全文获取类型
收费全文 | 9379篇 |
免费 | 359篇 |
国内免费 | 25篇 |
专业分类
化学 | 6031篇 |
晶体学 | 77篇 |
力学 | 236篇 |
综合类 | 1篇 |
数学 | 1513篇 |
物理学 | 1905篇 |
出版年
2023年 | 48篇 |
2022年 | 65篇 |
2021年 | 132篇 |
2020年 | 185篇 |
2019年 | 160篇 |
2018年 | 215篇 |
2017年 | 182篇 |
2016年 | 329篇 |
2015年 | 276篇 |
2014年 | 316篇 |
2013年 | 579篇 |
2012年 | 637篇 |
2011年 | 650篇 |
2010年 | 389篇 |
2009年 | 342篇 |
2008年 | 560篇 |
2007年 | 481篇 |
2006年 | 480篇 |
2005年 | 479篇 |
2004年 | 369篇 |
2003年 | 315篇 |
2002年 | 273篇 |
2001年 | 167篇 |
2000年 | 127篇 |
1999年 | 98篇 |
1998年 | 83篇 |
1997年 | 86篇 |
1996年 | 125篇 |
1995年 | 77篇 |
1994年 | 78篇 |
1993年 | 69篇 |
1992年 | 66篇 |
1991年 | 55篇 |
1990年 | 55篇 |
1989年 | 53篇 |
1988年 | 42篇 |
1987年 | 37篇 |
1986年 | 51篇 |
1985年 | 78篇 |
1984年 | 73篇 |
1983年 | 54篇 |
1982年 | 66篇 |
1981年 | 47篇 |
1980年 | 66篇 |
1979年 | 49篇 |
1978年 | 58篇 |
1977年 | 46篇 |
1976年 | 44篇 |
1975年 | 41篇 |
1973年 | 36篇 |
排序方式: 共有9763条查询结果,搜索用时 31 毫秒
1.
Peralta Cecilia Mariana Acosta Gimena Henestrosa Cecilia Gil Raúl Andrés Fernández Liliana Patricia 《Journal of Analytical Chemistry》2022,77(3):308-317
Journal of Analytical Chemistry - The present development involved a flow injection strategy using a mini-column of multiwalled carbon nanotubes and fluorescent detection (λex of 283 nm,... 相似文献
2.
Verdecho María-José Alarcón-Valero Faustino Pérez-Perales David Alfaro-Saiz Juan-José Rodríguez-Rodríguez Raúl 《Central European Journal of Operations Research》2021,29(4):1231-1251
Central European Journal of Operations Research - Sustainability practice within supply chains remains in an early development phase. Enterprises still need tools that support the integration of... 相似文献
3.
Dr. Antonio M. Rodríguez Dr. Pilar Prieto Prof. Antonio de la Hoz Prof. Ángel Díaz-Ortiz D. Raúl Martín Prof. José I. García 《ChemistryOpen》2015,4(3):308-317
The aim of this work was to determine the parameters that have decisive roles in microwave-assisted reactions and to develop a model, using computational chemistry, to predict a priori the type of reactions that can be improved under microwaves. For this purpose, a computational study was carried out on a variety of reactions, which have been reported to be improved under microwave irradiation. This comprises six types of reactions. The outcomes obtained in this study indicate that the most influential parameters are activation energy, enthalpy, and the polarity of all the species that participate. In addition to this, in most cases, slower reacting systems observe a much greater improvement under microwave irradiation. Furthermore, for these reactions, the presence of a polar component in the reaction (solvent, reagent, susceptor, etc.) is necessary for strong coupling with the electromagnetic radiation. We also quantified that an activation energy of 20–30 kcal mol−1 and a polarity (μ) between 7–20 D of the species involved in the process is required to obtain significant improvements under microwave irradiation. 相似文献
4.
