Anderson结构稀土钼铬多金属氧酸盐的合成与表征

A new kind of Anderson-type chromium-molybdates containing the rare earth elements are synthesized， which have the general molecular formula of (NH₄)₆[CrMo₅Ln(OH₂)₂O₂₄H₆]·xH₂O (Ln=La，Ce，Pr，Nd，Sm，Gd and Yb). The components of these heteropoly complexes are determined by chemical elemental analysis， ICP and TG-DTA. And IR， UV， ESR，XPS and ¹H NMR are also applied to characterize the complexes as well. The results indicate that the structures of these complexes are Anderson B type and the rare earth elements are in the inner sphere of the heteropoly salts. The thermal stabilities of these complexes studied by TG-DTA show that the range of pyrolysis temperature is between 490℃ and 500℃.     

稀土与β-二酮及2-（2-吡啶）苯并咪唑三元配合物的研究

As useful fluorescent reagent, rare earth complexes with β-diketones have been　extensively studied. Four new rare earth (La, Eu) ternary complexes with　β-diketones, (benzoylacetone (Hbza), 2-thenoyltrifluoroacetone, (HTTA)) and organic base (2-(2-pyridyl) benzimidazole, (Hpbi)) have been synthesized and characterized by elemental analysis, IR, NMR. The general formulae of these complexes are ［Ln(bza)₃(Hpbi)］ and［Ln(TTA)₃(Hpbi)］. The effects of coordinated base on UV, especially on fluorescent properties of the complexes were discussed. The results showed that the dehydro-Hpbi, pbi^{－, strongly enhances the fluorescence of the complexes.}     

三元稀土配合物RE(NTA)2AA的合成、共聚反应性及荧光性能研究

Four new ternary rare earth complexes RE(NTA)₂AA (RE=Sm³⁺， Eu³⁺， Tb³⁺， Dy³⁺) have been synthesized by the reaction of rare earth chloride(RECl₃·6H₂O) with Acrylic Acid (HAA) and 4，4，4-trifluoro-1-(3-pyridyl)-1，3-butanedione(NTA) in alcohol. The copolymerization of the complexes RE(NTA)₂AA (RE=Sm³⁺， Eu³⁺) with methyl methacrylate (MMA) has been studied by 2， 2-azobis-isobutyronitrile as an initiator. Influence of adding Eu(Ⅲ) and 2，2′-bipyridine(bipy) into copolymer Eu(NTA)₂AA-co-MMA on fluorescence property of the Eu copolymer was investigated. The compositions of the complexes and copolymer were characterized by means of elemental analysis and FTIR. The heat decomposing behaviors of the complexes were determined by TG-DTA. The glass transition temperature and molecular weight were obtained by DSC and GPC. The results of fluorescence properties show that the Eu， Sm complexes and Eu copolymer can efficiently emit fluorescence， but the Tb and Dy complexes only emit the fluorescence of β-diketone ligand.     

微波辐射固相法合成缩二脲铜配合物

The copper(Ⅱ) complexes of biuret have been synthesized by solid phase reaction with microwave irradiation. The compositions and structures of the complexes are characterized by elemental analysis, molar conductance, in-frared spectra, electronic spectra, magnetic susceptibility, thermogravimetric and differential thermal analysis, X-ray powder diffraction. The two complexes have the compositions of [Cu(bi)₂]Cl₂(A) and [Cu(bi)₂](NO₃)₂(B)(bi=NH₂CONHCONH₂) and the molecular formulae of CuC₄H₁₀O₄N₆Cl₂ and CuC₄H₁₀O₁₀N₈, respectively. The molar conductance data show that the complexes are 1∶2 electrolyte. Infrared spectra of the complexes show oxygen atoms have been coordinated with divalent copper ion. The thermal decomposition processes of the complexes show that the final residues are all cupper oxide. The results of indexes to the X-ray powder diffraction data indicate that the crystal structure of the complexes belong to monoclinic system, the lattice parameters are: a=0.6976nm,b=1.1546 nm,c=2.1689nm,β=96.80°,V=1.7346nm³ for A; and a=0.7096nm,b=1.1359 nm,c=2.1002 nm,β=97.05°,V=1.6800nm³ for B, respectively.     

金刚烷胺邻香兰素Schiff碱稀土配合物的合成、表征及抗菌活性研究

The new solid complexes [LnL₂(NO₃)₂]NO₃ (L=C₁₈H₂₃NO₂, N-2-hydroxy-3-methoxy-benzaldehyde-1-aminoadamanantane, Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y) of rare earth nitrates with Schiff base derived from o-vanillin and adamantaneamine have been synthesized in non-aqueous system and characterized by elemental analysis, molar conductance, infrared spectra, ¹H NMR spectra, thermal analysis. The coordination modes of the bonding in these complexes were discussed and the possible structure were proposed. Every central Ln(Ⅲ) ion in the complexes coordinates with both two Schiff base ligands via four oxygen atoms of the phenol hydroxy groups and methoxy groups and two nitrates via their four oxygen atoms. Their coordination numbers are eight. In addition, the antibacterial activity of the Schiff base ligand and the complexes were studied.     

