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1.
Metallo-beta-lactamase L1, secreted by pathogenic Stenotrophomonas maltophilia, is a dinuclear Zn(II)-containing enzyme that hydrolyzes almost all known penicillins, cephalosporins, and carbapenems. The presence of Zn(II) ions in both metal binding sites is essential for full enzymatic activity; however, the mechanism of physiological metal incorporation is unknown. To probe metal incorporation, L1 was over-expressed in minimal media with (mmL1+Zn) and without (mmL1-Zn) Zn(II) added to the media, and the resulting proteins were purified and characterized. The mmL1+Zn sample was bound by a Q-Sepharose column, exhibited steady-state kinetic properties, bound Zn(II), existed as a tetramer, and yielded fluorescence emission and CD spectra similar to L1 overexpressed in rich media. On the other hand, the mmL1-Zn sample did not bind to a Q-Sepharose column, and gel filtration studies demonstrated that this protein was monomeric. The mmL1-Zn sample exhibited a lower kcat value, bound less Zn(II), and yielded fluorescence emission and CD spectra consistent with this enzyme being folded improperly. Taken together, these data demonstrate that the proper folding of L1 requires the presence of Zn(II) and suggest that in vitro, thermodynamic metal binding studies do not accurately reflect physiological metal incorporation into L1.  相似文献   

2.
Metal complexes of d-glucose (d-Glc) from large cation containing dibromo-dichloro salts of dipositive metals [NEt4]2[MBr2Cl2] (M = Mn, Co, Ni, Cu and Zn) and the disodium salt of glucose were synthesized from a MeOH:MeCN mixture. The complexes were characterized by UV-vis absorption, circular dichroism, IR and proton magnetic resonance spectroscopies, and by elemental analysis, and were found to be Na[M(d-Glc)(OMe)Cl]. Cyclic voltammetric studies of these complexes, in the acidic to neutral pH range, indicated no dissociation, even in highly acidic conditions.This paper is dedicated to Professor Richard H. Holm (Harvard University) on the occasion of his 60th birthday.  相似文献   

3.
Improved ways to cleave peptide chains at engineered sites easily and specifically would form useful tools for biochemical research. Uses of such methods include the activation or inactivation of enzymes or the removal of tags for enhancement of recombinant protein expression or tags used for purification of recombinant proteins. In this work we show by gel electrophoresis and mass spectroscopy that salts of Co(II) and Cu(II) can be used to cleave fusion proteins specifically at sites where sequences of His residues have been introduced by protein engineering. The His residues could be either consecutive or spaced with other amino acids in between. The cleavage reaction required the presence of low concentrations of ascorbate and in the case of Cu(II) also hydrogen peroxide. The amount of metal ions required for cleavage was very low; in the case of Cu(II) only one to two molar equivalents of Cu(II) to protein was required. In the case of Co(II), 10 molar equivalents gave optimal cleavage. The reaction occurred within minutes, at a wide pH range, and efficiently at temperatures ranging from 0 degrees C to 70 degrees C. The work described here can also have implications for understanding protein stability in vitro and in vivo.  相似文献   

4.
Bidentate ligands 2,2′-biquinoline (biq) and 6,6′-dimethyl-2,2′-bipyridine (dmbpy) with steric hindrance substituents cis to the nitrogen atoms have been used in the synthesis of transition metal complexes. Six new doubly end-on azido-bridged binuclear complexes [M2(biq)21,1-N3)2(N3)2] (M = Ni (1), M = Co (2)), [M2(biq)21,1-N3)2Cl2] (M = Ni (3), M = Co (4)), [M2(dmbpy)21,1-N3)2(N3)2] (M = Ni (5), M = Co (6)) and one end-to-end thiocyanato-bridged polymeric [Ni(dmbpy)(μ1,3-SCN)(NCS)]n (7) have been synthesized and characterized by single crystal X-ray diffraction analysis and magnetic studies. Complexes 1-6 comprise five-coordinate M(II) ions bridged by two end-on azide ligands. The bridging M-N-M bond angles are in the small range 104.1-105.2°. Complex 7 consists of a singly thiocyanate-bridged Ni(II) chain in which Ni(II) ions are five-coordinate. This research suggests that the bulky ligands play a key role in the formation of five-coordinate coordination structure. All complexes display intramolecular intermetallic ferromagnetic coupling with JNiNi and JCoCo of ca. 23 or 13 cm−1 based on the Hamiltonian (S1 = S2 = 1 for Ni2, or 3/2 for Co2). The singly SCN-bridged chainlike complex 7 shows intrachain ferromagnetic interaction with J = 3.96(2) cm−1 and D = −4.55(8) cm−1 (. Magneto-structural correlationship has been investigated.  相似文献   

