含硅原料对合成氮氧化硅粉末的影响

本文通过对比实验，分别以（１）天然石英粉（２）硅酸钠（３）碳酸钠与天然石英粉（４）活性ＳｉＯ２等为原料合成氮氧化硅（Ｓｉ２Ｎ２Ｏ）粉末，实验结果表明：直接碳热还原氮化天然石英粉，难以合成Ｓｉ２Ｎ２Ｏ。而以（２），（３）两种原料虽然能合成较纯的Ｓｉ２Ｎ２Ｏ粉末，且工艺简单，但原料中ＳｉＯ２含量太低，应用价值不大，而用活性ＳｉＯ２为原料，能合成较高纯度的Ｓｉ２Ｎ２Ｏ尽管工艺较（２），（３）复杂，但此法     

Aspirin analogues as dual cyclooxygenase-2/5-lipoxygenase inhibitors: synthesis, nitric oxide release, molecular modeling, and biological evaluation as anti-inflammatory agents

Analogues of aspirin were synthesized through an efficient one-step reaction in which the carboxyl group was replaced by an ethyl ester, and/or the acetoxy group was replaced by an N-substituted sulfonamide (SO(2)NHOR(2):R(2) =H, Me, CH(2)Ph) pharmacophore. These analogues were designed for evaluation as dual cyclooxygenase-2 (COX-2) and 5-lipoxygenase (5-LOX) inhibitors. In vitro COX-1/COX-2 isozyme inhibition studies identified compounds 11 (CO(2) H, SO(2)NHOH), 12 (CO(2)H, SO(2)NHOCH(2)Ph), and 16 (CO(2)Et, SO(2)NHOH) as highly potent and selective COX-2 inhibitors (IC(50) range: 0.07-0.7 μM), which exhibited appreciable in vivo anti-inflammatory activity (ED(50) range: 23.1-31.4 mg kg(-1)). Moreover, compounds 11 (IC(50) =0.2 μM) and 16 (IC(50) =0.3 μM), with a sulfohydroxamic acid (SO(2)NHOH) moiety showed potent 5-LOX inhibitory activity. Furthermore, the SO(2)NHOH moiety present in compounds 11 and 16 was found to be a good nitric oxide (NO) donor upon incubation in phosphate buffer at pH 7.4. Molecular docking studies in the active binding site of COX-2 and 5-LOX provided complementary theoretical support for the experimental biological structure-activity data acquired.     

陶粒-锰砂双层滤料滤池同时去除地下水中铁锰研究

传统除铁锰的方法是一级除铁、二级除锰。采用接触氧化一药剂氧化法。利用陶粒-锰砂双层滤料滤池可同时去除铁和锰,即通过一级曝气、药剂氧化和过滤即可同时去除铁和锰。简化了传统的二级曝气、过滤的长流程设计。除铁除锰滤料无需成熟期,无需除锰前处理,可直接生产应用。     

Syntheses and characterization of new nickel coordination polymers with 4,4'-dipyridylsulfide. Dynamic rearrangements of one-dimensional chains responding to external stimuli: temperature variation and guest releases/re-inclusions

