全文获取类型
收费全文 | 2075篇 |
免费 | 171篇 |
国内免费 | 6篇 |
专业分类
化学 | 1551篇 |
晶体学 | 7篇 |
力学 | 43篇 |
数学 | 300篇 |
物理学 | 351篇 |
出版年
2024年 | 2篇 |
2023年 | 35篇 |
2022年 | 50篇 |
2021年 | 67篇 |
2020年 | 120篇 |
2019年 | 98篇 |
2018年 | 40篇 |
2017年 | 40篇 |
2016年 | 150篇 |
2015年 | 112篇 |
2014年 | 103篇 |
2013年 | 123篇 |
2012年 | 151篇 |
2011年 | 198篇 |
2010年 | 109篇 |
2009年 | 78篇 |
2008年 | 138篇 |
2007年 | 127篇 |
2006年 | 100篇 |
2005年 | 107篇 |
2004年 | 76篇 |
2003年 | 51篇 |
2002年 | 47篇 |
2001年 | 12篇 |
2000年 | 19篇 |
1999年 | 12篇 |
1998年 | 10篇 |
1997年 | 5篇 |
1996年 | 9篇 |
1995年 | 7篇 |
1994年 | 9篇 |
1993年 | 4篇 |
1992年 | 4篇 |
1991年 | 7篇 |
1989年 | 2篇 |
1987年 | 4篇 |
1986年 | 7篇 |
1985年 | 2篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1982年 | 3篇 |
1979年 | 1篇 |
1978年 | 3篇 |
1976年 | 3篇 |
1975年 | 2篇 |
1974年 | 1篇 |
1967年 | 1篇 |
排序方式: 共有2252条查询结果,搜索用时 15 毫秒
71.
72.
In this paper, an approach for controlling the macro-step size in connection with co-simulation methods [1, 2, 4] is suggested. The investigated step-size controller is tailored for semi-implicit co-simulation techniques. Concretely, we consider predictor/corrector co-simulation approaches [3]. By comparing variables from the predictor and the corrector step, an error estimator for the local error can be constructed. Making use of the estimated local error, a step-size controller for the macro step-size can be implemented. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
73.
Andrea Thom Tim Ricken Joachim Bluhm Renatus Widmann Martin Denecke Tobias Gehrke 《PAMM》2015,15(1):433-434
To simulate the processes of methane oxidation in landfill cover layers, a new computational model was created. The purpose of the model is to allow a forecast on the performance of methanotrophic activity in landfill cover layers under changing environmental conditions. Therefore, a thermodynamic consistent model based on the well-known Theory of Porous Media (TPM) combined with the mixture theory was developed, which analyzes the relevant gas productions of methane, oxygen and carbon dioxide. Diffusion, advection and conversion processes are considered as well as the energy production during methane oxidation. With the help of the thermal imaging technique a new experimental setup was developed in order to validate the coupled model in terms of the heat generation. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
74.
This contribution presents the characterisation of an incompressible carbon black-filled elastomer as one characteristical example for highly filled rubber. It shows a strongly pronounced non-linear viscoelastic behaviour and the most important characteristic is the extremely long relaxation time which has to be taken into account. The material model is developed with respect to uniaxial tension data. The basis in the development of a phenomenological model is given by the basic elasticity. For this evaluation the long term relaxation behaviour results in a complex experimental procedure. Therefore, special attention has to be paid according to an optimised experimental process in order to get the necessary reference data in an adequate and reproduceable way [1]. With this model basis further investigations are taken into account concerning the time-dependent viscoelasticity. Therefore, cyclic deformations from zero up to a maximum of deformation are considered for different strain rates. Furthermore, the relaxation behaviour is investigated for multiple strain levels. The phenomena which are observed in the experimental results yield in a purely viscoelastic model, based on a rheological analogous model consisting of an equilibrium spring and several Maxwell-elements which contain nonlinear relations for the relaxation times of the dashpot elements [1,2]. The material model's numerical realisation is accomplished in two ways. Because of its numerical simplicity especially according to the parameter identification the model is restricted only to the simple case of uniaxial tension. A second, alternative implementation is executed providing the benefit that more complex deformation conditions can also be taken into account. Therefore, the general, three-dimensional finite model is implemented in an open-source Finite Element library [3]. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
75.
