全文获取类型
收费全文 | 15097篇 |
免费 | 1696篇 |
国内免费 | 4574篇 |
专业分类
化学 | 16465篇 |
晶体学 | 420篇 |
力学 | 481篇 |
综合类 | 146篇 |
数学 | 1664篇 |
物理学 | 2191篇 |
出版年
2024年 | 10篇 |
2023年 | 140篇 |
2022年 | 184篇 |
2021年 | 363篇 |
2020年 | 465篇 |
2019年 | 381篇 |
2018年 | 388篇 |
2017年 | 452篇 |
2016年 | 607篇 |
2015年 | 545篇 |
2014年 | 785篇 |
2013年 | 1228篇 |
2012年 | 1584篇 |
2011年 | 914篇 |
2010年 | 775篇 |
2009年 | 978篇 |
2008年 | 1115篇 |
2007年 | 1202篇 |
2006年 | 1124篇 |
2005年 | 1072篇 |
2004年 | 976篇 |
2003年 | 810篇 |
2002年 | 643篇 |
2001年 | 508篇 |
2000年 | 489篇 |
1999年 | 442篇 |
1998年 | 392篇 |
1997年 | 373篇 |
1996年 | 340篇 |
1995年 | 370篇 |
1994年 | 315篇 |
1993年 | 231篇 |
1992年 | 285篇 |
1991年 | 207篇 |
1990年 | 163篇 |
1989年 | 120篇 |
1988年 | 90篇 |
1987年 | 66篇 |
1986年 | 68篇 |
1985年 | 49篇 |
1984年 | 34篇 |
1983年 | 18篇 |
1982年 | 23篇 |
1981年 | 10篇 |
1980年 | 8篇 |
1979年 | 5篇 |
1978年 | 4篇 |
1977年 | 5篇 |
1972年 | 2篇 |
1936年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
91.
本文采用超声法制备了柚皮素(NAR)与β-环糊精(βCD)的包合物.粉末-X射线衍射(XRD)和红外吸收光谱(IR)测定均表明形成的包合物具有不同于主客体的新的结构性质.1H NMR与ROESY核磁共振(NMR)实验表明NAR以苯环端从βCD的宽口端进入,并形成稳定的超分子包合物.量子化学计算分析NAR/βCD包合物的形成过程表明,驱动力源于焓驱动与氢键弱相互作用力;能隙和结合能分析得到的最优包合模式与NMR研究结果一致;ONIOM分层计算验证了上述结果.分子对接模拟出的最优包合模式也与量子化学计算、NMR的分析结果吻合.本文获取了清晰的NAR/βCD包合物构型及其形成机理,为该超分子药物的定量构效关系研究提供了理论参考. 相似文献
92.
C.E. Satheesh Pushpanathan N. Sathish Kumar P. Raghavendra Kumara Ramasamy Karvembu Amar Hosamani M. Nethaji 《应用有机金属化学》2019,33(10)
Two new half‐sandwich Ru (II)(p‐cymene) complexes ( 1 and 2 ) containing dopamine‐based (N, O) Schiff base ligands ( L 1 H and L 2 H ) were synthesized and characterized by FT‐IR, UV–Visible and 1H & 13C NMR spectral techniques, and elemental analyses. The spectroscopic and analytical data revealed monobasic bidentate coordination of the ligands with Ru ion. The molecular structures of L 1 H , L 2 H and 2 were further confirmed by single crystal X‐ray diffraction study. Complexes 1 and 2 have been employed as catalysts in the transfer hydrogenation of ketones using 2‐propanol as a hydrogen source at 85 °C under base‐free condition. Good to the excellent yield of secondary alcohols, gram scale synthesis, and high TON and TOF made this catalytic system interesting. 相似文献
93.
94.
95.
能源互联网呈现物理信息深度融合的趋势,为电力系统管理研究定义了新的研究框架。作为一个先进的复杂系统,能源互联网信息物理系统(Energy Internet Cyber-Physical System,ECPS)在其发展过程中面临着一些新的挑战,其中一个就是耦合结构下的风险管理。本文结合复杂网络理论和风险传递理论,着重在拓扑层面分析了ECPS跨空间交互机理,并在此基础上定义了交互路径和交互系数;接着建立了ECPS跨空间风险传递模型,量化描述了风险的传递和演化过程,并进行了风险影响评估;最后,通过仿真实验分析了三种不同交互系数节点故障的风险传递过程和不同攻击模式下系统的崩溃过程。对仿真结果的讨论阐述了能源互联网风险跨空间传递的特点,为更深入地研究ECPS的风险管理提供了参考。 相似文献
96.
