全文获取类型
收费全文 | 2972篇 |
免费 | 192篇 |
国内免费 | 178篇 |
专业分类
化学 | 1480篇 |
晶体学 | 42篇 |
力学 | 77篇 |
综合类 | 12篇 |
数学 | 269篇 |
物理学 | 726篇 |
综合类 | 736篇 |
出版年
2023年 | 32篇 |
2022年 | 60篇 |
2021年 | 50篇 |
2020年 | 65篇 |
2019年 | 56篇 |
2018年 | 53篇 |
2017年 | 60篇 |
2016年 | 95篇 |
2015年 | 74篇 |
2014年 | 124篇 |
2013年 | 156篇 |
2012年 | 191篇 |
2011年 | 181篇 |
2010年 | 114篇 |
2009年 | 109篇 |
2008年 | 146篇 |
2007年 | 168篇 |
2006年 | 140篇 |
2005年 | 135篇 |
2004年 | 96篇 |
2003年 | 78篇 |
2002年 | 78篇 |
2001年 | 70篇 |
2000年 | 69篇 |
1999年 | 52篇 |
1998年 | 42篇 |
1997年 | 58篇 |
1996年 | 68篇 |
1995年 | 53篇 |
1994年 | 57篇 |
1993年 | 49篇 |
1992年 | 44篇 |
1991年 | 20篇 |
1990年 | 30篇 |
1989年 | 33篇 |
1988年 | 31篇 |
1987年 | 19篇 |
1986年 | 28篇 |
1985年 | 22篇 |
1983年 | 18篇 |
1982年 | 18篇 |
1981年 | 10篇 |
1980年 | 15篇 |
1979年 | 17篇 |
1978年 | 11篇 |
1977年 | 23篇 |
1976年 | 13篇 |
1975年 | 18篇 |
1974年 | 10篇 |
1971年 | 9篇 |
排序方式: 共有3342条查询结果,搜索用时 18 毫秒
921.
CO2 capture from binary mixture via forming hydrate with the help of tetra-n-butyl ammonium bromide 总被引:2,自引:0,他引:2 下载免费PDF全文
Hydrate formation rate and separation effect on the capture of CO2 from binary mixture v/a forming hydrate with 5 wt% tetra-n-butyl ammonium bromide (TBAB) solution were studied.The results showed that the induction time was 5 min,and the hydrate formation process pressure of 7.30 MPa.The CO2 recovery was about 45% in the feed pressure range from 4.30 to 7.30 MPa.Under the feed pressure of 4.30 MPa,the maximum separation factor and CO2 concentration in hydrate phase were 7.3 and 38.2 tool%,respectively.The results demonstrated that TBAB accelerated hydrate formation and enriched CO2 in hydrate phase under the gentle condition. 相似文献
922.
Two new organic photochromic compounds based on pyrazolone were synthesized and further characterized by elemental analysis,
MS, IR spectra, and 1H NMR spectra. The photochromic properties and photochemical kinetics of them have been studied by UV absorption spectra under
irradiation of 365 nm light. The photochromism of pyrazolone derivatives in the solid state has been so far explained only
in terms of the light-induced change of absorption and their crystal structures, which is caused by the shift of the tautomeric
equilibrium between the enol and keto forms. In this work, their IR spectra have been measured before and after irradiation.
Based on the IR spectra and crystal structure analysis, a reasonable mechanism was proposed, the photochromic phenomenon may
be due to the photoisomerization from enol-form to keto-form through proton transfer. 相似文献
923.
Alexander Jakob Tobias Rüffer Rainer F. Winter Heinrich Lang 《Journal of organometallic chemistry》2009,694(22):3542-5577
A straightforward synthesis methodology for the preparation of heterobimetallic [(η5-C5H5)(η5-C5H4-C5Me4)M] (3a, M = Fe; 3b, M = Ru) and [(η5-C5H5)((μ-η5:η5-C5H4-C5Me4)TiCl3)M] (4a, M = Fe; 4b, M = Ru) in which early and late transition metals are connected by a fulvalenediyl bridge is reported.The structures of molecules 3b and 4a in the solid state are discussed. Most noteworthy in 4a is the exo arrangement of the iron and titanium atoms coordinated by the fulvalenediyl unit which itself is twisted with a dihedral angle between the joined cyclopentadienyl rings of 19.33(9)°. Electrochemical, UV/Vis/NIR spectroscopic and spectroelectrochemical experiments on 4a and Cp∗TiCl3, for comparison, provide evidence for some transfer of electronic information between the conjoined ferrocene and half-sandwich titanocene trichloride subunits of 4a. Evidence comes from systematic potential shifts and the presence of a fairly intense Fe → Ti charge-transfer absorption band that vanishes upon oxidation and reduction of 4a. 相似文献
924.
The Pd‐catalyzed homodimerization with respect to arylsulfonyl chlorides as an efficient method for the synthesis of biaryls has been developed. This desulfonylative reaction which was performed at reflux in 1,4‐dioxane for 4 h under air afforded the desired products in good to excellent yields. 相似文献
925.
