全文获取类型
收费全文 | 2967篇 |
免费 | 895篇 |
国内免费 | 178篇 |
专业分类
化学 | 3237篇 |
晶体学 | 22篇 |
力学 | 82篇 |
综合类 | 31篇 |
数学 | 235篇 |
物理学 | 433篇 |
出版年
2024年 | 6篇 |
2023年 | 81篇 |
2022年 | 98篇 |
2021年 | 100篇 |
2020年 | 217篇 |
2019年 | 138篇 |
2018年 | 126篇 |
2017年 | 85篇 |
2016年 | 321篇 |
2015年 | 299篇 |
2014年 | 316篇 |
2013年 | 393篇 |
2012年 | 337篇 |
2011年 | 219篇 |
2010年 | 132篇 |
2009年 | 121篇 |
2008年 | 119篇 |
2007年 | 152篇 |
2006年 | 123篇 |
2005年 | 110篇 |
2004年 | 115篇 |
2003年 | 85篇 |
2002年 | 31篇 |
2001年 | 46篇 |
2000年 | 34篇 |
1999年 | 28篇 |
1998年 | 19篇 |
1997年 | 25篇 |
1996年 | 41篇 |
1995年 | 18篇 |
1994年 | 17篇 |
1993年 | 12篇 |
1992年 | 11篇 |
1991年 | 16篇 |
1990年 | 5篇 |
1989年 | 7篇 |
1988年 | 7篇 |
1987年 | 3篇 |
1986年 | 3篇 |
1985年 | 6篇 |
1984年 | 6篇 |
1983年 | 3篇 |
1982年 | 4篇 |
1981年 | 2篇 |
1979年 | 1篇 |
1959年 | 1篇 |
1957年 | 1篇 |
排序方式: 共有4040条查询结果,搜索用时 15 毫秒
101.
Aerobic Double Dehydrogenative Cross Coupling between Cyclic Saturated Ketones and Simple Arenes 下载免费PDF全文
Dr. Nicolas Gigant Prof. Dr. Jan‐E. Bäckvall 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(20):5890-5894
The synthesis of 3‐aryl‐2‐cyclohexenones is a topic of current interest as they are not only privileged structures in bioactive molecules, but they are also relevant feedstocks for the synthesis of substituted phenols or anilines, which are ubiquitous structural elements both in drug design and medicinal chemistry. A simple and sustainable one‐pot aerobic double dehydrogenative reaction under mild conditions for the introduction of arenes in the β‐position of cyclic ketones has been developed. Starting from the corresponding saturated ketone, this reaction sequence proceeds under relatively low Pd catalyst loading and involves catalytic amounts of electron‐transfer mediators (ETMs) under ambient oxygen pressure. 相似文献
102.
Coumaraz‐2‐on‐4‐ylidene: Ambiphilic N‐Heterocyclic Carbenes with a Tunable Electronic Structure 下载免费PDF全文
Hayoung Song Hyunho Kim Prof. Eunsung Lee 《Angewandte Chemie (International ed. in English)》2018,57(28):8603-8607
Herein, a coumaraz‐2‐on‐4‐ylidene ( 1 ) as a new example of an ambiphilic N‐heterocyclic carbene, having electronic properties that can be fine‐tuned, is reported. The N‐carbamic and aryl groups on the carbene carbon center provide exceptionally high electrophilicity and nucleophilicity simultaneously to the carbene center, as evidenced by the 77Se NMR chemical shifts of their selenoketone derivatives and the CO stretching strengths of their rhodium carbonyl complexes. Since the precursors of 1 could be synthesized from various functionalized Schiff bases in a practical and scalable manner, the electronic properties of 1 can be fine‐tuned in a quantitative and predictable way by using the Hammett σ constant of the functional groups on aryl ring. The facile electronic tuning capability of 1 may be applicable to eliciting novel properties in main‐group and transition‐metal chemistry. 相似文献
103.
《Journal of polymer science. Part A, Polymer chemistry》2018,56(9):959-967
In this work, a novel synthetic path for preparing semi‐armotic components modified polyamide 6 was developed by caprolactam as solvent of purified terephthalic acid and 1,6‐hexanediamine. First, the ring opening reaction and poly‐addition of caprolactam were initiated by 1,6‐hexanediamine to generate a prepolymer containing amino groups in both ends, then followed by the poly‐condensation reaction with purified terephthalic acid, a long chain copolymer was produced, which the reaction time was reduced by 4 h compared with conventional hydrolytic ring‐opening polymerization of pure caprolactam. By varying the ratio of terephthalic acid and 1,6‐hexanediamine, a series of copolymers with different number average molecular weight and physical properties were prepared. Analytical results showed that the conversion percentage of caprolactam is significantly increased by the proposed method. Furthermore, this new copolymers exhibited excellent transparence and high decomposition temperature. Besides, the copolymers with average molecular weight ≥15,000 present good mechanical properties, making it a potentially useful application in plastics, textile yarn, and membranes. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 959–967 相似文献
104.
