全文获取类型
收费全文 | 4311篇 |
免费 | 821篇 |
国内免费 | 487篇 |
专业分类
化学 | 3258篇 |
晶体学 | 36篇 |
力学 | 214篇 |
综合类 | 45篇 |
数学 | 480篇 |
物理学 | 1586篇 |
出版年
2024年 | 2篇 |
2023年 | 75篇 |
2022年 | 93篇 |
2021年 | 111篇 |
2020年 | 176篇 |
2019年 | 194篇 |
2018年 | 156篇 |
2017年 | 126篇 |
2016年 | 237篇 |
2015年 | 202篇 |
2014年 | 255篇 |
2013年 | 300篇 |
2012年 | 363篇 |
2011年 | 366篇 |
2010年 | 272篇 |
2009年 | 293篇 |
2008年 | 308篇 |
2007年 | 268篇 |
2006年 | 256篇 |
2005年 | 224篇 |
2004年 | 165篇 |
2003年 | 140篇 |
2002年 | 171篇 |
2001年 | 151篇 |
2000年 | 90篇 |
1999年 | 101篇 |
1998年 | 61篇 |
1997年 | 59篇 |
1996年 | 67篇 |
1995年 | 43篇 |
1994年 | 54篇 |
1993年 | 32篇 |
1992年 | 20篇 |
1991年 | 42篇 |
1990年 | 37篇 |
1989年 | 29篇 |
1988年 | 12篇 |
1987年 | 12篇 |
1986年 | 11篇 |
1985年 | 19篇 |
1984年 | 6篇 |
1983年 | 6篇 |
1982年 | 3篇 |
1981年 | 5篇 |
1970年 | 1篇 |
1966年 | 1篇 |
1964年 | 1篇 |
1962年 | 1篇 |
1959年 | 1篇 |
1936年 | 1篇 |
排序方式: 共有5619条查询结果,搜索用时 265 毫秒
11.
Jiang Wang Pan‐Lin Shao Xin Lin Baode Ma Jialin Wen Xumu Zhang 《Angewandte Chemie (International ed. in English)》2020,59(41):18166-18171
An unprecedented Ir/f‐amphox‐catalyzed asymmetric hydrogenation of racemic 2,3‐syn‐dihydroxy‐1,4‐diones is presented involving dynamic kinetic resolution, which produces (1R,2R,3R,4R)‐tetraols. This protocol constitutes an efficient and straightforward approach to accessing sugar alcohols bearing four contiguous stereocenters. The strategy exhibits various advantages over existing methods, including excellent yields (up to 98 %), exceptional stereoselectivities (up to 99:1 dr, 99.9 % ee), operational simplicity and substrate generality. Moreover, the nature of the reaction was revealed as a stepwise transformation by in situ Fourier‐transform infrared spectroscopy and isolation of intermediates. 相似文献
12.
Wang Xia Qian‐Jin An Shao‐Hua Xiang Shaoyu Li Yong‐Bin Wang Bin Tan 《Angewandte Chemie (International ed. in English)》2020,59(17):6775-6779
N‐arylcarbazole structures are important because of their prevalence in natural products and functional OLED materials. C?H amination of arenes has been widely recognized as the most efficient approach to access these structures. Conventional strategies involving transition‐metal catalysts suffer from confined substrate generality and the requirement of exogenous oxidants. Organocatalytic enantioselective C–N chiral axis construction remains elusive. Presented here is the first organocatalytic strategy for the synthesis of novel axially chiral N‐arylcarbazole frameworks by the assembly of azonaphthalenes and carbazoles. This reaction accommodates broad substrate scope and gives atropisomeric N‐arylcarbazoles in good yields with excellent enantiocontrol. This approach not only offers an alternative to metal‐catalyzed C–N cross‐coupling, but also brings about opportunities for the exploitation of structurally diverse N‐aryl atropisomers and OLED materials. 相似文献
13.
14.