5.
The complexes of Cu(I), Cu(II), Ni(II), Zn(II) and Co(II) with a new polypyridyl ligand, 2,3-bis(2-pyridyl)-5,8-dimethoxyquinoxaline (L), have been synthesized and characterized. The crystal structures of these complexes have been elucidated by X-ray diffraction analyses and three types of coordination modes for L were found to exist in them. In the dinuclear complex [Cu(I)L(CH3CN)]2·(ClO4)2 (1), L acts as a tridentate ligand with two Cu(I) centers bridged by two L ligands to form a box-like dimeric structure, in which each Cu(I) ion is penta-coordinated with three nitrogen atoms and a methoxyl oxygen atom of two L ligands, and an acetonitrile. In [Cu(II)L(NO3)2]·CH3CN 2, the Cu(II) center is coordinated to the two nitrogen atoms of the two pyridine rings of L which acts as a bidentate ligand. The structures of [Ni(II)L(NO3)(H2O)2]·2CH3CN·NO3 (3), [Zn(II)L(NO3)2 (H2O)]·2CH3CN (4) and [Co(II)LCl2(H2O)] (5) are similar to each other in which L acts as a tridentate ligand by using its half side, and the metal centers are coordinated to a methoxyl oxygen atom and two bipyridine nitrogen atoms of L in the same side. The formation of infinite quasi-one-dimensional chains (1, 4 and 5) or a quasi-two-dimensional sheet (2) assisted by the intra- or intermolecular face-to-face aryl stacking interactions and hydrogen bonds may have stabilized the crystals of these complexes. Luminescence studies showed that 1 exhibits broad, structureless emissions at 420 nm in the solid state and at 450 nm in frozen alcohol frozen glasses at 77 K. Cyclic voltammetric studies of 1 show the presence of an irreversible metal-centered reduction wave at approximately −0.973 V versus Fc+/0 and a quasi-reversible ligand-centered reduction couple at approximately −1.996 V versus Fc+/0. The solution behaviors of these complexes have been further studied by UV-Vis and ESR techniques.  相似文献   

6.
The two complexes containing bioactive ligands of the type and [Fe(L)] (PF6)2 (1) (where L = [1-{[2-{[2-hydroxynaphthalen-1-yl)methylidine]amino}phenyl)imino] methyl}naphthalene-2-ol]) and [Co(L1L2)] (PF6)3 (2) (where L1L2 = mixed ligand of 2-seleno-4-methylquinoline and 1,10-phenanthroline in the ratio 1:2, respectively) were synthesized and structurally characterized. The DNA binding property of the complexes with calf thymus DNA has been investigated using absorption spectra, viscosity measurements, and thermal denaturation experiments. Intrinsic binding constant Kb has been estimated at room temperature. The absorption spectral studies indicate that the complexes intercalate between the base pairs of the CT-DNA tightly with intrinsic DNA binding constant of 2.8 × 105 M?1 for (1) and 4.8 × 105 M?1 for (2) in 5 mM Tris-HCl/50 mM NaCl buffer at pH 7.2, respectively. The oxidative cleavage activity of (1) and (2) were studied by using gel electrophoresis and the results show that complexes have potent nuclease activity.  相似文献   

7.
Stereoselective coordination affording a luminescent tcc-isomer of dihalobis(diimine)Co(II) family in which two photoactive diimine ligands (LNO2?) are unsymmetrical and non-equivalent is reported (LNO2? = (E)-3-nitro-N-(pyridine-2-ylmethylene)aniline; ? = dihedral angle between the diimine unit including pyridine ring and the phenyl ring planes; tcc refers trans-cis-cis positions with respect to pyridine nitrogen-imine nitrogen-chloride donors). The single step reaction of 2-pyridinecarboxaldehyde, 3-nitro aniline and anhydrous cobalt dichloride affords only the tcc-(LNO2?1)(LNO2?2)CoIICl2 as the product which is characterized by IR, Mass, UV-Vis spectra and magnetic susceptibility measurements. Single crystal X-ray structure determination has established the orientation of the two ligands in the crystal as (LNO233.7)(LNO279.7)CoIICl2·0.25CH3OH (1). The isomer is luminescent in frozen methanol glass at 77 K with the excitation and emission maxima respectively at 370 and 525 nm. The average luminescence life time is 1.86 ns measured on exciting at 356 nm. Density functional theory (DFT) calculation shows that the non-equivalence of the two diimine ligands prevails in the gas phase also and the geometry is (LNO241.0)(LNO260.5)CoIICl2. The calculation has identified four types of closely spaced localized π orbitals as unoccupied photoactive molecular orbitals (UPMOs). TD-DFT calculations have assigned the Co(II) to π charge transfer (MLCT) and π to π of charge transfer (LLCT) as the primary origin of absorption above 340 nm in methanol. Pendant nitro groups of the ligands and their intermolecular interactions have been the driving force of the stereoselectivity of the product. The binuclear L4Co2Cl4 unit of 1 has constructed the helical 2D assembly and cis-CoCl2 mediated strong inter-helices H-bonding interactions result the channeled 3D framework. Geometry optimization of other possible ttt, ctc, ccc and cct isomers has established that in the gas phase, the tcc-isomer is more stable at least by 20-42 kJ mol−1 compared to other isomers where the two diimine ligands are equivalent.  相似文献   

