全文获取类型
收费全文 | 789篇 |
免费 | 27篇 |
国内免费 | 2篇 |
专业分类
化学 | 417篇 |
晶体学 | 1篇 |
力学 | 12篇 |
数学 | 112篇 |
物理学 | 276篇 |
出版年
2023年 | 8篇 |
2021年 | 15篇 |
2020年 | 20篇 |
2019年 | 11篇 |
2018年 | 29篇 |
2017年 | 17篇 |
2016年 | 32篇 |
2015年 | 30篇 |
2014年 | 29篇 |
2013年 | 53篇 |
2012年 | 50篇 |
2011年 | 49篇 |
2010年 | 30篇 |
2009年 | 37篇 |
2008年 | 44篇 |
2007年 | 37篇 |
2006年 | 25篇 |
2005年 | 28篇 |
2004年 | 23篇 |
2003年 | 14篇 |
2002年 | 9篇 |
2001年 | 5篇 |
2000年 | 8篇 |
1999年 | 11篇 |
1998年 | 12篇 |
1997年 | 6篇 |
1996年 | 10篇 |
1995年 | 6篇 |
1994年 | 11篇 |
1993年 | 5篇 |
1992年 | 11篇 |
1991年 | 6篇 |
1990年 | 7篇 |
1989年 | 13篇 |
1988年 | 12篇 |
1987年 | 7篇 |
1986年 | 6篇 |
1985年 | 5篇 |
1984年 | 7篇 |
1983年 | 6篇 |
1982年 | 6篇 |
1981年 | 13篇 |
1980年 | 7篇 |
1978年 | 3篇 |
1976年 | 3篇 |
1975年 | 4篇 |
1974年 | 4篇 |
1973年 | 5篇 |
1969年 | 4篇 |
1961年 | 3篇 |
排序方式: 共有818条查询结果,搜索用时 390 毫秒
71.
High‐throughput workflow for identification of phosphorylated peptides by LC‐MALDI‐TOF/TOF‐MS coupled to in situ enrichment on MALDI plates functionalized by ion landing 下载免费PDF全文
Lukáš Krásný Petr Pompach Marcela Strnadová Radovan Hynek Karel Vališ Vladimír Havlíček Petr Novák Michael Volný 《Journal of mass spectrometry : JMS》2015,50(6):802-811
We report an MS‐based workflow for identification of phosphorylated peptides from trypsinized protein mixtures and cell lysates that is suitable for high‐throughput sample analysis. The workflow is based on an in situ enrichment on matrix‐assisted laser desorption/ionization (MALDI) plates that were functionalized by TiO2 using automated ion landing apparatus that can operate unsupervised. The MALDI plate can be functionalized by TiO2 into any array of predefined geometry (here, 96 positions for samples and 24 for mass calibration standards) made compatible with a standard MALDI spotter and coupled with high‐performance liquid chromatography. The in situ MALDI plate enrichment was compared with a standard precolumn‐based separation and achieved comparable or better results than the standard method. The performance of this new workflow was demonstrated on a model mixture of proteins as well as on Jurkat cells lysates. The method showed improved signal‐to‐noise ratio in a single MS spectrum, which resulted in better identification by MS/MS and a subsequent database search. Using the workflow, we also found specific phosphorylations in Jurkat cells that were nonspecifically activated by phorbol 12‐myristate 13‐acetate. These phosphorylations concerned the mitogen‐activated protein kinase/extracellular signal‐regulated kinase signaling pathway and its targets and were in agreement with the current knowledge of this signaling cascade. Control sample of non‐activated cells was devoid of these phosphorylations. Overall, the presented analytical workflow is able to detect dynamic phosphorylation events in minimally processed mammalian cells while using only a short high‐performance liquid chromatography gradient. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
72.
