Lacunary silicotungstic heteropoly salts as high-performance catalysts in oxidation of cyclopentene

The development of polyoxometalates for olefin oxidation is critical to achieving the green chemical process of the C5 fraction further processing.Di-lacunary silicotungstic anions were easily obtained by continuously adjusting the p H instead of the traditional step-by-step method,which exhibited excellent performance in the catalytic oxidation of cyclopentene(CPE)to aldehydes or alcohols.The 93.69%CPE conversion and 97.15%total product selectivity(41.38%for glutaraldehyde(GA)and 55.77%for 1,2-cyclopentanediol(1,2-diol)were achieved by using H_(2)O_(2)as the oxidant and acetonitrile as the solvent.Through complementary characterization,it was found that the optimized di-lacunary silicotungstic polyoxometalate retained a complete Keggin structure,and exhibited better catalytic activity and stability than the mono-lacunary or saturated silicodecatungstate because it exposed more catalytic active centers.Furthermore,in situ FT-IR spectra was utilized to monitor the reaction process,revealing the formation of the active species W(O_(2))on the di-lacunary silicotungstic polyoxometalate and the intermediate epoxycyclopentane during the catalytic oxidation of cyclopentene.

Syntheses and Application of All-lithium Salts of Heteropolyacid as Electrolyte of Lithium-ion Battery

The all-lithium salts of heteropoly acid Li_xXM_ 12O_ 40(HPA-Li)(X=P, Si; M=Mo, W) were obtained via ion exchange and characterized by means of IR and UV spectroscopies, TG and elemental analyses. The conductivity of the electrolytic solution consisting of Li_3PW_ 12O_ 40 and PC/DME mixing solvent(1/2.5, volume ratio) is up to 7.2×10 -2 S/cm, being higher than that of LiClO_4 as the electrolyte. The all-lithium salts were used as electrolytes in secondary lithium-ion batteries. The discharge capacity of the PAS/Li batteries with Li_3PW_ 12O_ 40 electrolyte solutions reaches to 148 (mA·h)/g and the cyclic life is up to 380 times, much better than those of commercialized products with LiClO_4 and LiAsF_6 as electrolytes.

HYDROXYLATION OF BENZENE BY HETEROPOLY ACIDS(SALTS)CONTAINING VANADIUM

Direct hydroxylation of benzene catalyzed by vanadium-con- taining heteropoly compounds with Keggin or Dawson structure has been investigated.The effects of several factors upon the hydroxylation reaction have also been examined.It is indicated that the highest yield of phenol reached 76%(based on H_2O_(?))with 99.4～100% selectivity.

Physiological Mechanism of Salicylic Acid for Alleviation of Salt Stress in Rice

Soil salinity is one of the most important problems of crop production in estuarine and coastal zones. Improvement in salt tolerance of major food crops is an important way for the economic utilization of coastal zones. This study proved that the application of salicylic acid(SA) improved the growth and yield under salt stress conditions and investigated its physiological mechanisms for salt tolerance. The investigation on the effect of SA for salt tolerance during germination showed that the decreased rates of germination and growth(in terms of shoot and root lengths) by the salt stress were significantly increased by the SA application(SA + NaCl). The treatment of SA to the high and low saline soils enhanced the growth, yield and nutrient values of rice. The effects of SA on Na^+, K^+ and Cl~– ionic accumulation were traced under salt stress condition by inductively coupled plasma optical emission spectrometry and ion chromatography. It was revealed that the increased accumulation of Na^+ and Clˉ ions by the salt stress were reduced by SA application. An increased concentration of endogenous SA level was detected from the SA-treated rice varieties(ASD16 and BR26) by liquid chromatography electrospray Ionization-tandem mass spectrometry. The activities of antioxidant enzymes such as superoxide dismutase, catalase and peroxidase were increased by salt stress whereas decreased by the SA application. The study proved that the application of SA could alleviate the adverse effects of salt stress by the regulation of physiological mechanism in rice plants. In spite of salt stress, it can be applied to the coastal and estuarine regions to increase the rice production.

