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1.
A novel series of Co(II), Ni(II), Cu(II), Zn(II), and VO(IV) complexes has been synthesized from the Schiff base derived from 4-[(3,4-dimethoxybenzylidene)amino]-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one and 1,2-diaminobenzene. Structural features were determined by analytical and spectral techniques. Binding of synthesized complexes with calf thymus DNA (CT DNA) was studied by spectroscopic methods and viscosity measurements. Experimental results indicate that the complexes are able to form adducts with DNA and to distort the double helix by changing the base stacking. Lower DNA affinity of the VO(IV) complex is caused by the change of coordination geometry by the vanadyl ion resulting in a somewhat unfavorable configuration for the DNA binding. Oxidative DNA cleavage activities of the complexes were studied with supercoiled (SC) pUC19 DNA using gel electrophoresis; the mechanism studies revealed that the hydroxyl radical is likely to be the reactive species responsible for the cleavage of pUC19 DNA by the synthesized complexes. The in vitro antimicrobial screening effects of the investigated compounds were monitored by the disc diffusion method. The synthesized Schiff base complexes exhibit higher antimicrobial activity than the respective free Schiff base.  相似文献   

2.
Five tridecapeptide lactones, named theonellapeptolides Ia (1), Ib (2), Ic (3), Id (4), and Ie (5), were isolated from the Okinawan marine sponge Theonella swinhoei. Following the structure elucidation of theonellapeptolide Id (4), the structures of theonellapeptolides Ia (1), Ib (2), Ic (3), and Ie (5) were determined on the basis of chemical and physicochemical evidence including high performance liquid chromatography and circular dichroism combined analysis of the amino acid compositions. Theonellapeptolides Ib (2), Ic (3), Id (4), and Ie (5) exhibit moderate cytotoxic activity towards for L1210 in vitro (IC50 1.6, 1.3, 2.4, and 1.4 micrograms/ml, respectively), and theonellapeptolide Ie (5) exhibits ion-transport activities for Na+ and K+ ions.  相似文献   

3.
通过E-[4-[2-(4-羟基苯基)乙烯基]吡啶与1,n-二溴烷烃亲核取代反应合成了4,4′-[1,n-亚烷基双[(E)-2-(4-氧苯基)乙烯基]]双吡啶[n=2(Ia),3(Ib),4(Ic),6(Id)].用元素分析、红外、紫外和质子核磁共振谱鉴定了Ia~Id的结构.将Ia~Id的稀溶液用中压汞灯和低压汞灯交替照射,发现其分子内光环加成反应的存在,并且随着亚烷基碳链的延长,反应速度加快.研究还发现锌离子可以与吡啶环上氮原子发生螯合作用使分子内光环加成反应加快.本文化合物荧光很弱,在较高浓度下有较强分子间激基缔合物荧光.  相似文献   

4.
Few novel binuclear Schiff base metal complexes [M2LCl3], where M = Cu(II) and Zn(II); L= 2,6-bis-({2-[(3-hydroxy-4-nitrobenzylidene)amino]ethylimino}methyl)-4-methylphenol (BHEM), 2,6-bis-({2-[(3,4-dimethoxybenzylidene)amino]ethylimino} methyl)-4-methylphenol (BDEM) and 2,6-bis-({2-[(2,3,5-trichlorobenzylidene)amino]ethylimino}methyl)-4-methylphenol (BTEM), have been synthesized and characterized by analytical and spectral data. The data suggest that BHEM/BDEM/BTEM ligands afford square-pyramidal/distorted square-pyramidal geometry on metalation with Zn(II)/Cu(II). The binding behaviour of these complexes with DNA has been investigated using electronic absorption spectroscopy as well as viscosity and voltammetric measurements; the results show that they interact with DNA through intercalating way. From the DNA cleavage study of these complexes, investigated by gel electrophoresis, we found that they efficiently cleave supercoiled pUC19 DNA in the presence of a reducing agent (3-mercaptopropionic acid) and on irradiation with UV light of 360 nm wavelength. The mechanism reveals that singlet oxygen (1O2) plays a significant role in the photo cleavage. The superoxide dismutase (SOD) mimetic activity of the synthesized complexes demonstrates that most of the complexes have promising SOD-mimetic activity. The antimicrobial study indicates that the complexes inhibit the growth of bacteria and fungi more than the free ligands.  相似文献   