O. A. Luk´yanov G. V. Pokhvisneva T. V. Ternikova G. A. Smirnov 《Russian Chemical Bulletin》2015,64(5):1062-1064
Chlorides and anhydrides of carboxylic (including dicarboxylic) acids react with salts of 1-methoxy-3-methyl-1-triazene 2-oxides to give the corresponding 3-acyl-1-methoxy-3-methyl-1-triazene 2-oxides. 相似文献
73.
Lukáš Grajciar 《Journal of computational chemistry》2015,36(20):1521-1535
A new low‐memory modification of the density fitting approximation based on a combination of a continuous fast multipole method (CFMM) and a preconditioned conjugate gradient solver is presented. Iterative conjugate gradient solver uses preconditioners formed from blocks of the Coulomb metric matrix that decrease the number of iterations needed for convergence by up to one order of magnitude. The matrix‐vector products needed within the iterative algorithm are calculated using CFMM, which evaluates them with the linear scaling memory requirements only. Compared with the standard density fitting implementation, up to 15‐fold reduction of the memory requirements is achieved for the most efficient preconditioner at a cost of only 25% increase in computational time. The potential of the method is demonstrated by performing density functional theory calculations for zeolite fragment with 2592 atoms and 121,248 auxiliary basis functions on a single 12‐core CPU workstation. © 2015 Wiley Periodicals, Inc. 相似文献
74.
Single‐Crystal‐to‐Single‐Crystal Transition in an Enantiopure [7]Helquat Salt: The First Observation of a Reversible Phase Transition in a Helicene‐Like Compound 下载免费PDF全文
Dr. Naba K. Nath Lukáš Severa Dr. Roman A. Kunetskiy Prof. Ivana Císařová Prof. Michal Fulem Prof. Květoslav Růžička Dr. Dušan Koval Dr. Václav Kašička Dr. Filip Teplý Prof. Panče Naumov 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(39):13508-13512
Here it is reported that crystals of an enantiopure [7]helquat salt undergo reversible thermal solid–solid phase transition at 404 K. Differential scanning calorimetry (DSC), capillary electrophoresis (CE), and X‐ray diffraction analysis were used to unravel the mechanistic details of this process. The single‐crystal‐to‐single‐crystal course enabled direct monitoring of the structural changes by in situ variable‐temperature X‐ray diffraction, thus providing the first direct evidence of a solid phase transition in a helicene‐like compound. 相似文献
75.
76.
Prashar D Cui D Bandyopadhyay D Luk YY 《Langmuir : the ACS journal of surfaces and colloids》2011,27(21):13091-13096
This work describes a general approach for preventing protein aggregation and surface adsorption by modifying proteins with β-cyclodextrins (βCD) via an efficient water-driven ligation. As compared to native unmodified proteins, the cyclodextrin-modified proteins (lysozyme and RNase A) exhibit significant reduction in aggregation, surface adsorption and increase in thermal stability. These results reveal a new chemistry for preventing protein aggregation and surface adsorption that is likely of different mechanisms than that by modifying proteins with poly(ethylene glycol). 相似文献
77.
Joy A Cohen DM Luk A Anim-Danso E Chen C Kohn J 《Langmuir : the ACS journal of surfaces and colloids》2011,27(5):1891-1899
A focused library of methacrylate terpolymers was synthesized to explore the effects of varying surface chemistry and adhesive peptide ligands on cell function. The chemical diversity of methacrylate monomers enabled construction of a library of polymers in which one can systematically vary the chemical composition to achieve a wide range of contact angle, Young's modulus, and T(g) values. Furthermore, the materials were designed to allow surface immobilization of bioactive peptides. We then examined the effects of these material compositions on protein adsorption and cell attachment, proliferation, and differentiation. We observed that chemical composition of the polymers was an important determinant for NIH 3T3 cell attachment and proliferation, as well as human mesenchymal stem cell differentiation, and correlated directly with the ability of the polymers to adsorb proteins that mediate cell adhesion. Importantly, functionalization of the methacrylate terpolymer library with an adhesive GRGDS peptide normalized cellular responses. RGD-functionalized polymers uniformly exhibited robust attachment, proliferation, and differentiation irrespective of the underlying substrate chemistry. These studies provide a library-based approach to rapidly explore the biological functionality of biomaterials with a wide range of compositions and highlight the importance of cell and protein cell adhesion in predicting their performance. 相似文献
78.
