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   1424篇
  免费   143篇
  国内免费   289篇
化学   1104篇
晶体学   12篇
力学   18篇
综合类   14篇
数学   36篇
物理学   672篇
  2023年   14篇
  2022年   12篇
  2021年   27篇
  2020年   51篇
  2019年   34篇
  2018年   30篇
  2017年   52篇
  2016年   57篇
  2015年   44篇
  2014年   77篇
  2013年   124篇
  2012年   99篇
  2011年   126篇
  2010年   82篇
  2009年   107篇
  2008年   107篇
  2007年   119篇
  2006年   97篇
  2005年   71篇
  2004年   55篇
  2003年   61篇
  2002年   45篇
  2001年   30篇
  2000年   40篇
  1999年   35篇
  1998年   36篇
  1997年   44篇
  1996年   27篇
  1995年   19篇
  1994年   25篇
  1993年   34篇
  1992年   25篇
  1991年   13篇
  1990年   4篇
  1989年   9篇
  1988年   5篇
  1987年   2篇
  1986年   6篇
  1985年   1篇
  1984年   1篇
  1983年   2篇
  1982年   3篇
  1981年   1篇
  1980年   1篇
  1974年   1篇
  1973年   1篇
排序方式: 共有1856条查询结果,搜索用时 282 毫秒
31.
A new on-off fluorescent probe 1 for Cu2+ based on Schiff base compound was designed and synthesized by one-step reaction. The single probe 1 exhibited strong green fluorescence emission. A fluorescence quenching effect and faint color change were observed as soon as the Cu2+ was added to the probe system in H2O/EtOH (v/v = 8:2, HEPES buffer, 0.05 M, pH = 7.4) solution. Other common metal cations did not cause the changes in the fluorescence and color of the probe 1. The optical properties were studied by the fluorescence emission and UV–Vis spectra. Meanwhile, the geometry optimizations of probe 1 and the [1-Cu2+] coordination complexes were also carried out by DFT using the Gaussian 09 program, in which the B3LYP function was used. Based on experimental measurement and theoretical analysis, we can know that the combination ratio of the probe and Cu2+ is 2:1 and the limit of detection (LOD) is as low as 5.3 × 10?9 M Besides, the probe 1 was also used to analyze the Cu2+ in living cells.  相似文献   
32.
Friedel-Crafts polycondensation of β-resorcylic acid (BRA) with p-xylylene dichloride (PXDC) or 4,4′-dichloromethyldiphenyl ether (DDE) in dioxane could be effected without simultaneous decarboxylation of BRA. The similar polycondensation of BRA with PXDC, DDE, or 4,4′-dichloroacetyldiphenyl ether (DADE) in nitrobenzene or in the absence of solvent at 150°C was associated with decarboxylation of BRA. Polymers having structures isomeric with those of the polycondensation product of BRA formed with subsequent in situ decarboxylation were prepared by Friedel-Crafts polycondensation of resorcinol with the above dichlorides. All the polymer samples were characterized, and those with related structures were compared. The ion-exchange properties of the polymer sample prepared from BRA and DDE in dioxane were studied.  相似文献   
33.
High-quality cysteamine-coated CdTe quantum dots (CA-CdTe QDs) were successfully synthesized in aqueous phase by a facile one-pot method. Through hydroxylamine hydrochloride-promoted kinetic growth strategy, water-soluble CA-CdTe QDs could be obtained conveniently in a conical flask by a stepwise addition of raw materials. The photoluminescence quantum yield (PL QY) of the obtained QDs reached 9.2% at the emission peak of 520 nm. The optical property and the morphology of the QDs were characterized by UV–vis absorption spectra, photoluminescence spectra (PL) and transmission electron microscopy (TEM) respectively. Furthermore, the fluorescence of the resultant QDs was quenched by copper (II) (Cu2+) and mercury (II) (Hg2+) meanwhile. It is worthy of note that to separately detect Hg2+, cyanide ion could be used to eliminate the interference of Cu2+. Under the optimal conditions, the response was linearly proportional to the logarithm of Hg2+ concentration over the range of 0.08–3.33 μM with a limit of detection (LOD) of 0.07 μM.  相似文献   
34.
The objective of this work is to study electron-vibrational interaction (EVI) and concentration quenching and their manifestation in experimental photoluminescence spectra of Cu+ ion in various lithium based phosphors namely, Li2SO4, LiNaSO4 and LiKSO4. The main parameters of EVI, such as the Stokes shift, Huang-Rhys factor and zero-phonon line positions, were estimated. The studied systems shows strong electron lattice coupling. The validity of results was established by modeling the shape of the emission spectra, which was found to be in good agreement with experimental photoluminescence spectra. The concentration quenching study is also carried out for these compounds. The studied systems correspond to the nearest neighbor energy transfer mechanism.  相似文献   
35.