Effect of Ascorbic Acid and Silicium on Photosynthesis, Antioxidant Enzyme Activity, and Fatty Acid Contents in Canola Exposure to Salt Stress

The effects of exogenous ascorbic acid and silicium on leaf fresh weigh, seed yield, photosynthesis, changes of the activities of major antioxidant enzymes, nitrate reductase activity, proline accumulation, chlorophyll content, and fatty acid composition were investigated in salt-stressed canola. A hydroponic pot experiment was conducted based on randomized complete block design, factorial arrangement was used with 16 combinations of salinity stress （0, 100, 200, and 300 mmol L-1 NaC1）, ascorbic acid （0 and 30 mmol L-1）, and silicium （2 and 4 mmol L-1 from potassium silicate） with three replicates. The results showed that salinity significantly decreased leaf area and leaf fresh weight, seed yield, photosynthesis, nitrate reductase activity, chlorophyll content, and seed protein percentage. Conversely, respiration, antioxidant enzymes activity, proline accumulation, and linolenic acid percentage increased due to salt stress. Ascorbic acid application improved photosynthesis and seed yield and mitigated antioxidant enzyme activity. In addition, nitrate reductase activity and chlorophyll a and b were positively affected by ascorbic acid. Regarding silicium application, that was found that leaf area, leaf fresh weight, seed yield and photosynthesis, ascorbate peroxidase activity, nitrate reductase activity, and chlorophyll content increased, while respiration decreased. Furthermore, silicium had not significant effect on antioxidant enzyme activity. In general, ascorbic acid and silicium were involved in the defensive mechanisms against salinity stress and it can be suggested that, ascorbic acid and silicium application had positive effect on canola growth under conditions of salt stress.

Effects of Cinnamic Acid on Bacterial Community Diversity in Rhizosphere Soil of Cucumber Seedlings Under Salt Stress

To investigate the effects of a plant autotoxin, cinnamic acid, on bacterial communities in the rhizosphere soil of cucumber seedlings under salt stress, we used cucumber as the experimental material, cinnamic acid as the autotoxin, and NaCl to apply salt stress. Bacterial communities in the rhizosphere soil were analyzed using polymerase chain reaction （PCR）, denaturing gradient gel electrophoresis （DGGE）, and clone sequencing. Salt stress decreased the diversity of bacterial species in rhizosphere soil of cucumber seedlings at several growth stages. Cinnamic acid exacerbated the effects of salt stress at high concentrations, but alleviated its effects at low concentrations. Cloning and sequencing results indicated that DGGE bands amplified from soil samples showed high homology to uncultured bacterial species. Cinnamic acid at 50 mg kg^-1 soil improved cucumber growth and was the most effective treatment to alleviate the effects of salt stress on bacterial communities.

Toluene Alkylation with Methanol to p-Xylene over Heteropoly Acids Supported by Clay

The alkylation of toluene with methanol for the selective formation of p-xylene was systematically studied. Very few studies have been reported on the use of superacids such as heteropolyacids on cheap supports, such as clay. This article deals with the use of different heteropoly acids （HPAs）, viz, Dodeca-Tungstophosphoric acid [H3PO4.12WO3.xH2O] （TPA）, Dodeca-Molyhdo phosphoric acid ammonium salt hydrate [H12Mo12N3O40P＋aq] （DMAA）, Dodeca-Molyhdo Phosphoric acid （PMA） on clay （MontmoriUonite, K-10） and as such plain clay. This comparative study reveals that 20%PMA/Clay shows 62% toluene conversion and 100% selectivity toward p-xylene.

