啤酒酵母生理代谢过程中钠、钾、镁、钙离子含量变化的跟踪检测

采用空气-乙炔火焰原子吸收光谱法分别测定了啤酒酵母发酵液中的Na^ 、K^ 、Mg^2 、Ca^2 离子动态变化中的含量,用La^3 盐消除P对Ca^3 的干扰,以Sr^2 盐作为Na^ 、K^ 的消电离剂。本实验室采用配制培养基,通过对不同种类及不同发酵阶段培养的发酵液样品进行测定,以研究在啤酒酵母生长代谢过程中Na^ 、K^ 、Mg^2 、Ca^2 离子代谢动态变化。方法的Na^ 、K^ 、Mg^2 、Ca^2 相对标准偏差(RSD)分别为0．31％,0．73％。1．78％,0．28％;样品加标回收率为98％-107％;检出限：Na^ 为0．159mg／L,K^ 为0．789nag／L,Mg^2 为0．039mg／L,Ca^2 为0．029mg／L。该方法简便快速,具有很好的精密度。     

ICP-AES法同时测定烧结矿中CaO、MgO、SiO2、Al2O3、MnO和P

目前,在不锈钢炼铁工艺中,烧结矿的生产节奏越来越快,分析质量的要求也越来越高,以往采用化学方法对烧结矿的控制分析已不能适应大生产的需要。用X荧光光谱仪对烧结矿进行工艺控制分析已成为当今冶金行业控制分析的趋势。X荧光分析需要大量的标准样品,但与被测矿成分完全一致的标样不易制备。本法采用ICP-AES技术,在待测溶液中加入钇内标,采用基体匹配消除基体铁的影响,同时测定烧结矿中CaO、MgO、SiO2、Al2O3、MnO和P六种组分。     

PdH2、YH2分子的结构与势能函数

用密度泛函理论的B3LYP方法,对钯和钇原子采用SDD收缩价基函数,氢原子采用6-311＋＋G**全电子基函数,对PdH2和YH2体系的结构进行优化计算,得到PdH2分子最稳态为C2v构型,电子组态为1A1,平衡核间距RPdH=0.1692 nm,键角∠HPdH=29.4°,离解能De=5.5212 eV,基态简正振动频率:ν1(b2)=1470.1 cm－1、ν2(a1)=1007.9 cm－1、ν3(a1)=2907.0 cm－1.YH2分子最稳态也为C2v构型,电子组态2A1,RYH=0.1962 nm,∠HYH=114.3°,De=5.6691 eV,基态简正振动频率:ν1(b2)=1457.9 cm－1、ν2(a1)=476.0 cm－1、ν3(a1)=1506.3 cm－1.由微观过程的可逆性原理分析了分子的可能离解极限.并用多体项展式理论方法分别导出基态PdH2和YH2分子的势能函数,其等值势能面图准确地再现了PdH2和YH2分子的结构特征和离解能,由此讨论了Pd ＋ H2和Y ＋ H2分子反应的势能面静态特征.     

NbS_(2-x)Se_x的制备、表征及其摩擦学性能

本文采用固相反应合成了NbS2-xSex纳米材料。并分别采用XRD、SEM、TEM、HRTEM进行了结构、形貌和成分的分析表征。系统研究了合成温度、保温时间及不同掺杂量对产物晶型和形貌演化的影响及规律性。结果表明Se的掺杂使NbS2-x Sex的形貌由纳米带(板)转变为纳米片,衍射峰明显宽化,峰强变弱,晶粒细化。且掺杂量、保温温度及时间对产物的形貌影响较大;在750℃下保温2 h得到的掺杂5at%Se的NbS1.9Se0.1形貌良好。将NbS2-xSex作为液体石蜡油的添加剂的UMT-2摩擦学实验结果表明掺杂后的NbS2-xSex具有优异的摩擦性能,其中掺杂5at%的Se在750℃下保温2 h的NbS1.9Se0.1摩擦性能最佳,同时对其摩擦机理进行了解释。     

