含有弱金属-氮键的磷钼酸有机衍生物的研究

［（ＥＤＴＢ）Ｍ］（ＣＨ３ＣＯＯ）２和Ｈ３ＰＭｏ１２Ｏ４０在无水乙醇中反应得到［（ＥＤＴＢ）Ｍ］（ＨＰＭｏ１２Ｏ４０），Ｍ为Ｃｕ、Ｃｏ，ＥＤＴＢ为Ｎ，Ｎ，Ｎ′，Ｎ′－四［（２－苯并咪唑）甲基］－１，２－乙二胺。测定了它们的ＩＲ、ＨＮＭＲ、紫外－可见光谱和元素分析以及对酯化和乙酸环己酯热消除反应的催化活性。

Influence of solution temperature on corrosion resistance of Zn-Ca phosphate conversion coating on biomedical Mg-Li-Ca alloys

The influence of phosphating bath at different temperatures on the formation and corrosion property of calcium-modified zinc phosphate conversion coating （Zn-Ca-P coating） on Mg-Li-Ca alloy was investigated. The morphologies, elemental distribution and chemical structures of the coatings were examined via SEM, EPMA, EDS, XRD and FT-IR. The corrosion resistance was assessed by hydrogen evolution, potentiodynamic polarization and EIS. The results show that the coating is composed of single element Zn and ZnO at below 45 ℃;whereas the coatings are predominantly characterized by Zn3（PO4）2·4H2O and small amount of element zinc and ZnO at above 50 ℃. Mg-Li-Ca alloy with Zn-Ca-P coatings prepared at 55 ℃ has the highest corrosion resistance. However, the hydrogen evolution rates of the coatings obtained at 40-50 ℃ is accelerated due to the galvanic corrosion between the imperfection of the single element Zn coating and the Mg substrate.

Corrosion resistance of cerium-doped zinc calcium phosphate chemical conversion coatings on AZ31 magnesium alloy

Zinc calcium phosphate （Zn-Ca-P） coating and cerium-doped zinc calcium phosphate （Zn-Ca-Ce-P） coating were prepared on AZ31 magnesium alloy. The chemical compositions, morphologies and corrosion resistance of coatings were investigated through energy-dispersive X-ray spectroscopy （EDS）, X-ray photoelectron spectroscopy （XPS）, X-ray diffraction （XRD）, electron probe micro-analysis （EPMA） and scanning electron microscopy （SEM） together with hydrogen volumetric and electrochemical tests. The results indicate that both coatings predominately contain crystalline hopeite （Zn3（PO4）2·4H2O）, Mg3（PO4）2 and Ca3（PO4）2, and traces of non-crystalline MgF2 and CaF2. The Zn-Ca-Ce-P coating is more compact than the Zn-Ca-P coating due to the formation of CePO4, and displays better corrosion resistance than the Zn-Ca-P coating. Both coatings protect the AZ31 Mg substrate only during an initial immersion period. The micro-galvanic corrosion between the coatings and their substrates leads to an increase of hydrogen evolution rate （HER） with extending the immersion time. The addition of Ce promotes the homogenous distribution of Ca and formation of hopeite. The Zn-Ca-Ce-P coating has the potential for the primer coating on magnesium alloys.

Synthesis of Crystalline Hydroxyapatite from CaCO_3 and CaHPO_4·2H_2O by Mechanochemical Method

The mixture of CaHPO 4·2H 2O and CaCO 3 was ground in an aqueous system under appropriate conditions to investigate the mechanochemical reaction for the synthesis of crystalline hydroxyapatite (HA) powder. Hydroxyapatite of high crystallinity powder including trace Ca 10 (PO 4) 6CO 3(OH) and Ca 9HPO 4(PO 4) 6OH can be synthesized by mechanical activation without further thermal treatment at a high temperature. The synthesis reaction during the grinding process was almost completed within 1h. The as-ground powder exhibits a particle distribution of 20-100nm in size with a spherical or rodlike morphology. The composition and degree of crystallinity of the mechanochemical synthesized hydroxyapatite powders were coincident with the cement-type hydroxyapatite.