Jinxiong Lin Dr. Friedrich Wossidlo. Dr. Nathan T. Coles Manuela Weber Dr. Simon Steinhauer Priv.-Doz. Dr. Tobias Böttcher Prof. Dr. Christian Müller 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(7):e202104135
A phosphinine-borane adduct of a Me3Si-functionalized phosphinine and the Lewis acid B(C6F5)3 has been synthesized and characterized crystallographically for the first time. The reaction strongly depends on the nature of the substituents in the α-position of the phosphorus heterocycle. In contrast, the reaction of B2H6 with various substituted phosphinines leads to an equilibrium between the starting materials and the phosphinine–borane adducts that is determined by the Lewis basicity of the phosphinine. The novel phosphinine borane adduct ( 6 -B(C6F5)3) shows rapid and facile insertion and [4+2] cycloaddition reactivity towards phenylacetylene. A hitherto unknown dihydro-1-phosphabarrelene is formed with styrene. The reaction with an ester provides a new, facile and selective route to 1-R-phosphininium salts. These salts then undergo a [4+2] cycloaddition in the presence of Me3Si−C≡CH and styrene to cleanly form unprecedented derivatives of 1-R-phosphabarrelenium salts. 相似文献
76.
Tobias G. Brevé Mike Filius Sven Weerdenburg Stefan J. van der Griend Tim P. Groeneveld Dr. Antonia G. Denkova Dr. Rienk Eelkema 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(10):e202103523
Stimuli-responsive soft materials enable controlled release of loaded drug molecules and biomolecules. Controlled release of potent chemotherapeutic or immunotherapeutic agents is crucial to reduce unwanted side effects. In an effort to develop controlled release strategies that can be triggered by using Cerenkov luminescence, we have developed polymer hydrogels that can release bovine serum albumin and immunoglobulin G by using light (254 nm–375 nm) as a trigger. We describe the synthesis and photochemical characterization of two light sensitive phenacyl bis-azide crosslinkers that are used to prepare transparent self-supporting hydrogel patches. One crosslinker was designed to optimize the overlap with the Cerenkov luminescence emission window, bearing an π-extended phenacyl core, resulting in a high quantum yield (14 %) of photocleavage when irradiated with 375 nm light. We used the extended phenacyl crosslinker for the preparation of protein-loaded dextran hydrogel patches, which showed efficient and selective dosed release of bovine serum albumin or immunoglobulin G after irradiation with 375 nm light. Cerenkov-triggered release is as yet inconclusive due to unexpected side-reactivity. Based on the high quantum yield, efficient release and large overlap with the Cerenkov window, we envision application of these photosensitive soft materials in radiation targeted drug release. 相似文献
77.
Tobias Dunaj Prof. Dr. Carsten von Hänisch 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(69):e202202932
In this work, we report the preparation of multiple interpnictogen chain compounds with three consecutive pnictogen atoms and terminal Ar2Bi fragments (Ar=Ph, Mes). Symmetrical compounds of the form Ar2Bi−E(tBu)−Bi2Ar ( 1 : Ar=Ph, E=P; 2 : Ar=Ph, Mes, E=As) as well as ternary interpnictogen compounds of the form Ar2Bi−E1(tBu)−E2tBu2 (Ar=Ph, Mes; 4 : E1=P, E2=As; 5 : E1=P, E2=Sb; 6 : E1=As, E2=P) were prepared. The decomposition in solution at room temperature and under the influence of light was studied for compounds 1 – 6 . The reactivity of 1Ph and 2Ph with the small N-heterocyclic carbene 1,3,4,5-tetramethylimidazol-2-ylidene (Me2IMe) was also studied. In the case of 1Ph , the formation and consecutive decomposition of Me2IMe=PtBu ( 8 ) was observed in solution. Hence, it was shown that 1Ph can react as a “masked phosphinidene”. In the case of 2Ph , no reaction with Me2IMe was observed. All isolated compounds were analysed by NMR and IR spectroscopy, mass spectrometry, elemental analysis and single-crystal X-ray diffraction. 相似文献
78.
