Reaction of Cu(II) nitrate with a new pyrazole-based Schiff base ligand, 5-methyl-3-formylpyrazole-N-(2′-methylphenoxy)methyleneimine (MPzOA), afforded two types of Cu(II) complexes at different reaction temperatures, [Cu(MPzOA)(NO3)]2 (1) and [Cu(3,7,11,15-tetramethylporphyrin)(H2O)](NO3)2 (2), reported together with a Ni(II) complex, [Ni(MPzOA)2(H2O)2]Br2 (3). The compounds are characterized by single crystal X-ray structure analyses along with several physico-chemical and spectral parameters. Complex 1 is authenticated as a bis(μ-pyrazolato)dicopper(II), while 2 is a porphyrinogen and 3 is a distorted octahedral complex. Structural analyses of the complexes reveal that 1 crystallized in monoclinic P21/n space group while 2 and 3 crystallized in monoclinic C2/c space group. DNA-binding studies of the complexes have shown that the complexes interact with CT-DNA. DNA-cleavage studies with plasmid DNA have shown that 1 and 2 induce extensive DNA cleavage in the presence of H2O2 as an additive, whereas there is no change in degradation of super-coiled DNA by 3 in the presence of additive. The antimicrobial studies of the complexes against Escherichia coli DH5α bacteria strain indicated that all the complexes were capable of killing E. coli with different LD50 values. 相似文献
In this paper we present a spectral technique for building asymptotic expansions which describe periodic processes in conservative and self-excited systems without assuming the oscillations to be weakly nonlinear. The small parameter of the expansion is connected with the ratio of the amplitudes of higher than the first harmonics in contrast to the traditional parameter connected with weak nonlinearity. In the case of an oscillator with power nonlinearity the frequency of the main harmonic and the complex amplitudes of higher harmonics are computed as the expansions of either integer (for weakly nonlinear oscillations) or algebraic (for strong nonlinearity) functions of the complex amplitude of the first harmonic depending on the character of the initial conditions and the maximum power of the nonlinear term in the equation. In the simplest case of weakly nonlinear oscillations the complete asymptotic expansion is shown to be valid in the whole domain of the periodic motions of definite type until the separatrix is reached. The expressions for the first terms of the expansion for concrete examples coincide with the expressions obtained both with the use of other methods and by expanding the exact solutions. For some special cases of the strongly nonlinear oscillations the comparison of the results with known exact solutions is carried out as well as the criteria of convergence of the expansions are determined. 相似文献
Two Ni(II) complexes, [Ni(pbth)2] and [Ni(ptt)2(en)2] {Hpbth = N-picolinoyl-N′-benzothioylhydrazide, Hptt = 5-(pyridine-4-yl)-2H-1,2,4-triazole-3-thione} have been synthesized and characterized by physico-chemical and spectroscopic methods. [Ni(pbth)2] contains a pair of N-picolinoyl-N′-benzothioylhydrazide ligands coordinated via their thione sulfur, pyridyl nitrogen and hydrazinic nitrogen atoms, forming two C2N2Ni and two CSN2Ni five-membered chelate rings. The intermediate compound 1-isonicotinoyl-3-thiosemicarbazide is converted to 5-(pyridine-4-yl)-2H-1,2,4-triazole-3-thione in the presence of ethanolic NaOH, giving the complex [Ni(ptt)2(en)2] in which the ptt ligands coordinate through their triazole ring nitrogen atoms, while four more nitrogens from two ethylenediamine ligands complete the octahedral structure. The crystal structures of the complexes involve various types of intermolecular extended hydrogen bonds, forming supramolecular frameworks. Cyclic voltammetry studies of both complexes show quasi-reversible redox behavior. Density Functional Theory electronic structure calculations corroborate our experimental findings. 相似文献
Reported are multi‐component one‐pot syntheses of chiral complexes [M(LROR′)Cl2] or [M(LRSR′)Cl2] from the mixture of an N‐substituted ethylenediamine, pyridine‐2‐carboxaldehyde, a primary alcohol or thiol and MCl2 utilizing in‐situ formed cyclized Schiff bases where a C?O bond, two stereocenters, and three C?N bonds are formed (M=Zn, Cu, Ni, Cd; R=Et, Ph; R′=Me, Et, nPr, nBu). Tridentate ligands LROR′ and LRSR′ comprise two chiral centers and a hemiaminal ether or hemiaminal thioether moiety on the dipicolylamine skeleton. Syn‐[Zn(LPhOMe)Cl2] precipitates out readily from the reaction mixture as a major product whereas anti‐[Zn(LPhOMe)Cl2] stays in solution as minor product. Both syn‐[Zn(LPhOMe)Cl2] and anti‐[Zn(LPhOMe)Cl2] were characterized using NMR spectroscopy and mass spectrometry. Solid‐state structures revealed that syn‐[Zn(LPhOMe)Cl2] adopted a square pyramidal geometry while anti‐[Zn(LPhOMe)Cl2] possesses a trigonal bipyramidal geometry around the Zn centers. The scope of this method was shown to be wide by varying the components of the dynamic coordination assembly, and the structures of the complexes isolated were confirmed by NMR spectroscopy, mass spectrometry, and X‐ray crystallography. Syn complexes were isolated as major products with ZnII and CuII, and anti complexes were found to be major products with NiII and CdII. Hemiaminals and hemiaminal ethers are known to be unstable and are seldom observed as part of cyclic organic compounds or as coordinated ligands assembled around metals. It is now shown, with the support of experimental results, that linear hemiaminal ethers or thioethers can be assembled without the assistance of Lewis acidic metals in the multi‐component assembly, and a possible pathway of the formation of hemiaminal ethers has been proposed. 相似文献
