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   3465篇
  免费   312篇
  国内免费   686篇
化学   2837篇
晶体学   130篇
力学   122篇
综合类   13篇
数学   53篇
物理学   1308篇
  2024年   2篇
  2023年   160篇
  2022年   90篇
  2021年   106篇
  2020年   191篇
  2019年   120篇
  2018年   128篇
  2017年   156篇
  2016年   211篇
  2015年   219篇
  2014年   254篇
  2013年   337篇
  2012年   306篇
  2011年   234篇
  2010年   253篇
  2009年   261篇
  2008年   165篇
  2007年   298篇
  2006年   237篇
  2005年   132篇
  2004年   108篇
  2003年   110篇
  2002年   88篇
  2001年   109篇
  2000年   48篇
  1999年   82篇
  1998年   36篇
  1997年   3篇
  1996年   5篇
  1995年   2篇
  1994年   2篇
  1993年   1篇
  1992年   1篇
  1991年   1篇
  1990年   1篇
  1989年   1篇
  1988年   1篇
  1987年   1篇
  1986年   1篇
  1985年   2篇
排序方式: 共有4463条查询结果,搜索用时 158 毫秒
31.
Fungal infections pose a serious threat to human health. Polyoxometalates (POMs) are metal–oxygen clusters with potential application in the control of microbial infections. Herein, the Ag3PW12O40 composites have been synthesized and verified by Fourier transform infrared (FT-IR) spectrum, transmission electron microscopy (TEM), scanning electron microscope (SEM), elemental analysis, and X-ray diffraction (XRD). The antifungal activities of Ag3PW12O40 were screened in 19 Candida species strains through the determination of minimum inhibitory concentration (MIC) by the microdilution checkerboard technique. The minimum inhibitory concentration (MIC50) values of Ag3PW12O40 are 2~32 μg/mL to the Candida species. The MIC80 value of Ag3PW12O40 to resistant clinical isolates C. albicans HL963 is 8 μg/mL, which is lower than the positive control, fluconazole (FLC). The mechanism against C. albicans HL963 results show that Ag3PW12O40 can decrease the ergosterol content. The expressions of ERG1, ERG7, and ERG11, which impact on the synthesis of ergosterol, are all prominently upregulated by Ag3PW12O40. It indicates that Ag3PW12O40 is a candidate in the development of new antifungal agents.  相似文献   
32.
Chen  Li  Chen  Yu  Miao  Lili  Gao  Yiming  Di  Junwei 《Journal of Solid State Electrochemistry》2020,24(2):411-420
Journal of Solid State Electrochemistry - In this work, we reported the photocurrent switching effect on BiVO4 semiconductor as well as its application for construction of a new cathodic...  相似文献   
33.
Versatile graphdiyne (GDY) substrate has been modified by numerous transition metals and resulting composites showed excellent photo/electro-catalytic performance. However, GDY materials modified by actinides that are stockpiled waste product due to large-scale use in nuclear industry, are particularly scarce and remains great challenge. To deeply understand the structural properties, GDY complexating actinyl (AnmO2)n+ (An = U, Np, Pu; m = VI, V) species with its atomistic pore was investigated by relativistic density functional theory (DFT). The GDY pore was found suitable to hold actinyl species, by forming organometallic AnC dative bonds. This chemical coupling interaction was further confirmed by quantum theory of atoms-in-molecule and electronic structure calculations. The GDY-uranyl(V), for instance, shows a π(UC) bonding HOMO, which is anticipated to improve electron transfer between ligand and metal. Orbital structures and compositions of complexes suggest their implication towards catalysis, which were further corroborated by calculations on redox potentials of GDY-actinyl complexes. Hence, our results show the potential applications of GDY complexating actinyl species towards novel catalytic surfaces.  相似文献   
34.
A library of rare-earth metal derivatives supported by an aminophenoxy ligand was prepared and their catalytic performance in lactide polymerization was investigated. It was found that the synthetic strategy had a profound effect on the formation of aminophenoxy rare-earth metal complexes. Amine elimination between Ln[N(SiMe3)2]3(μ-Cl)Li(THF)3 (Ln = Yb, Y) and 1 equiv. of the aminophenol [HONH] ([HONH] = ο-OCH3-C6H4NHCH2(3,5-tBu2-C6H2-2-OH)) in toluene gave the unexpected heterobimetallic bis(aminophenoxy) rare-earth metal complexes [ON]2LnLi(THF)2 (Ln = Yb ( 1 ), Y ( 2 )). When the reactions were carried out in THF and TMEDA, amine elimination produced the aminophenoxy rare-earth metal amide complexes {[ON]LnN(SiMe3)2}2 (Ln = Yb ( 5 ), Y ( 6 )) in ca 85% isolated yields. Complexes 5 and 6 could also be obtained from salt metathesis reaction of {[ON]LnCl(THF)}2 (Ln = Yb ( 3 ), Y ( 4 )) with NaN(SiMe3)2 in a 1:2 molar ratio. In addition, treatment of complexes 3 and 4 with NaOAr (Ar = &bond;C6H4-4-tBu) and (SiMe3)2NC(NPri)2Na in 1:4 and 1:2 molar ratios provided the corresponding aminophenoxy rare-earth metal derivatives {[ON](μ-OAr)Ln(μ-OAr)Na(THF)2}2 (Ln = Yb ( 7 ), Y ( 8 )) and {[ON]Ln[(iPrN)2CN(SiMe3)2]}2 (Ln = Yb ( 9 ), Y ( 10 )), respectively. These complexes were fully characterized, and their molecular structures were determined using single-crystal X-ray diffraction. Polymerization experiments showed that complexes 1 , 2 , 5 , 6 , 9 and 10 were highly active for the ring-opening polymerization of l -lactide in toluene, and complex 1 promoted l -lactide polymerization in a controlled fashion. The polymerization of rac-lactide initiated by the neutral aminophenoxy rare-earth metal complexes 5 , 6 , 9 and 10 in THF afforded heterotactic polymers.  相似文献   
35.