Removal of magnesium and calcium from electric furnace titanium slag by H_3PO_4 oxidation roasting-leaching process

H3PO4 oxidation roasting followed by HCl acid leaching was proposed to remove magnesium and calcium from electric furnace titanium slag containing 3.12% MgO and 0.86% CaO. XRF, XRD and SEM techniques were used to characterize the composition, mineral phase component and microstructure of the titanium slag. The H3PO4 oxidation thermodynamic, mineral phase transformation, microstructure, element distribution in titanium slag during H3PO4 oxidation process and leaching process were investigated. The thermodynamic analysis indicated that H3PO4 could promote the decomposition of MgTi2O5 and CaSiO3. The results indicated that H3PO4 could effectively promote the transformation of titanium-bearing mineral to rutile and enrich the impurities in MxTi（3-x）O5 into phosphate which could be removed by acid leaching process. Under the studied conditions, the leaching rates of magnesium and calcium reached 94.68% and 87.19%, respectively. The acid leached slag containing 0.19% MgO and 0.13% CaO（mass fraction） was obtained.

Effects of Urea Ammonium Chloride of Different Fertilization Patterns on Maize Yield and Yield Components

[Objective] To understand the application effects of urea ammonium chloride fertilizer on maize production. [Methods] A field plot experiment was conducted to study the effects of urea ammonium chloride of different fertilization patterns on summer maize yield and yield components. [Results] Urea ammonium chloride had a long fertilizer effect and the same yield-increasing effect with urea, which could im- prove the agronomic traits and economic traits of maize apparently and the applica- tion of urea ammonium chloride with nutrient reduction of 40% （namely just use urea ammonium chloride equaled 60% pure nitrogen）, had the same yield-increasing effect with urea of traditional fertilization patterns, and input-output ratio was high and the economic benefit was remarkable. [Conclusion] To provide scientific theoretical direc- tion for large area popularization and application of urea ammonium chloride.

Effects of Superphosphate Addition on NH_3 and Greenhouse Gas Emissions During Vegetable Waste Composting

To study the effects of superphosphate（SP） on the NH_3 and greenhouse gas emissions,vegetable waste composting was performed for 27 days using 6 different treatments. In addition to the controls,five vegetable waste mixtures（0.77m^3 each） were treated with different amounts of the SP additive, namely, 5%, 10%,15%, 20% and 25%. The ammonia volatilization loss and greenhouse gas emissions were measured during composting.Results indicated that the SP additive significantly decreased the ammonia volatilization and greenhouse gas emissions during vegetable waste composting. The additive reduced the total NH_3 emission by 4.0% to 16.7%. The total greenhouse gas emissions（CO_2-eq） of all treatments with SP additives were decreased by 10.2% to 20.8%, as compared with the controls. The NH_3 emission during vegetable waste composting had the highest contribution to the greenhouse effect caused by the four different gases.The amount of NH_3（CO_2-eq）from each treatment ranged from 59.90 to 81.58 kg/t; NH_3（CO_2-eq） accounted for 69% to 77% of the total emissions from the four gases. Therefore, SP is a cost-effective phosphorus-based fertilizer that can be used as an additive during vegetable waste composting to reduce the NH_3 and greenhouse gas emissions as well as to improve the value of compost as a fertilizer.

Construction of Recombinant Retroviral Vector Containing HIV-1 Tat Gene and Functional Detection of Expressed Tat in Target Cells

