全文获取类型
收费全文 | 37407篇 |
免费 | 6126篇 |
国内免费 | 9893篇 |
专业分类
化学 | 28000篇 |
晶体学 | 936篇 |
力学 | 2394篇 |
综合类 | 1066篇 |
数学 | 5458篇 |
物理学 | 15572篇 |
出版年
2024年 | 30篇 |
2023年 | 318篇 |
2022年 | 794篇 |
2021年 | 865篇 |
2020年 | 1056篇 |
2019年 | 1123篇 |
2018年 | 1022篇 |
2017年 | 1242篇 |
2016年 | 1233篇 |
2015年 | 1669篇 |
2014年 | 1848篇 |
2013年 | 2492篇 |
2012年 | 2555篇 |
2011年 | 3911篇 |
2010年 | 3132篇 |
2009年 | 3128篇 |
2008年 | 2839篇 |
2007年 | 2591篇 |
2006年 | 2477篇 |
2005年 | 2482篇 |
2004年 | 2760篇 |
2003年 | 1972篇 |
2002年 | 1943篇 |
2001年 | 1740篇 |
2000年 | 1343篇 |
1999年 | 943篇 |
1998年 | 675篇 |
1997年 | 507篇 |
1996年 | 420篇 |
1995年 | 385篇 |
1994年 | 337篇 |
1993年 | 625篇 |
1992年 | 661篇 |
1991年 | 449篇 |
1990年 | 436篇 |
1989年 | 407篇 |
1988年 | 183篇 |
1987年 | 132篇 |
1986年 | 106篇 |
1985年 | 88篇 |
1984年 | 94篇 |
1983年 | 86篇 |
1982年 | 65篇 |
1981年 | 42篇 |
1980年 | 49篇 |
1979年 | 33篇 |
1978年 | 17篇 |
1977年 | 16篇 |
1976年 | 14篇 |
1971年 | 12篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
71.
噪声免疫腔增强光外差分子光谱技术(NICE-OHMS)是目前世界上最灵敏的激光吸收光谱技术,其在低压环境中具有极高的探测灵敏度。然而当测量样品处于大气压时,NICE-OHMS系统的探测灵敏度会大幅下降。主要原因之一是大气压下获取最大NICE-OHMS信号幅度的条件与低气压下不同。通过对大气压NICE-OHMS理论进行分析,分析了影响信号幅度的参数,并通过数值模拟来寻找最佳的实验条件。本文着重讨论影响信号的主要参数包括光学腔腔长L,调制系数β,探测相位θ。其中,由于在NICE-OHMS中使用DeVoe-Brewer技术将调制频率ν_m锁定到Fabry-Parot(FP)腔的自由光谱区(FSR)。因此FP腔的腔长决定了ν_m,同时还作用于信号幅度S■。模拟结果显示,当腔长增大时,由于ν_m随之减小,载波和边带的光谱成分相互重叠部分增大,因此线型函数的幅度逐渐减小。而吸收信号幅度随着腔长的增加而逐渐增加,色散信号幅度先增大后减小,并且在腔长等于8 cm时达到最大值。调制系数β会影响频率调制后激光载波和边带的幅度大小,并且影响信号线型。随着腔长的增加,最大信号幅度对应的β值也随之增加。在相同腔长下,色散信号的最佳β值小于吸收信号,更容易使用电光调制器实现。最后分析了参数的可实现性,分析了不同种类激光器的频率调谐能力,压电陶瓷的扫描宽度等。以乙炔气体为例,大气压下NICE-OHMS的谱线半宽达到~3 GHz,而光谱覆盖范围大于10 GHz。分布反馈式半导体激光器(DFB)与外腔二极管激光器(ECDL)的频率调谐范围可以达到30 GHz以上,但是由于激光线宽宽,得到的PDH锁定性能欠佳。回音壁模式激光器(WGM)和掺饵光纤激光器(EDFL)线宽为百Hz量级,是目前高灵敏NICE-OHMS系统中常用的光源。但是WGM目前可以实现了5 GHz的激光频率调谐范围,而EDFL的外部电压可控制的调谐范围仅为3 GHz。使用精细度为55000的腔进行模拟,调制系数β=1,腔长大于8 cm时,可使用WGM激光器实现,腔长大于25 cm时,可以使用EDFL激光器实现。而对于在设计光学腔中常用的伸缩长度为25μm的PZT,随着腔长的增加,对应的腔模频移范围逐渐减小,在腔长为典型的40 cm时,扫描范围大于12 GHz。 相似文献
72.
