全文获取类型
收费全文 | 9263篇 |
免费 | 770篇 |
国内免费 | 493篇 |
专业分类
化学 | 5929篇 |
晶体学 | 106篇 |
力学 | 426篇 |
综合类 | 48篇 |
数学 | 1314篇 |
物理学 | 2703篇 |
出版年
2023年 | 121篇 |
2022年 | 272篇 |
2021年 | 289篇 |
2020年 | 309篇 |
2019年 | 293篇 |
2018年 | 283篇 |
2017年 | 252篇 |
2016年 | 364篇 |
2015年 | 354篇 |
2014年 | 410篇 |
2013年 | 700篇 |
2012年 | 678篇 |
2011年 | 702篇 |
2010年 | 454篇 |
2009年 | 391篇 |
2008年 | 460篇 |
2007年 | 385篇 |
2006年 | 376篇 |
2005年 | 322篇 |
2004年 | 252篇 |
2003年 | 249篇 |
2002年 | 227篇 |
2001年 | 202篇 |
2000年 | 183篇 |
1999年 | 155篇 |
1998年 | 90篇 |
1997年 | 89篇 |
1996年 | 96篇 |
1995年 | 68篇 |
1994年 | 102篇 |
1993年 | 76篇 |
1992年 | 91篇 |
1991年 | 75篇 |
1990年 | 60篇 |
1989年 | 53篇 |
1988年 | 54篇 |
1987年 | 48篇 |
1986年 | 46篇 |
1985年 | 66篇 |
1984年 | 69篇 |
1983年 | 43篇 |
1982年 | 70篇 |
1981年 | 57篇 |
1980年 | 59篇 |
1979年 | 53篇 |
1978年 | 58篇 |
1977年 | 55篇 |
1976年 | 47篇 |
1975年 | 38篇 |
1973年 | 39篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Włodzimierz Makulski Adam Tulewicz Andrzej Leś 《Magnetic resonance in chemistry : MRC》2014,52(3):106-110
In a recent 17O NMR spectra of liquid sulfur trioxide, several unexpected peaks appeared with the temperature‐dependent integrated peak ratio. In order to interpret NMR spectra and assign peaks to possible molecular structures, the theoretical quantum mechanical density functional theory and Møller–Plesset second‐order perturbation theory calculations were performed. It is suggested that in the liquid sulfur trioxide, apart from monomeric SO3, a significant amount of (SO3)3 cyclic trimers should appear. No theoretical data support hypothesis on (SO3)2 dimers formation. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
992.
Dr. Mariane Le Fur Nicholas J. Rotile Carlos Correcher Dr. Veronica Clavijo Jordan Alana W. Ross Prof. Ciprian Catana Prof. Peter Caravan 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(4):1490-1494
Gadolinium-based contrast agents (GBCAs) are used to provide diagnostic information in clinical magnetic resonance (MR) examinations. Gadolinium (Gd) has been detected in the brain, bone and skin of patients, months and years following GBCA administration, raising concerns about long term toxicity. Despite increased scrutiny, the concentration, chemical form and fate of the retained gadolinium species remain unknown. Importantly, the whole body biodistribution and organ clearance of GBCAs is poorly understood in humans. Gadolinium lacks suitable isotopes for nuclear imaging. We demonstrate that the yttrium-86 isotope can be used as a gadolinium surrogate. We show that Gd and their analogous Y complexes have similar properties both in solution and in vivo, and that yttrium-86 PET can be used to track the biodistribution of GBCAs over a two-day period. 相似文献
993.
Henry W. Orton Dr. Jan Stanek Dr. Tobias Schubeis Dylan Foucaudeau Claire Ollier Dr. Adrian W. Draney Dr. Tanguy Le Marchand Dr. Diane Cala-De Paepe Prof. Dr. Isabella C. Felli Prof. Dr. Roberta Pierattelli Prof. Dr. Sebastian Hiller Dr. Wolfgang Bermel Dr. Guido Pintacuda 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(6):2400-2405
994.
Johannes C. B. Dietschreit Annika Wagner T. Anh Le Philipp Klein Prof. Dr. Hermann Schindelin Prof. Dr. Till Opatz Prof. Dr. Bernd Engels Prof. Dr. Ute A. Hellmich Prof. Dr. Christian Ochsenfeld 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(31):12769-12773
The absence of fluorine from most biomolecules renders it an excellent probe for NMR spectroscopy to monitor inhibitor–protein interactions. However, predicting the binding mode of a fluorinated ligand from a chemical shift (or vice versa) has been challenging due to the high electron density of the fluorine atom. Nonetheless, reliable 19F chemical-shift predictions to deduce ligand-binding modes hold great potential for in silico drug design. Herein, we present a systematic QM/MM study to predict the 19F NMR chemical shifts of a covalently bound fluorinated inhibitor to the essential oxidoreductase tryparedoxin (Tpx) from African trypanosomes, the causative agent of African sleeping sickness. We include many protein–inhibitor conformations as well as monomeric and dimeric inhibitor–protein complexes, thus rendering it the largest computational study on chemical shifts of 19F nuclei in a biological context to date. Our predicted shifts agree well with those obtained experimentally and pave the way for future work in this area. 相似文献
995.