5.
The base-induced ring cleavage of 4-nitro-(Ia), 4-ethoxycarbonyl- (Ib) and 4-acetyl-5-methylisoxazole (Ic) and the conversion of the resulting β-cyanoenolates and β-enaminonitriles into 5-aminoazoles and 4-cyanoazoles was studied.  相似文献   

6.
New N2O2 donor type Schiff bases have been designed and synthesized by condensing acetylaceto-4-aminoantipyrine/acetoacetanilido-4-aminoantipyrine with 2-amino benzoic acid in ethanol. Solid metal complexes of the Schiff bases with Cu(II), Ni(II), Co(II), Mn(II), Zn(II), VO(IV), Hg(II) and Cd(II) metal ions were synthesized and characterized by elemental analyses, magnetic susceptibility, molar conduction, FAB Mass, IR, UV-Vis., 1H NMR, and ESR spectral studies. The data show that the complexes have a composition of the ML type. The UV-Vis., magnetic susceptibility, and ESR spectral data of the complexes suggest a square planar geometry around the central metal ion, except for VO(IV) complexes, which have square-pyramidal geometry. The redox behavior of copper and vanadyl complexes has been studied by cyclic voltammetry. The nuclease activity of the above metal complexes shows that the complexes cleave DNA through redox chemistry. In the presence of H2O2, all the complexes are capable of cleaving calf thymus DNA plasmids, in order to compare the cleavage efficiency of all metal complexes in the two different ligand environments. In this assay, Cu(II), Ni(II), Co(II), and Zn(II) exhibit more cleavage efficiency than other metal ions. This article was submitted by the authors in English.  相似文献   

7.
通过E-[4-[2-(4-羟基苯基)乙烯基]吡啶与1,n-二溴烷烃亲核取代反应合成了4,4’-[1,n-亚烷基双[(E)-2-(4-氧苯基)乙烯基]]双吡啶[n=2(Ia),3(Ib),4(Ic),6(Id)].用元素分析、红外、紫外和质子核磁共振谱鉴定了Ia-Id的结构.将Ia-Id的稀溶液用中压汞灯和低压汞灯交替照射,发现其分子内光环加成反应的存在,并且随着亚烷基碳链的延长,反应速度加快.研究还发现锌离子可以与毗陡环上氮原子发生螯合作用使分子内光环加成反应加快.本文化合物荧光很弱,在较高浓度下有较强分子间激基缔合物荧光.  相似文献   

8.
《Liquid crystals》1998,25(6):655-660
Two binary mixtures, prepared from either 4-cyanophenyl 4-hexadecyloxybenzoate (Ib) or 4-nitrophenyl 4-hexadecyloxybenzoate (Ic), with 4-carboxyphenyl 4-hexadecyloxybenzoate (Ia), were thermally characterized to construct the phase diagrams for the two systems Ia/Ib and Ia/Ic. Due to differences in the smectic layering between the individual components of each system, phase separation took place either in the solid or in the mesophase. A mathematical relation was derived to calculate the composition of each phase in the solid state. Another two phase diagrams were constructed for binary mixtures of the linear dimer molecule, 4-hexadecyloxybenzoic acid (III) with either the acid Ia or its isomeric derivative, 4-hexadecyloxyphenyl 4-carboxybenzoate (II).  相似文献   

