全文获取类型
收费全文 | 105460篇 |
免费 | 19419篇 |
国内免费 | 12089篇 |
专业分类
化学 | 73996篇 |
晶体学 | 1154篇 |
力学 | 6579篇 |
综合类 | 787篇 |
数学 | 12428篇 |
物理学 | 42024篇 |
出版年
2024年 | 261篇 |
2023年 | 2286篇 |
2022年 | 2628篇 |
2021年 | 3576篇 |
2020年 | 4601篇 |
2019年 | 4197篇 |
2018年 | 3705篇 |
2017年 | 3336篇 |
2016年 | 5267篇 |
2015年 | 5035篇 |
2014年 | 6117篇 |
2013年 | 7939篇 |
2012年 | 9626篇 |
2011年 | 10085篇 |
2010年 | 6761篇 |
2009年 | 6587篇 |
2008年 | 7026篇 |
2007年 | 6208篇 |
2006年 | 5890篇 |
2005年 | 4831篇 |
2004年 | 3703篇 |
2003年 | 2971篇 |
2002年 | 2899篇 |
2001年 | 2359篇 |
2000年 | 2127篇 |
1999年 | 2266篇 |
1998年 | 1862篇 |
1997年 | 1835篇 |
1996年 | 1827篇 |
1995年 | 1533篇 |
1994年 | 1344篇 |
1993年 | 1133篇 |
1992年 | 981篇 |
1991年 | 875篇 |
1990年 | 718篇 |
1989年 | 566篇 |
1988年 | 424篇 |
1987年 | 344篇 |
1986年 | 355篇 |
1985年 | 299篇 |
1984年 | 164篇 |
1983年 | 125篇 |
1982年 | 105篇 |
1981年 | 68篇 |
1980年 | 47篇 |
1979年 | 12篇 |
1973年 | 4篇 |
1957年 | 35篇 |
1936年 | 3篇 |
1930年 | 3篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
111.
Yimei Wang Yi Qiao Xiaomin Xu Xiaohong Ding Weiwei Li Bo Yuan Haiyan Xu 《Biomedical chromatography : BMC》2019,33(8)
A sensitive and reliable LC–MS/MS method was developed and validated for simultaneous quantification of the major components of Huangqi–Honghua extact in rat plasma, including hydroxysafflor yellow A (HSYA), astragaloside IV (ASIV), calycosin‐7‐O‐β‐d ‐glucoside (CAG), calycosin, calycosin‐3′‐O‐glucuronide (C‐3′‐G) and calycosin‐3′‐O‐sulfate (C‐3′‐S). After extraction by protein precipitation with acetonitrile and methanol from plasma, the analytes were separated on a Hypersil BDS C18 column by gradient elution with acetonitrile and 5 mM ammonium acetate. The detection was carried out on a triple quadrupole tandem mass spectrometer equipped with electrospray ionization source switched between negative and positive modes. HSYA was monitored in negative ionization mode from 0 to 4.9 min, and ASIV, CAG, calycosin, C‐3′‐G and C‐3′‐S were determined in positive ionization mode from 4.9 to 10 min. The lower limits of quantification of the analytes were 6.25 ng/mL for HSYA, 0.781 ng/mL for CAG and 1.56 ng/mL for ASIV and calycosin. The intra‐ and inter‐assay precision (RSD) values were within 13.43%, and accuracy (RE) ranged from ?8.75 to 9.92%. The validated method was then applied to the pharmacokinetic study of HSYA, ASIV, CAG, calycosin, C‐3′‐G and C‐3′‐S in rat after an oral administration of Huangqi–Honghua extract. 相似文献
112.
