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101.
Halder M Headley LS Mukherjee P Song X Petrich JW 《The journal of physical chemistry. A》2006,110(28):8623-8626
An analysis is provided of the subnanosecond dynamic solvation of ionic liquids in particular and ionic solutions in general. It is our hypothesis that solvation relaxation in ionic fluids, in the nonglassy and nonsupercooled regimes, can be understood rather simply in terms of the dielectric spectra of the solvent. This idea is suggested by the comparison of imidazolium ionic liquids with their pure organic counterpart, butylimidazole (J. Phys. Chem. B 2004, 108, 10245-10255). It is borne out by a calculation of the solvation correlation time from frequency dependent dielectric data for the ionic liquid, ethylammonium nitrate, and for the electrolyte solution of methanol and sodium perchlorate. Very good agreement is obtained between these theoretically calculated solvation relaxation functions and those obtained from fluorescence upconversion spectroscopy. Our comparisons suggest that translational motion of ions may not be the predominant factor in short-time solvation of ionic fluids and that many tools and ideas about solvation dynamics in polar solvents can be adapted to ionic fluids. 相似文献
102.
Halder S Acharyya R Peng SM Lee GH Drew MG Bhattacharya S 《Inorganic chemistry》2006,45(24):9654-9663
Reaction of 2-(4'-R-phenylazo)-4-methylphenols (R = OCH3, CH3, H, Cl, and NO2) with [Ru(dmso)(4)Cl2]affords a family of five ruthenium(III) complexes, containing a 2-(arylazo)phenolate ligand forming a six-membered chelate ring and a tetradentate ligand formed from two 2-(arylazo)phenols via an unusual C-C coupling linking the two ortho carbons of the phenyl rings in the arylazo fragment. A similar reaction with 2-(2'-methylphenylazo)-4-methylphenol with [Ru(dmso)(4)Cl2] has afforded a similar complex, in which one 2-(2'-methylphenylazo)-4-methylphenolate ligand is coordinated forming a six-membered chelate ring, and the other two ligands have undergone the C-C coupling reaction, and the coupled species is coordinated as a tetradentate ligand forming a five-membered N,O-chelate ring, a nine-membered N,N-chelate ring, and another five-membered chelate ring. Reaction of 2-(2',6'-dimethylphenylazo)-4-methylphenol with [Ru(dmso)(4)Cl2] has afforded a complex in which two 2-(2',6'-dimethylphenylazo)-4-methylphenols are coordinated as bidentate N,O-donors forming five- and six-membered chelate rings, while the third one has undergone cleavage across the N=N bond, and the phenolate fragment, thus generated, remains coordinated to the metal center in the iminosemiquinonate form. Structures of four selected complexes have been determined by X-ray crystallography. The first six complexes are one-electron paramagnetic and show rhombic ESR spectra. The last complex is diamagnetic and shows characteristic 1H NMR signals. All the complexes show intense charge-transfer transitions in the visible region and a Ru(III)-Ru(IV) oxidation on the positive side of SCE and a Ru(III)-Ru(II) reduction on the negative side. 相似文献
103.
Mukherjee P Crank JA Halder M Armstrong DW Petrich JW 《The journal of physical chemistry. A》2006,110(37):10725-10730
Dynamic solvation of the dye, coumarin 153, is compared in an ionic liquid that forms micelles in water against the bulk solvent. This provides the unprecedented opportunity of investigating the behavior of the ionic liquid in two globally different configurations. It is proposed that the imidazolium moiety is in both cases responsible for the majority of the solvation, which manifests itself in the first 100 ps. Exploiting the use of ionic liquids capable of accommodating specific structures thus provides a deeper insight into how solutes interact with these fascinating and interesting solvents (at least those that are imidazolium based) that are gaining ever increasing interest in the scientific community. 相似文献
104.
105.