8.
In this work we present the synthesis, structural and spectroscopic characterisation of a series of cobalt(II) and zinc(II) coordination compounds with benzimidazole (bz) and its 2-benzimidazole derivatives: 2-aminobenzimidazole (2ab), albendazole (abz) and tris(2-benzimidazolylmethyl)amine (ntb). The compounds were evaluated for their in vitro antimicrobial activity against Staphylococcus aureus, Micrococcus luteus, Salmonella typhi, Pseudomonas aeruginosa, Escherichia coli and Proteus vulgaris. Their cytotoxic activity was also evaluated using human cancer lines, HeLa, HCT-15 and SKLU-1. The halide tetrahedral compounds [Co(bz)2Br2] 3, [Zn(2ab)2Cl2] · 0.5H2O 11, [Co(abz)Cl2(H2O)] · 3H2O 14, [Co(abz)Br2(H2O)] 15, [Zn(abz)Cl2(H2O)] · 3H2O 17 and [Zn(abz)Br2(H2O)] · H2O 18 displayed similar minimal inhibition concentration (MIC) values against Micrococcus luteus and Escherichia coli, comparable to those of amoxicillin and chloramphenicol. Additionally, 11 showed a wide range of activity towards Gram(+) and Gram(−) microorganisms. The tetradentate ntb and its trigonal bipyramidal cobalt(II) and zinc(II) compounds were active, regardless of the anion present in the complex. Compound [Co(abz)Cl2(H2O)] · 3H2O 14 showed promising activity in HeLa cells, while [Co(ntb)Br]Br · H2O 21 inhibited Hela and HCT-15 cell lines.  相似文献   

9.
周宁一 《微生物学通报》2016,43(6):1404-1404
正随着采矿业的迅速发展,越来越多的重金属通过多种途径进入土壤环境中,对生态环境造成了不可估量的破坏并严重威胁人类健康。铅锌在工业上具有非常重要的作用且其应用极为广泛,而他们具有的难去除、难迁移和生物累积等特性使得铅锌在环境中的污染尤为突出。通过微生物的生长代谢,有效降低土壤重金属毒性,是促进植物生长的重要步骤之一。同时也要求微生物自身具有抵抗重金属的功能,根际微生  相似文献   

10.
Four new coordination complexes, NiII(L)2 (1), [CoIII(L)2]ClO4 (2), [Zn(HL)(L)]ClO4 · H2O (3) and [Zn(L)2][Zn(L)(HL)]ClO4 · 7H2O (4) (where L is a monoanion of a Schiff base ligand, N′-[(2-pyridyl)methylene]salicyloylhydrazone (HL) with NNO tridentate donor set), have been synthesised and systematically characterised by elemental analysis, spectroscopic studies and room temperature magnetic susceptibility measurements. Single crystal X-ray diffraction analysis reveals that 1 is a neutral complex, while 2-4 are cationic complexes. Among them, 4 is a rare type of cationic complex with two molecules in the asymmetric unit. The ligand chelates the metal centre with two nitrogen atoms from the pyridine and imino moieties and one oxygen atom coming from its enolic counterpart. All the reported complexes show distorted octahedral geometry around the metal centres, with the two metal-N (imino) bonds being significantly shorter than the two metal-N (Py) bonds.  相似文献   

