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1.
The interaction of BSA and FeIII complexes ([FeIII(gly)(H2O)4]2+, [FeIII(ida)(H2O)3]+, and [FeIII(nta)(H2O)2], gly—glyane, ida—iminodiacetic acid, nta—triglycolamic acid) as well as the sonocatalytic damage to BSA was studied by UV-vis and fluorescence spectra. In addition, the influences of ultrasonic irradiation time and FeIII complex concentration were also examined on the sonocatalytic damage to BSA. The results showed that the fluorescence quenching of BSA solution caused by the FeIII complexes belonged to the static quenching process. The BSA and FeIII complexes interacted with each other mainly through weak interaction and coordinate actions. The binding association constants (K) and binding site numbers (n) were calculated. The results were as follows: K 1 = 0.5353 × 104 l mol−1 and n 1 = 0.9812 for [FeIII(gly)(H2O)4]2+, K 2 = 1.4285 × 104 l mol−1 and n 2 = 1.0899 for [FeIII(ida)(H2O)3, and K 3 = 0.4411 × 104 l mol−1 and n 3 = 0.9471 for [FeIII(nta)(H2O)2]. Otherwise, under ultrasonic irradiation the BSA were obviously damaged by the FeIII complexes. The damage degree rose up with the increase of ultrasonic irradiation time and FeIII complex concentration. And that, [FeIII(nta)(H2O)2] exhibited in a way higher sonocatalytic activity than [FeIII(gly)(H2O)4]2+ and [FeIII(ida)(H2O)3]+.  相似文献   

2.
The composition of complexes formed upon the extraction of UVI and ThIV nitrates with O-n-nonyl(N,N-dibutylcarbamoylmethyl) methyl phosphinate (L) from solutions of nitric acid without additional solvent was determined by 31P NMR spectroscopy. The structures of the complexes formed were studied by IR spectroscopy. Uranium(VI) is extracted from 3 and 5 M solutions of HNO3 as the [UO2(L)2(NO3)2] complex, while thorium(IV) is extracted from 5 M HNO3 as the [Th(L)3(NO3)3]+·NO 3 complex. In both cases, ligand L has bidentate coordination. Ligand L contacts with 3 and 5 M nitric acid to form adducts L·HNO3 and L· (HNO3)2, respectively. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2460–2464, November, 2005.  相似文献   

3.
A dinuclear macrocyclic ligand containing [12]aneN3 and its two transition metal complexes, [Zn2L(OAc)2](ClO4)2 (1) and [Cu2L(OAc)2](ClO4)2 (2) have been synthesized and characterized on the basis of elemental analyses, molar conductivities, 1H-n.m.r, IR spectra, electronic spectra and thermal analysis. In addition, the studies on the hydrolysis of a caboxy ester, 4-nitrophenyl acetate (NA), promoted by the two complexes were also investigated. The experimental results indicated that the two complexes can efficiently catalyze hydrolysis of NA, and the kNA for complexes (1) and (2) at pH 7.25, 25 °C, were calculated to be 4.46 × 10−2 and 4.21 × 10−2 m−1 s−1, respectively, which are better than those of the corresponding mononuclear complex in the same conditions.  相似文献   

4.
A new ligand H2L, 1,7-di(1-phenyl-3-methyl-5-pyrazolone-4-benzylidene)diethenetriamine and its three transition metal complexes, ML · nH2O [M=Cu(II), n=2; M=Zn(II), n=0.5; M=Ni(II) (1), n=3] have been synthesized in anhydrous EtOH and characterized on the basis of elemental analyses, molar conductivities, i.r. spectra, u.v. spectra and thermal analyses. In addition, the DNA-binding properties of the ligand and its complexes have been investigated by absorption, fluorescence and viscosity measurements. The experimental results indicated that the ligand and the complex (1) can bind to DNA , but the other two complexes can’t; the binding affinity of the complex (1) is higher than that of the ligand and the intrinsic binding constant kb of the complex (1) is 7.893×105 m−1.  相似文献   

