全文获取类型
收费全文 | 80540篇 |
免费 | 14490篇 |
国内免费 | 8983篇 |
专业分类
化学 | 56126篇 |
晶体学 | 817篇 |
力学 | 5308篇 |
综合类 | 457篇 |
数学 | 9406篇 |
物理学 | 31899篇 |
出版年
2024年 | 81篇 |
2023年 | 1697篇 |
2022年 | 1827篇 |
2021年 | 2684篇 |
2020年 | 3495篇 |
2019年 | 3269篇 |
2018年 | 2858篇 |
2017年 | 2642篇 |
2016年 | 3964篇 |
2015年 | 3843篇 |
2014年 | 4589篇 |
2013年 | 5937篇 |
2012年 | 7573篇 |
2011年 | 7761篇 |
2010年 | 5247篇 |
2009年 | 5031篇 |
2008年 | 5450篇 |
2007年 | 4844篇 |
2006年 | 4369篇 |
2005年 | 3640篇 |
2004年 | 2814篇 |
2003年 | 2227篇 |
2002年 | 2063篇 |
2001年 | 1659篇 |
2000年 | 1493篇 |
1999年 | 1652篇 |
1998年 | 1391篇 |
1997年 | 1359篇 |
1996年 | 1356篇 |
1995年 | 1112篇 |
1994年 | 1001篇 |
1993年 | 821篇 |
1992年 | 731篇 |
1991年 | 633篇 |
1990年 | 547篇 |
1989年 | 417篇 |
1988年 | 359篇 |
1987年 | 287篇 |
1986年 | 270篇 |
1985年 | 228篇 |
1984年 | 162篇 |
1983年 | 116篇 |
1982年 | 89篇 |
1981年 | 74篇 |
1980年 | 66篇 |
1979年 | 34篇 |
1978年 | 31篇 |
1977年 | 42篇 |
1976年 | 31篇 |
1973年 | 29篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
991.
Chun‐Hua Yang Yu‐Shi Zhang Wen‐Wen Fan Dr. Gong‐Qing Liu Prof. Dr. Yue‐Ming Li 《Angewandte Chemie (International ed. in English)》2015,54(43):12636-12639
A direct and catalyst‐free method for the intramolecular aminoboration of unfunctionalized olefins is reported. In the presence of BCl3 (1 equiv) as the sole boron source, intramolecular aminoboration of sulfonamide derivatives of 4‐penten‐1‐amines, 5‐hexen‐1‐amines, and 2‐allylanilines proceeded readily without the use of any catalyst. The boronic acids obtained after hydrolysis could be converted into the corresponding pinacol borates in a straightforward manner by treatment with pinacol under anhydrous conditions. 相似文献
992.
Reconstitution of Biosynthetic Machinery for the Synthesis of the Highly Elaborated Indole Diterpene Penitrem 下载免费PDF全文
Dr. Chengwei Liu Koichi Tagami Dr. Atsushi Minami Tomoyuki Matsumoto Jens Christian Frisvad Hideyuki Suzuki Jun Ishikawa Katsuya Gomi Prof. Dr. Hideaki Oikawa 《Angewandte Chemie (International ed. in English)》2015,54(19):5748-5752
Penitrem A is one of the most elaborated members of the fungal indole diterpenes. Two separate penitrem gene clusters were identified using genomic and RNA sequencing data, and 13 out of 17 transformations in the penitrem biosynthesis were elucidated by heterologous reconstitution of the relevant genes. These reactions involve 1) a prenylation‐initiated cationic cyclization to install the bicyclo[3.2.0]heptane skeleton (PtmE), 2) a two‐step P450‐catalyzed oxidative processes forming the unique tricyclic penitrem skeleton (PtmK and PtmU), and 3) five sequential oxidative transformations (PtmKULNJ). Importantly, without conventional gene disruption, reconstitution of the biosynthetic machinery provided sufficient data to determine the pathway. It was thus demonstrated that the Aspergillus oryzae reconstitution system is a powerful method for studying the biosynthesis of complex natural products. 相似文献
993.
