全文获取类型
收费全文 | 9988篇 |
免费 | 430篇 |
国内免费 | 87篇 |
专业分类
化学 | 6808篇 |
晶体学 | 91篇 |
力学 | 264篇 |
综合类 | 1篇 |
数学 | 1731篇 |
物理学 | 1610篇 |
出版年
2023年 | 77篇 |
2022年 | 56篇 |
2021年 | 182篇 |
2020年 | 209篇 |
2019年 | 250篇 |
2018年 | 158篇 |
2017年 | 159篇 |
2016年 | 384篇 |
2015年 | 288篇 |
2014年 | 320篇 |
2013年 | 603篇 |
2012年 | 607篇 |
2011年 | 653篇 |
2010年 | 453篇 |
2009年 | 404篇 |
2008年 | 586篇 |
2007年 | 630篇 |
2006年 | 494篇 |
2005年 | 547篇 |
2004年 | 440篇 |
2003年 | 350篇 |
2002年 | 287篇 |
2001年 | 125篇 |
2000年 | 95篇 |
1999年 | 67篇 |
1998年 | 72篇 |
1997年 | 88篇 |
1996年 | 99篇 |
1995年 | 89篇 |
1994年 | 80篇 |
1993年 | 95篇 |
1992年 | 74篇 |
1991年 | 76篇 |
1990年 | 69篇 |
1989年 | 64篇 |
1988年 | 48篇 |
1987年 | 54篇 |
1986年 | 64篇 |
1985年 | 102篇 |
1984年 | 99篇 |
1983年 | 77篇 |
1982年 | 66篇 |
1981年 | 70篇 |
1980年 | 62篇 |
1979年 | 64篇 |
1978年 | 67篇 |
1977年 | 41篇 |
1976年 | 40篇 |
1975年 | 50篇 |
1974年 | 53篇 |
排序方式: 共有10000条查询结果,搜索用时 22 毫秒
61.
62.
Dipl.‐Chem. Jan Tillmann Dipl.‐Chem. Josef Heinrich Wender Dr. Ute Bahr Dr. Michael Bolte Dr. Hans‐Wolfram Lerner Prof. Dr. Max C. Holthausen Prof. Dr. Matthias Wagner 《Angewandte Chemie (International ed. in English)》2015,54(18):5429-5433
Silicon analogues of the most prominent carbon nanostructures, namely, hollow spheroidals such as C60 and the fullerene family, have been unknown to date. Herein we show that discrete Si20 dodecahedra, stabilized by an endohedral guest and valence saturation, are accessible in preparative yields through a chloride‐induced disproportionation reaction of hexachlorodisilane in the presence of tri(n‐butyl)amine. X‐ray crystallography revealed that each silicon dodecahedron contains an endohedral chloride ion that imparts a net negative charge. Eight chloro substituents and twelve trichlorosilyl groups are attached to the surface of each cluster in a strictly regioregular arrangement, a thermodynamically preferred substitution pattern according to quantum‐chemical assessment. Our results demonstrate that the wet‐chemical self‐assembly of a complex, monodisperse Si nanostructure is possible under mild conditions starting from simple Si2 building blocks. 相似文献
63.
Various types of carbon nanoparticles were directly mixed with microbial cells of Gluconobacter oxydans within a 3-D bionanocomposite in order to prepare a highly sensitive ethanol biosensor with a short response time. From all carbonaceous nanomaterials tested, single- or multi-walled carbon nanotubes provided the highest sensitivity of detection (117–121 µA cm?2 mM?1), but from a practical point of view, Ketjen black 300 and 600 provide very low detection limit (2–6 µM) and high sensitivity for the ethanol analysis (84–88 µA cm?2 mM?1)with a shortresponse time (14–33 s). Moreover, the price of Ketjen black is a few orders of magnitude lower compared to that of carbon nanotubes. Finally, the study showed that the morphology of nanoparticles rather than their surface modification is the key element in achieving high sensitivity of ethanol detection. 相似文献
64.
Gluconobacter oxydans bacteria exhibit a unique metabolism for quick and incomplete oxidation of a wide range of different compounds (aldoses, ketoses, mono- and poly-alcohols, etc.). Such biotransformation efficiency with simple biomass production led to the industrial applications of these bacteria in the production of several important commodities. Their respiratory activity can also be successfully studied and used in the field of bioelectrochemistry. The main aim of this review is to present various strategies to improve selectivity of assays using intact/treated cells of G. oxydans, to introduce the application of G. oxydans-based biosensors in selective monitoring of analytes during biotransformation processes and to provide information about utilizable sugars in fermentation media or in biological oxygen demand value determination. The final part of the review describes potential application of G. oxydans cells in the generation of electricity from complex fuels within microbial fuel cells by advanced direct electron transfer route between bacterial cells and electrodes. 相似文献
65.
