滇韭挥发性成分分析

用同时蒸馏萃取装置提取挥发油并用气相色谱-质谱联用仪对滇韭挥发性成分进行了分离和鉴定,分离并鉴定出95个组分,占峰面积的71 50%,用面积归一化法测定了各种成分的质量分数,其主要挥发性成分为:w(三甲基磷化硫醚) =0 15%,w(丁基丙烯基硫醚) =0 03%,w(1, 2 二乙硫基乙烯) =0 38%,w(烯丙基甲基硫醚) =0 79%,w(二烯丙基硫醚) =0 11%,w(2 甲氧基茴香硫醚) =0 15%,w(甲基乙基二硫醚) =0 02%,w(二甲基二硫醚) =0 08%,w(二烯丙基二硫醚) =0 10%,w(二丙基二硫醚) =1 03%,w〔(甲硫基)二甲基二硫醚〕=0 17%,w(甲基1 丙烯基二硫醚) =0 32%,w(二2 羟基乙基二硫醚) =0 11%,w(二甲基三硫醚) =0 02%,w(甲基2 丙烯基三硫醚) =0 06%,w(二2 丙烯基三硫醚) =0 45%,w(二丙基三硫醚) =1 54%,w(二甲基四硫醚) =0 39%,w(4H 噻唑) =0 02%,w(4, 5 二甲基噻唑) =0 50%,w(4, 5 二甲基异噻唑) =0 06%,w(5 甲氧基噻唑) =0 24%,w(3, 4 二甲基异噻唑) =0 22%,w(3, 4 二甲基噻吩) =0 27%,w(4H 2 乙基噻吩) =0 02%,w(1, 3 二噻烷) =0 03%,w(1, 3, 5 三噻烷) =0 03%,w(1, 2 二硫戊环) =0 09%,w〔2, 4 二硫杂戊烷〕=0 98%,w(3, 5 二乙基1, 2, 4 三硫戊环) =0 55%,w(二甲基亚砜) =0 05%,w(3 甲硫基丁醛) =0 02%,w(2 甲基硫代乙酸) =0 37%,w     

Reactions of organic disulfides and gold(i) complexes

Gold-thiolate/disulfide exchange reactions of (p-SC(6)H(4)Cl)(2) with Ph(3)PAu(SC(6)H(4)CH(3)), dppm(AuSC(6)H(4)CH(3))(2), and dppe(AuSC(6)H(4)CH(3)) (2) were investigated. The rate of reactivity of the gold-thiolate complexes with (p-SC(6)H(4)Cl)(2) is: dppm(AuSC(6)H(4)CH(3))(2)> dppe(AuSC(6)H(4)CH(3))(2)>Ph(2)PAu (SC(6)H(4)CH(3)). This order correlates with conductivity measurements and two ionic mechanisms have been evaluated. (1)H NMR experiments demonstrate that in the reaction of dppm(AuSC(6)H(4)CH(3))(2) with (p-SC(6)H(4)Cl)(2), the mixed disulfide, ClC(6)H(4)SSC(6)H(4)CH(3), forms first, followed by the formation of (p-SC(6)H(4)CH(3))(2). The rate law is first order in (pp-SC(6)H (4)Cl)(2) and partial order in dppm(AuSC(6)H(4)CH(3))(2). Results from electrochemical and chemical reactivity studies suggest that free thiolate is not involved in the gold-thiolate/disulfide exchange reaction. A more likely source of ions is the dissociation of a proton from the methylene backbone of the dppm ligand which has been shown to exchange with D(2)O. The implications of this are discussed in terms of a possible mechanism for the gold-thiolate/disulfide exchange reaction.     

