全文获取类型
收费全文 | 164685篇 |
免费 | 4152篇 |
国内免费 | 2212篇 |
专业分类
化学 | 91397篇 |
晶体学 | 1833篇 |
力学 | 7343篇 |
综合类 | 104篇 |
数学 | 16561篇 |
物理学 | 53811篇 |
出版年
2021年 | 1386篇 |
2020年 | 1744篇 |
2019年 | 1798篇 |
2018年 | 2018篇 |
2017年 | 1909篇 |
2016年 | 3204篇 |
2015年 | 2241篇 |
2014年 | 3253篇 |
2013年 | 7479篇 |
2012年 | 6254篇 |
2011年 | 7582篇 |
2010年 | 5186篇 |
2009年 | 5207篇 |
2008年 | 6711篇 |
2007年 | 6690篇 |
2006年 | 6231篇 |
2005年 | 5734篇 |
2004年 | 5002篇 |
2003年 | 4359篇 |
2002年 | 4421篇 |
2001年 | 4529篇 |
2000年 | 3375篇 |
1999年 | 2620篇 |
1998年 | 2268篇 |
1997年 | 2241篇 |
1996年 | 2025篇 |
1995年 | 2006篇 |
1994年 | 1977篇 |
1993年 | 1779篇 |
1992年 | 2048篇 |
1991年 | 2177篇 |
1990年 | 1935篇 |
1989年 | 1926篇 |
1988年 | 1860篇 |
1987年 | 1748篇 |
1986年 | 1689篇 |
1985年 | 2190篇 |
1984年 | 2318篇 |
1983年 | 1882篇 |
1982年 | 2065篇 |
1981年 | 1953篇 |
1980年 | 1866篇 |
1979年 | 2011篇 |
1978年 | 2179篇 |
1977年 | 2050篇 |
1976年 | 2094篇 |
1975年 | 2010篇 |
1974年 | 2065篇 |
1973年 | 2048篇 |
1972年 | 1343篇 |
排序方式: 共有10000条查询结果,搜索用时 156 毫秒
41.
Dong Zhang 《Discrete Mathematics》2018,341(1):25-32
In this paper, we reveal the connection between the independent number of a graph and the topological multiplicity of the maximal eigenvalue of the corresponding graph 1-Laplacian. The pseudo independent number of a graph is introduced, which provides a better lower estimate of the topological multiplicity of the maximum eigenvalue. The technique of our proof is based on the localization property of the eigenvector for graph 1-Laplacian, the Krasnoselski genus, and its relation to the topological join. 相似文献
42.
Ziritaxestat is a first-in-class autotoxin inhibitor. The purpose of this study was to develop a liquid chromatography/electrospray ionization tandem mass spectrometric (LC–MS/MS) method for the determination of ziritaxestat in rat plasma. The plasma sample was deproteinated using acetonitrile and then separated on an Acquity BEH C18 column with water containing 0.1% formic acid and acetonitrile as mobile phase, which was delivered at 0.4 ml/min. Ziritaxestat and the internal standard (crizotinib) were quantitatively monitored with precursor-to-product transitions of m/z 589.3 > 262.2 and m/z 450.1 > 260.2, respectively. The total running time was 2.5 min. The method showed excellent linearity over the concentration range 0.5–2000 ng/ml, with correlation coefficient >0.9987. The extraction recovery was >82.09% and the matrix effect was not significant. Inter- and intra-day precisions (RSD) were <11.20% and accuracies were in the range of −8.50–7.45%. Ziritaxestat was demonstrated to be stable in rat plasma under the tested conditions. The validated LC–MS/MS method was successfully applied to study the pharmacokinetic profiles of ziritaxestat in rat plasma after intravenous and oral administration. Pharmacokinetic results demonstrated that ziritaxestat displayed a short half-life (~3 h) and low bioavailability (20.52%). 相似文献
43.
