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   1272篇
  免费   74篇
  国内免费   273篇
化学   1121篇
晶体学   7篇
力学   70篇
综合类   1篇
数学   174篇
物理学   246篇
  2023年   9篇
  2022年   10篇
  2021年   27篇
  2020年   23篇
  2019年   19篇
  2018年   34篇
  2017年   25篇
  2016年   27篇
  2015年   28篇
  2014年   44篇
  2013年   125篇
  2012年   106篇
  2011年   121篇
  2010年   64篇
  2009年   92篇
  2008年   79篇
  2007年   76篇
  2006年   48篇
  2005年   71篇
  2004年   140篇
  2003年   108篇
  2002年   78篇
  2001年   26篇
  2000年   21篇
  1999年   21篇
  1998年   26篇
  1997年   20篇
  1996年   19篇
  1995年   8篇
  1994年   6篇
  1993年   9篇
  1992年   8篇
  1991年   4篇
  1989年   8篇
  1987年   3篇
  1986年   4篇
  1984年   5篇
  1983年   4篇
  1982年   3篇
  1980年   5篇
  1979年   7篇
  1978年   6篇
  1974年   4篇
  1973年   4篇
  1972年   5篇
  1971年   3篇
  1970年   3篇
  1967年   4篇
  1959年   3篇
  1929年   4篇
排序方式: 共有1619条查询结果,搜索用时 31 毫秒
81.
This work depicts the original combination of electrochemiluminescence (ECL) and bipolar electrochemistry (BPE) to map in real-time the oxidation of silicon in microchannels. We fabricated model silicon-PDMS microfluidic chips, optionally containing a restriction, and monitored the evolution of the surface reactivity using ECL. BPE was used to remotely promote ECL at the silicon surface inside microfluidic channels. The effects of the fluidic design, the applied potential and the resistance of the channel (controlled by the fluidic configuration) on the silicon polarization and oxide formation were investigated. A potential difference down to 6 V was sufficient to induce ECL, which is two orders of magnitude less than in classical BPE configurations. Increasing the resistance of the channel led to an increase in the current passing through the silicon and boosted the intensity of ECL signals. Finally, the possibility of achieving electrochemical reactions at predetermined locations on the microfluidic chip was investigated using a patterning of the silicon oxide surface by etched micrometric squares. This ECL imaging approach opens exciting perspectives for the precise understanding and implementation of electrochemical functionalization on passivating materials. In addition, it may help the development and the design of fully integrated microfluidic biochips paving the way for development of original bioanalytical applications.  相似文献   
82.
Unprecedented metalated phosphonite boranes were prepared from PH-substituted precursors and silyl amides. Although potassium derivatives were thermally stable and could even be isolated and structurally characterised, lithiated analogues proved to be unstable towards self-condensation under cleavage of LiOR at ambient temperature. Reaction studies revealed that the metalated phosphonite boranes exhibit ambiphilic character. Their synthetic potential as nucleophilic building blocks was demonstrated in the synthesis of the first stannylated phosphonite representing a new structural motif in phosphine chemistry.  相似文献   
83.
Lanthanide complexes (Ln=Eu, Tb, and Yb) that are based on a C2‐symmetric cyclen scaffold were prepared and characterized. The addition of fluoride anions to aqueous solutions of the complexes resulted in the formation of dinuclear supramolecular compounds in which the anion is confined into the cavity that is formed by the two complexes. The supramolecular assembly process was monitored by UV/Vis absorption, luminescence, and NMR spectroscopy and high‐resolution mass spectrometry. The X‐ray crystal structure of the europium dimer revealed that the architecture of the scaffold is stabilized by synergistic effects of the Eu? F? Eu bridging motive, π stacking interactions, and a four‐component hydrogen‐bonding network, which control the assembly of the two [EuL] entities around the fluoride ion. The strong association in water allowed for the luminescence sensing of fluoride down to a detection limit of 24 nM .  相似文献   
84.