Schlueter JA Park H Halder GJ Armand WR Dunmars C Chapman KW Manson JL Singleton J McDonald R Plonczak A Kang J Lee C Whangbo MH Lancaster T Steele AJ Franke I Wright JD Blundell SJ Pratt FL deGeorge J Turnbull MM Landee CP 《Inorganic chemistry》2012,51(4):2121-2129
The structural and magnetic properties of the newly crystallized CuX(2)(pyzO)(H(2)O)(2) (X = Cl, Br; pyzO = pyrazine-N,N'-dioxide) coordination polymers are reported. These isostructural compounds crystallize in the monoclinic space group C2/c with, at 150 K, a = 17.0515(7) ?, b = 5.5560(2) ?, c = 10.4254(5) ?, β = 115.400(2)°, and V = 892.21(7) ?(3) for X = Cl and a = 17.3457(8) ?, b = 5.6766(3) ?, c = 10.6979(5) ?, β = 115.593(2)°, and V = 950.01(8) ?(3) for X = Br. Their crystal structure is characterized by one-dimensional chains of Cu(2+) ions linked through bidentate pyzO ligands. These chains are joined together through OH···O hydrogen bonds between the water ligands and pyzO oxygen atoms and Cu-X···X-Cu contacts. Bulk magnetic susceptibility measurements at ambient pressure show a broad maximum at 7 (Cl) and 28 K (Br) that is indicative of short-range magnetic correlations. The dominant spin exchange is the Cu-X···X-Cu supersuperexchange because the magnetic orbital of the Cu(2+) ion is contained in the CuX(2)(H(2)O)(2) plane and the X···X contact distances are short. The magnetic data were fitted to a Heisenberg 1D uniform antiferromagnetic chain model with J(1D)/k(B) = -11.1(1) (Cl) and -45.9(1) K (Br). Magnetization saturates at fields of 16.1(3) (Cl) and 66.7(5) T (Br), from which J(1D) is determined to be -11.5(2) (Cl) and -46.4(5) K (Br). For the Br analog the pressure dependence of the magnetic susceptibility indicates a gradual increase in the magnitude of J(1D)/k(B) up to -51.2 K at 0.84 GPa, suggesting a shortening of the Br···Br contact distance under pressure. At higher pressure X-ray powder diffraction data indicates a structural phase transition at ~3.5 GPa. Muon-spin relaxation measurements indicate that CuCl(2)(pyzO)(H(2)O)(2) is magnetically ordered with T(N) = 1.06(1) K, while the signature for long-range magnetic order in CuBr(2)(pyzO)(H(2)O)(2) was much less definitive down to 0.26 K. The results for the CuX(2)(pyzO)(H(2)O)(2) complexes are compared to the related CuX(2)(pyrazine) materials. 相似文献
106.
Dhamodharan V Harikrishna S Jagadeeswaran C Halder K Pradeepkumar PI 《The Journal of organic chemistry》2012,77(1):229-242
Various biologically relevant G-quadruplex DNA structures offer a platform for therapeutic intervention for altering the gene expression or by halting the function of proteins associated with telomeres. One of the prominent strategies to explore the therapeutic potential of quadruplex DNA structures is by stabilizing them with small molecule ligands. Here we report the synthesis of bisquinolinium and bispyridinium derivatives of 1,8-naphthyridine and their interaction with human telomeric DNA and promoter G-quadruplex forming DNAs. The interactions of ligands with quadruplex forming DNAs were studied by various biophysical, biochemical, and computational methods. Results indicated that bisquinolinium ligands bind tightly and selectively to quadruplex DNAs at low ligand concentration (~0.2-0.4 μM). Furthermore, thermal melting studies revealed that ligands imparted higher stabilization for quadruplex DNA (an increase in the T(m) of up to 21 °C for human telomeric G-quadruplex DNA and >25 °C for promoter G-quadruplex DNAs) than duplex DNA (ΔT(m) ≤ 1.6 °C). Molecular dynamics simulations revealed that the end-stacking binding mode was favored for ligands with low binding free energy. Taken together, the results indicate that the naphthyridine-based ligands with quinolinium and pyridinium side chains form a promising class of quadruplex DNA stabilizing agents having high selectivity for quadruplex DNA structures over duplex DNA structures. 相似文献
107.
