全文获取类型
收费全文 | 740篇 |
免费 | 35篇 |
国内免费 | 1篇 |
专业分类
化学 | 505篇 |
晶体学 | 2篇 |
力学 | 7篇 |
数学 | 77篇 |
物理学 | 185篇 |
出版年
2023年 | 4篇 |
2022年 | 7篇 |
2021年 | 11篇 |
2020年 | 20篇 |
2019年 | 18篇 |
2018年 | 10篇 |
2016年 | 13篇 |
2015年 | 16篇 |
2014年 | 27篇 |
2013年 | 23篇 |
2012年 | 37篇 |
2011年 | 37篇 |
2010年 | 29篇 |
2009年 | 18篇 |
2008年 | 31篇 |
2007年 | 39篇 |
2006年 | 36篇 |
2005年 | 37篇 |
2004年 | 38篇 |
2003年 | 19篇 |
2002年 | 22篇 |
2001年 | 13篇 |
2000年 | 14篇 |
1999年 | 10篇 |
1998年 | 5篇 |
1997年 | 9篇 |
1996年 | 9篇 |
1995年 | 11篇 |
1994年 | 15篇 |
1993年 | 6篇 |
1992年 | 15篇 |
1991年 | 8篇 |
1990年 | 3篇 |
1989年 | 6篇 |
1988年 | 11篇 |
1987年 | 17篇 |
1986年 | 8篇 |
1985年 | 20篇 |
1984年 | 3篇 |
1983年 | 3篇 |
1982年 | 8篇 |
1981年 | 7篇 |
1980年 | 9篇 |
1979年 | 6篇 |
1978年 | 6篇 |
1977年 | 6篇 |
1976年 | 7篇 |
1975年 | 8篇 |
1962年 | 3篇 |
1898年 | 2篇 |
排序方式: 共有776条查询结果,搜索用时 890 毫秒
11.
The products of the reaction of OClO with NO3 were investigated between 220 and 298 K using a flow reactor and infrared, visible, and ultraviolet analysis. At temperatures below 250 K new infrared and ultraviolet absorption features were observed and assigned to the novel compound chloryl nitrate (O2ClONO2). Additionally, ClO and NO2 were observed as reaction products, indicating the existence of a second reaction channel. O2ClONO2 formation predominates at temperatures below 230 K. The reaction rate constant at 220 K is estimated to be on the order of 10(-14) cm3 molecule-1 s-1 in 1-5 Torr of helium. These observations suggest that O2ClONO2 may exist in the terrestrial stratosphere. 相似文献
12.
Dr. Pradip Ghosh Sander de Vos Dr. Martin Lutz Dr. Frederic Gloaguen Prof. Dr. Philippe Schollhammer Dr. Marc-Etienne Moret Prof. Dr. Robertus J. M. Klein Gebbink 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(55):12560-12569
Homogeneous electrocatalytic proton reduction is reported using cobalt complex [ 1 ](BF4)2. This complex comprises two bis(1-methyl-4,5-diphenyl-1H-imidazol-2-yl)methane (HBMIM ) ligands that contain an acidic methylene moiety in their backbone. Upon reduction of [ 1 ](BF4)2 by either electrochemical or chemical means, one of its HBMIM ligands undergoes deprotonation under the formation of dihydrogen. Addition of a mild proton source (acetic acid) to deprotonated complex [ 2 ](BF4) regenerates protonated complex [ 1 ](BF4)2. In presence of acetic acid in acetonitrile solvent [ 1 ](BF4)2 shows electrocatalytic proton reduction with a kobs of ≈200 s−1 at an overpotential of 590 mV. Mechanistic investigations supported by DFT (BP86) suggest that dihydrogen formation takes place in an intramolecular fashion through the participation of a methylene C−H bond of the HBMIM ligand and a CoII−H bond through formal heterolytic splitting of the latter. These findings are of interest to the development of responsive ligands for molecular (base)metal (electro)catalysis. 相似文献
13.
Wuister SF de Mello Donegá C Meijerink A 《Journal of the American Chemical Society》2004,126(33):10397-10402
Luminescence temperature antiquenching (LTAQ) is observed for water-soluble CdTe quantum dots (QDs) capped with aminoethanethiol (AET). The efficient exciton emission (quantum efficiency of approximately 40% at 300 K) is quenched almost completely as the QD solutions are cooled to below 230 K and is fully recovered around 270 K upon warming up to room temperature (LTAQ). Temperature-dependent lifetime measurements show that the quenching rate is high, resulting in an on/off behavior. No LTAQ is observed for CdTe QDs capped with aminoundecanethiol (AUT). The LTAQ is explained by the influence of solvent freezing on the surface of the QD core. Freezing of the solvation water molecules surrounding the QD will induce strain in the capping shell, due to the interaction between water and the charged heads of the capping molecules. Short carbon chains (AET) will propagate the strain to the QD surface, creating surface quenching states, whereas long and flexible chains (AUT) will dissipate the strain, thus avoiding surface distortion. Freezing-point depression by the addition of methanol results in a lowering of the transition temperature. Additional support is provided by the size dependence of the LTAQ: smaller particles, with higher local ionic strength due to a higher density of charged NH(3)(+) surface groups, experience a lower transition temperature due to stronger local freezing-point depression. 相似文献
14.
Gantenberg M Halupka M Sander W 《Chemistry (Weinheim an der Bergstrasse, Germany)》2000,6(10):1865-1869
The pulse deposition technique allows selectively the isolation of monomeric or dimeric formic acid in argon matrices at 7 K. Warming of matrices containing the monomer M from 7 K to 40 K results in the decrease of M and formation of a dimer B. This dimer is also labile, and further warming finally produces a second dimer A. By comparison with density functional theory (DFT) calculations and gas phase IR spectra taken from the literature, the latter dimer A was identified as the C2h-symmetrical cyclic dimer. The unstable dimer B was identified as the acyclic Cs-symmetrical dimer. An activation energy of 2.3 kcal mol(-1) was calculated for the B --> A rearrangement at the B3LYP/ 6-311 ++ G(d,p) level of theory, which is in qualitative agreement with the experimental finding of a slow thermal reaction under the conditions of matrix isolation. 相似文献
15.
A series of commercial monomeric and polymeric C(18), C(27), and C(30) stationary phases were compared with immobilized poly(ethylene-co-acrylic acid) stationary phases synthesized in-house. The columns were characterized on the basis of methylene selectivity, silanol activity, metal activity, pore size, shape selectivity, and the ability to separate tocopherol isomers and carotenoid isomers. Monomeric and polymeric C(30) phases were shown to yield excellent separations of the tocopherol isomers while the polymeric C(30) and polyethylene phases were more appropriate to the separation of carotenoids. 相似文献
16.
Uranium (VI) can be determined by adsorptive voltammetric techniques, as its chloranilic acid complex, over a wide concentration range. Differential pulse polarography is useful for quantification of uranium between 0.1 and 1.5 mg/l; for the range from 10 to 500 g/l differential pulse voltammetry and for ultra-trace analysis between 0.024 and 40 g/l adsorptive stripping voltammetry are preferred. The standard deviation for the 3-detection limit of 24 ng/l uranium was found to be 8%. In the trace analysis of metals in aquatic environmental systems by adsorptive stripping voltammetry it is normally necessary to decompose polluted water samples by UV irradiation or microwave digestion. The advantage of the developed method is the fact that no sample pretreatment is necessary.Dedicated to Professor R. Geyer on the occasion of his 80th birthday 相似文献
17.
18.
19.
20.