11.
We have prepared and structurally characterized six-coordinate Fe(II), Co(II), and Ni(II) complexes of types [MII(HL1)2(H2O)2][ClO4]2 (M = Fe, 1; Co, 3; and Ni, 5) and [MII(HL2)3][ClO4]2 · MeCN (M = Fe, 2 and Co, 4) of bidentate pyridine amide ligands, N-(phenyl)-2-pyridinecarboxamide (HL1) and N-(4-methylphenyl)-2-pyridinecarboxamide (HL2). The metal centers in bis(ligand)-diaqua complexes 1, 3 and 5 are coordinated by two pyridyl N and two amide O atoms from two HL1 ligands and six-coordination is completed by coordination of two water molecules. The complexes are isomorphous and possess trans-octahedral geometry. The metal centers in isomorphous tris(ligand) complexes 2 and 4 are coordinated by three pyridyl N and three amide O atoms from three HL2 ligands. The relative dispositions of the pyridine N and amide O atoms reveal that the pseudo-octahedral geometry have the meridional stereochemistry. To the best of our knowledge, this work provides the first examples of structurally characterized six-coordinate iron(II) complexes in which the coordination is solely by neutral pyridine amide ligands providing pyridine N and amide O donor atoms, with or without water coordination. Careful analyses of structural parameters of 1-5 along with that reported in the literature [MII(HL1)2(H2O)2][ClO4]2 (M = Cu and Zn) and [CoIII(L2)3] have allowed us to arrive at a number of structural correlations/generalizations. The complexes are uniformly high-spin. Spectroscopic (IR and UV/Vis) and redox properties of the complexes have also been investigated.  相似文献   

12.
Synthesis, structure and spectroscopic characterization of 2-thiophenealdehyde-N(4)-napthylthiosemicarbazone and its complexes with biologically important Zn(II) and toxic Hg(II) metal ions have been reported. The crystal structure of the complexes reveals that both are distorted tetrahedral. In the Hg(II) complex the ligand is neutral and mondented where as in Zn(II) complex the ligand is bidented and anionic. Whereas conductivity measurement study shows both the complexes are molecular species. The beautiful changes in absorption spectra along with isosbestic points upon addition of respective metal salts to the ligand solution convincingly support the formation of metal complexes in solution phase. The other spectroscopic studies also show good correlation with their solid state structures.  相似文献   

13.
In our efforts to investigate the relationships between the structures of ligands and their complexes, two structurally related ligands, 1-(2-pyridylmethyl)-1H-benzimidazole (L1) and 1-(4-pyridylmethyl)-1H-benzimidazole (L2), and their four complexes, [Zn(L1)2Cl2] (1), [Hg(L1)Br2] (2), {[Zn(L2)Cl2](CH3CN)} (3) and [Hg(L2)Br2]2(CH3CN)2 (4) were synthesized and structurally characterized by elemental analyses, IR spectra and single-crystal X-ray diffraction analysis. Structural analyses show that 1 has a mononuclear structure, and 2 and 3 both take 1D structure. While 4 takes a dinuclear structure. 1, 2 and 4 were further linked into higher-dimensional supramolecular networks by weak interactions, such as C-H?Cl and C-H?Br H-bonding, C-H?π, and π?π stacking interactions. The structural differences of 1-4 may be attributed to the difference of the spatial positions of the terminal N donor atoms in the pendant pyridyl groups in L1 and L2, in which the pyridine rings may act as the directing group for coordination and the benzimidazole rings act as the directing group for π?π stacking and C-H?π interactions. The luminescent properties of the corresponding complexes and ligands have been further investigated.  相似文献   

14.
Previous studies revealed that Mn(II) is accumulated in cultured glial cells to concentrations far above those present in whole brain or in culture medium. The data indicated that Mn(II) moves across the plasma membrane into the cytoplasm by facilitated diffusion or counter-ion transport with Ca(II), then into mitochondria by active transport. The fact that 1–10 M Mn(II) ions activate brain glutamine synthetase makes important the regulation of Mn(II) transport in the CNS. Since Cu(II) and Zn(II) caused significant changes in the accumulation of Mn(II) by glia, the mechanisms by which these ions alter the uptake and efflux of Mn(II) ions has been investigated systematically under chemically defined conditions. The kinetics of [54MN]-Mn(II) uptake and efflux were determined and compared under four different sets of conditions: no adducts, Cu(II) or Zn(II) added externally, and with cells preloaded with Cu(II) or Zn(II) in the presence and absence of external added metal ions. Zn(II) ions inhibit the initial velocity of Mn(II) uptake, increase total Mn(II) accumulated, but do not alter the rate or extent Mn(II) efflux. Cu(II) ions increase both the initial velocity and the net Mn(II) accumulated by glia, with little effect on rate or extent of Mn(II) efflux. These results predict that increases in Cu(II) or Zn(II) levels may also increase the steady-state levels of Mn(II) in the cytoplasmic fraction of glial cells, which may in turn alter the activity of Mn(II)-sensitive enzymes in this cell compartment.  相似文献   

