火焰原子吸收光谱法测定奶类食品中铜锌铁锰

对火焰原子吸收光谱法(FAAS)测定乳品中铜、锌、铁、锰的条件进行了试验和优化。对方法的干扰因素,准确度和精密度也作了试验。乳品试样用HNO3-HClO4混合酸消化处理。所得溶液蒸发至近干,用稀硝酸(1 99)溶解盐类,溶液经定容后供作FAAS测定。对4元素的测定时,吸光度与浓度之间呈良好线性关系,所求得的线性回归方程及其相关系数可作佐证。应用所提出的方法测定了3种不同的乳制品中的铜、锌、铁及锰,测定值的RSD值均小于3.5%,回收率在93.0%~103.0%之间。     

示波极谱法直接快速测定痕量锑的研究

在0.06 mol.L-1硫酸溶液中,Sb(Ⅲ)与焦性没食子酸络合物产生一个灵敏的导数极谱波,峰电位为-0.4 V(vs.SCE),有微量Se(Ⅳ)存在下,灵敏度大为提高,锑浓度在0.03~1.2 mg.L-1范围内峰高与浓度呈线性关系,应用于锌电解液中痕量锑的测定。检出限为0.004 mg.L-1,RSD为1.8%~2.2%,回收率为95.0%~105.0%。     

荧光光谱法研究锌(Ⅱ)存在下诺氟沙星与牛血清白蛋白的结合作用

在模拟生理条件下,用荧光光谱法研究了诺氟沙星对牛血清白蛋白以及锌(Ⅱ)对诺氟沙星和牛血清白蛋白荧光光谱特性的影响。实验结果表明,诺氟沙星和锌(Ⅱ)都可以使牛血清白蛋白的荧光强度发生猝灭。根据荧光猝灭双倒数图计算诺氟沙星和牛血清白蛋白之间的结合常数为6.80×105,结合位点数为1.21。由此可见,诺氟沙星和牛血清白蛋白之间有很强的结合作用,这为诺氟沙星在体内被蛋白质储存和转运提供了条件。并且在锌(Ⅱ)存在下,诺氟沙星与牛血清白蛋白的结合作用有所增强。荧光猝灭双倒数图计算的结果表明,诺氟沙星和牛血清白蛋白之间的结合常数和结合位点数均随锌(Ⅱ)浓度的增大而增大。通过对锌(Ⅱ)、诺氟沙星和牛血清白蛋白的结合反应的研究,进一步探讨了诺氟沙星、锌(Ⅱ)在生物体内与蛋白质相互作用的机理。     

Metal-chelating properties of carvedilol: an antihypertensive drug with antioxidant activity

Carvedilol (CarvH) (1-[carbazolyl-(4)-oxyl]-3-[2-methoxyphenoxyethyl)-amino]-2-propanol, an antihypertensive agent with β-blocker function, has been shown to act as an antioxidant. The antioxidative properties can be correlated with metal chelating ability of the drug. Iron(III), zinc(II), and copper(II) complexes of carvedilol were synthesized and characterized with respect to their structural and spectroscopic properties. Metal interaction involves O and N donors from the aliphatic moiety of carvedilol. NMR studies allowed us to obtain the structural information on metal coordination and to suggest that the physiological concentration of carvedilol and free metal ions may be enough for a protective effect by metal chelation.     

CRYSTAL STRUCTURE AND THERMAL ANALYSIS OF A 4,4′-BIPY-BRIDGED BINUCLEAR ZINC(II) COMPLEX, 2[R2NCS2]2 · Zn(4,4′-BIPY) (R=PIPERIDYL)

Abstract

The crystal structure of the title complex 2[R₂NCS₂]₂ · Zn(4,4′-bipy) (R = Piperidyl), 1, revealed that it consists of dimers made up from two crystallographically independent molecules. Each zinc atom in 1 forms a 5-coordinate pseudo-square-based pyramidal arrangement (with four Zn-S and one Zn-N interactions). Bondlengths to Zn with the coordinating atoms are comparable to those in other Zn(II) dithiocarbamate complexes. The piperidine ring has a chair conformation. To allow improved packing, the title complex molecules form an approximately linear arrangement extending along both a and b. TGA showed that 1 is decomposed in two close steps to produce ZnS as identified by residual weight. The complex 1 crystallizes in the monoclinic space group C2/c with cell parameters: a = 22.021(5), b = 22.215(3), c = 17.537(2) Å, β = 93.49(2)°, V = 8563(3) ų and Z = 8. The structure was refined by full-matrix least-squares methods to R = 0.067, R_w = 0.114.     