氟化钙的分子动力学模拟——晶态、超离子态、熔融态和急冷非晶态

采用键序参数方法研究了Ca~(2+)亚晶格和F~-亚晶格,表明两者均可用键取向正态分布模型描述。超离子相Ca~(2+)亚晶格稳定地维持其原fcc结构,而F~-亚晶格表现为原sc结构的随机畸变。熔融相的模拟给出了实验上难以分离的三种径向分布函数。急冷非晶相的模拟表明体系是以Ca~(2+)离子为中心的等效球的无规密堆,由于Ca(2+)与其邻近的F~-离子没有形成某种确定的构形,体系不够稳定。     

尖晶石CuM2O4(M=Al、Fe、Cr)催化甲醇重整反应的特性

采用柠檬酸络合法,经900 ℃热处理制备了CuAl₂O₄、CuFe₂O₄和CuCr₂O₄三种尖晶石,并进行了甲醇重整性能评价。结合XRD、H₂-TPR、SEM和BET等表征,研究了铜基尖晶石的催化特性。结果表明,三种铜基尖晶石的形貌和大小有极大差异,表现出不同的催化性能,CuAl₂O₄尖晶石获得最优的稳定性和最低的CO选择性,CuFe₂O₄尖晶石上CO选择性最高且稳定性差,CuCr₂O₄尖晶石上石墨碳沉积最严重。根据长时间评价结果和表征数据发现,在反应气氛中铜基尖晶石不稳定,通过释放活性铜而起催化作用;同时铜的烧结长大与积炭现象共同影响催化性能。     

TiO_2空心微球负载钒、铈催化剂的制备及其对氯苯催化燃烧性能研究

采用水热法制备TiO2空心球,以TiO2空心球为载体,采用等体积浸渍法分别制备了不同V负载量(3%~10%)的V2O5/TiO2和稀土改性后的V2O5-CeO2/TiO2催化剂,利用XRD,SEM,EDS,TEM对TiO2空心球及V2O5-CeO2/TiO2催化剂进行了表征,结果表明,空心球TiO2分散性良好,粒径在1.5μm左右,且其为锐钛矿结构,负载的V和大部分的Ce均匀分散在TiO2空心球体内部或者表面而未破坏TiO2空心球结构。考察了催化剂对氯苯的催化燃烧性能,活性评价结果表明当V负载量在5%时,V2O5/TiO2催化剂对氯苯催化燃烧性能最佳,在掺杂10%的稀土Ce后,催化燃烧氯苯的活性得到明显提高。     

添加磷、硼、硅和铝的锂离子电池材料LiNiO2研究

研究了添加元素磷，硼硅和铝对锂离子蓄电池材料LiNiO2的影响。添加磷，硼、硅和铝的目的是提高LiNiO2的放电平台和充放电稳定性，增加循环寿命并且提高充放电能量，在n(LiOH):n(Ni(OH)2)为1.1:1.0的材料中分别加入P2O5;H3BO3,SiO2,Al2O3，保持4种元素与锂的摩尔比值分别为0.01,0.02,0.03,0.04和0.05，分析测定了样品的充放电曲线和循环伏安曲线，并采用XRD对样品的放电过程和合成产品进行了结构分析，结果证明，当n(P)/n(Ni)=0.02,n(B)/n(Ni)=0.03,n(Si)/n(Ni)\0.02,n(Al)/n(Ni)=0.02时，LiNiO2的放电电压提高，添加元素使LiNiO2在充放电过程中的晶型转变过程发生改变，使六方晶系向单斜晶系转变的趋势变小，这将改善LiNiO2的循环性能，但没有影响锂离子的嵌入和脱嵌机理，XRD分析表明，添加磷和铝使LiNiO2的层状结构更完善，同时增加了活性，但添加硼和硅以后，LiNiO2的XRD图上的衍射峰（003）强度度减弱，衍射峰（018）和（019）峰也有改变，这证明B和Si影响了LiNiO2性能。     

