全文获取类型
收费全文 | 30226篇 |
免费 | 4239篇 |
国内免费 | 2739篇 |
专业分类
化学 | 20590篇 |
晶体学 | 285篇 |
力学 | 2011篇 |
综合类 | 279篇 |
数学 | 3304篇 |
物理学 | 10735篇 |
出版年
2024年 | 105篇 |
2023年 | 592篇 |
2022年 | 914篇 |
2021年 | 960篇 |
2020年 | 1118篇 |
2019年 | 1086篇 |
2018年 | 921篇 |
2017年 | 822篇 |
2016年 | 1290篇 |
2015年 | 1278篇 |
2014年 | 1547篇 |
2013年 | 2063篇 |
2012年 | 2645篇 |
2011年 | 2674篇 |
2010年 | 1662篇 |
2009年 | 1641篇 |
2008年 | 1749篇 |
2007年 | 1670篇 |
2006年 | 1508篇 |
2005年 | 1242篇 |
2004年 | 955篇 |
2003年 | 803篇 |
2002年 | 756篇 |
2001年 | 575篇 |
2000年 | 571篇 |
1999年 | 678篇 |
1998年 | 589篇 |
1997年 | 585篇 |
1996年 | 667篇 |
1995年 | 513篇 |
1994年 | 472篇 |
1993年 | 392篇 |
1992年 | 375篇 |
1991年 | 325篇 |
1990年 | 259篇 |
1989年 | 204篇 |
1988年 | 157篇 |
1987年 | 137篇 |
1986年 | 129篇 |
1985年 | 118篇 |
1984年 | 88篇 |
1983年 | 61篇 |
1982年 | 41篇 |
1981年 | 36篇 |
1980年 | 18篇 |
1978年 | 19篇 |
1977年 | 23篇 |
1976年 | 20篇 |
1975年 | 28篇 |
1974年 | 27篇 |
排序方式: 共有10000条查询结果,搜索用时 46 毫秒
921.
Palladium-benzimidazolium salt catalyst systems have been studied for the Suzuki coupling. A different substitutent effect has been uncovered with respect to nitrogen substituents in the benzimidazolium salts from the palladium-imidazolium salt analogs. A practical and highly active palladium catalyst system, PdCl2/N,N′-dibenzylbenzimidazolium chloride 2, has been identified for the Suzuki coupling of aromatic halides with arylboronic acids. The coupling of a wide array of aromatic halides with arylboronic acids with the PdCl2-2 catalyst system gave good to excellent yields. The effective palladium loading could be as low as 0.0001 mol% and 0.01-0.1 mol% for iodide and bromide substrates, respectively. The coupling of unactivated aromatic chlorides with arylboronic acids also gave good results using Cs2CO3 as base with a 2 mol% palladium loading. The electronic factors from aromatic halides exert a significant influence on the Suzuki coupling catalyzed by the PdCl2-2 system while the electronic effect from the arylboronic counterparts is negligible. The aromatic halides with modest steric hindrance could also couple smoothly with phenylboronic acids using the PdCl2-2 catalyst system. 相似文献
922.
Hedstrom JA Toney MF Huang E Kim HC Volksen W Magbitang T Miller RD 《Langmuir : the ACS journal of surfaces and colloids》2004,20(5):1535-1538
Materials with nanometer size heterogeneities are commonplace in the chemical and biological sciences (e.g, polymer blends, microemulsions, gels) and often exhibit complex morphologies. Although this morphology has a dramatic effect on the materials' properties, it is often difficult to accurately characterize. We describe a method, using small-angle X-ray scattering data, of generating representative three-dimensional morphologies of isotropic two-phase materials where the morphology is disordered, and we apply this to thin films containing nanometer sized pores with a range of porosities (4-44%). These representations provide a visualization of the pore morphology, give the pore size scale and extent of interconnection, and permit the determination of the transitions from closed pore to interconnected pores to bicontinuous morphology. 相似文献
923.
