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Bioanalysis assays that reliably quantify biotherapeutics and biomarkers in biological samples play pivotal roles in drug discovery and development. Liquid chromatography coupled with mass spectrometry (LC–MS), owing to its superior specificity, faster method development and multiplex capability, has evolved as one of the most important platforms for bioanalysis of biotherapeutics, particularly new scaffolds such as half-life extension platforms for proteins and peptides, as well as antibody drug conjugates. Intact LC–MS analysis is orthogonal to bottom-up surrogate peptide approach by providing whole molecule quantitation and high-level sequence and structure information. Here we review the latest development in LC–MS bioanalysis of intact proteins and peptides by summarizing recent publications and discussing the important topics such as the comparison between top-down intact analysis and bottom-up surrogate peptide approach, as well as simultaneous quantitation and catabolite identification. Key bioanalytical issues around intact protein bioanalysis such as sensitivity, data processing strategies, specificity, sample preparation and LC condition are elaborated. For peptides, topics including quantitation of intact peptide vs. digested surrogate peptide, metabolites, sensitivity, LC condition, assay performance, internal standard and sample preparation are discussed. 相似文献
3.
We present a higher-order cut cell immersed boundary method (IBM) for the simulation of high Mach number flows. As a novelty on a cut cell grid, we evaluate an adaptive local time stepping (LTS) scheme in combination with an artificial viscosity–based shock-capturing approach. The cut cell grid is optimized by a nonintrusive cell agglomeration strategy in order to avoid problems with small or ill-shaped cut cells. Our approach is based on a discontinuous Galerkin discretization of the compressible Euler equations, where the immersed boundary is implicitly defined by the zero isocontour of a level set function. In flow configurations with high Mach numbers, a numerical shock-capturing mechanism is crucial in order to prevent unphysical oscillations of the polynomial approximation in the vicinity of shocks. We achieve this by means of a viscous smoothing where the artificial viscosity follows from a modal decay sensor that has been adapted to the IBM. The problem of the severe time step restriction caused by the additional second-order diffusive term and small nonagglomerated cut cells is addressed by using an adaptive LTS algorithm. The robustness, stability, and accuracy of our approach are verified for several common test cases. Moreover, the results show that our approach lowers the computational costs drastically, especially for unsteady IBM problems with complex geometries. 相似文献
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高速公路PPP项目属于具有经营收益的准经营性项目,政府制定有效的激励措施,可以鼓励项目公司发挥专业的建设和运营能力,提高项目质量和收益水平。本文以VFM作为政府绩效评价指标,通过构建完全信息静态博弈模型,研究了PPP项目股权结构、质量水平与VFM之间的关系,结果发现:虽然社会资本较多持有项目公司股份有助于提高VFM水平,但随着社会资本方股权比例的增加,项目质量水平在不断降低,所以政府应该将社会资本方的持股比例控制在一定范围内,在保证项目质量的同时达到VFM最大化,从而降低政府方风险,提高社会效益。在高速公路PPP项目中,政府应优化股权决策,激励项目公司改善项目质量和水平,为公私双方带来良好的绩效水平。 相似文献
6.
电子输运现象包含一系列很重要的材料性质,并可以用来提供关于载体物理系统的很多信息。在
最近的二三十年,人们逐渐认识到除了电子能谱之外,电子在布里渊区的几何性质,比如贝利曲率和
轨道磁矩,会在电子输运中起到关键性的作用。在线性输运现象中的此种关联已引起广泛的兴趣并得
到深入的研究。然而,在非线性输运现象中的电子几何性质的作用的研究最近才逐渐起步。此种关联
可以大大加深对各种非线性输运现象的认识,并对如何从材料控制上调节非线性现象的强度提供有价
值的研究视角和指导原则。基于此背景,本文试图引入研究输运现象的半经典理论框架,并在几种输
运现象中举例说明贝利相的作用。 相似文献
7.