ZrO2对Cu/CeO2-ZrO2水煤气变换催化剂结构、性能的影响

采用共沉淀法制备了系列Cu／CeO2-ZrO2水煤气变换（WGS）催化剂。用N2物理吸附、XRD和H2-TPR手段研究了ZrO2组分对催化剂的织构、物相、还原性能、热稳定性以及WGS反应活性的影响。结果表明。添加ZrO2组分均提高了催化剂的比表面积。且随ZrO2含量的增加，孔径逐渐向小孔集中，即大孔数量减少，小孔数量增加。最可几孔径移至1．9nm左右，并逐渐增强。ZrO2的加入能有效地抑制CeO2晶粒的长大，同时适量的ZrO2可使铜铈基催化剂在WGS反应过程中保持较高的Cu分散度。从而使其具有较高的活性和稳定性。当催化剂中ZrO2含量为10％。反应温度为200℃时，WGS应中CO的转化率达到73．7％。     

纳米复合光催化剂TiO_2-ZrO_2的制备、表征及其光催化活性

通过溶胶-凝胶技术制备了不同比例(3:1、1:1、1:3)的纳米复合光催化材料TiO2-ZrO2,采用XRD、N2吸附、SEM-EDX和TPD等测试手段对其进行了表征,探讨了比例不同的TiO2-ZrO2结构的变化规律以及这种变化对催化剂催化活性的影响.通过紫外区和可见区的光催化降解染料亚甲基蓝、罗丹明B的实验,考察了其光催化活性.实验结果表明,不同比例的纳米复合光催化材料TiO2-ZrO2的催化活性均高于单体TiO2和单体ZrO2.     

Nouvelle Synthese Des 2-Thioxoethylphosphonates, 2- mercaptovinylphosphonates, 2-Phosphoryl-3-thioxopropanoates, 2-Thiomethylvinylphosphonates, 2-Thioethoxycarbonylmethylvinylphosphonates

The cyanomethylphosphonates 1 and the ethyl phosphoacetates 2 were reacted with some fluorophenylisothiocyanates to give the 2-thioxoethylphosphonates 3 in tautomeric equilibrium with the corresponding 2-mercaptovinylphosphonates 3 ′ and the 2-phosphoryl-3-thioxopropanoates 4 , respectively. Reaction of the cyanomethylphosphonates 1 with fluorophenylisothiocyanates in presence of methyliodide furnished the 2- thiometylvinylphosphonates 5 . The 2-mercaptovinylphosphonates 3 ′ reacted with ethyl chloroacetate in refluxing ethanol in the presence of triethylamine to give S-substitued derivatives 6 .     

Thiocyanation, Halogenation, Dehalogenation, Transhalogenation, and Nitration of 2-Substituted 4-(2-Furyl)thiazoles

Bromination and thiocyanation of 2-amino- and 2-acetylamino-4-(2-furyl)thiazoles when 1 mol of reagent is used at 10°C are directed to the 5 position. Formation of 5'-bromo-substituted derivatives when the reaction temperature is raised is the result of a secondary, thermodynamically controlled process. Monohalogenation and mononitration of 4-(2-furyl)-2-methylthiazole are directed to the 5' position. Nitration of 2-acetylamino-4-(5-nitro-2-furyl)thiazole by a nitrating mixture is accompanied by oxidative cleavage of the 5-nitrofuran moiety and leads to formation of 5,5'- and 3',5'-dinitro derivatives.     

