水/油型微乳液中球形及棒状钛酸锶钡纳米粒子的控制合成

Barium strontium titanate nanoparticles with spherical and rod-like morphologies were synthesized in water/Triton X-100/n-hexanol/cyclohexane quaternary reverse microemulsion solution. The influences of the molar ratio of water to surfactant (ω₀) and the concentration of reactants on the morphology and size of barium strontium titanate nanoparticles were studied. The structure, compositions and morphology of the prepared products were characterized by XRD, SAED, ICP, EDS and TEM. The results show that the obtained Ba_0.7Sr_0.3TiO₃ spherical nanoparticles with diameters of 20～100 nm and the Ba_0.7Sr_0.3TiO₃ nanorods with diameters of 70～120 nm and lengths up to 600～800 nm are a single crystal, with a cubic phase. The molar ratio for barium, strontium and titanate in products is about 0.7:0.3:1.     

钛酸锌的制备及其对高氯酸铵热分解的催化性能

ZnTiO₃ nanocrystals were prepared by sol-gel method, using Zn(NO₃)₂ and Ti(C₄H₉O)₄ in the topic. The as-prepared ZnTiO₃ nanocrystals were characterized by XRD, FTIR and TEM, and the catalytic performance of ZnTiO₃ nanocrystals of different contents for the ammonium perchlorate(AP)decomposition was investigated by thermal analysis. The results indicate that ZnTiO₃ with pure cube structure can be synthesized at 600 ℃ by this procedure,which was spheroid with particle size of about 60~100 nm. The results expressed that the low temperature decomposition peaks of AP is advanced by 17 ℃ and the high temperature decomposition peaks of AP is advanced by 24 ℃ when adding 5% nanoparticle ZnTiO₃ powder. The catalytic effects of ZnTiO₃ powders on the high temperature decomposition of AP are less than that of nanometer metal powders, but all the micron metal powders decrease the low decomposition temperature of AP.     

La2O2S∶Mn2+荧光粉的微波合成及其荧光特性

Using La₂(SO₄)3 and the active carbon powder as reactants, La₂O₂S∶Mn²⁺ red phosphor was synthesized by microwave radiation method. The phosphor was characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), laser-diffraction size analyzer and fluorospectrophotometer. The XRD analysis showed that the phosphor was pure phase La₂O₂S. The phosphor of La₂O₂S∶Mn²⁺ showed hexagonal crystal structure with diverse shapes, such as spherical and rod, with average particle size of 10.22 μm. The emission and excitation spectra of the phosphor were determined by fluorospectrophotometer and the results showed that the excitation spectrum of the phosphor under 600 nm emission wavelength was excitation bands between 250 nm and 350 nm with a peak value of 303 nm. Then ,when exicited under UV 303 nm, the phosphor showed broad band emission of 550~700 nm with a peak at 607 nm. In addition, the optimal effects were obtained for the phosphor preparation when the concentration of the activator Mn²⁺ was x_Mn=0.01, the ratio of C and O (n_C / n_O) in the reactants was 0.6∶1, and the time of reaction was about 1 h. La₂O₂S∶Mn²⁺ has strong absorption of UV spectrum and can emit bright red light.     

溶胶凝胶法制备Nd2O3改性钛酸钡陶瓷的研究

The technological condition for the preparation of BaTiO₃ ceramics doped with Nd₂O₃ by Sol-Gel was deter-mined through orthogonal experiment. When n_Ba(Ac)2∶n_Ti(OC4H9)4∶n_Nd2O3∶n_{CH3(CH2)2CH2OH}∶n_H2O=1.00∶1.00∶0.003∶7.30∶37.04, pH=3.5,T=25℃,the light-yellow-transparent-stable solution and thorough transparent gel was generat-ed, the transforming time of solution to gel was 25h. The crystal structure and particle size of BaTiO₃ ceramics doped with Nd₂O₃ were studied by SEM and X-ray respectively, the type of the crystal was tetragonal, the particle size was about 24.7nm. The dielectric constant (ε) and dielectric loss (tanδ) of BaTiO₃ ceramics doped with Nd₂O₃ were determined between 10⁴～10⁶Hz, and the results showed that the dielectric constant was increased obviously, the dielectric loss was decreased clear and the resistivity (ρ_V) was also decreased noticeably.     