4-(3-吲哚基)-3-丁烯-2-酮苯甲酰腙Schiff碱过渡金属配合物的合成、表征及生物活性研究

A Schiff base ligand 4-[indol-3-yl]-but-3-en-2-one benzoyl hydrazone (HL), and its four transition metal complexes (ML₂，M=Cu(Ⅱ), Ni(Ⅱ), Zn(Ⅱ) and Co(Ⅱ)) have been prepared and characterized by means of elemental analysis, EI-MS, molar conductivity, IR, UV-Vis and ¹H NMR. The results showed that HL as a bidentate ligand coordinated with transition metal ions to form four-coordination complexes. The antibacterial activity was studied by using the filter scraps diffusion method, and the results indicated that the ligand and the complexes had a low bacteriostatic activity against S. Aureu, P. Aeruginosa and E. Coli. The low in vitro antitumor activity of the title complexes was also observed by using MTT method against KB, A2780, Bel7402 and HELF.     

一种新型2，6-吡啶二甲酸镓(Ⅲ)配合物的合成、结构及抑菌活性研究(英)

A novel coordination polymer [NaGa(dipic)₂(H₂O)₂]_n was synthesized by the reaction of gallium(Ⅲ) trichloride with Na-salt of 2,6-pyridinedicarboxylic acid and its crystal structure was determined by X-ray diffraction method. The crystal belongs to monoclinic, space group Cc; the unit cell parameters are a=1.502 9(3), b=1.228 1(3) and c=0.872 38(17) nm, β=92.85(3)°, and Z=4, V=1.608 2(6) nm³, F(000)=920. Infrared, electronic absorption, ¹H NMR spectra, as well as the thermal behavior are reported. The antibacterial activity of the gallium(Ⅲ) complex has been studied against Escherichia coli, Bacillus subtilis and Staphylococcus aureus in order to check its potential for chemotherapy agent. The activity is notable and higher than that of the H₂L. CCDC: 240619.     

鼓形有机锡氧簇合物[nBuSn(O)(NNA)]6的合成、晶体结构及生物活性

The title complex [ⁿBuSn(O)(NNA)]₆(1), was synthesized by the reaction of ⁿBuSn(O)OH with naphthalene acetic acid in 1∶1 molar radio, where HNNA=naphthalene acetic acid. The complex was characterized by IR, ¹H NMR spectra and elemental analysis. The crystal structure was determined by X-ray diffraction method. It crystallizes in monoclinic system with space group P2₁/n. The crystal data are: a=2.647 1(5) nm, b=1.412 9(3) nm, c=2.805 7(6) nm, β=116.185(3)°, Z=4, V=9.417(3) nm³, D_c=1.595 g·cm^-3, μ=1.632 mm^-1, F(000)=4 512, R₁=0.050 3, wR₂=0.131 2. The structure shows a distorted octahedral configuration with six-coordination for the central tin atom. The bioactivity test shows that the Sn(Ⅳ) complex has selective antibacterial property. CCDC: 752497.     

N，N，N′，N′-四丁基丙二酰胺从硝酸盐介质中萃取铈(Ⅲ)

Study on the extraction and separation of rare earth with new extractants is important in the rare earth chemistry and nuclear reprocessing. In this work， the extraction of Ce(Ⅲ) with N，N，N′，N′-tetrabutylmalonamide (TBMA) in toluene from nitrate media has been investigated. The effect of the concentration of nitric acid， TBMA and salt-ing-out agent (LiNO₃) and also the temperature on the distribution ratios was examined. The stoichiometries of the extracted complexes were determined to be Ce(NO₃)₃·3TBMA and Ce(NO₃)₃·4TBMA， respectively. The ap-parent extraction constants and the enthalpy of the extraction were calculated based on the extraction data， which are logK_ex1=3.97， logK_ex2=4.75 and Δ_rH_m^?=-31.25kJ·mol^-1， respectively. The IR spectra of the loaded organic phase supported the suggested extraction mechanism.     