Ag-Doped Free-Standing 2D TiO2 Sheets: Electronic,Optical, Magnetic,and Self-Healing Behaviour

Beyond a critical doping level, Ag–2D TiO₂ sheets (ATO) are deemed to be a flexible transparent conductor, useful for visible-range functional photonic/optoelectronic devices/sensors, sunlight-sensitive catalysis, and light-activated resistive switching. Due to the lack of control of surface energy which often leads to the formation of structural defects and even dimensionality crossover (2D to 0D) of materials during doping reaction, it is challenging to obtain ATO with a controlled doping level. Gauging the urgency, therefore we report the surface energy-controlled synthesis of ATO employing liquid phase exfoliation of TiO₂ and subsequent hydrothermal Ag-doping in the presence of Hexamethylenetetramine (HMTA). Electron microscopy and atomic force microscopy reveal ATO sheets with large lateral dimensions. 6-fold, 4-fold, and strain-mediated crystallographic phases of 2D ATO have been revealed by high-resolution electron imaging. Successful tuning of the band gap down to ~2 eV with Ag doping up to ~10 % is obtained. Synthesized 2D ATO have been investigated for their electrical, optical, optoelectronic, photoluminescence, and ferromagnetic behaviour. Visible light-sensitive thermally/structurally robust semiconductor/conductor via tuneable doping will pave the way for their flexible as well as wearable device applications. Self-healing effect of AFM tip-generated mechanical stress has also been demonstrated.     

Rhenium(V) Complexes of N,N′-Ethylenebis(2-mercaptopropanamide). Synthesis,Characterization, and X-ray Crystal Structures

The preparation of benzoyl-protectcd N,N′-ethylenebis(2-mercaptopropanamide) (H₄emp) and its ligand-exchange reaction with ReO₂(en)₂Cl are described. Three diastereomers, [syn-ReO(meso-emp)]; [anti-ReO(meso-emp)]-, and a pair of cnantiomers, [ReO(rac-emp)]-, were formed due to syn and anti orientation of the two methyl groups of the ligand relative to the ReO core. The diastereomers were separated by reverse phase C₁₈ semipreparative HPLC and isolated as salts of [Ph₄As][ReO-(emp)]. The structures of [Ph₄ As][ReO(meso-emp)] were determined by single-crystal X-ray analyses. [Ph₄As][syn-ReO(mesocmp)]H₂O crystallizes in triclinic space group Pl with a = 10.326(3) Å, b = 13.672(4) A, c = 14.023(5) Å, α = 61.20(2)°, β =74.74(3)°, γ= 75.68(2)° V = 1656.6(8) ų, Z = 2, Dc = 1.676 gmL^?1, F(000) = 824 and R = 0.0329 for 5877 unique reflections. For (he complex [Ph₄As][anti-ReO(meso-emp)], the crystal data are: monoclinic, space group P2₁/n, a = 9.128(2) Å, b = 24.284(7) Å, c = 14.112(4) Å, β = 93.41(2)° V = 3122.5(15) À³, Z = 4, Dc = 1.740 gmL^?1, F(000) = 1608 and R = 0.0361 for 5487 unique reflections. In both structures the rhenium atom is penta-coordinated and in an approximately square pyramidal environment.     

5,5-Diethylbarbiturato complexes of copper(II) with (2-aminoethyl)piperidine, -pyrrolidine,and -morpholine: syntheses,crystal structures,spectroscopic, and thermal properties

Three new complexes, [Cu(barb)₂(aepip)] · 0.5H₂O (1), [Cu(barb)₂(aepyrd)] (2), and [Cu(barb)₂(aemrph)] (3), have been synthesized by reaction of 5,5-diethlybarbiturate anion (barb) with copper(II) in the presence of (2-aminoethyl)piperidine (aepip), -pyrrolidine (aepyrd), and -morpholine (aemrph). All complexes were characterized by elemental analysis, spectroscopic (IR and UV/Vis), thermal (DTA-TGA), and magnetic susceptibility measurements. X-ray single crystal diffraction shows that 1 and 2 are discrete mononuclear species, in which copper(II) is coordinated by two bidentate barb ligands and a chelating aepip or aepyrd, forming a square-pyramidal coordination geometry. Complexes 1 and 2 show unequal coordination of barb, one N-coordinate, and one bidentate. Complex 3 is also mononuclear, but copper(II) is square-planar with two N-coordinated barb and one bidentate aemorph. Molecules of 1–3 are bridged by strong hydrogen bonds to generate 1-D or 2-D supramolecular networks. Spectral and thermal data for 1–3 are in agreement with crystal structures.     

