全文获取类型
收费全文 | 23768篇 |
免费 | 4399篇 |
国内免费 | 4728篇 |
专业分类
化学 | 12440篇 |
晶体学 | 397篇 |
力学 | 820篇 |
综合类 | 407篇 |
数学 | 2009篇 |
物理学 | 6532篇 |
无线电 | 10290篇 |
出版年
2024年 | 87篇 |
2023年 | 367篇 |
2022年 | 700篇 |
2021年 | 757篇 |
2020年 | 736篇 |
2019年 | 799篇 |
2018年 | 683篇 |
2017年 | 832篇 |
2016年 | 962篇 |
2015年 | 1206篇 |
2014年 | 1471篇 |
2013年 | 1778篇 |
2012年 | 2010篇 |
2011年 | 2103篇 |
2010年 | 1804篇 |
2009年 | 1959篇 |
2008年 | 2093篇 |
2007年 | 1972篇 |
2006年 | 1768篇 |
2005年 | 1464篇 |
2004年 | 1218篇 |
2003年 | 955篇 |
2002年 | 1062篇 |
2001年 | 918篇 |
2000年 | 797篇 |
1999年 | 485篇 |
1998年 | 305篇 |
1997年 | 224篇 |
1996年 | 219篇 |
1995年 | 175篇 |
1994年 | 155篇 |
1993年 | 164篇 |
1992年 | 99篇 |
1991年 | 92篇 |
1990年 | 67篇 |
1989年 | 60篇 |
1988年 | 66篇 |
1987年 | 55篇 |
1986年 | 44篇 |
1985年 | 47篇 |
1984年 | 24篇 |
1983年 | 28篇 |
1982年 | 14篇 |
1981年 | 17篇 |
1980年 | 9篇 |
1979年 | 10篇 |
1978年 | 6篇 |
1976年 | 5篇 |
1974年 | 4篇 |
1973年 | 5篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
992.
993.
Lingli Lei Yuanyuan Zhang Ying Jiang Lulu Xiong Yingshuai Liu Chang Ming Li 《Electroanalysis》2021,33(10):2180-2186
Biomimetic electrochemical sensors are very promising not only due to their lower expense and longer stability than conventional enzymatic ones, but they also often suffer from simultaneously achieving high sensitivity and good selectivity. Here we present a well-defined Au@Co3O4/CeO2 yolk-shell nanostructure (YSN) that is first synthesized and exploited as highly efficient electrocatalysts for hydrogen peroxide (H2O2) detection. The introduced CeO2 in Co3O4 matrix greatly facilitates the migration of lattice oxygen, which increases the concentration of surface oxygen vacancies (Oa), remarkably enhancing the adsorption ability of H2O2 and promoting the decomposition of H2O2 for faster electron transfer than pristine Au@Co3O4 core-shell nanostructure (CSN). The abundant Oa of Au@Co3O4/CeO2 YSN is confirmed by X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR). The as-prepared biomimetic sensor delivers a wide dynamic range (5.0 nM to 5.4 μM), a low limit of detection (LOD) (2.74 nM), and a high sensitivity (35.67 μA μM−1 cm−2), paving a new way to construct an ultrasensitive and selective enzyme-free biomimetic electrochemical sensor. Furthermore, the sensor is used to real-time monitor H2O2 released from human cervical cancer cells (HeLa) and human umbilical vein endothelial cells (HUVEC), demonstrating its great potential in practical applications. 相似文献
994.
Transformation thermodynamics as a major extension of transformation optics has recently received considerable attention. In this paper, we present two-dimensional (2D) and three-dimensional (3D) diamond-shaped transient thermal cloaks with non-singular homogeneous material parameters. The absence of singularity in the parameters results from the fact that the linear coordinate transformation is performed by expanding a line segment rather than a point into a region, while the mechanism behind the homogeneity is the homogeneous stretching and compression along orthogonal directions during the transformation. Although the derived parameters remain anisotropic, we further show that this can be circumvented by considering a layered structure composed of only four types of isotropic materials based on the effective medium theory. Numerical simulation results confirm the good performance of the proposed cloaks. 相似文献
995.
Trehalose-protected lipid membranes for determining membrane protein structure and insertion 总被引:1,自引:0,他引:1
Tang M Waring AJ Hong M 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2007,184(2):222-227
Trehalose preserves lipid bilayers during dehydration and rehydration by replacing water to form hydrogen bonds between its own OH groups and lipid headgroups. We compare the lipid conformation and dynamics between trehalose-protected lyophilized membranes and hydrated membranes, to assess the suitability of the trehalose-containing membrane as a matrix for membrane protein structure determination. (31)P spectra indicate that the lipid headgroup of trehalose-protected dry POPC membrane (TRE-POPC) have an effective phase transition temperature that is approximately 50K higher than that of the hydrated POPC membrane. In contrast, the acyl chains have similar transition temperatures in the two membranes. Intramolecular lipid (13)C'-(31)P distances are the same in TRE-POPC and crystalline POPC, indicating that the lipid headgroup and glycerol backbone conformation is unaffected by trehalose incorporation. Intermolecular (13)C-(31)P distances between a membrane peptide and the lipid headgroups are 10% longer in the hydrated membrane at 226 K than in the trehalose-protected dry membrane at 253 K. This is attributed to residual motions in the hydrated membrane, manifested by the reduced (31)P chemical shift anisotropy, even at the low temperature of 226 K. Thus, trehalose lyoprotection facilitates the study of membrane protein structure by allowing experiments to be conducted at higher temperatures than possible with the hydrated membranes. 相似文献
996.
