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   26919篇
  免费   4283篇
  国内免费   4043篇
化学   20617篇
晶体学   424篇
力学   1315篇
综合类   296篇
数学   2951篇
物理学   9642篇
  2024年   94篇
  2023年   489篇
  2022年   929篇
  2021年   1016篇
  2020年   1063篇
  2019年   1127篇
  2018年   947篇
  2017年   988篇
  2016年   1289篇
  2015年   1333篇
  2014年   1669篇
  2013年   2072篇
  2012年   2483篇
  2011年   2540篇
  2010年   1946篇
  2009年   1836篇
  2008年   1947篇
  2007年   1802篇
  2006年   1684篇
  2005年   1345篇
  2004年   987篇
  2003年   783篇
  2002年   740篇
  2001年   652篇
  2000年   583篇
  1999年   481篇
  1998年   358篇
  1997年   312篇
  1996年   266篇
  1995年   254篇
  1994年   233篇
  1993年   168篇
  1992年   146篇
  1991年   135篇
  1990年   121篇
  1989年   89篇
  1988年   73篇
  1987年   53篇
  1986年   61篇
  1985年   49篇
  1984年   19篇
  1983年   18篇
  1982年   19篇
  1981年   6篇
  1980年   7篇
  1979年   8篇
  1978年   3篇
  1971年   4篇
  1957年   4篇
  1936年   4篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
931.
Polydimethylsiloxane has been dominantly employed as the substrate material for microchip capillary electrophoresis. The poor surface chemistry, however, generates inconsistent electroosmotic flow under the electrophoretic condition, limiting its broader applications. In this work, different polyelectrolytes, including polydiallyldimethylammonium chloride, polyvinyl sulfate, and dextran sulfate, were successfully deposited onto polydimethylsiloxane microchannel surfaces. The polyelectrolyte coated polydimethylsiloxane microchannel showed improved consistency and reproducibility in electroosmotic flow under an electric field over the uncoated native microchannel.  相似文献   
932.
933.
The bivalent ligand approach has been utilized not only to study the underlying mechanism of G protein-coupled receptors dimerization and/or oligomerization, but also to enhance ligand affinity and/or selectivity for potential treatment of a variety of diseases by targeting this process. Substance abuse and addiction have made both the prevention and the treatment of human immunodeficiency virus (HIV) infection more difficult to tackle. Morphine, a mu opioid receptor (MOR) agonist, can accelerate HIV infection through up-regulating the expression of the chemokine receptor CCR5, a well-known co-receptor for HIV invasion to the host cells and this has been extensively studied. Meanwhile, two research groups have described the putative MOR-CCR5 heterodimers in their independent studies. The purpose of this paper is to report the design and synthesis of a bivalent ligand to explore the biological and pharmacological process of the putative MOR-CCR5 dimerization phenomenon. The developed bivalent ligand thus contains two distinct pharmacophores linked through a spacer; ideally one of which will interact with the MOR and the other with the CCR5. Naltrexone and Maraviroc were selected as the pharmacophores to generate such a bivalent probe. The overall reaction route to prepare this bivalent ligand was convergent and efficient, and involved sixteen steps with moderate to good yields. The preliminary biological characterization showed that the bivalent compound 1 retained the pharmacological characteristics of both pharmacophores towards the MOR and the CCR5 respectively with relatively lower binding affinity, which tentatively validated our original molecular design.  相似文献   
934.
Ma Y  Chi X  Yan X  Liu J  Yao Y  Chen W  Huang F  Hou JL 《Organic letters》2012,14(6):1532-1535
A per-hydroxylated pillar[6]arene was prepared. Single-crystal X-ray analysis demonstrated that its molecules are arranged in an up-to-down manner to form infinite channels in the solid state. Its host-guest complexation with a series of bispyridinium salts in solution was further investigated. It was found that the per-hydroxylated pillar[6]arene could form a 1:1 complex with paraquat in acetone with an association constant of 2.2 × 10(2) M(-1). This complex is a [2]pseudorotaxane as shown by its crystal structure, which is the first pillar[6]arene-based host-guest complex crystal structure.  相似文献   
935.
A 3-D platinum(II)-based spirometal complex has been designed and synthesized to suppress aggregation and excimer emission. A prototype phosphorescent organic light-emitting device exhibits the high-performance orange emission with an external quantum efficiency of up to 5.2%.  相似文献   
936.
A stepwise surface functionalization methodology was applied to nanostructured ZnO films grown by metal organic chemical vapor deposition (MOCVD) having three different surface morphologies (i.e., nanorod layers (ZnO films-N), rough surface films (ZnO films-R), and planar surface films (ZnO films-P). The films were grown on glass substrates and on the sensing area of a quartz crystal microbalance (nano-QCM). 16-(2-Pyridyldithiol)-hexadecanoic acid (PDHA) was bound to ZnO films-N, -R, and -P through the carboxylic acid unit, followed by a nucleophilic displacement of the 2-pyridyldithiol moiety by single-stranded DNA capped with a thiol group (SH-ssDNA). The resulting ssDNA-functionalized films were hybridized with complementary ssDNA tagged with fluorescein (ssDNA-Fl). In a selectivity control experiment, no hybridization occurred upon treatment with non complementary DNA. The ZnO films' surface functionalization, characterized by FT-IR-ATR and fluorescence spectroscopy and detected on the nano-QCM, was successful on films-N and -R but was barely detectable on the planar surface of films-P.  相似文献   
937.
