全文获取类型
收费全文 | 1671篇 |
免费 | 49篇 |
国内免费 | 3篇 |
专业分类
化学 | 1317篇 |
晶体学 | 16篇 |
力学 | 19篇 |
数学 | 48篇 |
物理学 | 323篇 |
出版年
2023年 | 7篇 |
2021年 | 21篇 |
2020年 | 17篇 |
2019年 | 26篇 |
2018年 | 14篇 |
2017年 | 15篇 |
2016年 | 15篇 |
2015年 | 28篇 |
2014年 | 27篇 |
2013年 | 78篇 |
2012年 | 78篇 |
2011年 | 87篇 |
2010年 | 46篇 |
2009年 | 38篇 |
2008年 | 91篇 |
2007年 | 103篇 |
2006年 | 82篇 |
2005年 | 102篇 |
2004年 | 90篇 |
2003年 | 69篇 |
2002年 | 67篇 |
2001年 | 48篇 |
2000年 | 37篇 |
1999年 | 31篇 |
1998年 | 30篇 |
1997年 | 22篇 |
1996年 | 30篇 |
1995年 | 17篇 |
1994年 | 20篇 |
1993年 | 26篇 |
1992年 | 29篇 |
1991年 | 22篇 |
1990年 | 14篇 |
1989年 | 25篇 |
1988年 | 7篇 |
1987年 | 9篇 |
1986年 | 21篇 |
1985年 | 22篇 |
1984年 | 23篇 |
1983年 | 11篇 |
1982年 | 24篇 |
1981年 | 17篇 |
1980年 | 12篇 |
1979年 | 21篇 |
1978年 | 13篇 |
1977年 | 17篇 |
1976年 | 14篇 |
1975年 | 16篇 |
1974年 | 12篇 |
1973年 | 11篇 |
排序方式: 共有1723条查询结果,搜索用时 31 毫秒
71.
[reaction: see text] A copper fluoride-catalyzed cyanomethylation that can be applied to a wide range of ketones and aldehydes was developed using TMSCH(2)CN as a nucleophile. The reaction was extended to a conceptually more advanced copper alkoxide-catalyzed direct addition of alkylnitriles to aldehydes, which can act as a surrogate direct catalytic aldol reaction of esters. These reactions can be applied to the first catalytic enantioselective cyanomethylation of ketones and direct catalytic enantioselective cyanomethylation of aldehydes. 相似文献
72.
An enzyme reactor consisting of a 2.6-m-long silicon capillary with glucose oxidase immobilized on the inner surface was fabricated using micromachining techniques. A V-shaped groove of 100 μm width, formed by anisotropic etching, was anodically bonded to a glass plate to create the capillary. Glucose oxidase was covalently immobilized with 3-aminopropyltriethoxysilane and glutaraldehyde. The reactor was evaluated by connecting it to a Flow injection analysis system for glucose detection. Glucose concentrations were in the range of 10−3 to 5 × 10−2M with a volume of 0.2 μl of glucose solution. 相似文献
73.
S Fujimoto K Murakami T Hosoda Y Yamamoto K Watanabe Y Morinaka A Ohara 《Chemical & pharmaceutical bulletin》1992,40(5):1231-1235
Acid phosphatase isozyme was highly purified from rat liver mitochondrial fraction. The enzyme showed an isoelectric point value of above 9.5 on isoelectric focusing, and the apparent molecular weight was estimated to be 32000 by Sephadex G-100 gel filtration or 16000 by sodium dodecyl sulfate-polyacrylamide gel electrophoresis. The enzyme catalyzed the hydrolysis of adenosine 5'-triphosphate, adenosine 5'-diphosphate, thiamine pyrophosphate, inorganic pyrophosphate, and phosphoprotein such as casein and phosvitin, but not of several phosphomonoesters, except for p-nitrophenyl phosphate and o-phosphotyrosine. The enzyme was not inhibited by L-(+)-tartrate, and was significantly activated by Fe2+ and reducing agents such as ascorbic acid, L-cysteine,and dithiothreitol. The enzyme was found to be distributed in various rat tissues including liver, spleen, kidney, small intestine, lung, stomach, brain and heart, but not in skeletal muscle. 相似文献
74.
The liquid-liquid extraction of copper(I) with 12-, 13-, 15- and 16-membered cyclic tetrathio ethers ([n]aneS4, where n represents the total number of carbon and sulphur atoms in the cyclic ligand ring) was examined stoichiometrically using picrate ion (Pic?) for the formation of the ion pair. Copper(I) was extracted with four ligands (L) into 1,2-dichloroethane as the ion-pair compound, [Cu(I)L]+Pic?. The extraction constant, Kex, with each ligand was determined. As the ring size of cyclic tetrathio ethers increases, the log Kex values, including that previously reported for [14]aneS4, increase from 7.7 to 9.4. The value of Δ log Kex, which represents the increase in log Kex due to the addition of one carbon atom to the macrocyclic ring, was large between [13]aneS4 and [14]aneS4 (Δ log Kex=1.0) and small between [14]aneS4 and [15]aneS4 (Δ log Kex=0.1). 相似文献
75.