Xianjun Lang Wei Hao Wan Ru Leow Shuzhou Li Jincai Zhao Xiaodong Chen 《Chemical science》2015,6(8):5000-5005
The selective oxidation of sulfides into sulfoxides receives much attention due to industrial and biological applications. However, the realization of this reaction with molecular oxygen at room temperature, which is of importance towards green and sustainable chemistry, remains challenging. Herein, we develop a strategy to achieve the aerobic oxidation of sulfides into sulfoxides by exploring the synergy between a tertiary amine and titanium dioxide via visible-light photoredox catalysis. Specifically, titanium dioxide can interact with triethylamine (TEA) to form a visible-light harvesting surface complex, preluding the ensuing selective redox reaction. Moreover, TEA, whose stability was demonstrated by a turnover number of 32, plays a critical role as a redox mediator by shuttling electrons during the oxidation of sulfide. This work suggests that the addition of a redox mediator is highly functional in establishing visible-light-induced reactions via heterogeneous photoredox catalysis. 相似文献
926.
4,5‐Dihydro‐1,2,3‐oxadiazole: A Very Elusive Key Intermediate in Various Important Chemical Transformations 下载免费PDF全文
Prof. Dr. Klaus Banert Neeraj Singh Benjamin Fiedler Prof. Dr. Joachim Friedrich Marcus Korb Prof. Dr. Heinrich Lang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(43):15092-15099
4,5‐Dihydro‐1,2,3‐oxadiazoles are postulated to be key intermediates in the industrial synthesis of ketones from alkenes, in the alkylation of DNA in vivo, and in the decomposition of N‐nitrosoureas; they are also a subject of great interest for theoretical chemists. In the presented report, the formation of 4,5‐dihydro‐1,2,3‐oxadiazole and the subsequent decay into secondary products have been studied by NMR monitoring analysis. The elusive properties evading characterization have now been confirmed by 1H, 13C, and 15N NMR spectroscopy, and relevant 2D experiments at very low temperatures. Our experiments with suitably substituted N‐nitrosoureas using thallium(I) alkoxides as bases under apolar conditions answer important questions on the existence and the secondary products of 4,5‐dihydro‐1,2,3‐oxadiazole. 相似文献
927.
The Interaction of Water with Free Mn4O4+ Clusters: Deprotonation and Adsorption‐Induced Structural Transformations 下载免费PDF全文
Dr. Sandra M. Lang Prof. Dr. Thorsten M. Bernhardt Denis M. Kiawi Dr. Joost M. Bakker Dr. Robert N. Barnett Prof. Dr. Uzi Landman 《Angewandte Chemie (International ed. in English)》2015,54(50):15113-15117
As the biological activation and oxidation of water takes place at an inorganic cluster of the stoichiometry CaMn4O5, manganese oxide is one of the materials of choice in the quest for versatile, earth‐abundant water splitting catalysts. To probe basic concepts and aid the design of artificial water‐splitting molecular catalysts, a hierarchical modeling strategy was employed that explores clusters of increasing complexity, starting from the tetramanganese oxide cluster Mn4O4+ as a molecular model system for catalyzed water activation. First‐principles calculations in conjunction with IR spectroscopy provide fundamental insight into the interaction of water with Mn4O4+, one water molecule at a time. All of the investigated complexes Mn4O4(H2O)n+ (n=1–7) contain deprotonated water with a maximum of four dissociatively bound water molecules, and they exhibit structural fluxionality upon water adsorption, inducing dimensional and structural transformations of the cluster core. 相似文献
928.
Spontaneous Self‐Assembly of γ‐Cyclodextrins in Dilute Solutions with Tunable Sizes and Thermodynamic Stability 下载免费PDF全文
Jing Zhou Dr. Panchao Yin Yunyi Gao Lang Hu Prof. Dr. Tianbo Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(26):9563-9568
The behavior in dilute solution of phosphate‐functionalized γ‐cyclodextrin macroanions with eight charges on the rim was explored. The hydrophilic macroions in mixed solvents show strong attraction between each other, mediated by the counterions, and consequently self‐assemble into blackberry‐type hollow spherical structures. Time‐resolved laser light scattering (LLS) measurements at high temperature ruled out the possibility of hydrogen bonding as the main driving force in the self‐assembly and indicated the good thermodynamic stability of assemblies regulated by the charge. The transition from single macroions to blackberries can be tuned by adjusting the content of organic solvent. The sizes of blackberries vary with the charge density of γ‐cyclodextrin by adjusting pH. It is the first report that pure cyclodextrins can generate supramolecular structures by themselves in dilute solution. The unique solution behavior of macroions provides a new opportunity to assemble cyclodextrin into functional materials and devices. 相似文献
929.
930.
Two dinuclear lanthanide complexes with pentadentate ligand 3‐[bis(pyridine‐2‐ylmethyl)amino]propane‐1,2‐diol (H2L), formulated as [Ln2(HL)2(NO3)2(H2O)2] · 1.5NO3 · 0.5I [Ln = Tb ( ZTU‐1 ) and Eu ( ZTU‐2 ); ZTU = Zhaotong University] were synthesized and structurally characterized. ZTU‐1 and ZTU‐2 are isomorphous and feature a butterfly‐like arrangement. The fluorescence properties of ZTU‐1 and ZTU‐2 are investigated and slow magnetic relaxation behavior is observed in ZTU‐1 . 相似文献