首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   16136篇
  免费   2607篇
  国内免费   1754篇
化学   11857篇
晶体学   205篇
力学   855篇
综合类   81篇
数学   1642篇
物理学   5857篇
  2024年   64篇
  2023年   332篇
  2022年   589篇
  2021年   580篇
  2020年   669篇
  2019年   662篇
  2018年   592篇
  2017年   522篇
  2016年   751篇
  2015年   793篇
  2014年   1008篇
  2013年   1235篇
  2012年   1436篇
  2011年   1520篇
  2010年   1088篇
  2009年   929篇
  2008年   1063篇
  2007年   978篇
  2006年   857篇
  2005年   740篇
  2004年   549篇
  2003年   465篇
  2002年   427篇
  2001年   309篇
  2000年   308篇
  1999年   258篇
  1998年   230篇
  1997年   209篇
  1996年   186篇
  1995年   147篇
  1994年   187篇
  1993年   135篇
  1992年   127篇
  1991年   96篇
  1990年   90篇
  1989年   85篇
  1988年   46篇
  1987年   31篇
  1986年   34篇
  1985年   29篇
  1984年   22篇
  1983年   11篇
  1982年   15篇
  1981年   7篇
  1980年   17篇
  1979年   7篇
  1976年   10篇
  1975年   7篇
  1974年   8篇
  1973年   7篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
221.
An absorption and emission spectroscopic characterisation of the combined wild-type LOV1-LOV2 domain string (abbreviated LOV1/2) of phot from the green alga Chlamydomonas reinhardtii is carried out at pH 8. A LOV1/2-MBP fusion protein (MBP=maltose binding protein) and LOV1/2 with a His-tag at the C-terminus (LOV1/2-His) expressed in an Escherichia coli strain are investigated. Blue-light photo-excitation generates a non-fluorescent intermediate photoproduct (flavin-C(4a)-cysteinyl adduct with absorption peak at 390 nm). The photo-cycle dynamics is studied by dark-state absorption and fluorescence measurement, by following the temporal absorption and emission changes under blue and violet light exposure, and by measuring the temporal absorption and fluorescence recovery after light exposure. The fluorescence quantum yield, phi(F), of the dark adapted samples is phi(F)(LOV1/2-His) approximately 0.15 and phi(F)(LOV1/2-MBP) approximately 0.17. A bi-exponential absorption recovery after light exposure with a fast (in the several 10-s range) and a slow component (in the near 10-min range) are resolved. The quantum yield of photo-adduct formation, phi(Ad), is extracted from excitation intensity dependent absorption measurements. It decreases somewhat with rising excitation intensity. The behaviour of the combined wildtype LOV1-LOV2 double domains is compared with the behaviour of the separate LOV1 and LOV2 domains.  相似文献   
222.
There is increasing interest in developing single-walled carbon nanotubes (SWNTs)-based optical biosensors for remote or in vitro and in vivo sensing because the near-IR optical properties of SWNTs are very sensitive to surrounding environmental changes. Many enzyme-catalyzed reactions yield hydrogen peroxide (H(2)O(2)) as a product. To our knowledge, there is no report on the interaction of H(2)O(2) with SWNTs from the optical sensing point of view. Here, we study the reaction of H(2)O(2) with an aqueous suspension of water-soluble (ws) HiPco SWNTs encased in the surfactant sodium dodecyl sulfate (SDS). The SWNTs are optically sensitive to hydrogen peroxide in pH 6.0 buffer solutions through suppression of the near-IR absorption band intensity. Interestingly, the suppressed spectral intensity of the nanotubes recovers by increasing the pH, by decomposing the H(2)O(2) into H(2)O and O(2) with the enzyme catalase, and by dialytically removing H(2)O(2). Preliminary studies on the mechanisms suggest that H(2)O(2) withdraws electrons from the SWNT valence band by charge transfer, which suppresses the nanotube spectral intensity. The findings suggest possible enzyme-assisted molecular recognition applications by selective optical detection of biological species whose enzyme-catalyzed products include hydrogen peroxide.  相似文献   
223.
This paper introduces an experiment about waste liquid recovery and effect evaluation in laboratory. Through this experiment, the basic operations of crystal preparation, chemical analysis and instrumental analysis are further consolidated. At the same time, it allows students to experience a series of possible problems of condition selection and control in the process of waste liquid treatment. We hope to improve the students' ability to analyze and solve problems, enhance their interest in learning, and strengthen their humanistic education.  相似文献   
224.