Toxicity of Certain Penta-Coordinated Organotin(IV) and Tetra-Coordinated Tin(II) Complexes of Heterocyclic beta-Diketones Against the Larvae of Aedes Aegypti (Liston)

Some organotin(IV) and tin(II) complexes of composition R(3)Sn[R'COC:CON(C(6)H(5))N:CCH(3)] (where R=C(4)H(9), R'=CH(3), C(3)H(5), p-ClC(6)H(4); R=C(6)H(5), R'=C(6)H(5) and p-ClC(6)H(4)) and Sn[p-ClC(6)H(4)COC:CON(C(6)H(5))N:CCH(3)](2) were screened for their toxicity against Aedes aegypti larvae. Organotin(IV) complexes were more active than tin(II) complexes.     

Controlled synthesis and optical spectroscopy of lanthanide-doped KLaF₄ nanocrystals

KLaF(4), as a good host matrix for trivalent lanthanide (Ln(3+)) ions to fabricate upconversion (UC) or downconversion (DC) phosphors, has been rarely reported. Herein, monodisperse (～10 nm) cubic-phase Ln(3+)-doped KLaF(4) nanocrystals (NCs) were synthesized via a facile thermal decomposition method. Upon excitation at 980 nm, UC luminescence properties of KLaF(4):Ln(3+)/Yb(3+) (Ln = Tm, Ho, Er) NCs were comprehensively surveyed. Particularly, after coating an inert KLaF(4) shell, the green and red UC luminescence intensity of KLaF(4):Er(3+)/Yb(3+) NCs was enhanced ～35 times, and the corresponding UC lifetimes of (4)S(3/2) and (4)F(9/2) levels of Er(3+) were observed significantly prolonged from 42 and 68 μs in core-only NCs to 87 and 136 μs in core/shell counterparts. Furthermore, intense DC luminescence was also achieved in Ce(3+)/Tb(3+) and Eu(3+) doped KLaF(4) NCs, with absolute quantum yields of 39.8% (Tb(3+)) and 17.3% (Eu(3+)). The luminescence lifetimes of (5)D(0) (Eu(3+)) and (5)D(4) (Tb(3+)) were determined to be 4.2 and 4.7 ms, respectively. Water-soluble Ln(3+)-doped KLaF(4) NCs featuring excellent monodispersion, long luminescence lifetime, and high UC/DC efficiency may have versatile and promising applications as luminescent nano-biolabels.     

Structure Determination and Anti-Inflammatory Activity of some Purine Complexes

Organomercury(II)-purine derivatives of the type, p-MeOC(6)H(4)HgL(1) (I), p-NO(2)C(6)H(4)HgCl(L(2))(II), p-MeC(6)H(4)HgCl(L(3))(III) and p-NO(2)C(6)H(4)HgCl(L(3))(IV) [ HL(1) = theophylline, L(2) = theobromine, L(3) = caffeine] have been synthesised and characterised on the basis of spectral studies (IR, UV, (1)H & (13)C NMR). The complexes have been screened for anti-inflammatory activity.     

Interaction of Pd(II) and Pt(II) Amino Acid Complexes With Dinucleotides

The interaction of the dinucleotides d(ApG) and d(ApA) with [Pd(aa)Cl(2)], where aa = L- or D-histidine or the methyl ester of L-histidine, and with [Pt(Met)Cl(2)], where Met = L-methionine was studied by (1)H and (13)C NMR and CD measurements. In the case of the L-histidine and L-histidineOMe, the reaction with d(ApG) appeared to give the bifunctional adducts Pd(L-Histidine)N1(1)N7(2) and Pd(L-HisOMe)N1(1)N7(2), but the behavior with D-histidine suggested the formation of the monofunctional adduct Pd(D-His)N7(2). The reaction of L-histidine with d(ApA) seemed to form the bimetallic adduct (L-His)PdN7(1)N7(2)Pd(L-His). The Pt(II)-L-methionine complex in both reactions with d(ApG) and d(ApA) seemed to yield mainly adducts Pt(L-Met)N7(1)N7(2) but the existence of adducts Pt(L-Met)N1(1)N7(2) cannot be ruled out.     