Jing Cao Wenjie Ma Kangjie Lyu Lin Zhuang Hengjiang Cong Hexiang Deng 《Chemical science》2020,11(15):3978
We report the design and synthesis of a titanium catecholate framework, MOF-217, comprised of 2,4,6-tri(3,4-dihydroxyphenyl)-1,3,5-triazine (TDHT) and isolated TiO6 clusters, with 2-fold interpenetrated srs topology. The dynamics of the organic linker, breaking the C3h symmetry, allowed for reversible twist and sliding between interpenetrated frames upon temperature change and the inclusion of small molecules. Introduction of 28 wt% imidazole into the pores of MOF-217, 28% Im-in-MOF-217, resulted in four orders of magnitude increase in proton conductivity, due to the appropriate accommodation of imidazole molecules and their proton transfer facilitated by the H-bond to the MOF structure across the pores. This MOF-based proton conductor can be operated at 100 °C with a proton conductivity of 1.1 × 10−3 S cm−1, standing among the best performing anhydrous MOF proton conductors at elevated temperature. The interframe dynamics represents a unique feature of MOFs that can be accessed in the future design of proton conductors.Twist and sliding dynamics observed in a titanium catecholate MOF induced by imidazole for efficient proton conduction. 相似文献
996.
Wasiu Olalekan Afolabi Ahmed Hussein Francis Oluwole Shode Marilize Le Roes-Hill Fanie Rautenbach 《Molecules (Basel, Switzerland)》2020,25(23)
Leptospermum petersonii (family Myrtaceae) is often cultivated for ornamental purposes but also serves as a rich source of bioactive essential oils. While several studies focused on the activities of the essential oils, this study analysed the potential of spent L. petersonii leaves as a natural food preservative. Method: We investigated the in vitro antioxidant and antimicrobial activities of crude L. petersonii extracts against activities of the purified isolated flavonoid, 6-methyltectochrysin, which was characterized using spectroscopic methods. The antioxidant assays followed ORAC, FRAP and TEAC tests. The antimicrobial activities of the extract and purified flavonoid were analysed against six multi-drug resistant microbial strains in broth dilution assays. Result: The results revealed that both the crude extracts and isolated 6-methyltectochrysin exhibited positive radical ion scavenging antioxidant potential, however the crude extract was about 6-fold more potent antioxidant than the purified 6-methyltectochrysin. The crude extract also showed strong antimicrobial activities against Bacillus cereus, and even more potent antimicrobial agent than the reference ampicillin antibiotic against Klebsiella pneumoniae subsp. pneumoniae. A higher resistance was observed for the tested Gram-negative strains than for the Gram-positive ones. 6-methyltectochrysin was generally inactive in the antimicrobial assays. Conclusion: The crude methanolic extract showed significant bioactivity which validates the medicinal relevance of the plant. The observed biological activities, especially against a notorious strain of B. cereus, suggest that L. petersonii could be a promising natural source of food preservatives. 相似文献
997.
Duong Quoc Hoan Le Thi Hoa Trinh Thi Huan Nguyen Huu Dinh 《Journal of heterocyclic chemistry》2020,57(4):1720-1728
An efficient and simple method has been reported for the synthesis of 4-(1-Chloro-1-nitroethyl)-6,7-dimethoxy-2-methylquinazoline ( 2 ) as a key compound for further transformation to other novel 6,7-dimethoxy-2-methyl-4-substituted quinazolines. The structure of the synthesized compounds was characterized by spectroscopic methods. The pathway of some unprecedented reactions was proposed. (E)-1-(6,7-dimethoxy-2-methylquinazolin-4-yl)-3-(4-nitrophenyl)prop-2-en-1-one (11) exhibits high in vitro cytotoxicity on three cell lines, Hepatocellular carcinoma (Hep-G2), Human lung carcinoma (LU-1), and Human breast carcinoma (MCF-7) with IC50 of 2.1, 11.6 and 2.2 μM, respectively. 相似文献
998.