5.
The interaction of [K2FeIII 4(O)2(OOCCMe3)10(HOOCCMe3)2(H2O)2]n with 2-pyridinecarboxaldehyde results in a mixed-valence complex FeIIFeIII 33-O)22-OOCCMe3)7L2··2.5MeCN·3H2O (L = 2-NC5H4COOH0.75K0.25). The structure of the complex was established by X-ray analysis. The magnetic properties of the complex were studied. Dedicated to Academician A. L. Buchachenko on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2145–2148, September, 2005.  相似文献   

6.
Dinuclear copper(II) complexes with acyldihydrazones of 2-hydroxy-5-nitroacetophenone (H4L) of the composition Cu2(Py)xmEtOH were synthesized and characterized. In these complexes, the coordination polyhedra of the copper atoms are linked to each other by a polymethylene chain of different lengths, from one to five monomer units. The structure of the [Cu2L·4Mrf] complex (Mrf is morpholine) based on acyldihydrazone of malonic acid was established by X-ray diffraction. The copper(II) atoms in this complex are [4+1]-coordinated and are spaced by 6.94 Å. At room temperature, the signal in the ESR spectra of solutions of the complexes based on acyldihydrazones of malonic, succinic, glutaric, and adipic acids has a seven-line hyperfine structure with the constant of (35.3–38.8)·10−4 cm−1 (g = 2.109–2.112) due to exchange interactions between unpaired electrons and two equivalent copper nuclei. An increase in the length of the polymethylene chain to five monomer units hinders exchange interactions, and the ESR signal of the complex based on acyldihydrazone of pimelic acid has a four-line hyperfine structure with a Cu = 72.7·10−4 cm−1 typical of mononuclear copper(II) complexes. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 229–234, February, 2007.  相似文献   

7.
A new ligand, 2-carboxybenzaldehyde-(4’-hydroxy)benzoylhydrazone(H2L) and its ZnII and NiII complexes have been synthesized and characterized on the basis of elemental analyses, molar conductivities, 1H-NMR, IR spectra and thermal analyses. In addition, DNA-binding properties of these two metal complexes were investigated using spectrometric titrations, ethidium bromide displacement experiments, and viscosity measurements. The results show that the two complexes, especially the NiII complex, strongly bind with calf-thymus DNA, presumably via an intercalation mechanism. The intrinsic binding constants of the ZnII and NiII complexes with DNA are 2.46 × 105 and 7.94 × 105 M −1, respectively.  相似文献   

8.
Bipyrimidines have been chosen as (N∧N)(N∧N) bridging ligands for connecting metal centers. IrIII-LnIII (Ln = Nd, Yb, Er) bimetallic complexes [Ir(dfppy)2(μ-bpm)Ln(TTA)3]Cl were synthesized by using Ir(dfppy)2(bpm)Cl as the ligand coordinating to lanthanide complexes Ln(TTA)3·2H2O. The stability constants between Ir(dfppy)2(bpm)Cl and lanthanide ions were measured by fluorescence titration. The obvious quenching of visible emission from IrIII complex in the IrIII-LnIII (Ln = Nd, Yb, Er) bimetallic complexes indicates that energy transfer occurred from IrIII center to lanthanides. NIR emissions from NdIII, YbIII, and ErIII were obtained under the excitation of visible light by selective excitation of the IrIII-based chromophore. It was proven that Ir(dfppy)2(bpm)Cl as the ligand could effectively sensitize NIR emission from NdIII, YbIII, and ErIII.  相似文献   

9.
New mononuclear and dinuclear complexes [3-hydroxyethyl-1,3,5,8,11pentaazacyclotridecane]copper(II) (1)/nickel(II) (2) perchlorate and O,O ethane bridged bis-copper(II) (3)/nickel(II) (4) macrocycles have been synthesized and characterized by various spectroscopic techniques, viz. i.r., n.m.r., e.p.r., u.v.–vis. and conductance measurements. Spectral data and conductance measurements reveal that all the complexes are consistent with square-planar geometry and are ionic in nature. The catalytic activity of the dinuclear Cu(II) complex (3) in the presence of pyrocatechol was determined spectrometrically by monitoring the increase of the o-benzoquinone characteristic absorption band at 25,000 cm−1 with respect to time in DMF saturated with molecular oxygen. The kinetic parameters Vmax (2.8×10−3 M s−1) and KM (1.4×10−3 mm) have been determined by Michaelis–Menten method. Electrochemistry of the dinuclear Cu(II) complex has been studied in the presence of molecular oxygen with pyrocatechol and without pyrocatechol at a scan rate of 0.1 V s−1 by cyclic voltammetry. On addition of pyrocatechol, complex shows a shift in Epc, Epa and E1/2 values indicating the oxidation of substrate (pyrocatechol).  相似文献   