In our laboratory, we have been studying the reductive processes that occur during matrix-assisted laser desorption/ionization (MALDI) experiments. Recently, we have finished an analysis of the DHB matrix effect on the azo group in cyclic peptides. However, deep understanding of disulfide bond behaviour during a mass spectrometry (MS) experiment is much more important in proteomics as its reduction can cause serious errors in protein spectra interpretation. Therefore, we have focused on intra- and intermolecular disulfide bonds as well as disulfide bonds connecting cysteine and 2-thio-5-nitrobenzoic acid (TNB, Ellman's reagent modification) in model peptides during MALDI MS measurements. While the reduction was not observed for intra- and intermolecular cysteine-cysteine disulfide bonds, the disulfide connection between cysteine and TNB was always affected. It was proved that TNB and Ellman's reagent can act as a matrix itself. The results obtained enabled us to propose a reaction mechanism model which is able to describe the phenomena observed during the desorption/ionization process of disulfide-containing molecules. 相似文献
79.
Fiala R Spacková N Foldynová-Trantírková S Sponer J Sklenár V Trantírek L 《Journal of the American Chemical Society》2011,133(35):13790-13793
In this work, a novel NMR method for the identification of preferential coordination sites between physiologically relevant counterions and nucleic acid bases is demonstrated. In this approach, the NMR cross-correlated relaxation rates between the aromatic carbon chemical shift anisotropy and the proton-carbon dipolar interaction are monitored as a function of increasing Na(+), K(+), and Mg(2+) concentrations. Increasing the counterion concentration modulates the residence times of the counterions at specific sites around the nucleic acid bases. It is demonstrated that the modulation of the counterion concentration leads to sizable variations of the cross-correlated relaxation rates, which can be used to probe the site-specific counterion coordination. In parallel, the very same measurements report on the rotational tumbling of DNA, which, as shown here, depends on the nature of the ion and its concentration. This methodology is highly sensitive and easily implemented. The method can be used to cross-validate and/or complement direct but artifact-prone experimental techniques such as X-ray diffraction, NMR analysis with substitutionary ions, and molecular dynamics simulations. The feasibility of this technique is demonstrated on the extraordinarily stable DNA mini-hairpin d(GCGAAGC). 相似文献
80.
Lísa M Netušilová K Franěk L Dvořáková H Vrkoslav V Holčapek M 《Journal of chromatography. A》2011,1218(42):7499-7510
Fatty acid (FA) and triacylglycerol (TG) composition of natural oils and fats intake in the diet has a strong influence on the human health and chronic diseases. In this work, non-aqueous reversed-phase (NARP) and silver-ion high-performance liquid chromatography with atmospheric pressure chemical ionization mass spectrometry detection and gas chromatography with flame-ionization detection (GC/FID) and mass spectrometry detection are used for the characterization of FA and TG composition in complex samples of animal fats from fallow deer, red deer, sheep, moufflon, wild boar, cock, duck and rabbit. The FA composition of samples is determined based on the GC/FID analysis of FA methyl esters. In total, 81 FAs of different acyl chain length, double bond (DB) number, branched/linear, cis-/trans- and DB positional isomers are identified. TGs in animal fats contain mainly monounsaturated and saturated FAs. High amounts of branched and trans-FAs are observed in the samples of ruminants. In NARP mode, individual TG species are separated including the separation of trans- and branched TGs. Silver-ion mode provides the separation of TG regioisomers, which enables the determination of their ratios. Great differences in the preference of unsaturated and saturated FAs in the sn-2 position on the glycerol skeleton are observed among individual animal fats. Unsaturated FAs are preferentially occupied in the sn-2 position in all animal samples except for wild boar with the strong preference of saturated FAs in the sn-2 position. 相似文献