Pd nanoparticles (NPs) with a small size and narrow size distribution were prepared from the decomposition of Pd(OAc)(2) in a series of hydroxyl-functionalized ionic liquids (ILs) comprising the 1-(2'-hydroxylethyl)-3-methylimidazolium cation and various anions, viz. [C(2)OHmim][OTf] (2.4 ± 0.5 nm), [C(2)OHmim][TFA] (2.3 ± 0.4 nm), [C(2)OHmim][BF(4)] (3.3 ± 0.6 nm), [C(2)OHmim][PF(6)] (3.1 ± 0.7 nm) and [C(2)OHmim][Tf(2)N] (4.0 ± 0.6 nm). Compared with Pd NPs isolated from the non-functionalized IL, [C(4)mim][Tf(2)N] (6.2 ± 1.1 nm), it would appear that the hydroxyl group accelerates the formation of the NPs, and also helps to protect the NPs from oxidation once formed. Based on the amount of Pd(OAc)(2) that remains after NP synthesis (under the given conditions) the ease of formation of the Pd NPs in the [C(2)OHmim](+)-based ILs follows the trend [Tf(2)N](-), [PF(6)](-) > [BF(4)](-) > [OTf](-) > [TFA](-). Also, the ability of the [C(2)OHmim](+)-based ILs to prevent the Pd NPs from undergoing oxidation follows the trend [Tf(2)N](-) > [PF(6)](-) > [TFA](-) > [OTf](-) > [BF(4)](-). DFT calculations were employed to rationalize the interactions between Pd NPs and the [C(2)OHmim](+) cation and the various anions.  相似文献   
938.
Wang J  Wang X  Li Y  Yan S  Zhou Q  Gao B  Peng J  DU J  Fu Q  Jia S  Zhang J  Zhan L 《Analytical sciences》2012,28(3):237-241
In the present study, we aimed to develop a nucleic acid lateral-flow method for the rapid and sensitive detection of multiple bacteria that contaminate platelet concentrations (PCs). Polymerase chain reaction (PCR) amplicons were produced by a set of board-range primers that recognize the conserved region of bacteria 16S rDNA, followed by hybridization with both an FITC (fluorescein isothiocyanate)-labelled probe and biotin-labelled probe, and then a nucleic acid lateral-flow dipstick (LFD) assay. The LFD accurately identified 7 species of bacteria, but had no cross-reactivity with human genomic DNA. The limit of detection (LOD) of the LFD assay was as low as 10(1) copies/μL of 16S rDNA for plasmid. In the case of spiked PCs without enrichment, the detection limit of LFD for K. pneumonia was 5 CFU/mL, 6.5 × 10(4) CFU/mL for the S. epidermidis and 35 CFU/mL for P. aeruginosa.  相似文献   
939.
A multi-nanoparticle-embedded amorphous aluminum/magnesium oxides (AAMO) core/mesoporous silica (mSiO(2)) shell structure has been successfully synthesized by calcining the presynthesized catalyst precursor-containing layered double hydroxide (LDH) core/mesoporous silica shell composite. The well-dispersed catalytic nanoparticles were fixed at the interface between AAMO core and mesoporous SiO(2) shell, i.e., at the inner pore mouths of the mesoporous SiO(2) shell, which could effectively prevent nanoparticles from growth and/or aggregation with each other and in the meantime allow efficient access of reactants to the catalytic NPs. The final core/shell composite was found to be an efficient and highly recyclable heterogeneous catalyst.  相似文献   
940.
Yu Z  Wei X  Yan J  Tu Y 《The Analyst》2012,137(8):1922-1929
With TiO(2) nanoparticles as carrier, a supported nano-material of Au atomic cluster/TiO(2) nano-hybrid was synthesized. It was then modified onto the surface of indium tin oxide (ITO) by Nafion to act as a working electrode for exciting the electrochemiluminescence (ECL) of luminol. The properties of the nano-hybrid and the modified electrode were characterized by XRD, XPS, electronic microscopy, electrochemistry and spectroscopy. The experimental results demonstrated that the modification of this nano-hybrid onto the ITO electrode efficiently intensified the ECL of luminol. It was also revealed that the ECL intensity of luminol on this modified electrode showed very sensitive responses to oxygen and hydrogen peroxide. The detection limits for dissolved oxygen and hydrogen peroxide were 2 μg L(-1) and 5.5 × 10(-12) M, respectively. Besides the discussion of the intensifying mechanism of this nano-hybrid for ECL of luminol, the developed method was also applied for monitoring dissolved oxygen and evaluating the scavenging efficiency of reactive oxygen species of the Ganoderma lucidum spore.  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