Reductive smelting of spent lead–acid battery colloid sludge in a molten Na_2CO_3 salt

Lead extraction from spent lead–acid battery paste in a molten Na2CO3 salt containing Zn O as a sulfur-fixing agent was studied. Some influencing factors, including smelting temperature, reaction time, Zn O and salt dosages, were investigated in detail using single-factor experiments. The optimum conditions were determined as follows: T = 880°C; t = 60 min; Na2CO3/paste mass ratio = 2.8:1; and the Zn O dosage is equal to the stoichiometric requirement. Under the optimum conditions, the direct recovery rate of lead reached 98.14%. The results suggested that increases in temperature and salt dosage improved the direct recovery rate of lead. XRD results and thermodynamic calculations indicated that the reaction approaches of lead and sulfur were Pb SO4→Pb and Pb SO4→Zn S, respectively. Sulfur was fixed in the form of Zn S, whereas the molten salt did not react with other components, serving only as a reaction medium.

Alkali salts of heteropoly tungstates: Efficient catalysts for the synthesis of biodiesel from edible and non-edible oils

Alkali salts of tungsten based heteropoly acids with different central atom such as P, Si and Co were prepared and evaluated for transes- terification of both edible and non-edible oils to their corresponding fatty acid methyl esters. The catalyst of sodium salt of tungstic acid with Co as central atom （Na5CoW12O40） showed optimum activity towards transesterification compared with other heteropoly tungstates. The catalysts activities were correlated with the observed physico-chemical characteristics derived from FT-infrared （FT-IR）, X-ray diffraction （XRD）, temperature-programmed desorption of ammonia （NH3-TPD） and carbon dioxide （CO2-TPD）. The Na5CoW12O40 catalyst exhibiting high activity even at 65 ℃ is due to the presence of strong acidic as well as basic sites. The disclosed catalyst is tolerable towards water and free fatty acids present in the oils. The influence of catalyst loading, reaction time and reaction temperature is studied to optimize the reaction parameters.

Effect of acid phosphatase produced by Trichoderma asperellum Q1 on growth of Arabidopsis under salt stress

Salt stress is a major environmental factor that inhibits crop growth.Trichoderma spp.are the most efficient biocontrol fungi and some of the strains can stimulate plant growth.Phosphate solubilization is known as one of the main mechanisms in promoting plant growth,but the underlying mechanisms of phosphate solubilization in the salinity still need to be explored.The Trichoderma asperellum Q1 isolated and identified in our lab is a beneficial rhizosphere biocontrol fungus with a high phosphate solubilization activity.It could produce acid and alkaline phosphatases when using insoluble organic phosphorus as the sole phosphorus source,the salt stress increased the phosphorus-solubilization ability of the strain and the activities of the two enzymes.Furthermore,an acid phosphatase was purified from the fermentation broth by ammonium sulphate precipitation,ion-exchange,and gel filtration chromatography.Its molecular weight was 55 k Da as determined by SDS-PAGE.The purified acid phosphatase was used to investigate growth performance of Arabidopsis thaliana by plate assay and the result showed that it contributed to Arabidopsis growth by transforming organic phosphate into a soluble inorganic form under salt stress.To our knowledge,this is the first report on acid phosphatase purification from T.asperellum and its function in regulation of plant growth under salt stress.

CATIONIC RING-OPENING POLYMERIZATION OF TETRAHYDROFURAN WITH KEGGIN-TYPE HETEROPOLYCOMPOUNDS AS SOLID ACID CATALYSTS

Three Keggin-type heteropolyanions, namely H3PMo12O40-13H2O, （NH4）3PMo12O40·4H2O and H3PW12O40·13H2O were prepared and tested in the ring-opening polymerization reaction of tetrahydrofuran. The effects of the counter-cation （H＋, NH4＋） and the peripheral atoms （Mo, W） on the polymerization were investigated. It has been found that when the protons of H3PMo12O40·13H2O were replaced by the ammonium cations the polymerization rate decreased dramatically. Whereas, when the peripheral atoms （Mo） were replaced by their homologous （W）, the polymerization rate increased twofold. As for the viscosity average molecular weight （My） of polymer products, it was found that the high molecular weight （7930） was obtained by using H3PW12O40·13H2O. The molecular weight （My） obtained by H3PMo12O40·13H2O and （NH4）H3PMo12O40·13H2O was 6470 and 6810, respectively.

