全文获取类型
收费全文 | 2072篇 |
免费 | 418篇 |
国内免费 | 510篇 |
专业分类
化学 | 2053篇 |
晶体学 | 25篇 |
力学 | 8篇 |
综合类 | 11篇 |
数学 | 29篇 |
物理学 | 874篇 |
出版年
2024年 | 5篇 |
2023年 | 14篇 |
2022年 | 57篇 |
2021年 | 93篇 |
2020年 | 79篇 |
2019年 | 80篇 |
2018年 | 59篇 |
2017年 | 75篇 |
2016年 | 71篇 |
2015年 | 139篇 |
2014年 | 129篇 |
2013年 | 184篇 |
2012年 | 161篇 |
2011年 | 180篇 |
2010年 | 166篇 |
2009年 | 175篇 |
2008年 | 150篇 |
2007年 | 194篇 |
2006年 | 130篇 |
2005年 | 140篇 |
2004年 | 142篇 |
2003年 | 122篇 |
2002年 | 82篇 |
2001年 | 47篇 |
2000年 | 51篇 |
1999年 | 45篇 |
1998年 | 41篇 |
1997年 | 19篇 |
1996年 | 33篇 |
1995年 | 19篇 |
1994年 | 19篇 |
1993年 | 14篇 |
1992年 | 16篇 |
1991年 | 8篇 |
1990年 | 8篇 |
1989年 | 6篇 |
1988年 | 3篇 |
1987年 | 4篇 |
1986年 | 6篇 |
1985年 | 3篇 |
1982年 | 2篇 |
1981年 | 4篇 |
1980年 | 7篇 |
1979年 | 5篇 |
1978年 | 4篇 |
1977年 | 3篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1969年 | 1篇 |
排序方式: 共有3000条查询结果,搜索用时 15 毫秒
141.
Julie Andrez Dr. Jacques Pécaut Pierre‐Alain Bayle Dr. Marinella Mazzanti 《Angewandte Chemie (International ed. in English)》2014,53(39):10448-10452
The synthesis, structure, and reactivity of stable homoleptic heterometallic LnL4K2 complexes of divalent lanthanide ions with electron‐rich tris(tert‐butoxy)siloxide ligands are reported. The [Ln(OSi(OtBu)3)4K2] complexes (Ln=Eu, Yb) are stable at room temperature, but they promote the reduction of azobenzene to yield the KPhNNPh radical anion as well as the reductive cleavage of CS2 to yield CS32? as the major product. The EuIII complex of the radical anion PhNNPh is structurally characterized. Moreover, [Yb(OSi(OtBu)3)4K2] can reduce CO2 at room temperature. Release of the reduction products in D2O shows the quantitative formation of both oxalate and carbonate in a 1:2.2 ratio. The bulky siloxide ligands enforce the labile binding of the reduction products providing the opportunity to establish a closed synthetic cycle for the YbII‐mediated CO2 reduction. These studies show that the presence of four electron‐rich siloxide ligands renders their EuII and YbII complexes highly reactive. 相似文献
142.
Discovery of Cell‐Permeable Inhibitors That Target the BRCT Domain of BRCA1 Protein by Using a Small‐Molecule Microarray 下载免费PDF全文
Zhenkun Na Sijun Pan Dr. Mahesh Uttamchandani Prof. Dr. Shao Q. Yao 《Angewandte Chemie (International ed. in English)》2014,53(32):8421-8426
BRCTs are phosphoserine‐binding domains found in proteins involved in DNA repair, DNA damage response and cell cycle regulation. BRCA1 is a BRCT domain‐containing, tumor‐suppressing protein expressed in the cells of breast and other human tissues. Mutations in BRCA1 have been found in ca. 50 % of hereditary breast cancers. Cell‐permeable, small‐molecule BRCA1 inhibitors are promising anticancer agents, but are not available currently. Herein, with the assist of microarray‐based platforms, we have discovered the first cell‐permeable protein–protein interaction (PPI) inhibitors against BRCA1. By targeting the (BRCT)2 domain, we showed compound 15 a and its prodrug 15 b inhibited BRCA1 activities in tumor cells, sensitized these cells to ionizing radiation‐induced apoptosis, and showed synergistic inhibitory effect when used in combination with Olaparib (a small‐molecule inhibitor of poly‐ADP‐ribose polymerase) and Etoposide (a small‐molecule inhibitor of topoisomerase II). Unlike previously reported peptide‐based PPI inhibitors of BRCA1, our compounds are small‐molecule‐like and could be directly administered to tumor cells, thus making them useful for future studies of BRCA1/PARP‐related pathways in DNA damage and repair response, and in cancer therapy. 相似文献
143.
Back Cover: Motion Capture and Manipulation of a Single Synthetic Molecular Rotor by Optical Microscopy (Angew. Chem. Int. Ed. 38/2014) 下载免费PDF全文
144.
Inside Back Cover: Self‐Assembly of a 3d–5f Trinuclear Single‐Molecule Magnet from a Pentavalent Uranyl Complex (Angew. Chem. Int. Ed. 49/2014) 下载免费PDF全文
145.
