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1.
The self-assembly of [M(L)]Cl2·2H2O (M = Ni2+ and Cu2+, L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18,07.12]docosane) with sodium 1,2,4-benzenetricarboxylate (Na3btcb) and KNO3 generates the 1D hydrogen-bonded polymers with formulas [Ni(L)(H2btcb?)2] (1) and [Cu(L)(NO3)2] (2). These polymer complexes have been characterized by X-ray crystallography, spectroscopy and cyclic voltammetry. The crystal structure of 1 shows a distorted octahedral coordination geometry around the nickel(II) ion, with the four secondary amines of the macrocycle and two carboxylate oxygen atoms of the H2btcb? ligand in the trans position. In 2, the coordination environment around the central copper(II) ion reveals an axially elongated octahedron with four Cu–N bonds and two oxygen atoms of the nitrate ligand in the trans position. The cyclic voltammograms of the complexes undergo two one-electron waves corresponding to MII/MIII and MII/MI processes. The electronic spectra and electrochemical behavior of the complexes are significantly affected by the nature of the axial ligands.  相似文献   

2.
Mixed ligand complexes of CoII, NiII and CuII with dicarboxylic amino acids (aspartic, glutamic or H2ADA) as primary ligands and 8-hydroxyquinoline as a secondary ligand were prepared and characterized by elemental analysis, conductivity measurements, thermal analysis, cyclic voltammetry, and electronic and infrared (IR) spectroscopy. Cyclic voltammetry reveals a reversibility of the CuII/CuI couple, while the reactions of the CoII and NiII complexes are irreversible. All complexes have a metal-to-ligand ratios of 1:1:1 and octahedral structures are suggested to be attained by interactions among both of the amino acids and 8-hydroxyquinoline anions with the metal ions. The reaction orders and activation energies have been computed by means of the Coats–Redfern and Horowitz–Metzger equations. The biological activity of selected complexes as anti-fungal agents has been tested.  相似文献   

3.
Surface modification of nanocrystalline TiO2 particles (45 Å) with bidentate benzene derivatives (catechol, pyrogallol, and gallic acid) was found to alter optical properties of nanoparticles. The formation of the inner-sphere charge–transfer complexes results in a red shift of the semiconductor absorption compared to unmodified nanocrystallites. The binding structures were investigated by using FTIR spectroscopy. The investigated ligands have the optimal geometry for chelating surface Ti atoms, resulting in ring coordination complexes (catecholate type of binuclear bidentate binding–bridging) thus restoring in six-coordinated octahedral geometry of surface Ti atoms. From the Benesi–Hildebrand plot, the stability constants at pH 2 of the order 103 M−1 have been determined.  相似文献   

4.
Reactions of 2,3,5,6-tetra(2-pyridyl) pyrazine (tppz) with [ML6][X]2 (L = CH3CN, H2O;X = [BF4], [ClO4], [NO3] [BArF](BArF - B[3,5-C6H3(CF3)2]4) lead to the high-yield formation of mononuclear [M(tppz)2]2+, (M = MnII, FeII, CoII, and NiII) and dinuclear [Ni2(tppz)(CH3CN)6]4+ species. The new compounds were fully characterized by X-ray crystallographic, spectroscopic, and magnetic susceptibility measurements. Surprisingly, the 2:1 M:tppz reactions did not lead to isolation of the dinuclear species except in the case of Ni(II). It was further noted that even in the case of the Ni reactions, the nuclearity of the product depends on the choice of anions and the reaction conditions. Magnetic measurements of the mononuclear species [Co(tppz)2]2+ revealed thermally induced spin-crossover behavior from a high-spin S = 3/2 at higher temperatures to a low-spin S = 1/2 complex at lower temperatures. The dinuclear compound [Ni2(tppz)(CH3CN)6]4+ exhibits a weak anti-ferromagnetic interaction through the bridging tppz ligand.  相似文献   

5.
Efficient, low-cost enzymatic hydrolysis of lignocellulosic residues is essential for cost-effective production of bioethanol. The production of β-glucosidase, β-xylosidase and xylanase by Colletotrichum graminicola was optimized using Response Surface Methodology (RSM). Maximal production occurred in wheat bran. Sugarcane trash, peanut hulls and corncob enhanced β-glucosidase, β-xylosidase and xylanase production, respectively. Maximal levels after optimization reached 159.3 ± 12.7 U g−1, 128.1 ± 6.4 U g−1 and 378.1 ± 23.3 U g−1, respectively, but the enzymes were produced simultaneously at good levels under culture conditions optimized for each one of them. Optima of pH and temperature were 5.0 and 65 °C for the three enzymes, which maintained full activity for 72 h at 50 °C and for 120 min at 60 °C (β-glucosidase) or 65 °C (β-xylosidase and xylanase). Mixed with Trichoderma reesei cellulases, C. graminicola crude extract hydrolyzed raw sugarcane trash with glucose yield of 33.1% after 48 h, demonstrating good potential to compose efficient cocktails for lignocellulosic materials hydrolysis.  相似文献   