Two new coordination complexes based on benzimidazole dicarboxylic acid, Zn(Hbidc)?H2O ( 1 ) and Cd(Hbidc)(H2O) ( 2 ), have been synthesized under hydrothermal conditions. The complexes were characterized using elemental analysis, infrared and UV–visible spectroscopies, powder X‐ray diffraction, thermogravimetry and single‐crystal X‐ray diffraction. Structural analyses showed that the crystal structures of 1 and 2 are different, due to the various modes of linking of the benzimidazole dicarboxylic acid. Complex 1 has a two‐dimensional network structure and 2 has a three‐dimensional network structure. In addition, we studied the performance of the fluorescence response of two complexes. Results showed that the complexes can be used as chemical sensors for multifunctional testing, such as for UO22+, xanthine and Fe3+ ions. Even if the concentration is very low, they could also be detected, showing that coordination complexes 1 and 2 have very high fluorescence sensitivity. The detection limit for UO22+ is 5.42 nM ( 1 ) and 0.02 nM ( 2 ), that for xanthine is 1.37 nM ( 1 ) and 0.28 nM ( 2 ), and that for Fe3+ ions is 0.76 nM ( 1 ) and 0.62 nM ( 2 ). 相似文献
97.
Yan‐Ping Zhang Yue Li Guan‐Cheng Xu Jin‐Yu Li Hua‐Ying Luo Jin‐Yao Li Li Zhang Dian‐Zeng Jia 《应用有机金属化学》2019,33(3)
Two new complexes, namely [Cu6L6] ( 1 ) and [Zn(HL)2] ( 2 ) (H2L = N‐(1‐phenyl‐3‐methyl‐4‐propenylidene‐5‐pyrazolone)‐2‐furancarboxylic acid hydrazide), have been synthesized and characterized. Single crystal X‐ray analysis indicates that complex 1 has a hexanuclear structure and complex 2 exhibits a mononuclear structure. The DNA/bovine serum albumin (BSA) binding properties of complexes 1 and 2 were investigated by absorption spectroscopy and fluorescence quenching. Both complexes could effectively intercalate to DNA with calculated quenching constants of 2.6 × 105 and 1.25 × 105 M?1, respectively. The quenching mechanism of the intrinsic fluorescence of BSA by the complexes was found to be a static one. The cytotoxicities of 1 and 2 were investigated in two human tumor cell lines, human esophageal cancer cells (Eca‐109) and cervical cancer cells (HeLa). Complex 1 exhibits higher antitumor activity than 2 . Furthermore, 1 can inhibit HeLa cells by inducing apoptosis and G0/G1 phase cell cycle arrest. All results demonstrate that 1 and 2 both have DNA/BSA binding capacity and antitumor activity. 相似文献
98.
Two LnIII ions are sandwiched by dinuclear CoII building blocks derived from a tris‐triazamacrocyclic ligand bearing pendant carboxylic acid functionality, 1,3,5‐tris((4,7‐bis(2‐carboxyethyl)‐1,4,7‐triazacyclonon‐1‐yl)methyl)‐benzene (H6L), giving rising to two nanoscale heterometallic metal–organic cages formulated as [Co4Ln2(LH2.5)2(H2O)4]·(ClO4)6·NO3·nH2O [Ln = Dy, n = 12 ( 1 ); Ln = Yb, n = 9 ( 2 )], whose internal cavity accommodates a guest NO3? anion. Their hexanuclear cage‐like architectures are maintained both in solution and solid states as confirmed by mass spectrum as well as X‐ray diffraction experiments. These two cages display ligand‐based fluorescence emissions and therefore both were chosen to be operated as fluorescent chemosensors for the detection of nitroaromatic compounds. Attractively, these metal–organic cages allow highly selective and sensitive detection of picric acid (PA) over other nitroaromatics in solution and suspension, and the fluorescence resonance energy transfer (FRET) between the cage probes and PA is mainly responsible for the remarkable detection efficiency. 相似文献
99.
Dr. Lauren E. Longobardi Prof. Alois Fürstner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(43):10063-10068
The hydroboration of internal alkynes with pinacolborane as the reagent catalyzed by [Cp*RuCl]4 results in good to excellent levels of regio- as well as stereoselectivity, provided that the triple bond bears one linear and one singly-branched substituent. In such cases, the reaction follows an unusual trans-addition mode and places the boron entity distal to the branching point. The resulting alkenyl boronates, which are difficult to make otherwise, can be engaged in numerous enabling downstream processes. 相似文献
100.
Guillaume Erbland Dr. Seifallah Abid Yohan Gisbert Nathalie Saffon-Merceron Yuichiro Hashimoto Leonardo Andreoni Théo Guérin Dr. Claire Kammerer Prof. Dr. Gwénaël Rapenne 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(71):16328-16339
The design and synthesis of two families of molecular-gear prototypes is reported, with the aim of assembling them into trains of gears on a surface and ultimately achieving controlled intermolecular gearing motion. These piano-stool ruthenium complexes incorporate a hydrotris(indazolyl)borate moiety as tripodal rotation axle and a pentaarylcyclopentadienyl ligand as star-shaped cogwheel, equipped with five teeth ranging from pseudo-1D aryl groups to large planar 2D paddles. A divergent synthetic approach was followed, starting from a pentakis(p-bromophenyl)cyclopentadienyl ruthenium(II) complex as key precursor or from its iodinated counterpart, obtained by copper-catalyzed aromatic Br/I exchange. Subsequent fivefold cross-coupling reactions with various partners allowed high structural diversity to be reached and yielded molecular-gear prototypes with aryl-, carbazole-, BODIPY- and porphyrin-derived teeth of increasing size and length. 相似文献