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   32561篇
  免费   249篇
  国内免费   301篇
化学   13285篇
晶体学   282篇
力学   1482篇
综合类   12篇
数学   9439篇
物理学   8611篇
  2023年   41篇
  2022年   62篇
  2021年   100篇
  2020年   114篇
  2019年   111篇
  2018年   1252篇
  2017年   1491篇
  2016年   827篇
  2015年   653篇
  2014年   602篇
  2013年   850篇
  2012年   3381篇
  2011年   2626篇
  2010年   1933篇
  2009年   1642篇
  2008年   840篇
  2007年   884篇
  2006年   871篇
  2005年   4646篇
  2004年   4090篇
  2003年   2465篇
  2002年   619篇
  2001年   313篇
  2000年   123篇
  1999年   204篇
  1998年   142篇
  1997年   109篇
  1996年   99篇
  1995年   70篇
  1994年   69篇
  1993年   44篇
  1992年   189篇
  1991年   177篇
  1990年   159篇
  1989年   119篇
  1988年   110篇
  1987年   69篇
  1986年   49篇
  1985年   58篇
  1984年   55篇
  1983年   37篇
  1979年   39篇
  1978年   40篇
  1976年   92篇
  1975年   45篇
  1974年   50篇
  1973年   49篇
  1972年   39篇
  1969年   37篇
  1966年   37篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
The achievements in the area of enzyme stabilization based on electrolytes, polyelectrolytes and polyols is reviewed, in the context of biosensor applications. Both the storage and operational stabilities of the biosensors can be improved using these stabilizers. The deactivation of the enzymes used for the development of biosensors from thermal shock, proteolytic degradation, and non-specific metal-catalyzed oxidation can be drastically reduced with the use of one or more of these stabilizers. It is attempted to deconvolute the effect of these additives on (a) the storage stability or shelf life, and (b) the operational stabilities of the biosensors. Even though there are a large number of techniques and reports dealing with enzyme stabilization, their application to biosensor technology is still very limited. It is thus concluded that the use of the existing enzyme stabilization techniques will have a drastic effect on the storage and operational stabilities of biosensors in the near future.  相似文献   
992.
With the accomplishment of Human Genome Project (HGP), single nucleotide polymorphism (SNP) and mutation detection in human genome are becom-ing a new researching focus. These researches can help us to understand the phenotype diversity of indi-vidual, disease susceptibility and drug resistance of different colonies. Traditional method used for muta-tion detection is slab gel electrophoresis, which re-mains labor-intensive and time-consuming because of the requirement of radioactivity or te…  相似文献   
993.
Hydrogen is a kind of clean, sustainable and renewable energy carrier. Of the problems to be solved for the utilization of hydrogen energy, how to store and transport hydrogen has been given high priority on the research agenda. Recently, carbon nanotubes (CNTs) were reported to be very promising candidates for hydrogen uptake[1], which may have possibility to satisfy the benchmark set by the US Department of Energy (DOE) Hydrogen Plan for fuel cell powered vehicles: a gravimetric density …  相似文献   
994.
New type of spherical pore Al alloy foam with low porosity and high strength   总被引:15,自引:0,他引:15  
The Ultra Light Metal Structure with variouskinds of pores (open, close) realizes the lightness andmultifunction of structural material. The functionsinclude lightness (ρ < 1), high specific strength, highenergy absorption, sound insulation, heat insulationand electromagnetism shield. It is one of the hotspotsin material research nowadays[1— . The requirements 6]of high speed movement and high technology make Alalloy foam, which has higher specific st…  相似文献   
995.
Symmetric dipyrrylketones 1 a , b were synthesized in two steps from the corresponding α‐free pyrroles, by reaction with thiophosgene followed by oxidative hydrolysis under basic conditions. The dipyrrylketones produced the corresponding 5‐chloro‐dipyrrinium salts or 5‐ethoxy‐dipyrrins on reaction with phosgene or Meerwein’s salt, respectively. Boron complexation of the dipyrrins afforded the corresponding 8‐functionalized BODIPYs (borondipyrromethenes) in high yields. The 5‐chloro‐dipyrrinium salts reacted with methoxide or ethoxide ions to produce monopyrrole esters, presumably via a 5,5‐dialkoxy‐dipyrromethane intermediate. In contrast, 8‐chloro‐BODIPYs underwent a variety of nucleophilic substitutions of the chloro group in the presence of alkoxide ions, Grignard reagents, and thiols. In the presence of excess alkoxide or Grignard reagent, at room temperature or above, substitution at the boron center also occurred. The 8‐chloro‐BODIPY was a particularly useful reagent for the preparation of 8‐aryl‐, 8‐alkyl‐, and 8‐vinyl‐substituted BODIPYs in very high yields, using Pd0‐catalyzed Stille cross‐coupling reactions. The X‐ray structures of eleven BODIPYs and two pyrroles are presented, and the spectroscopic properties of the synthesized BODIPYs are discussed.  相似文献   
996.