Yoshiki Shibuya Ryoichi Tatara Yivan Jiang Yang Shao‐Horn Jeremiah A. Johnson 《Journal of polymer science. Part A, Polymer chemistry》2019,57(3):448-455
The properties of polymeric materials are dictated not only by their composition but also by their molecular architecture. Here, by employing brush‐first ring‐opening metathesis polymerization (ROMP), norbornene‐terminated poly(ethylene oxide) (PEO) macromonomers ( MM‐n , linear architecture), bottlebrush polymers ( Brush‐n , comb architecture), and brush‐arm star polymers ( BASP‐n , star architecture), where n indicates the average degree of polymerization (DP) of PEO, are synthesized. The impact of architecture on the thermal properties and Li+ conductivities for this series of PEO architectures is investigated. Notably, in polymers bearing PEO with the highest degree of polymerization, irrespective of differences in architecture and molecular weight (~100‐fold differences), electrolytes with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) as an Li+ source exhibit normalized ionic conductivities (σn) within only 4.9 times difference (σn = 29.8 × 10?5 S cm?1 for MM‐45 and σn = 6.07 × 10?5 S cm?1 for BASP‐45 ) at a concentration of Li+ r = [Li+]/[EO] = 1/12 at 50 °C. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 448–455 相似文献
15.
Dr. Baiqi Shao Dr. Sikang Wan Chenjing Yang Dr. Jianlei Shen Dr. Yiwen Li Prof. Hongpeng You Prof. Dong Chen Prof. Chunhai Fan Prof. Kai Liu Prof. Hongjie Zhang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(41):18370-18374
The self-assembly of inorganic nanoparticles into well-ordered structures in the absence of solvents is generally hindered by van der Waals forces, leading to random aggregates between them. To address the problem, we functionalized rigid rare-earth (RE) nanoparticles with a layer of flexible polymers by electrostatic complexation. Consequently, an ordered and solvent-free liquid crystal (LC) state of RE nanoparticles was realized. The RE nanomaterials including nanospheres, nanorods, nanodiscs, microprisms, and nanowires all show a typical nematic LC phase with one-dimensional orientational order, while their microstructures strongly depend on the particles’ shape and size. Interestingly, the solvent-free thermotropic LCs possess an extremely wide temperature range from −40 °C to 200 °C. The intrinsic ordering and fluidity endow anisotropic luminescence properties in the system of shearing-aligned RE LCs, offering potential applications in anisotropic optical micro-devices. 相似文献
16.
Dr. Xiaolong Zu Yuan Zhao Dr. Xiaodong Li Runhua Chen Weiwei Shao Li Li Panzhe Qiao Prof. Wensheng Yan Prof. Yang Pan Qian Xu Prof. Junfa Zhu Prof. Yongfu Sun Prof. Yi Xie 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2023,135(1):e202215247
Herein, we first design a model of reversible redox-switching metal–organic framework single-unit-cell sheets, where the abundant metal single sites benefit for highly selective CO2 reduction, while the reversible redox-switching metal sites can effectively activate CO2 molecules. Taking the synthetic Cu-MOF single-unit-cell sheets as an example, synchrotron-radiation quasi in situ X-ray photoelectron spectra unravel the reversible switching CuII/CuI single sites initially accept photoexcited electrons and then donate them to CO2 molecules, which favors the rate-liming activation into CO2δ−, verified by in situ FTIR spectra and Gibbs free energy calculations. As an outcome, Cu-MOF single-unit-cell sheets achieve near 100 % selectivity for CO2 photoreduction to CO with a high rate of 860 μmol g−1 h−1 without any sacrifice reagent or photosensitizer, where both the activity and selectivity outperform previously reported photocatalysts evaluated under similar conditions. 相似文献
17.