15.
16.
Using a non-planar tridentate ligand 2,6-bis(pyrazol-1-ylmethyl)pyridine (L5) two new coordination complexes [(L5)CoII(H2O)3]Cl2 (1) and [(L5)NiII(H2O)2Cl]Cl·H2O (2) have been synthesized and structurally characterized. Complex 1 has N3O3 distorted octahedral environment around CoII with coordination by L5 (two pyrazole and a pyridine nitrogen in a facial mode) and three water molecules. Complex 2 has N3O2Cl distorted octahedral geometry around NiII with meridional L5 coordination, two water molecules, and a Cl ion. Analysis of the crystal packing diagram reveals the involvement of solvent (water as metal-coordinated and as solvent of crystallization) and counteranion (Cl) to play significant roles in generating 1D chains, involving O-H···Cl, and O-H···O interactions.  相似文献   

17.
Four new Co(II) coordination complexes, [Co(o-phta)(pz)2]n1, [Co(PTA)2(Imh)2]·(HPTA)·H2O 2, {[Co(pdc)2(H2O)]·(ppz)·2H2O}n3, [K2Co2(ox)(btec)(CH3OH)2]n4, (H2phta = o-phthalic acid, pz = pyrazole, HPTA = p-toluic acid, ppz = piperazine, Imh = imidazole, H2pdc = pyridine-2,5-dicarboxylic acid, H2(ox) = oxalic acid, H4btec = 1,2,4,5-benzenetetracarboxylic acid), were hydrothermally synthesized and characterized by X-ray single crystal diffraction, IR, UV–Vis absorption spectrum, TG analysis and elemental analysis. The surface photovoltage properties of the four Co(II) complexes were investigated by the surface photovoltage spectroscopy (SPS). The structural analyses indicate that complexes 1 and 3 are 1D coordination polymers and complex 2 is a mononuclear molecular complex. Complexes 1, 2 and 3 are connected into 2D supramolecules by hydrogen bonds, respectively. Complex 4 is a coordination polymer with 3D structure, exhibiting a 4-nodal(4,5,6,12)-connected topology with a Schläfli symbol of (410)2(424·632·810)(45·6)2(49·65·8). The results of SPS show the four complexes exhibit obvious photovoltaic responses in 300–800 nm, which indicates they all possess photo-electric conversion properties. By the comparative analysis of the SPS, it is found that structure of the complex, species of ligand and coordination micro-environment of the Co(II) ion affect the SPS. The relationships between SPS and UV–Vis absorption spectra are discussed.  相似文献   

18.
Three cis‐selective Co(II)‐salen complexes have been developed for the asymmetric cyclopropanation of para‐fluorinated styrenes with ethyl diazoacetate. Increasing the steric reach of the C2‐symmetric ligand side chains improved the enantiomeric ratio of the reaction from 28:1 to 66:1. The methodology was exemplified by the gram‐scale synthesis of a lead compound for the treatment of castration‐resistant prostate cancer (CRPC), as well as a structurally related analog.  相似文献   

19.
The adsorption of Zn(II) ions from aqueous solution by chitosan derivatives (KCTS and HKCTS) was studied in a batch adsorption system. The adsorption capacities and rates of Zn(II) ions onto chitosan derivatives were evaluated. The adsorption isothermal data could be well interpreted by the Langmuir and Freundlich models. The kinetic experimental data properly correlated with the second-order kinetic model, which indicates that the chemical adsorption is the rate-limiting step. The apparent adsorption activation energy were 25.47 kJ mol and 5.473 kJ mol, respectively, and the second-order adsorption constant for KCTS and HKCTS were 0.00311 g (mg min)−1 and 0.005 g (mg min)−1, respectively.  相似文献   

20.
Interaction of cadmium(II) or zinc(II) acetate with 1,2-bis(4-pyridyl)ethane (bpe) in the presence of dioxime(1,2-cyclohexanedionedioxime = NioxH2 or diphenylglyoxime = dpgH2) resulted in three complexes with the compositions [Cd2(CH3COO)4(NioxH2)2(bpe)(H2O)2] (1), [Cd(CH3COO)2(bpe)(H2O)]n (2) and [Zn(CH3COO)2(NioxH2)(bpe)(H2O)]n (3), which were characterized by single-crystal X-ray diffraction, elemental analysis, IR, and luminescence spectroscopy. Dioxime-containing binuclear molecule 1 and 1D linear polymer 3 possess moderate luminescence properties, while the dioxime-free 1D polymer 2 demonstrates strong blue luminescence.  相似文献   

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