Diaminodiacid Bridges to Improve Folding and Tune the Bioactivity of Disulfide‐Rich Peptides 下载免费PDF全文
Ye Guo De‐Meng Sun Feng‐Liang Wang Yao He Prof. Lei Liu Prof. Chang‐Lin Tian 《Angewandte Chemie (International ed. in English)》2015,54(48):14276-14281
Disulfide‐rich peptides containing three or more disulfide bonds are promising therapeutic and diagnostic agents, but their preparation is often limited by the tedious and low‐yielding folding process. We found that a single cystine‐to‐diaminodiacid replacement could significantly increase the folding efficiency of disulfide‐rich peptides and thus improve their production yields. The practicality of this strategy was demonstrated by the synthesis and folding of derivatives of the μ‐conotoxin SIIIA, the preclinical hormone hepcidin, and the trypsin inhibitor EETI‐II. NMR and X‐ray crystallography studies confirmed that these derivatives of disulfide‐rich peptide retained the correct three‐dimensional conformations. Moreover, the cystine‐to‐diaminodiacid replacement enabled structural tuning, thereby leading to an EETI‐II derivative with higher bioactivity than the native peptide. 相似文献
994.
A Facile and Universal Top‐Down Method for Preparation of Monodisperse Transition‐Metal Dichalcogenide Nanodots 下载免费PDF全文
Xiao Zhang Zhuangchai Lai Zhengdong Liu Chaoliang Tan Ying Huang Dr. Bing Li Dr. Meiting Zhao Prof. Linghai Xie Prof. Wei Huang Prof. Hua Zhang 《Angewandte Chemie (International ed. in English)》2015,54(18):5425-5428
Despite unique properties of layered transition‐metal dichalcogenide (TMD) nanosheets, there is still lack of a facile and general strategy for the preparation of TMD nanodots (NDs). Reported herein is the preparation of a series of TMD NDs, including TMD quantum dots (e.g. MoS2, WS2, ReS2, TaS2, MoSe2 and WSe2) and NbSe2 NDs, from their bulk crystals by using a combination of grinding and sonication techniques. These NDs could be easily separated from the N‐methyl‐2‐pyrrolidone when post‐treated with n‐hexane and then chloroform. All the TMD NDs with sizes of less than 10 nm show a narrow size distribution with high dispersity in solution. As a proof‐of‐concept application, memory devices using TMD NDs, for example, MoSe2, WS2, or NbSe2, mixed with polyvinylpyrrolidone as active layers, have been fabricated, which exhibit a nonvolatile write‐once‐read‐many behavior. These high‐quality TMD NDs should have various applications in optoelectronics, solar cells, catalysis, and biomedicine. 相似文献
995.
Highly Efficient Solid‐Phase Labeling of Saccharides within Boronic Acid Functionalized Mesoporous Silica Nanoparticles 下载免费PDF全文
Xianghua Pan Yang Chen Peixuan Zhao Daojin Li Dr. Zhen Liu 《Angewandte Chemie (International ed. in English)》2015,54(21):6173-6176
Labeling is critical for the detection, quantitation, and structural identification of saccharides. However, conventional liquid‐phase labeling suffers from apparent disadvantages, such as time‐consuming, the presence of excessive labeling reagent, and high applicable saccharide concentration. A solid‐phase approach is presented for highly efficient labeling of saccharides, using boronic acid functionalized mesoporous silica nanoparticles (MSNs) as a selective extraction sorbent and nanoscale reactor. The solid‐phase labeling approach exhibited several significant advantages, including: much faster reaction speed (taking only 2 min), high product purity, and much lower applicable saccharide concentration (four orders of magnitude lower than that of liquid‐phase labeling). Thus, this labeling approach opens up new avenues to the facile and efficient labeling of saccharides. 相似文献
996.
