全文获取类型
收费全文 | 15869篇 |
免费 | 2986篇 |
国内免费 | 2056篇 |
专业分类
化学 | 11551篇 |
晶体学 | 207篇 |
力学 | 1018篇 |
综合类 | 130篇 |
数学 | 1599篇 |
物理学 | 6406篇 |
出版年
2024年 | 69篇 |
2023年 | 362篇 |
2022年 | 698篇 |
2021年 | 645篇 |
2020年 | 760篇 |
2019年 | 786篇 |
2018年 | 662篇 |
2017年 | 620篇 |
2016年 | 853篇 |
2015年 | 912篇 |
2014年 | 1010篇 |
2013年 | 1249篇 |
2012年 | 1522篇 |
2011年 | 1463篇 |
2010年 | 981篇 |
2009年 | 1063篇 |
2008年 | 1120篇 |
2007年 | 942篇 |
2006年 | 875篇 |
2005年 | 731篇 |
2004年 | 542篇 |
2003年 | 400篇 |
2002年 | 366篇 |
2001年 | 313篇 |
2000年 | 246篇 |
1999年 | 255篇 |
1998年 | 195篇 |
1997年 | 193篇 |
1996年 | 158篇 |
1995年 | 156篇 |
1994年 | 116篇 |
1993年 | 121篇 |
1992年 | 98篇 |
1991年 | 86篇 |
1990年 | 65篇 |
1989年 | 42篇 |
1988年 | 43篇 |
1987年 | 34篇 |
1986年 | 30篇 |
1985年 | 30篇 |
1984年 | 16篇 |
1983年 | 20篇 |
1982年 | 6篇 |
1981年 | 9篇 |
1980年 | 6篇 |
1979年 | 9篇 |
1977年 | 4篇 |
1975年 | 5篇 |
1965年 | 4篇 |
1957年 | 3篇 |
排序方式: 共有10000条查询结果,搜索用时 296 毫秒
911.
A Bioorthogonal Small‐Molecule‐Switch System for Controlling Protein Function in Live Cells
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Peng Liu Abram Calderon Dr. Georgios Konstantinidis Dr. Jian Hou Dipl. Stephanie Voss Dr. Xi Chen Fu Li Soumya Banerjee Dr. Jan‐Erik Hoffmann Christiane Theiss Dr. Leif Dehmelt Dr. Yao‐Wen Wu 《Angewandte Chemie (International ed. in English)》2014,53(38):10049-10055
Chemically induced dimerization (CID) has proven to be a powerful tool for modulating protein interactions. However, the traditional dimerizer rapamycin has limitations in certain in vivo applications because of its slow reversibility and its affinity for endogenous proteins. Described herein is a bioorthogonal system for rapidly reversible CID. A novel dimerizer with synthetic ligand of FKBP′ (SLF′) linked to trimethoprim (TMP). The SLF′ moiety binds to the F36V mutant of FK506‐binding protein (FKBP) and the TMP moiety binds to E. coli dihydrofolate reductase (eDHFR). SLF′‐TMP‐induced heterodimerization of FKBP(F36V) and eDHFR with a dissociation constant of 0.12 μM . Addition of TMP alone was sufficient to rapidly disrupt this heterodimerization. Two examples are presented to demonstrate that this system is an invaluable tool, which can be widely used to rapidly and reversibly control protein function in vivo. 相似文献
912.
Po‐Yeng Feng Yi‐Hung Liu Prof. Tien‐Sung Lin Prof. Shie‐Ming Peng Prof. Ching‐Wen Chiu 《Angewandte Chemie (International ed. in English)》2014,53(24):6237-6240
Chemical reduction of a hydroxyphenyl‐substituted borane triggers a sequential electron‐ and intramolecular hydrogen‐atom‐transfer process to afford a hydridoborate phenoxide dianion. On the other hand, hydrogen‐atom abstraction of the borane leads to the isolation of a neutral borylated phenoxyl radical, which can be transformed to the corresponding benzoquinone borataalkene derivative by reduction with cobaltocene. 相似文献
913.
Hao Sun Xiao You Yishu Jiang Guozhen Guan Xin Fang Jue Deng Peining Chen Dr. Yongfeng Luo Prof. Huisheng Peng 《Angewandte Chemie (International ed. in English)》2014,53(36):9526-9531
Electrically conducting wires play a critical role in the advancement of modern electronics and in particular are an important key to the development of next‐generation wearable microelectronics. However, the thin conducting wires can easily break during use, and the whole device fails to function as a result. Herein, a new family of high‐performance conducting wires that can self‐heal after breaking has been developed by wrapping sheets of aligned carbon nanotubes around polymer fibers. The aligned carbon nanotubes offer an effective strategy for the self‐healing of the electric conductivity, whereas the polymer fiber recovers its mechanical strength. A self‐healable wire‐shaped supercapacitor fabricated from a wire electrode of this type maintained a high capacitance after breaking and self‐healing. 相似文献
914.
Enantioselective and Regioselective Pyrone Diels–Alder Reactions of Vinyl Sulfones: Total Synthesis of (+)‐Cavicularin
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Peng Zhao Prof. Dr. Christopher M. Beaudry 《Angewandte Chemie (International ed. in English)》2014,53(39):10500-10503
The total synthesis of (+)‐cavicularin is described. The synthesis features an enantio‐ and regioselective pyrone Diels–Alder reaction of a vinyl sulfone to construct the cyclophane architecture of the natural product. The Diels–Alder substrate was prepared by a regioselective one‐pot three‐component Suzuki reaction of a non‐symmetric dibromoarene. 相似文献
915.