Torin F. Stetina Aurora E. Clark Xiaosong Li 《International journal of quantum chemistry》2019,119(1):e25802
Despite fundamental importance, the experimental characterization of the hydrogen bond network, particularly in multicomponent protic solutions, remains a challenge. Although recent work has experimentally validated that the oxygen K-edge X-ray absorption spectra is sensitive to local hydrogen bond patterns in pure water and aqueous alcohol solutions, the generality of this observation is unknown—as is the sensitivity to the electronic structure of the alcohol cosolvent. In this work, we investigate the electronic structure of water solvated alcohol model geometries using energy specific time-dependent density functional theory to calculate oxygen K-edge X-ray excitations. We find that the geometry of dangling hydrogen bonds in pure water is the main contributor to the pre-edge feature seen in the X-ray absorption spectra, agreeing with previous experimental and theoretical work. We then extend this result to solvated alcohol systems and observe a similar phenomenon, yet importantly, the increase of electron donation from alkyl chains to the alcohol OH group directly correlates to the strength of the core excitation on the dangling hydrogen bond model geometry. This trend arises from a stronger transition dipole moment due to electron localization on the OH group. 相似文献
44.
Dr. Felix Pape Lea T. Brechmann Jun.-Prof. Dr. Johannes F. Teichert 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(4):985-988
Copper(I)–N-heterocyclic-carbene (NHC) complexes enabled the catalytic generation of nucleophilic hydrides from dihydrogen (H2) and their subsequent transfer to allylic chlorides. The highly chemoselective catalyst displayed no concomitant hydrogenation reactivity; in fact, the terminal double bond formed in the hydride transfer remained intact. Switching to deuterium gas (D2) allowed for regioselective monodeuteration with excellent isotope incorporation. 相似文献
45.
Dr. Weixin Zou Lixia Xu Yu Pu Haojie Cai Xiaoqian Wei Yidan Luo Dr. Lulu Li Prof. Dr. Bin Gao Prof. Dr. Haiqin Wan Prof. Dr. Lin Dong 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(19):5058-5064
Bimetallic AgPd nanoparticles have been synthesized before, but the interfacial electronic effects of AgPd on the photocatalytic performance have been investigated less. In this work, the results of hydrogen evolution suggest that the bimetallic AgPd/g-C3N4 sample has superior activity to Ag/g-C3N4 and Pd/g-C3N4 photocatalysts. The UV/Vis diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, CO adsorption diffuse reflectance FTIR spectroscopy, and FTIR results demonstrate that in the AgPd/g-C3N4, the surface electronic structures of Pd and Ag are changed, which is beneficial for faster photogenerated electron transfer and greater H2O molecule adsorption. In situ ESR spectra suggest that, under visible light irradiation, there is more H2O dissociation to radical species on the AgPd/g-C3N4 photocatalyst. Furthermore, DFT calculations confirm the interfacial electronic effects of AgPd/g-C3N4, that is, Pdδ−⋅⋅⋅Agδ+, and the activation energy of H2O molecule dissociation on AgPd/g-C3N4 is the lowest, which is the main contributor to the enhanced photocatalytic H2 evolution. 相似文献
46.
Monoester‐diterpenoid alkaloids are the main bioactive components of Sini decoction, which is a well‐known traditional Chinese medicine formula for the treatment of myocardial infarction (MI) and heart failure in China. In this work, an ultra‐high‐performance liquid chromatography–mass spectrometry combined with microdialysis method was successfully established and applied for investigating for the first time comparative plasma pharmacokinetics of three monoester‐diterpenoid alkaloids (benzoylmesaconitine, benzoylaconitine and benzoylhypacoitine) in normal and MI rats after oral administration of Sini decoction. The statistical results of pharmacokinetic parameters demonstrated that benzoylmesaconitine, benzoylaconitine and benzoylhypacoitine showed lower peak concentration, longer half‐life, smaller area under the concentration–time curve, slower clearance, time to peak concentration and mean residence time in MI rats than in normal rats (p < 0.05), which indicated that monoester‐diterpenoid alkaloids exhibited lower systemic exposure and slower elimination in the MI rats. The results provided the experimental basis for understanding the metabolic fate and therapeutic effects of Sini decoction. 相似文献
47.
