全文获取类型
收费全文 | 349篇 |
免费 | 32篇 |
专业分类
化学 | 286篇 |
晶体学 | 2篇 |
力学 | 6篇 |
数学 | 28篇 |
物理学 | 59篇 |
出版年
2023年 | 4篇 |
2022年 | 4篇 |
2021年 | 7篇 |
2020年 | 10篇 |
2019年 | 9篇 |
2017年 | 5篇 |
2016年 | 25篇 |
2015年 | 5篇 |
2014年 | 23篇 |
2013年 | 14篇 |
2012年 | 6篇 |
2011年 | 19篇 |
2010年 | 6篇 |
2009年 | 7篇 |
2008年 | 12篇 |
2007年 | 13篇 |
2006年 | 22篇 |
2005年 | 10篇 |
2004年 | 13篇 |
2003年 | 9篇 |
2002年 | 8篇 |
2001年 | 9篇 |
1997年 | 4篇 |
1996年 | 12篇 |
1995年 | 8篇 |
1993年 | 8篇 |
1992年 | 5篇 |
1991年 | 3篇 |
1989年 | 5篇 |
1988年 | 6篇 |
1987年 | 3篇 |
1983年 | 4篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1980年 | 4篇 |
1979年 | 3篇 |
1978年 | 2篇 |
1972年 | 5篇 |
1970年 | 4篇 |
1968年 | 3篇 |
1966年 | 5篇 |
1965年 | 3篇 |
1964年 | 5篇 |
1956年 | 2篇 |
1955年 | 2篇 |
1924年 | 2篇 |
1910年 | 2篇 |
1903年 | 3篇 |
1896年 | 3篇 |
1884年 | 2篇 |
排序方式: 共有381条查询结果,搜索用时 15 毫秒
1.
Robin F. Weitkamp Beate Neumann Hans‐Georg Stammler Berthold Hoge 《Angewandte Chemie (International ed. in English)》2020,59(14):5494-5499
We report on the first examples of isolated silanol–silanolate anions, obtained by utilizing weakly coordinating phosphazenium counterions. The silanolate anions were synthesized from the recently published phosphazenium hydroxide hydrate salt with siloxanes. The silanol–silanolate anions are postulated intermediates in the hydroxide‐mediated polymerization of aryl and alkyl siloxanes. The silanolate anions are strong nucleophiles because of the weakly coordinating character of the phosphazenium cation, which is perceptible in their activity in polysiloxane depolymerization. 相似文献
2.
In this contribution we report on fluorotrimethyl[(Z)-pentafluoropropen-1-yl]phosphorane as a phosphorus based fluorinating reagent. Its solid state structure can be described as a trigonal bipyramid featuring elongated axial bonds due to the formation of a 3-center 4-electron bond. Abstraction of the fluoride ion leads to a shortening of the axial P–C bond. Thus the title compound can be utilized for substitution of bromine with fluorine and for the transfer of fluoride ions onto electrophilic compounds. Reaction with Sn(C2F5)2Br2 afforded salt [P(CH3)3(C3F5)]2[Sn(C2F5)2F4]. When fluorotrimethyl[(Z)-pentafluoropropen-1-yl]phosphorane was treated with P(C2F5)2F the primarily produced anion is sufficiently nucleophilic to attack the propenyl group of the cation in β-position to the phosphorus atom to yield zwitterionic [Me3PCF=C(CF3)–PF3(C2F5)2]. 相似文献
3.
Paul Kautny Dorian Bader Dr. Berthold Stöger Prof. Dr. Georg A. Reider Prof. Dr. Johannes Fröhlich Dr. Daniel Lumpi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(52):18887-18898
To shed light on intramolecular charge‐transfer phenomena in 1,2,3‐triazole‐linked materials, a series of 1,2,3‐triazole‐linked push–pull chromophores were prepared and studied experimentally and computationally. Investigated modifications include variation of donor and/or acceptor strength and linker moiety as well as regioisomers. Photophysical characterization of intramolecular charge‐transfer features revealed ambipolar behavior of the triazole linker, depending on the substitution position. Furthermore, non‐centrosymmetric materials were subjected to second‐harmonic generation measurements, which revealed the high nonlinear optical activity of this class of materials. 相似文献
4.
Many authors have recognized that traffic under the traditional car‐following model (CFM) is subject to flow instabilities. A recent model achieves stability using bilateral control (BCM)—by looking both forward and backward [1]. (Looking back may be difficult or distracting for human drivers, but is not a problem for sensors.) We analyze the underlying systems of differential equations by studying their eigenvalues and eigenvectors under various boundary conditions. Simulations further confirm that bilateral control can avoid instabilities and reduce the chance of collisions. 相似文献
5.