9.
The photoinduced exchange reactions of cytosine (Ia) and 5-methylcytosine (IIa) with N alpha-acetyl-L-lysine, a derivative of the common amino acid L-lysine, were studied. These reactions of Ia and IIa at pH 7.5 produce, respectively, 2-N-acetylamino-6-(1-cytosinyl)hexanoic acid (Ib) and 2-N-acetylamino-6-(1-(5-methylcytosinyl]hexanoic acid (IIb) as major final products. In addition, small amounts of the corresponding deamination products were formed in the 5-methylcytosine-N alpha-acetyl-L-lysine and cytosine-N alpha-acetyl-L-lysine systems, namely 2-N-acetylamino-6-(1-thyminyl)-hexanoic acid and 2-N-acetylamino-6-(1-uracilyl)hexanoic acid. The compounds Ib and IIb were deacetylated by acid hydrolysis to yield the corresponding lysine products: 2-amino-6-(1-cytosinyl)hexanoic acid (Ic) and 2-amino-6-(1-(5-methylcytosinyl]hexanoic acid (IIc). The compound Ic was identified as a product in the photoreaction of cytosine with L-lysine at near neutral pH, while IIc is found as a product in the corresponding reaction of 5-methylcytosine. The occurrence of the above photoexchange reactions at pH values near those found in physiological systems could have biological implications; in particular, our observations suggest that cytosine and 5-methylcytosine residues, contained in DNA, might react with the epsilon-amino groups of lysine residues in proteins upon UV irradiation of nucleosomes and other DNA-protein complexes under physiological conditions.  相似文献   

10.
Two binary mixtures, prepared from either 4-cyanophenyl 4-hexadecyloxybenzoate (Ib) or 4-nitrophenyl 4-hexadecyloxybenzoate (Ic), with 4-carboxyphenyl 4-hexadecyloxybenzoate (Ia), were thermally characterized to construct the phase diagrams for the two systems Ia/Ib and Ia/Ic. Due to differences in the smectic layering between the individual components of each system, phase separation took place either in the solid or in the mesophase. A mathematical relation was derived to calculate the composition of each phase in the solid state. Another two phase diagrams were constructed for binary mixtures of the linear dimer molecule, 4-hexadecyloxybenzoic acid (III) with either the acid Ia or its isomeric derivative, 4-hexadecyloxyphenyl 4-carboxybenzoate (II).  相似文献   

11.
A new series of transition metal complexes of Cu(II), Ni(II), Co(II), Mn(II), Zn(II), Cd(II), Hg(II), and VO(IV) have been designed and synthesized from the Schiff base derived from cinnamidene-4-aminoantipyrine and 2-aminophenol by involving the carbonyl group of 4-aminoantipyrine. The structural features have been arrived from their elemental analyses, magnetic susceptibility, molar conduction, FAB mass, IR, UV-Vis, 1H NMR and ESR spectral studies. The data show that the complexes have composition of the ML2 type. The UV-Vis, magnetic susceptibility, and ESR spectral data of the complexes suggest an octahedral geometry around the central metal ion except the VO(IV) complex, which has a square-pyramidal geometry. The redox behavior of the copper and vanadyl complexes has been studied by cyclic voltammetry. The antimicrobial activity of the ligand and its complexes has been extensively studied on microorganisms such as Salmonella typhi, Staphylococcus aureus, Escherichia coli, Bacillus subtilis, Aspergillus niger, and Rhizoctonia bataicola. It has been found that most of the complexes have higher activities than that of the free ligand. The nuclease activity of the above metal complexes shows that the complexes cleave DNA through redox chemistry. In the presence of H2O2, the complexes are capable of cleaving calf thymus DNA. The text was submitted by the authors in English.  相似文献   

12.
Mass spectra of two diaroylglyoximes (Ia and Ib) are reported and compared with those of the corresponding dehydration products, 3,4-diaroyl-1,2,5-oxadiazoles (IIIa and IIIb, respectively). In Ia and Ib, unlike in diarylglyoximes (Id and Ie), the largest ion is [M — 18]+, but this does not form in the ion source by a simple thermal dehydration. Similar spectra have been obtained for an alkyl aroyl derivative of glyoxime (Ic) and an isonitroso-β-diketone (II). A specific electron-impact-induced rearrangement leading to the formation of carboxylic acids has been observed in the mass spectra of all the acylated oximes under investigation.  相似文献   