Targeted residue screening requires the use of reference substances in order to identify potential residues. This becomes a difficult issue when using multi-residue methods capable of analyzing several hundreds of analytes. Therefore, the capability of in silico fragmentation based on a structure database (“suspect screening”) instead of physical reference substances for routine targeted residue screening was investigated. The detection of fragment ions that can be predicted or explained by in silico software was utilized to reduce the number of false positives. These “proof of principle” experiments were done with a tool that is integrated into a commercial MS vendor instrument operating software (UNIFI) as well as with a platform-independent MS tool (Mass Frontier). A total of 97 analytes belonging to different chemical families were separated by reversed phase liquid chromatography and detected in a data-independent acquisition (DIA) mode using ion mobility hyphenated with quadrupole time of flight mass spectrometry. The instrument was operated in the MSE mode with alternating low and high energy traces. The fragments observed from product ion spectra were investigated using a “chopping” bond disconnection algorithm and a rule-based algorithm. The bond disconnection algorithm clearly explained more analyte product ions and a greater percentage of the spectral abundance than the rule-based software (92 out of the 97 compounds produced ≥1 explainable fragment ions). On the other hand, tests with a complex blank matrix (bovine liver extract) indicated that the chopping algorithm reports significantly more false positive fragments than the rule based software.
3-(Phenylseleno) propylammonium acetate, C9H14NSe+ C2H3O2–, L1, the first example of a selenium bearing acetate salt has been synthesized and characterized by spectroscopic, NMR, DSC and
single crystal X-ray crystallographic techniques. L1 crystallizes with one cation–anion pair in the asymmetric unit. Reactions of L1 with four different metal salts revealed four new selenium bearing compounds (1–4) whose identities are characterized by spectroscopic and NMR techniques. The crystal structure of Compound 1, [C9H14NSe]2+ [ClO4]2–, whose crystal structure has been confirmed. It crystallizes with two independent cation–anion pairs in the asymmetric unit.
Both L1 and Compound 1 display strong N–H···O hydrogen bond intermolecular interactions which help stabilize crystal packing in the unit cell. 相似文献
Compared to pyrolytic graphite (PG) and pyrolytically coated polycrystalline graphite (PCPG), which are commonly employed substrates for graphite furnace atomic absorption spectrometry (GFAAS), highly oriented pyrolytic graphite (HOPG) is characterized by a high degree ofc-axis alignment with relatively few active sites and imperfections present on the surface. The usefulness of HOPG and commercial PG platforms for the determination of lead, copper, and aluminum by GFAAS was compared. Qualitative comparison of the absorption profiles and temperature optimizations suggest that lead, copper with a chemical modifier (palladium), and aluminum interact similarly with the two graphite substrates, while copper without a modifier interacts less strongly with HOPG than with PG. These results are in agreement with previous studies that have demonstrated that copper interacts strongly with PG and PCPG. HOPG and PG were employed for the determination of a pine needles standard reference material (SRM) and Fraser fir (Abies fraseri) samples. The analyses of the SRM gave good agreement with the certified value using both substrates, and comparable values were obtained for the samples. These results suggest that HOPG may be useful as a model for PG or PCPG when techniques such as scanning tunneling microscopy that require a high degree ofc-axis alignment are employed. 相似文献
A two-photon Ramsey-fringe experiment with a supersonic beam of SF6 has been performed with an interzone distance of up to 50 cm. Using a He-seeded beam with 50% of SF6, the two-photon transition P(4)E0 in the 2ν3 band reveals its magnetic hyperfine structure and the periodicity of the fringes is 500 Hz. The strength of the central fringe
of the main hyperfine component corresponds to a flux of 1010–1011useful molecules/s, which is very promising for a new frequency standard in the 30-THz spectral region.
Received: 27 April 2001 / Revised version: 18 June 2001 / Published online: 18 July 2001 相似文献