Objective: To construct recombinant retroviral vector containing HIV-1 Tatgene and evaluate the junction of the expressed Tat in target cells. Methods: HIV-1 Tat_(101) genewas recovered from pEV plasmid by Hind Ⅲ digestion and cloned into expression plasmid LZESpBMN-Z toconstruct recombinant retroviral expression plasmid named LZRS-Tat_(101). Using the method ofcalcium phosphate, the construct of LZRS-Tat_(101) was then transfected into packaging cell linesPhoenix (ΦNX) which contained env and gal genes encoding structural proteins and pol gene codingfor 3 enzymes ( reverse transcriptase, protease and integrate) essential for retroviral integrationand replication . The stable transfected cell lines was obtained using puromycin to screen for morethan 3 days. Then, immunohistochemical (IHC ) staining was carried out to detect the expressionlevel of Tat_(101) protein in both transiently and stably trancfected ΦNX, respectively. Thesupematants containing recombinant virus collected from transient and stable transfected cells wereemployed to infect 293 cells, respectively, and the expressed Tat in 293 cells was tested by Westernblot. Meantime, the supematants of infected 293 cells was further added to HL3T1 cells which wereHela cell lines containing an HIV-1-LTR/CAT reporter construct to establish a co-culture system.After co-culture for 72 hours, the protein was extracted from HL3T1 cells and used for CAT activityassay. Results: After LZRS- Tat_(101) was transfected into ΦNX, the amount of expressed Tat intransient transfection cells was significantly higher than that in stable transfection cells; Tatcould be detected not only in 293 cells but also in the supematants from 293 cells culture, and Tatin the supematants could activate HIV-1 LTR promoter in HL3T1, resulting in high 'expression of CATlocated at the downstream of LTR. Conclusion: The construct of recombinant retrovirus LZRS-Tat_(101) could express Tat protein in target cells and the expressed Tat was functionally activeand can really exhibit the ability to activate transcription.

Roles of TRESK,a novel two-pore domain K+channel,in pain pathway and general anesthesia

TRESK is the most recently reported two-pore domain K^＋ channel, and different from other two-pore domain channels in gene, molecular structure, electrophysiological and pharmacological properties. Although the current knowledge of this potassium channel is inadequate, researches have demonstrated that TRESK is remarkablely linked to acute and chronic pain by activation of calcineurin. The fact that TRESK is sensitive to volatile anesthetics and localization in central nerve system implies that TRESK may play a very important role in the mechanism mediating general anesthesia. The further research of TRESK may contribute to explore the underlying mechanism of some pathological conditions and yield novel treatments for some diseases.

Facile hydrothermal synthesis of TiO_2-Ca P nano-films on Ti6Al4V alloy

Ti6Al4V alloy was subjected to hydrothermal treatment in the concentrated Ca3(PO4)2, Ca HPO4 and Ca(H2PO4)2 solutions for bioactive surface modification. The treated samples are covered by films composed of nano-particles with the size of 60-240 nm. Such film can also be grown on the strut surface of a Ti6Al4 V scaffold prepared by electron beam melting(EBM) technology. XPS analysis indicates that Ti element on the surface presents as TiO2, and Ca and P elements are in the form of calcium phosphate. XRD and Raman analyses show that the surface layer is composed of anatase TiO2 and hydroxyapatite. Potentiodynamic polarization test in a Ca-free Hank's balanced solution demonstrates that the treated sample has markedly improved corrosion resistance compared with the polished sample. The present work provides a bioactive surface modification method that is easily-operated, low-temperature, less corrosion, and applicable to porous Ti6Al4 V alloy for biomedical applications.

Microstructure and properties of biodegradable β-TCP reinforced Mg-Zn-Zr composites

Magnesium alloys have good biocompatibility, but their mechanical properties and corrosion resistance may not be satisfied for using as degradable materials within bone due to its high corrosion rate in the physiological environment. Nano β-TCP particles were added into Mg-Zn-Zr alloy to improve its microstructure and the properties. As-extruded Mg-3Zn-0.8Zr alloy and Mg-3Zn-0.8Zr/xβ-TCP （x=0.5%, 1.0% and 1.5%） composites were respectively fabricated. The grains of Mg-Zn-Zr/β-TCP composites were significantly refined. The results of the tensile tests indicate that the ultimate tensile strength and the elongation of composites were improved with the addition of β-TCP. The electrochemical test result in simulation body fluid shows that the corrosion resistance of the composites was strongly enhanced comparing with that of the alloy. The corrosion potential of Mg-3Zn0.8-Zr/1.0β-TCP composite is 1.547 V and its corrosion current density is 1.20×10 6 A/cm 2 .

