全文获取类型
收费全文 | 1081篇 |
免费 | 58篇 |
国内免费 | 5篇 |
专业分类
化学 | 888篇 |
晶体学 | 1篇 |
力学 | 11篇 |
数学 | 131篇 |
物理学 | 113篇 |
出版年
2023年 | 8篇 |
2022年 | 14篇 |
2021年 | 36篇 |
2020年 | 32篇 |
2019年 | 32篇 |
2018年 | 24篇 |
2017年 | 23篇 |
2016年 | 50篇 |
2015年 | 36篇 |
2014年 | 32篇 |
2013年 | 66篇 |
2012年 | 84篇 |
2011年 | 104篇 |
2010年 | 48篇 |
2009年 | 39篇 |
2008年 | 84篇 |
2007年 | 79篇 |
2006年 | 60篇 |
2005年 | 54篇 |
2004年 | 47篇 |
2003年 | 39篇 |
2002年 | 31篇 |
2001年 | 9篇 |
2000年 | 17篇 |
1999年 | 9篇 |
1998年 | 9篇 |
1997年 | 4篇 |
1996年 | 12篇 |
1995年 | 11篇 |
1994年 | 8篇 |
1993年 | 3篇 |
1992年 | 7篇 |
1991年 | 2篇 |
1990年 | 2篇 |
1989年 | 6篇 |
1988年 | 2篇 |
1987年 | 2篇 |
1986年 | 4篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1935年 | 1篇 |
1934年 | 2篇 |
排序方式: 共有1144条查询结果,搜索用时 31 毫秒
91.
Ravi P. Agarwal Victoria Otero-Espinar Kanishka Perera 《Journal of Mathematical Analysis and Applications》2007,331(2):1263-1274
The aim of this paper is to employ variational techniques and critical point theory to prove some sufficient conditions for the existence of multiple positive solutions to a nonlinear second order dynamic equation with homogeneous Dirichlet boundary conditions. 相似文献
92.
Julia C.C. Tsai Victoria C.P. Chen M. Bruce Beck Jining Chen 《Annals of Operations Research》2004,132(1-4):207-221
In this paper, a decision-making framework (DMF) based on stochastic dynamic programming (SDP) is presented for a wastewater treatment system, consisting of a liquid treatment line with eleven levels and a solid treatment line with six levels (Chen and Beck, 1997). A continuous-state SDP solution approach based on the OA/MARS method (Chen, Ruppert, and Shoemaker, 1999) is employed, which provides an efficient method for representing a wide range of possible influent conditions. The DMF is used to evaluate current and emerging technologies for the multi-level liquid and solid lines of the wastewater treatment system. At each level, one technology unit is selected out of a set of options which includes the empty unit. The DMF provides a comparison on possible technologies for screening which types of technologies may best be further developed in order for an urban wastewater infrastructure to be judged progressively more sustainable. The results indicate that one or a pair of technologies are dominant in each level. The cheap, lower-technology unit processes receive a mixed review. Some of them are selected as the most promising technology units while the others are not considered as good candidates. 相似文献
93.
94.
Olivia Schimming Dr. Victoria L. Challinor Dr. Nicholas J. Tobias Dr. Hélène Adihou Peter Grün Laura Pöschel Dr. Christian Richter Prof. Dr. Harald Schwalbe Prof. Dr. Helge B. Bode 《Angewandte Chemie (International ed. in English)》2015,54(43):12702-12705
Pyrrolizidine alkaloids (PAs) are widespread plant natural products with potent toxicity and bioactivity. Herein, the identification of bacterial PAs from entomopathogenic bacteria using differential analysis by 2D NMR spectroscopy (DANS) and mass spectrometry is described. Their biosynthesis was elucidated to involve a non‐ribosomal peptide synthetase. The occurrence of these biosynthesis gene clusters in Gram‐negative and Gram‐positive bacteria indicates an important biological function in bacteria. 相似文献
95.
Dynamics of Fluorescent Dyes Attached to G‐Quadruplex DNA and their Effect on FRET Experiments
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)
Siri Søndergaard Dr. Mikayel Aznauryan Emil K. Haustrup Prof. Birgit Schiøtt Prof. Victoria Birkedal Prof. Ben Corry 《Chemphyschem》2015,16(12):2562-2570
FRET spectroscopy is a promising approach for investigating the dynamics of G‐quadruplex DNA folds and improving the targeting of G‐quadruplexes by potential anticancer compounds. To better interpret such experiments, classical and replica‐exchange molecular dynamics simulations and fluorescence‐lifetime measurements are used to understand the behavior of a range of Cy3‐based dyes attached to the 3′ end of G‐quadruplex DNA. The simulations revealed that the dyes interact extensively with the G‐quadruplex. Identification of preferred dye positions relative to the G‐quadruplex in the simulations allows the impact of dye–DNA interactions on FRET results to be determined. All the dyes show significant deviations from the common approximation of being freely rotating and not interacting with the host, but one of the Cy3 dye analogues is slightly closer to this case. 相似文献
96.
