全文获取类型
收费全文 | 1880篇 |
免费 | 89篇 |
国内免费 | 3篇 |
专业分类
化学 | 1168篇 |
晶体学 | 11篇 |
力学 | 65篇 |
数学 | 154篇 |
物理学 | 574篇 |
出版年
2023年 | 22篇 |
2022年 | 22篇 |
2021年 | 59篇 |
2020年 | 64篇 |
2019年 | 49篇 |
2018年 | 44篇 |
2017年 | 37篇 |
2016年 | 90篇 |
2015年 | 50篇 |
2014年 | 91篇 |
2013年 | 122篇 |
2012年 | 124篇 |
2011年 | 155篇 |
2010年 | 104篇 |
2009年 | 92篇 |
2008年 | 123篇 |
2007年 | 74篇 |
2006年 | 73篇 |
2005年 | 81篇 |
2004年 | 48篇 |
2003年 | 41篇 |
2002年 | 28篇 |
2001年 | 19篇 |
2000年 | 17篇 |
1999年 | 23篇 |
1998年 | 8篇 |
1997年 | 15篇 |
1996年 | 15篇 |
1995年 | 12篇 |
1994年 | 15篇 |
1993年 | 19篇 |
1992年 | 13篇 |
1991年 | 17篇 |
1990年 | 11篇 |
1989年 | 13篇 |
1988年 | 12篇 |
1987年 | 9篇 |
1986年 | 12篇 |
1985年 | 14篇 |
1984年 | 18篇 |
1983年 | 13篇 |
1982年 | 11篇 |
1981年 | 8篇 |
1979年 | 6篇 |
1978年 | 8篇 |
1977年 | 10篇 |
1976年 | 14篇 |
1975年 | 5篇 |
1974年 | 8篇 |
1973年 | 4篇 |
排序方式: 共有1972条查询结果,搜索用时 46 毫秒
11.
12.
Chakrabarty D Seth D Chakraborty A Sarkar N 《The journal of physical chemistry. B》2005,109(12):5753-5758
The effects of confinement of the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate on solvation dynamics and rotational relaxation of Coumarin 153 (C-153) in Triton X-100/cyclohexane microemulsions have been explored using steady-state and picosecond time-resolved emission spectroscopy. The steady-state and rotational relaxation data indicate that C-153 molecules are incorporated in the core of the microemulsions. The average rotational relaxation time increases with increase in w ([bmim][BF(4)]/[TX-100]) values. The solvent relaxation in the core of the microemulsion occurs on two different time scales and is almost insensitive to the increase in w values. The solvent relaxation is retarded in the pool of the microemulsions compared to the neat solvent. Though, the retardation is very small compared to several-fold retardation of the solvation time of the conventional solvent inside the pool of the microemulsions. 相似文献
13.
Patra S Sarkar B Ghumaan S Patil MP Mobin SM Sunoj RB Kaim W Lahiri GK 《Dalton transactions (Cambridge, England : 2003)》2005,(7):1188-1194
The isomeric title complexes were obtained in almost equimolar ratio from the reaction of Ru(trpy)Cl3 and L. Crystal structure analyses of the perchlorate hemihydrates, electrochemical and spectroscopic (NMR, UV/VIS, EPR) studies, supported by DFT calculations, reveal distinct differences between the isomeric redox series [1]n+(tetrazine-Nt trans to Cl) and [2]n+(pyrazolyl-Np trans to Cl; n= 0, 1, 2). The latter system with the pi acceptors trpy and tetrazine in the equatorial plane and the pyrazolyl and chloride donors in the axial positions exhibits facilitated oxidation, lower energy MLCT transitions, more balanced chelate coordination, and a higher g anisotropy in the oxidised (RuIII) state. According to partially resolved EPR spectra of one-electron reduced neutral compounds and they have the unpaired electron predominantly in the tetrazine ring of L. 相似文献
14.
Indole-2-yl-prop-2-ynyl sulfides, under thiophenol-mediated alkenyl radical cyclization conditions, afforded exclusively 4-thiophenyl-2,3,4,9-tetrahydrothiopyrano[2,3-b]indoles or 3-thiophenylmethyl-2,3,8-trihydrothieno[2,3-b]indoles depending on the substituent at the indole nitrogen. 相似文献
15.
16.
Rita Das Nigamananda Das Anadi C. Dash Ansuman Roy Shyamal K. Sarkar 《Transition Metal Chemistry》1996,21(1):90-94
Summary The reaction of ()-(tetren)CoOH2+ with S2O
3
2-
in the 7.25–8.28 pH range at 20–40 °C yielded S- (yellow) and O- (purple) bonded thiosulfato(tetren)cobalt(III) complexes, the former in larger quantities. The rate determining step is preceded by diffusion-controlled ion-pair [(tetren)CoOH2+,S2O
3
2-
] formation. Replacement of coordinated OH- by S2O
3
2-
is interpreted in terms of an internal conjugate base mechanism: (tetren)CoOH2+ (tetren-H)CoOH
2
2+
, the reactive amido conjugate base being generated by intramolecular proton transfer from the coordinated NH site.In acid medium the S-bonded (tetren)Co(S2O3)+ is highly stable to redox decomposition, in contrast to its pentaammine analogue. The complex however, undergoes base hydrolysis yielding the corresponding hydroxo complex. The rate and activation parameters for the base hydrolysis have been reported. Photolysis of O- and S-bonded isomers of [(tetren)CoS2O3]+ in acidic medium at 254 and 313 nm, respectively, yielded aquation products accompanied by some decomposition of S2O
3
2-
. 相似文献
17.
18.
19.
Polygonal (mainly triangular) silver nanoprisms were prepared by reducing silver perchlorate in formamide in the presence of polyethylene glycol (PEG) at room temperature. The reduction of silver ions by formamide leads to the deposition of arrays of triangular shaped silver nanoparticles on the glass walls of the container, accompanied by evolution of CO2 gas. In the presence of poly(N-vinyl-2-pyrrolidone) (PVP) and PEG (1:1), both nanospheres and nanoprisms are formed. 相似文献
20.
Sarkar B Kaim W Klein A Schwederski B Fiedler J Duboc-Toia C Lahiri GK 《Inorganic chemistry》2003,42(20):6172-6174
The Ru(2)(III,II) mixed-valent state is strongly stabilized in [(bpy)(2)Ru(mu-bttz)Ru(bpy)(2)](5+) (3(5+), bttz = 3,6-bis(2-thienyl)-1,2,4,5-tetrazine, as evident from lowered oxidation potentials and isolability, a strongly increased comproportionation constant K(c) = 10(16.6), and a high-energy intervalence charge transfer band at 10100 cm(-1). Curiously, no such effects were observed for the diosmium(III,II) analogue, whereas the related systems [(bpy)(2)M(mu-bmptz)M(bpy)(2)](5+), bmptz = 3,6-bis(4-methyl-2-pyridyl)-1,2,4,5-tetrazine, exhibit conventional behavior, i.e., a slightly higher K(c) value of the Os(2)(III,II) analogue. EPR signals were observed at 4 K for 3(5+) but not for the other mixed-valent species, and high-frequency (285 GHz) EPR was employed to study the diruthenium(II) radical complexes 2(3+) and 3(3+). 相似文献