Highly Efficient and Selective Removal of Pb（II） ions by Sulfur-Containing Calcium Phosphate Nanoparticles

A facile one-step co-precipitation method was demonstrated to fabricate amorphous sulfurcontaining calcium phosphate （SCP） nanoparticles, in which the sulfur group was in-situ introduced into calcium phosphate. The resulting SCP exhibited a noticeable enhanced performance for Pb（II） removal in comparison with hydroxyapatite （HAP）, being capable of easily reducing 20 ppm of Pb（II） to below the acceptable standard for drinking water within less than 10 min. Remarkably, the saturated removal capacities of Pb（II） on SCP were as high as 1720.57 mg/g calculated by the Langmuir isotherm model, exceeding largely that of the previously reported absorbents. Significantly, SCP displayed highly selective removal ability toward Pb（II） ions in the presence of the competing metal ions （Ni（II）, Co（II）, Zn（II）, and Cd（II））. Further investigations indicated that such ultra-high removal efficiency and preferable affinity of Pb（II） ions on SCP may be reasonably ascribed to the formation of rodlike hydroxypyromorphite crystals on the surface of SCP via dissolution-precipitation and ion exchange reactions, accompanied by the presence of lead sulfide precipitates. High removal efficiency, fast removal kinetics and excellent selectivity toward Pb（II） made the obtained SCP material an ideal candidate for Pb（II） ions decontamination in practical application.

Effect of calcium compounds on direct reduction and phosphorus removal of high-phosphorus iron ore

The increasing demand for iron ore in the world causes the continuous exhaustion of magnetite resources.The utilization of high-phosphorus iron ore becomes the focus.With calcium carbonate(CaCO_(3)),calcium chloride(CaCl_(2)),or calcium sulfate(CaSO_(4))as additive,the process of direct reduction and phosphorus removal of high-phosphorus iron ore(phosphorus mainly occurred in the form of Fe_(3)PO_(7) and apatite)was studied by using the technique of direct reductiongrinding-magnetic separation.The mechanism of calcium compounds to reduce phosphorus was investigated from thermodynamics,iron metallization degree,mineral composition and microstructure.Results showed that Fe_(3)PO_(7) was reduced to elemental phosphorus without calcium compounds.The iron-phosphorus alloy was generated by react of metallic iron and phosphorus,resulting in high phosphorus in reduced iron products.CaCO_(3) promoted the reduction of hematite and magnetite,and improved iron metallization degree,but inhibited the growth of metallic iron particles.CaCl_(2) strengthened the growth of iron particles.However,the recovery of iron was reduced due to the formation of volatile FeCl_(2).CaSO_(4) promoted the growth of iron particles,but the recovery of iron was drastically reduced due to the formation of non-magnetic FeS.CaCO_(3),CaCl_(2) or CaSO_(4) could react with Fe_(3)PO_(7) to form calcium phosphate(Ca_(3)(PO_(4))_(2)).With the addition of CaCO_(3),Ca_(3)(PO_(4))_(2) was closely combined with fine iron particles.It is difficult to separate iron and phosphorus by grinding and magnetic separation,resulting in the reduced iron product phosphorus content of 0.18%.In the presence of CaCl_(2) or CaSO_(4),the boundary between the generated Ca_(3)(PO_(4))_(2) and the metallic iron particles was obvious.Phosphorus was removed by grinding and magnetic separation,and the phosphorus content in the reduced iron product was less than 0.10%.

