全文获取类型
收费全文 | 1430篇 |
免费 | 133篇 |
国内免费 | 124篇 |
专业分类
化学 | 352篇 |
晶体学 | 3篇 |
力学 | 636篇 |
综合类 | 16篇 |
数学 | 183篇 |
物理学 | 497篇 |
出版年
2023年 | 7篇 |
2022年 | 17篇 |
2021年 | 23篇 |
2020年 | 30篇 |
2019年 | 27篇 |
2018年 | 26篇 |
2017年 | 40篇 |
2016年 | 46篇 |
2015年 | 62篇 |
2014年 | 66篇 |
2013年 | 87篇 |
2012年 | 86篇 |
2011年 | 70篇 |
2010年 | 54篇 |
2009年 | 68篇 |
2008年 | 57篇 |
2007年 | 80篇 |
2006年 | 81篇 |
2005年 | 81篇 |
2004年 | 74篇 |
2003年 | 57篇 |
2002年 | 60篇 |
2001年 | 53篇 |
2000年 | 54篇 |
1999年 | 48篇 |
1998年 | 43篇 |
1997年 | 41篇 |
1996年 | 30篇 |
1995年 | 38篇 |
1994年 | 34篇 |
1993年 | 28篇 |
1992年 | 16篇 |
1991年 | 21篇 |
1990年 | 20篇 |
1989年 | 12篇 |
1988年 | 18篇 |
1987年 | 5篇 |
1986年 | 5篇 |
1985年 | 4篇 |
1984年 | 3篇 |
1983年 | 3篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1979年 | 4篇 |
1978年 | 2篇 |
1975年 | 1篇 |
1969年 | 1篇 |
排序方式: 共有1687条查询结果,搜索用时 656 毫秒
21.
The binding constants, K′, for the reaction between some alkyldimethylbenzylammonium bromide homologues (alkyl = methyl, ethyl, propyl, butyl, hexyl,
decyl, and dodecyl, respectively) and β-cyclodextrin in water at 25.0 ± 0.1 ∘C have been determined, by applying the spectral displacement technique with phenolphthalein as the displacing anion. It has
been shown that the ln K′ values increase linearly with the number of carbon atoms in the alkyl chain for the salts whose alkyl chain has at least
four carbon atoms. The ln K′ values estimated for the parent compound benzyltrimetylammonium bromide and its two nearest homologues are distinctly lower
than might be expected by extrapolation of the linear relation found for the higher homologues. Assuming that it is the organic
cation that undergoes association with β-cyclodextrin, then one may suppose that a change occurs in the mode of inclusion of the cation upon passing to higher homologues.
In the case of the lighter homologues, it is the phenylene group that undergoes inclusion. This model of inclusion is confirmed
by analysis of rotating-frame overhauser effect spectroscopy (ROESY) spectra. 相似文献
22.
目的探讨经颈内静脉原位导丝法换置中心静脉长期血液透析导管在维持性血液透析(MHD)患者中的应用价值。方法选取近3年在颈内静脉留置的中心静脉长期血液透析导管因功能障碍后,并经颈内静脉原位导丝法换置长期导管,术后及每次透析后均改用尿激酶封管患者16例(原位换置组);选取同期首次经颈内静脉留置中心静脉长期血液透析导管,普通肝素封管患者20例作为对照组;分析两组患者围术期泵控血流量及随访期的反应及开存期率、次开存期率。结果围术期泵控血流量原位换置组高于对照组,有统计学差异(P<0.05);两组比较感染例次/1000导管日0.9%与1.0%,无统计学差异(P>0.05)。原位换置组围术期未发生中重度并发症,12个月开存期率81.2%、次开存期率93.8%;对照组开存期率为65%、次开存期率85%;两组比较无统计学差异(P>0.05)。结论颈内静脉原位导丝法换置中心静脉长期血液透析导管,在MHD患者中的使用是安全的、可行的。 相似文献
23.
Significant increases in the measured elastic moduli with decreasing indentation depth have been previously found in various polymers by indentation tests with a Berkovich tip at micro-to nanometer length scales. These increases in the determined elastic moduli were related to second order displacement gradients which increase with decreasing depth when a conical tip is applied. When a spherical tip is applied, such depth dependence should not be present as the second order displacement gradients remain essentially unchanged with indentation depth. However, these gradients should be proportional to the radius of the spherical tip. To examine the notion of second order displacement gradient dependence in measurements of elastic moduli, indentation experiments are conducted on epoxy with spherical tips of different nominal radii. Accounting for tip imperfections, an increase in the determined elastic moduli is found with decreasing tip radius, which corroborates the notion of second order displacement gradient dependence. 相似文献
24.
25.
