全文获取类型
收费全文 | 2367篇 |
免费 | 84篇 |
国内免费 | 23篇 |
专业分类
化学 | 1466篇 |
晶体学 | 7篇 |
力学 | 42篇 |
数学 | 400篇 |
物理学 | 559篇 |
出版年
2023年 | 9篇 |
2022年 | 27篇 |
2021年 | 29篇 |
2020年 | 38篇 |
2019年 | 29篇 |
2018年 | 30篇 |
2017年 | 36篇 |
2016年 | 61篇 |
2015年 | 59篇 |
2014年 | 62篇 |
2013年 | 121篇 |
2012年 | 186篇 |
2011年 | 176篇 |
2010年 | 123篇 |
2009年 | 110篇 |
2008年 | 158篇 |
2007年 | 164篇 |
2006年 | 167篇 |
2005年 | 203篇 |
2004年 | 138篇 |
2003年 | 124篇 |
2002年 | 115篇 |
2001年 | 19篇 |
2000年 | 23篇 |
1999年 | 15篇 |
1998年 | 15篇 |
1997年 | 15篇 |
1996年 | 33篇 |
1995年 | 17篇 |
1994年 | 17篇 |
1993年 | 19篇 |
1992年 | 11篇 |
1991年 | 5篇 |
1990年 | 8篇 |
1989年 | 12篇 |
1988年 | 5篇 |
1987年 | 4篇 |
1986年 | 7篇 |
1985年 | 12篇 |
1984年 | 10篇 |
1983年 | 10篇 |
1982年 | 9篇 |
1981年 | 10篇 |
1980年 | 5篇 |
1979年 | 7篇 |
1977年 | 4篇 |
1976年 | 3篇 |
1973年 | 5篇 |
1972年 | 3篇 |
1970年 | 2篇 |
排序方式: 共有2474条查询结果,搜索用时 17 毫秒
271.
Robert D. Bongard Michael Lepley Khushabu Thakur Marat R. Talipov Jaladhi Nayak Rachel A. Jones Lipinski Chris Bohl Noreena Sweeney Ramani Ramchandran Rajendra Rathore Daniel S. Sem 《BMC biochemistry》2017,18(1):10
Background
Protein tyrosine phosphatases (PTPs) like dual specificity phosphatase 5 (DUSP5) and protein tyrosine phosphatase 1B (PTP1B) are drug targets for diseases that include cancer, diabetes, and vascular disorders such as hemangiomas. The PTPs are also known to be notoriously difficult targets for designing inihibitors that become viable drug leads. Therefore, the pipeline for approved drugs in this class is minimal. Furthermore, drug screening for targets like PTPs often produce false positive and false negative results.Results
Studies presented herein provide important insights into: (a) how to detect such artifacts, (b) the importance of compound re-synthesis and verification, and (c) how in situ chemical reactivity of compounds, when diagnosed and characterized, can actually lead to serendipitous discovery of valuable new lead molecules. Initial docking of compounds from the National Cancer Institute (NCI), followed by experimental testing in enzyme inhibition assays, identified an inhibitor of DUSP5. Subsequent control experiments revealed that this compound demonstrated time-dependent inhibition, and also a time-dependent change in color of the inhibitor that correlated with potency of inhibition. In addition, the compound activity varied depending on vendor source. We hypothesized, and then confirmed by synthesis of the compound, that the actual inhibitor of DUSP5 was a dimeric form of the original inhibitor compound, formed upon exposure to light and oxygen. This compound has an IC50 of 36 μM for DUSP5, and is a competitive inhibitor. Testing against PTP1B, for selectivity, demonstrated the dimeric compound was actually a more potent inhibitor of PTP1B, with an IC50 of 2.1 μM. The compound, an azo-bridged dimer of sulfonated naphthol rings, resembles previously reported PTP inhibitors, but with 18-fold selectivity for PTP1B versus DUSP5.Conclusion
We report the identification of a potent PTP1B inhibitor that was initially identified in a screen for DUSP5, implying common mechanism of inhibitory action for these scaffolds.272.