When finally processed to provide the function for which the latex was selected―binding, protecting, finishing―components such as surfactant, costabilizer or initiator become generally useless, not to say detrimental. In this study, we show that miniemulsion photopolymerization provides a suitable method to create latex without the apparent addition of these three compounds. Indeed, UV-driven monomer self-initiation can create initiating radicals without the aid of initiator, the fast in situ photogenerated polymer can hinder Ostwald ripening with the assistance of external costabilizer, and finally, UV-transparent clay can replace conventional surfactant to ensure colloidal stabilization. Each strategy has been developed individually before being combined together to end up with a unique miniemulsion procedure free of initiator, costabilizer and surfactant. Such approach paves the way to a simplified and environmentally improved pathway towards aqueous polymer dispersions.  相似文献   
85.
The search for more biocompatible alternatives to Gd3+‐based MRI agents, and the interest in 52Mn for PET imaging call for ligands that form inert Mn2+ chelates. Given the labile nature of Mn2+, high inertness is challenging to achieve. The strongly preorganized structure of the 2,4‐pyridyl‐disubstituted bispidol ligand L1 endows its Mn2+ complex with exceptional kinetic inertness. Indeed, MnL1 did not show any dissociation for 140 days in the presence of 50 equiv. of Zn2+ (37 °C, pH 6), while recently reported potential MRI agents MnPyC3A and MnPC2A‐EA have dissociation half‐lives of 0.285 h and 54.4 h under similar conditions. In addition, the relaxivity of MnL1 (4.28 mm ?1 s?1 at 25 °C, 20 MHz) is remarkable for a monohydrated, small Mn2+ chelate. In vivo MRI experiments in mice and determination of the tissue Mn content evidence rapid renal clearance of MnL1. Additionally, L1 could be radiolabeled with 52Mn and the complex revealed good stability in biological media.  相似文献   
86.
87.
<正>SnO_2 nanorods were deposited on the Si substrates in an aqueous solution containing both SnCl_4 and CO(NH_2)_2.It is found that different self-assembled patterns of SnO_2 nanorods can be obtained by changing the deposition conditions such as the molar ratio of CO(NH_2)_2 to SnCl_4 and the pretreatment of the substrate.Scattered SnO_2 nanorods,for example,can be changed into flower-like patterns when the molar ratio of CO(NH_2)_2 to SnCl_4 is raised,and well-aligned nanorod arrays can be formed when the pretreatment of the substrate is changed.In addition,some interesting patterns,e.g.tree-like patterns,can also be observed.  相似文献   
88.
In this study, factors affecting the crystal structure of flame-synthesized Y 2 O 3 :Eu particles were inves- tigated, especially the particle size effect and its interaction with Eu doping concentration. Polydisperse Y 2 O 3 :Eu (size range 200 nm to 3 m) powder samples with Eu doping concentrations from 2.5 mol% to 25 mol% were generated in either H 2 /air or H 2 /O 2 substrate-free flames. The crystal structure of the powder samples was determined by powder X-ray diffraction (XRD), which was complemented...  相似文献   
89.
A series of gem-dimethyl-bearing C-glucosides were designed and synthesized as SGLT2 inhibitors,with anhydrous aluminum chloride-mediated Friedel-Crafts alkylation to construct the gem-dimethyl functionality being the key step.The in vivo anti-hyperglycemic activity was evaluated with mice oral glucose tolerance test(OGTT),and all the synthesized compounds showed significant but less potent anti-hyperglycemic activity than the positive control dapagliflozin.  相似文献   
90.
PM2.5 samples for 24 h were collected during winter in Tianjin,China. The ambient mass concentration and chemical composition of the PM2.5 were determined. Ionic species were analyzed by ion chromatog-raphy,while carbonaceous species were determined with the IMPROVE thermal optical reectance(TOR) method,and inorganic elements were measured by inductively coupled plasma-atomic emission spec-trometer. The daily PM2.5 mass concentrations ranged from 48.2 to 319.2 g/m3 with an arithmetic average of 144.6 g/m3. ...  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