Nonclassical light states are important for both conceptual and practical reasons: they are basic ingredients in testing and exploring quantum foundations, and are crucial resources in quantum technologies. Various useful criteria have been developed to detect nonclassicality in the literature, and several meaningful measures of nonclassicality have been introduced and measured experimentally. In this work, by use of a non-Hermitian generalization of the Wigner-Yanase-Dyson skew information and playing with operator ordering in evaluating average photon number, we develop a novel family of criteria for detecting nonclassicality of light based on Lieb's concavity, which is a deep and powerful result concerning interaction between quantum states and observables. We elucidate the information-theoretic as well as the physical meaning of the criteria, and illustrate their effectiveness in capturing and quantifying nonclassicality of various important light states. 相似文献
113.
114.
Chunhong Wang Qi Cui Zhixin Zhang Prof. Zhu-Jun Yao Dr. Shaozhong Wang Prof. Zhi-Xiang Yu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(42):9821-9826
1,3-Azaprotio transfer of propargylic α-ketocarboxylate oximes, a new type of alkynyl oximes featuring an ester tether, has been explored by taking advantage of gold catalysis. The incorporation of an oxygen atom to the chain of alkynyl oximes led to the formation of two different oxa-cyclic nitrones. It was found that internal alkynyl oximes with an E-configuration deliver five-membered nitrones, whereas terminal alkynyl oximes with an E-configuration afford six-membered nitrones. DFT calculations on four possible pathways supported a stepwise formation of C−N and C−H bonds, in which a 1,3-acyloxy-migration competes with the 1,3-azaprotio-transfer, especially in the case of internal alkynyl oximes. The relative nucleophilic properties of oxygen in the carbonyl group and the nitrogen in the oxime, the electronic effects of alkynes, and the influence of the ring system have been investigated computationally. 相似文献
115.
Ling-Yang Hsu Qiumin Liang Zhiheng Wang Hsin-Hung Kuo Wun-Shan Tai Shi-Jian Su Xiuwen Zhou Yi Yuan Yun Chi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(67):15375-15386
Iridium complexes bearing chelating cyclometalates are popular choices as dopant emitters in the fabrication of organic light-emitting diodes (OLEDs). In this contribution, we report a series of blue-emitting, bis-tridentate IrIII complexes bearing chelates with two fused five-six-membered metallacycles, which are in sharp contrast to the traditional designs of tridentate chelates that form the alternative, fused five-five metallacycles. Five IrIII complexes, Px-21 – 23 , Cz-4 , and Cz-5 , have been synthesized that contain a coordinated dicarbene pincer chelate incorporating a methylene spacer and a dianionic chromophoric chelate possessing either a phenoxy or carbazolyl appendage to tune the coordination arrangement. All these tridentate chelates afford peripheral ligand–metal–ligand bite angles of 166–170°, which are larger than the typical bite angle of 153–155° observed for their five-five-coordinated tridentate counterparts, thereby leading to reduced geometrical distortion in the octahedral frameworks. Photophysical measurements and TD-DFT studies verified the inherent transition characteristics that give rise to high emission efficiency, and photodegradation experiments confirmed the improved stability in comparison with the benchmark fac-[Ir(ppy)3] in degassed toluene at room temperature. Phosphorescent OLED devices were also fabricated, among which the carbazolyl-functionalized emitter Cz-5 exhibited the best performance among all the studied bis-tridentate phosphors, showing a maximum external quantum efficiency (EQEmax) of 18.7 % and CIEx,y coordinates of (0.145, 0.218), with a slightly reduced EQE of 13.7 % at 100 cd m−2 due to efficiency roll-off. 相似文献
116.
Shi-Chun Mao Zhaohui Zhang Jiansen Gao Zhen-Sen Wu 《Waves in Random and Complex Media》2019,29(1):54-62
A solution to the problem of Gaussian beam scattering by an anisotropically coated circular cylinder is presented. The incident Gaussian beam source is expanded as an approximate expression in the simple form with a Tayor’s series. The transmitted field in the anisotropically coated region is expressed as a infinite summation of eigen plane waves with different polar angles. The unknown coefficients of the scattered fields are obtained with the aid of the boundary conditions. The infinite series can be truncated under the prerequisite of achieving the solution convergence. Only the case of transverse-electric polarization is discussed. The similar formulation of transverse-magnetic polarization can be obtained by adopting the similar method. Some numerical results are presented and discussed. The result is in agreement with that available as expected when the Gaussian beam degenerates to a plane wave incidence case. 相似文献
117.