6.
Two chiral Schiff base-containing complexes, [Cu(L1)](ClO4)2·H2O (1, L1 = (S,S)-N1,N2-bis((1H-imidazol-4-yl)methylene)cyclohexane-1,2-diamine) and [Ni(L2)2](ClO4)2 (2, L2 = (S,S)-N1-((1H-imidazol-4-yl)methylene)cyclohexane-1,2-diamine) were synthesized from the reaction mixture of 1H-imidazole-4-carbaldehyde, (S,S)-1,2-diaminocyclohexane and Cu(ClO4)2·6H2O or Ni(ClO4)2·6H2O in methanol. Single-crystal X-ray diffraction analyses reveal that the in situ generated chiral Schiff base ligands L1 and L2 are bisubstituted and monosubstituted, respectively, corresponding to the different metal ions CuII and NiII. Variable-frequency and -temperature dielectric properties of 1 and 2 have been studied.  相似文献   

7.
Transition metal complexes [M(Hbta)(H2O)4] [M=Co(II) (1), Ni(II) (2), H3bta=1,3,5-benzenetriacetic acid] have been prepared by reaction of H3bta with the M(OH)2 in water by hydrothermal method. The complexes were characterized by X-ray crystallography and electrospray mass spectrometry. The coordination geometries around Co(II) and Ni(II) atoms are both distorted octahedral with O6 donor set. And the conformation of flexible triacid is cis, trans, trans in the title complexes.  相似文献   

8.
The complexes [Ni(L2)](ClO4)2·H2O (1) and [Cu(L2)]Cl2·4H2O (2) have been synthesized and characterized by X-ray crystallography, electronic absorption and cyclic voltammetry. The crystal structure of 1 reveals a distorted octahedral geometry with four nitrogen atoms of the macrocycle and two nitrogen atoms of the pendant pyridylmethyl groups. The structure of 2 shows that the complex is centrosymmetric and the metal center has a tetragonally distorted octahedral environment. The electronic spectra and electrochemical behaviors of the complexes are significantly affected by the presence of the pendant arms.  相似文献   

9.
The trinuclear manganese(II) complexes, [MnII3(OAc)4(pap)2(H2O)2] and [MnII3(OAc)4(5-Cl-pap)2(MeOH)2] were prepared by the reaction of tridentate Schiff base ligands X-papH (X=H, Cl), [N-2-pyridiylmethylidene-2-hydroxy-5-substituted-phenylamine], and MnII(OAc)2·2H2O. In the molecular structures of these complexes, two terminal manganese ions are coordinated with one oxygen and two nitrogen atoms of X-pap, two oxygen atoms of OAc and a solvent molecule, to form a distorted octahedral structure where the central manganese ion resides on a center of symmetry and is surrounded by an O6 donor set of four oxygen atoms from four bridging OAc and two phenolic oxygen atoms of two X-pap ligands.  相似文献   

10.
Berkleasmium sp. Dzf12, an endophytic fungus from Dioscorea zingiberensis, is a high producer of spirobisnaphthalenes with various bioactivities. The exopolysaccharide (EPS) produced by this fungus also shows excellent antioxidant activity. In this study, the experimental designs based on statistics were employed to evaluate and optimize the medium for EPS production in liquid culture of Berkleasmium sp. Dzf12. For increasing EPS yield, the concentrations of glucose, peptone, KH2PO4, MgSO4·7H2O and FeSO4·7H2O in medium were optimized using response surface methodology (RSM). Both the fractional factorial design (FFD) and central composite design (CCD) were applied to optimize the main factors which significantly affected EPS production. The concentrations of glucose, peptone and MgSO4·7H2O were found to be the main effective factors for EPS production by FFD experimental analysis. Based on the further CCD optimization and RSM analysis, a quadratic polynomial regression equation was derived from the EPS yield and three variables. Statistical analysis showed the polynomial regression model was in good agreement with the experimental results with the determination coefficient (adj-R2) as 0.9434. By solving the quadratic regression equation, the optimal concentrations of glucose, peptone and MgSO4·7H2O for EPS production were determined as 63.80, 20.76 and 2.74 g/L, respectively. Under the optimum conditions, the predicted EPS yield reached the maximum (13.22 g/L). Verification experiment confirmed the validity with the actual EPS yield as 13.97 g/L, which was 6.29-fold in comparison with that (2.22 g/L) in the original basal medium. The results provide the support data for EPS production in large scale and also speed up the application of Berkleasmium sp. Dzf12.  相似文献   