Crystal structures and dynamic rearrangements of one-dimensional coordination polymers with 4,4'-dipyridylsulfide (dps) have been studied. Reaction of Ni(NO(3))(2)·6H(2)O with dps in EtOH yielded [Ni(dps)(2)(NO(3))(2)] ·EtOH (1), which had channels filled with guest EtOH molecules among the four Ni(dps)(2) chains. This coordination polymer reversibly transformed the channel structure responding to temperature variations. Immersion of 1 in m-xylene released guest EtOH molecules to yield a guest-free coordination polymer [Ni(dps)(2)(NO(3))(2)] (2a), which was also obtained by treatment of Ni(NO(3))(2)·6H(2)O with dps in MeOH. On the other hand, removal of the guest molecules from 1 upon heating at 130 °C under reduced pressure produced a guest-free coordination polymer [Ni(dps)(2)(NO(3))(2)] (2b). Although the 2a and 2b guest-free coordination polymers have the same formula, they showed differences in the assembled structures of the one-dimensional chains. Exposure of 2b to EtOH vapor reproduced 1, while 2a did not convert to 1 in a similar reaction. Reaction of Ni(NO(3))(2)·6H(2)O with dps in acetone provided [Ni(dps)(NO(3))(2)(H(2)O)] ·Me(2)CO (4) with no channel structure. When MeOH or acetone was used as a reaction solvent, the [Ni(dps)(2)(NO(3))(2)] · (guest molecule) type coordination polymer, which was observed in 1, was not formed. Nevertheless, the reaction of Ni(NO(3))(2)·6H(2)O with dps in MeOH/acetone mixed solution produced [Ni(dps)(2)(NO(3))(2)]·0.5(MeOH·acetone) (5), which has an isostructural Ni-dps framework to 1.     

新型配合物[Cu_2(phen)_2(OH)_2(H_2O)_2][Cu_2(phen)_2(OH)_2Cl_2]Cl_2·6H_2O的合成与性质研究

采用溶液法合成了分子式为[Cu2(phen)2(OH)2(H2O)2][Cu2(phen)2(OH)2Cl2]Cl2.6H2O的配合物。通过元素分析、红外光谱、紫外光谱和X-射线单晶衍射对配合物进行了表征;此外,还对该配合物进行了非等温热分解动力学研究。研究表明,配合物中有两组双核配位单元,分别为[Cu2(phen)2(OH)2(H2O)2]2+和[Cu2(phen)2(OH)2Cl2];两个配位单元的中心原子铜均为五配位的,具有扭曲的四方锥结构,配合物通过氢键作用形成超分子结构。此配合物的热分解反应是分两步进行的,第一步反应的动力学方程为dαdT=Aφ.exp-E()R T3/2[(1-α)43(1-α)-13-]1-1,活化能E=151.8kJ/mol,指前因子lgA=16.9435;第二步反应的动力学方程为dαdT=Aφ.exp-E()R T32[(1-α)43(1-α)-13-]1-1,活化能E=201.5kJ/mol,指前因子lgA=7.5447。     

BaF2/BaO替代对钡镓锗酸盐玻璃结构的影响

用Raman光谱技术研究了Ga2O3/GaF3GeO2二元玻璃的结构,并用XRD技术和Raman光谱技术研究了BaF2/BaOGa2O3GeO2系统玻璃的结构。讨论了BaF2替代BaO对玻璃结构的影响。结果表明:摩尔组成为20BaO15Ga2O365GeO2玻璃的主要亚稳相是BaGa2·Ge2O8,而以BaF2替代玻璃中的全部BaO后,玻璃的主要亚稳相转变为BaGe2O5。玻璃中引入氟化物后,其中频段强Raman散射峰宽化,主峰值向高频方向移动,表明在玻璃中形成一些较大的四面体环。同时玻璃高频段最强的振动峰同样移向高频,高频带低频侧的肩明显减弱。这些变化可解释为玻璃中Q2振动模的减少和Ga,Ge四面体的对称性降低,使Raman光谱中的高频成分增加。     

Ag(I)(Et(2)PCH(2)CH(2)PPh(2))(2)]NO(3): An Antimitochondrial Silver Complex

The silver(I) complex [Ag(eppe)(2)]NO(3) (eppe = Et(2)PCH(2)CH(2)PPh(2)) is shown by X-ray crystallography to be tetrahedral with Ag - PEt(2) and Ag - P Ph(2) bond lengths of 2.482 and 2.518 A, respectively. The complex is selectively antimitochondrial and inhibits the growth of a number of yeast strains in non-fermentable media at concentrations as low as 2.5 muMu and induces the mitochondrial mutation petite The effect is largely reversed by the presence of aspirin. The complex is shown to be stable in the cell culture media and in the presence of glutathione, but readily reacts with disulfides of oxidized glutathione and serum albumin. Surprisingly, neither [Au(eppe)(2)]Cl nor [Au(eppe)(2)]Cl (dppe = Ph(2)PCH(2)CH(2)PPh(2)) showed any mitochondrial selectivity in the same screening protocol.     

