全文获取类型
收费全文 | 65226篇 |
免费 | 15883篇 |
国内免费 | 157篇 |
专业分类
化学 | 67393篇 |
晶体学 | 142篇 |
力学 | 2510篇 |
综合类 | 2篇 |
数学 | 6527篇 |
物理学 | 4692篇 |
出版年
2024年 | 384篇 |
2023年 | 4151篇 |
2022年 | 1689篇 |
2021年 | 2806篇 |
2020年 | 4870篇 |
2019年 | 2572篇 |
2018年 | 2979篇 |
2017年 | 1095篇 |
2016年 | 6064篇 |
2015年 | 5902篇 |
2014年 | 5351篇 |
2013年 | 6137篇 |
2012年 | 4329篇 |
2011年 | 2294篇 |
2010年 | 4143篇 |
2009年 | 4008篇 |
2008年 | 2201篇 |
2007年 | 1880篇 |
2006年 | 1172篇 |
2005年 | 1077篇 |
2004年 | 851篇 |
2003年 | 787篇 |
2002年 | 667篇 |
2001年 | 411篇 |
2000年 | 441篇 |
1999年 | 275篇 |
1998年 | 251篇 |
1997年 | 289篇 |
1996年 | 333篇 |
1995年 | 301篇 |
1994年 | 253篇 |
1993年 | 369篇 |
1992年 | 254篇 |
1985年 | 230篇 |
1984年 | 271篇 |
1982年 | 251篇 |
1981年 | 279篇 |
1980年 | 298篇 |
1979年 | 263篇 |
1978年 | 296篇 |
1977年 | 399篇 |
1976年 | 464篇 |
1975年 | 537篇 |
1974年 | 521篇 |
1973年 | 348篇 |
1972年 | 395篇 |
1971年 | 369篇 |
1970年 | 556篇 |
1969年 | 433篇 |
1968年 | 469篇 |
排序方式: 共有10000条查询结果,搜索用时 10 毫秒
951.
Dr. Szilárd Varga Péter Angyal Gábor Martin Dr. Orsolya Egyed Dr. Tamás Holczbauer Dr. Tibor Soós 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(32):13649-13653
We report 8-step syntheses of (−)-minovincine and (−)-aspidofractinine using easily available and inexpensive reagents and catalyst. A key element of the strategy was the utilization of a sequence of cascade reactions to rapidly construct the penta- and hexacyclic frameworks. These cascade transformations included organocatalytic Michael-aldol condensation, a multistep anionic Michael-SN2 cascade reaction, and Mannich reaction interrupted Fischer indolization. To streamline the synthetic routes, we also investigated the deliberate use of steric effect to secure various chemo- and regioselective transformations. 相似文献
952.
Yu-Rong Chen Dr. Annavareddi Naresh Dr. Suh-Yuen Liang Dr. Chun-Hung Lin Dr. Rong-Jie Chein Dr. Hsiao-Ching Lin 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(32):13639-13643
The 1,3-enyne moiety is commonly found in cyclohexanoid natural products produced by endophytic and plant pathogenic fungi. Asperpentyn ( 1 ) is a 1,3-enyne-containing cyclohexanoid terpenoid isolated from Aspergillus and Pestalotiopsis. The genetic basis and biochemical mechanism of 1,3-enyne biosynthesis in 1 , and other natural products containing this motif, has remained enigmatic despite their potential ecological roles. Identified here is the biosynthetic gene cluster and characterization of two crucial enzymes in the biosynthesis of 1 . A P450 monooxygenase that has a dual function, to first catalyze dehydrogenation of the prenyl chain to generate a cis-diene intermediate and then serve as an acetylenase to yield an alkyne moiety, and thus the 1,3-enyne, was discovered. A UbiA prenyltransferase was also characterized and it is unusual in that it favors transferring a five-carbon prenyl chain, rather than a polyprenyl chain, to a p-hydroxybenzoic acid acceptor. 相似文献
953.
Laura Sinatra Jan J. Bandolik Dr. Martin Roatsch Melf Sönnichsen Dr. Clara T. Schoeder Dr. Alexandra Hamacher Andrea Schöler Prof. Dr. Arndt Borkhardt Prof. Dr. Jens Meiler Dr. Sanil Bhatia Prof. Dr. Matthias U. Kassack Prof. Dr. Finn K. Hansen 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(50):22681-22687
954.
Markus Hecht Dr. Pawaret Leowanawat Tabea Gerlach Dr. Vladimir Stepanenko Dr. Matthias Stolte Prof. Dr. Matthias Lehmann Prof. Dr. Frank Würthner 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(39):17232-17238
A new perylene bisimide (PBI), with a fluorescence quantum yield up to unity, self-assembles into two polymorphic supramolecular polymers. This PBI bears four solubilizing acyloxy substituents at the bay positions and is unsubstituted at the imide position, thereby allowing hydrogen-bond-directed self-assembly in nonpolar solvents. The formation of the polymorphs is controlled by the cooling rate of hot monomer solutions. They show distinctive absorption profiles and morphologies and can be isolated in different polymorphic liquid-crystalline states. The interchromophoric arrangement causing the spectral features was elucidated, revealing the formation of columnar and lamellar phases, which are formed by either homo- or heterochiral self-assembly, respectively, of the atropoenantiomeric PBIs. Kinetic studies reveal a narcissistic self-sorting process upon fast cooling, and that the transformation into the heterochiral (racemic) sheetlike self-assemblies proceeds by dissociation via the monomeric state. 相似文献
955.