Electrospinning-derived Tb2(WO4)3:Eu(3+) nanowires: energy transfer and tunable luminescence properties

One-dimensional Tb(2)(WO(4))(3) and Tb(2)(WO(4))(3):Eu(3+) nanowires have been prepared by a combination method of sol-gel process and electrospinning. X-Ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), photoluminescence (PL), low voltage cathodoluminescence (CL) and time-resolved emission spectra as well as kinetic decays were used to characterize the resulting samples. The as-obtained precursor samples present fiber-like morphology with uniform size, and Tb(2)(WO(4))(3) and Tb(2)(WO(4))(3):Eu(3+) nanowires were formed after annealing. Under ultraviolet excitation and low-voltage electron beams excitation into WO(4)(2-) and the f-f transition of Tb(3+), the Tb(2)(WO(4))(3) samples show the characteristic emission of Tb(3+) corresponding to (5)D(4)-(7)F(6, 5, 4, 3) transitions due to an efficient energy transfer from WO(4)(2-) to Tb(3+), while Tb(2)(WO(4))(3):Eu(3+) samples mainly exhibit the characteristic emission of Eu(3+) corresponding to (5)D(0)-(7)F(0, 1, 2) transitions due to an energy transfer occurs from WO(4)(2-) and Tb(3+) to Eu(3+). The increase of Eu(3+) concentration leads to the increase of the energy transfer efficiency from Tb(3+) to Eu(3+). The PL color of Tb(2)(WO(4))(3):x mol% Eu(3+) phosphors can be tuned from green to red easily by changing the doping concentration (x) of Eu(3+), making the materials have potential applications in fluorescent lamps and color display fields.     

Behaviour of the Antitumor Agent Vanadocene Dichloride in Physiological and Therapeutic Media, Blood Plasma and Human Blood - An EPR Study

By means of EPR spectroscopy the behaviour of the vanadocene dichloride (I), Cp(2)VCl(2) (Cp=eta(5)-C(5)H(5)), in various deoxygenated and non-deoxygenated physiological media and therapeutic solution as well as in blood plasma and stabilized human blood was studied. On the basis of measured values of isotropic spectroscopic splitting factor g(iso) and isotropic hyperfine coupling constant A(iso), the vanadocene species, [Cp(2)V(H(2)O)Cl](+) (II; g(iso)= 1.985, |A(iso)| = 7.68 mT), [Cp(2)V(H(2)O)(2)](2+) (III; g(iso)= 1.983, |A(iso)| = 7.92 mT), [Cp(2)V(OH(2) (IV; g(iso)= 1.991, |A(iso)| = 6.285 mT), [Cp(2)VCl(DMSO)](+) (V; g(iso)= 1.985, |A(iso)| = 7.69 mT), the vanadyl species [VO(DMSO)(5)](2+) (VI; g(iso)= 1.964, |A(iso)| = 10.78mT) and [VO(H(2)O)(5)](2+) (VII; g(iso)= 1.955, |A(iso)| = 11.56 mT) have been identified. From the measurements it follows that I does not react in its first coordination sphere with any component of a system used other than water and DMSO, resp. As to water-containing media, its behaviour is fully consistent with that of I in pure aqueous media. It was found the only vanadocene species present after application of the therapeutic solution of I into human blood to be IV not interacting in its first coordination sphere with any blood component.     