Yossi Azar Martin Hoefer Idan Maor Rebecca Reiffenhäuser Berthold Vöcking 《Mathematical Programming》2017,163(1-2):445-469
A powerful algorithmic technique for truthful mechanism design is the maximal-in-distributional-range (MIDR) paradigm. Unfortunately, many such algorithms use heavy algorithmic machinery, e.g., the ellipsoid method and (approximate) solution of convex programs. In this paper, we present a correlated rounding technique for designing mechanisms that are truthful in expectation. It is elementary and can be implemented quickly. The main property we rely on is that the domain offers fractional optimum solutions with a tree structure. In auctions based on the generalized assignment problem, each bidder has a publicly known knapsack constraint that captures the subsets of items that are of value to him. He has a private valuation for each item and strives to maximize the value of assigned items minus payment. For this domain we design a truthful 2-approximate MIDR mechanism for social welfare maximization. It avoids using the ellipsoid method or convex programming. In contrast to some previous work, our mechanism achieves exact truthfulness. In restricted-related scheduling with selfish machines, each job comes with a public weight, and it must be assigned to a machine from a public job-specific subset. Each machine has a private speed and strives to maximize payments minus workload of jobs assigned to it. Here we design a mechanism for makespan minimization. This is a single-parameter domain, but the approximation status of the optimization problem is similar to unrelated machine scheduling: The best known algorithm obtains a (non-truthful) 2-approximation for unrelated machines, and there is 1.5-hardness. Our mechanism matches this bound with a truthful 2-approximation. 相似文献
6.
Harry Biller Swantje Lerch Katharina Tölke Dr. Hans-Georg Stammler Prof. Dr. Berthold Hoge Prof. Dr. Thomas Strassner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(53):13325-13329
We synthesized new imidazolium-based tunable aryl alkyl ionic liquids (TAAILs) with the weakly coordinating tetrakis(pentafluoroethyl)gallate anion, [Ga(C2F5)4]−. Phenyl and phenyl derivatives (2-Me, 4-OMe, 2,4-F) were combined with varying alkyl chain lengths at the imidazolium core leading to TAAILs, which were investigated with regard to their viscosity, conductivity, and electrochemical window and compared to EMIM and BMIM standard cations. Remarkable low viscosities of 29 cP at 25 °C for [BMIM][Ga(C2F5)4] were achieved. However, the EMIM and BMIM gallates show electrochemical instability, releasing pentafluoroethane at a voltage of 1.5 V. The 2-Me-substituted gallate-TAAILs slowly decompose over several weeks, whereas all other gallate-TAAILs showed no decomposition at all. With electrochemical windows of up to 5.15 V and low viscosities in a range of 66–162 cP, the gallate-TAAILs are promising candidates as electrolytes in electrochemical applications. 相似文献
7.
Natalia Tiessen Dr. Nico Schwarze Mira Keßler Beate Neumann Dr. Hans-Georg Stammler Prof. Dr. Berthold Hoge 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(43):11041-11044
While alkyl-substituted siloxanes are widely known, virtually nothing is known about perfluoroalkyl siloxanes and their congener species, the silanols and silanolates. We recently reported on the tris(pentafluoroethyl)silanide ion, [Si(C2F5)3]−, which features Lewis amphoteric character deriving from the pentafluoroethyl substituents and their strong electron-withdrawing properties. Transferring this knowledge, we investigated the Lewis amphoteric behavior of the tris(pentafluoroethyl)silanolate, [Si(C2F5)3O]−. In order to examine such Lewis amphoteric behavior, we first developed a strategy for the synthesis of the corresponding silanol Si(C2F5)3OH, which readily condenses at room temperature to the hexakis(pentafluoroethyl)disiloxane, (C2F5)3SiOSi(C2F5)3. Deprotonation of Si(C2F5)3OH employing a sterically demanding phosphazene base allows the characterization of the first example of a dimeric triorganosilanolate: the dianionic hexakis(pentafluoroethyl)disilanolate, [{Si(C2F5)3O}2]2−, implies Lewis amphoteric character of the monomeric [Si(C2F5)3O]− anion. 相似文献
8.
Dino Berthold Arne G. A. Geissler Sabrina Giofr Bernhard Breit 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(29):10099-10102
The rhodium‐catalyzed asymmetric intramolecular hydroamination of sulfonyl amides with terminal allenes is reported. It provides selective access to 5‐ and 6‐membered N‐heterocycles, scaffolds found in a large range of different bioactive compounds. Moreover, gram scale reactions, as well as the application of suitable product transformations to natural products and key intermediates thereof are demonstrated. 相似文献
9.
10.