Analysis of 2-(2-Phenylethyl)chromones by UPLC-ESI-QTOF-MS and Multivariate Statistical Methods in Wild and Cultivated Agarwood

Agarwood is the fragrant resinous material mainly formed from species of Aquilaria. 2-(2-phenylethyl)chromones, especially the highly oxidized 5,6,7,8-tetrahydro-2-(2-phenylethyl)chromones, are the main representative compounds from agarwood. It is important to determine whether agarwood in trade is from cultivated trees or natural trees in the Convention on the International Trade in Endangered Species (CITES). We characterized the 2-(2-phenylethyl)chromones in agarwood by ultra-performance liquid chromatography coupled with electrospray ionization mass spectrometry (UPLC–ESI-QTOF-MS) and differentiated wild from cultivated agarwood by metabolomic analysis. A total of 141 chromones including 50 potentially new compounds were evaluated as belonging to four structural classes (unoxidized 2-(2-phenylethyl)chromones, 5,6,7,8-tetrahydro-2-(2-phenylethyl)-chromones, bi-2-(2-phenylethyl)chromones, and tri-2-(2-phenylethyl)chromones). The metabolic difference between wild and cultivated agarwood was analyzed by component analysis (PCA) and orthogonal partial least squares discriminant analysis (OPLS-DA). Fourteen markers of metabolisms in wild and cultivated agarwood were constructed (e.g., 6,7-dimethoxy-2-(2-phenylethyl)chromone, 6,8-dihydroxy-2-(2-phenylethyl)chromone, 6-methoxy-2-(2-phenylethyl)chromone, etc.). These results indicated that UPLC–ESI-QTOF-MS-based metabonomics analysis in agarwood may be useful for distinguishing wild agarwood from cultivated agarwood.     

Binuclear Rhodium(II) Complexes With Selective Antibacterial Activity

Binuclear rhodium(II) complexes [Rh(2)Cl(2)(mu-OOCR)(2)(N-N)(2)] {R = H, Me; N-N = 2,2'-bipyridine (bpy), 1,10-phenanthroline (phen)} and [Rh(2)(mu-OOCR)(2)(N-N)(2)(H(2)O)(2)](RCOO)(2) (R = Me, Et;) have been synthesized and their structure and properties have been studied by electronic, IR and (1)H NMR spectroscopy. Antibacterial activity of these complexes against Escherichia coli and Staphylococcus aureus has been investigated. The most active antibacterial agents against E. coli were [Rh(2)Cl(2)(mu-OOCR)(2)(N-N)(2)] and [Rh(2)(mu-OOCR)(2)(N-N)(2)(H(2)O)(2)](RCOO)(2) {R = H and Me} which were considerably more active than the appropriate nitrogen ligands. The complexes show low activity against S. aureus. The activity of the complexes [Rh(2)(OOCR)(2)(N-N)(2)(H(2)O)(2)](OOCR)(2) against E. coli decreases in the series: R=H congruent withCH(3)>C(2)H(5)>C(3)H(7) congruent withC(4)H(9). The reverse order was found in the case of S. aureus.     

