铜锌超氧化物歧化酶与苏氨酸钴(Ⅱ)的相互作用

采用Vis,ICP及酶活性测定等方法,研究铜锌超氧歧化酶(Cu_2Zn_2SOD)与苏氨酸钴(Ⅱ)(Co(Thr)_n)的直接相互作用以及外加苏氨酸钴(Ⅱ)的量、溶液pH值对此类相互作用的影响。结果发现:在水溶液中原酶活性中心处的Zn(Ⅱ)离子可被外加的苏氨酸钴(Ⅱ)部分诱导、交换出来,而溶液中外加的Co(Thr)_n中的Co(Ⅱ)进入酶的活性中心,形成“Co-SOD”酶衍生物,并相应影响了酶的催化活性。与此同时,外加苏氨酸钴(Ⅱ)的量、溶液pH值对此类相互作用进行有重要的影响。     

Mononuclear manganese carboxylate complexes: Synthesis and structural studies

Several manganese carboxylates complexes having Pz^iPr2H (3,5-diisopropylpyrazole), Tp^Ph,Me (hydrotris(3-phenyl,5-methyl-pyrazol-1-yl)borate), Tp^ipr2 (hydrotris(3,5-diisopropyl-pyrazol-1-yl)borate) as supporting ligands have been synthesised and structurally characterized. Single-crystal X-ray diffraction studies suggest that the manganese center in complexes (Pz^iPr2H)₄Mn(NO₂–OBz)₂ (5) and (Pz^iPr2H)₄Mn(F–OBz)₂ (6) have same coordination environment and geometry whereas the complex [Tp^Ph,MeMn(OAc)Pz^Ph,MeH] (7) has a five coordinate manganese center. In all these complexes, the carboxylate groups are coordinated as monodentate and the uncoordinated oxygen atom of the carboxylate groups form intramolecular hydrogen bonds with the NH group of the corresponding coordinated pyrazole (Pz^iPr2H/Pz^Ph,MeH). The complexes 5–8 and 10 were tested for their superoxide dismutase activity and it was found that only complex 7 has SOD activity as its structure is very similar to the active site structure of the native Mn–SOD enzyme. The SOD activity studies on these carboxylate complexes suggest that any model compound with analogous active site structure and intramolecular hydrogen bonding may be a suitable mimic for the Mn–SOD enzyme.     

Physicochemical characterization of Cu(II) complexes with SOD-like activity,theoretical studies and biological assays

The mononuclear Cu(II) complex, [Cu(o-Va)₂(H₂O)₂] (o-HVa = o-vanillin, 2-hydroxy-3-methoxybenzaldehyde) has been synthesized and characterized by elemental analyses, FTIR, FT-Raman, and electronic spectroscopies and compared with the results obtained for the free ligand. The optimized geometry, the harmonic vibrational frequencies and the electronic transitions of the complex and the ligand were calculated using methods based on the density functional theory. Antimicrobial activity against Escherichia coli and Staphylococcus aureus and SOD-mimic activities of the complex were studied and compared with the analogous copper complex with vanillin, [Cu(Va)₂(H₂O)₂]. Stability of the compounds in the essayed solution and with time was determined by means of conductimetric measurements. Their redox behavior was studied by cyclic voltammetry and was compared with that observed for the ligands. The complexes undergo two main reductions and one oxidation processes involving the metal center and the coordinated ligand, respectively.     

Hot-electron reliability improvement using perhydropolysilazane spin-on-dielectric passivation buffer layers for AlGaN/GaN HEMTs

We investigate the effects of perhydropolysilazane spin-on-dielectric (SOD) buffer layer adopted prior to Si₃N₄ passivation on the dc drain current level and degradation after the electrical stress in the AlGaN-GaN high electron mobility transistors (HEMTs). The SOD-buffered HEMTs show ∼1.6 times greater drain current densities (∼257 mA/mm) than those of the devices with conventional-Si₃N₄ passivations (∼155 mA/mm). After the hot electron stresses (step-wise and constant) applied to the devices, it is also found that the SOD-buffered structure produces greatly improved device reliability in terms of the dc current collapse (15% for step-stress and constant stress) compared to the conventional structure (25% for each case). We propose that the enhancement of SOD-buffered structure in dc current collapse is due to the reduction in surface state density at the passivation interface and the suppressed electron trapping.     

Bacterial sensitivity and SOD behavior of N-pyrone glucosamine Schiff base Fe(III) complex: conjoint experimental-DFT evaluation

Iron and sugar are essential components of life processes. In the evident interest toward Fe(III) compounds to explore the ability of sugars toward metallotherapy, a systematic hyphenated DFT-experimental study of a novel sugar Schiff base Fe(III) complex of general composition [Fe(L)(OH)], where L = N-dehydroacetic acid-glucosamine (dha-glsH₂), is presented. Based on various experimental spectrometric and spectroscopic characterization techniques in combination with theoretical data, a suitable distorted tetragonal structure is suggested for the complex. In addition to the formulation of the synthesized complex, superoxide dismutase (SOD) mimetic, and antimicrobial actions have also been the active goal of the work. A promising superoxide dismutazing potential with IC₅₀ = 69 μM was found. But on the other hand antibacterial action of the complex has shown less sensitivity to be called as efficient bactericidal agent.     