Analysis of Organic Acids Accumulated in Kochia Scoparia Shoots and Roots by Reverse-phase High Performance Liquid Chromatography Under Salt and Alkali Stress

Several organic acids accumulated in Kochia Scoparia shoots and roots were studied by means of reverse-phase high performance liquid chromatography with a C18 column. Five types of binary organic acids were separated. The organic acid concentrations were determined in K. Scoparia seedlings stressed by saline （NaCI） and alkaline （NaHCO3） at the same Na^＋ concentration. Concentrations of organic acids are stimulated by alkaline because the cells will adjust their pH values through the accumulation of organic acids, when the environment is basic. The concentrations of oxalic acid and succinic acid are higher than those of other organic acids, including tartaric acid and malic acid, and the concentration of citric acid is the lowest. The concentrations of the organic acids in the roots are higher than those in the shoots under salt（NaCI） stress, but the results are opposite while the roots are under alkali （ NaHCO3 ） stress. This indicates that there are different adaptive strategies for K. Scopar/a seedlings in organic acid metabolism under salt and alkali stress.

Effects of Exogenous Trehalose on the Metabolism of Sugar and Abscisic Acid in Tomato Seedlings Under Salt Stress

Salt stress a ects the growth and development of plants, which results in a decrease in crop quality and yield. In this study, we used tomato seedlings treated with salt and trehalose as experimental materials and analyzed them using the technique for order preference by similarity to ideal solution analysis to select the optimal trehalose concentration for treatment. We also determined the contents of sugar and abscisic acid (ABA) and detected the expression of genes involved in the metabolism of sugar and ABA by quantitative real-time PCR. Results showed that the optimal trehalose concentration was 2 mmol/L for tomato seedlings under salt stress. Exogenous trehalose decreased the starch content and increased the soluble sugar con- tent by a ecting the expression of genes related to the metabolism of starch and soluble sugar. Exogenous trehalose altered the accumulation and distribution of sugar by inducing the upregulation of sugar transporter genes. Furthermore, trehalose increased the ABA content to induce salt stress response by regulating the expression of genes related to the synthesis and metabolism of ABA. In conclusion, trehalose can e ectively alleviate salt stress and enhance salt tolerance of tomato. These ndings provide a novel perspective and a better resource to investigate the salt tolerance mechanism and a new method for alleviating salt stress in tomato.

Cloning of Bile Salt Hydrolase Gene and Its Expression in Lactic Acid Bacteria

According to the sequence of the bile salt hydrolase （BSH） gene of Bifidobacterium and the restriction enzyme cutting sites of expression vector pNZ8148, primers were designed and the bile salt hydrolase （BSH） gene was gotten from Bacillus bifidus ATCC 29521 by PCR. BSH gene was inserted into lactic acid bacteria expression vector pNZ8148 to construct the recombinant pNZ8148-BSH. The recombinant pNZ8148-BSH was transferred into lactic acid bacteria NZ9000 with electrotransformation method. And the recombinant which could express BSH protein was obtained. It was identified by SDS-PAGE electrophoresis and activity verification. The result could provide a rationale reference for expressing BSH in lactic acid bacteria.

Hydroxylation of Benzene with Hydrogen Peroxide over Highly Efficient Molybdovanadophosphoric Heteropoly Acid Catalysts

Keggin 类型 molybdovanadophosphoric heteropoly 酸， H3+nPMo12-nVnO40 (n = 1 3 ) ，被一个新奇环境联盟者准备良性的方法，和他们的催化表演在冰川的醋酸和 acetonitrile 的混合溶剂作为氧化剂与氢过氧化物经由苯的 hydroxylation 被评估到酚。各种各样的反应参数例如反应时间，反应温度，到氢过氧化物的苯的比率，水的氢过氧化物的集中，到在溶剂和催化剂集中的 acetonitrile 的冰川的醋酸的比率，被改变获得最佳的反应条件。H3+nPMo12-nVnO40 (n = 1 3 ) 被揭示是为苯的 hydroxylation 的高度有效的催化剂。在 H5PMo12-nVnO40 的情况下，有 100% 的酚的选择的 34.5% 的苯的变换能以最佳的反应条件被获得。