天然药物高三尖杉酯碱和三尖杉酯碱是从三尖杉植物的叶和茎中分离得到的微量生物碱,是手性化合物。结构上,二者不仅含有一个共同的母核三尖杉碱,酯基侧链的α位也均为手性叔醇。因母核三尖杉碱和酯基侧链较大的空间位阻,两个结构片段的酯化偶联具有较大的挑战性。设计合成位阻较小的侧链中间体是酯化反应发生的关键。因此,化学家们相继合成了结构多样的α-羰基羧酸侧链以及含有杂环的侧链中间体,如四元内酯杂环侧链、四氢呋喃杂环侧链、六氢吡喃杂环侧链、七元内酯杂环侧链,并成功地完成了高三尖杉酯碱、三尖杉酯碱和同属其他活性生物碱的合成。本文基于本课题组的相关研究,根据侧链片段的构建策略和方法,综述了天然药物高三尖杉酯碱、三尖杉酯碱以及其他天然产物的合成研究。不仅总结了近几年来的新进展,还对我国老一辈的科学家们在此方面作出的贡献进行了回顾。 相似文献
105.
在讲解量气管调节问题时,通过在连通量气管左右2管的橡皮管上夹一个止水夹,控制了右管液面与右管的相对位移,减少了变量,待右管调节完成后,固定右管不动,打开止水夹,使左右2管相通,让液面通过压强差自动调节至相平。 相似文献
106.
Qiwen Zhou Dr. Wei Meng Prof. Jing Yang Prof. Haifeng Du 《Angewandte Chemie (International ed. in English)》2018,57(37):12111-12115
A novel chiral ammonia borane was designed and developed through the dehydrogenation of ammonia borane with a chiral phosphoric acid, which was highly effective for the asymmetric transfer hydrogenation of imines and β‐enamino esters to afford high levels of reactivities and enantioselectivities. Significantly, this chiral ammonia borane can be continuously regenerated during the transfer hydrogenation with the assistance of water and ammonia borane, which made it possible to obtain satisfactory results using only 0.1 mol % of the chiral phosphoric acid. Notably, the role of chiral phosphoric acid is to produce the chiral ammonia borane. 相似文献
107.
Palladium‐Catalyzed Reductive [5+1] Cycloaddition of 3‐Acetoxy‐1,4‐enynes with CO: Access to Phenols Enabled by Hydrosilanes 下载免费PDF全文
Li‐Jun Wu Prof. Dr. Ren‐Jie Song Prof. Dr. Shenglian Luo Prof. Dr. Jin‐Heng Li 《Angewandte Chemie (International ed. in English)》2018,57(40):13308-13312
A new palladium‐catalyzed reductive [5+1] cycloaddition of 3‐acetoxy‐1,4‐enynes with CO, enabled by hydrosilanes, has been developed for delivering valuable functionalized phenols. This methodology employs hydrosilanes as the external reagent to facilitate the [5+1] carbonylative benzannulation. The reaction is a conceptually and mechanistically novel carbonylative cycloaddition route for the construction of substituted phenols, through the formation of four new chemical bonds, with excellent functional‐group tolerance. 相似文献
108.
Synthesis of Spirocyclic Ethers by Enantioselective Copper‐Catalyzed Carboetherification of Alkenols 下载免费PDF全文
Shuklendu D. Karyakarte Chanchamnan Um Ilyas A. Berhane Prof. Sherry R. Chemler 《Angewandte Chemie (International ed. in English)》2018,57(39):12921-12924
Spirocyclic ethers can be found in bioactive compounds. This copper‐catalyzed enantioselective alkene carboetherification provides 5,5‐, 5,6‐ and 6,6‐spirocyclic products containing fully substituted chiral carbon centers with up to 99 % enantiomeric excess. This reaction features the formation of two rings from acyclic substrates, 1,1‐disubstituted alkenols functionalized with either arenes, alkenes, or alkynes, and clearly constitutes a powerful way to synthesize chiral spirocyclic ethers. 相似文献
109.
Recent progress of fully synthetic carbohydrate-based vaccine using TLR agonist as build-in adjuvant
This review highlights recent advances in developing full synthetic carbohydrate antigen based vaccines, with an emphasis on the structure-activity relationships that provide a primary basis for future vaccine design and immunotherapy developing. 相似文献
110.