Jochen C. Lauer Dr. Avinash S. Bhat Chantal Barwig Nathalie Fritz Tobias Kirschbaum Dr. Frank Rominger Prof. Dr. Michael Mastalerz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(51):e202201527
The pollution of groundwater with nitrate is a serious issue because nitrate can cause several diseases such as methemoglobinemia or cancer. Therefore, selective removal of nitrate by efficient binding to supramolecular hosts is highly desired. Here we describe how to make [2+3] amide cages in very high to quantitative yields by applying an optimized Pinnick oxidation protocol for the conversion of corresponding imine cages. By NMR titration experiments of the eight different [2+3] amide cages with nitrate, chloride and hydrogen sulfate we identified one cage with an unprecedented high selectivity towards nitrate binding vs. chloride (S=705) or hydrogensulfate (S>13500) in CD2Cl2/CD3CN (1 : 3). NMR experiments as well as single-crystal structure comparison of host-guest complexes give insight into structure-property-relationships. 相似文献
79.
Dmytro Makarov András Telek Tobias Becker Marie-Kristin von Wrisberg Sabine Schneider Pavel Kielkowski 《Journal of mass spectrometry : JMS》2022,57(3):e4812
The identification and quantification of modified peptides are critical for the functional characterization of post-translational protein modifications (PTMs) to elucidate their biological function. Nowadays, quantitative mass spectrometry coupled with various bioinformatic pipelines has been successfully used for the determination of a wide range of PTMs. However, direct characterization of low abundant protein PTMs in bottom-up proteomic workflow remains challenging. Here, we present the synthesis and evaluation of tandem mass spectrometry tags (TMT) which are introduced via click-chemistry into peptides bearing alkyne handles. The fragmentation properties of the two mass tags were validated and used for screening in a model system and analysis of AMPylated proteins. The presented tags provide a valuable tool for diagnostic peak generation to increase confidence in the identification of modified peptides and potentially for direct peptide-PTM quantification from various experimental conditions. 相似文献
80.
Maximilian Knies Dr. Matthias F. Groh Tobias Pietsch Mai Lê Anh Prof. Dr. Michael Ruck 《ChemistryOpen》2021,10(2):110-116
Bi2S3 was dissolved in the presence of either AuCl/PtCl2 or AgCl in the ionic liquids [BMIm]Cl ⋅ xAlCl3 (BMIm=1-n-butyl-3-methylimidazolium; x=4–4.3) through annealing the mixtures at 180 or 200 °C. Upon cooling to room temperature, orange, air-sensitive crystals of [BMIm](Bi4S4)[AlCl4]5 ( 1 ) or Ag(Bi7S8)[S(AlCl3)3]2[AlCl4]2 ( 2 ) precipitated, respectively. 1 did not form in the absence of AuCl/PtCl2, suggesting an essential role of the metal cations. X-ray diffraction on single-crystals of 1 revealed a monoclinic crystal structure that contains (Bi4S4)4+ heterocubanes and [AlCl4]− tetrahedra as well as [BMIm]+ cations. The intercalation of the ionic liquid was confirmed via solid state NMR spectroscopy, revealing unusual coupling behavior. The crystal structure of 2 consists of (Bi7S8)5+ spiro-dicubanes, [S(AlCl3)3]2− tetrahedra triples, isolated [AlCl4]− tetrahedra, and heavily disordered silver(I) cations. No cation ordering took place in 2 upon slow cooling to 100 K. 相似文献