Clinical Non-inferiority Trial on Treatment of Coronary Heart Disease Angina Pectoris of Xin-blood Stasis Syndrome Type with Lyophilized Salvia Salt of Lithospermic Acid Powder for Injection

Objective： To evaluate the effectiveness and safety of lyophilized Salvia salt of lithospermic acid powder for injection （SSLA） in treating coronary heart diseases angina pectoris （CHD-AP） of Xin-blood stasis syndrome type, and to conduct the non-inferiority trial with Danshen injection （丹参注射液, DSI） as positive control. Methods： An non-inferiority clinical layered, segmented, randomized, and blinded trial on three parallel and multiple centered groups was conducted in 480 patients with stable effort angina grade Ⅰ , Ⅱand Ⅲ, who had two or more times of attack every week. The 240 patients in test group A were treated with SSLA 200 mg added in 250 ml of 5% glucose solution for intravenous dripping every day; the 120 patients in test group B were treated with SSLA but the dosage doubled; and the 120 patients in the control group were treated with DSI 20 ml daily in the same method as SSLA was given. The clinical effectiveness and safety were evaluated after the patients were treated for 14 days. Results： The results showed that the markedly effective rate in test groups A, B and control group was 37.45 %, 36.75 % and 30.09 % respectively, while the total effective rate in them was 88.09%, 89.74% and 67.26% respectively. Statistical significance was shown in comparisons of the therapeutic effect between control group with test group A and test group B, with that in the two test groups superior to that in the control group, and non-inferiority trial showed eligibility （P〈0.01）. Adverse reaction appeared in 8 patients in the test groups and 2 in the control group. Conclusion： SSLA has definite therapeutic effect in treating patients with CHD-AP, with its effect not inferior to that of DSI, and no evident toxic-adverse reaction.

Increasing Fatty Acids in Rice Root Improves Silence of Rice Seedling to Salt Stress

Salt stress is one of the major abiotic stresses around the world, and salt salinity is one of the major constrains affecting rice production (Tu et al, 2014;Reddy et al, 2017). According to the statistics, more than one billion hectares of the land in the major continents are affected by salinity (Fageria et al, 2012;Zhou et al, 2018). Rice is a salt sensitive crop, considered more sensitive to salt stress during early stage (Hasanuzzaman et al, 2009). Understanding the method to improve plant salt tolerance is a potential way to enhance agriculture productivity in the future (Jing and Zhang, 2017). Polyunsaturated fatty acid (PUFA) on plasma membrane plays important roles in salt tolerance through enhancing the activity of Na^+/H^+ transporters (López-Pérez et al, 2009).

Synthesis, Characterization and Inhibition Effects of Vanadium Substituted Dawson-type Heteropoly Acids(Mo, P)

Four new vanadium substituted Dawson-type heteropoly acids H7[P2Mo17VO62]·39H2O（1）, H8[P2Mo16V2O62]·41H2O（2）, H9[P2Mo15V3O62]·51H2O（3） and H8[P2Mo14V4O62H2]·45H2O（4） were prepared respec-tively. Their structures were determined by IR and ICP. The inhibition effects of vanadium substituted Dawson-type heteropoly acids（Mo, P） on free radical polymerization of methyl methacrylate（MMA） were investigated by dilatometry. The results show that the rate of the polymerization of MMA decreases and the inhibition effects of the four heteropoly acids reach the inhibitor performance of hydroquinone at a certain ratio.