单分散超细ZnO粉体的制备与表征

Monodispersed superfine ZnO powders with particle size of about 200～400nm were successfully prepared by the decompressed distillation process with n-butyl alcohol as the solvent. The starting materials were Zn(NO₃)2·6H₂O and NH₃·H₂O. TG-DSC， XRD， TEM and BET surface areas techniques were used to characterize the precursor and as-prepared superfine ZnO powders. In the preparation process of superfine ZnO powders， two techniques including the decompressed distillation with n-butyl alcohol and washing with absolute ethanol were used to avoid agglomeration. It is showed that the decompressed distillation process has a better effect in avoiding ag-glomeration than washing with absolute ethanol. The precursor obtained by the decompressed distillation technique has a lower calcination temperature than the one obtained by washing with absolute ethanol. Zincite phase of ZnO with some impurities was obtained when the precursor was calcined at 200℃ for 2h. After it was calcined at 300℃ for 2h， pure superfine ZnO powder was obtained.     

微波辐照方式对CdS和Bi2S3纳米粒子结晶度的影响

The effect of traveling microwave irradiation on the crystallinities of CdS nanoparticles and Bi₂S₃ nanorods was studied. Results showed that as compared with stationary microwave irradiation the crystallinities and the crystal growth of sulfide nanoparticles were improved. Traveling microwave irradiation can supply narrower frequency distribution and stronger power density of irradiation， CdS nanoparticles and Bi₂S₃ nanorods obtained are better in crystallinities and larger in size than under stationary microwave irradiation.     

结晶碳酸钕的水热合成、外观形貌及其组成

Crystalline neodymium carbonates were prepared by treating the amorphous precipitate formed from the reaction between neodymium chloride and ammonium bicarbonate under hydrothermal condition. Their composition, morphology and crystal phase were identified by means of elemental analysis, SEM and XRD. It was found that Nd₂(CO₃)₃·2.5H₂O with tengerite-type structure and sheet morphology was obtained when the feed molar ratio(FMR=n_(NH4)2CO2/n_NdCl3)was 2 or 1.8 and hydrothermally treated at 150 ℃ for 12h. However, orthogonal NdOHCO₃ particles agglomerated with long rod crystals were formed when lowering FMR to 1.5 under the same hydrothermal condition. Phase transformation from tengerite-type Nd₂(CO₃)₃·2.5H₂O to orthogonal NdOHCO₃ was occurred when increasing hydrothermal temperature or prolonging hydrothermal time, which is beneficial to the preparation of neodymium hydroxyl-carbonate with neodymium oxide content higher than 70%.     

反相微乳液法合成SrTiO3纳米棒

SrTiO₃ nanorods were synthesized in cetanyl trimethyl ammonium bromide (CTAB) reverse microemulsion containing CTAB, n-hexanol, n-octane and water with Ba(OH)₂ as reactants. The effects of different conditions such as ω₀ [ω₀=n_H2O/ n_CTAB], aging time and the concentration of reactants on the formation of the nanorods were studied. Transmission electron microscope (TEM), electron diffraction (ED) and X-ray diffraction(XRD)were used to characterize the morphology and the structure of the synthesized nanorods. The results show that SrTiO₃ nanorods with a length of 260～2 000 nm and a diameter of 50～100 nm belonging to single crystal are single cubic system. The molar ratio of Sr to Ti of products is 1.0 as determinded by ICP.     

简捷水热前驱物技术制备钛酸钡纳米棒与纳米球

A facile synthesis route has been developed to prepare barium titanate nanoparitcles via a low temperature (120 ℃) hydrothermal decomposition of single-source metal-organic precursor. A mixture of tetramethylammonium hydroxide (TMAH) and distilled water was used as reaction media, and Barium titanium ethyl-hexano- isoproxide [BaTi(O₂CC₇H₁₅)(OC₃H₇)₅] was used as precursor. The architecture of products can be selectively controlled from nanorods to nanospheres by adjusting the precursor′s concentration in the reaction system. Powder X-ray diffraction (XRD) analysis indicated that the products were in cubic phase. Transmission electronic microscopy (TEM) observation showed that the nanospheres were 30～50 nm in diameter, and the nanorods were 5～10 nm in diameter and 100～600 nm in length, respectively. Phase transformation behavior of the as-prepared products was also investigated.     

VOx / Titanate复合材料纳米棒的水热合成及其电化学性能研究

Vanadium oxide/titanate composites nanorods (VO_x/ Titanate-CNRs) were synthesized in high yield by using titanate nanotubes as templates and V₂O₅·nH₂O sol as the precursors under hydrothermal conditions (200 ℃, 48 h). Samples were characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy dispersive analysis by X-ray (EDAX). X-ray diffraction structure determination showed that this new phase had the composition of V₃O₇·H₂O and crystallized with orthorhombic symmetry. SEM and TEM tests showed that the samples were uniform straight rods with the diameter range from around 100 to 300 nm and the length over 10 μm. The chemical compositions of the samples were determined with EDXA. The electrochemical tests of samples (titanates nanotubes, V₂O₅ and VO_x/ Titanate-CNRs) prove that VO_x/ Titanate-CNRs exhibit a better electrochemical performance.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.