Radical Compatibility with Nonaqueous Electrolytes and Its Impact on an All‐Organic Redox Flow Battery 下载免费PDF全文
Dr. Xiaoliang Wei Dr. Wu Xu Dr. Jinhua Huang Dr. Lu Zhang Dr. Eric Walter Dr. Chad Lawrence Dr. M. Vijayakumar Dr. Wesley A. Henderson Dr. Tianbiao Liu Dr. Lelia Cosimbescu Dr. Bin Li Dr. Vincent Sprenkle Dr. Wei Wang 《Angewandte Chemie (International ed. in English)》2015,54(30):8684-8687
Nonaqueous redox flow batteries hold the promise of achieving higher energy density because of the broader voltage window than aqueous systems, but their current performance is limited by low redox material concentration, cell efficiency, cycling stability, and current density. We report a new nonaqueous all‐organic flow battery based on high concentrations of redox materials, which shows significant, comprehensive improvement in flow battery performance. A mechanistic electron spin resonance study reveals that the choice of supporting electrolytes greatly affects the chemical stability of the charged radical species especially the negative side radical anion, which dominates the cycling stability of these flow cells. This finding not only increases our fundamental understanding of performance degradation in flow batteries using radical‐based redox species, but also offers insights toward rational electrolyte optimization for improving the cycling stability of these flow batteries. 相似文献
997.
Yunlong Liu Prof. Chunfeng Zhang Rui Wang Bo Zhang Prof. Zhanao Tan Prof. Xiaoyong Wang Prof. Min Xiao 《Angewandte Chemie (International ed. in English)》2015,54(21):6222-6226
By creating two triplet excitons from one photo‐excited singlet exciton, singlet fission in organic semiconductors has drawn tremendous attention for its potential applications in boosting the efficiency of solar conversion. Here, we show that this carrier‐multiplication effect can also be used to dramatically improve the nonlinear optical response in organic materials. We have observed large optical nonlinearity with a magnitude of χ(3) up to 10?9 esu in pentacene films, which is further shown to be a result of singlet fission by monitoring the temporal dynamics. The potential application of such efficient nonlinear optical response has been demonstrated with a singlet‐fission‐induced polarization rotation. 相似文献
998.
Crystalline Hetero‐Stereocomplexed Polycarbonates Produced from Amorphous Opposite Enantiomers Having Different Chemical Structures 下载免费PDF全文
Dr. Ye Liu Meng Wang Wei‐Min Ren Yue‐Chao Xu Prof. Dr. Xiao‐Bing Lu 《Angewandte Chemie (International ed. in English)》2015,54(24):7042-7046
Stereocomplexation is the stereoselective interaction between two opposite enantiomeric polymers through an interlocked orderly assembly. Most studies focus on the stereocomplex formation from the crystalline opposite enantiomers having the identical structure; nevertheless, rare examples were reported regarding the crystalline stereocomplexes from enantiomeric polymers having different chemical structures. Herein we show a strategy for polymer orderly assembly through the formation of crystalline hetero‐stereocomplexed polymeric materials by the cocrystallization of amorphous isotactic polycarbonates with different chemical structures and opposite configurations. The behaviors in the crystalline state are significantly different from that of the component enantiomeric polymers or their homo‐stereocomplexes. This study is expected to open up a new way to prepare various semicrystalline materials having a wide variety of physical properties and degradability. 相似文献
999.
Rhodium‐Catalyzed Enantioselective Intramolecular CH Silylation for the Syntheses of Planar‐Chiral Metallocene Siloles 下载免费PDF全文
Dr. Qing‐Wei Zhang Kun An Li‐Chuan Liu Yuan Yue Prof. Dr. Wei He 《Angewandte Chemie (International ed. in English)》2015,54(23):6918-6921
Reported herein is the rhodium‐catalyzed enantioselective C? H bond silylation of the cyclopentadiene rings in Fe and Ru metallocenes. Thus, in the presence of (S)‐TMS‐Segphos, the reactions took place under very mild conditions to afford metallocene‐fused siloles in good to excellent yields and with ee values of up to 97 %. During this study it was observed that the steric hindrance of chiral ligands had a profound influence on the reactivity and enantioselectivity of the reaction, and might hold the key to accomplishing conventionally challenging asymmetric C? H silylations. 相似文献
1000.
Cover Picture: Reconstitution of Biosynthetic Machinery for the Synthesis of the Highly Elaborated Indole Diterpene Penitrem (Angew. Chem. Int. Ed. 19/2015) 下载免费PDF全文