全文获取类型
收费全文 | 5243篇 |
免费 | 182篇 |
国内免费 | 37篇 |
专业分类
化学 | 3422篇 |
晶体学 | 18篇 |
力学 | 244篇 |
数学 | 858篇 |
物理学 | 920篇 |
出版年
2023年 | 22篇 |
2022年 | 56篇 |
2021年 | 85篇 |
2020年 | 72篇 |
2019年 | 82篇 |
2018年 | 70篇 |
2017年 | 70篇 |
2016年 | 148篇 |
2015年 | 132篇 |
2014年 | 171篇 |
2013年 | 289篇 |
2012年 | 350篇 |
2011年 | 439篇 |
2010年 | 237篇 |
2009年 | 240篇 |
2008年 | 307篇 |
2007年 | 334篇 |
2006年 | 336篇 |
2005年 | 309篇 |
2004年 | 241篇 |
2003年 | 237篇 |
2002年 | 217篇 |
2001年 | 76篇 |
2000年 | 81篇 |
1999年 | 59篇 |
1998年 | 71篇 |
1997年 | 72篇 |
1996年 | 68篇 |
1995年 | 51篇 |
1994年 | 55篇 |
1993年 | 46篇 |
1992年 | 37篇 |
1991年 | 28篇 |
1990年 | 29篇 |
1989年 | 22篇 |
1988年 | 25篇 |
1987年 | 17篇 |
1986年 | 13篇 |
1985年 | 32篇 |
1984年 | 25篇 |
1983年 | 14篇 |
1982年 | 20篇 |
1981年 | 14篇 |
1980年 | 20篇 |
1979年 | 26篇 |
1978年 | 18篇 |
1977年 | 13篇 |
1976年 | 14篇 |
1975年 | 13篇 |
1973年 | 12篇 |
排序方式: 共有5462条查询结果,搜索用时 203 毫秒
231.
Dr. Quentin Bonnin Tereza Edlová Dr. E. Daiann Sosa Carrizo Prof. Dr. Paul Fleurat-Lessard Dr. Stéphane Brandès Dr. Hélène Cattey Dr. Philippe Richard Prof. Dr. Pierre Le Gendre Dr. Adrien T. Normand 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(72):18175-18187
Cationic amidotitanocene complexes [Cp2Ti(NPhAr)][B(C6F5)4] (Cp=η5-C5H5; Ar=phenyl ( 1 a ), p-tolyl ( 1 b ), p-anisyl ( 1 c )) were isolated. The bonding situation was studied by DFT (Density Functional Theory) using EDA-NOCV (Energy Decomposition Analysis with Natural Orbitals for Chemical Valence). The polar Ti−N bond in 1 a–c features an unusual inversion of σ and π bond strengths responsible for the balance between stability and reactivity in these coordinatively unsaturated species. In solution, 1 a–c undergo photolytic Ti−N cleavage to release Ti(III) species and aminyl radicals ⋅ NPhAr. Reaction of 1 b with H3BNHMe2 results in fast homolytic Ti−N cleavage to give [Cp2Ti(H3BNHMe2)][B(C6F5)4] ( 3 ). 1 a–c are highly active precatalysts in olefin hydrogenation and silanes/amines cross-dehydrogenative coupling, whilst 3 efficiently catalyzes amine-borane dehydrogenation. The mechanism of olefin hydrogenation was studied by DFT and the cooperative H2 activation key step was disclosed using the Activation Strain Model (ASM). 相似文献
232.
Anaí Duarte Wilson Cunico Claudio M.P. Pereira Alex F.C. Flores Rogério A. Freitag Geonir M. Siqueira 《Ultrasonics sonochemistry》2010,17(2):281-283
An ultrasound-enhanced method has been developed for the synthesis of a variety of thioesters from benzoyl chlorides and 2-mercaptobenzoxa(thia)zoles. Applying this methodology, 14 compounds were synthesized in excellent yields. 相似文献
233.
Mi-Yeon Jang Xiao-Ping Song Mathy Froeyen Philippe Marlière Eveline Lescrinier Jef Rozenski Piet Herdewijn 《Chemistry & biology》2013,20(3):416-423
- Download : Download high-res image (116KB)
- Download : Download full-size image
234.
Dr. Debangshu Chaudhuri Dr. Eva Sigmund Annemarie Meyer Lisa Röck Philippe Klemm Sebastian Lautenschlager Agnes Schmid Shane R. Yost Prof. Dr. Troy Van Voorhis Dr. Sebastian Bange Prof. Dr. Sigurd Höger Prof. Dr. John M. Lupton 《Angewandte Chemie (International ed. in English)》2013,52(50):13449-13452
235.
Dr. Tran Quang Hung Dr. Ferial Terki Dr. Souleymane Kamara Mourad Dehbaoui Prof. Salam Charar Brajalal Sinha Prof. CheolGi Kim Dr. Philippe Gandit Il'ya A. Gural'skiy Dr. Gabor Molnar Dr. Lionel Salmon Dr. Helena J. Shepherd Dr. Azzedine Bousseksou 《Angewandte Chemie (International ed. in English)》2013,52(4):1058-1058
236.