The kinetics of the dissipation of chlortetracycline in the aquatic environment was studied over a period of 90 days using microcosm experiments and distilled water controls. The distilled water control experiments, carried out under dark conditions as well as exposed to natural sunlight, exhibited biphasic linear rates of dissipation. The microcosm experiments exhibited triphasic linear rates of degradation both in the water phase (2.7 × 10−2, 7 × 10−3, 1.3 × 10−3 μg g−1 day–1) and the sediment phase (3.4 × 10−2, 6 × 10−3, 1 × 10−3 μg g−1 day–1). The initial slow rate of dissipation in the dark control (3 × 10−3 μg g−1 day–1) was attributed to a combination of evaporation and hydrolysis, whereas the subsequent fast rate (1.8 × 10−3 μg g−1 day–1) was attributed to a combination of evaporation, hydrolysis, and microbial degradation. For the sunlight-exposed control, the initial slow rate of dissipation (1.5 × 10−3 μg g−1 day–1) was attributed to a combination of evaporation, hydrolysis, and photolysis, whereas the subsequent fast rate was attributed to a combination of evaporation, hydrolysis, photolysis, and microbial degradation (5.1 × 10−3 μg g−1 day–1). The initial fast rate of dissipation in the water phase of the microcosm experiment is attributed to a combination of evaporation, hydrolysis, photolysis, and microbial degradation, whereas all subsequent slow rates in the water phase and all rates of degradation in the sediment phase are attributed to microbial degradation of the colloidal and sediment particle adsorbed antibiotic. A multiphase zero-order kinetic model is presented that takes into account (a) dissipation of the antibiotic via evaporation, hydrolysis, photolysis, microbial degradation, and adsorption by colloidal and sediment particles and (b) the dependence of the dissipation rate on the concentration of the antibiotic, type and count of microorganisms, and type and concentration of colloidal particles and sediment particle adsorption sites within a given aquatic environment. 相似文献
48.
David E. Delgado Lauren F. Sturdy Craig W. Burkhart Kenneth R. Shull 《Journal of Polymer Science.Polymer Physics》2019,57(18):1246-1254
The utility of the quartz crystal microbalance (QCM) as a high‐frequency rheometer operating at 15 MHz was demonstrated. High‐frequency data obtained from a series of rubbery materials were compared with results obtained from traditional dynamic mechanical analysis (DMA) at much lower frequencies. The high‐frequency data enable meaningful shift factors to be obtained at temperatures much further above glass‐transition temperature (T g) than would otherwise be possible, giving a more complete picture of the temperature dependence of the viscoelastic properties. The QCM can also be used to quantify mass uptake and changes in viscoelastic properties during sample oxidation. The viscoelastic response spanning the full range of behaviors from the rubber to glassy regimes was found to fit well with a six‐element model consisting of three power‐law springpot elements. One of these elements is particularly sensitive to the behavior in the transition regime where the phase angle is maximized. The value of this quantity is obtained from the maximum phase angle, which can be obtained from a temperature sweep at fixed frequency, proving a means for more detailed frequency‐dependent rheometric information to be obtained from a fixed‐frequency measurement at a range of temperatures. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1246–1254 相似文献
49.
In this paper, an unstable linear time invariant (LTI) ODE system is stabilized exponentially by the PDE compensato—a wave equation with Kelvin‐Voigt (K‐V) damping. Direct feedback connections between the ODE system and wave equation are established: The velocity of the wave equation enters the ODE through the variable vt(1,t); meanwhile, the output of the ODE is fluxed into the wave equation. It is found that the spectrum of the system operator is composed of two parts: point spectrum and continuous spectrum. The continuous spectrum consists of an isolated point , and there are two branches of asymptotic eigenvalues: the first branch approaches to , and the other branch tends to ?∞. It is shown that there is a sequence of generalized eigenfunctions, which forms a Riesz basis for the Hilbert state space. As a consequence, the spectrum‐determined growth condition and exponential stability of the system are concluded. 相似文献
50.
Abigail O. Delawder Anusree Natraj Nathan D. Colley Tiana Saak Angelique F. Greene 《Supramolecular chemistry》2019,31(8):523-531
ABSTRACTAlthough it is well known that viologen radical cations can self-assemble into stacks or complexes on account of radical-radical pairing interactions, it has only recently been demonstrated that reduction of main-chain polyviologens integrated into hydrogel networks can trigger actuation. In these earlier examples, hydrogels comprising oligoethylene glycol-based polyviologens and poly(ethylene glycol) were functionalized with terminal azide groups to prepare ‘click’-based gels. Here, we report a new structural design for the functional polyviologen that consists of main-chain viologen subunits separated by hexamethylene groups instead of glycols and is capped at each end with styrene groups. Activation of this viologen-based macrocrosslinker was achieved using chemical- and photoreduction methods and its ability to undergo intramolecular chain-folding was monitored by absorption spectroscopy. Acrylate-based organogels and hydrogels were also prepared and a comparison was carried out to assess the actuator performance in each gel in terms of the rate of contraction and changes in stiffness. 相似文献