Raman spectroscopy (RS) has potential for disease classification within the gastrointestinal tract (GI). A near-infrared (NIR) fiber-optic RS system has been developed previously. This study reports the first in vivo Raman spectra of human gastrointestinal tissues measured during routine clinical endoscopy. This was achieved by using this system with a fiber-optic probe that was passed through the endoscope instrument channel and placed in contact with the tissue surface. Spectra could be obtained with good signal-to-noise ratio in 5 s. The effects on the spectra of varying the pressure of the probe tip on the tissue and of the probe-tissue angle were determined and shown to be insignificant. The limited set of spectra from normal and diseased tissues revealed only subtle differences. Therefore, powerful spectral-sorting algorithms, successfully implemented in prior ex vivo studies, are required to realize the full diagnostic potential of RS for tissue classification in the GI.  相似文献   
225.
新型光学活性α-氨基磷酸及其酯合成进展   总被引:3,自引:1,他引:3  
α-氨基膦酸酯是一类很重要的天然氨基酸类似物,具有新颖的化学结构和多 种生理活性。综述了近年来光学活性α-氨基膦酸及酯的合成进展。  相似文献   
226.
The bridged tri-imidazoliums 3.3X^--5.3X^-(X^-=PF6^-,Br^-,I^-)and bis-imidazoliums 6.2PF6^- were synthesized by N-quaternization of imidazole derivative 1 in acetonitrile under reflux.UV spectroscopic titration experiments showed that the halide salts and hexafluorophosphate salts of these imidazoliums exhibited good recognition toward anions in water and in acetonitrile,respectively.  相似文献   
227.
环氧丙烯酸酯的紫外光固化   总被引:8,自引:0,他引:8  
制备了适于配制紫外光固化涂料的环氧丙烯酸酯,研究了反应温度、阻聚剂、催化剂等因素对环氧树脂与丙烯酸反应的影响;讨论了反应机理和动力学;并利用红外光谱观察了产物的紫外光固化行为。季铵盐能有效地催化环氧树脂和丙烯酸的反应,当其用量为0.6%~1.2%时,在90~110℃反应4.5~8小时后,环氧基转化率大于97%。由此配制的光固化涂料经紫外光辐照能快速固化。  相似文献   
228.
The electronic singlet vertical excited states of photosynthetic reaction center (PSRC) in Rhodopseudomonas (Rps.) viridis were investigated by ZINDO and INDO/S methods. The effects of the interactions of pigment-pigment and pigment-protein on the electronic excitations were examined. The calculation results showed that the interactions of pigment-pigment and pigment-protein play an important role in reasonably assigning the experimental absorption and circular dichroism (CD) spectra of PSRC in Rps. virids. By comparing the theoretically computed excited states with the experimental absorption and CD spectra, satisfactory assignments of the experimental spectroscopic peaks were achieved.  相似文献   
229.
The stereo- and regioselective synthetic route to pimaraditerpenes, employing an angular hydroxymethyl directed intramolecular Diels-Alder reaction of the decaline intermediate, has been developed. This synthetic approach allows prompt access to both natural pimaraditerpenes and the unnatural regioisomers, which would be potentially new anti-inflammatory pimaraditerpenes.  相似文献   
230.
A new two-dimensional (2d) iron phosphate, (C2N2H10)Fe2O(PO4)2, has been synthesized under hydrothermal conditions in the system of FeCl3-H3PO4-C2N2H8-H2O. The crystal data is: space group P21/c, a=10.670(1) Å, b=10.897(1) Å, c=9.918(1) Å, β=105.632(1)°, Z=4. The layered structure consists of double sheet layers, of composition Fe2O(PO4)2, built from FeO5 trigonal bipyramids and PO4 tetrahedra. The amine holds the layers together via H-bonding. The study of the magnetic properties reveals two magnetic transitions at 160 and 30 K with spin-glass-like behavior below 160 K. By varying the hydrothermal conditions, three other iron phosphates were synthesized: the one-dimensional (1d) (C2N2H10)Fe(HPO4)2(OH)·H2O, the 2d (C2N2H10)Fe2(PO4)2(OH)2, and the three-dimensional (3d) (C2N2H10)2Fe4O(PO4)4·H2O. The 1d compound can be used as the starting reagent in the synthesis of both the 2d compound and the 3d lipscombite Fe3(PO4)2(OH)2 due to the similar building blocks in their structures. In the 3d phosphate (C2N2H10)2Fe4O(PO4)4·H2O, manganese can substitute for half of the iron atoms. Magnetic study shows ordering transitions at about 30 K, however, manganese substitution depresses the magnetic ordering temperature.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号