全文获取类型
收费全文 | 1605篇 |
免费 | 87篇 |
国内免费 | 3篇 |
专业分类
化学 | 1087篇 |
晶体学 | 8篇 |
力学 | 27篇 |
数学 | 300篇 |
物理学 | 273篇 |
出版年
2024年 | 5篇 |
2023年 | 33篇 |
2022年 | 33篇 |
2021年 | 31篇 |
2020年 | 59篇 |
2019年 | 69篇 |
2018年 | 31篇 |
2017年 | 31篇 |
2016年 | 72篇 |
2015年 | 62篇 |
2014年 | 51篇 |
2013年 | 68篇 |
2012年 | 105篇 |
2011年 | 102篇 |
2010年 | 55篇 |
2009年 | 38篇 |
2008年 | 68篇 |
2007年 | 88篇 |
2006年 | 72篇 |
2005年 | 80篇 |
2004年 | 55篇 |
2003年 | 41篇 |
2002年 | 37篇 |
2001年 | 17篇 |
2000年 | 20篇 |
1999年 | 18篇 |
1998年 | 15篇 |
1997年 | 17篇 |
1996年 | 16篇 |
1994年 | 8篇 |
1993年 | 9篇 |
1992年 | 19篇 |
1991年 | 11篇 |
1990年 | 9篇 |
1989年 | 11篇 |
1988年 | 10篇 |
1987年 | 12篇 |
1986年 | 15篇 |
1985年 | 11篇 |
1984年 | 13篇 |
1983年 | 10篇 |
1982年 | 9篇 |
1981年 | 9篇 |
1980年 | 15篇 |
1979年 | 17篇 |
1976年 | 15篇 |
1975年 | 12篇 |
1973年 | 18篇 |
1969年 | 5篇 |
1932年 | 4篇 |
排序方式: 共有1695条查询结果,搜索用时 15 毫秒
61.
62.
Blanka Wladislaw Liliana Marzorati Jonas Gruber 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4):185-188
Abstract Some new norbornene thioester derivatives of endo configuration are sinthesized. Proofs are provided that thioester group has more preference for endo configuration than the ester group. 相似文献
63.
Jonas Örtegren Philippe Busson Ulf W. Gedde Anders Hult Anders Eriksson Mikael Lindgren 《Liquid crystals》2013,40(6):861-868
We report second harmonic generation in a ferroelectric liquid crystalline trimer and ferroelectric liquid crystalline dendrimers of first, second and third generation. Thin cells were filled with the compounds by capillary forces at elevated temperature, and cooled from the surface stabilized ferroelectric state to below the glass transition temperature, while kept in an electric field. The cone motion viscosity and the threshold electric field for unwinding of the helix axis of the chiral tilted smectic mesophases were studied separately at elevated temperature, and these data were used to optimize the preparation of the films. The measured response time was between 0.3 and 3ms, which corresponds to a cone motion viscosity between 0.5 and 50 Pa s. Second harmonic generation was studied both at elevated temperature with an electric field and at room temperature with and without electric field. The first generation dendrimer exhibited a strong increase in the second order non-linear optical response with time at room temperature. The d 23-coefficient of this dendrimer was approximately four times larger than for the other macromolecules and was 0.045 pm V-1. The relatively large d-coefficient of the first generation dendrimer is ascribed to crystallization, which improved the orientation of the molecular dipoles. 相似文献
64.
Linda Axelsson Jean-Baptiste VeronJonas Sävmarker Jonas LindhLuke R. Odell Mats Larhed 《Tetrahedron letters》2014
A palladium(II)-catalyzed decarboxylative protocol for the synthesis of aryl ketones has been developed. The addition of TFA was shown to improve the reaction yield and employing THF as solvent enabled the use of solid nitriles and in only a small excess. Using this method, five different benzoic acids reacted with a wide range of nitriles to produce 29 diverse (hetero)aryl ketone derivatives in up to 94% yield. 相似文献
65.
Nina Bergman Denys Shevchenko Jonas Bergquist 《Analytical and bioanalytical chemistry》2014,406(1):49-61
This review summarizes various approaches for the analysis of low molecular weight (LMW) compounds by different laser desorption/ionization mass spectrometry techniques (LDI-MS). It is common to use an agent to assist the ionization, and small molecules are normally difficult to analyze by, e.g., matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS) using the common matrices available today, because the latter are generally small organic compounds themselves. This often results in severe suppression of analyte peaks, or interference of the matrix and analyte signals in the low mass region. However, intrinsic properties of several LDI techniques such as high sensitivity, low sample consumption, high tolerance towards salts and solid particles, and rapid analysis have stimulated scientists to develop methods to circumvent matrix-related issues in the analysis of LMW molecules. Recent developments within this field as well as historical considerations and future prospects are presented in this review. 相似文献
66.