Synthesis of phosphate-embedded calcium alginate beads for Pb(Ⅱ) and Cd(Ⅱ) sorption and immobilization in aqueous solutions

The phosphate-embedded calcium alginate beads were successfully synthesized based on sodium alginate, calcium dihydrogen phosphate and sodium hydrogen carbonate. Scanning electron microscopy, Fourier transformed infrared (FTIR) spectroscopy and X-ray diffraction (XRD) were conducted to characterize the morphology and structure of the phosphate-embedded calcium alginate beads. The effects of pH and the initial concentration of the metal ions on Pb(II) and Cd(II) sorption by the beads were investigated. The optimal pH values for Pb(II) and Cd(II) sorption are 4.0 and 5.5, respectively. The optimal initial concentrations of Pb(II) and Cd(II) are 200 mg/L and 25 mg/L, correspondingly, and the removal efficiencies are 94.2% and 80%,respectively. The sorption mechanism is that the heavy metal ions accessed the beads firstly due to the large surface area, combinedwith OH?, and then precipitated with phosphate radical, which was proven by FTIR and XRD. The sorption of Pb(II) and Cd(II) isfitted to Langmuir isotherm model with R2 values of 0.9957 and 0.988, respectively. The sorption capacities of Pb(II) and Cd(II) are263.16 mg/g and 82.64 mg/g, respectively. The results indicate that the phosphate-embedded calcium alginate beads could be appliedto treating Pb(II)/Cd(II)-containing wastewater and it could be implied that the synthesized beads also could be used as a kind of soil ameliorant for remediation of the heavy metal contaminated paddy soil.

Preparation of calcium phosphate coating on pure titanium substrate by electrodeposition method

The influences of pH value, electrolyte temperature and loading time on depositing calcium phosphate coating on pure titanium substrate by electrodeposition process were investigated. The process was carried out with an electrochemical work-station supplying a direct current power at potential of -0.8V （vs SCE）. The electrolyte consists of 7 mmol·L-1 CaCl2·2H2O, 3 mmol·L-1 Ca（H2PO4）2·H2O and 2.5% H2O2. NaOH and HCl solutions were used to adjust pH value. The deposited samples were characterized by X-ray diffraction and scanning electron microscope. The comparison of the deposits obtained at lower and higher pH values demonstrates that the crystallization process at the interface is favoured by high pH value. With temperature increasing, the deposited hydroxyapatite is occasionally of plate-like shape, and the width and the length of the deposited calcium phosphates at 65 ℃ are larger than those at 55 ℃. Therefore, it is confirmed that the morphology and microstructure of electrochemically deposited calcium phosphates can be regulated. Additionally, the coating formed in electrolyte with H2O2 additive is homogeneous and the evolution of H2 bubble can be eliminated.

Inorganic Phosphorus Fractions and Phosphorus Availability in a Calcareous Soil Receiving 21-Year Superphosphate Application

A long-term （21-year） field experiment was performed to study the responses of soil inorganic P fractions and P availability to annual fertilizer P application in a calcareous soil on the Loess Plateau of China. Soil Olsen-P contents increased by 3.7, 5.2, 11.2 and 20.6 mg P kg-1 after 21-year annual fertilizer P application at 20, 39, 59, and 79 kg P ha-1, respectively. Long-term fertilizer P addition also increased soil total P and inorganic P （Pi） contents significantly. The contents of inorganic P fractions were in the order of Ca10-P 〉 Cas-P 〉 Fe-P 〉 A1-P 〉 occluded P 〉 Ca2-P in the soil receiving annual fertilizer P application. Fertilizer P application increased Cas-P, A1-P and Ca2-P contents as well as their percentages relative to Pi. Pi application increased Fe-P and occluded P contents but nor their percentages. Soil Ca10- P content remained unchanged after fertilizer P application while its percentage relative to Pi declined with increasing fertilizer P rate. All Pi fractions but Ca10-P were correlated with Olsen-P significantly. 90% of variations in Olsen-P could be explained by Pi fractions, and the direct contribution of Cas-P was predominant. Long-term annual superphosphate application would facilitate the accumulation of soil Cas-P, and thus improve soil P availability.

