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91.
Otsuki J Omokawa N Yoshiba K Yoshikawa I Akasaka T Suenobu T Takido T Araki K Fukuzumi S 《Inorganic chemistry》2003,42(9):3057-3066
Two new ditopic ligands, 5,5"-azobis(2,2'-bipyridine) (5,5"-azo) and 5,5"-azoxybis(2,2'-bipyridine) (5,5"-azoxy), were prepared by the reduction of nitro precursors. Mononuclear and dinuclear Ru(II) complexes having one of these bridging ligands and 2,2'-bipyridine terminal ligands were also prepared, and their properties were compared with previously reported Ru(II) complexes having 4,4"-azobis(2,2'-bipyridine) (4,4"-azo). The X-ray crystal structure showed that 5,5"-azo adopts the trans conformation and a planar rodlike shape. The X-ray crystal structure of [(bpy)(2)Ru(5,5"-azo)Ru(bpy)(2)](PF(6))(4) (Ru(5,5"-azo)Ru) showed that the bridging ligand is in the trans conformation and nearly planar also in the complex and the metal-to-metal distance is 10.0 A. The azo or azoxy ligand in these complexes exhibits reduction processes at less negative potentials than the terminal bpy's due to the low-lying pi level. The electronic absorption spectra for the complexes having 5,5"-azo or 5,5"-azoxy exhibit an extended low-energy metal-to-ligand charge-transfer absorption. The ligands, 5,5"-azo and 5,5"-azoxy, and the mononuclear complex, [(bpy)(2)Ru(5,5"-azo)](2+), isomerize reversibly upon light irradiation. The low-energy MLCT state sensitizes the isomerization of the azo moiety in this complex. While [(bpy)(2)Ru(4,4"-azo)Ru(bpy)(2)](PF(6))(4) exhibits light switch properties, namely, significant electrochromism and a large luminescence enhancement, upon reduction, Ru(5,5"-azo)Ru does not show these properties. The radical anion formation upon reduction of these complexes has been confirmed by ESR spectroscopy. 相似文献
92.
The use of novel water-in-oil microemulsions in microemulsion electrokinetic chromatography 总被引:3,自引:0,他引:3
We describe the novel use of water-in-oil (W/O) microemulsions to achieve unique separations in microemulsion electrokinetic chromatography (MEEKC). The choice and concentration of the buffer type, surfactant and co-surfactant were all examined and optimized. Separations of a range of neutral and acidic analytes was shown to be markedly different to that obtained by (oil-in-water) O/W MEEKC. Neutral solutes are separated by virtue of their solubility (log P) values in O/W MEEKC with the more water-insoluble solutes migrating last. This separation process does not occur in W/O, as neutral solutes are not separated in order of log P. 相似文献
93.
94.
Quantile regression is applied in two retail credit risk assessment exercises exemplifying the power of the technique to account for the diverse distributions that arise in the financial service industry. The first application is to predict loss given default for secured loans, in particular retail mortgages. This is an asymmetric process since where the security (such as a property) value exceeds the loan balance the banks cannot retain the profit, whereas when the security does not cover the value of the defaulting loan then the bank realises a loss. In the light of this asymmetry it becomes apparent that estimating the low tail of the house value is much more relevant for estimating likely losses than estimates of the average value where in most cases no loss is realised. In our application quantile regression is used to estimate the distribution of property values realised on repossession that is then used to calculate loss given default estimates. An illustration is given for a mortgage portfolio from a European mortgage lender. A second application is to revenue modelling. While credit issuing organisations have access to large databases, they also build models to assess the likely effects of new strategies for which, by definition, there is no existing data. Certain strategies are aimed at increasing the revenue stream or decreasing the risk in specific market segments. Using a simple artificial revenue model, quantile regression is applied to elucidate the details of subsets of accounts, such as the least profitable, as predicted from their covariates. The application uses standard linear and kernel smoothed quantile regression. 相似文献
95.
Joe Iannelli 《国际流体数值方法杂志》2005,49(11):1261-1286
The second of a two‐paper series, this paper details a solver for the characteristics‐bias system from the acoustics–convection upstream resolution algorithm for the Euler and Navier–Stokes equations. An integral formulation leads to several surface integrals that allow effective enforcement of boundary conditions. Also presented is a new multi‐dimensional procedure to enforce a pressure boundary condition at a subsonic outlet, a procedure that remains accurate and stable. A classical finite element Galerkin discretization of the integral formulation on any prescribed grid directly yields an optimal discretely conservative upstream approximation for the Euler and Navier–Stokes equations, an approximation that remains multi‐dimensional independently of the orientation of the reference axes and computational cells. The time‐dependent discrete equations are then integrated in time via an implicit Runge–Kutta procedure that in this paper is proven to remain absolutely non‐linearly stable for the spatially‐discrete Euler and Navier–Stokes equations and shown to converge rapidly to steady states, with maximum Courant number exceeding 100 for the linearized version. Even on relatively coarse grids, the acoustics–convection upstream resolution algorithm generates essentially non‐oscillatory solutions for subsonic, transonic and supersonic flows, encompassing oblique‐ and interacting‐shock fields that converge within 40 time steps and reflect reference exact solutions. Copyright © 2005 John Wiley & Sons, Ltd. 相似文献
96.
