitous detoxifying superfamily enzymes. The zeta class GST from Arabidopsis thaliana （AtGSTZ） can efficiently degrade dichloroacetic acid （DCA）, which is a common carcinogenic contaminant in drinking water. Ser73 in AtGSTZ is a conserved residue at Glutathione binding site （G-site）. Compared with the equivalent residues in other GSTs, the catalytic and structural properties of Ser73 were poorly investigated. In this article, site-saturation mutagenesis was performed to characterize the detailed role of Ser73. The DCA dechlorinating （DCA-DC） activity showed that most of the mutants had less than 3% of the wild-type activity, except S73T and S73A showing 43.48% and 21.62% of the wild-type activity, respectively, indicating that position 73 in AtGSTZ showed low mutational substitutability. Kinetic experiments revealed that mutants S73T, S73A, and S73G showed low binding affinity and catalytic efficiency toward DCA, 1.8-, 3.1-, and 10.7- fold increases in KmDcA values and 4.0-, 9.6-, and 34.1- fold decreases in Kcat- DCA/KmDCA values, respectively, compared to the wild type. Thermostability and refolding experiments showed that the wild type mainmined more thermostability and recovered activity. These results demonstrated the important role of Ser73 in catalytic activity and structural stability of the enzyme. Such properties of Ser73 could be particularly crucial to the molecular evolution of AtGSTZ and might, therefore, help explain why Ser73 is conserved in all GSTs. This conclusion might provide insights into the directed evolution of the DCA-DC activity of AtGSTZ.

Characterization of a thermostable manganese-containing superoxide dismutase from inshore hot spring thermophile Thermus sp.JM1

A thermostable superoxide dismutase （SOD） from the inshore thermophile Thermus sp. JM1 was purified to homogeneity by steps of fractional ammonium sulfate precipitation, DEAE-Sepharose chromatography and Phenyl-Sepharose chromatography. The specific activity of the purified native enzyme was 1 656 U/mg. A sod gene from this strain was cloned and overexpressed in Escherichia coli （E. coli）. The prepared apo-enzyme of the purified recombinant SOD （rSOD） was reconstituted with either Fe or Mn by means of incubation with appropriate metal salts. As a result, only Mn 2＋ - reconstituted rSOD （Mn-rSOD） exhibited the specific activity of 1 598 U/mg. SOD from Thermus sp. JM1 was Mn-SOD, judging by the specific activities analysis of Fe or Mn reconstituted rSODs and the insensitivity of the native SOD to both cyanide and H 2 O 2 . Both the native SOD and Mn- rSOD were determined to be homotetramers with monomeric molecular mass of 26 kDa and 27.5 kDa, respectively. They had high thermostability at 50 ° C and 60 ° C, and showed striking stability across a wide pH span from 4.0 to 11.0.