Reactions of Pd(II) and Pt(II) Complexes With Tetraethylthiouram Disulfide

The reactions of tetraethylthiouram disulfide (DTS), an inhibitor of the nephrotoxicity of Pt(II) drugs, an efficient agent in the treatment of chronic alcoholism, in the treatment of HIV infections, AIDS and heavy metal toxicity, and a fungicide and herbicide, with K(2)[PtCl(4)], in ratio 1:1 and 1:2, gave the compounds [PtCl(2)DTS] and [Pt(S(2)CNEt(2))(2)] respectively. The reaction of the complexes K(2)[PdCl(4)], Pd(AcO)(2) and [PdCl(2)(PhCN)(2)], where PhCN = Benzonitrile, with tetraethylthiouram disulfide in ratio 1:1 or 1:2, yielded orange crystals identified as [Pd(S(2)CNEt(2))(2)]. The crystals were suitable for study by X-ray diffraction. The -S-S- bridge in the tetraethylthiouram disulfude molecule was broken and the two molecules of the thiocarbamate derivative were bound to the Pd(II) by the equivalents sulfur atoms. All the compounds were characterized by IR, (1)H and (13)C NMR spectroscopies.     

Synthesis and Biological Activity of Manganese (II) Complexes of Phthalic and Isophthalic Acid: X-Ray Crystal Structures of [Mn(ph)(Phen)(2)(H(2)O)]. 4H(2)O, [Mn(Phen)(2)(H(2)O)(2)](2)(Isoph)(2)(Phen). 12H(2)O and {[Mn(Isoph)(bipy)](4). 2.75biby}(n)(phH(2) = Phthalic Acid; isoph = Isophthalic Acid; phen = 1,10-Phenanthroline; bipy = 2,2-Bipyridine)

Manganese(II) acetate reacts with phthalic acid (phH(2)) to give [Mn(ph)].0.5H(2)O (1). Reaction of 1 with 1,10-phenanthroline produces [Mn(ph)(phen)].2H(2)O (2) and [Mn(ph)(phen)(2)(H(2)O)].4H(2)O (3). Reaction of isophthalic acid (isophH(2)) with manganese(II) acetate results in the formation of [Mn(isoph)].2H(2)O (4). The addition of the N,N-donor ligands 1,10-phenanthroline or 2,2'-bipyridine to 4 leads to the formation of [Mn(2) (isoph)(2)(phen)(3))].4H(2)O (5), [(Mn(phen)(2)(H(2)O)(2)](2)(isoph)(2)(phen).12H(2)O (6) and {[Mn(isoph)(bipy)](4).2.75 biby}(n) (7), respectively. Molecular structures of 3, 6 and 7 were determined crystallographically. In 3 the phthalate ligand is bound to the manganese via just one of its carboxylate groups in a monodentate mode with the remaining coordination sites filled by four phenanthroline nitrogen and one water oxygen atoms. In 6 the isophthalates are uncoordinated with the octahedral manganese center ligated by two phenanthrolines and two waters. In 7 the Isophthalate ligands act as bridges resulting in a polymeric structure. One of the carboxylate groups is chelating a single manganese with the other binding two metal centres in a bridging bidentate mode. The phthalate and isophthalate complexes, the metal free ligands and a number of simple manganes salts were each tested for their ability, to inhibit the growth of Candida albicans. Only the "metal free" 1,10-phenanthroline and its manganese complexes were found to be active.     

2-(2-(6-氯己氧基)乙氧基)乙氨的合成

2-(2-氨基乙氧基)乙醇溶于乙醇,用叔丁氧羰基酸酐(Boc2O)进行氨基保护得,N-叔丁氧羰基-2-(2-氨基乙氧基)乙醇,与1-氯-6-溴己烷在正已烷及50% NaOH和四丁基溴化铵作用下缩合,得N-叔丁氧羰基-2-(2-(6-氯己氧基)乙氧基)乙氨,最后在二氯甲烷及三氟乙酸混合液中脱保护,得标题化合物,总收率11...     