针对二硫化钼(MoS2)因易团聚导致去除六价铬[Cr(Ⅵ)]容量低的问题, 利用六方氮化硼(BN)良好的吸附性和化学稳定性, 以多巴胺作为BN改性剂, 通过煅烧法和水热法制得碳掺杂六方氮化硼(c-BN)负载MoS2纳米复合材料(c-BN@MoS2). 研究了室温条件下c-BN@MoS2对Cr(Ⅵ)的吸附还原和助催化降解有机污染物的性能. 实验结果表明, c-BN@MoS2在40 min内对50 mg/L的Cr(Ⅵ)吸附还原去除率高达95%以上, 且以将 Cr(Ⅵ)还原至Cr(Ⅲ)为主, 在pH值为2、 温度为25 ℃条件下去除Cr(Ⅵ)最大容量可达401 mg/g, 显著高于 MoS2(98 mg/g). 分析显示, c-BN不仅提高了MoS2的平均孔径, 还可促进MoS2生成金属特性的1T相, 有利于吸附Cr(Ⅵ)和加快氧化还原过程中的电子转移. 在Fe2+/PMS(过一硫酸氢盐)催化体系加入c-BN@MoS2, 该体系对磺胺甲恶唑的降解性能明显增强, 其反应速率常数提高3倍, 这主要归因于c-BN@MoS2明显加快了Fe3+到Fe2+的转变, 导致更多?OH产生, 达到增强降解污染物的目标. 相似文献
997.
对多原子体系的量子动力学计算非常重要, 然而, 对含六原子以上的分子体系进行精确量子动力学计算仍具挑战性. 面向过程的基函数定制(PBFC)-并行迭代(PI)方法是一种高效的量子动力学方法, 已应用于对含九原子的丙二醛异构体系的氢迁移速率的精确量子计算. 本综述首先阐明了PBFC的基本思想, 之后重点回顾了PBFC-PI方法的具体内容、 该方法与其它方法的结合及其应用方面的新进展. 应用这些方法实现了对单氢迁移、 协同双氢迁移和分步双氢迁移3种类型基准体系的大规模并行计算, 有助于获得对氢迁移过程的新认识. 相似文献
998.
A novel Ca(Ⅱ) coordination polymer,[Ca L2(H2O)2]n (1,HL=4-acetylphenoxyacetic acid) has been synthesized with 4-acetylphenoxyacetic acid,Ca(ClO_4)2·4H2O and Na OH as raw materials.Complex 1 was characterized by elemental analysis and single-crystal X-ray diffraction analysis.The results show that the Ca(Ⅱ)ion is eight-coordinated in a distorted triangular dodecahedral geometric configuration with six carboxylate Oatoms of four L ligands and two O atoms of two coordinated water molecules.Complex 1 forms a one-dimensional chained structure by the bridging effect of carboxylate O atoms.The antitumor activity of HLligand and complex 1 has also been investigated. 相似文献
999.
Deng Xi Wu Liling Deng Yunmeng Huang Siqi Sun Mengtian Wang Xiaowu Liu Qiong Li Ming Li Zhi 《Journal of Sol-Gel Science and Technology》2021,100(3):477-488
Journal of Sol-Gel Science and Technology - This work presents a facile synthesis approach of methyltriethoxysilane (MTES) based aerogels using pure water as the only solvent, and the effects of... 相似文献
1000.
Donglin He Chengxi Zhao Dr. Linjiang Chen Dr. Marc A. Little Dr. Samantha Y. Chong Rob Clowes Katherine McKie Mark G. Roper Graeme M. Day Dr. Ming Liu Prof. Andrew I. Cooper 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(41):10589-10594
Ethyl acetate is an important chemical raw material and solvent. It is also a key volatile organic compound in the brewing industry and a marker for lung cancer. Materials that are highly selective toward ethyl acetate are needed for its separation and detection. Here, we report a trianglimine macrocycle ( TAMC ) that selectively adsorbs ethyl acetate by forming a solvate. Crystal structure prediction showed this to be the lowest energy solvate structure available. This solvate leaves a metastable, “templated” cavity after solvent removal. Adsorption and breakthrough experiments confirmed that TAMC has adequate adsorption kinetics to separate ethyl acetate from azeotropic mixtures with ethanol, which is a challenging and energy-intensive industrial separation. 相似文献