金的高选择性浮选分离研究

研究了氯化钠和四丁基溴化铵分离金的行为及与一些金属离子分离的条件。实验结果表明,当溶液中氯化钠和四丁基溴化铵的浓度分别为2.5×10-3mol/L和4.0×10-4mol/L时,Au(Ⅲ)可与Ga(Ⅲ)、Co(Ⅱ)、Pd(Ⅱ)、Zn(Ⅱ)、Rh(Ⅲ)、Al(Ⅲ)、Cd(Ⅱ)、Ce(Ⅳ)、Fe(Ⅲ)、Ru(Ⅲ)、Cu(Ⅱ)、W(Ⅵ)、Ti(Ⅳ)、Pb(Ⅱ)、Sb(Ⅲ)、V(Ⅴ)、Pt(Ⅳ)、Mn(Ⅱ)I、n(Ⅲ)、Sn(Ⅳ)、Ni(Ⅱ)I、r(Ⅳ)和Cr(Ⅲ)离子定量分离,对合成水样中Au(Ⅲ)的分离和测定,结果满意。     

Formation mechanism for hexagonal-structured self-assemblies of nanocrystalline titania templated by cetyltrimethylammonium bromide

Hexagonal-structured self-assemblies of nanocrystalline (anatase) titania templated by cetyltrimethylammonium bromide (C(16)H(33)N(CH(3))(3)Br; CTAB) (Hex-ncTiO(2)/CTAB Nanoskeleton) were formed after mixing of aqueous solutions containing CTAB spherical micelles and titanium oxysulfate acid hydrate (TiOSO(4).xH(2)SO(4).xH(2)O) as a titania precursor in the absence of any other additives. Formation mechanism of the Hex-ncTiO(2)/CTAB Nanoskeleton was examined in terms of the reaction temperature, titania precursor/CTAB mixing ratio, surfactant type, electrostatic interaction, micelle formation and molecular component. We found that crystal growth of crystalline (anatase) titania (polymorphic crystallization) was promoted with higher temperature and lower titania precursor content in aqueous solutions. In addition, we revealed that the crystalline (anatase) titania was formed in polycation, poly(allylamine hydrochloride ([CH(2)CH(CH(2)NH(2))HCl](n); PAH), and formamide (HCONH(2)) solutions. On the other hand, no titania formation was observed in anionic systems such as sodium dodecyl sulfate (CH(3)(CH(2))(11)OSO(3)Na; SDS) and poly(sodium 4-styrenesulfonate ([C(8)H(7)SO(3)Na](n); PSSS). This indicates that hydrolysis reaction of the titania precursor is initiated by not only cations but also nitrogen atoms in molecules and polymers. Hexagonally structure was formed in only cationic surfactant micellar solutions but not in polycation solutions and formamide.     

Enhanced emission of ultra-small-sized LaF(3):RE(3+) (RE = Eu, Tb) nanoparticles through 1,2,4,5-benzenetetracarboxylic acid sensitization

Uniform, ultra-small-sized and well-water-dispersible LaF(3) nanoparticles doped with trivalent rare earth (RE) ions (Eu(3+) or Tb(3+)) have been synthesized by a simple, low temperature synthesis route. The nanoparticles, with sizes of about 3.2 nm (for those doped with Eu(3+)) and 3.0 nm (for those doped with Tb(3+)), are roughly spherical and monodisperse. 1,2,4,5-Benzenetetracarboxylic acid (labeled as BA) as sensitizer has been bonded to the surface of the nanoparticles, which can sensitize the emission of RE(3+) in the LaF(3) nanoparticles. The BA-LaF(3):RE(3+) (RE = Eu or Tb) nanoparticles have a broad absorption band in the UV domain, and show enhanced luminescence of RE(3+) based on an energy transfer from BA ligands to RE(3+) ions (i.e. the so-called "antenna effect"). Due to the dual protection of organic ligands (BA) and inorganic matrices (LaF(3)), BA-LaF(3):RE(3+) (RE = Eu or Tb) nanoparticles have longer excited state lifetimes than LaF(3):RE(3+) (RE = Eu or Tb) nanoparticles as well as lanthanide coordination polymers of BA.     

