5-芳胺-4,7-吲唑二酮的合成

以1,4-对醌、芳肼为原料,通过Aza-Nenitzescu反应、氧化银氧化得到吲唑醌,亲核试剂(各种芳香胺)在Ce3 催化下与吲唑醌发生迈克尔加成反应,得到一系列5-芳氨基基取代的吲唑醌.化合物结构经元素分析、IR及1H NMR证实.初步的生理活性研究表明,这些化合物具有良好的抗哮喘活性.     

Determination of hydrolyzable tannins in the fruit of Terminalia chebula Retz. by high-performance liquid chromatography and capillary electrophoresis

A RP-HPLC method for determining fourteen components (gallic acid, chebulic acid, 1,6-di-O-galloyl-D-glucose, punicalagin, 3,4,6-tri-O-galloyl-D-glucose, casuarinin, chebulanin, corilagin, neochebulinic acid, terchebulin, ellagic acid, chebulagic acid, chebulinic acid, and 1,2,3,4,6-penta-O-galloyl-D-glucose) in the fruit of Terminalia chebula Retz. is described. The separation was achieved within 80 min using a binary gradient with mobile phases consisting of a pH 2.7 phosphoric acid solution and an 80% CH3CN solution. Capillary electrophoretic analyses were also attempted, and it was found that CZE (25 mM Na2B4O7, 5 mM NaH2PO4, pH 7.0) was an efficient method for the separation of gallotannins, while an MEKC method (25 mM Na2B4O7, 5 mM NaH2PO4, 20 mM SDS, pH 7.0, and 10% acetonitrile) provided a better separation for most of the tannins examined. The HPLC and CE methods developed were both successfully applied to the assay of tannins in commercial samples of Chebulae Fructus.     

钴(II)-联吡啶-α-氨基酸的热力学和动力学研究

关于联吡啶为第一配体的二元、三元配合物的热力学和动力学性质的研究,以铜（Ⅱ）作为中心离子最为多见,而以钴（Ⅱ）作为中心离子的报导较少．实验表明,过渡金属钻（Ⅱ）能与大多数的生物配体、大π共轭体系形成相当稳定的二元、三元配合物,是生物功能模拟的一个具有应用价值的中心离子·钴（Ⅱ）卟啉可以代替铁（Ⅱ）卟啉,模拟血红蛋白、肌红蛋白[1],在生物体内起到输送氧的作用．为了充分了解钴（Ⅱ）与生物配体的配伍能力、配位方式以及其配位过程的动态行为,为推动钴（Ⅱ）配合物及其生物功能的模拟研究,本文分别采用PH电位法…     

液相合成γ-丁内酯用新型催化剂的开发

采用共沉淀法开发了绿铜锌矿型１，４－丁二醇液相合成γ－丁内酯用新型催化剂，经直接还原，１，４－丁二醇转化率约１００％，γ－丁内酯收率高于９２％；用ＤＳＣ技术选定了还原条件，运用ＸＲＤ和ＸＰＳ等技术优化了催化剂配方；考察了催化剂的稳定性，并获得了反应速率方程。     

铜(II)-5-取代邻菲啰啉-二氧四胺大环三元体系的稳定性研究

The stability of copper (Ⅱ)-13-(2'-Hydroxy-3',5'-substituted benzyl)-1,4,8,11-tetraazacyclotetradecane-12, 14-dione(RTADO-14) binary complex compounds and of copper (Ⅱ)-5-substituted-1,10-phenanthrolines(R'TADO)-RTADO-14 ternary complex compounds was studied by means of pH titration method at 25.0±0.1 ℃ and I=0.1mol?dm-3KNO3. The formation constants of binary and ternary complexes were obtained. The structures of the binary and ternary complxes and the effects fo substituents on macrocyclic ligands and on R'Phen were also discussed.     

Voltammetric determination of uric acid by using gold nanotubule electrode

Gold nanotubule membranes were prepared by using electroless deposition of gold within the pores and surfaces of polycarbonate track-etched membranes.And the gold nanotubule membrane was used as an electrode for determination of uric acid in urine samples for the first time.In Britton-Robinson buffer of pH 4.56,uric acid exhibited well-defined differential pulse voltammograms.And the interference between coexistent ascorbic acid and uric acid was overcome owing to the attractive ability of the gold nanotubule electrode to yield a large anodic peak difference ca.0.404 V(vs.SCE).The proposed method was then applied to the determination of uric acid in urine without any pretreatment.     