Thermal and Spectral Behaviour of 5-chloro-2-methoxybenzoates of Heavy Lanthanides and Yttrium

5-Chloro-2-methoxybenzoates of heavy lanthanides and yttrium were obtained as di- or tetrahydrates with a metal to ligand ratio of 1:3 and general formula: Ln(C₈H₆ClO₃)₃⋅nH₂O, where n=2 for Ln=Tb, Dy, Y and n=4 for Ln=Ho, Er, Tm, Yb, Lu. The complexes were characterized by elemental analysis, IR and FIR spectra, thermogravimetric studies, X-ray diffraction and magnetic measurements. The carboxylate group appears to be a symmetrical, bidentate, chelating ligand. All complexes are polycrystalline compounds. Their thermal stabilities were determined in air and in nitrogen atmospheres. When heated they dehydrate to form anhydrous salts which next in air are decomposed to the oxides of the respective metals while in nitrogen to the mixtures of carbon and oxides or carbon and oxychlorides of respective metals. The complexes are more stable in air than in nitrogen. The solubilities of yttrium and heavy lanthanide 5-chloro-2-methoxybenzoates in water at 293 K are of the order of 10^–3 mol dm^–3 The magnetic moments of the complexes were determined over the range 77–298 K. They obey the Curie–Weiss law. The values of μ_eff calculated for all compounds are close to those obtained for Ln³⁺ by Hund and Van Vleck. The results indicate that there is no influence of the ligand field of 4f electrons on lanthanide ions and the metal ligand bonding is mainly electrostatic in nature. This revised version was published online in August 2006 with corrections to the Cover Date.     

利用手持技术改进测定乙醇分子结构实验

利用压强传感器代替排水集气法,改进测定乙醇分子结构实验的仪器装置,并探索最佳反应条件。另外,设计两个空白实验,结合压强变化曲线对实验误差进行相关讨论。     

物质分配系数的测定实验改进

实验教学目的是从解决实际问题出发,以实验技术训练和实验设计思想培养为目标。介绍了将单一的物质分配系数测定实验改进为综合实验,提高了实验效果及实验资源利用率。     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

Calculation of enthalpies of hydrogenation of hydrocarbons

Sets of hydrogen molecule equivalents have been developed which permit the calculation of hydrogenation of different types of carbon-carbon bonds from ab initio total energies (3-21G and 6-31G* basis sets, and, to a more limited extent, for MP2/6-31G* data) of reactants and products. The calculated enthalpies of hydrogenation are in good agreement with experiment for unstrained molecules, with average errors on the order of 2 kcal/mol. The 6-31G* equivalents allow the enthalpies for strained molecules to be calculated accurately, but the 3-21G equivalents do not. The equivalents for both basis sets have been tested by calculating the enthalpies of hydrogenation of carbon-carbon bonds in nitrogen- and oxygen-containing organic molecules, free radicals, and classical carbocations. The results are in good agreement with experiment in most cases.     

Neutral diterpenoids of oleoresins of five species of conifers of Transcarpathia

The compositions of the neutral diterpenoids of the oleoresins of five species of conifers growing in the Transcarpathia have been studied. It has been found that the oleoresins ofAbies alba M.,Larix decidua M., andPicea excelsa L. contain more than 50% of neutral diterpenoids. The group and qualitative compositions of the oxygen-containing diterpenoids have been determined. In the oleoresins ofAbies alba,Picea excelsa, andPicea abies tertiary alcohols — cis-abienol and isocembrol — predominate, while inLarix decidua the main component is the hydroxy ester larixyl acetate. Primary alcohols related to the resin acids have been found in all the oleoresins investigated. Features of the distribution of diterpenoids according to the species of conifers have been revealed. The results obtained are necessary for the chemotaxonomy of conifers of the family Pinceae.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodynkh Soedinenii, No. 6, pp. 812–816, November–December, 1988.     

Neutral diterpenoids of oleoresins of five species of conifers of Transcarpathia

The compositions of the neutral diterpenoids of the oleoresins of five species of conifers growing in the Transcarpathia have been studied. It has been found that the oleoresins ofAbies alba M.,Larix decidua M., andPicea excelsa L. contain more than 50% of neutral diterpenoids. The group and qualitative compositions of the oxygen-containing diterpenoids have been determined. In the oleoresins ofAbies alba,Picea excelsa, andPicea abies tertiary alcohols — cis-abienol and isocembrol — predominate, while inLarix decidua the main component is the hydroxy ester larixyl acetate. Primary alcohols related to the resin acids have been found in all the oleoresins investigated. Features of the distribution of diterpenoids according to the species of conifers have been revealed. The results obtained are necessary for the chemotaxonomy of conifers of the family Pinceae.     

光谱仪测试范围的扩展

由于石化行业的生产需要，其材质的使用具有多样性和广泛性，经常会出现顾客委托的测试样品的一个或几个元素跨越光谱仪现有测试程序测量范围的情况。本法通过对光谱仪测试原理的认识，根据光谱仪的测试能力及标样的采集，实现了一个或几个元素测量范围的扩展，并对其测量的影响因素进行了研究。