四元体系CdCl2-LaCl3-(9.7%)HCl-H2O在298K的相平衡及其固相化合物的研究

The equilibrium solubility of the LaCl₃-CdCl₂-(9.7%)HCl-H₂O quaternary system at 298K was determined and the phase diagram was constructed. The results show that the system is complicated with four equilibrium solid- phases CdCl₂·H₂O， 8CdCl₂·LaCl₃·16H₂O(8∶1 type)， 4CdCl₂·LaCl₃·12H₂O(4∶1 type) and LaCl₃·7H₂O， respectively. The two new compounds 8CdCl₂·LaCl₃·16H₂O(8∶1 type) and 4CdCl₂·LaCl₃·12H₂O(4∶1 type) are congruently soluble in ～9.7% HCl-H₂O medium and have not yet been reported in literatures. Both com-pounds have been prepared from the system and have been characterized by XRD， TG-DTG and DSC.     

三元体系YCl3-CdCl2-H2O和四元体系YCl3-CdCl2-HCl(～8.8%)-H2O (25 ℃)的相平衡及其固相新化合物的研究

The equilibrium solubilities of the ternary system YCl₃-CdCl₂-H₂O, the quaternary system YCl₃-CdCl₂-HCl(～8.8%)-H₂O were determined at 25 ℃ and the phase diagrams were constructed. The results show that the ternary system was complicated with six equilibrim solid phases CdCl₂·2.5H₂O, CdCl₂·H₂O, 8CdCl₂·YCl₃·15H₂O (8∶1 type), 4CdCl₂·YCl₃·13H₂O(4∶1 type), 5CdCl₂·2YCl₃·26H₂O (5∶2 type) and YCl₃·6H₂O. The quaternary system was also complicated with four equilibrim solid phase CdCl₂·H₂O, 4CdCl₂·YCl₃·13H₂O (4∶1 type), 5CdCl₂·2YCl₃·26H₂O(5∶2 type) and YCl₃·6H₂O. Among the three new compounds 8CdCl₂·YCl₃·15H₂O, 4CdCl₂·YCl₃·13H₂O and 5CdCl₂·2YCl₃·26H₂O, 8CdCl₂·YCl₃·15H₂O was a kind of metastable compound only in ternary system, and it was changed into 4CdCl₂·YCl₃·13H₂O with time. Both 4∶1 type and 5∶2 type existed in ternary and quaternary system, but they were also congruently soluble compounds in quaternary system. They have been prepared from the system and have been characterized by XRD, TC-DTG and DSC.     

三种1,10-邻菲咯啉-铜(Ⅱ)-L-氨基酸配合物与DNA的相互作用

The Interaction of three complexes [Cu(phen)(Gly)(H₂O)]·ClO₄·2.5H₂O (1), [Cu(phen)(L-Val)(H₂O)]·ClO₄ (2) and [Cu(phen)(L-Ile)(H₂O)]·ClO₄ (3) (phen=1,10-phenanthroline, Gly=glycinate, L-Val=L-valinate, L-Ile=L-isoleucinate) with DNA have been investigated by electronic absorption spectroscopy, ethidium bromide(EB) fluorescence spectroscopy, viscosity and gel electrophoresis measurements. The intensity of maximal absorption peaks from absorption spectra are weakened with dropping DNA into the complexes. The emission intensity of EB-DNA systems in fluorescence spectroscopy have descended 50%, when the data of C_Cu / C_DNA is 30～40. Moreover, the viscosity of DNA increase and then decrease with the increasing of complexes. All of the results indicate that the interaction of complexes with DNA are partial intercalation, and the result of agarose gel electrophoresis show that the complexes can cleave pBR322 DNA in the present of H₂O₂ / vitamin C.     