13.
Two novel Schiff bases, 4,4′-methylenedianilidene-bis(3-methoxy-4-hydroxy-benzaldehyde) (L1) and 4,4′-methylenedianilidene-bis(3,4-dimethoxybenzaldehyde) (L2), have been prepared by condensing 4,4′-methylenedianiline (MDA) with vanillin and 3,4-dimethoxybenzaldehyde (DMB) respectively in ethanolic medium. Metal complexes of the above Schiff bases are prepared from salts of Cu(II), Zn(II), Co(II) and VO(IV). They are characterized by elemental analysis, molar conductivity, magnetic moment measurements, IR, 1H NMR, UV-Vis., FAB Mass, and EPR spectra. The elemental analysis data exhibit the formation of 1: 1 [M: L] ratio. The mode of bonding and the geometry of the complexes have been confirmed on the basis of IR, UV-Vis. and magnetic moment measurements. These data reveal a square-planar geometry for all the complexes except VO(IV) which has square-pyramidal geometry. The molar conductance measurements of the Schiff base complexes reveal the existence of non-electrolytic nature. The interactions of complexes with calf thymus DNA (CT-DNA) have been investigated by electronic absorption spectroscopy, viscosity measurements and cyclic voltammetry. The results indicate that the complex can bind to DNA by intercalation modes. The Schiff bases and their metal complexes have been evaluated for their antifungal and antibacterial activities against different species of pathogenic fungi and bacteria and their results are compared with standard drugs.  相似文献   

14.
Four novel oxovanadium(IV) binuclear complexes have been synthesized, namely [(VO)2(IPHTA) (L)2SO4 (L denotes 2,2′-bipyridine (bpy); 1,10-phenanthroline (phen); 4,4′-dimethyl-2,2′-bipyridine (Me2bpy) and 5-nitro-1,10-phenanthroline (NO2-phen)), where IPHTA is the isophthalate dianon. Based on elemental analyses, molar conductivity measurements, IR and electronic spectra studies, it is proposed that these complexes have IPHTA-bridged structures and consist of two vanadium(IV) atoms in a square-pyramidal environment. The complexes [(VO)2(IPHTA)(Me2bpy)2]SO4 (1) and [(VO)2(IPHTA)(bpy)2]SO4 (2) were characterized by variable temperature magnetic susceptibility (4–300 K) and the data could be well fitted by the least-squares method to a susceptibility equation derived from the spin Hamiltonian operator, . The exchange integral, J, was found to be −26.8 cm−1 for (1) and −31.0 cm−1 for (2). These results are commensurate with antifferomagnetic interactions between two oxovanadium(IV) ions within each molecule. The influence of different terminal ligands on magnetic interactions between the metals of this kind of complexes is also discussed.  相似文献   

15.
Russian Journal of Coordination Chemistry - Complexes CuL1 ? MeOH (Ia), NiL1 ? MeOH (Ib), CоL1 ? MeOH (Ic), CuL2 (IIa), NiL2 (IIb), and CоL2 (IIc) of the tetradentate...  相似文献   

