全文获取类型
收费全文 | 68714篇 |
免费 | 9636篇 |
国内免费 | 9884篇 |
专业分类
化学 | 50426篇 |
晶体学 | 860篇 |
力学 | 3536篇 |
综合类 | 553篇 |
数学 | 8517篇 |
物理学 | 24342篇 |
出版年
2024年 | 153篇 |
2023年 | 912篇 |
2022年 | 1949篇 |
2021年 | 2109篇 |
2020年 | 2074篇 |
2019年 | 2238篇 |
2018年 | 1873篇 |
2017年 | 1894篇 |
2016年 | 2777篇 |
2015年 | 2969篇 |
2014年 | 3502篇 |
2013年 | 4940篇 |
2012年 | 5661篇 |
2011年 | 6863篇 |
2010年 | 4657篇 |
2009年 | 4791篇 |
2008年 | 4686篇 |
2007年 | 4094篇 |
2006年 | 3769篇 |
2005年 | 3444篇 |
2004年 | 3951篇 |
2003年 | 2882篇 |
2002年 | 2679篇 |
2001年 | 1961篇 |
2000年 | 1375篇 |
1999年 | 1190篇 |
1998年 | 1007篇 |
1997年 | 844篇 |
1996年 | 759篇 |
1995年 | 658篇 |
1994年 | 573篇 |
1993年 | 849篇 |
1992年 | 825篇 |
1991年 | 551篇 |
1990年 | 565篇 |
1989年 | 476篇 |
1988年 | 242篇 |
1987年 | 146篇 |
1986年 | 178篇 |
1985年 | 182篇 |
1984年 | 142篇 |
1983年 | 115篇 |
1982年 | 84篇 |
1981年 | 79篇 |
1980年 | 64篇 |
1979年 | 54篇 |
1978年 | 37篇 |
1977年 | 49篇 |
1976年 | 33篇 |
1974年 | 32篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
191.
The aim of this article is to derive stable generalized sampling in a shift-invariant space by using some special dual frames in L2(0,1). These sampling formulas involve samples of filtered versions of the functions in the shift-invariant space. The involved samples are expressed as the frame coefficients of an appropriate function in L2(0,1) with respect to some particular frame in L2(0,1). Since any shift-invariant space with stable generator is the image of L2(0,1) by means of a bounded invertible operator, our generalized sampling is derived from some dual frame expansions in L2(0,1). 相似文献
192.
193.
用密度泛函B3LYP方法研究了过渡金属钐类卡宾与乙烯的环丙烷化反应的机理。对三种不同的钐的SS试剂CH_3SmCH_2X(其中X=Cl、Br和Ⅰ)分别和CH_2CH_2反应的各反应物、中间体、过渡态和产物构型的全部结构几何参数进行了优化,用内禀反应坐标(IRC)计算和频率分析方法,对过渡态进行了验证。结果表明:CH_3SmCH_2X(其中X=Cl、Br和Ⅰ)与CH_2CH_2环丙烷化反应按亚甲基转移通道(通道A)和卡宾金属化通道(通道B)都可以进行,与锂类卡宾的反应机理相同,只是按亚甲基转移通道(通道A)进行反应较容易一些,而且此反应在较低的温度下就可以发生。 相似文献
194.
介绍了19世纪存在于澳大利亚土著中的一种婚姻形式—级别婚,从群论的角度说明级别婚的三种主要形式都对应于一个对称群,从而可以用几何方法形象的表示这种婚姻形式;进而,从对称的观点说明婚姻形式从简单到复杂的演化过程,代数上对应于对称群阶数的增加,几何上则对应于对称性的加强. 相似文献
195.
