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   610篇
  免费   35篇
  国内免费   6篇
化学   482篇
力学   7篇
数学   72篇
物理学   90篇
  2023年   1篇
  2022年   6篇
  2021年   9篇
  2020年   9篇
  2019年   17篇
  2018年   11篇
  2017年   10篇
  2016年   20篇
  2015年   18篇
  2014年   21篇
  2013年   36篇
  2012年   55篇
  2011年   72篇
  2010年   35篇
  2009年   27篇
  2008年   58篇
  2007年   33篇
  2006年   36篇
  2005年   38篇
  2004年   27篇
  2003年   28篇
  2002年   24篇
  2001年   11篇
  2000年   8篇
  1999年   2篇
  1998年   2篇
  1997年   3篇
  1996年   3篇
  1995年   4篇
  1994年   1篇
  1993年   2篇
  1992年   2篇
  1991年   2篇
  1990年   2篇
  1989年   2篇
  1988年   1篇
  1987年   1篇
  1985年   4篇
  1984年   2篇
  1983年   1篇
  1982年   1篇
  1981年   1篇
  1980年   1篇
  1979年   1篇
  1975年   1篇
  1967年   1篇
  1879年   1篇
排序方式: 共有651条查询结果,搜索用时 546 毫秒
71.
The aim of this work is to establish the existence of multi-peak solutions for the following class of quasilinear problems
$$ - \mbox{div} \bigl(\epsilon^{2}\phi\bigl(\epsilon|\nabla u|\bigr)\nabla u \bigr) + V(x)\phi\bigl(\vert u\vert\bigr)u = f(u)\quad\mbox{in } \mathbb{R}^{N}, $$
where \(\epsilon\) is a positive parameter, \(N\geq2\), \(V\), \(f\) are continuous functions satisfying some technical conditions and \(\phi\) is a \(C^{1}\)-function.
  相似文献   
72.
A new series of sulfonamide substituted 1,5‐diarylimidazole, possessing C‐2 alkylthio moiety, were synthesized for their cyclooxygense‐2 (COX‐2) inhibitory activity starting from condensation of N,N‐dibenzylaminosulfonylphenacylamine hydrochloride ( 2 ) and corresponding isothiocyanate in the presence of Et3N, followed by alkylation in the basic medium. In concomitant with these intermediates, 2‐arylamino‐5‐arylthiazole derivatives 5 were also produced. The ratio of these two products was variable with different isothiocyanates. Final debenzylation was achieved using concentrated sulfuric acid to give the title sulfonamides 8 .  相似文献   
73.
We modified membrane-active peptides with synthetic recognition modules to foster peptide assembly at the lipid-water interface. The designed recognition strategy has been previously reported: tris-cyanuric acid and tris-melamine have been found to bind selectively to each another when membrane-anchored. We designed this interaction to occur between two membrane-active peptides, forming a heteromeric complex at the lipid-water interface that exhibits superior membrane binding and permeation compared to the monomeric peptides, presumably because of the higher avidity of the assembled structure. These conjugates do not assemble appreciably in solution but assemble at the lipid-water interface, with surface binding of the peptide acting cooperatively with molecular recognition to yield improved binding and permeation. Furthermore, we find that specific recognition between tris-cyanuric acid phospholipid (TCA-PE) at low surface concentration and tris-melamine magainin (TMM) or hexa-melamine magainin (HMM) results in highly lytic binding, whereas no binding is detectable in the absence of lipid recognition. These findings suggest a noncovalent strategy to enhance peptide membrane activity, which may lead to the discovery of more potent surface-active agents such as antimicrobials.  相似文献   
74.
Catalytic hydrogenation of lactic acid to propylene glycol was performed over various metals (Ag, Co, Cu, Ni, Pt, and Ru) supported on silica prepared by an incipient wetness impregnation method. The loading amount of each metal was 5 wt%. Crystallinity of the synthesized catalysts was investigated by X-ray diffraction (XRD), and the BET method was utilized to examine the surface area. Pore volume and pore size of catalysts were determined using BJH analysis of the N2 adsorption isotherm. Particle sizes of various metals were determined from transmission electron microscopy (TEM) images. The catalytic activity was found to be strongly dependent on the supported metal. Among catalysts tested, Ru/SiO2 showed the highest propylene glycol yield. The yield of propylene glycol increased with pressure, and the highest yield was achieved at 130 °C.  相似文献   
75.
An organic-assisted alkaline extraction method was developed for the determination of hexavalent chromium (Cr(VI)) in plastics. The solubilization of polymer as a pre-step of the alkaline extraction provided good extraction efficiency of Cr(VI) from the sample. The optimization of the experimental conditions affecting the extraction and UV–vis spectrophotometric analysis was accomplished by evaluating the recovery rate of Cr(VI) through the analysis of Cr(VI) in in-house polymer reference materials (RMs). With the proposed method, most of the Cr(VI) in polymers was released within a short extraction time of 30 min and the Cr(III)-DPCO complex can be kept stable for 24 h. The heating for the extraction of the Cr(VI) was not necessary. The optimal pH of the final solution was fixed at 2.0. The proposed extraction method was applied successfully for the determination of Cr(III) and Cr(VI) in spiked samples. The practical applicability of this new method was evaluated through the analysis of Cr(VI) in in-house polymer RMs. The good linearity was demonstrated at desired concentrations of the range 0–3.3 mg L−1. The detection limits were quite low, varying from 0.0061 to 0.0285 mg L−1. The recovery of Cr(VI) was between 97 and 106%, and the relative standard deviation (R.S.D.) was below 6%.  相似文献   
76.