Olivier Herbinet Benoit Husson Hervé Le Gall Frédérique Battin-Leclerc 《国际化学动力学杂志》2020,52(12):1006-1021
In the context of better understanding pollutant formation from internal combustion engines, new experimental speciation data were obtained in a high-pressure jet-stirred reactor for the oxidation of three molecules, which are considered in surrogates of diesel fuel, n-heptane, ethylbenzene, and n-butylbenzene. These experiments were performed at pressures up to 10 bar, at temperatures ranging from 500 to 1 100 K, and for a residence time of 2 s. Based on results previously obtained close to the atmospheric pressure for the same molecules, the pressure effect on fuel conversion and product selectivity was discussed. In addition, for the three fuels, the experimental temperature dependence of species mole fractions was compared with simulations using recent literature models with generally a good agreement. For n-heptane, the obtained experimental data, at 10 bar for stoichiometric mixtures, included the temperature dependence of the mole fractions of the reactants and those of 21 products. Interestingly, the formation of species previously identified as C7 diones was found significantly enhanced at 10 bar compared with lower pressures. The oxidation of ethyl- and n-butylbenzenes was investigated at 10 bar for equivalence ratios of 0.5, 1, and 2. The obtained experimental data included the temperature dependence of the mole fractions of the reactants and those of 13 products for the C8 fuels and of 19 products for the C10 one. For ethylbenzene under stoichiometric conditions, the pressure dependence (from 1 to 10 bar) of species mole fraction was also recorded and compared with simulations with more deviations obtained than for temperature dependence. For both aromatic reactants, a flow rate analysis was used to discuss the main pressure influence on product selectivities. 相似文献
999.
Antoine Bardin Pierre-Yves Le Gac Hervé Bindi Bruno Fayolle 《Journal of polymer science. Part A, Polymer chemistry》2020,58(22):3170-3182
This publication highlights the structure–property relationships in several thermoplastic elastomers (TPEs): one poly(ether-block-amide) and two thermoplastic polyurethane elastomers with ester and ether soft blocks. Structural changes are induced by chemical degradation from virgin samples through hydrolysis and oxidation. Molar mass measurements show an exclusive chain scission mechanism for all TPEs, regardless of the chemical modification condition. Mechanical behavior was nevertheless obtained from uniaxial tensile testing and fracture testing while considering the essential work of fracture (EWF) concept. During the macromolecular scission process, elongation at break shows a plateau followed by a drop, while stress at break decreases steadily. Once again, the trend is identical for all TPEs in all conditions considered. The βwp parameter determined using the EWF concept exhibits an interesting sensitivity to scissions (i.e., molar mas decrease). Plotting elongation at break as a function of molar mass reveals a strong correlation between these two parameters. This master curve is particularly remarkable considering the range of TPEs and chemical breakdown pathways considered (hydrolysis and oxidation at several temperatures). Relevant structure–property relationships are proposed, highlighting that molar mass is a predominant parameter for determining the mechanical properties of thermoplastic elastomers. 相似文献
1000.
Rosales-Conrado N León-González ME Pérez-Arribas LV Polo-Díez LM 《Analytical and bioanalytical chemistry》2008,390(2):759-768
Chlorophenoxy acid herbicides are intensively applied to get rid of unwanted plants because of their low cost and selectivity.
Due to their toxicity, which depends on their chemical form, the European Community has established legal directives to restrict
their use and to control their maximum residue levels in several matrices. Determination of chlorophenoxy acids—2,4-dichlorophenoxyacetic
acid (2,4-D), 4-chloro-2-methylphenoxyacetic acid (MCPA), 2-(2,4-dichlorophenoxy)propanoic acid (2,4-DP), 2-(4-chloro-2-methylphenoxy)propanoic
acid (MCPP), 4-(4-chloro-2-methylphenoxy)butanoic acid (MCPB) and 2-(2,4,5-trichlorophenoxy)propanoic acid (2,4,5-TP) in spiked
human urine samples has been carried out by capillary LC, after solid-phase extraction on a column packed with silica C18 restricted-access material. Chromatographic analysis was performed in gradient-elution mode at 25 °C, with injection of 20 μL
low-organic-solvent composition herbicide solutions for focusing purposes on the head of the capillary column, and diode array
detection at 232 nm. Urine samples collected during 24 h from healthy and unexposed volunteers were spiked in the concentration
range 25–150 μg L−1; recoveries obtained were between 66 and 100% (n = 6 for each spiked level) and RSDs (relative standard deviations) were between 1 and 5%. Detection limits in the urine samples
from volunteers were between 3.5 and 6.0 μg L−1. The developed methodology has allowed the clean-up and preconcentration of low volumes of untreated human urine without
previous treatment, showing the effectiveness of the employed SPE sorbent for extracting the target analytes and ultimately
resulting in the reduction of the sample-preparation time. 相似文献