Encarnación Algaba René van den Brink Chris Dietz 《Journal of Optimization Theory and Applications》2017,172(3):1008-1022
Games under precedence constraints model situations, where players in a cooperative transferable utility game belong to some hierarchical structure, which is represented by an acyclic digraph (partial order). In this paper, we introduce the class of precedence power solutions for games under precedence constraints. These solutions are obtained by allocating the dividends in the game proportional to some power measure for acyclic digraphs. We show that all these solutions satisfy the desirable axiom of irrelevant player independence, which establishes that the payoffs assigned to relevant players are not affected by the presence of irrelevant players. We axiomatize these precedence power solutions using irrelevant player independence and an axiom that uses a digraph power measure. We give special attention to the hierarchical solution, which applies the hierarchical measure. We argue how this solution is related to the known precedence Shapley value, which does not satisfy irrelevant player independence, and thus is not a precedence power solution. We also axiomatize the hierarchical measure as a digraph power measure. 相似文献
273.
Chris Lambie-Hanson 《Israel Journal of Mathematics》2017,220(2):617-648
Covering matrices were used by Viale in his proof that the Singular Cardinals Hypothesis follows from the Proper Forcing Axiom and later by Sharon and Viale to investigate the impact of stationary reflection on the approachability ideal. In the course of this work, they isolated two reflection principles, CP and S, which may hold of covering matrices. In this paper, we continue previous work of the author investigating connections between failures of CP and S and variations on Jensen’s square principle. We prove that, for a regular cardinal λ > ω 1, assuming large cardinals, □(λ, 2) is consistent with CP(λ, θ) for all θ with θ + < λ. We demonstrate how to force nice θ-covering matrices for λ which fail to satisfy CP and S. We investigate normal covering matrices, showing that, for a regular uncountable κ, □ κ implies the existence of a normal ω-covering matrix for κ + but that cardinal arithmetic imposes limits on the existence of a normal θ-covering matrix for κ + when θ is uncountable. We introduce the notion of a good point for a covering matrix, in analogy with good points in PCF-theoretic scales. We develop the basic theory of these good points and use this to prove some non-existence results about covering matrices. Finally, we investigate certain increasing sequences of functions which arise from covering matrices and from PCF-theoretic considerations and show that a stationary reflection hypothesis places limits on the behavior of these sequences. 相似文献
274.
Chris Lambie-Hanson 《Annals of Pure and Applied Logic》2017,168(1):50-71
Bounded stationary reflection at a cardinal λ is the assertion that every stationary subset of λ reflects but there is a stationary subset of λ that does not reflect at arbitrarily high cofinalities. We produce a variety of models in which bounded stationary reflection holds. These include models in which bounded stationary reflection holds at the successor of every singular cardinal and models in which bounded stationary reflection holds at but the approachability property fails at μ. 相似文献
275.
Hampton MA Plackowski C Nguyen AV 《Langmuir : the ACS journal of surfaces and colloids》2011,27(7):4190-4201
The surface oxidation of sulfide minerals, such as galena (PbS), in aqueous solutions is of critical importance in a number of applications. A comprehensive understanding of the formation of oxidation species at the galena surface is still lacking. Much controversy over the nature of these oxidation products exists. A number of oxidation pathways have been proposed, and experimental evidence for the formation of elemental sulfur, metal polysulfides, and metal-deficient lead sulfides in acidic conditions has been shown and argued. This paper provides further insight into the electrochemical behavior of galena at pH 4.5. Utilizing a novel experimental system that combines in situ electrochemical control and AC mode atomic force microscopy (AFM) surface imaging, the formation and growth of nanoscopic domains on the galena surface are detected and examined at anodic potentials. AFM phase images indicate that these domains have different material properties to the underlying galena. Continued oxidation results in nanoscopic pitting and the formation of microscopic surface domains, which are confirmed to be elemental sulfur by Raman spectroscopy. Further clarification of the presence of elemental sulfur is provided by Cryo-XPS. Polysulfide and metal-deficient sulfide could not be detected within this system. 相似文献
276.
McCullough BJ Bristow T O'Connor G Hopley C 《Rapid communications in mass spectrometry : RCM》2011,25(10):1445-1451
The design and development of a novel extractive electrospray ionisation (EESI) device for on-line reaction monitoring is described. The EESI apparatus uses a secondary, grounded nebuliser to produce an analyte aerosol and a Venturi pump is then used to transfer a sample of the aerosol to an electrospray source where it is ionised. The EESI apparatus was then tested with a variety of small, organic molecules to assess sensitivity, linearity and dynamic range. The performance of the technique will depend on the mass spectrometer used for the experiments; in the configurations used here it has a usable dynamic range of around 3.5 orders of magnitude with a linear range of around 2.5 orders of magnitude and is capable of analysing species present down to low μg/mL with signal-to-noise ratio greater than 2.5. The use of EESI for reaction monitoring was validated using a series of mock reaction mixtures and then used to monitor the base hydrolysis of ethyl salicylate to salicylic acid. 相似文献
277.