Dr. Samuel Stolz Dr. Aliaksandr V. Yakutovich Dr. Jan Prinz Dr. Thomas Dienel Dr. Carlo A. Pignedoli Prof. Dr. Harald Brune Dr. Oliver Gröning Dr. Roland Widmer 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(41):18336-18340
Enantioselectivity in heterogeneous catalysis strongly depends on the chirality transfer between catalyst surface and all reactants, intermediates, and the product along the reaction pathway. Herein we report the first enantioselective on-surface synthesis of molecular structures from an initial racemic mixture and without the need of enantiopure modifier molecules. The reaction consists of a trimerization via an unidentified bonding motif of prochiral 9-ethynylphenanthrene (9-EP) upon annealing to 500 K on the chiral Pd3-terminated PdGa{111} surfaces into essentially enantiopure, homochiral 9-EP propellers. The observed behavior strongly contrasts the reaction of 9-EP on the chiral Pd1-terminated PdGa{111} surfaces, where 9-EP monomers that are in nearly enantiopure configuration, dimerize without enantiomeric excess. Our findings demonstrate strong chiral recognition and a significant ensemble effect in the PdGa system, hence highlighting the huge potential of chiral intermetallic compounds for enantioselective synthesis and underlining the importance to control the catalytically active sites at the atomic level. 相似文献
956.
Dr. Hui Wang Dr. Changcheng Jing Dr. Adam Noble Prof. Dr. Varinder Kumar Aggarwal 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(39):17005-17018
The stereospecific 1,2-migration of boronate complexes is one of the most representative reactions in boron chemistry. This process has been used extensively to develop powerful methods for asymmetric synthesis, with applications spanning from pharmaceuticals to natural products. Typically, 1,2-migration of boronate complexes is driven by displacement of an α-leaving group, oxidation of an α-boryl radical, or electrophilic activation of an alkenyl boronate complex. The aim of this article is to summarize the recent advances in the rapidly expanding field of electrophile-induced stereospecific 1,2-migration of groups from boron to sp2 and sp3 carbon centers. It will be shown that three different conceptual approaches can be utilized to enable the 1,2-migration of boronate complexes: stereospecific Zweifel-type reactions, catalytic conjunctive coupling reactions, and transition metal-free sp2–sp3 couplings. A discussion of the reaction scope, mechanistic insights, and synthetic applications of the work described is also presented. 相似文献
957.
Guoyu Zhang Song Zhou Dr. Liang Fu Dr. Pinhong Chen Prof. Yibiao Li Prof. Dr. Jianping Zou Prof. Dr. Guosheng Liu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(46):20619-20624
The first copper-catalyzed asymmetric cyanation and etherification reactions of enamides have been established, where a carbon-centered radical adjacent to a nitrogen atom (CRAN) is enantioselectively trapped by a chiral copper(II) species. Moreover, the asymmetric cyanation of vinyl esters was disclosed as well. These reactions feature very mild reaction conditions and high functional group tolerance, and give a series of chiral α-cyano amides, α-cyano esters and α-hemiaminals in good yields with excellent enantioselectivity. The chiral α-cyano amides can be easily converted into enantioenriched 1,2-diamines and amino acids. 相似文献
958.
Yufei Shu Dr. Xing Lin Dr. Haiyan Qin Zhuang Hu Prof. Yizheng Jin Prof. Xiaogang Peng 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(50):22496-22507
This article offers a materials-chemistry perspective for colloidal quantum dots (QDs) in the field of display, including QD-enhanced liquid-crystal-display (QD-LCD) and QD-based light-emitting-diodes (QLEDs) display. The rapid successes of QDs for display in the past five years are not accidental but have a deep root in both maturity of their synthetic chemistry and their unique chemical, optical, and optoelectronic properties. This article intends to discuss the natural match of QD emitters for display and chemical means to eventually bring about their full potential. 相似文献
959.
Dr. Shuang Pan Dr. Haiyang Zou Aurelia C. Wang Dr. Zewei Wang Jiwoo Yu Chuntao Lan Qiliang Liu Prof. Zhong Lin Wang Prof. Tianquan Lian Prof. Juan Peng Prof. Zhiqun Lin 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(35):15052-15059
Despite recent progress in producing perovskite nanowires (NWs) for optoelectronics, it remains challenging to solution-print an array of NWs with precisely controlled position and orientation. Herein, we report a robust capillary-assisted solution printing (CASP) strategy to rapidly access aligned and highly crystalline perovskite NW arrays. The key to the CASP approach lies in the integration of capillary-directed assembly through periodic nanochannels and solution printing through the programmably moving substrate to rapidly guide the deposition of perovskite NWs. The growth kinetics of perovskite NWs was closely examined by in situ optical microscopy. Intriguingly, the as-printed perovskite NWs array exhibit excellent optical and optoelectronic properties and can be conveniently implemented for the scalable fabrication of photodetectors. 相似文献
960.
Tao Ding Liyuan Zhu Yuxin Fang Yangluorong Liu Wei Tang Prof. Dr. Peng Zou 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(51):23133-23137
The spatial arrangement of chromosome within the nucleus is linked to genome function and gene expression regulation. Existing genome-wide mapping methods often rely on chemically crosslinking DNA with protein baits, which raises concerns of artifacts being introduced during cell fixation. By genetically targeting a photosensitizer protein to specific subnuclear locations, we achieved blue-light-activated labeling of local DNA with a bioorthogonal functional handle for affinity purification and sequence identification through next-generation sequencing. When applied to the nuclear lamina in human embryonic kidney 293T cells, it revealed lamina-associated domains (LADs) that cover 37.6 % of the genome. These LADs overlap with heterochromatin hallmarks and are depleted with CpG islands. This simple labeling method avoids the harsh treatment of chemical crosslinking and is generally applicable to the genome-wide high-resolution mapping of the spatial chromosome organization in living cells. 相似文献