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   14810篇
  免费   2553篇
  国内免费   2072篇
化学   13093篇
晶体学   273篇
力学   146篇
综合类   69篇
数学   67篇
物理学   5787篇
  2024年   89篇
  2023年   193篇
  2022年   724篇
  2021年   685篇
  2020年   1088篇
  2019年   781篇
  2018年   631篇
  2017年   643篇
  2016年   925篇
  2015年   857篇
  2014年   974篇
  2013年   1189篇
  2012年   994篇
  2011年   881篇
  2010年   725篇
  2009年   712篇
  2008年   788篇
  2007年   770篇
  2006年   665篇
  2005年   564篇
  2004年   564篇
  2003年   503篇
  2002年   1018篇
  2001年   386篇
  2000年   302篇
  1999年   248篇
  1998年   257篇
  1997年   214篇
  1996年   180篇
  1995年   170篇
  1994年   157篇
  1993年   80篇
  1992年   97篇
  1991年   61篇
  1990年   74篇
  1989年   60篇
  1988年   30篇
  1987年   26篇
  1986年   27篇
  1985年   21篇
  1984年   19篇
  1983年   8篇
  1982年   15篇
  1981年   13篇
  1979年   7篇
  1978年   3篇
  1977年   3篇
  1975年   6篇
  1974年   2篇
  1973年   4篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
71.
《Electroanalysis》2004,16(16):1305-1310
A novel amperometric biosensor was constructed for the determination of phenols in pure organic phase. This biosensor was fabricated by immobilizing tyrosinase in a titania sol‐gel membrane which was obtained with a vapor deposition method. This method was facile and avoided the calcination step needed in conventional titania sol‐gel process. The titania sol‐gel membrane could effectively retain the essential water layer around the enzyme molecule needed for maintaining its activity in organic phase. The experimental parameters such as solvent and operating potential were optimized. At ?100 mV this biosensor showed a good amperometric response to phenols in pure chloroform without any mediator and rehydration of the enzyme. For catechol determination the sensor exhibited a fast response of less than 5 seconds. The sensitivity of different phenols was as follows: catechol > phenol > p‐cresol. Additionally, the apparent Michaelis‐Menten constants of the encapsulated tyrosinase to catechol, phenol and p‐cresol were found to be 0.15±0.003, 0.17±0.008 and 0.21±0.004 mM, respectively. The biosensor had also good reproducibility and stability. This work provided a promising platform for the construction of pure organic phase biosensors and the determination of substrates with poor water solubility.  相似文献   
72.
The theory of new type detectors based on the quenching of secondary emission in direct-gap semiconductors (lines of Raman light scattering due to interaction between free and bound excitons in the crystal, and also bands of edge radiation) caused by IR or submillimeter radiation is proposed. The results obtained are confirmed by the experiment performed for CdS crystal excited by ultraviolet radiation of mercury lamp, at liquid helium temperature.  相似文献   
73.
Summary A major objective of the DIVERSOMER® technology is to provide pure and characterized compounds for biological testing in order to prevent false negatives in our libraries. On several occasions, analysis of the final products by1H-NMR and MS, has revealed by-products from the polystyrene solid support. Subsequently, three alternative methods were studied to remove polystyrene by-products; (i) prewashing of the resin prior to execution of the synthesis; (ii) pretreatment of the resin with the cleavage conditions consistent with the solid-phase synthesis reaction scheme; and (iii) parallel purification.  相似文献   
74.
随着激光技术的发展,近年来出现了与散射光频加宽相应的光子相干光谱即准弹性光散射。于是,利用光散射(也称弹性光散射)法不仅能获得高聚物的各种物性参数如分子量(?),第二维利系数A_2和均方旋转半径(),而且还能得到大分子在溶液中的动态参数,即扩散系数D_0。由D_0求得流体力学半径R_H。本文只涉及小角度准弹性光散射(1°<θ<7°)对稀溶液范围的平动扩散系数的测定。与文献比较,表明方法是成功的。  相似文献   
75.