Wei‐Ling Wang Jian‐Wei Xu Yee‐Hing Lai 《Journal of polymer science. Part A, Polymer chemistry》2006,44(13):4154-4164
Bipyridinophane–fluorene conjugated copolymers have been synthesized via Suzuki and Heck coupling reactions from 5,8‐dibromo‐2,11‐dithia[3]paracyclo[3](4,4′)‐2,2′‐bipyridinophane and suitable fluorene precursors. Poly[2,7‐(9,9‐dihexylfluorene)‐co‐alt‐5,8‐(2,11‐dithia[3]paracyclo[3](4,4′)‐2,2′‐bipyridinophane)] ( P7 ) exhibits large absorption and emission redshifts of 20 and 34 nm, respectively, with respect to its planar reference polymer Poly[2,7‐(9,9‐dihexylfluorene)‐co‐alt‐1,4‐(2,5‐dimethylbenzene)] ( P11 ), which bears the same polymer backbone as P7 . These spectral shifts originate from intramolecular aromatic C? H/π interactions, which are evidenced by ultraviolet–visible and 1H NMR spectra as well as X‐ray single‐crystal structural analysis. However, the effect of the intramolecular aromatic C? H/π interactions on the spectral shift in poly[9,9‐dihexylfluorene‐2,7‐yleneethynylene‐co‐alt‐5,8‐(2,11‐dithia[3]paracyclo[3](4,4′)‐2,2′‐bipyridinophane)] ( P10 ) is much weaker. Most interestingly, the quenching behaviors of these two conjugated polymers are largely dependent on the polymer backbone. For example, the fluorescence of P7 is efficiently quenched by Cu2+, Co2+, Ni2+, Zn2+, Mn2+, and Ag+ ions. In contrast, only Cu2+, Co2+, and Ni2+ ions can partially quench the fluorescence of P10 , but much less efficiently than the fluorescence of P7 . The static Stern–Volmer quenching constants of Cu2+, Co2+, and Ni2+ ions toward P7 are of the order of 106 M?1, being 1300, 2500, and 37,300 times larger than those of P10 , respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4154–4164, 2006 相似文献
196.
LI Ya-feng~ ** ZHANG Li-mei~ WU Lei-lei~ WANG Sheng-hai~ WANG Hai-lian~ SHANG Xuan-xuan~ . College of Chemistry Molecular Engineering . College of Mathematics Physics Qingdao University of Science & Technology Qingdao P. R. China 《高等学校化学研究》2006,(6)
IntroductionThe interest in polyoxometalates that are widelyused in medical chemistry, catalyst reactions, and ma-terial sciences stems from their complicated aggregatesformed by means of corner-, edge- and face-sha-ring[1—4]. The exploitation of new str… 相似文献
197.
198.
The aggregation of dansyl chloride (DNS-Cl) in acetone has been studied in detail by steady-state fluorescence techniques.It has been demonstrated that DNS-Cl is stable in acetone during purification and aggregation study processes.The aggregates are not solvolyzed in acetone,and do not take part n any chemical reactions either.It has been found that DNS-Cl tends to aggregate even when its concentration is much lower than its solubility in acetone.The aggregation is reversible,and both the aggregation and the deaggregation are very slow processes.Introduction of SDS has a positive effect upon the formation and stabilization of the aggregates. 相似文献
199.
本文对二种新合成的2,3-二羟基萘二钼和四钼多酸有机衍生物[n-Bu)4N]2[Mo2O5(OC10H6O)2](Ⅰ)和[n-Bu)4N]2[Mo4O10(OC10H6O)2(OCH3)2](Ⅱ)进行了红外光谱与核磁共振波谱研究,发现[Mo2O5]^2 中钼氧多桥键的红外振动频率较[Mo4O10(OCH3)2]^2 中钼氧多桥键的红外振动频率红移,而在配合物Ⅱ中2,3-二羟基中芳环的^1H化学位移较配合物Ⅰ中向低场移动。同时还发现含二钼配位中心[Mo2O5]^2 的[Mo2O5(OC10H6O)2]^2-与含四钼配位中心[Mo4O10(OCH3)2]^2 的[Mo4O10(OC10H6O)2(OCH3)2]^2-生成条件的差异仅仅只在反应体系的pH值的微小变化,说明钼多酸有机衍生物阴离子是对体系酸碱度极为敏感的物质。 相似文献
200.
Gianluigi Luppi Rodrigo J. Corrêa Angelo C. Pinto Quirinus B. Broxterman Claudia Tomasini 《Tetrahedron》2006,62(51):12017-12024
The first total synthesis of (R)-convolutamydine A has been achieved by the organocatalytic addition of acetone to 4,6-dibromoisatin. The absolute configuration was determined by single crystal X-ray diffraction. DFT studies were used to model the transition states for the aldol reaction and equilibrium geometries of the post-aldol reaction intermediates. The DFT study revealed that the aldol bond forming reaction was considerably endothermic. 相似文献