Reactions of 1,3-dioxacycloalkanes and their 2-arsena, 2-bora, 2-germa, 2-sila,and 2-thia analogs with nitriles

New reactions of five-, six-, and seven-membered 1,3-dioxacycloalkanes and their 2-arsena, 2-bora, 2-germa, 2-sila, and 2-thia analogs with nitriles giving rise to 1,3-oxazacycloalkanes and then to amino alcohols are surveyed. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1499–1507, July, 2005.     

Reaction of 1, 1-Di-p-methoxyphenyl-2, 2-dinitroethylene and 1, 1-Di-O-methoxyphenyl-2, 2-dinitroethylene with 1-Benzyl-1, 4-dihydronicotinamide： Evidence for Concerted Electron-hydrogen Atom Transfer Mechanism

1,1-Di-p-methoxyphenyl-2, 2-dinitroethylene reacts with 1-benzyl-1, 4-dihydronicotinamide (BNAH) in deaerated acetonitrile to give 1,1-di-p-methoxyphenyl-2, 2-dinitroethane,while 1,1-di-O-methoxyphenyl-2, 2-dinitroethylene fails to react with BNAH under the same conditions, which provides evidence for a concerted electron-hydrogen atom transfer mechanism.     

离子色谱法测定尿液中的C2O42-、Ca2+、Mg2+

利用离子色谱法测定尿液中的草酸根、钙、镁离子：测定草酸根时，先在尿液中加入氯化钙使之转化成草酸钙沉淀，分离后用盐酸溶解草酸钙沉淀，然后进行测定测定钙、镁离子时，在酸性尿液中加入氧化剂过硫酸钾，在微沸状态下氧化尿液中的有机物，从而避免对色谱柱的污染：草酸根、钙、镁离子的回收率分别为108．3％～109．7％、94．9％～100．7％、97．2％～97.4％，相对标准偏差分别为2．4％、2.5％、3．1％。     

Study on Chemisorption, Catalytic Behavior, and Stability of Supported Au Catalyst for the Propylene Epoxidation Reaction

The supported Au/TiO2 and Au/TiO2-SiO2 catalysts were prepared by deposition precipitation method. The TPD study reveals that propylene oxide competes with propylene to be adsorbed on the same adsorptive center-Tin site on the surface of the catalyst and that the adsorbing capacity of the catalyst for propylene oxide is larger than that for propylene. Catalytic behavior for propylene epoxidation with H2 and O2 was tested in a micro-reactor. Under typical conditions, the selectivity for propylene oxide is over 87%. The TG curves show that PO successive oxidation cause carbon deposition on the active center and deactivation of the Au catalysts. Because the amounts of Tin site decrease significantly, and consequently the separation between Tin sites increases, the Au/TiO2-SiO2 catalyst is more stable than Au/TiO2.     

Volumetric Properties of Nucleic Acid Bases and Nucleosides in Aqueous Ethanol, 1,2-Ethanediol, 2-Propanol, and 2-Methyl-2-Propanol at 25°C

Partial molar volumes of cytosine, uracil, thymine, cytidine, uridine, thymidine, and adenosine have been measured in different concentrations of aqueous ethanol, 1,2-ethanediol, 2-propanol, and 2-methyl-2-propanol at 25°C using densimetry. These data are utilized in conjunction with the partial molar volumes of these nucleic acid bases and nucleosides in water reported earlier to deduce the partial molar volumes of transfer from water to aqueous alcohol or diol. The results are explained in terms of likely solute–solvent interactions; the role of solvent in these interactions is discussed. The partial molar volume data are also used to calculate the contribution of –CH₂- groups in the nucleic acid base or solvent and of ribose in the nucleoside to the partial molar volume of transfer. The validity of group additivity in these systems is discussed.