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   78187篇
  免费   23319篇
  国内免费   18430篇
化学   49024篇
晶体学   944篇
力学   5411篇
综合类   230篇
数学   10391篇
物理学   53936篇
  2024年   455篇
  2023年   658篇
  2022年   641篇
  2021年   537篇
  2020年   789篇
  2019年   1317篇
  2018年   1308篇
  2017年   1947篇
  2016年   2050篇
  2015年   2269篇
  2014年   2079篇
  2013年   3858篇
  2012年   4132篇
  2011年   6967篇
  2010年   9762篇
  2009年   10014篇
  2008年   3221篇
  2007年   2708篇
  2006年   2430篇
  2005年   2962篇
  2004年   4347篇
  2003年   3302篇
  2002年   3115篇
  2001年   3336篇
  2000年   2385篇
  1999年   2611篇
  1998年   2270篇
  1997年   2006篇
  1996年   2339篇
  1995年   2800篇
  1994年   2829篇
  1993年   3101篇
  1992年   2716篇
  1991年   2309篇
  1990年   1984篇
  1989年   2073篇
  1988年   1943篇
  1987年   1132篇
  1986年   1252篇
  1985年   863篇
  1984年   996篇
  1982年   894篇
  1981年   730篇
  1980年   769篇
  1979年   527篇
  1978年   531篇
  1977年   636篇
  1976年   1043篇
  1973年   437篇
  1972年   532篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
851.
Sol-gel polyimide-silica composite membrane: gas transport properties   总被引:2,自引:0,他引:2  
The effect of introduction of silica particles prepared by the sol-gel technique on the gas transport properties of a polyimide film was studied. The sorption and permeation of N2, O2, CO2, H2 and CH4 were studied and correlated with morphological changes in the polymer structure. From sorption isotherms, we observed that the composite membrane presents higher solubility coefficients than the polyimide one. The solubility coefficient ratio between the composite and the polyimide is about 1.5–2.0. The isotherms were analyzed in terms of the dual mode sorption. The Henry's coefficient and the Langmuir's affinity and saturation constants were obtained allowing to calculate the Langmuir to Henry concentration ratios as function of the gas pressure. These ratios decrease until zero within a certain pressure range as long as the Langmuir's mode is acting and they are higher for the polyimide membrane when compared with the composite one. This study was completed with calorimetric measurements during the sorption. The gas interaction energy in kJ/mol decreases within the same pressure range as previously described. The measured energies are higher for the polyimide film when compared with the composite one because the polyimide membrane presents a stronger energetic effect caused by a higher Langmuir's contribution. From permeation studies at 3.155 Pa, the composite membrane showed higher permeability coefficients and permselectivities than the polyimide one. All these results were explained, taking into account the difference on the imidization degree of both membranes and the morphological changes which may be induced by the silica nodules in the organic/inorganic interphases.  相似文献   
852.
以紫外光谱、荧光光谱、粘度法和凝胶电泳方法研究了全反式维甲酸合钇(Ⅲ)配合物与DNA的作用。结果表明,该配合物能在生理条件下比配体和金属离子更有效地切割质粒DNA,体系离子强度和pH值的变化对配合物的切割活性有较大影响,自由基捕捉剂的加入不影响配合物的切割活性。该配合物对DNA的切割可能通过水解机理进行。该配合物可使DNA的粘度增加,使EB-DNA体系的荧光强度和DNA溶液的紫外吸收强度降低。据此推断,该配合物主要以嵌入方式与DNA作用。  相似文献   
853.
Selenium nanoparticles were prepared by a reverse microemulsion system. Sodium selenosulfate was used as selenium source. The results showed that hydrochloric acid concentration and reaction temperature had great influence on the morphology of products. The crystalline selenium nanowires and amorphous selenium nanorods were obtained in given condition.  相似文献   
854.
制备了K[Fe(acaccn)(CN)2]·2H2O.并测定了晶体结构.  相似文献   
855.
