全文获取类型
收费全文 | 2106篇 |
免费 | 125篇 |
国内免费 | 13篇 |
专业分类
化学 | 1572篇 |
晶体学 | 10篇 |
力学 | 65篇 |
数学 | 321篇 |
物理学 | 276篇 |
出版年
2024年 | 5篇 |
2023年 | 15篇 |
2022年 | 23篇 |
2021年 | 41篇 |
2020年 | 31篇 |
2019年 | 41篇 |
2018年 | 33篇 |
2017年 | 41篇 |
2016年 | 88篇 |
2015年 | 55篇 |
2014年 | 110篇 |
2013年 | 132篇 |
2012年 | 163篇 |
2011年 | 185篇 |
2010年 | 110篇 |
2009年 | 111篇 |
2008年 | 144篇 |
2007年 | 136篇 |
2006年 | 121篇 |
2005年 | 113篇 |
2004年 | 115篇 |
2003年 | 81篇 |
2002年 | 72篇 |
2001年 | 35篇 |
2000年 | 32篇 |
1999年 | 22篇 |
1998年 | 22篇 |
1997年 | 20篇 |
1996年 | 17篇 |
1995年 | 11篇 |
1994年 | 12篇 |
1993年 | 6篇 |
1992年 | 7篇 |
1991年 | 8篇 |
1989年 | 3篇 |
1988年 | 5篇 |
1987年 | 6篇 |
1986年 | 4篇 |
1985年 | 18篇 |
1984年 | 6篇 |
1983年 | 3篇 |
1982年 | 4篇 |
1981年 | 6篇 |
1980年 | 4篇 |
1979年 | 6篇 |
1977年 | 4篇 |
1975年 | 3篇 |
1973年 | 2篇 |
1971年 | 2篇 |
1958年 | 2篇 |
排序方式: 共有2244条查询结果,搜索用时 15 毫秒
101.
A General Method for Preparing Bridged Organosilanes with Pendant Functional Groups and Functional Mesoporous Organosilicas
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Prof. Jana Hodačová Dr. Guillaume Toquer Dr. Xavier Cattoën Dr. Michel Wong Chi Man 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(33):10371-10382
New organosilica precursors containing two triethoxysilyl groups suitable for the organosilica material formation through the sol‐gel process were designed and synthesised. These precursors display alkyne or azide groups for attaching targeted functional groups by copper‐catalysed azide–alkyne cycloaddition (CuAAC) and can be used for the preparation of functional organosilicas following two strategies: 1) the functional group is first appended by CuAAC under anhydrous conditions, then the functional material is prepared by the sol‐gel process; 2) the precursor is first subjected to the sol‐gel process, producing porous, clickable bridged silsesquioxanes or periodic mesoporous organosilicas (PMOs), then the desired functional groups are attached by means of CuAAC. Herein, we show the feasibility of both approaches. A series of bridged bis(triethoxysilane)s with different pending organic moieties was prepared, demonstrating the compatibility of the first approach with many functional groups. In particular, we demonstrate that organic functional molecules bearing only one derivatisation site can be used to produce bridged organosilanes and bridged silsesquioxanes. In the second approach, clickable PMOs and porous bridged silsesquioxanes were prepared from the alkyne‐ or azide‐containing precursors, and thereafter, functionalised with complementary model azide‐ or alkyne‐containing molecules. These results confirmed the potential of this approach as a general methodology for preparing functional organosilicas with high loadings of functional groups. Both approaches give rise to a wide range of new functional organosilica materials. 相似文献
102.
Craig J. Richmond Roc Matheu Dr. Albert Poater Dr. Laura Falivene Dr. Jordi Benet‐Buchholz Dr. Xavier Sala Prof. Luigi Cavallo Prof. Antoni Llobet 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(52):17282-17286
Extremely slow and extremely fast new water oxidation catalysts based on the Ru–bda (bda=2,2′‐bipyridine‐6,6′‐dicarboxylate) systems are reported with turnover frequencies in the range of 1 and 900 cycles s?1, respectively. Detailed analyses of the main factors involved in the water oxidation reaction have been carried out and are based on a combination of reactivity tests, electrochemical experiments, and DFT calculations. These analyses give a convergent interpretation that generates a solid understanding of the main factors involved in the water oxidation reaction, which in turn allows the design of catalysts with very low energy barriers in all the steps involved in the water oxidation catalytic cycle. We show that for this type of system π‐stacking interactions are the key factors that influence reactivity and by adequately controlling them we can generate exceptionally fast water oxidation catalysts. 相似文献
103.