The gas‐phase free radical initiated peptide sequencing (FRIPS) fragmentation behavior of o‐TEMPO‐Bz‐conjugated peptides with an intra‐ and intermolecular disulfide bond was investigated using MSn tandem mass spectrometry experiments. Investigated peptides included four peptides with an intramolecular cyclic disulfide bond, Bactenecin (RLC RIVVIRVC R), TGF‐α (C HSGYVGVRC ), MCH (DFDMLRC MLGRVFRPC WQY) and Adrenomedullin (16–31) (C RFGTC TVQKLAHQIY), and two peptides with an intermolecular disulfide bond. Collisional activation of the benzyl radical conjugated peptide cation, which was generated through the release of a TEMPO radical from o‐TEMPO‐Bz‐conjugated peptides upon initial collisional activation, produced a large number of peptide backbone fragments in which the S? S or C? S bond was readily cleaved. The observed peptide backbone fragments included a‐, c‐, x‐ or z‐types, which indicates that the radical‐driven peptide fragmentation mechanism plays an important role in TEMPO‐FRIPS mass spectrometry. FRIPS application of the linearly linked disulfide peptides further showed that the S? S or C? S bond was selectively and preferentially cleaved, followed by peptide backbone dissociations. In the FRIPS mass spectra, the loss of ?SH or ?SSH was also abundantly found. On the basis of these findings, FRIPS fragmentation pathways for peptides with a disulfide bond are proposed. For the cleavage of the S? S bond, the abstraction of a hydrogen atom at Cβ by the benzyl radical is proposed to be the initial radical abstraction/transfer reaction. On the other hand, H‐abstraction at Cα is suggested to lead to C? S bond cleavage, which yields [ion ± S] fragments or the loss of ?SH or ?SSH. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   
77.
78.
Qualitative and quantitative profiling of six different categories of urinary phospholipids (PLs) from patients with prostate cancer was performed to develop an analytical method for the discovery of candidate biomarkers by shotgun lipidomics method. Using nanoflow liquid chromatography–electrospray ionization–tandem mass spectrometry, we identified the molecular structures of a total of 70 PL molecules (21 phosphatidylcholines (PCs), 11 phosphatidylethanolamines (PEs), 17 phosphatidylserines (PSs), 11 phosphatidylinositols (PIs), seven phosphatidic acids, and three phosphatidylglycerols) from urine samples of healthy controls and prostate cancer patients by data-dependent collision-induced dissociation. Identified molecules were quantitatively examined by comparing the MS peak areas. From statistical analyses, one PC, one PE, six PSs, and two PIs among the PL species showed significant differences between controls and cancer patients (p < 0.05, Student’s t test), with concentration changes of more than threefold. Cluster analysis of both control and patient groups showed that 18:0/18:1-PS and 16:0/22:6-PS were 99% similar in upregulation and that the two PSs (18:1/18:0, 18:0/20:5) with two PIs (18:0/18:1 and 16:1/20:2) showed similar (>95%) downregulation. The total amount of each PL group was compared among prostate cancer patients according to the Gleason scale as larger or smaller than 6. It proposes that the current study can be utilized to sort out possible diagnostic biomarkers of prostate cancer.  相似文献   
79.
Three gallosilicate natrolites with closely similar chemical composition but differing in the distribution of Si and Ga over crystallographically different tetrahedral sites (T-sites) show striking differences in their cation exchange performance. The ability to exchange Na(+) by the larger alkali metal cations decreases upon increasing the size of the cation, as expected, but also with the degree of T-atom ordering. To seek an insight into this phenomenon, the crystal structures of 11 different zeolites, which show variations in degree of T-atom ordering, nature of countercation, and hydration state, have been refined using synchrotron diffraction data. While the three as-made sodium materials were characterized to have a low, medium, and high degree of ordering, respectively, their pore sizes are close to the size of the bare Na(+) cation and much smaller than that of the larger alkali cations, which are nonetheless exchanged into the materials, each one at a different level. Interestingly, large differences are also manifested when the Na(+) back-exchange is performed on the dehydrated K(+) forms, with crystallographic pore sizes too small even to allow the passage of Na(+). Although the thermodynamic data point to small differences in the enthalpy of the Na(+)/K(+) exchange in the three materials, comparison of the "static" crystallographic pore sizes and the diameter of the exchanged cations lead us to conclude that during the exchange process these zeolites undergo significant deformations that dynamically open the pores, allowing cation traffic even for Cs(+) in the case of the most disordered material. In addition to the very large topological flexibility typical of the natrolite framework, we propose as a hypothesis that there is an additional flexibility mechanism that decreases the rigidity of the natrolite chain itself and is dependent on preferential siting of Si or Ga on crystallographically different T-sites.  相似文献   
80.
Photochromic compound-conjugated fluorescent fullerene-silica nanoparticles prepared by the reverse-microemulsion method was utilized for photoswitchable cellular imaging by repeatable irradiation of ultraviolet and visible light.  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