11.
The crystallization of proteins makes it possible to determine their structure by X-ray crystallography, and is therefore important for the analysis of protein structure-function relationships. L2 lipase was crystallized by using the J-tube counter diffusion method. A crystallization consisting of 20% PEG 6000, 50 mM MES pH 6.5 and 50 mM NaCl was found to be the best condition to produce crystals with good shape and size (0.5 × 0.1 × 0.2 mm). The protein concentration used for the crystallization was 3 mg/mL. L2 lipase crystal has two crystal forms, Shape 1 and Shape 2. Shape 2 L2 lipase crystal was diffracted at 1.5 Å and the crystal belongs to the orthorhombic space group P212121, with unit-cell parameters a = 72.0, b = 81.8, c = 83.4 Å, α = β = γ = 90°. There is one molecule per asymmetric unit and the solvent content of the crystals is 56.9%, with a Matthew’s coefficient of 2.85 Å Da−1. The 3D structure of L2 lipase revealed topological organization of α/β-hydrolase fold consisting of 11 β-strands and 13 α-helices. Ser-113, His-358 and Asp-317 were assigned as catalytic triad residues. One Ca2+ and one Zn2+ were found in the L2 lipase molecule.  相似文献   

12.
The interactions between chemosensors, 3-amino-5-(4,5,6,7-tetrahydro-1H-indol-2-yl)isoxazole-4-carboxamide (AIC) derivatives, and different anions (F Cl, Br, AcO, and H2PO4) have been theoretically investigated using DFT approaches. It turned out that the unique selectivity of AIC derivatives for F is ascribed to their ability of deprotonating the host sensors. Frontier molecular orbital (FMO) analyses have shown that the vertical electronic transitions of absorption and emission for the sensing signals are characterized as intramolecular charge transfer (ICT). The study of substituent effects suggests that all the substituted derivatives are expected to be promising candidates for fluoride chemosensors both in UV-vis and fluorescence spectra except for derivative with benzo[d]thieno[3,2-b]thiophene fragment that can serve as ratiometric fluorescent fluoride chemosensor only.  相似文献   

13.
The current study was performed to investigate mitochondrial protection and anti-aging activity of Astragalus polysaccharides (APS) and the potential underlying mechanism. Lipid peroxidation of liver and brain mitochondria was induced by Fe2+–Vit C in vitro. Thiobarbituric acid (TBA) colorimetry was used to measure the content of thiobarbituric acid reactive substances (TBARS). Mouse liver mitochondrial permeability transition (PT) was induced by calcium overload in vitro and spectrophotometry was used to measure it. The scavenging activities of APS on superoxide anion (O2•−) and hydroxyl radical (•OH), which were produced by reduced nicotinamide adenine dinucleotide (NADH)—N-Methylphenazonium methyl sulfate (PMS) and hydrogen peroxide (H2O2)–Fe2+ system respectively, were measured by 4-nitrobluetetrazolium chloride (NBT) reduction and Fenton reaction colorimetry respectively. The Na2S2O3 titration method was used to measure the scavenging activities of APS on H2O2. APS could inhibit TBARS production, protect mitochondria from PT, and scavenge O2•−, •OH and H2O2 significantly in a concentration-dependent manner respectively. The back of the neck of mice was injected subcutaneously with D-galactose to induce aging at a dose of 100 mg/kg/d for seven weeks. Moreover, the activities of catalase (CAT), surperoxide dismutase (SOD) and glutathione peroxidase (GPx) and anti-hydroxyl radical which were assayed by using commercial monitoring kits were increased significantly in vivo by APS. According to this research, APS protects mitochondria by scavenging reactive oxygen species (ROS), inhibiting mitochondrial PT and increasing the activities of antioxidases. Therefore, APS has the effect of promoting health.  相似文献   