16.
The ligand 3-[2,2'-methylenebis(4,6-di- tert-butylphenol)-5- tert-butylsalicylidene-(2,6-diisopropyl)phenylimine] (L(1)H 3) was reacted with MCl 4 (M = Ti, Zr) or MCl 5 (M = Nb, Ta) to give complexes of the type [MCl 2(L(1)H 2) 2] (M = Ti (1); Zr (2)), [NbCl 3( L (1)H)] (3), or [TaCl 4(L(1)H 2)] (4), respectively. Single crystal X-ray diffraction of 1- 4 revealed common "iminium" species resulting in zwitterionic complexes. Reaction of [V(N p-tol)(O n-Pr) 3] with L (1)H3 afforded [{(VN p-tol)(L(1)H)} 2(mu-O n-Pr)2] (5), and a second complex [(VO) 2(mu-O)(L(3)H) 2] (6)(L(3)H being derived from 3-[2,2'-methylenebis(4,6-di-tert-butylphenol)-5-tert-butylsalicylidene- p-tolylimine]). The condensation reaction between 3-[2,2'-methylenebis(4,6-di-tert-butylphenol)-5-tert-butyl-2-hydroxybenzaldehyde] (L(0)H 3) and o-phenylenediamine (1,2-diaminobenzene) afforded two products: a pseudo-16-membered hydrogen bonded macrocyclic structure {1,2-bis-3-[2,2'-methylenebis(4,6-di-tert-butylphenol)-5-tert-butylsalicylidene-benzyldiimine]} (L(5)H6), or the benzimidazolyl bearing ligand (L(6)H 3). The reaction of L (5)H6 or L(6)H 3 with [VO(O n-Pr) 3] under varying conditions produced the complexes [(VO)(L(5)H 4)] (7), [(VO) 2(L(5)H)] (8), or [VO(L(6)H 2) 2] (9). L (0)H 3 was reacted with a number of anilines to give the proligands {3-[2,2'-methylenebis(4,6-di- tert-butylphenol)-5-tert-butylsalicylidene-R-imine]}, where R = NC 6H 5 (L(2)H3), NC 6H 4-Me (L(3)H 3), and NC 6H 2-Me 3 (L(4)H 3). Reactions of these ligands with [VO(O n-Pr) 3] formed bischelating complexes of the form [(VO)(L(2-4)H 2)2] (10, 11, and 12, respectively). The reaction of L (1)H 3 with trimethylaluminum led to a bis-aluminum complex {(AlMe 2)[AlMe(NCMe)] L (1)} (13). The ability of complexes 1-12 to polymerize ethylene in the presence of an organoaluminum cocatalyst was investigated. Procatalysts 1 and 2 were found to produce negligible activities in the presence of dimethylaluminum chloride (DMAC) and the reactivator ethyltrichloroacetate (ETA), whereas 3 and 4 were found to be completely inactive for polymerization using a variety of different organoaluminum cocatalysts. Using the combination of DMAC and ETA, complexes 5-12 were found to be highly active catalysts; in all cases, the polymer formed was of high molecular weight linear polyethylene.  相似文献   

17.
Chelates of the type M(L)2 {where, M ?= ?Co(II), Ni(II) and Cu(II), and L ?= ?3-{(E)-[(2-hydroxy-3-methoxyphenyl)methylidene]amino}pyridin-4(1H)-one)} were synthesized by using the Schiff base ligand in the stochiometric ratio 2:1 (L:M) and Schiff base ligand (L) was synthesized by simple condensation between 2-hydroxy-3-methoxybenzaldehyde with 3-aminopyridin-4-ol. The structure and formation of synthesized compounds were established by different analytical and spectroscopic methods like, elemental analysis, UV- spectroscopy, FT-IR, Proton and Carbon NMR, mass spectrometry and Powder XRD. Further, the synthesized chelates screened for the DNA binding studies of Calf Thymus (CT)-DNA by exploiting electronic absorption spectra, relative viscosity measurements and thermal denaturation methods. The proposed DNA binding mode supports the enhancement in the binding activity of the complexes in presence of newly synthesized ligand. The cleavage activities of the PUC-18 DNA in the presence and the absence of the complexes were recorded with the help of gel-electrophoresis. The cleavage experiment results reveals that all the synthesized chelates can cleave pUC-18 DNA effectively.  相似文献   

