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991.
Mohammad A. Alim A.K. BatraSudip Bhattacharjee M.D. Aggarwal 《Physica B: Condensed Matter》2011,406(5):1088-1095
The lithium niobate (LiNbO3 or LN) single crystal is grown in-house. The ac small-signal electrical characterization is conducted over a temperature range 35≤T≤150 °C as a function of measurement frequency (10≤f≤106 Hz). Meaningful observation is noted only in a narrow temperature range 59≤T≤73 °C. These electrical data when analyzed via complex plane formalisms revealed single semicircular relaxation both in the complex capacitance (C?) and in the modulus (M?) planes. The physical meaning of this kind of observation is obtained on identifying the relaxation type, and then incorporating respective equivalent circuit model. The simplistic non-blocking nature of the equivalent circuit model obtained via M?-plane is established as the lumped relaxation is identified in the C?-plane. The feature of the eventual equivalent circuit model allows non-blocking aspect for the LN crystal attributing to the presence of the operative dc conduction process. Identification of this leakage dc conduction via C?-plane is portrayed in the M?-plane where the blocking nature is removed. The interacting interpretation between these two complex planes is successfully presented. 相似文献
992.
The trans influence of various phosphine ligands (L) in direct as well as dissociative reductive elimination pathways yielding CH(3)CH(3) from Pd(CH(3))(2)L(2) and CH(3)Cl from Pd(CH(3))(Cl)L(2) has been quantified in terms of isodesmic reaction energy, E(trans), using the MPWB1K level of density functional theory. In the absence of a large steric effect, E(trans) correlated linearly with the activation barrier (E(act)) of both direct and dissociation pathways. The minimum of molecular electrostatic potential (V(min)) at the lone pair region of phosphine ligands has been used to assess their electron donating power. E(trans) increased linearly with an increase in the negative V(min) values. Further, the nature of bonds that are eliminated during reductive elimination have been analyzed in terms of AIM parameters, viz. electron density (ρ(r)), Laplacian of the electron density (?(2)ρ(r)), total electron energy density (H(r)), and ratio of potential and kinetic electron energy densities (k(r)). Interestingly, E(act) correlated inversely with the strength of the eliminated metal-ligand bonds measured in terms of the bond length or the ρ(r). Analysis of H(r) showed that elimination of the C-C/C-Cl bond becomes more facile when the covalent character of the Pd-C/Pd-Cl bond increases. Thus, AIM details clearly showed that the strength of the eliminated bond is not the deciding factor for the reductive elimination but the nature of the bond, covalent or ionic. Further, a unified picture showing the relationship between the nature of the eliminated chemical bond and the tendency of reductive elimination is obtained from the k(r) values: the E(act) of both direct and dissociative mechanisms for the elimination of CH(3)CH(3) and CH(3)Cl decreased linearly when the sum of k(r) at the cleaved bonds showed a more negative character. It means that the potential electron energy density dominates over the kinetic electron energy density when the bonds (Pd-C/Pd-Cl) become more covalent and the eliminated fragments attain more radical character leading to the easy formation of C-C/C-Cl bond. 相似文献
993.
Ramakrishnan S Shakthipriya D Suresh E Periasamy VS Akbarsha MA Palaniandavar M 《Inorganic chemistry》2011,50(14):6458-6471
The dinuclear copper(II) complexes [Cu(2)(LH)(2)(diimine)(2)(ClO(4))(2)](ClO(4))(2) (1-4), where LH = 2-hydroxy-N-[2-(methylamino)ethyl]benzamide and diimine = 2,2'-bipyridine (bpy; 1), 1,10-phenanthroline (phen; 2), 5,6-dimethyl-1,10-phenanthroline (5,6-dmp; 3), and dipyrido[3,2-d:2',3'-f]quinoxaline (dpq; 4), have been isolated and characterized. The X-ray crystal structure of complex 1 contains two copper(II) centers bridged by the phenolate moiety of the amide ligand. All of the complexes display a ligand-field band (630-655 nm) and the PhO(-)-to-Cu(II) ligand-to-metal charge-transfer band (405-420 nm) in solution. Absorption and emission spectral studies and viscosity measurements indicate that complex 4 interacts with calf thymus DNA more strongly than all of the other complexes through strong partial intercalation of the extended planar ring (dpq) with a DNA base stack. Interestingly, 3 exhibits a DNA binding affinity higher than 2, suggesting the involvement in hydrophobic interaction of coordinated 5,6-dmp with the DNA surface. In contrast to the increase in relative viscosities of DNA bound to 2-4, a decrease in viscosity of DNA bound to 1 is observed, indicating a shortening of the DNA chain length through formation of kinks or bends. All of the complexes exhibit an ability to cleave DNA (pUC19 DNA) in a 5% DMF/5 mM Tris-HCl/50 mM NaCl buffer at pH 7.1 in the absence of an oxidant at 100 μM complex concentration, which varies as 4 > 2 > 1 > 3. The order of DNA the cleavage ability at 30 μM concentration in the presence ascorbic acid is 4 > 2 > 1 > 3, and, interestingly, 4 alone shows an ability to convert supercoiled DNA into nicked-coiled DNA even at 6 μM concentration, beyond which complete degradation is observed and the pathway of oxidative DNA cleavage involves hydroxyl radicals. In the presence of distamycin, all of the complexes, except 3, show decreased DNA cleavage activity, suggesting that the complexes prefer to bind in the DNA minor groove. All of the complexes exhibit prominent DNA cleavage even at very low concentrations (nM) in the presence of H(2)O(2) as an activator, with the order of cleavage efficiency being 3 > 2 > 4 > 1. Studies on the anticancer activity toward HEp-2 human larynx cell lines reveal that the ability of the complexes to kill the cancer cell lines varies as 3 > 4 > 2 > 1. Also, interestingly, the IC(50) value of 3 is lower than that of cisplatin, suggesting that the hydrophobicity of methyl groups on the 5 and 6 positions of the complex enhances the anticancer activity. The mode of cell death effected by the complex has been explored by using various biochemical techniques like comet assay, mitochondrial membrane potency, and Western blotting. The complex has been found to induce nuclear condensation and fragmentation in cell lines. Also, it triggers activation of caspases by releasing cytochrome c from mitochondria to cytosol, suggesting that it induces apoptosis in cells via the mitochondrial pathway. 相似文献
994.