N,N'-二四唑胺和邻菲啰啉与碱土金属钙、锶混配配合物的合成与表征

以N,N’－二四唑胺（C2H3N9）和邻菲哕啉（C12H8N2）为配体合成碱土金属Ca,Sr的含能配合物,并对配合物进行了基础的物化表征。化学分析和元素分析确定配合物的组成为Ca（C2HN9）（C12H8N2）：（H2O）。（1）和Sr（C2HN9）（C12H8N2）2（H2O）2（2）。溶解性实验表明,常温下配合物难溶于水加热时溶解,且不溶于甲醇、乙腈等有机溶剂。红外光谱分析表明,配体邻菲啰啉以双齿螯合形式与中心离子配位,配体N,N’－二四唑胺中N原子参与了配位。TG—DTG热分析显示配合物在氮气气氛、研究温度范围内有三个热分解过程,最终分解产物可能分别为以CaO与SrO为主的混合物。     

Interaction of Some Non-Platinum Metal Anticancer Complexes With Nucleotides and DNA and The Two-Pole Complementary Principle (TPCP) Arising Therefrom

The binding modes of some non-platinum metal anticancer complexes, Cp(2)TiCl(2), Cp(2)ZrCl(2), (CH(3))(2)SnCl(2), (C(2)H(5))(2)SnCl(2), (C(2)H(5))(2)SnCl(2)(phen) (phen=Phenanthroline) and cis-Ru(II)Cl(2)(DMSO)(3) (DMSO) (cis-RDT) with nucleotides and DNA in aqueous solution at physiological pH values were investigated by various modern techniques. 5'-dGMP with Cp(2)TiCl(2) or cis-RDT forms chelate complexes in which both N(7) and phosphate of dGMP bind to the metal center. Whereas Cp(2)ZrCl(2) and all the diorganotin compounds can bind dGMP only via the phosphate group. The investigations of the interactions between Cp(2)TiCl(2) or (C(2)H(5))(2)SnCl(2) and DNA indicate that there are two types of binding sites on DNA for Cp(2)TiCl(2), i.e., the base nitrogen rings and the phosphate group, while (C(2)H(5))(2)SnCl(2) can bind to DNA only via the phosphate group. At last, by carefully comparing and analysing the binding modes-activity relationships of the above anticancer complexes and other non-platinum and platinum anticancer complexes, a hypothesis named "Two-Pole Complementary Principle" was put forward.     

粉煤灰及膨润土对Ni^2＋，Zn^2＋，Cd^2＋，Pb^2＋的吸附研究

研究了粉煤灰和膨润土对溶液中有毒重金属离子Ni~(2 )、Zn~(2 )、Pb~(2 )、Cd~(2 )的吸附能力。动态吸附试验显示,吸附过程是快速的。试验结果表明:粉煤灰对Zn~(2 )的吸附能力和膨润土相当,对Ni~(2 )、Cd~(2 )的吸附能力均大于膨润土。平衡吸附模型说明在高浓度下,Ni~(2 )、Zn~(2 )、Pd~(2 )在粉煤灰中,Ni~(2 )、Pd~(2 )在膨润土中的吸附符合Langmuir模式。试验还表明:随着吸附剂中Ni~(2 )、Zn~(2 )、Pb~(2 )、Cd含量增加,粉煤灰和膨润土对Ni~(2 )、Zn~(2 )、Pb~(2 )、Cd~(2 )的吸附百分率下降。     

Antitumour Metallocenes: Effect of DMSO on the Stability of Cp(2)TiX(2) and Implications for Anticancer Activity

The rate of hydrolysis of the aromatic rings of Cp(2)TiX(2) [X = CI 1, O(2)CCCl(3)8 and O(2)CCH(2)NH(3)Cl 13], in aqueous solutions, 10%DMSO and 100% DMSO have been studied by (1)H NMR spectroscopy. Rapid hydrolysis of both the carboxylate and cyclopentadienyl ligands in Cp(2)TiX(2)[X = O(2)CCCl(3),O(2)CCH(2)NH(3)Cl] occurs in DMSO to give biologically inactive species. The rate of these reactions are concentration dependent as dilution of these samples with saline or water to give the therapeutic conditions of 10%DMSO/90%H(2)O slows the hydrolysis chemistry. In contrast, samples of Cp(2)TiX(2) [X = CI 1, O(2)CCH(2)NH(3)Cl13 ], dissolved in water give solutions containing the presumed antitumour active species in which the halide or glycine ligands have been hydrolysed but the Cp rings remain metal bound.     