Substituting CF2 for O4′ in Components of Nucleic Acids: Towards Systems with Reduced Propensity to Form Abasic Lesions 下载免费PDF全文
Dr. Yevgen P. Yurenko Dr. Jan Novotný Prof. Dr. Vladimir Sklenář Prof. Dr. Radek Marek 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(49):17933-17943
Intrinsic structural features and energetics of nucleotides containing variously fluorinated sugars as potential building blocks of DNA duplexes and quadruplexes are explored systematically using the modern methods of density functional theory (DFT) and quantum chemical topology (QCT). Our results suggest that fluorination at the 2′‐β or 2′‐α,β positions somewhat stabilizes in vacuo the AI relative to the BI conformations. In contrast, substitution of the CF2 group for the O4′ atom (O4′‐CF2 modification) leads to a preference of the BI relative to AI DNA‐like conformers. All the studied modifications result in a noticeable increase in the stability of the glycosidic bond [estimated by the relaxed force constants (RFC) approach], with particularly encouraging results for the O4′‐CF2 derivative. Consequently, the O4′‐CF2 modified systems are suggested and explored as promising scaffolds for the development of duplex and quadruplex structures with reduced propensity to form abasic lesions and to undergo DNA damage. 相似文献
66.
Josef Janča 《International Journal of Polymer Analysis and Characterization》2015,20(8):671-680
Micro-thermal field-flow fractionation was used to characterize the particle size distribution of nanometer-sized diamond nanoparticles. Although the experimental conditions were chosen to perform high-speed separation, and, consequently, the resolution achieved experimentally was not very high, the application of the original correction method for the zone spreading allowed for obtaining of very good calculated particle size distribution or, explicitly, a true polydispersity index of the diamond nanoparticle sample. The future use of several samples of diamond nanoparticles of different average sizes and different surface chemistries should allow deeper insight into the effect of these particulate characteristics on the retention in micro-thermal field-flow fractionation. 相似文献
67.
Metal‐Catalyzed β‐Functionalization of Michael Acceptors through Reductive Radical Addition Reactions 下载免费PDF全文
Dr. Jan Streuff Prof. Dr. Andreas Gansäuer 《Angewandte Chemie (International ed. in English)》2015,54(48):14232-14242
Transition‐metal‐catalyzed radical reactions are becoming increasingly important in modern organic chemistry. They offer fascinating and unconventional ways for connecting molecular fragments that are often complementary to traditional methods. In particular, reductive radical additions to α,β‐unsaturated compounds have recently gained substantial attention as a result of their broad applicability in organic synthesis. This Minireview critically discusses the recent landmark achievements in this field in context with earlier reports that laid the foundation for today′s developments. 相似文献
68.
Synthesis and EPR/UV/Vis‐NIR Spectroelectrochemical Investigation of a Persistent Phosphanyl Radical Dication 下载免费PDF全文
Kai Schwedtmann Stephen Schulz Felix Hennersdorf Prof. Dr. Thomas Strassner Dr. Evgenia Dmitrieva Prof. Dr. Jan J. Weigand 《Angewandte Chemie (International ed. in English)》2015,54(38):11054-11058
The reaction of the bis(imidazoliumyl)‐substituted PI cation [(2‐ImDipp)P(4‐ImDipp)]+ ( 10 +) (2‐Im=imidazolium‐2‐yl; 4‐Im=imidazolium‐4‐yl; Dipp=2,6‐di‐isopropylphenyl) with trifluoromethanesulfonic acid (HOTf) or methyl trifluoromethylsulfonate (MeOTf) yields the corresponding protonated [(2‐ImDipp)PH(4‐ImDipp)]2+ ( 11 2+) and methylated [(2‐ImDipp)PMe(4‐ImDipp)]2+ ( 12 2+) dications, respectively. EPR/UV/Vis‐NIR spectroelectrochemical investigation of the low‐coordinated PI cation 10 + predicted a stable and “bottleable” P‐centered radical dication [(2‐ImDipp)P(4‐ImDipp)]2+. ( 13 2+.). The reaction of 10 + with the nitrosyl salt NO[OTf] yields the persistent phosphanyl radical dication 13 2+. as triflate salt in crystalline form. Quantum chemical investigation revealed an exceptional high spin density at the P atom. 相似文献
69.
Olefin‐Directed Palladium‐Catalyzed Regio‐ and Stereoselective Oxidative Arylation of Allenes 下载免费PDF全文
Dr. Can Zhu Bin Yang Dr. Tuo Jiang Prof. Dr. Jan‐E. Bäckvall 《Angewandte Chemie (International ed. in English)》2015,54(31):9066-9069
An olefin‐directed palladium‐catalyzed oxidative regio‐ and stereoselective arylation of allenes to afford 1,3,6‐trienes has been established. A number of functionalized allenes, including 2,3‐ and 3,4‐dienoates and 3,4‐dienol derivatives, have been investigated and found to undergo the olefin‐directed allene arylation. The olefin moiety has been proven to be a crucial element for the arylating transformation. 相似文献
70.
Dr. Saurabh S. Chitnis Prof. Neil Burford Prof. Jan J. Weigand Dr. Robert McDonald 《Angewandte Chemie (International ed. in English)》2015,54(27):7828-7832
Reactions of triarylphosphines with fluoroantimony(III) triflates give phosphine antimony(III) complexes, which undergo spontaneous reductive elimination of fluorophosphonium cations. The resulting phosphine antimony(I) complexes catenate to give the first examples of cationic antimony bicyclic compounds, [(R3P)4Sb6]4+, featuring a bicyclo[3.1.0]hexastibine framework stabilized by four phosphine ligands. The unprecedented 14‐electron redox process illustrates the generality of the reductive catenation method. 相似文献