Yoshida N Ishizuka T Yofu K Murakami M Miyasaki H Okada T Nagata Y Itaya A Cho HS Kim D 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(12):2854-2866
A series of zinc(II) porphyrin-imide dyads (ZP-Im), in which an electron donating ZP moiety is directly connected to an electron accepting imide moiety in the meso position, have been prepared for the examination of energy gap dependence of intramolecular electron transfer reactions with large electronic coupling. The nearly perpendicular conformation of the imide moiety towards the porphyrin plane has been revealed by Xray crystal structures. The energy gap for charge separation, 1ZP* - Im --> ZP+ - Im-, is varied by changing the electron accepting imide moiety to cover a range of about 0.8 eV in DMF. Definitive evidence for electron transfer has been obtained in three solvents (toluene, THF, and DMF) through picosecond-femtosecond transient absorption studies, which have allowed us to determine the rates of photoinduced charge separation, 1ZP* - Im --> ZP+ - Im-, and subsequent thermal charge recombination ZP+ - Im- --> ZP - Im. The free-energy gap dependence (energy gap law) has been probed from the normal to the nearly top region for the charge separation rate alone, and only the inverted region for the charge recombination rate. Although both of the energy gap dependencies can be approximately reproduced by means of the simplified semiclassical equation, when we take into consideration the effect of the high frequency vibrations replaced by one mode of averaged frequency, many features, including the effects of solvent polarity and the electron tunneling matrix element on the energy gap law, differ considerably from those of the previously studied porphyrin-quinone systems, which have weaker interchromophore electronic interactions. 相似文献
76.
77.
Wataru Sugimoto Masashi Omoto Katsunori Yokoshima Yasushi Murakami Yoshio Takasu 《Journal of solid state chemistry》2004,177(12):4542-4545
An ion-exchangeable ruthenate with a layered structure, K0.2RuO2.1, was prepared by solid-state reactions. The interlayer cation was exchanged with H+, C2H5NH3+, and ((C4H9)4N+) through proton-exchange, ion-exchange, and guest-exchange reactions. The electrical and magnetic properties of the products were characterized by DC resistivity and susceptibility measurements. Layered K0.2RuO2.1 exhibited metallic conduction between 300 and 13 K. The products exhibited similar magnetic behavior despite the differences in the type of interlayer cation, suggesting that the ruthenate sheet in the protonated form and the intercalation compounds possesses metallic nature. 相似文献
78.
Suginome M Ohmura T Miyake Y Mitani S Ito Y Murakami M 《Journal of the American Chemical Society》2003,125(37):11174-11175
Enantioenriched beta-borylallylsilanes were synthesized by palladium-catalyzed enantioface-selective addition of the silicon-boron bond to terminal allenes using a palladium catalyst possessing a chiral monodentate phosphine ligand. Use of a silylborane bearing a chiral auxiliary on the boron atom was beneficial to gain enantioface selectivities as high as 96% de. 相似文献
79.
Takiue T Hirose D Murakami D Sakamoto H Matsubara H Aratono M 《The journal of physical chemistry. B》2005,109(34):16429-16434
The interfacial tension gamma of the hexane solution of 1H,1H-perfluorononanol (FDFC(9)OH) and its omega-hydrogenated analogue, 1H,1H,9H-perfluorononanol (HDFC(9)OH), against water was measured as a function of pressure and concentration at 298.15 K in order to clarify the effect of omega-dipole on the orientation of fluorononanol molecules from the viewpoint of volume. The adsorbed films of both alcohols exhibit two kinds of phase transitions among three different states: the gaseous, expanded, and condensed states. The partial molar volume changes of adsorption - in the expanded and condensed states were evaluated and compared between the two systems. The - values of both alcohols are negative, and thus the alcohol molecules have smaller volume in the adsorbed film than in the bulk solution. Furthermore, the value was obtained through the evaluation of by the density measurement of the bulk hexane solution. It was found that the value of HDFC(9)OH is smaller than that of FDFC(9)OH in the condensed state. On the basis of three matters concerning the molecular structure of alcohols, the occupied area at the interface, and the orientation of FDFC(9)OH in the adsorbed film deduced from the earlier results of X-ray reflectivity measurement, the mean tilt angle of HDFC(9)OH from the interface normal in the condensed film was estimated to be 15 degrees . The thermodynamic estimation demonstrated here is highly valuable one to provide structure information on an adsorbed film. 相似文献
80.
Itaru Yamashita Youhei Kawabata Tadashi Kato Masakatsu Hato Hiroyuki Minamikawa 《Colloids and surfaces. A, Physicochemical and engineering aspects》2004,250(1-3):485-490
Small angle X-ray scattering (SAXS) is measured for the lamellar phase in aqueous systems of 1-o-β-3,7-dimethyoctyl-D-glucopyranoside (β-Glc(Ger)), which has recently been prepared by us, 1-o-β-decyl-D-glucopyranoside (β-GlcC10), and 1-o-β-octyl-D-glucopyranoside (β-GlcC8). The repeat distance d obtained from the position of the diffraction peak does not follow the swelling law d = 2δhc/hc, where δhc and hc are the thickness and the volume fraction of the hydrophobic layer, respectively. This may result from the fact that δhc increases and, equivalently, the surface area per surfactant molecule (as) decreases with increasing concentration. So we calculate δhc and as from the observed d value at each concentration using the above swelling law. The half-thickness δhc increases in the order β-GlcC8 < β-Glc(Ger) < β-GlcC10 at a fixed concentration. On the other hand, the data on as for β-GlcC10 and β-GlcC8 lie on the same line and the data for β-Glc(Ger) lies above this line. These results suggest that the cross-sectional area of the geranyl chain is larger than that of the glucose headgroup. Existence of water filled defects in bilayer sheets is also discussed based on the SAXS pattern and the concentration dependence of d. 相似文献