全文获取类型
收费全文 | 8202篇 |
免费 | 1020篇 |
国内免费 | 2058篇 |
专业分类
化学 | 9352篇 |
晶体学 | 80篇 |
力学 | 80篇 |
综合类 | 77篇 |
数学 | 26篇 |
物理学 | 1665篇 |
出版年
2024年 | 86篇 |
2023年 | 346篇 |
2022年 | 409篇 |
2021年 | 376篇 |
2020年 | 542篇 |
2019年 | 445篇 |
2018年 | 323篇 |
2017年 | 347篇 |
2016年 | 407篇 |
2015年 | 363篇 |
2014年 | 359篇 |
2013年 | 619篇 |
2012年 | 482篇 |
2011年 | 459篇 |
2010年 | 385篇 |
2009年 | 462篇 |
2008年 | 447篇 |
2007年 | 490篇 |
2006年 | 411篇 |
2005年 | 444篇 |
2004年 | 376篇 |
2003年 | 345篇 |
2002年 | 290篇 |
2001年 | 255篇 |
2000年 | 265篇 |
1999年 | 247篇 |
1998年 | 197篇 |
1997年 | 180篇 |
1996年 | 159篇 |
1995年 | 139篇 |
1994年 | 106篇 |
1993年 | 112篇 |
1992年 | 89篇 |
1991年 | 64篇 |
1990年 | 39篇 |
1989年 | 21篇 |
1988年 | 38篇 |
1987年 | 25篇 |
1986年 | 24篇 |
1985年 | 39篇 |
1984年 | 15篇 |
1983年 | 7篇 |
1982年 | 11篇 |
1981年 | 11篇 |
1980年 | 7篇 |
1979年 | 8篇 |
1978年 | 2篇 |
1975年 | 1篇 |
1974年 | 3篇 |
1959年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
1.
Weiyi Li Geng Leng Caiqin Li Yajing Lyu 《International journal of quantum chemistry》2020,120(8):e26150
The mechanisms of CO2 coupling with the propargylic alcohol using alkali carbonates M2CO3 (M = Li, Na, K, Cs) have been investigated by means of density functional theory calculations. The calculations reveal that the target product tetronic acid (TA) is yielded through two stages: (a) the formation of the α-alkylidene cyclic carbonate (αACC) intermediate via Cs2CO3-mediated carboxylative cyclization of the propargylic alcohol with CO2, and (b) the conversion of the αACC intermediate with Cs2CO3 to produce the cesium salt of the TA. Since the overall kinetic barriers for the two stages are comparable and affordable, the excellent chemoselectivity to the TA should be primarily originated from the high thermodynamic stability of the cesium salt of the TA. Moreover, relative to the TA, the possibility to yield the by-product acyclic carbonate can be excluded due to the both kinetics and thermodynamic inferiority. This result is different from the organic base-mediated reaction. Alternatively, our calculations predict that CsHCO3 together generated with the cesium salt of the TA might also be an available mediating reagent for the incorporation of CO2 with the propargylic alcohol. Compared to other alkali carbonates M2CO3 (M = Li, Na, K), the stronger basicity of Cs2CO3 and the lower ionic potential of cesium ion can raise the effective concentration of the αACC intermediate, and thus the conversion of the αACC intermediate into the cesium salt of the TA can be achieved with high yield. 相似文献
2.
Dr. Wan‐Ling Liu Ni‐Shin Yang Ya‐Ting Chen Stephen Lirio Cheng‐You Wu Prof. Chia‐Her Lin Prof. Hsi‐Ya Huang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):115-119
A green and sustainable strategy synthesizes clinical medicine warfarin anticoagulant by using lipase‐supported metal–organic framework (MOF) bioreactors (see scheme). These findings may be beneficial for future studies in the industrial production of chemical, pharmaceutical, and agrochemical precursors. 相似文献
3.