Cationic Vesicles Based on Amphiphilic Pillar[5]arene Capped with Ferrocenium: A Redox‐Responsive System for Drug/siRNA Co‐Delivery
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Peng Wei Sisi Huang Prof. Dr. Yuxin Pei Wei Zhao Prof. Dr. Zhichao Pei 《Angewandte Chemie (International ed. in English)》2014,53(48):13126-13130
A novel ferrocenium capped amphiphilic pillar[5]arene (FCAP) was synthesized and self‐assembled to cationic vesicles in aqueous solution. The cationic vesicles, displaying low cytotoxicity and significant redox‐responsive behavior due to the redox equilibrium between ferrocenium cations and ferrocenyl groups, allow building an ideal glutathione (GSH)‐responsive drug/siRNA co‐delivery system for rapid drug release and gene transfection in cancer cells in which higher GSH concentration exists. This is the first report of redox‐responsive vesicles assembled from pillararenes for drug/siRNA co‐delivery; besides enhancing the bioavailability of drugs for cancer cells and reducing the adverse side effects for normal cells, these systems can also overcome the drug resistance of cancer cells. This work presents a good example of rational design for an effective stimuli‐responsive drug/siRNA co‐delivery system. 相似文献
916.
Frontispiece: Re‐Appearance of Cooperativity in Ultra‐Small Spin‐Crossover [Fe(pz){Ni(CN)4}] Nanoparticles
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
917.
Xiaonan Duan Dr. Stéphane C. Corgié Prof. Daniel J. Aneshansley Prof. Peng Wang Prof. Larry P. Walker Prof. Emmanuel P. Giannelis 《Chemphyschem》2014,15(5):974-980
We report a new family of hierarchical hybrid catalysts comprised of horseradish peroxidase (HRP)–magnetic nanoparticles for advanced oxidation processes and demonstrate their utility in the removal of phenol from water. The immobilized HRP catalyzes the oxidation of phenols in the presence of H2O2, producing free radicals. The phenoxy radicals react with each other in a non‐enzymatic process to form polymers, which can be removed by precipitation with salts or condensation. The hybrid peroxidase catalysts exhibit three times higher activity than free HRP and are able to remove three times more phenol from water compared to free HRP under similar conditions. In addition, the hybrid catalysts reduce substrate inhibition and limit inactivation from reaction products, which are common problems with free or conventionally immobilized enzymes. Reusability is improved when the HRP–magnetic nanoparticle hybrids are supported on micron‐scale magnetic particles, and can be retained with a specially designed magnetically driven reactor. The performance of the hybrid catalysts makes them attractive for several industrial and environmental applications and their development might pave the way for practical applications by eliminating most of the limitations that have prevented the use of free or conventionally immobilized enzymes. 相似文献
918.
Band‐Gap Manipulations of Monolayer Graphene by Phenyl Radical Adsorptions: A Density Functional Theory Study
下载免费PDF全文
![点击此处可从《Chemphyschem》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Phenyl radical (Ph.) adsorption on monolayer graphene sheets is used to investigate the band‐gap manipulation of graphene through density functional theory. Adsorption of a single Ph. on graphene breaks the aromatic π‐bond and generates an unpaired electron, which is delocalized to the ortho or para position. Adsorption of a second radical at the ortho or para position saturates the radical by electron pairing and results in semiconducting graphene. Adsorption of a second radical at the ortho position (ortho–ortho pairing) is found to be more favorable than adsorption at the para position (ortho–para pairing), and the ortho–ortho pairing has stronger effects on band‐gap opening compared with ortho–para pairing. Adsorption of even numbers of Ph. on graphene by ortho–ortho and ortho–para pairings, in general, increases the band gap. Our study shows promise of band‐gap manipulation in monolayer graphene by Ph. adsorption, leading to potential wider applications of graphene. 相似文献
919.
靶向抑制DNA拓扑异构酶的抗肿瘤药物研究 总被引:1,自引:0,他引:1
DNA拓扑异构酶是真核细胞和原核细胞中的一种基本酶,广泛存在于细胞核中,对DNA的转录、复制以及基因表达过程中的DNA拓扑结构的改变起着重要的作用。研究发现DNA拓扑异构酶在肿瘤组织中高度表达,许多抗肿瘤药物的作用机制与抑制拓扑异构酶有关,目前拓扑异构酶已成为筛选抗肿瘤药物的重要靶点。 相似文献
920.
通过水热合成法,合成了4个配位聚合物:[Mn(H2O)(PTZDA)(BDC)]n(1)、[Co(H2O)(PTZDA)(BDC)]n(2)、[Zn(H2O)(PTZDA)(BDC)]n(3)、[Cd(H2O)(PTZDA)(BDC)]n(4)(PTZDA=2,4-二氨基-6-(2′-吡啶)-均三嗪,H2BDC=对苯二甲酸),并分别用X射线单晶衍射、元素分析、红外光谱、差热分析和X-射线粉末衍射表征了这4个配合物。晶体结构分析表明,在配合物1~4中,配体PTZDA与中心金属离子螯合配位,金属离子通过配体BDC2-连结成一维链状结构,一维链之间通过氢键作用连接成三维超分子结构。磁性和荧光分析表明,配合物1和2具有非常弱的反铁磁作用;配合物3和4的荧光均为配体发光。 相似文献