15℃时NaCl-CO(NH2)2-H2O2-H2O四元体系相平衡

为了改进过氧化尿素合成的生产工艺,采用等温法测定了15℃时NaCl-CO(NH2)2-H2O2-H2O四元体系及其三元子体系CO(NH2)2-H2O2-H2O和NaCl-CO(NH2)2-H2O的相平衡数据,依据所绘相图分析,结合热重和XRD表征,得出实验条件下NaCl和尿素能形成新的加合物CO(NH2)2×NaCl,其热稳定性比纯尿素高. 根据相图计算,15℃时CO(NH2)2-H2O2-H2O体系合成过氧化尿素的适宜条件范围较宽,在母液不利用的情况下H2O2的收率为58.08%;而在NaCl-CO(NH2)2-H2O2-H2O体系中,NaCl对过氧化尿素形成没有盐析效应.     

硫酸氢氯吡格雷合成工艺研究

以消旋的邻氯苯甘氨酸为原料,经酯化、光学拆分得到（＋）-邻氯苯甘氨酸甲酯,与对甲苯磺酸-2-噻吩乙酯缩合制得氯吡格雷关键中间体（S）-2-（2-噻吩乙胺基）-（2-氯苯基）乙酸甲酯,然后在无水甲酸和多聚甲醛中环合反应得到硫酸氢氯吡格雷。该合成方法具有原料价廉易得、反应条件温和、收率较高,产品质量好的特点,适合于工业化。     

Preparation of TiO(2) Nanocrystallite Powders Coated with 9 mol% ZnO for Cosmetic Applications in Sunscreens

The preparation of TiO(2) nanocrystallite powders coated with and without 9 mol% ZnO has been studied for cosmetic applications in sunscreens by a co-precipitation process using TiCl(4) and Zn(NO(3))(2)·6H(2)O as starting materials. XRD results show that the phases of anatase TiO(2) and rutile TiO(2) coexist for precursor powders without added ZnO (T-0Z) and calcined at 523 to 973 K for 2 h. When the T-0Z precursor powders are calcined at 1273 K for 2 h, only the rutile TiO(2) appears. In addition, when the TiO(2) precursor powders contain 9 mol% ZnO (T-9Z) are calcined at 873 to 973 K for 2 h, the crystallized samples are composed of the major phase of rutile TiO(2) and the minor phases of anatase TiO(2) and Zn(2)Ti(3)O(8). The analyses of UV/VIS/NIR spectra reveal that the absorption of the T-9Z precursor powders after being calcined has a red-shift effect in the UV range with increasing calcination temperature. Therefore, the TiO(2) nanocrystallite powders coated with 9 mol% ZnO can be used as the attenuate agent in the UV-A region for cosmetic applications in sunscreens.     

THPED化学镀铜溶液中Cu(Ⅱ)的存在形式与阴极还原

采用循环迭代法研究了以四羟丙基乙二胺(THPED)为配位剂的化学镀铜溶液中Cu(Ⅱ)的主要存在形式。通过循环伏安法,研究了Cu(Ⅱ)的阴极还原反应。研究表明:THPED(以T表示)与Cu(Ⅱ)形成的配合物主要是CuT(OH)2和CuT2(OH)2,其浓度分别占总Cu(Ⅱ)浓度的56%和42%。CuT(OH)2和CuT2(OH)2分别在电位-0.7V和-1.2V左右(均相对于饱和甘汞电极)发生如下不可逆的电化学还原:CuT(OH)2+2e-→Cu+T+2OH-和CuT2(OH)2+2e-→Cu+2T+2OH-。