本文报道了一个含混合多齿螯合配体的四核Mn配合物Na2[MnIII2MnII2(pdmH)2(L)2(N3)2]·2CH3OH·2H2O(1·2CH3OH·2H2O,pdmH2为2,6-吡啶二甲醇,H2L为2,6-吡啶二甲醇与2,2-二吡啶酮水合物的脱水物),并对其进行单晶结构分析、红外、元素分析和磁性研究。单晶结构分析表明,该化合物属于三斜晶系P1空间群,分子中2个Mn2+、2个Mn3+及6个来自pdmH-或L2-配体的O原子构成1个双缺口立方烷结构。磁性研究表明Mn2+与Mn3+之间为弱的反铁磁性耦合作用(J1=-0.89 cm-1,J2=-1.13 cm-1),Mn3+离子之间为稍强的铁磁性耦合作用(J3=3.20 cm-1),基态自旋值S=2,交流磁化率研究表明,在所测试条件下,其虚部没有表现出单分子磁体所具有的频率依赖现象。 相似文献
146.
Dr. Emiko Kazuma Minhui Lee Prof. Jaehoon Jung Prof. Michael Trenary Dr. Yousoo Kim 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(20):8034-8040
Chemical reactions induced by plasmons achieve effective solar-to-chemical energy conversion. However, the mechanism of these reactions, which generate a strong electric field, hot carriers, and heat through the excitation and decay processes, is still controversial. In addition, it is not fully understood which factor governs the mechanism. To obtain mechanistic knowledge, we investigated the plasmon-induced dissociation of a single-molecule strongly chemisorbed on a metal surface, two O2 species chemisorbed on Ag(110) with different orientations and electronic structures, using a scanning tunneling microscope (STM) combined with light irradiation at 5 K. A combination of quantitative analysis by the STM and density functional theory calculations revealed that the hot carriers are transferred to the antibonding (π*) orbitals of O2 strongly hybridized with the metal states and that the dominant pathway and reaction yield are determined by the electronic structures formed by the molecule–metal chemical interaction. 相似文献
147.
Dr. Hua Su Ben Niu Haoran Li Dr. Fei Liu Tinglian Yuan Prof. Hong-Yuan Chen Prof. Wei Wang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(43):19371-19376
The ordered assembly of molecules within a specific space of nanoscale, such as a surface, holds great promise in advanced micro-/nanostructure fabrication for various applications. Herein, we demonstrate the evanescent wave (EW)-guided organization of small molecules into a long-range ordered nanowire (NW) array. Experiment and simulation revealed that the orientation and periodicity of the NW array were feasibly regulated by altering the propagation direction and the wavelength of EW. The generality of this approach was demonstrated by using different molecule precursors. While existing studies on EW often took advantages of its near-field property for optical sensing, this work demonstrated the photochemical power of EW in the guided-assembly of small molecules for the first time. It also provides an enlightening avenue to periodic structure with fluorescence, promising for super-resolution microscopy and important devices applicable to optical and bio-related fields. 相似文献
148.
Yu Jiang Xiang Li Prof. David R. Walt 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(41):18166-18171
Alkaline phosphatase (ALP) is an important biomarker, as high levels of ALP in blood can indicate liver disease or bone disorders. However, current clinical blood tests only measure the total concentration of ALP but are unable to distinguish enzyme isotypes. Here, we demonstrate a novel and rapid approach to profile various ALP isozymes in blood via a single-molecule-analysis platform. The microarray platform provides enzyme kinetics of hundreds of individual molecules at high throughput. Using these single molecule kinetics, we characterize the different activity profiles of ALP isotypes. By analyzing both healthy and disease samples, we found the single molecule activity distribution of ALP in serum reflects the health status of patients. This result demonstrates the potential utility of the method for improving the conventional ALP test, as well as for analyzing other enzymatic biomarkers, including enzyme isotypes. 相似文献
149.
Dr. Andreas Lerchen Dr. Narasimhulu Gandhamsetty Elliot H. E. Farrar Dr. Nils Winter Dr. Johannes Platzek Dr. Matthew N. Grayson Prof. Dr. Varinder K. Aggarwal 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(51):23307-23311
(−)-Finerenone is a nonsteroidal mineralocorticoid receptor antagonist currently in phase III clinical trials for the treatment of chronic kidney disease in type 2 diabetes. It contains an unusual dihydronaphthyridine core. We report a 6-step synthesis of (−)-finerenone, which features an enantioselective partial transfer hydrogenation of a naphthyridine using a chiral phosphoric acid catalyst with a Hantzsch ester. The process is complicated by the fact that the naphthyridine exists as a mixture of two atropisomers that react at different rates and with different selectivities. The intrinsic kinetic resolution was converted into a kinetic dynamic resolution at elevated temperature, which enabled us to obtain (−)-finerenone in both high yield and high enantioselectivity. DFT calculations have revealed the origin of selectivity. 相似文献
150.
Yingying Wang Zhuangdong Yuan Yunjie Guo Xuxiao Ma Zitong Meng Jingquan Sha Haifeng Zhang 《无机化学与普通化学杂志》2020,646(20):1696-1701
Two dinuclear LnIII-based clusters, namely [Dy2L2(NO3)2(DME)4] ( 1 ) and [Gd2L2(NO3)2(DME)4] ( 2 ) [H2L = (E)-2-((2-hydroxybenzylidene)amino)phenol] were obtained under hydrothermal condition. Two LnIII ions are bridged by two phenolic hydroxyl oxygen atoms, and the distances of them are 3.829 Å (Dy1–Dy1A) and 3.860 Å (Gd1–Gd1A). Two Dy1–O–Dy1A and Gd1–O–Gd1A angles are 109.4° and 109.8°, respectively. Magnetic studies reveal a weak antiferromagnetic interaction between Gd ions in complex 2 , and single-molecule magnet behavior for 1 with Ueff = 49.9 K and τ0 = 1.54 × 10–6 s. 相似文献