Thermal Behaviour of Some New Polyoxometalate Complexes of Ciprofloxacin with Keggin-type Heteropoly Acids

Four polyoxometalate complexes, (CPFX·HCl)_3H_4SiW_~12 O_~40 , (CPFX·HCl)_3H_3PW_~12 O_~40 , (CPFX·HCl)_3H_3PMo_~12 O_~40 and (CPFX·HCl)_4H_4SiMo_~12 O_~40 , were prepared from ciprofloxacin hydrochloride(CPFX·HCl) reacting with H_nXM_~12 O_~40 ·nH_2O(X=P,Si; M=W,Mo) in an aqueous solution, and characterized by elemental analysis, IR spectrometry and TG-DTA. The IR spectrum confirms the presence of Keggin-type anions of heteropoly acids and the characteristic functional groups of ciprofloxacin. The TG/DTA curves show that their thermal decomposition is a multi-step process including simultaneous collapse of the Keggin-type structure. At first, these compounds had a mass loss of water molecules, then several other mass losses occured due to the decomposition of ciprofloxacin hydrochloride and its fragments with the degradation of Keggin anions. The end product of decomposition is the mixture of WO_3(or MoO_3) and SiO_2(or P_2O_5), identified by X-ray diffraction and IR spectroscopy. The possible thermal decomposition mechanisms of these complexes are proposed. This study exemplified that the thermal stability of the complexes containing tungsten is much better than that of the complexes containing molybdenum.

Effect of bile salts and bile acids on human gastric mucosal epithelial cells

Objective：To explore the effect of bile salt and bile acid on cultured eternalized human gastric mucosa epithelium GES-1 cells. Methods：Cultured eternalized human gastric mucosa epithelium GES-1 cells were treated with media containing 6 different kinds of bile salts and 3 different kinds of bile acids and their mixture with different concentrations： GCDC（glycochenodeoxychoμte）, GDC （glycodeoxychoμte）, GC（glycochoμte）, TCDC（taurochenodeoxychoμte）, TDC（taurodeoxychoμte）, TC （taurochoμte）, LCA （lithocholicacid）, CA（cholic acid）, DCA（deoxycholic acid）（50 μ mol/L,250 μ mol/L,500 μ mol/L,1000 μ mol/L）, DY（mixture of bile salts） and DS（mixture of bile acids）（250 μ mol/L,500 μ mol/L,1000 μ mol/L,1500 μ mol/L, 2000 μ mol/L）, in comparison with the control group（in normal media without bile salts and bile acids）. Cell proliferation was assessed by MTT（3-[4,5-Dimethylthiaolyl]-2,5- diphenyl-tetrazolium bromide） assay for 72 hours with different concentrations and the apoptotic cells were assayed by flow cytometry （FCM） with Annex V-FITC conjugated with propidium iodide（PI） staining for 24 hours with different concentrations（1500,2000 μt mol/L）. Results：There was no significant difference in morphology and cell proliferation in GC group after 24-72 h. Low concentration（50 μ mol/L） of GCDC, GDC, TCDC, TDC and TC accelerated gastric epithelial cell growth in a dosage-time dependent manner. At middle concentration （250-500 μ mol/L）, it showed positive effect after 24-48 h, while negative effect after 72 h. At high concentration（1000 μ mol/L）, it accelerated gastric epithelial cell growth after 24h and show consistent inhibition even leading to necrosis after 48-72 h. LCA and CA showed a positive effect on the concentration of 50 μ mol/L after 24-72 h, while 250-1000 μ mol/L showed a trend towards apoptosis after 24-72 h. At 50-500 μmol/L, DCA showed proliferation after 24 h and apoptosis after 48-72 h, but showed necrosis after 24-72 h at 1000 μmol/L. DY and DS could facilitate normal gastric mucosa epithelial cell growth at low concentration （250-500 μ mol/L）, however at 1000-2000 μ mol/L the trend shifted from apoptosis to necrosis. FCM with Annexin-V conjugated with PI staining revealed that GCDC, GDC, GC, TCDC, TDC, TC, LCA, CA, DCA, DY and DS induced apoptosis of human gastric mucosal epithelial cells. They were all significantly higher than that of the control（P 〈 0.05）, but there was no significant difference in GC group （P 〉 0.05）. The bile salts induced apoptosis in a time-dose-dependent manner. Conclusion：Our results suggested that bile acid and bile salt is the trigger of injury in human gastric mucosal epithelial cells.