CsCl-TmCl3-HCl-H2O(25 ℃)的相平衡及其固相化合物

The equilibrium solubilities of the quaternary system CsCl-TmCl₃-HCl-H₂O was determined at 25 ℃ and the corresponding equilibrium diagram was constructed. The diagram is a complicated system with limited solid solutions and formation of a new compound 3CsCl·2TmCl₃·14H₂O. The new compound has been characterized by XRD, TC-DTG and fluorescence spectrometry. Results show that upconversion spectrum exhibits at 335 nm when exciting at 860 nm, and fluorescence spectrum exhibits at 295 nm and 385 nm when exciting at 240 nm. The compound loses its crystal water by four steps at 50 to 250 ℃. Using a heat conduction calorimeter, the standard molar enthalpy of dissolution of 3CsCl·2TmCl₃·14H₂O was determined to be (-11.601 ± 0.050) kJ·mol^-1 at 298.15 K.     

三元体系Cu(NO3)2-EBU-H2O 30℃时等温溶度及其新相研究

The isothermal solubility of the ternary system Cu(NO₃)₂-EBU-H₂O at 30℃ has been studied for the first time and the solubility diagram and refractive indices diagram have been given. New phase Cu(NO₃)₂·2EBU has been found in this system， which dissolves incongruently in water .The phase has been characterized by element anal-ysis， IR spectra and X-ray diffraction powder analysis.     

[Ce(NO3)5H2O]·(C3H5N2)2的合成、晶体结构及热分析

Colorless crystal, [Ce(NO₃)₅H₂O]·(C₃N₂H₅)₂, has been obtained from the reaction of Ce(NO₃)₃ with imdazole in the aqueous solution and its crystal structure has been determined by single crystal X-ray diffraction techniques.The crystal belongs to triclinic, space group P1. The cell parameters are: a = 0.7489(1) um, b = 0.7914(2) nm, c = 1.8139(3) nm, a = 89.39(2)°, β = 89.37(l) °,γ = 63.18(2)°, Dc = 2.1g·cm^-3, Z = 2, R = 0.0319.In the compound, all of five nitrates are bidentate and one molecule of water is monodentate, the coordination number of Ce (Ⅲ) is 11.The processes of thermal decomposition of the compound was proposed by its TGcurve.     

通过β-FeOOH纳米棒无序聚集制备α-Fe2O3中空球

The α-Fe₂O₃ hollow spheres have been synthesized through the random aggregation of β-FeOOH nanorods in the C₂H₅OH/H₂O system. The phase transformation and the morphologies of the α-Fe₂O₃ hollow structure were investigated with XRD， SEM， TEM and selected area electron diffraction (SAED). These studies indicate that the second step is a dissolution-recrystallization process. Furthermore， the formation mechanism of the hollow spheres has been discussed. It is found that the presence of H₂O in the reaction system is essential to the final formation of the hollow spheres.     

Fe/La2O3纳米催化剂制备碳纳米管

Nanocrystalline LaFeO₃ was synthesised by the citrate method with La(NO₃)₃·6H₂O,Fe(NO₃)₃·9H₂O and citric acid as the raw materials. Before and after reduction, its structure was characterized by means of X-ray diffraction and transmission electron microscopy(TEM). And after reduction of LaFeO₃ oxide, the rare earth oxide, La₂O₃, prevents Fe particles from agglomerating and promotes the dispersion of nano-scale Fe particles (ca.40nm), which is one of the key factors for the growth of carbon nanotube. The carbon nanotubes from the catalytic de-composition of C₂H₂ were obtained using Fe/La₂O₃ nano-scale catalyst, which was formed from LaFeO₃ oxide as the catalyst precursor. The morphological structures of the carbon nanotube obtained have been examined by TEM. The results indicate that they are multi-walled nanotubes of good quality with inter diameter ranging from 20～25nm and length ranging from 25～40μm. The yields of carbon nanotube are 1.25g·gcat^-1 at the reaction temperature of 973K for 30min.     

以氯醌酸二价阴离子为桥联配体的Fe(Ⅲ)-Fe(Ⅲ)和Mn(Ⅱ)-Mn(Ⅱ)双核配合物的合成与磁性

Two new binuclear Fe(Ⅲ)-Fe(Ⅲ) and Mn(Ⅱ)-Mn(Ⅱ) complexes containing the dianions of chloranilic acids (CA) which act as bridging ligand in the complexes, have been synthesized namely [Fe₂(phen)₄(u-CA)](ClO₄)₄·2H₂O and [Mn₂(phen)₄(u-CA)](ClO₄)₂·3H₂O (phen = O-phenanthroline; CA = dianions of chloranilic acids). They have been characterized by elemental analyses, IR, electronic spectra, susceptibility and variable-temperature magnetic susceptibility. The results indicate that there is a antiferromagnetic interaction between metal ions in the complexes at low temperature. The observed data were well fitted to those from a Heisenberg model. The obtained parameters: J= -2.02cm^-1, g = 2.25 for Fe(Ⅲ)-Fe(Ⅲ) complex; J=-5.45cm^-1, g = 2.01 for Mn(Ⅱ)-Mn(Ⅱ) complex.     

