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排序方式: 共有171条查询结果,搜索用时 15 毫秒
1.
Dhar S Senapati D Das PK Chattopadhyay P Nethaji M Chakravarty AR 《Journal of the American Chemical Society》2003,125(40):12118-12124
A new class of ternary copper(II) complexes of formulation [Cu(L(n)B](ClO(4)) (1-4), where HL(n) is a NSO-donor Schiff base (HL(1), HL(2)) and B is a NN-donor heterocyclic base viz. 1,10-phenanthroline (phen) and 2,9-dimethyl-1,10-phenanthroline (dmp), are prepared, structurally characterized, and their DNA binding and photocleavage activities studied in the presence of red light. Ternary complex [Cu(L(3))(phen)](ClO(4)) (5) containing an ONO-donor Schiff base and a binary complex [Cu(L(2))(2)] (6) are also prepared and structurally characterized for mechanistic investigations of the DNA cleavage reactions. While 1-4 have a square pyramidal (4 + 1) CuN(3)OS coordination geometry with the Schiff base bonded at the equatorial sites, 5 has a square pyramidal (4 + 1) geometry with CuN(3)O(2) coordination with the alcoholic oxygen at the axial site, and 6 has a square planar trans-CuN(2)O(2) geometry. Binding of the complexes 1-4 to calf thymus DNA shows the relative order: phen > dmp. Mechanistic investigations using distamycin reveal minor groove binding for the complexes. The phen complexes containing the Schiff base with a thiomethyl or thiophenyl moiety show red light induced photocleavage. The dmp complexes are essentially photonuclease inactive. Complexes 5 and 6 are cleavage inactive under similar photolytic conditions. A 10 microM solution of 1 displays a 72% cleavage of SC DNA (0.5 microg) on an exposure of 30 min using a 603 nm Nd:YAG pulsed laser (60 mJ/P) in Tris-HCl buffer (pH 7.2). Significant cleavage of 1 is also observed at 694 nm using a Ruby laser. Complex 1 is cleavage inactive under argon or nitrogen atmosphere. It shows a more enhanced cleavage in pure oxygen than in air. Enhancement of cleavage in D(2)O and inhibition with sodium azide addition indicate the possibility of the formation of singlet oxygen as a reactive intermediate leading to DNA cleavage. The d-d band excitation with red light shows significant enhancement of cleavage yield. The results indicate that the phen ligand is necessary for DNA binding of the complex. Both the sulfur-to-copper charge transfer band and copper d-d band excitations helped the DNA cleavage. While the absorption of a red photon induces a metal d-d transition, excitation at shorter visible wavelengths leads to the sulfur-to-copper charge transfer band excitation at the initial step of photocleavage. The excitation energy is subsequently transferred to ground state oxygen molecules to produce singlet oxygen that cleaves the DNA. 相似文献
2.
Dulal C. Ghosh 《Journal of Chemical Sciences》1984,93(1):33-46
A cndo/2D study of the charge distribution obtained through Mulliken population analysis in the ground state of the title
compounds shows that the features of charge distribution found by severalab initio calculations are fairly well reproduced by this method. The one-particle density, the interference density at the mid-point
of the bond axis and the kinetic part of the interference energy calculated through the deorthogonalized density matrices
over a wide range of intermolecular separation between the donor and the acceptor show that the one-particle density and the
interference density steadily grow with decreasing internuclear separation, while the kinetic interference energy starts with
negative value at large distance, then decreases and passes through a minima near but above the equilibrium distance and then
increases rapidly below it conforming to the characteristic general behaviour of the kinetic component of Morse curve. The
orbital pairwise interference density and the corresponding kinetic energy components reveal that the orbitals involved in
the covalent binding are σ2p AO of B and 2S and σ2p AO of N and C atoms in H3B-NH3 and H3B-CO respectively. 相似文献
3.
4.
Maria G. Bettoli Lorenzo Cantelli Damiano Quarin Marzia Ravanelli Laura Tositti Ottavio Tubertini 《International journal of environmental analytical chemistry》2013,93(3-4):321-330
Abstract 210Pb is widely used to determine accumulation rates in order to obtain a time scale in environmental samples. The most accurate method uses the determination of 210Pb via its grand-daughter 210Po by alpha spectrometry. Unfortunately this method requires a complex wet-chemistry procedure to achieve the separation of 210Po from its matrix. In this work a simplified procedure for the chemical separation of 210Po is proposed and applied to three marine sediment cores and a 10 m snow core collected in Antarctica. The calculated sedimentation rates for marine sediments range from 0.053 to 0.071 cm y?1. The mean annual accumulation rate for the snow is 16.6 cm y?1 w.e. A comparison with literature data in the same region is given. 相似文献
5.