Highly Selective Dimerization and Trimerization of Isobutene to Linearly Linked Products by Using Nickel Catalysts 下载免费PDF全文
Prof. Arno Behr Nils Rentmeister Thomas Seidensticker Jonas Vosberg Dr. Stephan Peitz Dr. Dietrich Maschmeyer 《化学:亚洲杂志》2014,9(2):596-601
The unique linear linkage of isobutene to generate highly valuable C8 precursors for plasticizers is feasible by using special nickel catalysts. (4‐Cyclooctene‐1‐yl)(1,1,1,5,5,5‐hexafluoro‐2,4‐acetylacetonato)nickel and aluminum‐alkyl‐activated nickel acetylacetonates produce isobutene dimers with high selectivities of up to 95 %. Moreover, selectivity for the head‐to‐head products (2,5‐dimethylhexenes) is remarkably high at up to 99 %. Additionally, novel C12 isobutene trimers are also formed with a very high selectivity of up to 99 % for the linear linkage. The trimer structure (2,5,8‐trimethylnonenes) reflects the stepwise characteristic of the reaction mechanism. Pathways of insertion and activation and the deactivation processes of the catalyst are discussed in detail. 相似文献
67.
Jan Rosenboom Dr. Lukas Chojetzki Dr. Tim Suhrbier Dr. Jabor Rabeah Dr. Alexander Villinger Dr. Ronald Wustrack Dr. Jonas Bresien Prof. Dr. Axel Schulz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(36):e202200624
The activation of C−Br bonds in various bromoalkanes by the biradical [⋅P(μ-NTer)2P⋅] ( 1 ) (Ter=2,6-bis-(2,4,6-trimethylphenyl)-phenyl) is reported, yielding trans-addition products of the type [Br−P(μ-NTer)2P−R] ( 2 ), so-called 1,3-substituted cyclo-1,3-diphospha-2,4-diazanes. This addition reaction, which represents a new easy approach to asymmetrically substituted cyclo-1,3-diphospha-2,4-diazanes, was investigated mechanistically by different spectroscopic methods (NMR, EPR, IR, Raman); the results suggested a stepwise radical reaction mechanism, as evidenced by the in-situ detection of the phosphorus-centered monoradical [⋅P(μ-NTer)2P-R].< To provide further evidence for the radical mechanism, [⋅P(μ-NTer)2P-Et] ( 3Et ⋅) was synthesized directly by reduction of the bromoethane addition product [Br-P(μ-NTer)2P-Et] ( 2 a ) with magnesium, resulting in the formation of the persistent phosphorus-centered monoradical [⋅P(μ-NTer)2P-Et], which could be isolated and fully characterized, including single-crystal X-ray diffraction. Comparison of the EPR spectrum of the radical intermediate in the addition reaction with that of the synthesized new [⋅P(μ-NTer)2P-Et] radical clearly proves the existence of radicals over the course of the reaction of biradical [⋅P(μ-NTer)2P⋅] ( 1 ) with bromoethane. Extensive DFT and coupled cluster calculations corroborate the experimental data for a radical mechanism in the reaction of biradical [⋅P(μ-NTer)2P⋅] with EtBr. In the field of hetero-cyclobutane-1,3-diyls, the demonstration of a stepwise radical reaction represents a new aspect and closes the gap between P-centered biradicals and P-centered monoradicals in terms of radical reactivity. 相似文献
68.
Candida Manelfi Jonas Gossen Silvia Gervasoni Carmine Talarico Simone Albani Benjamin Joseph Philipp Francesco Musiani Giulio Vistoli Giulia Rossetti Andrea Rosario Beccari Alessandro Pedretti 《Molecules (Basel, Switzerland)》2021,26(4)
The 3CL-Protease appears to be a very promising medicinal target to develop anti-SARS-CoV-2 agents. The availability of resolved structures allows structure-based computational approaches to be carried out even though the lack of known inhibitors prevents a proper validation of the performed simulations. The innovative idea of the study is to exploit known inhibitors of SARS-CoV 3CL-Pro as a training set to perform and validate multiple virtual screening campaigns. Docking simulations using four different programs (Fred, Glide, LiGen, and PLANTS) were performed investigating the role of both multiple binding modes (by binding space) and multiple isomers/states (by developing the corresponding isomeric space). The computed docking scores were used to develop consensus models, which allow an in-depth comparison of the resulting performances. On average, the reached performances revealed the different sensitivity to isomeric differences and multiple binding modes between the four docking engines. In detail, Glide and LiGen are the tools that best benefit from isomeric and binding space, respectively, while Fred is the most insensitive program. The obtained results emphasize the fruitful role of combining various docking tools to optimize the predictive performances. Taken together, the performed simulations allowed the rational development of highly performing virtual screening workflows, which could be further optimized by considering different 3CL-Pro structures and, more importantly, by including true SARS-CoV-2 3CL-Pro inhibitors (as learning set) when available. 相似文献
69.
Stefan Dix Paul Golz Jonas R. Schmid Prof. Dr. Sebastian Riedel Prof. Matthew N. Hopkinson 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(45):11554-11558
Trifluoromethoxylated (hetero)arenes are of great interest for several disciplines, especially in agro- and medicinal chemistry. Radical C−H trifluoromethoxylation of (hetero)arenes represents an attractive approach to prepare such compounds, but the high cost and low atom economy of existing . OCF3 radical sources make them unsuitable for the large-scale synthesis of trifluoromethoxylated building blocks. Herein, we introduce bis(trifluoromethyl)peroxide (BTMP, CF3OOCF3) as a practical and efficient trifluoromethoxylating reagent that is easily accessible from inexpensive bulk chemicals. Using either visible light photoredox or TEMPO catalysis, trifluoromethoxylated arenes could be prepared in good yields under mild conditions directly from unactivated aromatics. Moreover, TEMPO catalysis allowed for the one-step synthesis of valuable pyridine derivatives, which have been previously prepared via multi-step approaches. 相似文献
70.