10.
The kinetics of the electron-transfer reactions between promazine (ptz) and [Co(en)2(H2O)2]3+ in CF3SO3H solution ([CoIII] = (2–6) × 10−3 m, [ptz] = 2.5 × 10−4 m, [H+] = 0.02 − 0.05 m, I = 0.1 m (H+, K+, CF3SO 3 ), T = 288–308 K) and [Co(edta)] in aqueous HCl ([CoIII] = (1 − 4) × 10−3 m, [ptz] = 1 × 10−4 m, [H+] = 0.1 − 0.5 m, I = 1.0 m (H+, Na+, Cl), T = 313 − 333 K) were studied under the condition of excess CoIII using u.v.–vis. spectroscopy. The reactions produce a CoII species and a stable cationic radical. A linear dependence of the pseudo-first-order rate constant (k obs) on [CoIII] with a non-zero intercept was established for both redox processes. The rate of reaction with the [Co(en)2(H2O)2]3+ ion was found to be independent of [H+]. In the case of the [Co(edta)] ion, the k obs dependence on [H+] was linear and the increasing [H+] accelerates the rate of the outer-sphere electron-transfer reaction. The activation parameters were calculated as follows: ΔH = 105 ± 4 kJ mol−1, ΔS = 93 ± 11 J K−1mol−1 for [Co(en)2(H2O)2]3+; ΔH = 67 ± 9 kJ mol−1, ΔS = − 54 ± 28 J K−1mol−1 for [Co(edta)].  相似文献   

11.
Six new macrocyclic complexes were synthesized by reaction of 1,4-bis(2-carboxyaldehyde phenoxy)butane with various diamines. Then, their nickel(II) perchlorate complexes were synthesized by the template effect by reaction of 1,4-bis(2-carboxyaldehyde phenoxy)butane, Ni(ClO4)2 · 6H2O and various diamines. The metal-to-ligand ratio of NiII metal complexes was found to be 1:1. The compounds are coordinated to the central metal as tetradentate O2N2 ligands The NiII complexes are proposed to exhibit tetrahedral geometry. NiII metal complexes are 1:2 electrolytes as shown by their molar conductivities (ΛM) in DMF (dimethyl formamide) at 10−3 m. The structure of NiII metal complexes is proposed from elemental analysis, f.t.-i.r., u.v.-vis., magnetic susceptibility measurements, molar conductivity measurements and mass spectra.  相似文献   

12.
Reactions of Pentapseudohalonitrosyl ferrate(II) with Morpholinobenzyl benzamide(MBB) and Piperidinobenzyl benzamide(PBB) formed complexes of the type, [Fe(X)3(NO)(L–L)] where X = CN, NCO and N 3 and L–L = Morpholinobenzyl benzamide(MBB) and Piperidinobenzyl benzamide(PBB). These compounds have been characterized by various physico-chemical techniques such as elemental analysis, molar conductance, magnetic susceptibility measurements, i.r., electronic spectra, thermal gravimetric analysis. The molecular modeling Studies have been carried out for structural analysis for some of the complexes have been carried out using Hyperchem release 7.52 professional version.  相似文献   

13.
The reactions of the tetranuclear hydroxo complexes [M42-OH)8(H2O)16]8+ (M = Zr or Hf) with the lacunary Keggin-type ([α-PW11O39]7−) and Dawson-type ([α 2-P2W17O61]10−) phosphotungstates in aqueous solutions produce the sandwich polyoxometalate complexes [M(α-PW11O39)2]10− (M = Zr (1) or Hf (2)) and [M(α 2-P2W17O61)2]16− (M = Zr (3) and Hf (4)). The complexes were isolated and structurally characterized as salts with potassium and dimethylammonium cations. The zirconium and hafnium atoms have a square antiprismatic coordination environment (coordination number is 8). In all complexes, the mutual arrangement of the ligands corresponds to the syn isomer. Hafnium complexes 2 and 4 are the first structurally characterized polyoxometalate complexes of this metal. The structures of the resulting compounds were confirmed also by 31P NMR spectroscopy in solution. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 214–218, February, 2007.  相似文献   