希土(Ⅲ)噻吩甲酰三氟丙酮和BipyO2/PhenNO三元配合物的合成和表征

The new ternary complexes of RE(TTA)₃(BipyO₂)·H₂O and RE(TTA)₃ (PhenNO)(where RE=Sm, Eu, Gd; TTA=thenoyltrifluoroacetonate; BipyO₂=2,2′-bipyridine-N,N′-dioxide; PhenNO=1,10-phenanthroline-N-oxide)have been synthesized. The composition and properties of complexes were studied by elemental analysis, UV spectrum, IR spectrum, DTA-TG and fluorescence spectrum. The effect of solvent on fluorescent intensity is discussed.     

(ZrO2)1-x(Yb2O3)x纳米晶的水热法合成及其烧结体的电性能

(ZrO₂)_1-x(Yb₂O₃)_x (x=0.07, 0.09, 0.11) nanocrystallites were hydrothermally prepared in basic media by using co-precipitated Zr(OH)₄ and Yb(OH)₃ as precursor. The nanocrystallites have small particle sizes of 5.8~7.5 nm, narrow size distribution, less agglomeration and high sinterability. The oxide-ionic conduction properties of the prepared ceramics were investigated by means of AC impedance spectroscope, oxygen concentration cell at 600~1 000 ℃. The results show that the ceramic with x=0.09 is superior to the ceramics with x=0.07 and 0.11 in oxide-ionic conduction.     

MgSO4·5Mg(OH)2·3H2O的水热合成及反应时间对其形貌的影响

Both whisker and nanometer MgSO₄·5Mg(OH)₂·3H₂O(MOS) were prepared by hydrothermal method at 140℃ for different times， using NaOH and MgSO₄·7H₂O as raw materials. The MgSO₄·5Mg(OH)₂·3H₂O part- icles were characterized by powder X-ray diffraction(XRD)，thermal analysis(TGA-DSC)， infrared spectroscopy(FT-IR)，transmission electron microscopy(SEM) and scanning electron microscopy(TEM). The size distribution in whisker-like and nanocrystalline materials are in the range of 10～50μm and 10～20nm respectively. The whisker MOS is metastable phase in MgSO₄-NaOH-H₂O system at 140℃，whereas nanometer MOS is stable phase.     

配位聚合物{[CoL][FeⅡFeⅢ(ox)3·1.5H2O]}∞的合成、波谱表征和磁学性质

A new Schiff base complex， CoL(ClO₄)·3H₂O (1) {L represents condensed from equal molar ratio of sali-cylaldehyde and diethylenetriamine} was synthesized and characterized. Further， a new coordination polymer， {[CoL][Fe^ⅡFe^Ⅲ(ox)₃·1.5H₂O]}_∞ (2)， was synthesized and characterized， where ox^2-=oxalate. The results of the IR and M?ssbauer spectra of 2 revealed that the coordination polymer exists 2-D layer structure in the solid state， and anions layer was formed by [^ⅡFe^Ⅲ(ox)₃]^- unit. The magnetic properties of 2 have been measured and the results indicate that there is magnetic ordering in the low temperature， which may arise from intermolecular ferromagnetic interactions or spin canted effects.     

Cs2SO4-C2H5OH-H2O三元体系30℃和50℃的平衡溶解度研究

The solubilities of Cs₂SO₄-C₂H₅OH-H₂O ternary system at 30℃ and 50℃ have been studied using microe-quipment for solubility determination. There appears two phases, alcoholic phase, water phase in the liquid phase. The solubilities of Cs₂SO₄ in water, C₂H₅OH and mixed solvent have been determined. The phase diagram indicated that C₂H₅OH might be salted out by Cs₂SO₄ from this system and the equilibrium solid phase is Cs₂SO₄.     