Experimental and Theoretical Studies on the Rearrangement of 2‐Oxoazepane α,α‐Amino Acids into 2′‐Oxopiperidine β2,3,3‐Amino Acids: An Example of Intramolecular Catalysis 下载免费PDF全文
Dr. Diego Núñez‐Villanueva Dr. M. Ángeles Bonache Laura Lozano Dr. Lourdes Infantes Prof. José Elguero Prof. Ibon Alkorta Prof. M. Teresa García‐López Dr. Rosario González‐Muñiz Dr. Mercedes Martín‐Martínez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2489-2500
Enantiopure β‐amino acids represent interesting scaffolds for peptidomimetics, foldamers and bioactive compounds. However, the synthesis of highly substituted analogues is still a major challenge. Herein, we describe the spontaneous rearrangement of 4‐carboxy‐2‐oxoazepane α,α‐amino acids to lead to 2′‐oxopiperidine‐containing β2,3,3‐amino acids, upon basic or acid hydrolysis of the 2‐oxoazepane α,α‐amino acid ester. Under acidic conditions, a totally stereoselective synthetic route has been developed. The reordering process involved the spontaneous breakdown of an amide bond, which typically requires strong conditions, and the formation of a new bond leading to the six‐membered heterocycle. A quantum mechanical study was carried out to obtain insight into the remarkable ease of this rearrangement, which occurs at room temperature, either in solution or upon storage of the 4‐carboxylic acid substituted 2‐oxoazepane derivatives. This theoretical study suggests that the rearrangement process occurs through a concerted mechanism, in which the energy of the transition states can be lowered by the participation of a catalytic water molecule. Interestingly, it also suggested a role for the carboxylic acid at position 4 of the 2‐oxoazepane ring, which facilitates this rearrangement, participating directly in the intramolecular catalysis. 相似文献
5.
6.
Unexpected benzimidazole ring formation from a quinoneimide species in the presence of ammonium acetate as supporting electrolyte used in the coupling of electrochemistry with mass spectrometry 下载免费PDF全文
7.
8.
This study compares the physicochemical properties of six electrolytes comprising of three salts: LiFTFSI, NaFTFSI and KFTFSI in two solvent mixtures, the binary (3EC/7EMC) and the ternary (EC/PC/3DMC). The transport properties (conductivity, viscosity) as a function of temperature and concentration were modeled using the extended Jones-Dole-Kaminsky equation, the Arrhenius model, and the Eyring theory of transition state for activated complexes. Results are discussed in terms of ionicity, solvation shell, and cross-interactions between electrolyte components. The application of the six formulated electrolytes in symmetrical activated carbon (AC)//AC supercapacitors (SCs) was characterized by cyclic voltammetry (CV), galvanostatic cycling with potential limitation (GCPL), electrochemical impedance spectroscopy (EIS) and accelerated aging. Results revealed that the geometrical flexibility of the FTFSI anion allows it to access and diffuse easily in AC whereas its counter ions (Li+, Na+ or K+) can remain trapped in porosity. However, this drawback was partially resolved by mixing LiFTFSI and KFTFSI salts in the electrolyte. 相似文献
9.
Simen Gjelseth Antonsen Arne Joakim C. Bunkan Tomas Mikoviny Yngve Stenstrøm Armin Wisthaler 《Molecular physics》2020,118(15)
The kinetics of the O3, OH and NO3 radical reactions with diazomethane were studied in smog chamber experiments employing long-path FTIR and PTR-ToF-MS detection. The rate coefficients were determined to be k CH2NN+O3?=?(3.2?±?0.4)?×?10?17 and k CH2NN+OH?=?(1.68?±?0.12)?×?10?10 cm3 molecule?1 s?1 at 295?±?3?K and 1013?±?30 hPa, whereas the CH2NN?+?NO3 reaction was too fast to be determined in the static smog chamber experiments. Formaldehyde was the sole product observed in all the reactions. The experimental results are supported by CCSD(T*)-F12a/aug-cc-pVTZ//M062X/aug-cc-pVTZ calculations showing the reactions to proceed exclusively via addition to the carbon atom. The atmospheric fate of diazomethane is discussed. 相似文献
10.
Mejía Hugo Fernando Giraldo Jiménez-Piqué Emilio Valdés Matías Procaccini Raúl Pellice Sergio 《Journal of Solid State Electrochemistry》2020,24(10):2451-2460
Journal of Solid State Electrochemistry - A novel material was developed using sol-gel chemistry and an environmental-friendly grafting process of clay nanoparticles. In a previous work of our... 相似文献