14.
Two novel cobalt(III) mixed-polypyridyl complexes [Co(bpy)2(dpta)]3+ and [Co(bpy)2(amtp)]3+ (bpy = 2,2′-bipyridine, dpta = dipyrido-[3,2-a;2′,3′-c]-thien-[3,4-c]azine, amtp = 3-amino-1,2,4-triazino[5,6-f]-1,10-phenanthroline) have been synthesized and characterized. The interaction of CoIII complexes with calf thymus DNA was investigated by spectroscopic and viscosity measurements. Results suggest that the two complexes bind to DNA via an intercalative mode. Moreover, CoIII complexes have been found to promote the photocleavage of plasmid DNA pBR322 under irradiation at 365 nm. The mechanism studies reveal that hydroxyl radical (OH) is likely to be the reactive species responsible for the cleavage of plasmid DNA by [Co(bpy)2(dpta)]3+ and superoxide anion radical (O 2 •− ) acts as the key role in the cleavage reaction of plasmid DNA by [Co(bpy)2(amtp)]3+.  相似文献   

15.
Pyrroloquinoline quinone (PQQ), an essential nutrient, antioxidant, redox modulator and nerve growth factor found in a class of enzymes called quinoproteins, was labeled with 99mTc by using stannous fluoride (SnF2) method. Radiolabeling qualification, quality control and characterization of 99mTc-PQQ and its biodistribution studies in mice were performed and discussed. Effects of pH values, temperature, time and reducing agents concentration on the radiolabeling yield were investigated. The quality control procedure of 99mTc-PQQ was determined by thin layer chromatography (TLC), radio high-performance liquid chromatography (RHPLC) and paper electrophoresis methods. The average radiolabeling yield was 94 ± 1% under optimum conditions of 0.99 mg of PQQ, 30 μg of SnF2, 0.5 mg of ethylenediaminetetraacetic acid disodium salt (EDTA-2Na) and 18.5 MBq of Na99mTcO4 at pH 6 and 25 °C with a response volume of 1 ± 0.1 mL. 99mTc-PQQ was stable and anionic. Lipid–water partition coefficient of 99mTc-PQQ was −1.49 ± 0.16. The pharmacokinetics parameters of 99mTc-PQQ were t 1/2α = 18.16 min, t 1/2β = 100.45 min, K 12 = 0.013 min−1, K 21 = 0.017 min−1, K e = 0.016 min−1, AUC (area under the curve) = 1040.78 ID% g−1 min and CL (plasma clearance) = 0.096 mL min−1. The dual-exponential equation was Y = 10.88e−0.038t  + 5.21e−0.0069t . The biodistribution of 99mTc-PQQ was studied in ICR (Institute for Cancer Research 7701 Burhelme Are., Fox Chase, Philadelphia, PA 1911 USA) mice. In vitro autoradiographic studies clearly showed that the 99mTc-PQQ radioactivity accumulated predominantly in the hippocampus and cortex, which had a high density of N-methyl-d-aspartate Receptor (NMDAR). The enrichment can be blocked by NMDAR redox modulatory site antagonists-ebselen (EB) and 99mTc-PQQ is therefore a promising candidate for the molecular imaging of NMDAR. To date, however, there have been no studies characterizing 99mTc-PQQ.  相似文献   

16.
The two complexes, [RE(Gly)4(Im)(H2O)](ClO4)3(s)(RE = Eu, Sm), have been synthesized and characterized. The standard molar enthalpies of reaction for the following reactions, RECl3·6H2O(s)+4Gly(s)+Im(s)+3NaClO4(s) = =[RE(Gly)4(Im)(H2O)](ClO4)3(s)+3NaCl(s)+5H2O(l), were determined by solution-reaction colorimetry. The standard molar enthalpies of formation of the two complexes at T = 298.15 K were derived as Δf H mΘ {Eu(Gly)4(Im)(H2O)}(ClO4)3(s)} = = −(3396.6±2.3) kJ mol−1 and Δf H mΘ {Sm(Gly)4(Im)(H2O)}(ClO4)3(s)} = −(3472.7±2.3) kJ mol−1, respectively.  相似文献   