Shih CM  Lin CH 《Electrophoresis》2005,26(11):2165-2171
The use of a low-temperature (0 degrees C) bath-assisted coupled capillary for the separation of naphthalene-2,3-dicarboxaldehyde (NDA)-derivatized dopamine and norepinephrine using the sweeping-micellar electrokinetic capillary chromatography (MEKC) mode is described. In this technique, a capillary consisting of two portions with different inside diameters is used. Therefore, the field strength inside the capillary is different. Hence, the electrophoretic migration velocities of the analytes and the electro-osmotic flow (EOF) also are different. Furthermore, when a portion of the capillary (wide portion, used for sweeping) is immersed in a low-temperature bath, the viscosity of the buffer and the retention factor of the analytes inside are increased. Thus, not only are the interactions between the SDS micelles and the analytes increased, but the SDS-analytes also move more slowly. As a result, a more complete separation can be achieved, even when the sample injection volume is large, up to approximately 2 microL. In general, when the volume of an injected sample is larger, the effects of sweeping and separation would become insufficient, especially when the retention values (k) of the analytes are quite different. However, this limitation can be improved when the low-temperature bath/coupled capillary/sweeping-MEKC mode is used.  相似文献   
76.
77.
A novel method for the determination of proteins in aqueous solutions has been developed based on the enhancement of resonance light scattering (RLS) of Ag nanoparticles in the presence of proteins. Factors including acidity of the media, concentration of Ag hydrosol, reaction time, temperature, and interference of non-protein substances were investigated. Under the optimal conditions, with the enhanced RLS signals at 452nm, the linear ranges of calibration curves were 0–0.8µgmL–1 for bovine serum albumin (BSA), 0–1.2µgmL–1 for human serum albumin (HSA), and 0–2.5µgmL–1 for human -IgG (-IgG), respectively. The detection limits were 1.3ngmL–1 for BSA, 10ngmL–1 for HAS, and 5.7ngmL–1 for -IgG.This method has been applied to the analysis of synthetic samples and real human serum samples, and the results were in good agreement with those reported by the hospital, indicating that the method presented here is not only sensitive and simple, but also reliable and suitable for practical applications.  相似文献   
78.
MCM-48 membranes have been prepared on alumina supports of different pore sizes. A battery of characterization techniques has been used to study the physical properties and the quality of the membranes prepared. The highest quality membranes were prepared on supports with pore size of up to 60 nm. The MCM-48 membranes were tested in the separation of gas phase mixtures and a cyclohexane/O2 selectivity higher than 270 was obtained. The selective separation of organic compounds from inert components is a result of the cooperative effects of capillary condensation in MCM-48 pores and of the specific interactions of the permeating compounds and the membrane material.  相似文献   
79.
IntroductionItilasbeenshot'-nthattileadditionofMnOpromotertoFocatal}stcanresultinaremarkableimprovementinthesclectivit}'to11ghtalkenesforCOh}!drogenationll'l.Ho-c'cvcr.thecadetofMnOonCH4formationandCOconversionisvery'ambigUouslltolMoreover.MnOpromotergrca…  相似文献   
80.
The π-π stacking interactions between maleimide's and nitrone's aromatic rings during the 1,3-dipolar cycloaddition were assumed to control the exo-endo selectivity of the reaction. The exo-endo ratios change during the reactions until they reach a constant value, which depends on the substituent. Electron-withdrawing groups favour the exo adduct while electron-donating groups favour the endo adduct. The nitrone ZnBr2 complexes react much more slowly than the free nitrone and the cycloaddition is exo selective in all cases independent of the substituents on the maleimide's aromatic ring. Thermal retrocycloaddition of the cycloadducts produce the corresponding nitrones. The ring opening in the presence of secondary amines did not induce imine formation. endo Adducts were shown for the first time to be the stable paramagnetic compounds.  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