14.
Tuberculosis (TB) is an infectious disease caused mainly by the bacillus Mycobacterium tuberculosis (Mtb), presenting 9.5 million new cases and 1.5 million deaths in 2014. The aim of this study was to evaluate a nanostructured lipid system (NLS) composed of 10% phase oil (cholesterol), 10% surfactant (soy phosphatidylcholine, sodium oleate), and Eumulgin® HRE 40 ([castor oil polyoxyl-40-hydrogenated] in a proportion of 3:6:8), and an 80% aqueous phase (phosphate buffer pH = 7.4) as a tactic to enhance the in vitro anti-Mtb activity of the copper(II) complexes [CuCl2(INH)2]·H2O (1), [Cu(NCS)2(INH)2]·5H2O (2) and [Cu(NCO)2(INH)2]·4H2O (3). The Cu(II) complex-loaded NLS displayed sizes ranging from 169.5 ± 0.7095 to 211.1 ± 0.8963 nm, polydispersity index (PDI) varying from 0.135 ± 0.0130 to 0.236 ± 0.00100, and zeta potential ranging from −0.00690 ± 0.0896 to −8.43 ± 1.63 mV. Rheological analysis showed that the formulations behave as non-Newtonian fluids of the pseudoplastic and viscoelastic type. Antimycobacterial activities of the free complexes and NLS-loaded complexes against Mtb H37Rv ATCC 27294 were evaluated by the REMA methodology, and the selectivity index (SI) was calculated using the cytotoxicity index (IC50) against Vero (ATCC® CCL-81), J774A.1 (ATCC® TIB-67), and MRC-5 (ATCC® CCL-171) cell lines. The data suggest that the incorporation of the complexes into NLS improved the inhibitory action against Mtb by 52-, 27-, and 4.7-fold and the SI values by 173-, 43-, and 7-fold for the compounds 1, 2 and 3, respectively. The incorporation of the complexes 1, 2 and 3 into the NLS also resulted in a significant decrease of toxicity towards an alternative model (Artemia salina L.). These findings suggest that the NLS may be considered as a platform for incorporation of metallic complexes aimed at the treatment of TB.  相似文献   

15.
In the search for new environmental friendly antifouling (AF) agents, four coumarins were isolated from the herbal plant Cnidium monnieri, known as osthole (1), imperatorin (2), isopimpinellin (3) and auraptenol (4). Furthermore, five coumarin derivatives, namely 8-epoxypentylcoumarin (5), meranzin hydrate (6), 2′-deoxymetranzin hydrate (7), 8-methylbutenalcoumarin (8), and micromarin-F (9) were synthesized from osthole. Compounds 1, 2, 4, 7 showed high inhibitory activities against larval settlement of Balanus albicostatus with EC50 values of 4.64, 3.39, 3.38, 4.67 μg mL−1. Compound 8 could significantly inhibit larval settlement of Bugula neritina with an EC50 value of 3.87 μg mL−1. The impact of functional groups on anti-larval settlement activities suggested that the groups on C-5′ and C-2′/C-3′ of isoamylene chian could affect the AF activities.  相似文献   

16.
Coordination complexes of formula [ML2], [CoL3], [Pd(HL)Cl2], [CuLCl(H2O)] and [CuL2(H2O)2] {L=anion of N-ethyl-N-(4-methylthiazol-2′-yl)thiourea; M=PtII, PdII or NiII} were prepared and characterized by elemental analyses, magnetic susceptibilities, and by IR, NMR, electronic and mass spectral measurements.  相似文献   

17.
Two novel 2D and 3D bimetallic CdIINiII coordination polymers, Cd(2Mpz)(H2O)Ni(CN)4 (I) (2Mpz: 2-methylpyrazine) and Cd(2Epz)(H2O)Ni(CN)4 (II) (2Epz: 2-ethylpyrazine), have been synthesized and characterized by elemental analysis, powder X-ray diffraction, IR spectra, fluorescent spectra, single crystal X-ray diffraction and thermogravimetric analysis. Based on the analysis of structures, it can be found that the Cd(II) ions in the two complexes have the similar octahedral coordination geometry of CdN5O, which are linked by [Ni(CN)4]2− units at the equatorial plane to form 2D sheet layers [CdNi(CN)4] n . However, it’s noted that the coordination environment of Ni(II) ions and action of ligands are different. All the Ni(II) ions in I are the five-coordinated pentahedron configuration and 2-methylpyrazine acts as a bridging ligand linking the Cd(II) and Ni(II) ions of the adjacent layers, leading to the 3D metal–organic framework. The structure of II indicates all the Ni(II) ions are the four-coordinated square plane and 2-ethylpyrazine is a terminal ligand coordinated to Cd(II) ions, forming the 2D layer structure. Moreover, the two complexes display significant thermal stability and fluorescent properties.  相似文献   