The rational designability and chemical tunability of metal-organic frameworks(MOFs)are enabling tributes to efficaciously enhance their room temperature phosphorescence(RTP)performance.A family of stable anionic MOFs,[Zn2(4,5-ImDC)2]M2(NKU-132,M=(CH3)2NH2or(CH2CH3)2NH2),featuring significant RTP have been synthesized.By rational cation selection and in-situ replacement from dimethylammonium to diethylammonium,the phosphorescence lifetime is increased from 30.88 to126.3 ms,along with less sensitivity to air.This work provides an anti-quenching and lifetime tuning example for RTP-MOFmaterials via facile host-guest chemistry.  相似文献   
36.
Cobalt oxide (Co3O4) modified anatase titanium dioxide nanotubes (ATNTs) have been investigated for the electrochemical sensing of hydrogen peroxide (H2O2). ATNTs have been synthesized by a two-step anodization process. ATNTs were then modified with Co3O4 employing chemical bath deposition method. The structure and morphology of ATNTs and their modification with Co3O4 has been confirmed by X-ray diffraction by scanning electron microscopy. H2O2 sensing has been studied in 0.1 M PBS solution, by cyclic voltammetry and amperometry. Variation in the peak positions and current densities was observed with addition of H2O2 for Co3O4 modified ATNTs. Sensitivity and limit of detection improved with modification of ATNTs with Co3O4 with precursor concentration up to 0.8 M. However, at higher precursor concentrations sensitivity and limit of detection toward H2O2 deteriorated. Co3O4 Modified ATNTS using 0.8 M precursor concentration are comparatively more suitable for H2O2 sensing applications due to the optimum formation of Co3O4/ATNTs heterojunctions.  相似文献   
37.
利用低温水热法在p-GaN薄膜上生长了铟(In)和镓(Ga)共掺杂的ZnO纳米棒。X射线衍射(XRD)、X射线光电子能谱(XPS)和X射线能量色谱仪(EDS)结果表明,In和Ga已固溶到ZnO晶格中。扫描电子显微镜(SEM)结果表明, ZnO纳米棒具有良好的c轴取向性,随着In和Ga共掺杂浓度的增加,纳米棒的直径减小,密度增加。XRD结果表明,In和Ga共掺杂引起ZnO晶格常数增大,导致(002)衍射峰向低角度方向偏移。同时,ZnO的光学性质受到In和Ga共掺杂的影响。与纯ZnO相比, 共掺杂ZnO纳米棒的紫外发射峰都出现轻微红移,这是表面共振和带隙重整效应综合作用的结果。I-V特性曲线表明,随着In和Ga共掺杂浓度的增加,n-ZnO纳米棒/p-GaN异质结具有更好的导电性。  相似文献   
38.
The novel three-component Fe3O4/TiO2/Ag composite mircospheres were prepared via a facile chemical deposition route. The Fe3O4/TiO2 mircospheres were first prepared by the solvothermal method, and then Ag nanoparticles were anchored onto the out-layer of TiO2 by the tyrosine-reduced method. The as-prepared magnetic Fe3O4/TiO2/Ag composite mircospheres were applied as photocatalysis for the photocatalytic degradation of methylene blue. The results indicate that the photocatalytic activity of Fe3O4/TiO2/Ag composite microspheres is superior to that of Fe3O4/TiO2 due to the dual effects of the enhanced light absorption and reduction of photoelectron–hole pair recombination in TiO2 with the introduction of Ag NPs. Moreover, these magnetic Fe3O4/TiO2/Ag composite microspheres can be completely removed from the dispersion with the help of magnetic separation and reused with little or no loss of catalytic activity.  相似文献   
39.
40.
Coupled shape oscillations and translational motion of an incompressible gas bubble in a vibrating liquid container is studied numerically. The bubble oscillation characteristics are mapped based on the bubble Bond number (Bo) and the ratio of the vibration amplitude of the container to the bubble diameter (A/D). At small Bo and A/D, the bubble oscillation is found to be linear with small amplitudes, and at large Bo and A/D, it is nonlinear and chaotic. This chaotic bubble oscillation is similar to those observed in two coupled nonlinear systems, here being the gas inside the bubble and its surrounding liquid. Further increases in the forcing, results in the bubble breakup due to large liquid inertia.  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