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   7783篇
  免费   377篇
  国内免费   7篇
化学   5284篇
晶体学   66篇
力学   301篇
数学   1172篇
物理学   1344篇
  2023年   51篇
  2022年   77篇
  2021年   112篇
  2020年   150篇
  2019年   142篇
  2018年   184篇
  2017年   146篇
  2016年   301篇
  2015年   244篇
  2014年   251篇
  2013年   552篇
  2012年   534篇
  2011年   595篇
  2010年   310篇
  2009年   285篇
  2008年   534篇
  2007年   543篇
  2006年   485篇
  2005年   452篇
  2004年   334篇
  2003年   313篇
  2002年   262篇
  2001年   103篇
  2000年   89篇
  1999年   77篇
  1998年   60篇
  1997年   45篇
  1996年   79篇
  1995年   54篇
  1994年   50篇
  1993年   52篇
  1992年   42篇
  1991年   32篇
  1990年   23篇
  1989年   31篇
  1988年   15篇
  1987年   23篇
  1985年   49篇
  1984年   36篇
  1983年   16篇
  1982年   48篇
  1981年   36篇
  1980年   47篇
  1979年   38篇
  1978年   32篇
  1977年   29篇
  1976年   42篇
  1975年   38篇
  1974年   26篇
  1973年   24篇
排序方式: 共有8167条查询结果,搜索用时 203 毫秒
91.
Sezgintürk MK  Dinçkaya E 《Talanta》2005,65(4):998-1002
In the work described here, a biosensor was developed for the determination of sulfite in food. Malva vulgaris tissue homogenate containing sulfite oxidase enzyme was used as the biological material. M. vulgaris tissue homogenate was crosslinked with gelatin using glutaraldehyde and fixed on a pretreated Teflon membrane. Sulfite was enzymatically converted to sulfate in the presence of the dissolved oxygen, which was monitored amperometrically. Sulfite determination was carried out by standard curves, which were obtained by the measurement of consumed oxygen level related to sulfite concentration. Several operational parameters had been investigated: the amounts of plant tissue homogenate and gelatin, percentage of glutaraldehyde, optimum pH and temperature. Also, some characterization studies were done. There was linearity in the range between 0.2 and 1.8 mM at 35 °C and pH 7.5. The results of real sample analysis obtained with the biosensor agreed well with the enzymatic reference method using spectrophotometric detection.  相似文献   
92.
We show that a protein with no intrinsic inorganic synthesis activity can be endowed with the ability to control the formation of inorganic nanostructures under thermodynamically unfavorable (nonequilibrium) conditions, reproducing a key feature of biological hard-tissue growth and assembly. The nonequilibrium synthesis of Cu(2)O nanoparticles is accomplished using an engineered derivative of the DNA-binding protein TraI in a room-temperature precursor electrolyte. The functional TraI derivative (TraIi1753::CN225) is engineered to possess a cysteine-constrained 12-residue Cu(2)O binding sequence, designated CN225, that is inserted into a permissive site in TraI. When TraIi1753::CN225 is included in the precursor electrolyte, stable Cu(2)O nanoparticles form, even though the concentrations of [Cu(+)] and [OH(-)] are at 5% of the solubility product (K(sp,Cu2O)). Negative control experiments verify that Cu(2)O formation is controlled by inclusion of the CN225 binding sequence. Transmission electron microscopy and electron diffraction reveal a core-shell structure for the nonequilibrium nanoparticles: a 2 nm Cu(2)O core is surrounded by an adsorbed protein shell. Quantitative protein adsorption studies show that the unexpected stability of Cu(2)O is imparted by the nanomolar surface binding affinity of TraIi1753::CN225 for Cu(2)O (K(d) = 1.2 x 10(-)(8) M), which provides favorable interfacial energetics (-45 kJ/mol) for the core-shell configuration. The protein shell retains the DNA-binding traits of TraI, as evidenced by the spontaneous organization of nanoparticles onto circular double-stranded DNA.  相似文献   
93.