Shiwei Pan Fan Chen Yanyan Zhang Liang Shao Prof. Dr. Lingling Chu 《Angewandte Chemie (International ed. in English)》2023,62(31):e202305426
A Markovnikov-selective hydrodifluoromethylation of alkynes with BrCF2H via nickel catalysis is described. This protocol proceeds via a migratory insertion of nickel hydride to alkyne followed by a CF2H-coupling, enabling straightforward access to diverse branched CF2H-alkenes with high efficiency and exclusive regioselectivity. The mild condition applies to a wide array of aliphatic and aryl alkynes with good functional group compatibility. Mechanistic studies are presented to support the proposed pathway. 相似文献
18.
Ya-Kui Sun Jin-Bao Qiao Yu-Meng Xin Qin Zhou Zhi-Hua Ma Hui Shao Yu-Ming Zhao 《Angewandte Chemie (International ed. in English)》2023,62(40):e202310917
Herein, we report a concise and divergent synthesis of the complex hasubanan alkaloids metaphanine and oxoepistephamiersine from commercially available and inexpensive cyclohexanedione monoethylene acetal. Our synthesis features a palladium-catalyzed cascade cyclization reaction to set the tricyclic carbon framework of the desired molecules, a regioselective Baeyer–Villiger oxidation followed by a MeNH2 triggered skeletal reorganization cascade to construct the benzannulated aza[4.4.3]propellane, and a strategically late-stage regio-/diastereoselective oxidative annulation of sp3 C−H bond to form the challenging THF ring system and hemiketal moiety in a single step. In addition, a highly enantioselective alkylation of cyclohexanedione monoethylene acetal paved the way for the asymmetric synthesis of target molecular. 相似文献
19.
Dr. Xianzhong Yang Weiping Li Ziyan Chen Dr. Meng Tian Jun Peng Jinrong Luo Yiwen Su Yuhan Zou Gao Weng Prof. Yuanlong Shao Prof. Shixue Dou Prof. Jingyu Sun 《Angewandte Chemie (International ed. in English)》2023,62(10):e202218454
Despite conspicuous merits of Zn metal anodes, the commercialization is still handicapped by rampant dendrite formation and notorious side reaction. Manipulating the nucleation mode and deposition orientation of Zn is a key to rendering stabilized Zn anodes. Here, a dual electrolyte additive strategy is put forward via the direct cooperation of xylitol (XY) and graphene oxide (GO) species into typical zinc sulfate electrolyte. As verified by molecular dynamics simulations, the incorporated XY molecules could regulate the solvation structure of Zn2+, thus inhibiting hydrogen evolution and side reactions. The self-assembled GO layer is in favor of facilitating the desolvation process to accelerate reaction kinetics. Progressive nucleation and orientational deposition can be realized under the synergistic modulation, enabling a dense and uniform Zn deposition. Consequently, symmetric cell based on dual additives harvests a highly reversible cycling of 5600 h at 1.0 mA cm−2/1.0 mAh cm−2. 相似文献
20.
Dr. Chi Zhang Dr. Meiling Shao Dr. Dongqing Wu Dr. Zhongyi Li Muzhi Zhao Xiangfei Zhang Prof. Bin Zhai Prof. Yunjun Luo Prof. Xiaoyu Li 《Angewandte Chemie (International ed. in English)》2023,62(52):e202314052
Azide compounds are widely used and especially, polymers bearing pendant azide groups are highly desired in numerous fields. However, harsh reaction conditions are always mandatory to achieve full azidation, causing severe side reactions and degradation of the polymers. Herein, we report the design and preparation of two azide ionic liquids (AILs) with azide anion and triethylene glycol (E3)-containing cation, [P444E3][N3] and [MIME3][N3]. Compared with the traditional sodium azide (NaN3) approach, both AILs showed much higher reaction rates and functional-group tolerance. More importantly, they could act as both reagents and solvents for the quantitative azidation of various polymeric precursors under mild conditions. Theoretical simulations suggested that the outstanding performance of AILs originated from the existence of ion pairs during the reaction, and the E3 moieties played a crucial role. Lastly, after the reaction, the AILs could be easily regenerated, presenting a safer, greener, and highly efficient synthesis route for azide polymers. 相似文献