18.
2-Phenyl-2-hydroxyethyl(aquo)cobaloxime(Ia) and the p-methyl (Ib) and p-cyano (Ic) derivatives have been synthesized and characterized. The parent compound and the p-methyl derivative decompose spontaneously both in the solid state and in methanol to give mixtures of the appropriate styrenes and acetophenones. Kinetics and product ratios of the decomposition of Ia and Ib in methanol have been studied as a function of temperature. Evidence is presented that both reaction pathways are ionic in nature and that an intermediate (presumed to be a phenethylcobaloxime carbonium ion) is involved in the styrene forming pathway. Acetophenones are apparently formed via a 1,2-hydride shift mechanism with solvent acting as a general base. Both reaction pathways show a large substituent effect with electron donating substituents increasing reactivity, Ic proved to be extraordinarily stable in methanol but decomposed readily in aqueous sulfuric acid to produce primarily p-cyanoacetophenone. Kinetic evidence for formation of a cationic intermediate is presented.  相似文献   

19.
Vanadium(IV) and -(III) complexes of a tetradentate N(2)OS Schiff base ligand H(2)L [derived from methyl 2-((beta-aminoethyl)amino)cyclopent-1-ene-1-dithiocarboxylate and salicylaldehyde] are reported. In all the complexes, the ligand acts in a bidentate (N,O) fashion leaving a part containing the N,S donor set uncoordinated. The oxovanadium(IV) complex [VO(HL)(2)] (1) is obtained by the reaction between [VO(acac)(2)] and H(2)L. In the solid state, compound 1 has two conformational isomers 1a and 1b; both have been characterized by X-ray crystallography. Compound 1a has the syn conformation that enforces the donor atoms around the metal center to adopt a distorted tbp structure (tau = 0.55). Isomer 1b on the other hand has an anti conformation with almost a regular square pyramidal geometry (tau = 0.06) around vanadium. In solution, however, 1 prefers to be in the square pyramidal form. A second variety of vanadyl complex [VO(L(cyclic))(2)](I(3))(2) (2) with a new bidentate O,N donor ligand involving isothiazolium moiety has been obtained by a ligand-based oxidation of the precursor complex 1 with iodine. Preliminary X-ray and FAB mass spectroscopic data of 2 have supported the formation of a heterocyclic moiety by a ring closure reaction involving a N-S bond. Vanadium(III) complex [V(acac)(HL)(2)] (3) has been obtained through partial ligand displacement of [V(acac)(3)] with H(2)L. Compound 3 has almost a regular octahedral structure completed by two bidentate HL ligands along with an acetylacetonate molecule. Electronic spectra, magnetism, EPR, and redox properties of these compounds are reported.  相似文献   

20.
Reaction of the tridentate ONO Schiff-base ligand 2-hydroxybenzoylhydrazone of 2-hydroxybenzoylhydrazine (H2L) with VO(acac)2 in ethanol medium produces the oxoethoxovanadium(V) complex [VO(OEt)L] (A), which reacts with pyridine to form [VO(OEt)L.(py)] (1). Complex 1 is structurally characterized. It has a distorted octahedral O4N2 coordination environment around the V(V) acceptor center. Both complexes A and 1 in ethanol medium react with neutral monodentate Lewis bases 2-picoline, 3-picoline, 4- picoline, 4-amino pyridine, imidazole, and 4-methyl imidazole, all of which are stronger bases than pyridine, to produce dioxovanadium(V) complexes of general formula BH[VO2L]. Most of these dioxo complexes are structurally characterized, and the complex anion [VO2L]- is found to possess a distorted square pyramidal structure. When a solution/suspension of a BH[VO2L] complex in an alcohol (ROH) is treated with HCl in the same alcohol, it is converted into the corresponding monooxoalkoxo complex [VO(OR)L], where R comes from the alcohol used as the reaction medium. Both complexes A and 1 produce the 4,4'-bipyridine-bridged binuclear complex [VO(OEt)L]2(mu-4,4'-bipy) (2), which, to the best of our knowledge, represents the first report of a structurally characterized 4,4'-bipyridine-bridged oxovanadium(V) binuclear complex. Two similar binuclear oxovanadium(V) complexes 3 and 4 are also synthesized and characterized. All these binuclear complexes (2-4), on treatment with base B, produce the corresponding mononuclear dioxovanadium(V) complexes (5-10).  相似文献   

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