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   1352篇
  免费   54篇
  国内免费   4篇
化学   940篇
晶体学   10篇
力学   45篇
数学   147篇
物理学   268篇
  2023年   6篇
  2022年   11篇
  2021年   14篇
  2020年   17篇
  2019年   21篇
  2018年   13篇
  2017年   10篇
  2016年   28篇
  2015年   32篇
  2014年   61篇
  2013年   71篇
  2012年   73篇
  2011年   101篇
  2010年   42篇
  2009年   47篇
  2008年   94篇
  2007年   84篇
  2006年   77篇
  2005年   65篇
  2004年   56篇
  2003年   35篇
  2002年   40篇
  2001年   15篇
  2000年   26篇
  1999年   18篇
  1998年   13篇
  1997年   9篇
  1996年   16篇
  1995年   11篇
  1994年   11篇
  1993年   15篇
  1992年   6篇
  1991年   9篇
  1990年   13篇
  1989年   13篇
  1988年   12篇
  1987年   10篇
  1985年   13篇
  1984年   12篇
  1983年   8篇
  1982年   12篇
  1981年   14篇
  1980年   17篇
  1979年   16篇
  1978年   11篇
  1977年   15篇
  1976年   7篇
  1975年   7篇
  1974年   19篇
  1973年   12篇
排序方式: 共有1410条查询结果,搜索用时 46 毫秒
991.
As a result of the growing recognition of Enterobacter sakazakii as an emergent pathogen, the International Dairy Federation (IDF) and the International Organization for Standardization (ISO) have standardized a reference method for the detection of E. sakazakii in milk powder products and powdered infant food formulas (IFF). The objectives of this study were to assess the applicability of the ISO-IDF draft standard, and to compare several chromogenic selective media for E. sakazakii [ready-to-use ESIATM, homemade E. sakazakii isolation agar, and Druggan-Forsythe-lversen (DFI) agar], and a selective media for Enterobacteriaceae Violet Red Bile Glucose (VRBG). We found that the method is sensitive, selective, and applicable to the analysis of powdered IFF, provided that some modifications are added. In particular, definition of typical colonies on chromogenic media should be less restrictive, and the possibility of using chromogenic media other than ESIA should be introduced. Any of the chromogenic media tested here could be used initially, since their performances were similar. In these media, alpha-glucosidase-positive but non-yellow-pigmented isolates should be also considered. Consequently, the yellow pigmentation test should be abandoned, or completed with another test in order to select colonies to confirm. Although the specificity of VRBG was relatively poor, it could be used as a second nonchromogenic medium.  相似文献   
992.
Most of the first-row transition-metal oxides, M(A)O(B) (M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn) were examined by static secondary ion mass spectrometry (s-SIMS) and laser ablation/ionization Fourier transform ion cyclotron resonance mass spectrometry (LA-FTICRMS). Positive and negative ions show strong correlation between the studied oxide and the detected cluster ions. Specific M(x)O(y) (+/-) species were systematically observed with both MS techniques for each investigated M(A)O(B) transition-metal oxide. Moreover, the ion composition and ion distribution are greatly dependent on the ionization technique. Laser ablation (LA)/ionization leads to larger cluster ions (ionic species with nearly hundred atoms were in particular detected for Sc2O3 and Y2O3 oxides), whereas hydrogenated, dihydrogenated, and sometimes trihydrogenated species were observed in s-SIMS. However, the ion distribution for a given M(x)O(y) (+/-) ion series (i.e. ions including the same number of metal atoms M) generally presented important similarities in both techniques.Finally, it was demonstrated that the chemical state of metal atoms in the observed ionic species is closely dependent on the metal electronic valence shell. High valence states (+III, +IV, +V, and +VI) are favored for metals with a less-than-half full valence shell configuration, whereas for other first-row transition metals (manganese, iron, cobalt, nickel, copper and zinc) lower metal valence states (0, +I or, +II) are involved.  相似文献   
993.
Several HLA-DR alleles present the immunodominant HA(306-318) peptide of haemagglutinin of the influenza virus to T cells. NMR data of the peptide in various water solutions exclude any alpha-helix or turn conformations. Circular dichroism and Fourier transform infrared spectroscopies indicate an estimated beta-extended structure in water of 31% and 28%, respectively, with spectra shape similar to the ones observed for beta-sheet containing proteins. The H/D amide exchange suggests a stable length-dependent interchain hydrogen-bonding. The partially beta-extended conformation of HA(306-318) in solution might be close to the one found in HA(306-318)-HLA-DR1 complex. These results suggest different interconverting extended conformations of HA(306-318), depending on the microenvironment of the solution medium. This flexibility emphasizes the ability of some peptides to fit more easily the binding site of several HLA-DR molecules. Similar results were obtained on the HIV P25(263-277) peptide which has been previously shown to be a good DR1 binder. From a vibrational point of view, infrared Amide I frequencies of secondary structures in peptides were ascertained. As previously demonstrated for proteins in solution, Fourier transform infrared and circular dichroism spectroscopies appear to be valuable tools for conformational properties of peptides. Their use may contribute to the detection of peptide conformation-binding relationship which has to be further tested by biochemical and biological studies.  相似文献   
994.
995.
996.
This article focuses on the emission of organometallic clusters upon kiloelectronvolt ion bombardment of self-assembled monolayers. It is particularly relevant for the elucidation of the physical processes underlying secondary ion mass spectrometry (SIMS). The experimental system, an overlayer of octanethiols on gold, was modeled by classical molecular dynamics, using a hydrocarbon potential involving bonding and nonbonding interactions (AIREBO). To validate the model, the calculated mass and energy distributions of sputtered atoms and molecules were compared to experimental data. Our key finding concerns the emission mechanism of large clusters of the form MxAuy up to M6Au5 (where M is the thiolate molecule), which were not observed under sub-kiloelectronvolt projectile bombardment. Statistically, they are predominantly formed in high-yield events, where many atoms, fragments, and (supra)molecular species are desorbed from the surface. From the microscopic viewpoint, these high-yield events mostly stem from the confinement of the projectile and recoil atom energies in a finite microvolume of the sample surface. As a result of the high local energy density, molecular aggregates desorb from an overheated liquidlike region surrounding the impact point of the projectile.  相似文献   
997.
The interaction between single-walled carbon nanotubes and photosynthetic reaction centers purified from purple bacterium Rhodobacter sphaeroides R-26 has been investigated. Atomic force microscopy studies provide evidence that reaction center protein can be attached effectively to the nanotubes. The typical diameter of the nanotube is 1-4 nm and 15 +/- 2 nm without and with the reaction centers, respectively. Light-induced absorption change measurements indicate the stabilization of the P+(Q(A)Q(B))- charge pair, which is formed after single saturating light excitation after the attachment to nanotubes. The separation of light-induced charges is followed by slow reorganization of the protein structure. The stabilization effect of light-initiated charges by the carbon nanotubes opens a possible direction of several applications, the most promising being in energy conversion and storage devices.  相似文献   
998.
Two very distinct chemical reactions, yet a single catalyst : A gold complex promotes the formation of tertiary enamines from a variety of terminal and internal alkynes. Subsequent addition of a terminal alkyne to the reaction mixture affords allenes (see scheme).