Molecular dynamics simulations of the displacement cascades in Fe-10%Cr systems are used to simulate the primary knocked-on atom events of the irradiation damage at temperatures 300,600,and 750 K with primary knockedon atom energies between 1 and 15 keV.The results indicate that the vacancies produced by the cascade are all in the central region of the displacement cascade.During the cascade,all recoil Fe and Cr atoms combine with each other to form Fe-Cr or Fe-Fe interstitial dumbbells as well as interstitial clusters.The number and the size of interstitial clusters increase with the energy of the primary knocked-on atom and the temperature.A few large clusters consist of a large number of Fe interstitials with a few Cr atoms,the rest are Fe-Cr clusters with small and medium sizes.The interstitial dumbbells of Fe-Fe and Fe-Cr are in the 111 and 110 series directions,respectively. 相似文献
26.
In this paper, the three-dimensional (3D) interfacial fracture is analyzed in a one-dimensional (1D) hexagonal quasicrystal (QC) coating structure under mechanical loading. A planar interface crack with arbitrary shape is studied by a displacement discontinuity method. Fundamental solutions of interfacial concentrated displacement discontinuities are obtained by the Hankel transform technique, and the corresponding boundary integral-differential equations are constructed with the superposition principle. Green’s functions of constant interfacial displacement discontinuities within a rectangular element are derived, and a boundary element method is proposed for numerical simulation. The singularity of stresses near the crack front is investigated, and the stress intensity factors (SIFs) as well as energy release rates (ERRs) are determined. Finally, relevant influencing factors on the fracture behavior are discussed. 相似文献
27.
G-quadruplexes (G4) are the most actively studied non-canonical secondary structures formed by contiguous repeats of guanines in DNA or RNA strands. Small molecule mediated targeting of G-quadruplexes has emerged as an attractive tool for visualization and stabilization of these structures inside the cell. Limited number of DNA and RNA G4-selective assays have been reported for primary ligand screening. A combination of fluorescence spectroscopy, AFM, CD, PAGE, and confocal microscopy have been used to assess a dimeric carbocyanine dye B6,5 for screening G4-binding ligands in vitro and in cellulo. The dye B6,5 interacts with physiologically relevant DNA and RNA G4 structures, resulting in fluorescence enhancement of the molecule as an in vitro readout for G4 selectivity. Interaction of the dye with G4 is accompanied by quadruplex stabilization that extends its use in primary screening of G4 specific ligands. The molecule is cell permeable and enables visualization of quadruplex dominated cellular regions of nucleoli using confocal microscopy. The dye is displaced by quarfloxin in live cells. The dye B6,5 shows remarkable duplex to quadruplex selectivity in vitro along with ligand-like stabilization of DNA G4 structures. Cell permeability and response to RNA G4 structures project the dye with interesting theranostic potential. Our results validate that B6,5 can serve the dual purpose of visualization of DNA and RNA G4 structures and screening of G4 specific ligands, and adds to the limited number of probes with such potential. 相似文献
28.
The unique optoelectronic properties of semiconductor quantum dots (QDs) make them well-suited as fluorescent bioprobes for use in various biological applications. Modification of CdSe/ZnS QDs with biologically relevant molecules provides for multipotent probes that can be used for cellular labeling, bioassays, and localized optical interrogation by means of fluorescence resonance energy transfer (FRET). Herein, we demonstrate the use of red-emitting streptavidin-coated QDs (QD605) as donors in FRET to introduce a competitive displacement-based assay for the detection of oligonucleotides. Various QD–DNA bioconjugates featuring 25-mer probe sequences diagnostic of Hsp23 were prepared. The single-stranded oligonucleotide probes were hybridized to dye-labeled (Alexa Fluor 647) reporter sequences, which were provided for a FRET-sensitized emission signal due to proximity of the QD and dye. The dye-labeled sequence was designed to be partially complementary and include base-pair mismatches to facilitate displacement by a more energetically favorable, fully complementary recognition motif embedded within a 98-mer displacer sequence. Overall, this study demonstrates proof-of-concept at the nM level for competitive displacement hybridization assays in vitro by reduction of fluorescence intensity that directly correlates to the presence of oligonucleotides of interest. This work demonstrates an analytical method that could potentially be implemented for monitoring of intracellular gene expression in the future. 相似文献
29.
Dihalocarbenes generated under phase transfer conditions add to cis and trans vinylic selenides to give the corresponding 1,1-dihalo-2-selenocyciopropanes with retention of configuration. 相似文献
30.
《合成通讯》2013,43(23):4301-4311
Abstract Reaction of trichloroacetaldehyde and acrylonitrile in the presence of a catalytic amount of copper (I) chloride in ionic liquid afforded 2,3,5‐trichloropyridine, fluorination of which with KF and CsF in ionic liquid afforded 3,5‐dichloro‐2‐fluoropyridine and 5‐chloro‐2,3‐dichloropyridine. Reaction of 2,3,5‐trichloropyridine, 3,5‐dichloro‐2‐fluoropyridine, or 5‐chloro‐2,3‐dichloropyride with 2‐(4‐hydroxyphenoxy)propionates in ionic liquid afforded the corresponding 2‐aryloxylpropionates in good yields. 相似文献