17.
We have measured the second acid dissociation constant, K 2a , at several ionic strengths for hydrogen telluride (H2Te) using the Charge Transfer to Solvent (CTTS) uv spectra of its anions HTe and Te2−. Since it is produced in our solutions, we have also determined the spectra of Te2 2− both in the uv and in the visible regions. At 25 C, K 2a = (1.28 ± 0.02) × 10−12 by extrapolation to zero ionic strength. Its value at an ionic strength equal to 0.5 mol.dm-3 was estimated to be (8.7 ± 0.2) × 10−12. The solution thermodynamics of these species are also discussed and comparisons are made to related acids.  相似文献   

18.
The IR and electronic absorption spectra of molten mixtures in the NaCl-CsCl-NaF-CoCl2, NaCl-KCl-NaF-CoCl2, and NaCl-KCl-NaKCO3-CoCl2 systems have been studied. The spectral data show that, for all molten mixtures, the composition ranges exist in which chloro fluoro Co(Cl n F m )(n + m = 4–6) and carbonato chloro CoCl(CO3)4 − n (n = 1–3) complex groups are formed at δ1 < δ1* and δ2 < δ2*1* = F/Co and δ2* = CO3/Co). At δ1 ≥ δ1* and δ2 ≥ δ2*, the mixtures contain complexes homoligand Co and CoF64− and Co(CO3)46−.  相似文献   

19.
The kinetics of the intra-molecular electron transfer of an adduct of l-ascorbic acid and the [Fe3IIIO(CH3COO)6(H2O)3]+ cation in aqueous acetate buffer was studied spectrophotometrically, over the ranges 2.55 ≤ pH ≤ 3.74, 20.0 ≤ θ ≤ 35.0 °C, at an ionic strength of 0.50 and 1.0 mol dm−3 (NaClO4). The reaction of l-ascorbic acid and the complex cation involves the rapid formation of an adduct species followed by a slower reduction in the iron centres through consecutive one-electron transfer processes. The final product of the reaction is aqueous iron(II) in acetate buffer. The proposed mechanism involves the triaqua and diaqua-hydroxo species of the complex cation, both of which form adducts with l-ascorbic acid. At 25 °C, the equilibrium constant for the adduct formation was found to be 86 ± 15 and 5.8 ± 0.2 dm3 mol−1 for the triaqua and diaqua-hydroxo species, respectively. The kinetic parameters derived from the rate expression have been found to be: k 0 = (1.12 ± 0.02) × 10−2 s−1 for the combined spontaneous decomposition and k 1 = (4.47 ± 0.06) × 10−2 s−1H 1 = 51.0 ± 2.3 kJ mol−1, ΔS 1 = −100 ± 8 J K−1 mol−1), k 2 = (4.79 ± 0.38) × 10−1 s−1H 2 = 76.5 ± 0.8 kJ mol−1, ΔS 2 = 6 ± 3 J K−1 mol−1) for the triaqua and diaqua-hydoxo species, respectively.  相似文献   

20.
New complexes of Cu(II), Zn(II) and Ni(II) with naringenin have been synthesized and characterized on the basis of elemental analyses, molar conductivities, 1H-n.m.r., i.r. spectra, u.v. spectra, thermal analyses, and fluorescence spectra. In addition, the suppression ratio for O2· (a) and OH· (b) of the complexes were studied by spectrophotometric methods. The results show that the effect of the Cu(II)-complex IC50 (a) = 0.003 μm, IC50 (b) = 0.06 μm is the most remarkable, and the average scavenger ability of the complexes (IC50=0.06–2.67μm) against OH· is higher than that of the ligand (IC50 = 28.5 μm). Taken together, these results indicate that the scavenger effect can be enhanced by the formation of metal-ligand coordination complexes, and the transition-metal ions may have differential and selective roles.  相似文献   

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