The purpose of this study is to investigate the influence of nickel, which is an alloying element in commonly used metallic biomaterials, on the biomaterials mineralization process. An electrochemical method was developed to quantify this metal ion in osteoblast-like cell culture medium (OST) by performing adsorptive cathodic stripping voltammetry (CSV) with dimethylglyoxime (DMG) at a mercury film microelectrode (MFM). The optimized analytical conditions and the square-wave CSV parameters for the analysis are: DMG concentration: 5.00 × 10−4 mol L−1; ammonium chloride buffer: 0.10 mol L−1 (pH 9.2); frequency: 50 Hz, amplitude 20 mV; step: 2 mV; adsorption time: 10 s, deposition potential: −0.70 V and reduction potential: −1.20 V. The limit of detection was 7.70 × 10−9 mol L−1 for an adsorption time of 10 s. The results achieved by CSV using the MFM were compared to those obtained by atomic absorption spectrometry (AAS) to ensure the reliability of the electrochemical method. The mineralization process was evaluated by biochemical and histochemical assays.  相似文献   
94.
3,4-Dimethylphosphorin is prepared in five steps from 2,3-dimethylbutadiene and 2-phenyl-4,5-dimethylphosphorin; this synthetic scheme is formally equivalent to a [4+2] cycloaddition between 2,3-dimethylbutadiene and HCP.  相似文献   
95.
Various magnesium organocuprates give conjugative addition products with α,β-ethylenic aldehydes, and even with acrolein. The enolates may be trapped with bromine or trimethylsilyl chloride.  相似文献   
96.
The beta(1-->4) glycosidic linkage found in lactose is a prevalent structural motif in many carbohydrates and glycoconjugates. Using UV and IR ion-dip spectroscopies to probe benzyl lactoside isolated in the gas phase, we find that the disaccharide unit adopts only a single, rigid structure. Its fully resolved infrared ion-dip spectrum is in excellent agreement with that of the global minimum structure computed ab initio. This has glycosidic torsion angles of phi(H) (H1-C1-O-C4') approximately 180 degrees and psi(H) (C1-O-C4'-H4') approximately 0 degrees which correspond to a rotation of approximately 150 degrees about the glycosidic bond compared to the accepted solution-phase conformation. We discuss the biological implications of this discovery and the generality of the strategies employed in making it.  相似文献   
97.
A new Li-containing quaternary nitride, Li4Sr3Ge2N6, was obtained as single crystals from constituent elements in molten Na. It crystallizes in space group C2/m (No. 12) with a=6.1398(7) Å, b=10.021(1) Å, c=6.3130(7) Å, β=91.279(2)°, and Z=2. It contains the first example of isolated nitridogermanate anions of Ge2N610−, which is also the first example of edge-sharing tetrahedral [GeN4].  相似文献   
98.
In the presence of AlCl3, [1-β-chloroethyl-3,4-dimethylphosphole]pentacarbonyltungsten(1) rearranges into [1-chloro-3,4-dimethyl-6,7-dihydrophosphepin]pentacarbonyltungsten (3).  相似文献   
99.
Phosphine oxides with at least one aryl-P bond are reduced into the corresponding phosphines by stoechiometric amounts of Mg-Cp2TiCl2 in boiling THF.  相似文献   
100.
Blends of immiscible polymers are often stabilized by block copolymers which can form non-aqueous micelles and microemulsions in the liquid polymers. The phase diagrans, apparent volumes and apparent heat capacities of model non-aqueous binary and ternary systems were studied in order to investigate the conditions under which such self-assembly systems could form. 1,2-Hexanediol, which can cosolubilize hexane and ethyleneglycol, forms inverse micelles in hexane and weak microaggregates in ethyleneglycol. Genapol X-060, a commercial alcoholic surfactant containing on the average an aliphatic chain of 13 carbons and 6 oxyethylenes (C13E6), forms microaggregates in poly(ethyleneglycol) 400. These self-assembly systems are strengthen in the presence of a third component which has an affinity for the inner phase.Presented at the Symposium, 76th CSC Congress, Sherbrooke, Quebec, May 30–June 3, 1993, honoring Professor Donald Patterson on the occasion of his 65th birthday.  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