  相似文献   

999.
Alpha, beta, gamma! Amino substituents in alpha and beta positions allow the isolation of free carbenes, but even in the gamma position, their strong π‐electron‐donating properties permit the synthesis of allenylidene lithium adducts and silver complexes (see picture), which are ideal precursors for the preparation of various transition‐metal–allenylidene complexes.

  相似文献   

1000.
Similarly to NHCs, CAACa and BACa react with CO2 to give the corresponding betaines. Based on the carbonyl stretching frequencies of cis‐[RhCl(CO)2(L)] complexes, the order of electron donor ability was predicted to be CAACa≈BACa>NHCs. When the betaines νasym(CO2) values are used, the apparent ordering is BACa>NHCs≈CAACa that indicates a limitation for the use of IR spectroscopy in the ranking of ligand σ‐donating ability. Although all carbenes react with carbon disulfide to give the corresponding betaines, a second equivalent of CS2 reacts with the BAC‐CS2 leading to a bicyclic thieno[2,3‐diamino]‐1,3‐dithiole‐2‐thione, which results from a novel ring expansion process. Surprisingly, in contrast to NHCs, CAAC a does not react with carbodiimide, whereas BACa exclusively gives a ring expanded product, analogous to that obtained with CS2. The intermediate amidinate can be trapped, using the lithium tetrafluoroborate adduct of BACb as a carbene surrogate.  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