Dr. Marzia Dell'Aera Dr. Filippo Maria Perna Dr. Paola Vitale Dr. Angela Altomare Prof. Alessandro Palmieri Dr. Lewis C. H. Maddock Leonie J. Bole Dr. Alan R. Kennedy Prof. Eva Hevia Prof. Vito Capriati 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(40):8742-8748
We report the first transition metal catalyst- and ligand-free conjugate addition of lithium tetraorganozincates (R4ZnLi2) to nitroolefins. Displaying enhanced nucleophilicity combined with unique chemoselectivity and functional group tolerance, homoleptic aliphatic and aromatic R4ZnLi2 provide access to valuable nitroalkanes in up to 98 % yield under mild conditions (0 °C) and short reaction time (30 min). This is particularly remarkable when employing β-nitroacrylates and β-nitroenones, where despite the presence of other electrophilic groups, selective 1,4 addition to the C=C is preferred. Structural and spectroscopic studies confirmed the formation of tetraorganozincate species in solution, the nature of which has been a long debated issue, and allowed to unveil the key role played by donor additives on the aggregation and structure of these reagents. Thus, while chelating N,N,N’,N’-tetramethylethylenediamine (TMEDA) and (R,R)-N,N,N’,N’-tetramethyl-1,2-diaminocyclohexane (TMCDA) favour the formation of contacted-ion pair zincates, macrocyclic Lewis donor 12-crown-4 triggers an immediate disproportionation process of Et4ZnLi2 into equimolar amounts of solvent-separated Et3ZnLi and EtLi. 相似文献
6.
7.
Dr. Alessandro Presentato Dr. Antonino Scurria Dr. Lorenzo Albanese Dr. Claudia Lino Dr. Marzia Sciortino Dr. Mario Pagliaro Dr. Federica Zabini Dr. Francesco Meneguzzo Prof. Rosa Alduina Dr. Domenico Nuzzo Dr. Rosaria Ciriminna 《ChemistryOpen》2020,9(5):628-630
Pectin extracted via hydrodynamic cavitation in water only from waste lemon peel and further isolated via freeze drying displays significant antibacterial activity against Staphylococcus aureus, a Gram positive pathogen which easily contaminates food. The antibacterial effect of the new IntegroPectin is largely superior to that of commercial citrus pectin, opening the way to advanced applications of a new bioproduct now obtainable in large amounts and at low cost from citrus juice industry's waste. 相似文献
8.
9.
A four step synthesis of 4(S)-oxazolidineacetic acid, 2-oxo benzyl ester (D-Oxac-OBn) from L-Asp-OH in 45% overall yield is reported. The formation of by-products is completely avoided, by microwave irradiation and by the use of caesium carbonate as base. Moreover the synthesis and IR and 1H NMR conformational analysis of the tetramers Boc-L-Val-D-Oxac-L-Ala-OBn and Boc-L-Val-D-Oxac-Aib-L-Ala-OBn in solution is reported. 相似文献
10.
Relying upon the fact that the density functional computation of the global hardness of the atoms of the elements are still at large and there is some mathematical in congruency between the theory and operational formula of finite difference approximation, we have suggested a radial‐dependent ansatz for evaluating global hardness of atoms as: η=a(7.2/r)+b (in eV), where, “a” and “b” are the constants and r is the absolute radius of atoms in angstrom unit. The ansatz is invoked to evaluate the global hardness of atoms of 103 element of the periodic table. The evaluated new set of global hardness is found to satisfy the sine qua non of a reasonable scale of hardness by exhibiting perfect periodicity of periods and groups and correlating the gross physicochemical properties of elements. The inertness of Hg and extreme reactivity Cs atoms are nicely correlated. The chemical reactivity and its variation in small steps in the series of lanthanide elements are also nicely reproduced. The results of the present semiempirical calculation also have strong correlation with the result of some sophisticated DFT calculation for a set of atoms. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 相似文献