Syntheses and structures of M–Na (M=Zn,Mn) coordination polymers in which ligands and Na ions exhibit complex coordination modes

The novel heteronuclear complexes [Na₂Zn(dipic)₂(H₂O)] _n (1) and [Na₂Mn(dipic)₂(H₂O)₂] _n (2) (H₂dipic?=?pyridine-2,6-dicarboxylic acid) were synthesized and characterized by single-crystal X-ray diffraction, analysis, IR spectroscopy and thermogravimetric analysis. Complex 1 consists of infinite 2D double layers, which are further attached into a 3D network through π–π stacking. All sodium ions are 3-coordinate. Complex 2 has an intricate 3D structure, in which two sodium ions are differently involved in forming polymeric coordination units, and are 3- and 7-coordinate, respectively. Dipic anions act as multidentate ligands showing novel and unprecedented bridging coordination modes. One ligand coordinates to three metal ions and with five bonds; the other coordinates five metal ions with nine bonds.     

Synthesis,structure and luminescent properties of zinc(II) and Hg(II) complexes with substituted 1,10-phenanthroline

Two d¹⁰ group 12 metal complexes, 2-(2-methoxyphenyl)-1,10-phenanthroline zinc dichloride (2a) and 2-(2-methoxyphenyl)-1,10-phenanthroline mercury dichloride (2b) were synthesized and characterized by IR, ¹H and ¹³C NMR as well as elemental analysis. Structure of 2b in the solid state was determined by single-crystal X-ray crystallography, revealing that 2b is four-coordinate in a distorted tetrahedral geometry with the methoxy group uncoordinated. Luminescent properties of 2a and 2b in solution and the solid state were studied.     

Syntheses and molecular structures of four inorganic–organic hybrid compounds from N-containing aromatic bases and perchlorometallates of Zn,Cu, Sn,and Fe

Four organic–inorganic crystals, [(HL1)₂(ZnCl₄)]·H₂O (1) (L1?=?2-methylquinoline), [(HL1)₂(CuCl₄)] (2), [(HL2)₂SnCl₆] (3) (L2?=?6-bromobenzo[d]thiazol-2-amine), and [(HL3)FeCl₄] (4) (L3?=?5,7-dimethyl-1,8-naphthyridine-2-amine), derived from N-containing aromatic Brønsted bases and metal(II) chlorides (zinc(II) chloride, copper(II) chloride dihydrate, tin(II) chloride dihydrate, and iron(III) chloride hexahydrate) were prepared at room temperature and characterized by IR, X-ray structure analysis, elemental analysis, and TG analysis. The crystals are built up by perchlorometallates (Zn, Cu, Sn, and Fe) associated with organic cations through multiple non-covalent associations. X-ray diffraction analysis reveals that 1 and 2 have 3-D network structures built from hydrogen bonds between the cations and chlorometallates. Water molecules play an important role in structure extension in 1. Anhydrous 3 and 4 produced from 2-aminoheterocyclic derivatives display 2-D sheet structures. Arrangements of anions and cations are dominated by shape and size of cations, and also by the different structures of the chlorometallates as well as non-bonding interactions in the crystal structures. Except for 1, the other compounds are thermally stable below 240°C.     

The introduction of antibacterial drug pipemidic acid into the POM field: Syntheses, characterization and antitumor activity

Two new compounds based on polyoxometalates (POMs) and the quinolone antibacterial drug pipemidic acid (HPPA), {[Ni(PPA)₂]H₄[SiW₁₂O₄₀]}·HPPA·3H₂O (1), and {[Zn(PPA)₂]₂H₄[SiW₁₂O₄₀]}·3H₂O (2), have been synthesized under hydrothermal conditions and structurally characterized by routine technique. Single-crystal X-Ray diffraction analysis shows that compound 1 is constructed by Keggin clusters grafted by binuclear nickel clusters, isolated HPPA and water molecules, while compound 2 consists of Keggin clusters grafted by binuclear zinc clusters and water molecules. Due to the selection of different transition metal (TM) ions, compounds 1 and 2 exhibit different structures and antitumor activities. Compound 1 possesses 0D structure and shows no antitumor activities. However, compound 2 possesses 1D structure and exhibits higher antitumor activities than its parent compound. The results show that introduction of different TM-PPA moieties onto the polyoxoanion surface can affect not only the final structures but also their antitumor activities.     

Early/Late Heteronuclear Complexes Bridged by Bifunctional Phosphorus-Based Ligands

Substituted bifunctional phosphorus-based ligands HX(CRR') n PR"H (or -PR" 2 ) [where X = O, S, NR', (substituted) cyclopentadienyl; n = 1, 2, 3; R, R', R" = alkyl, aryl, H] were employed as bridging ligands in the synthesis of early/late bridged transition metal complexes. Synthetic routes to the bifunctional ligands were also developed. First, mononuclear complexes, such as [TpZr(OCH 2 PPh 2 ) 3 ] (Tp = trispyrazolylborato), [Cp 2 Zr(1-O-2-PHR-C 6 H 10 )(Me)] (R = 2,4,6-Pr i 3 C 6 H 2 (Tipp)), [Cp 2 Zr(SCH 2 CH 2 PHR) 2 ] (R = Ph, Mes, Tipp), and phosphinoferrocene derivatives, were prepared. These complexes are suitable precursors for the introduction of a second metal (as in, for example, [TpZr( w -OCH 2 PPh 2 ) 3 Mo(CO) 3 ]).