Arbia Khemiri Bertrand Naudin Xavier Franck Philippe Chan Tchi Song Thierry Jouenne Pascal Cosette 《Analytical and bioanalytical chemistry》2013,405(30):9835-9842
In prokaryote organisms, N-glycosylation of proteins is often correlated to cell–cell recognition and extracellular events. Those glycoproteins are potential targets for infection control. To date, many surface-glycosylated proteins from bacterial pathogens have been described. However, N-linked Pseudomonas surface-associated glycoproteins remain underexplored. We report a combined enrichment and labeling strategy to identify major glycoproteins on the outside of microorganisms. More precisely, bacteria were exposed to a mix of biotinylated lectins able to bind with glycoproteins. The latter were then recovered by avidin beads, digested with trypsin, and submitted to mass spectrometry. The targeted mixture of glycoproteins was additionally deglycosylated in the presence of H2 18O to incorporate 18O during PNGase F treatment and were also analyzed using mass spectrometry. This approach allowed us to identify a few tens of potential N-glycoproteins, among which flagellin FliC was the most abundant. To detect the possible sites of FliC modifications, a de novo sequencing step was also performed to discriminate between spontaneous deamidation and N-glycan loss. This approach led to the proposal of three potential N-glycosylated sites on the primary sequence of FliC: N26, N69, and N439, with two of these three asparagines belonging to an N-X-(S/T) consensus sequence. These observations suggest that flagellin FliC is a heterogeneous protein mixture containing both O- and N-glycoforms. Figure
Analytical scenario developed for bacterial glycoprotein enrichment. This strategy includes three main steps: (1) exposure of Pseudomonas aeruginosa cells to a mixture of biotinylated lectins [wheat germ agglutinin (WGA) and concanavalin A (ConA)]; (2) enrichment of N-glycoproteins by elution with avidin beads; and (3) mass spectrometry (MS) identification and characterization of intact and deglycosylated peptides before and after H2 18O PNGase F enzymatic treatment, respectively 相似文献
237.
Irene C. Perez Caroline Le Guiner Weiyi Ni Jennifer Lyles Philippe Moullier Richard O. Snyder 《Analytical and bioanalytical chemistry》2013,405(30):9641-9653
Athletes who illicitly use drugs to enhance their athletic performance are at risk of being banned from sports competitions. Consequently, some athletes may seek new doping methods that they expect to be capable of circumventing detection. With advances in gene transfer vector design and therapeutic gene transfer, and demonstrations of safety and therapeutic benefit in humans, there is an increased probability of the pursuit of gene doping by athletes. In anticipation of the potential for gene doping, assays have been established to directly detect complementary DNA of genes that are top candidates for use in doping, as well as vector control elements. The development of molecular assays that are capable of exposing gene doping in sports can serve as a deterrent and may also identify athletes who have illicitly used gene transfer for performance enhancement. PCR-based methods to detect foreign DNA with high reliability, sensitivity, and specificity include TaqMan real-time PCR, nested PCR, and internal threshold control PCR. 相似文献
238.
Shuhai Lin Hongde Liu Basem Kanawati Liangfeng Liu Jiyang Dong Min Li Jiandong Huang Philippe Schmitt-Kopplin Zongwei Cai 《Analytical and bioanalytical chemistry》2013,405(15):5105-5117
In the wake of genomics, metabolomics characterizes the small molecular metabolites revealing the phenotypes induced by gene mutants. To address the metabolic signatures in the hippocampus of the amyloid-beta (Aβ) peptides produced in transgenic (Tg) CRND8 mice, high-field ion cyclotron resonance–Fourier transform mass spectrometry supported by LC-LTQ-Orbitrap was introduced to profile the extracted metabolites. More than 10,000 ions were detected in the mass profile for each sample. Subsequently, peak alignment and the 80 % rule followed by feature selection based on T score computation were performed. The putative identification was also conducted using the highly accurate masses with isotopic distribution by interfacing the MassTRIX database as well as MS/MS fragmentation generated in the LTQ-Orbitrap after chromatographic separation. Consequently, 58 differentiating masses were tentatively identified while up to 44 differentiating elemental compositions could not be biologically annotated in the databases. Nonetheless, of the putatively annotated masses, eicosanoids in arachidonic acid metabolism, fatty acid beta-oxidation disorders as well as disturbed glucose metabolism were highlighted as metabolic traits of Aβ toxicity in Tg CRND8 mice. Furthermore, a web-based bioinformatic tool was used for simulation of the metabolic pathways. As a result of the obtained metabolic signatures, the arachidonic acid metabolism dominates the metabolic perturbation in hippocampal tissues of Tg CRND8 mice compared to non-Tg littermates, indicating that Aβ toxicity functions neuroinflammation in hippocampal tissue and new theranostic opportunities might be offered by characterization of altered arachidonic acid metabolism for Alzheimer’s disease. 相似文献
239.
Manuel Alberto Flores‐Hidalgo Daniel Glossman‐Mitnik D. H. Galvan Diana Barraza‐Jimenez 《中国化学会会志》2013,60(8):1082-1091
Density Functional Theory employing hybrid and M06 functionals in combination with three different basis sets is used to calculate the ground state of a cage like (ZnO)12 nanocluster which has been consistently reported as the more stable cluster for its particular size. B3LYP and B3PW91 hybrid functionals combined with 6‐31+G*, Lanl2dz and SDD basis sets are employed to treat the ZnO molecular system. Alternatively, three M06 functionals in combination with three basis sets are employed in the nanostructure calculations. Results obtained by treating ZnO sodalite cage nanocluster with M06 functionals demonstrated comparable quality to results obtained with hybrid functionals. Within this study, efficient theoretical DFT methods with the widely known hybrid and the recently created M06 meta‐hybrid functionals are employed to study nanostructured ZnO. Our resulting parameters provide a fresh approach performance wise on the different theoretical methods to treat transition metal nanostructures, particularly, ZnO nanoclusters geometry and electronic structure. 相似文献
240.
Benoit Rigo Philippe Gautret Anne Legrand Samira El Ghammarti Daniel Couturier 《合成通讯》2013,43(18):2609-2615
Starting from the readily available N,O-bis trimethylsilyl pyroglutamate, an easy high yield one pot synthesis of ketone 1 was described. 相似文献