Arijit Jana Chiranjit Maity Suman Kumar Halder Keshab Chandra Mondal Bikash Ranjan Pati Pradeep Kumar Das Mohapatra 《Applied biochemistry and biotechnology》2012,167(5):1254-1269
Tannase production by newly isolated Penicillium purpurogenum PAF6 was investigated by ??one variable at a time?? (OVAT) approach followed by response surface methodology (RSM). Tannin-rich plant residues were used as supporting solid substrate and sole carbon source and, among them, tamarind seed was found to be the most favorable substrate than haritaki, pomegranate, tea leaf waste and arjun fruit. Physicochemical parameters were initially optimized using OVAT methodology and some important factors like incubation time, incubation temperature, substrate:moisture ratio as well as carbon, nitrogen and phosphate concentrations were verified with Box?CBehken design of response surface methodology. Phosphate source, nitrogen source and temperature were found as the most favorable variables in the maximization of production. Tannase production was enhanced from 1.536 U/g to 5.784 U/g using tamarind seed OVAT optimization and further enhancement up to 6.15 U/g following RSM. An overall 3.76- and 4.0-fold increases in tannase production were achieved in OVAT and RSM, respectively. 相似文献
108.
Ytterbium-sensitized thulium-doped fiber laser with a single-mode output operating at 1900-nm region
S. W. Harun A. Halder M. C. Paul S. M. M. Ali N. Saidin S. S. A. Damanhuri H. Ahmad S. Das M. Pal S. K. Bhadra 《中国光学快报(英文版)》2012,(10):39-41
A single-mode laser is demonstrated using a newly developed double-clad thulium-ytterbium-doped fiber (TYDF) in a linear cavity formed by two fiber Bragg gratings (FBGs). The YTF used is drawn from a D-shape preform fabricated using the modified chemical vapor deposition and solution doping technique. The laser is operated at 1 901.6 nm via the transition of thulium ions from 3F4 to 3H6 with the assistance of ytterbium to thulium ion energy transfer. The efficiencies of the laser are 0.71% and 0.75% at 927- and 905-nm multimode pumping, respectively. The thresholds of the launched pump power for 927- and 905-nm pumping are 1 314 and 1 458 mW, respectively. A 7-mW output is obtained at a 905-nm pump power of 2 400 mW. 相似文献
109.
The nanoporous metal-organic framework material Cu3(1,3,5-benzenetricarboxylate)2(H2O)3.{guest} exhibits anomalous compression under applied pressure that is associated with the hyper-filling of the pore network. This behavior involves a dramatic transition between a "hard" regime (bulk modulus, Khard approximately 118 GPa), where the pressure-transmitting fluid penetrates the framework cavities, and a "soft" regime (Ksoft approximately 30 GPa), where the guest-framework system compresses concertedly. Not only is the duality in compressibility triggered by the availability of potential guests but the size/penetrability of the guest molecules determines the pressure at which the hard-soft transition occurs. Specifically, the observed compression behavior depends on the size of the pressure-transmitting fluid molecules, the sample particle size (i.e., the extent of the pore network), and the rate at which the pressure is increased. The unprecedented pressure-induced phenomena documented here, illustrates the exotic high-pressure behaviors possible in this versatile class of advanced functional materials with broad implications for their structure-function relationships and accordingly their practical application. 相似文献
110.
In this paper a qualocation method is analysed for parabolicpartial differential equations in one space dimension. Thismethod may be described as a discrete H1-Galerkin method inwhich the discretization is achieved by approximating the integralsby a composite Gauss quadrature rule. An O (h4-i) rate of convergencein the Wi.p norm for i = 0, 1 and 1 p is derived for a semidiscretescheme without any quasi-uniformity assumption on the finiteelement mesh. Further, an optimal error estimate in the H2 normis also proved. Finally, the linearized backward Euler methodand extrapolated Crank-Nicolson scheme are examined and analysed. 相似文献