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.     

氯化钐与甘氨酸配合物Sm(Gly)2Cl3·3H2O热化学研究

A complex of samarium with glymine， [Sm(Gly)₂Cl₃·3H₂O]， was synthesized and characterized by DSC， TG and DTG. A possible mechanism of thermal decomposition of this complex was suggested. The heat capacities of the complex were measured by a precision adiabatic calorimeter over the temperature range from 82 to 375 K. The solution enthalpies of reactants [SmCl₃·6H₂O+2Gly] and the products [Sm(Gly)₂Cl₃·3H₂O+3H₂O] were determined by an isoperibel solution- reaction calorimeter at 298.15 K， respectively; the standard molar enthalpy of formation of [Sm(Gly)₂Cl₃·3H₂O] was calculated through a designed thermochemical cycle.     

(NH2CH2CH2NH3)4[WⅤO2(OC6H4O)2]2(NH3CH2CH2NH3)·H2O的合成、晶体结构、EPR以及与同构物的比较

Cis-dioxo-catecholatotungsten(Ⅴ) complex (NH₂CH₂CH₂NH₃)₄[W^ⅤO₂(OC₆H₄O)₂]₂(NH₃CH₂CH₂NH₃)·H₂O (1) was synthesized at room temperature by the reaction of tetrabutyl ammonium decatungstate with catechol in the mixed solvent of CH₃OH, CH₃CN and NH₂CH₂CH₂NH₂. The crystal structure of complex was determined by X-ray diffraction structural analysis. The results show that complex belongs to monoclinic system with space group P2₁/c,a=0.712 8(3) nm, b=3.082 3(11) nm, c=0.982 8(4) nm, β=102.639(6)°, V=2.106 8(14) nm³, Z=2, R₁=0.062 8, wR₂=0.183 7. Compared the complex with its analogous complexes (NH₂CH₂CH₂NH₃)₃[Mo^ⅤO₂(OC₆H₄O)₂], it is found that the coordination structure of W have no changes in the processing of electron transfer of tungsten-containing enzymes from the result of the similarity of the EPR spectra of the complexes and flavoenzyme from milk. CCDC: 272937.     

La2(CO3)3纳米线的微乳液法制备与表征

La₂(CO₃)₃ nanowires were prepared in the nonionic surfactant microemulsion(Triton X-100/cyclohexane/water)system. Transmission electron microscopy (TEM) and selected area electronic diffraction (SAED) were used to characterize the shape and size of the products. The results showed that the pH value and concentration of mother solution, temperature and aging time all could affect the morphology and size of the La₂(CO₃)₃ nanowires. The lengths of the nanowires were more than 10 μm and the diameters were in the range of 30～200 nm.     

γ-Fe2O3纳米粉的低热固相制备及其电磁损耗特性(英)

The Fe(OH)₃ precursor was prepared by solid -state reaction with Fe(NO₃)₃·9H₂O, NaOH and dispersed poly-ethylene glycol at low heating temperature(25 ℃). Synthesis of iron oxide (γ-Fe₂O₃) nanoparticle was achieved by thermal decomposition of Fe(OH)₃·xH₂O precursor. The nanoparticle was characterized by TG-DTA, X-ray diffra-ction, TEM etc. The results showed that the nanoparticle was composed of γ-Fe₂O₃ and was a better absorber for electromagnetic wave within the low frequency band.     

MgFe2O4纳米粉体的水热合成及其表征(英)

MgFe₂O₄ nanoparticles were hydrothermally synthesized at 150 ℃ using iron nitrate [Fe(NO₃)₃·9H₂O], magnesium nitrate [Mg(NO₃)₂·6H₂O] and sodium hydroxide (NaOH) as starting materials by carefully controlling the reaction conditions. The influences of several factors such as presence or absence of Na⁺, molar ratio of Fe³⁺ / Mg²⁺, concentration of mental ions, temperature and reaction time on resultant products were investigated in the hydrothermal process. The sample was characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM), and its magnetic properties were measured using vibrating sample magnetometer (VSM).