Multiple Stable Conformations Account for Reversible Concentration‐Dependent Oligomerization and Autoinhibition of a Metamorphic Metallopeptidase
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)
Mar López‐Pelegrín Dr. Núria Cerdà‐Costa Dr. Anna Cintas‐Pedrola Fátima Herranz‐Trillo Dr. Pau Bernadó Dr. Juan R. Peinado Dr. Joan L. Arolas Prof. Dr. F. Xavier Gomis‐Rüth 《Angewandte Chemie (International ed. in English)》2014,53(40):10624-10630
Molecular plasticity controls enzymatic activity: the native fold of a protein in a given environment is normally unique and at a global free‐energy minimum. Some proteins, however, spontaneously undergo substantial fold switching to reversibly transit between defined conformers, the “metamorphic” proteins. Here, we present a minimal metamorphic, selective, and specific caseinolytic metallopeptidase, selecase, which reversibly transits between several different states of defined three‐dimensional structure, which are associated with loss of enzymatic activity due to autoinhibition. The latter is triggered by sequestering the competent conformation in incompetent but structured dimers, tetramers, and octamers. This system, which is compatible with a discrete multifunnel energy landscape, affords a switch that provides a reversible mechanism of control of catalytic activity unique in nature. 相似文献
104.
Xavier Cattoën Achraf Noureddine Jonas Croissant Nirmalya Moitra Kristýna Bürglová Jana Hodačová Olivia de los Cobos Martine Lejeune Fabrice Rossignol Delphine Toulemon Sylvie Bégin-Colin Benoît P. Pichon Laurence Raehm Jean-Olivier Durand Michel Wong Chi Man 《Journal of Sol-Gel Science and Technology》2014,70(2):245-253
The combination of the copper-catalyzed alkyne-azide cycloaddition (CuAAC) reaction with sol–gel processing enables the versatile preparation of sol–gel materials under different shapes with targeted functionalities through a diversity-oriented approach. In this account, the development of the CuAAC reaction under anhydrous conditions for the synthesis of sol–gel precursors and for the assembling of magnetic nanoparticles on self-assembled monolayers is related, as well as the use of the classical CuAAC methodologies for the functionalization of mesoporous silica nanoparticles and microdots arrays. Coupling CuAAC and Sol–Gel will result in simplified preparations of multifunctional materials with controlled morphologies. 相似文献
105.
Javier Mateos Francesco Rigodanza Alberto Vega‐Pealoza Andrea Sartorel Mirco Natali Tommaso Bortolato Giorgio Pelosi Xavier Company Marcella Bonchio Luca Dell'Amico 《Angewandte Chemie (International ed. in English)》2020,59(3):1302-1312
Twelve naphthochromenone photocatalysts (PCs) were synthesized on gram scale. They absorb across the UV/Vis range and feature an extremely wide redox window (up to 3.22 eV) that is accessible using simple visible light irradiation sources (CFL or LED). Their excited‐state redox potentials, PC*/PC.? (up to 1.65 V) and PC.+/PC* (up to ?1.77 V vs. SCE), are such that these novel PCs can engage in both oxidative and reductive quenching mechanisms with strong thermodynamic requirements. The potential of these bimodal PCs was benchmarked in synthetically relevant photocatalytic processes with extreme thermodynamic requirements. Their ability to efficiently catalyze mechanistically opposite oxidative/reductive photoreactions is a unique feature of these organic photocatalysts, thus representing a decisive advance towards generality, sustainability, and cost efficiency in photocatalysis. 相似文献
106.
Lucie Appy Anaïs Depaix Xavier Bantreil Frédéric Lamaty Suzanne Peyrottes 《Phosphorus, sulfur, and silicon and the related elements》2020,195(11):930-931
AbstractWe have developed original one-pot and protecting group-free approaches, which are also user-friendly and reliable, to synthesize nucleotides and derivatives starting from nucleoside 5’-monophosphates. Both methods present convenient set-up, i.e., non-dry solvents and reagents, substrates in their sodium or acid form, and commercially available and cheap phosphorus reagents as sodium and potassium salts. 相似文献
107.
Siphamandla B. Simelane Monisola I. Ikhile Xavier Y. Mbianda 《Phosphorus, sulfur, and silicon and the related elements》2020,195(7):556-561
AbstractA series of 2-substituted vinylidene-1,1-bisphosphonate esters and their acids were synthesized and tested in vitro for activity against Plasmodium falciparum and Trypanosoma brucei. For each compound, % parasite viability in treated wells was calculated relative to untreated controls for both P. falciparum and T. brucei. Fifty percentage inhibitory concentration (IC50) was also determined for the compounds. Chloroquine and pentamidine were used as positive control drug standards for activity against P. falciparum and T. brucei, respectively. The esters had better antiparasitic activity compared to their corresponding acids. Some of the compounds reduced % parasite viability to as low as 24.3% for P. falciparum and down to 0.602% for T. brucei. Tetraethyl-2-(o-tolyl)-ethene-1,1-bisphosphonate (3b) recorded the best IC50 against T. brucei which was 0.0345?µmol/mL. 相似文献
108.