Benzene as a selective chemical ionization reagent gas

Dilute mixtures of C₆H₆ or C₆D₆ in He provide abundant [C₆H₆]^+· or [C₆D₆]^+· ions and small amounts of [C₆H₇]⁺ or [C₆D₇]⁺ ions as chemical ionization (CI) reagent ions. The C₆H₆ or C₆D₆ CI spectra of alkylbenzenes and alkylanilines contain predominantly M^+· ions from reactions of [C₆H₆]^+· or [C₆D₆]^+· and small amounts of MH⁺ or MD⁺ ions from reactions of [C₆H₇]⁺ or [C₆D₇]⁺. Benzene CI spectra of aliphatic amines contain M^+·, fragment ions and sample-size-dependent MH⁺ ions from sample ion-sample molecules reactions. The C₆D₆ CI spectra of substituted pyridines contain M^+· and MD⁺ ions in different ratios depending on the substituent (which alters the ionization energy of the substituted pyridine), as well as sample-size-dependent MH⁺ ions from sample ion-sample molecule reactions. Two mechanisms are observed for the formation of MD⁺ ions: proton transfer from [C₆D₆]^+· or charge transfer from [C₆D₆]^+· to give M^+·, followed by deuteron transfer from C₆D₆ to M^+·. The mechanisms of reactions were established by ion cyclotron resonance (ICR) experiments. Proton transfer from [C₆H₆]^+· or [C₆D₆]^+· is rapid only for compounds for which proton transfer is exothermic and charge transfer is endothermic. For compounds for which both charge transfer and proton transfer are exothermic, charge transfer is the almost exclusive reaction.     

Dispersion state of CuO on CeO2

XRD and XPS are used to study the dispersion state of CuO on ceria surface. The dispersion capacity values of CuO measured by the two methods are consistent, which are of 1.20 mmol CuO/100 m² CeO₂. In addition, the results reveal that highly dispersed Cu²⁺ ions are formed at low CuO loadings and that increasing the CuO content to a value higher than its dispersion capacity produces crystalline CuO after the surface vacant sites on CeO₂ are filled. The atomic composition of the outermost layer of the CuO/CeO₂ samples has been probed by using static secondary ion mass spectroscopy (SSIMS), and the ratim of Cu/Ce are found to be 0.93 and 0.46 for the 1.22 and 0.61 mmol CuO/CeO₂ samples respectively. Temperature-programmed reduction (TPR) profile with two reduction peaks at 156 and 165°C suggests that the reduction of highly dispersed Cu²⁺ ions consists of two steps and is easier than that of CuO crystallites, in which the TPR profile has only one reduction peak at about 249°C. The above experimental results are in good agreement with the prediction of the incorporation model. Project supported by the National Natural Science Foundation of China.     

6β-Acetoxy-7 α-Hydroxyroyleanone,A New Compound from Taiwania Cryptomerioides Hayata

Two crystalline compounds from the bark of Taiwania cryptomerioides Hayata were isolated. One of them was identified as 6,7-dehydroroyleanone and the other was shown to be a new derivative of royleanone having a structure of 6β-acetoxy-7α-hydroxyroyleanone.     

Reactions of hydrazoic acid on TiO2 nanoparticles: an experimental and computational study

This article reports the results of a computational and experimental study on the reaction of hydrazoic acid, HN3, adsorbed on 15-20 nm TiO2 particle films. Experimentally, FTIR spectra of HN3(a) have been measured by varying HN3 dosage, UV irradiation time and surface annealing temperature. Three sharp peaks, related to v(a)(NNN) of HN3(a) and N3(a) with different configurations in the 2000-2200 cm(-1) region, and a broad band absorption, related to associated and isolated HN(a) and HO(a) adsorptions in the 3000-3800 cm(-1) region, have been detected. Computationally, molecular structures, vibrational frequencies and adsorption energies of possible adsorbates including HN3 and its derivatives, N3, N2, NH, and H, have been predicted by first-principles calculations based on the density functional theory (DFT) and the pseudopotential method. On the basis of the experimental and computational results, the peak appeared at 2075 cm(-1), which increases at a faster rate with HN3 exposure time, is attributed to a stable adsorbate, N3-Ti(a), with the predicted adsorption energy, E(ads) = 13 kcal/mol. The peak at 2118 cm(-1), which survives at the highest surface temperature in the heating experiment, is attributable to the most stable adsorbate, Ti-N2N(H)-O(a) with E(ads) = 36 kcal/mol. The peak at 2170 cm(-1), which vanishes most readily in all of the aforementioned experiments, is related to less stable molecular adsorbates, end-on HN3-Ti(a) with E(ads) = 5 kcal/mol and side-on HN(N2)-Ti(a) with E(ads) = 8 kcal/mol. A potential energy diagram for the formation of various absorbates with their transition states has been established for the HN3/TiO2 system. On the basis of the predicted desorption energies, the four most stable products of the HN3 reaction on TiO2 are H-O(a), 118 kcal/mol; HN-O(a), 85 kcal/mol; Ti-N2N(H)-O(a), 36 kcal/mol; and N3-O(a), 19 kcal/mol.