Nonlinear Dynamics - Global dynamics of a flexible asymmetrical rotor resting on vibrating supports is investigated. Hamilton’s principle is used to derive the partial differential governing... 相似文献
118.
Prof. Jen-Shyang Ni Tianliang Min Yaxi Li Menglei Zha Dr. Pengfei Zhang Prof. Chun Loong Ho Prof. Kai Li 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(25):10265-10271
Planar luminogens have encountered difficulties in overcoming intrinsic aggregation-caused emission quenching by intermolecular π-π stacking interactions. Although excited-state double-bond reorganization (ESDBR) can guide us on designing planar aggregation-induced emission (AIE) luminogens (AIEgens), its mechanism has yet been elucidated. Major challenges in the field include methods to efficiently restrict ESDBR and enhance AIE performance without using bulky substituents (e.g., tetraphenylethylene and triphenylamine). In this study, we rationally developed fluoro-substituent AIEgens with stronger intermolecular H-bonding interaction for restricted molecular motions and increased crystal density, leading to decreased nonradiative decay rate by one order of magnitude. The adjusted ESDBR properties also show a corresponding response to variation in viscosity. Furthermore, their aggregation-induced reactive oxygen species (ROS) generations have been discovered. The application of such planar AIEgen in treating multidrug-resistant bacteria has been demonstrated in a mouse model. The relationship between ROS generation and distinct E/Z-configurational stacking behaviors have been further understood, providing a design principle for synthesizing planar AIEgen-based photosensitizers. 相似文献
119.
Understanding and control of the surface properties such as molecular orientations are of great importance in numerous applications of ionic liquids. However, there remain discrepancies among the previous experimental and theoretical studies on the surface orientation and structures of room temperature ionic liquids(RTIL) systems. In this article, the orientation of 1-butyl-3-methylimidazolium([bmin]) cation at the air/liquid interface of a characteristic RTIL, 1-butyl-3-methylimidazolium hexafluorophosphate([bmim][PF6]), was investigated by the sum frequency generation vibrational spectroscopy(SFG-VS). Detailed polarization and experimental configuration analyses of the SFG-VS spectra showed the possibility of a small spectral splitting in the CH3 symmetric stretching region, which can be further attributed to the probable existence of multiple orientations for the interfacial [bmim] cations. In addition, the(N)–CH3 vibrations were absent, ruling out the prediction by several recent molecular dynamics simulations which state that portions of the [bmim] cations orient with a standing-up(N)–CH3 group at the ionic liquid surface. Hence, new realistic theoretical models have to be developed to reflect the complex nature of the ionic liquid surface. 相似文献
120.
Understanding defect production in an hcp Zr crystal upon irradiation:An energy landscape perspective 下载免费PDF全文
Primary radiation damage in hcp Zr,including both defect production in a single collision cascade and damage buildup through cascade overlap,is investigated using molecular dynamics(MD)simulations from a potential energy landscape(PEL)perspective.It is found that the material’s response to an energetic particle can be understood as a trajectory in the PEL comprising a fast uphill journey and a slow downhill one.High-temperature-induced damage reduction and the difference in the radiation tolerance between metals and semiconductors can be both qualitatively explained by the dynamics of the trajectory associated with the topographic features of the system’s PEL.Additionally,by comparing irradiation and heating under a nearly identical condition,we find that large atomic displacements stemming from the extreme locality of the energy deposition in irradiation events are the key factor leading to radiation damage in a solid.Finally,we discuss the advantages of the PEL perspective and suggest that a combination of the PEL and the traditional crystallographic methods may provide more insights in future work. 相似文献