Novel monobasic tridentate ONS donor ligand (HL) was synthesized from the condensation reaction of chromone-3-carboxaldehyde with S-benzyldithiocarbazate (SBDTC). Reaction of the ligand with the metal ions copper(II), nickel(II), cobalt(II), oxidovanadium(IV), cerium(III), manganese(II), zinc(II), and cadmium(II) afforded dimeric complexes with the general formula [ML(Y)m(H2O)x]2·(Y)m·nH2O·zCH3OH, Y?=?NO3 or Cl, m?=?0–2, x?=?0–2, n?=?0–2, and z?=?0–1 for all complexes except oxidovanadium(IV) complex which has the formula [VOL(H2O)]2(SO4). Structures of the ligand and its metal complexes were established through elemental, spectroscopic data (FT-IR, UV-Vis, and mass), thermal analyses, as well as conductivity and magnetic susceptibility measurements. The geometrical structures of the metal complexes are octahedral and square planar. The ligand and its complexes were subjected to in vitro bioassays against the gram-negative and gram-positive bacteria and the fungus strain with good results for some of these compounds. The antitumor activity of the ligand and its copper(II) and oxidovanadium(IV) complexes were investigated against HepG2 cell line. The molecular parameters of the ligand and its metal complexes have been calculated on the basis of DFT level implemented in the Gaussian 09 program, and computed data were correlated with the experimental results. The HOMO→LUMO electron transition potentially occurs from S-benzyldithiocarbazate to chromone moieties with 4.048?eV. The Mn(II) complex has the highest value of energy barrier, while Cu(II) complex has the lowest value among the complexes. All synthesized complexes have energy gap lower than free ligand and therefore these complexes are more reactive than the free ligand. 相似文献
8.
电子输运现象包含一系列很重要的材料性质,并可以用来提供关于载体物理系统的很多信息。在
最近的二三十年,人们逐渐认识到除了电子能谱之外,电子在布里渊区的几何性质,比如贝利曲率和
轨道磁矩,会在电子输运中起到关键性的作用。在线性输运现象中的此种关联已引起广泛的兴趣并得
到深入的研究。然而,在非线性输运现象中的电子几何性质的作用的研究最近才逐渐起步。此种关联
可以大大加深对各种非线性输运现象的认识,并对如何从材料控制上调节非线性现象的强度提供有价
值的研究视角和指导原则。基于此背景,本文试图引入研究输运现象的半经典理论框架,并在几种输
运现象中举例说明贝利相的作用。 相似文献
9.
Optical fiber temperature sensors have been widely employed in enormous areas ranging from electric power industry, medical treatment, ocean dynamics to aerospace. Recently, graphene optical fiber temperature sensors attract tremendous attention for their merits of simple structure and direct power detecting ability. However, these sensors based on transfer techniques still have limitations in the relatively low sensitivity or distortion of the transmission characteristics, due to the unsuitable Fermi level of graphene and the destruction of fiber structure, respectively. Here, we propose a tunable and highly sensitive temperature sensor based on graphene photonic crystal fiber (Gr-PCF) with the non-destructive integration of graphene into the holes of PCF. This hybrid structure promises the intact fiber structure and transmission mode, which efficiently enhances the temperature detection ability of graphene. From our simulation, we find that the temperature sensitivity can be electrically tuned over four orders of magnitude and achieve up to ~ 3.34×10-3 dB/(cm·℃) when the graphene Fermi level is ~ 35 meV higher than half the incident photon energy. Additionally, this sensitivity can be further improved by ~ 10 times through optimizing the PCF structure (such as the fiber hole diameter) to enhance the light-matter interaction. Our results provide a new way for the design of the highly sensitive temperature sensors and broaden applications in all-fiber optoelectronic devices. 相似文献
10.
ABSTRACT In this paper, we present a systematic roadmap for developing a robust and parallel multi-material reactive hydrodynamic solver that integrates historically stable algorithms with new and current modern methods to solve explosive system design problems. The Ghost Fluid Method and Riemann solvers were used to enforce appropriate interface boundary conditions. Improved performance in terms of computational work and convergence properties was achieved by modifying a local node sorting strategy that decouples ghost nodes, allowing us to set material boundary conditions via an explicit procedure, removing the need to solve a coupled system of equations numerically. The locality and explicit nature of the node sorting concept allows for greater levels of parallelism and lower computational cost when populating ghost nodes. Non-linear numerical issues endemic to the use of real Equations of State in hydro-codes were resolved by using more thermodynamically consistent forms allowing us to accurately resolve large density gradients associated with high energy detonation problems at material interfaces. Pre-computed volume tables were implemented adding to the robustness of the solver base. 相似文献