Partial LAD regression uses the L
1 norm associated with least absolute deviations (LAD) regression while retaining the same algorithmic structure of univariate
partial least squares (PLS) regression. We use the bootstrap in order to assess the partial LAD regression model performance
and to make comparisons to PLS regression. We use a variety of examples coming from NIR experiments as well as two sets of
experimental data. 相似文献
97.
Benchmarking is a widely cited method to identify and adopt best-practices as a means to improve performance. Data envelopment
analysis (DEA) has been demonstrated to be a powerful benchmarking methodology for situations where multiple inputs and outputs
need to be assessed to identify best-practices and improve productivity in organizations. Most DEA benchmarking studies have
excluded quality, even in service-sector applications such as health care where quality is a key element of performance. This
limits the practical value of DEA in organizations where maintaining and improving service quality is critical to achieving
performance objectives. In this paper, alternative methods incorporating quality in DEA benchmarking are demonstrated and
evaluated. It is shown that simply treating the quality measures as DEA outputs does not help in discriminating the performance.
Thus, the current study presents a new, more sensitive, quality-adjusted DEA (Q-DEA), which effectively deals with quality
measures in benchmarking. We report the results of applying Q-DEA to a U.S. bank's 200-branch network that required a method
for benchmarking to help manage operating costs and service quality. Q-DEA findings helped the bank achieve cost savings and
improved operations while preserving service quality, a dimension critical to its mission. New insights about ways to improve
branch operations based on the best-practice (high-quality low-cost) benchmarks identified with Q-DEA are also described in
the paper. This demonstrates the practical need and potential benefits of Q-DEA and its efficacy in one application, and also
suggests the need for further research on measuring and incorporating quality into DEA benchmarking.
The review process of this paper was handled by the Edit-in-Chief Peter Hammer. 相似文献
98.
Selective reagent ionisation‐time of flight‐mass spectrometry: a rapid technology for the novel analysis of blends of new psychoactive substances 下载免费PDF全文
Matteo Lanza W. Joe Acton Philipp Sulzer Kostiantyn Breiev Simone Jürschik Alfons Jordan Eugen Hartungen Gernot Hanel Lukas Märk Tilmann D. Märk Chris A. Mayhew 《Journal of mass spectrometry : JMS》2015,50(2):427-431
In this study we demonstrate the potential of selective reagent ionisation‐time of flight‐mass spectrometry for the rapid and selective identification of a popular new psychoactive substance blend called ‘synthacaine’, a mixture that is supposed to imitate the sensory and intoxicating effects of cocaine. Reactions with H3O+ result in protonated parent molecules which can be tentatively assigned to benzocaine and methiopropamine. However, by comparing the product ion branching ratios obtained at two reduced electric field values (90 and 170 Td) for two reagent ions (H3O+ and NO+) to those of the pure chemicals, we show that identification is possible with a much higher level of confidence then when relying solely on the m/z of protonated parent molecules. A rapid and highly selective analytical identification of the constituents of a recreational drug is particularly crucial to medical personnel for the prompt medical treatment of overdoses, toxic effects or allergic reactions. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
99.
Jacob Joe AntonyPeriyasamy Sivalingam Durairaj SivaSoundararajan Kamalakkannan Kumarasamy AnbarasuRaman Sukirtha Muthukalingan KrishnanShanmugam Achiraman 《Colloids and surfaces. B, Biointerfaces》2011,88(1):134-140
The focus of the study is to compare the antibacterial efficacy of silver nanoparticles (AgNPs) fabricated by exploiting biological (a mangrove plant, Rhizophora apiculata) and chemical means (Glucose). The synthesized nanoparticles were characterised using UV-visible absorption spectrophotometry (UV-vis), Fourier transform Infra-red Spectroscopy (FTIR) and Transmission electron microscopy (TEM). Biologically synthesized silver nanoparticles (BAgNPs) were observed at 423 nm with particle sizes of 19-42 nm. The chemically synthesized silver nanoparticles (CAgNPs) showed a maximum peak at 422 nm with particle sizes of 13-19 nm. An obvious superiority of the antibacterial potency of BAgNPs compared to the CAgNPs as denoted by the zone of inhibition (ZoI) was noted when the nanoparticles were treated against seven different Microbial Type Culture Collection (MTCC) strains. The current study therefore elucidates that the synthesized AgNPs were efficient against the bacterial strains tested. 相似文献
100.
Lipid bilayers supported by porous biomaterials are being explored as models for cell membranes. Hydroxyapatite is a relevant material currently being used extensively for biomedical applications. In this study, hydroxyapatite films produced via a sol-gel chemistry route have been characterized and explored as a scaffolding material for lipid membranes. The hydroxyapatite has been characterized using XRD, SEM, and AFM, followed by vesicle-fusion of lipids characterized by fluorescence microscopy and fluorescence recovery after photobleaching (FRAP) to determine the diffusion coefficient of this system. The HA films produced in this work were found to produce slow lateral diffusion and, in the two-phase lipid systems, some domains were observed. The low lateral diffusion coefficients were believed to be a result of the large undulations present on the hydroxyapatite film surface. 相似文献