本文提出了分段式离子系列谱编码方法,实验证明具有很好的结构表征能力。本程序主要是以模式识别技术为基础,实现了对未知物谱图的KNN分类,进而得到未知物的主要结构特征。这个程序应用于有机化合物的分类,取得了满意的结果。  相似文献   
856.
Summary Eriochromecyanine RC has been used as chromogenic reagent for the photometric determination of rhodium(III) on a micro scale. A coloured Rh(III)-ECRC chelate with max 530 nm at pH 4.0 (25°C) is formed. A detailed study has been made concerning to characteristics, composition and stability of the chelate. Standard deviation was ±1.17%.
Über die photometrische Bestimmung von dreiwertigem Rhodium mit Eriochromcyanin RC
Zusammenfassung Ergebnisse einer Untersuchung über die Zusammensetzung und Stabilität des Komplexes werden mitgeteilt. Das Absorptionsmaximum liegt bei 530 nm (pH 4,0; 25°C). Bestimmungen konnten mit einer Standardabweichung von ±1,17% durchgeführt werden.
  相似文献   
857.
A novel 99mTc labeled complex, [N-[2-((2-oxo-2-(4-(3-phenylpropyl)piperazin-1-yl)ethyl) (2-mercaptoethyl)amino)acetyl]-2-aminoethanethiolato]Technetium(V) oxide (PPPE-MAMA’-99mTcO) ([ 99m Tc]-2) has been designed and prepared based on the integrated approach. The corresponding rhenium complex (PPPE-MAMA’-ReO)(Re-2) has been prepared and characterized. In vitro competition binding assays show moderate affinity of Re-2 towards σ1 and σ2 receptors with K i values of 8.67 ± 0.07 and 5.71 ± 1.88 μmol, respectively. Planar images obtained at 0.5 h, 4 h, 20 h after i.v. injection indicate the accumulation of [ 99m Tc]-2 in MCF-7 human breast tumor bearing mice at 20 h. Furthermore, the accumulation of [ 99m Tc]-2 has been inhibited at 20 h after co-injection of [ 99m Tc]-2 plus haloperidol (1 mg/kg). Biodistribution studies of [ 99m Tc]-2 display an in vivo tumor uptake of 0.14% ± 0.01% ID/g at 24 h post i.v. injection with a tumor/muscle ratio of 6.02 ± 0.87. The above results suggest that [ 99m Tc]-2, derived from a previously published lead compound, retains certain tumor uptake and affinity for σ receptors. [ 99m Tc]-2 may be used as a basis for further structural modifications to develop tumor imaging agents with high affinity for σ receptors.  相似文献   
858.
A new technique of searching the conformational space of transition states was used to explore the cause of the rate acceleration in the gem-dialkyl effect in intramolecular cyclization reactions. Several previous hypotheses were discarded and a new hypothesis was advanced based on this new data. This hypothesis, the “Facilitated Transition” hypothesis, states that increased steric hindrance reduces the overall activation energy by facilitating rotation through the transition state. The older “Reactive Rotamer” hypothesis was eliminated by generating all conformations of the starting materials using the and computer programs and demonstrating that no relationship is found between rate increase and a change in the concentration of “reactive rotamers”.  相似文献   
859.
研究了取代乙酸配体作为Nieulan催化剂对乙炔二聚反应性能的影响。结果表明,不同功能结构数目的影响,结果表明,不同功能结构数目的的氨羧配体均使催化剂的选择性提高。乙炔转化率略有下降,巯基乙酸配体的加入,则改变了乙炔二聚反应的机理,得到以乙醛为主的产物。  相似文献   
860.
A spectral-luminescent analysis has been made of the low-, medium-, and high-molecular mass fractions of sugar cane juice. The presence of pigments was detected in all the fractions. The medium-molecular-mass fraction was distinguished by the most considerable and most diverse composition of the pigments, a substantial contribution to which was made by the products of the alkaline decomposition of sugars. The amounts of pigments in all the fractions of the juice depended on the age of the plant. A pronounced dependence on the age of the plant was characteristic for the medium-molecular-mass fraction.B. I. Stepanov Institute of Physics, Belorussian Academy of Sciences, Minsk. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 456–459, May–June, 1993.  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