Kalidindi SB Yusenko K Fischer RA 《Chemical communications (Cambridge, England)》2011,47(30):8506-8508
The organometallic host-guest chemistry of porous covalent organic frameworks is explored by vapour phase infiltration of volatile organometallic precursors; namely, [Fe(η(5)-C(5)H(5))(2)], [Co(η(5)-C(5)H(5))(2)], and [Ru(cod)(cot)]. The unique arrangement of ferrocene molecules inside COF-102 is driven by π-π (host-guest) interactions and replicates the framework symmetry. 相似文献
995.
Kazi Sabnam BanuSandip Mondal Averi GuhaSudhanshu Das Tanmay ChattopadhyayEringathodi Suresh Ennio Zangrando 《Polyhedron》2011,30(1):163-168
Three new polymeric complexes of cadmium(II) with imidazole and its derivatives [imidazole (Im), benzimidazole (Bim) and 1-methylimidazole (Mim)] mediated by thiocyanate and dicyanamide (dca) anions have been synthesized and characterized by X-ray single crystal structure analysis. The structure analyses reveal that complexes [Cd(SCN)2(Bim)2]n (1) and [Cd(dca)2(Im)2]n (2) are 1D coordination polymers, whereas complex [Cd(dca)2(Mim)2]n (3) adopts a 2D network of (4, 4) topology and thereby suggests that the dimensionality of the coordination polymers are affected by the choice of the counter anions and by the organic ligands. All the species exhibit interesting luminescence property in methanol and in solid state originated from ligands-centered π-π* transitions. The π-π interactions occurring between organic rings (Im, Mim, and Bim) are observed to be important in controlling the fluorescence property of the species. 相似文献
996.
Abstract
Direct reductive amination of 1,3-diphenyl-1H-pyrazole-4-carbaldehyde and 3-(4-methylphenyl)-1-phenyl-1H-pyrazole-4-carbaldehyde with various substituted aromatic amines using NaBH4 in the presence of I2 as reducing agent is described. The reaction has been carried out in anhydrous methanol under neutral conditions at room temperature. The structure of newly synthesized diphenyl pyrazolylmethylanilines was established on the basis of IR, 1H, 13C NMR, and mass spectral data. All diphenyl pyrazolylmethylaniline derivatives were tested in vitro for their antifungal and antibacterial activity against different strains of fungi and bacteria. Most of the compound exhibited considerable antifungal activity but poor antibacterial activity against the test strains. 相似文献997.
G. ShankaraiahR. Sateesh Chandra Kumar B. PoornimaK. Suresh Babu 《Tetrahedron letters》2011,52(38):4885-4887
A simple and efficient stereoselective synthesis of naturally occurring pyrrolidine alkaloid, radicamine B has been accomplished in 13 steps from the commercially available starting materials with an overall yield of 9.75%. The synthesis utilizes Sharpless asymmetric epoxidation and Horner-Wadsworth-Emmons (HWE) olefination as key steps. 相似文献
998.
A. Vijay KumarV. Prakash Reddy C. Suresh ReddyK. Rama Rao 《Tetrahedron letters》2011,52(31):3978-3981
An efficient and conceptually new protocol for C-Se cross coupling of potassium selenocyanate with aryl halides via copper-catalyzed cascade reaction has been developed in water. Utilizing this protocol, a variety of aryl and heteroaryl halides were reacted with potassium selenocyanate to afford the corresponding diaryl selenides in moderate to good yields. 相似文献
999.
Solid-supported nano- and microparticles of Pd(0) (SS-Pd) were used as heterogeneous catalysts for aerobic oxidation of benzyl alcohols. Primary and secondary benzyl alcohols gave the corresponding products in good yields. In addition, the catalysts could be reused up to five runs without significant loss of activities. 相似文献
1000.
A fluorescent Zn2+ sensor based on the 2-(2-nitrostyryl)-8-methoxyquinoline (2-nitroSQ) has been designed, synthesized, and characterized by various spectral techniques. The designed fluorophore displays high selectivity, sensitive fluorescence enhancement (13-fold), and strong binding affinity toward Zn2+ among the various biologically significant metal ions examined in ACN-H2O (9:1, v/v). 相似文献