Redox Communication within Multinuclear Iron–Sulfur Complexes Related to Electronic Interplay in the Active Site of [FeFe]Hydrogenase 下载免费PDF全文
Kai‐Ti Chu Dr. Yu‐Chiao Liu Yi‐Lan Huang Dr. Gene‐Hsiang Lee Dr. Mei‐Chun Tseng Prof. Ming‐Hsi Chiang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(18):6852-6861
The one‐electron oxidations of a Fe2 complex lead to the formation of a persistent metal‐stabilized thiyl radical Fe2 species, mixed‐valent Fe4, and Fe8 complexes. The unpaired spin in the Fe2 radical species delocalizes over the Fe2 and the aromatic dithiolate, mostly on the terminal sulfur. The subsequent dimerization of the singly oxidized Fe2 to the Fe4 retains the partial thiyl radical character. For an analogue with less steric hindrance, the π–π stacking interaction between the dithiolato aromatic rings induces generation of the Fe8, in which process electronic structures of the species are modulated through reducing the thiyl radical to the thiolate. Electronic reorganization repeats when the Fe8 is converted to Fe4. Electronic interplay in the complexes decreases the energy gap of frontier MOs and buffers electronic impacts upon redox events. Easier accessible redox potentials and increased stability of the species are facilitated. The results demonstrate that electronic versatility of the benzenedithiolate exerts pronounced influences on electronic and coordination structure of the metal complexes. 相似文献
73.
74.
Zhen Xi 《中国科学:化学(英文版)》2015,(3):434-435
Redox-based post-translational modification of protein thiols has become an attractive strategy in cellular homeostasis and cell signaling.Due to the reductive end of the redox buffer network,the vicinal dithiol-containing proteins(VDPs)maintains an appropriate oxidation-reduction state of proteins through the reversible transformation from vicinal dithiols to disulfide,which is responsible for a variety of 相似文献
75.
76.
77.
Back Cover: Ligand Symmetry Modulation for Designing a Mesoporous Metal–Organic Framework: Dual Reactivity to Transition and Lanthanide Metals for Enhanced Functionalization (Chem. Eur. J. 27/2015) 下载免费PDF全文
78.
基于Hilbert空间标架理论,借助算子工具,用己有连续广义标架构造了新连续广义标架,并给出了有限个连续广义标架和构成新连续广义标架的充要条件,为构造连续广义标架提供了新方法。 相似文献
79.
Natural products with a variety of pharmacological effects are important sources for commercial drugs, and it is very crucial to develop effective techniques to selectively extract and isolate bioactive natural components from the plants against the background of sustainable development. Ionic liquids (ILs) are a kind of designable material with unique physicochemical properties, including good thermal stability, negligible vapor pressure, good solvation ability, etc. ILs have already been used in pharmaceuticals for extraction, purification, drug delivery, etc. It has been reported that multi-interactions, like hydrogen bonding, hydrophobic interactions, play important roles in the extraction of bioactive components from the plants. In this review, recent progress in the understanding of scientific essence of hydrogen bonding, the special interaction, in ILs was summarized. The extraction of various natural products, one important area in pharmaceutical, by conventional and functional ILs as well as the specific roles of multi-interactions in this process were also reviewed. Moreover, problems existing in bioactive compound extraction by ILs and the future developing trends of this area are given, which might be helpful for scientists, especially beginners, in this field. 相似文献
80.
Hui Li Jian Liu Juan Zhao Huiting He Dr. Dabo Jiang Prof. Steven Robert Kirk Prof. Qiong Xu Dr. Xianxiang Liu Prof. Dulin Yin 《ChemistryOpen》2021,10(4):477-485
A series of tetraimidazolium salts with different anions was prepared and applied in the isomerization of β-pinene oxide. After examining the activity of different catalysts, a remarkable enhancement of the selectivity of perillyl alcohol (47 %) was obtained over [PEimi][HNO3]4 under mild reaction conditions and using DMSO as the solvent. Furthermore, noncovalent interactions between solvent molecules and the catalyst were found by FT-IR spectroscopy and confirmed by computational chemistry. The homogeneous catalyst showed excellent stability and was reused up to six times without significant loss. 相似文献