The two‐step spin crossover in mononuclear iron(III) complex [Fe(salpm)2]ClO4 ? 0.5 EtOH ( 1 ) is shown to be accompanied by a structural phase transition as concluded from 57Fe Mössbauer spectroscopy and single crystal X‐ray diffraction, with spin‐state ordering on just one of two sub‐lattices in the intermediate magnetic and structural phase. The complex also exhibits thermal‐ and light‐induced spin‐state trapping (TIESST and LIESST), and relaxation from the LIESST and TIESST excited states occurs via the broken symmetry intermediate phase. Two relaxation events are evident in both experiments, that is, two T(LIESST) and two T(TIESST) values are recorded. The change in symmetry which accompanies the TIESST effect was followed in real time using single crystal diffraction. After flash freezing at 15 K the crystal was warmed to 40 K at which temperature superstructure reflections were observed to appear and disappear within a 10 000 s time range. In the frame of the international year of crystallography, these results illustrate how X‐ray diffraction makes it possible to understand complex ordering phenomena.  相似文献   
997.
The synthesis of a series of new lipid‐inspired ionic liquids through thiol‐ene “click” reaction with a single‐step process. This synthesis offers considerable promise as an efficient and orthogonal method to construct structurally diverse imidazolium‐type ionic liquids with linear and branched cationic tails, as well as versatility in the placement of the sulfur heteroatom. Profound solvent effect in this ene reaction regioselectivity has been observed.  相似文献   
998.
A novel variant of an iridium‐based organometallic catalyst was synthesized and used to enhance the NMR signals of pyridine in a heterogeneous phase by immobilization on polymer microbead solid supports. Upon administration of parahydrogen (pH2) gas to a methanol mixture containing the HET‐SABRE catalyst particles and the pyridine, up to fivefold enhancements were observed in the 1H NMR spectra after sample transfer to high field (9.4 T). Importantly, enhancements were not due to any residual catalyst molecules in solution, thus supporting the true heterogeneity of the SABRE process. Further significant improvements may be expected by systematic optimization of experimental parameters. Moreover, the heterogeneous catalyst is easy to separate and recycle, thus opening a door to future potential applications varying from spectroscopic studies of catalysis, to imaging metabolites in the body without concern of contamination from expensive and potentially toxic metal catalysts or accompanying organic molecules.  相似文献   
999.
1000.
Dissolution dynamic nuclear polarization (DNP) enables high‐sensitivity solution‐phase NMR experiments on long‐lived nuclear spin species such as 15N and 13C. This report explores certain features arising in solution‐state 1H NMR upon polarizing low‐γ nuclear species. Following solid‐state hyperpolarization of both 13C and 1H, solution‐phase 1H NMR experiments on dissolved samples revealed transient effects, whereby peaks arising from protons bonded to the naturally occurring 13C nuclei appeared larger than the typically dominant 12C‐bonded 1H resonances. This enhancement of the satellite peaks was examined in detail with respect to a variety of mechanisms that could potentially explain this observation. Both two‐ and three‐spin phenomena active in the solid state could lead to this kind of effect; still, experimental observations revealed that the enhancement originates from 13C→1H polarization‐transfer processes active in the liquid state. Kinetic equations based on modified heteronuclear cross‐relaxation models were examined, and found to well describe the distinct patterns of growth and decay shown by the 13C‐bound 1H NMR satellite resonances. The dynamics of these novel cross‐relaxation phenomena were determined, and their potential usefulness as tools for investigating hyperpolarized ensembles and for obtaining enhanced‐sensitivity 1H NMR traces was explored.  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