Biphenyl derivative N-allyl-N′-(4′-nitro[1,1′-biphenyl]-4-yl)thiourea (BP1) was synthesized as a functional fluorescent sensor for protons and their photophysical properties were studied. The influence of environment protonation on photophysical properties of the biphenyls in solutions was investigated using UV absorption, steady-state and time-resolved fluorescence spectroscopy. Semi-empirical and DFT calculations and optimization of the molecular structure of the biphenyl derivatives in vacuum, in polar solvents and in a proton-rich environment were conducted using the HyperChem, Amsol and Gaussian3 software package. Fluorescence quenching with addition of acidic acid was observed and the Stern-Volmer quenching rate constant was about 3.0×109 M−1 s−1. Intermolecular hydrogen bonds formations by the protons with the sulphur being substituted to the biphenyls generate charge movement and strong increase (×5) of the dipole moment of the fluorophore.  相似文献   
36.
2′-Deoxyguanosine (dG) suffers from oxidation by reactive oxygen species (ROS) to form 8-oxo-2′-deoxyguanosine (8-oxo-dG), which is regarded as a marker of oxidative stress in the cells. In our continuous study for the recognition molecule of 8-oxo-dG, 8-oxoGclamp and its derivatives have been identified as the selective fluorescent probe. However, it is an obstacle for further application that dG also forms a complex with 8-oxoGclamp, resulting in fluorescence quenching in less polar solvents. Quenching of the fluorescence of 8-oxoGclamp is thought to involve photo-induced electron transfer in the complex. It was hypothesized that the energy level of the excited state of 8-oxoGclamp and the HOMO energy of dG are the preliminary determinant of the quenching efficiency. Thus, fluorescence properties of the substituted derivatives at the 7-position of the 1,3-diazaphenoxazine part of 8-oxoGclamp were investigated. Among the new derivatives, fluorescence of the 7-phenyl substituted 8-oxoGclamp was not quenched by dG even in the stable complex, exhibiting the highest selectivity for 8-oxo-dG.  相似文献   
37.
Chloramphenicol (CAP) is a veterinary antibiotic that has been banned due to its severe side effects in humans. Through the application of manure, veterinary antibiotics can enter the soil, where they can be taken up by crops and vegetables and pose a potential health hazard to humans. Thus, it is highly desirable to develop a rapid and sensitive tool for on-site detection of CAP to ensure food safety and to control the abuse of antibiotics. To this end, nitrogen-doped graphene quantum dots (N-GQDs) were successfully prepared via microwave-assisted synthesis using citric acid and urea as carbon and nitrogen sources, respectively. Analytical results suggested that the interaction between N-GQDs and CAP could occurs via π-π stacking, which quenched N-GQD fluorescence. CAP spiked into chicken feed could be rapidly extracted with ethanol and quantified based on N-GQD fluorescence quenching without further separation. This method showed good recovery (97–102.6%), a low detection limit (1.8 ppm), and was not affected by interference from florfenicol, and thiamphenicol, legal substitute antibiotics. This method has excellent potential for determination of CAP in livestock feed and soil.  相似文献   
38.
近年来,在水溶性共轭聚合物(CPs)方面的研究备受瞩目,由于它包含了聚合物共轭主链良好的光电性质的同时还兼具了良好的水溶性,因此在光电功能信息器件中有着特殊的应用,并显著地推动了包括生物传感、电致发光器件、太阳电池和场效应晶体管等有机光电子材料及其器件的发展.本文对近几年来水溶性CPs的合成及其应用进展做出简要的总结,...  相似文献   
39.
The interaction between 3-thiol-4-(2,4-dichlorobenzylideneamino)-5-methyl-4H-1,2,4-triazole (CBTZ) and bovine serum albumin (BSA) under physiological conditions was investigated by fluorescence,UV-vis absorption and circular dichroism (CD) spectroscopy as well as molecular modeling methods. The result of fluorescence experiment indicates the static quenching as a result of the formation of the CBTZ-BSA complex. The binding constants (Ka) at different temperatures were calculated according to the modified St...  相似文献   
40.
通过分子荧光分析、紫外可见吸收光谱及粘度分析以及与溴化乙锭的竞争性实验对大黄素与DNA之问的作用模式进行了考察.在pH 7.4,低离子强度(30 mmol/L NaCl)及恒温37℃条件下反应35 min,大黄素的荧光强度随DNA加入浓度的增加而递减,紫外可见吸收光谱在380、475 nm处出现等吸收点并红移5nm,表...  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