Interaction of NPK Fertilizers During Their Transformation in Soils: Ⅲ. Transformations of Monocalcium Phosphate

Interactions of N, P and K fertilizers in soil-plant systems are widelyrecognized. This study focused on the transformations of monocalcium phosphate (Ca(H_2PO_4)_2) (MCP)with co-application of ammonium and potassium fertilizers in three different soils. The resultsshowed that after 1 d incubation a large portion of the MCP applied in the paddy, calcareous and redsoils became the water-insoluble form and the recoveries of P applied as Olsen P varied greatly inthese three soils. Application of ammonium sulfate ((NH_4)_2SO_4) (AS) or potassium chloride (KCl)reduced WSP significantly the soils with AS more effective than KCl in the calcareous soil, whilethe reverse occurred in the red soil. Meanwhile, in the paddy soil, co-application of the twofertilizers reduced WSP more than when the fertilizers were applied individually. The co-applicationof AS with MCP in the paddy and calcareous soils significantly reduced Olsen P, but the oppositeoccurred in the red soil. The experiment on the effect of different accompanying anions showed thatthe ammonium fertilizers (PNCl and PNS) reduced WSP more effectively than the correspondingpotassium fertilizers (PKCl and PKS) in the calcareous soil due to the difference of the cations,whereas in the red soil, the chlorides reduced WSP more effectively than the sulfates. Overall,co-application of ammonium or potassium fertilizers with MCP significantly decreased availability ofP from MCP during its transformation in soils, especially when MCP was applied in combination withammonium in the calcareous soil.

Leaching kinetics of calcium molybdate with hydrochloric acid in presence of phosphoric acid

Calcium molybdate(CaMoO4)is the main component of powellite and is a predominant intermediate in the pyrometallurgical and hydrometallurgical process of molybdenum.The extraction of Mo from CaMoO4 by a combination of phosphoric acid and hydrochloric acid was investigated.For further understanding of the leaching mechanism,the effects of five key factors were studied to describe the leaching kinetics.The results indicated that the dissolution rate of CaMoO4 was independent of the stirring speed.Mo extraction significantly increased with increasing HCl concentration and temperature,but decreased with increasing particle size.A shrinking core model with surface chemical reaction was found to withstand the dissolution of CaMoO4.The apparent activation energy was calculated to be 70.879 kJ/mol,and a semi-empirical equation was derived for the rate of reaction.

Theory and application research development of semi-solid forming in China

In order to adapt to the trend of ＂energy saving and emission reduction＂ and impel the practical application of semi solid processing （SSP） in China, the progress and application of semi-solid theory in China have been reviewed briefly and systematically. It was emphasized on basic theories, such as formation of globular grains, theology, high pressure solidification and plastic deformation and applications, such as material design, preparation of semi-solid billets （slurries）, thixoforming and application status, which are based on the advantage of semi-solid processing. The results show that the gap of SSP between world level and China exists, especially in application technologies, including market recognition, application fields exploiting, developing of billets （slurries） preparation technologies with low cost and special equipments. The prospect of semi-solid forming development path in China is presented. And we hope that application of SSP has great new breakthrough and development and China wilt be changed from a large metal processing country to a powerful metal processing country.

Potassium Fractions in Soils as Affected by Monocalcium Phosphate,Ammonium Sulfate,and Potassium Chloride Application

Soil potassium （K） deficiency has been increasing over recent decades as a result of higher inputs of N and P fertilizers concomitant with lower inputs of K fertilizers in China; however, the effects of interactions between N, P, and K of fertilizers on K status in soils have not been thoroughly investigated for optimizing N, P, and K fertilizer use efficiency. The influence of ammonium sulfate （AS）, monocMcium phosphate （MCP）, and potassium chloride application on K fractions in three typical soils of China was evaluated during 90-d laboratory soil incubation. The presence of AS significantly altered the distribution of native and added K in soils, while addition of MCP did not significantly affected K equilibrium in most cases. Addition of AS significantly increased water-soluble K （WSK）, decreased exchangeable K （EK） in almost all the soils except the paddy soil that contained considerable amounts of 2：1 type clay minerals with K added, retarded the formation of fixed K in the soils with K added, and suppressed the release of fixed K in the three soils without K added. These interactions might be expected to influence the K availability to plants when the soil was fertilized with AS. To improve K fertilizer use efficiency, whether combined application of AS and K was to be recommended or avoided should depend on K status of the soil, soil properties, and cropping systems.