Sunlight‐Driven Formation and Dissociation of a Dynamic Mixed‐Valence Thallium(III)/Thallium(I) Porphyrin Complex
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)
Victoria Ndoyom Luca Fusaro Vincent Dorcet Bernard Boitrel Stéphane Le Gac 《Angewandte Chemie (International ed. in English)》2015,54(12):3806-3811
Inspired by a Newton’s cradle device and interested in the development of redox‐controllable bimetallic molecular switches, a mixed‐valence thallium(III)/thallium(I) bis‐strap porphyrin complex, with TlIII bound out of the plane of the N core and TlI hung to a strap on the opposite side, was formed by the addition of TlOAc to the free base and exposure to indirect sunlight. In this process, oxygen photosensitization by the porphyrin allows the oxidation of TlI to TlIII. The bimetallic complex is dynamic as the metals exchange their positions symmetrically to the porphyrin plane with TlIII funneling through the macrocycle. Further exposure of the complex to direct sunlight leads to thallium dissociation and to total recovery of the free base. Hence, the porphyrin plays a key role at all stages of the cycle of the complex: It hosts two metal ions, and by absorbing light, it allows the formation and dissociation of TlIII. These results constitute the basis for the further design of innovative light‐driven bimetallic molecular devices. 相似文献
97.
98.
Christian Wenz Coral Barbas Ángeles López‐Gonzálvez Antonia Garcia Fernando Benavente Victoria Sanz‐Nebot Tim Blanc Gordon Freckleton Philip Britz‐McKibbin Meera Shanmuganathan Francois de l′Escaille Johann Far Rob Haselberg Sean Huang Carolin Huhn Martin Pattky David Michels Si Mou Feng Yang Christian Neusuess Nora Tromsdorf Edward E.K. Baidoo Jay D. Keasling SungAe Suhr Park 《Journal of separation science》2015,38(18):NA-NA
A collaborative study on the robustness and portability of a capillary electrophoresis‐mass spectrometry method for peptide mapping was performed by an international team, consisting of 13 independent laboratories from academia and industry. All participants used the same batch of samples, reagents and coated capillaries to run their assays, whereas they utilized the capillary electrophoresis‐mass spectrometry equipment available in their laboratories. The equipment used varied in model, type and instrument manufacturer. Furthermore, different types of sheath‐flow capillary electrophoresis–mass spectrometry interfaces were used. Migration time, peak height and peak area of ten representative target peptides of trypsin‐digested bovine serum albumin were determined by every laboratory on two consecutive days. The data were critically evaluated to identify outliers and final values for means, repeatability (precision within a laboratory) and reproducibility (precision between laboratories) were established. For relative migration time the repeatability was between 0.05 and 0.18% RSD and the reproducibility between 0.14 and 1.3% RSD. For relative peak area repeatability and reproducibility values obtained were 3–12 and 9–29% RSD, respectively. These results demonstrate that capillary electrophoresis‐mass spectrometry is robust enough to allow a method transfer across multiple laboratories and should promote a more widespread use of peptide mapping and other capillary electrophoresis‐mass spectrometry applications in biopharmaceutical analysis and related fields. 相似文献
99.
Chun Y. Chow Hélène Bolvin Victoria E. Campbell Régis Guillot Jeff W. Kampf Wolfgang Wernsdorfer Frédéric Gendron Jochen Autschbach Vincent L. Pecoraro Talal Mallah 《Chemical science》2015,6(7):4148-4159
We report here the synthesis and the investigation of the magnetic properties of a series of binuclear lanthanide complexes belonging to the metallacrown family. The isostructural complexes have a core structure with the general formula [Ga4Ln2(shi3–)4(Hshi2–)2(H2shi–)2(C5H5N)4(CH3OH)x(H2O)x]·xC5H5N·xCH3OH·xH2O (where H3shi = salicylhydroxamic acid and Ln = GdIII1; TbIII2; DyIII3; ErIII4; YIII5; YIII0.9DyIII0.16). Apart from the Er-containing complex, all complexes exhibit an antiferromagnetic exchange coupling leading to a diamagnetic ground state. Magnetic studies, below 2 K, on a single crystal of 3 using a micro-squid array reveal an opening of the magnetic hysteresis cycle at zero field. The dynamic susceptibility studies of 3 and of the diluted DyY 6 complexes reveal the presence of two relaxation processes for 3 that are due to the excited ferromagnetic state and to the uncoupled DyIII ions. The antiferromagnetic coupling in 3 was shown to be mainly due to an exchange mechanism, which accounts for about 2/3 of the energy gap between the antiferro- and the ferromagnetic states. The overlap integrals between the Natural Spin Orbitals (NSOs) of the mononuclear fragments, which are related to the magnitude of the antiferromagnetic exchange, are one order of magnitude larger for the Dy2 than for the Er2 complex. 相似文献
100.
Victoria L. Challinor Ryne C. Johnston Paul V. Bernhardt Reginald P. Lehmann Elizabeth H. Krenske James J. De Voss 《Chemical science》2015,6(10):5740-5745
A series of novel sesterterpenes (2–6) have been isolated from the roots of Aletris farinosa and structurally characterized by MS, NMR, and X-ray crystallography in conjunction with computational modeling. Their structures provide new insights into the mechanisms of sesterterpene biosynthesis. Specifically, we propose with support from density functional theory computations that the configuration at a single stereocenter determines the fate of a key tetracyclic carbocationic intermediate, derived from an oxidogeranylfarnesol precursor. Whereas one epimer of the carbocation undergoes H+ elimination to give 6, the other undergoes a spectacular cascade of seven 1,2-methyl and hydride migrations leading to the previously unreported carbon skeleton of 5. Theoretical calculations suggest that the cascade is triggered by substrate preorganization in the enzyme active site. 相似文献