18.
The three complexes [Fe(opo)3], [Cu(opo)2], and [Zn(opo)2] containing the non-innocent anionic ligand opo (opo = 9-oxido-phenalenone, Hopo = 9-hydroxyphenalonone) were synthesised from the corresponding acetylacetonates. [Zn(opo)2] was characterised using 1H nuclear magnetic resonance (NMR) spectroscopy, the paramagnetic [Fe(opo)3] and [Cu(opo)2] by electron paramagnetic resonance (EPR) spectroscopy. While the EPR spectra of [Cu(opo)2] and [Cu(acac)2] in dimethylformamide (DMF) solution are very similar, a rather narrow spectrum was observed for [Fe(opo)3] in tetrahydrofuran (THF) solution in contrast to the very broad spectrum of [Fe(acac)3] in THF (Hacac = acetylacetone, 2,4-pentanedione; acac = acetylacetonate). The narrow, completely isotropic signal of [Fe(opo)3] disagrees with a metal-centred S = 5/2 spin system that is observed in the solid state. We assume spin-delocalisation to the opo ligand in the sense of an opo to FeIII electron transfer. All compounds show several electrochemical opo-centred reduction waves in the range of −1 to −3 V vs. the ferrocene/ferrocenium couple. However, for CuII and FeIII the very first one-electron reductions are metal-centred. Electronic absorption in the UV to vis range are due to π–π* transitions in the opo core, giving Hopo and [Zn(opo)2] a yellow to orange colour. The structured bands ranging from 400 to 500 for all compounds are assigned to the lowest energy π−π* transitions. They show markedly higher intensities and slight shifts for the CuII (brown) and FeIII (red) complexes and we assume admixing metal contributions (MLCT for CuII, LMCT for FeIII). For both complexes long-wavelength absorptions assignable to d–d transitions were detected. Detailed spectroelectrochemical experiments confirm both the electrochemical and the optical assignments. Hopo and the complexes [Cu(opo)2], [Zn(opo)2], and [Fe(opo)3] show antiproliferative activities against HT-29 (colon cancer) and MCF-7 (breast cancer) cell lines in the range of a few µM, comparable to cisplatin under the same conditions.  相似文献   

19.
We report the influence of Al3+ doping on the microstructural and Mössbauer properties of ferrite nanoparticles of basic composition Ni0.2Cd0.3Fe2.5 - xAlxO4 (0.0 ≤ x ≤ 0.5) prepared through simple sol-gel method. X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray, transmission electron microscopy (TEM), Fourier transformation infrared (FTIR), and Mössbauer spectroscopy techniques were used to investigate the structural, chemical, and Mössbauer properties of the grown nanoparticles. XRD results confirm that all the samples are single-phase cubic spinel in structure excluding the presence of any secondary phase corresponding to any structure. SEM micrographs show the synthesized nanoparticles are agglomerated but spherical in shape. The average crystallite size of the grown nanoparticles was calculated through Scherrer formula and confirmed by TEM and was found between 2 and 8 nm (± 1). FTIR results show the presence of two vibrational bands corresponding to tetrahedral and octahedral sites. Mössbauer spectroscopy shows that all the samples exhibit superparamagnetism, and the quadrupole interaction increases with the substitution of Al3+ ions.  相似文献   

20.
The small molecule, meso-tetra(α,α,α,α-o-phenylacetamidophenyl) porphyrin (Mr1147.0) was used as complete antigen to elicit MAb through the immunization and cell fusion techniques. The MAb 1F2 obtained was demonstrated to be very pure by MALDI/TOFMS. The subtype of MAb 1F2 is IgG2a, which has a relative molecular weight of 156,678.8 Da.No significant change in the intensity of absorption peaks in UV and CD spectra was observed over a pH range between 6 and 12. The high stability of the abzyme and the tight binding between Fe porphyrin and antibody were also demonstrated. Vmax, Km, κcat, κcat/Km for abzyme are 5.18 × 10−8 Ms−1, 1.50 × 10−8 M, 0.518 s−1, 3.45 × 107 M−1s−1, respectively. The data obtained indicate that catalytic antibody has high catalytic activity. The chloroperoxidase activity of MAb 1F2-Fe porphyrin complex is stable from 10 °C to 60 °C.  相似文献   

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