Bivalent germanium was polarographically studied in sodium hydroxide solution at various concentrations. A well-defined reduction wave with half-wave potential varying from ?0.90 to ?0.98 volt vs. S.C.E. was observed for 1×10?4 M Ge(II) in concentration range of 0.2 to 2.0 F with respect to NaOH, and from ?0.70 to ?0.88 volt vs. S.C.E. in the pH range 9.0–12.1 at 25°. The value of id/C is 5.43 μα/mM and that of id/C mfor t1/8 is 5.21. Dependence of E1/2 upon pH is expressed by —E1/2 =0.18+0.058 pH. Experimental result suggests that the reaction proceeds in two-steps involving an irreversible two-electron reduction: Ge(OH)2+OH?→HGeO2?+H2O and HGeO2?+H2O+2e→Ge0+3OH?. 相似文献
924.
环状芴基张力半导体由于其特殊的分子结构,发射状排布的p轨道和纳米级空腔等诸多特点,引起了科学家广泛的关注.相对于直链型芴基半导体,环状芴基张力半导体展现出独特的光电性质.然而,迄今为止其振动性质没有被报道.对四元环芴的晶体与直链四聚芴粉末样品进行拉曼光谱表征和归一化处理,并结合理论计算.结果表明,与直链寡聚芴相比,环芴类似于碳纳米管的G峰发生了偏移,并且低频区域拉曼频移峰的峰强增加.其原因是由于张力的引入,改变了芴基主链的骨架和电子结构,加强芴骨架上π电子离域,同时使环芴中每个芴单元都参与到振动中.该研究结果为芴基张力半导体材料拉曼光谱的研究提供了一定的工作基础. 相似文献
925.
J. P. Huang 《Chemical physics letters》2004,390(4-6):380-383
Under the application of electric fields, the structure of electrorheological (ER) solids can be changed from the body-centered tetragonal lattice to other lattices. We have derived the dipole factor for the lattice by taking into account the local-field effect through the Ewald–Kornfeld formulation, and expressed it in the spectral representation exactly. It is found that when the ER solid is subject to a nonuniform ac electric field, the force acting on the microparticle can be affected by the structure transformation, and local-field effect as well as field frequency. Our results are very well understood in the spectral representation theory. 相似文献
926.
Wei-Cho Huang Cheng S. Gong George T. Tsao 《Applied biochemistry and biotechnology》2003,106(1-3):471-480
Pressure pulsation (PP) was investigated for its effects on oxygen transfer rate (OTR) measured by sulfite oxidation. By manipulating
airflow rate, 0.41–1.2 vvm, and a control valve in a 4-L bioreactor, the frequency of PP was varied at different gas pressures3–15
psig. A mathematical model of OTR was built and compared to experimental data. OTR was also examined at constant gas pressure,
4.5–15.0 psig. The results indicate a good agreement between measurement and model prediction. OTR above 9 psig during PP
showed significant enhancement at 25°C. This proves that PP not only affects the elevation of DO level, but also increases
the interfacial area and mass transfer coefficient. 相似文献
927.
动物体内的体液和肠胃等器官的环境各不相同,这就要求各种不同用途的载药体的降解性能必须满足特定环境的要求。同时,可降解材料在不同的降解介质中通常有着不同的降解表现,这也决定着可降解材料的运用环境。因此,有必要对降解性材料在不同降解介质中的降解性进行专门的研究,由CO2和环氧化物合成的脂肪族聚碳酸酯具有良好的生物降解性能。 相似文献
928.
以二苯腈二氯化钯为催化剂,在固液相转移条件下,芳基磺酰氯能与N,N-双烷基取代丙烯酰胺发生偶联反应,生成柏应的E式不饱和酰胺。 相似文献
929.
930.
Abstract— Acetone-sensitized photoinactivation and subsequent in vivo photoreactivation of tobacco mosaic virus (TMV) and potato virus X (PVX) ribonucleic acids (RNA's) were demonstrated. The photoreactivable sectors were comparable to those obtained for the same RNA's irradiated at 253·7 nm. Only dimers were detected in these RNA's. Irradiation of E. coli rRNA at a higher dose indicated that photoreversible pyrimidine dimers were the main photoproducts detected in the sensitized reaction, whereas pyrimidine hydrates were formed only in negligible amounts. These results have led us to conclude that photoreversible pyrimidine dimers constitute both a lethal and photorepairable type of lesion in u.v.-damaged viral RNA. 相似文献