Yeong‐Tarng Shieh Pei‐Yu Tai Chih‐Chia Cheng 《Journal of polymer science. Part A, Polymer chemistry》2019,57(21):2149-2156
Poly(methyl methacrylate) (PMMA) nanoparticles with a sensitive CO2‐responsive hydrophilic/hydrophobic surface that confers controlled dispersion and aggregation in water were prepared by emulsion polymerization at 50 °C under CO2 bubbling using amphiphilic diblock copolymers of 2‐dimethylaminoethyl methacrylate (DMAEMA) and N‐isopropyl acrylamide (NIPAAm) as an emulsifier. The amphiphilicity of the hydrophobic–hydrophilic diblock copolymer at 50 °C was triggered by CO2 bubbling in water and enabled the copolymer to serve as an emulsifier. The resulting PMMA nanoparticles were spherical, approximately 100 nm in diameter and exhibited sensitive CO2/N2‐responsive dispersion/aggregation in water. Using copolymers with a longer PNIPAAm block length as an emulsifier resulted in smaller particles. A higher concentration of copolymer emulsifier led to particles with a stickier surface. Given its simple preparation and reversible CO2‐triggered amphiphilic behavior, this newly developed block copolymer emulsifier offers a highly efficient route toward the fabrication of sensitive CO2‐stimuli responsive polymeric nanoparticle dispersions. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2149–2156 相似文献
4.
《Journal of separation science》2018,41(6):1319-1337
The present review discusses the theory and application of van't Hoff analysis in chiral chromatography, with main focus on liquid chromatography. The topics considered include the physical meaning of van't Hoff equation's parameters, interpretation of thermodynamic data in terms of retention and enantioseparation mechanisms, abnormal behavior of van't Hoff plots, and best practices to avoid biased results. 相似文献
5.
Lotfi Boudjema Dr. Jérôme Long Dr. Fabrice Salles Prof. Joulia Larionova Dr. Yannick Guari Prof. Philippe Trens 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(2):479-484
Porous coordination polymers are molecule-based materials presenting a high degree of tunability, which offer many advantages for targeted applications over conventional inorganic materials. This work demonstrates that the hydrophilic/hydrophobic character of Prussian blue analogues having a lipophilic feature may be tuned to optimize the gas adsorption properties. The role of the coordinatively unsaturated metal sites is emphasized through a combination of theoretical and experimental study of water, ethanol, and n-hexane adsorption. 相似文献
6.
Addition of functionalized zinc-copper reagents to the title complexes proceeds in a highly diastereoselective fashion to afford dienol complexes. The relative configurations of adducts 3d were determined by single X-ray diffraction analysis. 相似文献
7.
Regis Guyonnet 《Journal of statistical physics》1991,65(1-2):269-289
The NMR properties of nuclei linked to long linear polymer molecules are sensitive to the influence of hard walls. In this context, the residual energy of tensorial spin-spin interactions is calculated using a path integral approach. Several thermodynamic quantities of the polymer system (free energy, equation of state,...) are also expressed, taking chain stiffness effects and the presence of two repulsive walls into consideration. 相似文献
8.
9.
The breakthrough and stoichiometric SO2 adsorption efficiencies of a biomass supported Na2CO3 system (80 wt %Na2CO3/straw) have reached 48.9% and 80.6% respectively at a desulfurization temperature of 80℃. 相似文献
10.
应用密度泛函理论,本文系统地研究了O在Au(111)表面上的吸附能、吸附结构、功函数、电子密度和投影态密度,给出了覆盖度从0.11ML到1.0ML的范围内,O的吸附特性随覆盖度变化的规律.研究发现O的稳定吸附位为3重面心立方(fcc)洞位,O在fcc洞位的吸附能对覆盖度比较敏感,其值随着覆盖度的增加而减小;O诱导Au(111)表面功函数的变化量与覆盖度成近线性关系,原因是Au表面电子向O偏移,形成表面偶极子;O—Au的相互作用形成成键态和反键态,且反键态都被占据,造成O—Au键很弱,O吸附能较小.
关键词:
表面吸附
Au(111)表面
密度泛函理论
电子特性 相似文献