滇刺枣挥发性成分的研究

用同时蒸馏萃取方法收集滇刺枣的挥发性成分,所得到的滇刺枣挥发性成分的二氯甲烷浓缩液用气相色谱-质谱(GC-MS)法分离并分析鉴定其成分及质量分数,共鉴定出40个化合物,占总峰面积的79 07%,主要挥发性成分有:w〔邻苯二甲酸二(2 乙基)己酯〕=18 00%、w(邻苯二甲酸二丁酯)=12 33%、w〔5 己基二氢 2(3H) 呋喃酮〕=4 60%、w(2 十二烯 4 酮)=2 75%、w(2 十三烷酮)=2 25%、w(十四烷)=2 15%、w(二十烷)=1 44%、w(十四烷酮)=2 14%、w(E 2 癸烯醛)=2 07%、w(2 壬烯 4 酮)=2 00%、w(己酸己酯)=1 93%、w(壬醛)=1 87%、w(丙基丙二酸)=1 73%、w(5 甲基糠醛)=1 70%、w(二十九烷)=1 52%、w(十三酸乙酯)=1 52%、w(己酸乙酯)=1 46%、w(6 甲基 2 十三烷酮)=1 30%、w(十四酸乙酯)=1 09%、w(4 羟基 6 甲基 2H吡喃 2 酮)=1 09%、w(丁基化羟基甲苯)=1 02%等。     

Redox Chemistry and [Au(CN)(2)] in the Formation of Gold Metabolites

The role of hypochlorite ion, which can be generated by the enzyme myleoperoxidase, in the biochemistry of gold(I) anti-arthritic drugs was investigated. Sodium hypochlorite (OCl(-)) directly and rapidly oxidizes AuSTm, Au(CN)(2) (-), AuSTg (gold thioglucose) and auranofin (Et(3)PAuSATg). The resulting gold(III) species were detected by an Ion Chromotography Ion-Pairing technique that was developed to distinguish gold(I) and gold(III). Formation of Au(III) was also demonstrated spectrophotometrically after the conversion to AuCl(4) (-). The reactions of AuSTm, AuSTg, and auranofin are complex and gold(III) appears only after the initial oxidation of the thiolate (and phosphine) ligands.The enzymatic reaction, using MPO with H(2)O(2) and Cl(-) as substrates, leads to slow oxidation of Au(CN)(2) (-), AuSTm or AuSTg. The extent and rate of reaction depend on the concentrations of MPO, H(2)O(2), and Au(I). The continued presence of Au(I) during the initial stages of reaction (oxidation of the thiolates in AuSTm and AuSTg) and the conversion to Au(III) in the latter stages of the reaction were demonstrated. Au(CN)(2) (-), a gold metabolite, binds tightly to serum albumin. Unlike other gold(I) complexes, aurocyanide reacts almost negligibly at Cys-34 via ligand exchange. Instead, there is a strong association (K(1) = 5.5 x 10(4) and K(2) = 7.0 x 10(3); n(1) = 0.8 and n(2) = 3) of intact Au(CN)(2) (-). The full extent of binding is revealed only by equilibrium methods such as NMR or ultrafiltration; the bound gold dissociates extensively on conventional gel-exclusion columns and partially on Penefesky spun columns.The immunological and pharmacological significance of these results are discussed.     

Synthesis and "in Vitro" Trypanocidal Activity Evaluation of Some Organo-iron Compounds

Eight organo-iron ferrocene derivatives and arenocenium salts were prepared and evaluated by "in vitro" assay against one strain of Trypanosoma cruzi (Y). Six of the eight organo-iron compounds assayed, piperazinium diferrocenoate 1, eta(6)-(o-xylene)-eta(5)-(cyclopentadienyl) Iron(II) hexafluorophosphate 3, eta(6)-(mesitylene)-eta(5)-(cyclopentadienyl) iron(II) hexafluorphosphate 5, eta(6)-(durene)-eta(5)-(cyclopentadienyl) iron(II) hexafluorphosphate 6, eta(6)-(rho-chlorotoluene)-eta(5)-(cyclopentadienyl) Iron(II) hexafluorphosphate 7 and eta(6)-(chlorobenzene)-eta(5)-(cyclopentadienyl) iron(II) picrate 8 , were poorly active in the "in vitro" assays. Only two compounds 1,1'-(N-pyperidinocarbonyl) ferrocene 2(IC(50)=2.4 mug/mL) and eta(6)-(o-xylene)-eta(5)(cyclopentadienyl) iron(II) picrate 4 (IC(50)=12.08 mug/mL), were more active. Thus, some of the compounds are promising to be used against Chagas' disease as a prophylactic agents.     