Synthesis and Structure of Zinc Complex of N, N-bis ( benzimidazol-2-yl-methyl ) amine

Histidine is known to be an important biological ligand present at the active site of superoxide dismutases (SOD)1-2 and other metalloproteins. It appears to play a crucial role in the coordination chemistry of numerous metalloproteins. The ligand of di(2-benzimidazolyl-methyl)amine (L3) was chosen as the model compound of histidine. This paper reports the synthesis and crystal structure of Zn-L3 complex which is as the model compound of SOD.The complex, Zn(L3)2((ClO4)2(C2H5OH(C32H30N1…     

Assembly of layer-by-layer films of superoxide dismutase and gold nanorods:A third generation biosensor for superoxide anion

Based on the layer-by-layer self-assembly of positively charged cetyltrimethylammonium bromide (CTAB) wrapped gold na- norods (AuNRs) and negatively charged superoxide dismutase (SOD) from their aqueous solutions on cysteine modified gold electrode (Cys/Au), a third generation electrochemical biosensor ((SOD/AuNRs)2/Cys/Au) for superoxide anion (O2·-) was developed. The two layers assembly of SOD/AuNRs can significantly enhance the direct electron transfer between SOD and the electrode. The functional enzym...     

Binuclear copper and zinc complexes possessing bio-potential ligands: synthesis,characterization, antimicrobial,SOD mimetic,DNA binding,and cleavage studies

Schiff bases (L) viz, N,N′,N′′,N′′′-tetra-3,4-dimethoxybenzalidene-3,3′-diaminobenzidine (TDBD), N,N′,N′′,N′′′-tetra-4-hydroxy-3-methoxybenzalidene-3,3′-diaminobenzidine (THMBD), and N,N′,N′′,N′′′-tetra-3-hydroxy-4-nitrobenzalidene-3,3′-diaminobenzidine (THNBD) afford binuclear [M₂LCl₄] complexes where M = Cu(II) or Zn(II). These Schiff bases and their binuclear complexes have been characterized by analytical and spectral data showing square-planar geometry on metalation with Cu²⁺. Intercalative binding of these complexes with DNA has been investigated by electronic absorption spectroscopy, viscosity measurements, cyclic voltammetry, and differential pulse voltammetry. Control DNA cleavage experiments using pUC19 supercoiled (SC) DNA and minor groove binder distamycin suggest that these synthesized complexes bind to the major groove. In the presence of a reducing agent like 3-mercaptopropionic acid (MPA), they show chemical nuclease activity. They also show an efficient photo-induced DNA cleavage on irradiation with a monochromatic UV light of 360 nm in the presence of inhibitors. Control experiments indicate the inhibition of cleavage in the presence of singlet oxygen quencher like sodium azide and the enhancement of cleavage in D₂O show the formation of singlet oxygen as reactive species. The superoxide dismutase (SOD)-mimetic activity of the synthesized complexes has been assessed for their ability to inhibit the reduction of nitroblue tetrazolium chloride (NBT). The complexes have promising SOD-mimetic activity. The antimicrobial results indicate that the complexes inhibit the growth of bacteria and fungi more than free ligands.     

Syntheses and characterization of new tetraazamacrocyclic copper(II) complexes as a dual functional mimic enzyme (catalase and superoxide dismutase)

A series of macrocyclic complexes, [Cu(TAAP)]X₂, X?=?ClO₄ and CH₃COO; [Cu(TAAP)X]X, X?=?NO₃, Cl, and Br, have been synthesized by self-condensation of 5-amino-3-methyl-l-phenylpyrazole-4-carbaldehyde (AMPC) in the presence of copper(II). Elemental analyses and conductivity measurements confirm the stoichiometry of the ligand and complexes, while the characteristic absorption bands in IR spectra confirmed the formation of ligand framework around copper. Square-pyramidal and square-planar stereochemistries have been proposed for the five-coordinate (nitrato and halogeno) and four-coordinate (perchlorate and acetate) complexes. The electrochemical properties and thermal behaviors have been studied by cyclic voltammetry and TGA. Mimetics of antioxidant enzymes such as superoxide dismutase (SOD) and catalase demonstrated that there is a correlation between the observed redox properties and the SOD and catalase biomimetic catalytic activities of the copper(II) complexes.     

A study on some macrocyclic bicopper(Ⅱ) complexes as the model compounds of superoxide dismutase

24-Membered macrocyclic bicopper(Ⅱ) complexes wth bridging ligand imidzao-late,SCN-,N3-and H2O respectively were synthesized by condensation of diacetylpyridine with 3-oxapentane-1,5-diamine.As the model compounds of superoxide dismutase (SOD),the relationship between their SOD activities and properties of bridging ligands and redox potentials of copper(Ⅱ) were studied.