Zhou SN Reiner EJ Marvin CH Helm PA Brindle ID 《Rapid communications in mass spectrometry : RCM》2011,25(3):443-448
Although the two flame retardants 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH) and 1,2,5,6-tetrabromocyclooctane (TBCO) have been widely used, a selective instrumental method of analysis for these compounds has not been developed to date. In this study, we demonstrate the feasibility to utilize liquid chromatography/tandem mass spectrometry (LC/MS/MS) for the separation and analysis of α- and β-TBCO and α-, β-, γ-, and δ-TBECH. Acetone was initially used in a tetrahedron solvent system for LC optimization. A simple isocratic elution allowed near-baseline separation of these compounds. Different ionization approaches and mechanisms were investigated. The mass spectrometric transition of [M + O(2)](-) => Br(-) (459.8 => 78.9) was a selective detection method for the target analytes. Good instrument detection limits (5 pg for γ-/δ-TBECH, 125 pg for α-/β-TBECH, and 30 pg for α-/β-TBCO with 2.0 μL injection) were obtained. Excellent linearity up to 50 ng/μL (R(2) >0.999) was also achieved. This method has been applied to environmental samples (surface water) for screening purposes with recoveries ranging from 76-92% (CV%: 5-8%). This method shows significant improvement over previous methods. 相似文献
278.
Scott C Blackwell S Vernon L Kenny S Walls M Smith R 《The Journal of chemical physics》2011,135(17):174706
We present results of atomistic modelling of surface growth and sputtering using a multi-time scale molecular dynamics-on-the-fly kinetic Monte Carlo scheme which allows simulations to be carried out over realistic experimental times. The method uses molecular dynamics to model the fast processes and then calculates the diffusion barriers for the slow processes on-the-fly, without any preconceptions about what transitions might occur. The method is applied to the growth of metal and oxide materials at impact energies typical for both vapour deposition and magnetron sputtering. The method can be used to explain growth processes, such as the filling of vacancies and the formation of stacking faults. By tuning the variable experimental parameters on the computer, a parameter set for optimum crystalline growth can be determined. The method can also be used to model sputtering where the particle interactions with the surface occur at a higher energy. It is shown how a steady state can arise in which interstitial clusters are continuously being formed below the surface during an atom impact event which also recombine or diffuse to the surface between impact events. For fcc metals the near surface region remains basically crystalline during the erosion process with a pitted topography which soon attains a steady state roughness. 相似文献
279.
Diky V Chirico RD Kazakov AF Muzny CD Magee JW Abdulagatov I Kang JW Kroenlein K Frenkel M 《Journal of chemical information and modeling》2011,51(1):181-194
ThermoData Engine (TDE) is the first full-scale software implementation of the dynamic data evaluation concept, as reported recently in this journal. In the present paper, we describe development of an algorithmic approach to assist experiment planning through assessment of the existing body of knowledge, including availability of experimental thermophysical property data, variable ranges studied, associated uncertainties, state of prediction methods, and parameters for deployment of prediction methods and how these parameters can be obtained using targeted measurements, etc., and, indeed, how the intended measurement may address the underlying scientific or engineering problem under consideration. A second new feature described here is the application of the software capabilities for aid in the design of chemical products through identification of chemical systems possessing desired values of thermophysical properties within defined ranges of tolerance. The algorithms and their software implementation to achieve this are described. Finally, implementation of a new data validation and weighting system is described for vapor-liquid equilibrium (VLE) data, and directions for future enhancements are outlined. 相似文献
280.
Yu‐Fei Song De‐Liang Long Chris Ritchie Leroy Cronin 《Chemical record (New York, N.Y.)》2011,11(3):158-171
The latest advances in the area of polyoxometalate (POM)‐based inorganic/organic hybrid materials prepared by self‐assembly, covalent modification, and supramolecular interactions are presented. This Review is composed of five sections and documents the effect of organic cations on the formation of novel POMs, surfactant encapsulated POM‐based hybrids, polymeric POM/organic hybrid materials, POMs‐containing ionic crystals, and covalently functionalized POMs. In addition to their role in the charge‐balancing, of anionic POMs, the crucial role of organic cations in the formation and functionalization of POM‐based hybrid materials is discussed. DOI 10.1002/tcr.201100002 相似文献