Preparation and Anti-Tumour Activity of Some Arylbismuth(III) Oxine Complexes.

New arylbismuth(lll) oxinates, PhBi(MeOx)(2), (p-MeC(6)H(4))Bi(Ox)(2), (p-MeC(6)H(4))Bi(MeOx)(2), (p-ClC(6)H(4))Bi(Ox)(2), and (p-ClC(6)H(4))Bi(MeOx)(2) (Ox(-) = quinolin-8-olate and MeOx(-)=2-methylquinolin-8-olate) have been prepared by reaction of the appropriate diarylbismuth chlorides with Na(Ox) or Na(MeOx) in the presence of 15-crown-5. An X-ray crystallographic study has shown PhBi(MeOx)(2) to be a five coordinate monomer with distorted square pyramidal stereochemistry. Chelating MeOx ligands have a cisoid arrangement in the square plane and the phenyl group is apical. The lattice is stabilised by significant pi-pi interactions between centrosymmetric molecules. A range of these complexes has been shown to have high in vitro biological activity (comparable with or better than cisplatin) against L1210 leukaemia, the corresponding cisplatin resistant line, and a human ovarian cell line, SKOV-3. However, initial in vivo testing against a solid mouse plasmacytoma (PC6) and P388 leukaemia has not revealed significant activity.     

Surface and Internal Lipids of Calotropis gigantea L. Leaves

The surface and internal lipids of Calotropis gigantea L. (Ascelepiadaceae) leaves analysed. The surface lipids (0.8%, dry wt.) consisted of hydrocarbons (22.2%), ester waxes (20.7%), aldehydes (7.9%), triacylglycerols (4.6%), fatty acids (20.0%), sterols (13.2%), diacylglycerols (3.3%), monoacylglycerols (2.9%) and unidentified components (5.2%). The internal lipids (8.3%, dry wt.) contained 52.8, 21.7 and 25.5% non-polar, glyco- and phospholipids, respectively. The internal non-polar lipids were made up of pigments (13.5%), hydrocarbons (6.4%), ester waxes (6.2%), fatty acids (6.7%), sterols (5.7%), diacylglycerols (2.5%) and monoacylglycerols (2.3%). The glycolipids comprised esterified sterylglycosides (2.4%), monogalactosyldiglycerides (8.4%), sterylglycosides (1.7%), cerebrosides (2.3%). digalactosyldiglycerides (4.2%) and sulfoquinovosyldiglycerides (2.7%). The phospholipids were composed of cardiolipin (2.8%), phosphatidylglycerol (5.6%), phosphatidylethanolamine (4.0%), phosphatidylinositol (3.6%), phosphatidylcholine (8.3%) and phosphatidylserine (1.2%). All the internal lipid classes had high contents of linolenic, palmitic and linoleic acid whereas the surface lipids contained palmitic and stearic acids as major components.     