Ania Alik Chafiaa Bouguechtouli Manon Julien Wolfgang Bermel Rania Ghouil Sophie Zinn‐Justin Francois‐Xavier Theillet 《Angewandte Chemie (International ed. in English)》2020,59(26):10411-10415
Abundant phosphorylation events control the activity of nuclear proteins involved in gene regulation and DNA repair. These occur mostly on disordered regions of proteins, which often contain multiple phosphosites. Comprehensive and quantitative monitoring of phosphorylation reactions is theoretically achievable at a residue‐specific level using 1H‐15N NMR spectroscopy, but is often limited by low signal‐to‐noise at pH>7 and T>293 K. We have developed an improved 13Cα‐13CO correlation NMR experiment that works equally at any pH or temperature, that is, also under conditions at which kinases are active. This allows us to obtain atomic‐resolution information in physiological conditions down to 25 μm . We demonstrate the potential of this approach by monitoring phosphorylation reactions, in the presence of purified kinases or in cell extracts, on a range of previously problematic targets, namely Mdm2, BRCA2, and Oct4. 相似文献
109.
Contamination of the biosphere by heavy metals has been rising, due to accelerated anthropogenic activities, and is nowadays, a matter of serious global concern. Removal of such inorganic pollutants from aquatic environments via biological processes has earned great popularity, for its cost-effectiveness and high efficiency, compared to conventional physicochemical methods. Among candidate organisms, microalgae offer several competitive advantages; phycoremediation has even been claimed as the next generation of wastewater treatment technologies. Furthermore, integration of microalgae-mediated wastewater treatment and bioenergy production adds favorably to the economic feasibility of the former process—with energy security coming along with environmental sustainability. However, poor biomass productivity under abiotic stress conditions has hindered the large-scale deployment of microalgae. Recent advances encompassing molecular tools for genome editing, together with the advent of multiomics technologies and computational approaches, have permitted the design of tailor-made microalgal cell factories, which encompass multiple beneficial traits, while circumventing those associated with the bioaccumulation of unfavorable chemicals. Previous studies unfolded several routes through which genetic engineering-mediated improvements appear feasible (encompassing sequestration/uptake capacity and specificity for heavy metals); they can be categorized as metal transportation, chelation, or biotransformation, with regulation of metal- and oxidative stress response, as well as cell surface engineering playing a crucial role therein. This review covers the state-of-the-art metal stress mitigation mechanisms prevalent in microalgae, and discusses putative and tested metabolic engineering approaches, aimed at further improvement of those biological processes. Finally, current research gaps and future prospects arising from use of transgenic microalgae for heavy metal phycoremediation are reviewed. 相似文献
110.
Adrián Schwarzenberg Farid Ichou Richard B. Cole Xavier Machuron‐Mandard Christophe Junot Denis Lesage Jean‐Claude Tabet 《Journal of mass spectrometry : JMS》2013,48(5):576-586
Organophosphorus compounds have played important roles as pesticides, chemical warfare agents and extractors of radioactive material. Structural elucidation of phosphonates poses a particular challenge because their initial forms can be hydrolyzed, thus, degradation products may predominate in samples acquired in the field. The analysis of non‐volatile organophosphorus compounds and their degradation products is possible using electrospray tandem mass spectrometry ESI‐MS/MS. Here, we present a generic strategy that allows the unambiguous identification of substituents for two families of organophosphorus compounds: the phosphonates and phosphates. General fragmentation rules were deduced based on the study of decomposition pathways of 55 organophosphorus esters, including examples found in the literature. Multistage MS (MSn) experiments at high resolution in a hybrid mass spectrometer provide accurate mass measurements, whereas collision‐induced dissociation experiments in a triple quadrupole give access to small fragment ions. The creation of a specific nomenclature for each possible structure of organophosphorus compound, depending on the alkyl side chain linked to the oxygen, was achieved by applying these fragmentation rules. This led to the creation of an ‘identification tree’ based upon the unique consecutive decomposition pathways uncovered for each individual compound. Hence, seven structural motifs were created that orient an unequivocal identification using the ‘identification tree’. Despite the similar structures of the ensemble of phosphate and phosphonate esters, distinct identifications based upon characteristic neutral losses and diagnostic fragment ions were possible in all cases. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献