Different coordination modes of a tripod phosphine in gold(i) and silver(i) complexes

The following gold(I) and silver(I) complexes of the tritertiary phosphine 1,1,1- tris(diphenylphosphinomethyl)ethane, tripod , have been synthesised: Au(3)(tripod)X(3) [X = Cl(1), Br(2), I(3)]; [Au(3)(tripod)(2)Cl(2)]Cl (4); Au(tripod)X [X = Br(5), I(6)]; Ag(3)(tripod) (NO(3))(4) (7), Ag(tripod)NO(3) (8). They were characterized by X-ray diffraction (complexes 2, 3 and 4), (31)P NMR spectroscopy, electrospray and FAB mass spectrometry and infrared spectroscopy. Complexes 2 and 3 show a linear coordination geometry for Au(I), with relatively short Au-P bond distances. Complex 3 has a Au***Au intramolecular distance of 3.326 A degrees , while complex 2 had a short Au***Au intermolecular interaction of 3.048 A degrees . Complexes 4-6 were found by (31)P NMR spectroscopy studies to contain a mixture of species in solution, one of which crystallised as [Au(3)(tripod|)(2)Cl(2)]Cl which was shown by X-ray diffraction to contain both tetrahedral and linear Au(I), the first example of a Au(I) complex containing such a mixture of geometries. The reaction of [Au(3) (tripod)Cl(3)] (1) with tripod led successfully to the formation of [Au(3)(tripod|)(2)Cl(2)](+) and [Au(3)(tripod)(2)Cl(3)](+) and [Au(3)(tripod|)(3)Cl](2+). The silver(I) complexes, 7 and 8 appear to contain linear and tetrahedral Ag(I), respectively.     

Metallation of Isatin (2,3-Indolinedione). X-Ray Structure and Solution Behavior of Bis(Isatinato)Mercury(II)

The first X-ray structure of an isatin (2,3-indolinedione, isaH) metal complex, bis(isatinato)memury(II) (C(16)H(8)N(2)O(4)Hg) (1), was determined. (1) was obtained from the reaction of isaH with mercury(II) acetate in methanol. Analogously, treatment of sodium saccharinate and mercury(II) acetate in methanol yielded Hg(saccharinato)(2) (*)0.5CH(3)OH (3). (1) crystallizes in the monoclinic system, space group P2(1)/ a with a = 7.299(1) A, b = 8.192(1) A, c = 11.601(1) A , beta = 105.82(1) degrees , V = 667.4 A(3), Z = 2, D(calc) = 2.452 g cm(-3), MoKalpha radiation(lambda = 0.71073 A), mu = 115.5 cm(-1), F(000) = 460, 21(1) degrees C. The structure was refined on the basis of 2023 observed reflections to R= 0.044. The two deprotonated, non coplanar isa ligands are trans to each other in a head to tail orientation and bound to the Hg through the nitrogen in a linear N-Hg-N arrangement. The Hg atom is at the center of symmetry of the complex and displaced by 0.62 A from the two planes of the isa ligands (tau Hg-N1-C2-O2= -16 degrees ). The Hg-N bond length is 2.015 A. Nopi-aryl-memury(ll)-pi-aryl stacking interaction was observed either in the solid state or in the solution state. The IR, electronic, and (1)H and (13)CNMR spectral data of (1) and (3) suggest binding of the memury to the heterocyclic nitrogen, in agreement with the crystal structure determination of (1).     

Insights into the mode of action of the anti-Candida activity of 1,10-phenanthroline and its metal chelates

Metal complexes of malonie acid (metal = Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Ag(I)) were prepared and only the Ag(I) complex inhibited the growth of Candida albicans. Malonate complexes incorporating the chelating 1,10-phenanthroline (1,10-phen) ligand showed a range of activities: good (Mn(II), Cu(II), Ag(I)); moderate (Zn(II)); poor (Co(II), Ni(II)). Metal-free 1,10-phen and Ag(CH(3)CO(2)) were also highly active. The metal-free non-chelating ligands 1,7- phenanthroline and 4,7-phenanthroline were inactive and the Cu(II), Mn(II) and Zn(II) complexs of 1,7-phen displayed only marginal activity. Whereas the Cu(II) malonate/1,10-phen complex induces significant cellular oxidative stress the Zn(II) analogue does not.