全文获取类型
收费全文 | 492篇 |
免费 | 6篇 |
国内免费 | 2篇 |
专业分类
化学 | 389篇 |
晶体学 | 3篇 |
力学 | 3篇 |
数学 | 27篇 |
物理学 | 78篇 |
出版年
2022年 | 2篇 |
2021年 | 2篇 |
2017年 | 2篇 |
2015年 | 3篇 |
2014年 | 5篇 |
2013年 | 20篇 |
2012年 | 13篇 |
2011年 | 20篇 |
2010年 | 10篇 |
2009年 | 13篇 |
2008年 | 21篇 |
2007年 | 24篇 |
2006年 | 25篇 |
2005年 | 19篇 |
2004年 | 14篇 |
2003年 | 18篇 |
2002年 | 20篇 |
2001年 | 6篇 |
2000年 | 11篇 |
1999年 | 5篇 |
1998年 | 4篇 |
1997年 | 2篇 |
1996年 | 14篇 |
1995年 | 8篇 |
1994年 | 5篇 |
1993年 | 11篇 |
1992年 | 12篇 |
1991年 | 8篇 |
1990年 | 16篇 |
1989年 | 13篇 |
1988年 | 8篇 |
1987年 | 7篇 |
1985年 | 16篇 |
1984年 | 13篇 |
1983年 | 13篇 |
1982年 | 8篇 |
1981年 | 7篇 |
1980年 | 14篇 |
1979年 | 12篇 |
1978年 | 8篇 |
1977年 | 8篇 |
1976年 | 5篇 |
1975年 | 7篇 |
1974年 | 8篇 |
1972年 | 4篇 |
1971年 | 1篇 |
1970年 | 1篇 |
1969年 | 1篇 |
1968年 | 4篇 |
1967年 | 3篇 |
排序方式: 共有500条查询结果,搜索用时 15 毫秒
1.
Hyperfine interaction constants (HFICs) of dangling bonds for CN and SiN films were calculated by density-functional theory. The averaged 14N isotropic HFICs for C dangling bonds are almost equal to those for Si dangling bonds. The anisotropic 14N HFICs calculated for C dangling bonds are larger than those for Si dangling bonds by a factor 2. The calculated results were compared with experimental results obtained by electron spin resonance and electron nuclear double resonance. It was indicated that the carbon dangling bonds are located such that they avoid N atoms in CN films. 相似文献
2.
Air containing particulate material was passed continuously for one month through a low-volume air sampler equipped with a cyclone to exclude particulates greater than 10 μm in diameter. The samples and filters were ashed in a low-temperature plasma and, after addition of In2O3 support, palladium internal standard and graphite buffer, the ashes were analyzed by a.c. are emission spectrometry. Standard samples were prepared from a commercial standard containing 49 elements. The procedure allows the determination of 14 trace metals (Ag, Al, Cr, Cu, Fe, Ga, Mn, Mo, Ni, Pb, Sn, Ti, V, Zn) with relative standard deviations of 1.4–15.1%. The procedure has been applied successfully to monthly determinations of the average atmospheric concentrations of these elements in Kobe City for the past three years. 相似文献
3.
Motohiko Hikuma Haruo Obana Takeo Yasuda Isao Karube Shuichi Suzuki 《Analytica chimica acta》1980,116(1):61-67
The sensor consists of immobilized E. coli (which contains glutamate decarboxylase) and a carbon dioxide gas-sensor. Continuous introduction of sample solution into a flow system incorporating the sensor gives a potential which increases until a steady state is reached after 5 min. Measurements can also be made with only a 1- or 3-min introduction period with little loss of sensitivity. Calibration plots of mV measurements vs. logarithmic glutamic acid concentration are linear in the range 100–800 mg l-1. The sensor is highly selective, stable and reproducible. It has been applied to the determination of glutamic acid in fermentation broths. 相似文献
4.
The number of perfect rnatchings for the linear 2 × 2 ×n cubic lattice was analytically derived by diagonalizing the skew—symmetric 4n × 4n determinant, whose non—zero off—diagonal elements are either ±1 or ±i (pure imaginary number). The basic formulation invoking the matrix manipulation follows that of Kasteleyn, but the result obtained in this paper is the first example of the analytical solution for a special case of the three-dimensional Ising model.received by the Publisher 20 September 1989 相似文献
5.
Funyu S Isobe T Takagi S Tryk DA Inoue H 《Journal of the American Chemical Society》2003,125(19):5734-5740
Visible light irradiation of a reaction mixture of carbonyl-coordinated tetra(2,4,6-trimethyl)phenylporphyrinatoruthenium(II) (Ru(II)TMP(CO)) as a photosensitizer, hexachloroplatinate(IV) as an electron acceptor, and an alkene in alkaline aqueous acetonitrile induces selective epoxidation of the alkene with high quantum yield (Phi = 0.6, selectivity = 94.4% for cyclohexene and Phi = 0.4, selectivity = 99.7% for norbornene) under degassed conditions. The oxygen atom of the epoxide was confirmed to come from a water molecule by an experiment with H(2)(18)O. cis-Stilbene was converted into its epoxide, cis-stilbeneoxide, without forming trans-stilbeneoxide. trans-Stilbene, however, did not exhibit any reactivity. Under neutral conditions, an efficient buildup of the cation radical of Ru(II)TMP(CO) was observed at the early stage of the photoreaction, while an addition of hydroxide ion caused a rapid reaction with the cation radical to promote the reaction with reversion to the starting Ru(II)TMP(CO). A possible involvement of a higher oxidized state of Ru such as Ru(IV), Ru(V), Ru(VI) through a dismutation of the Ru(III) species was excluded by an experiment with Ru(VI)TMP(O)(2). Decarbonylation of the Ru complex was also proven to be invalid. A reaction mechanism involving an electron transfer from the excited triplet state of Ru(II)TMP(CO) to hexachloroplatinate(IV) and subsequent formation of OH(-)-coordinated Ru(III) species, leading to an oxo-ruthenium complex as the key intermediate of the photochemical epoxidation, was postulated. 相似文献
6.
Sakae Uemura Haruo Miyoshi Masaya Okano Isao Morishima Toshiro Inubushi 《Journal of organometallic chemistry》1979,165(1):9-19
Treatment of norbornene, norbornadiene, benzonorbornadiene, and chloro- and methoxy-benzonorbornadiene with thallium(III) acetate in methanol affords only the corresponding cis-exo-acetoxythallation adducts in a sharp contrast to oxymercuration of such strained olefins where methoxymercuration prevails. In the cases of substituted benzonorbornadienes the products are obtained as the regioisomeric mixtures, the isomer ratio being determined by 13C NMR. In the cases of 5-norbornene-2,3-dicarboxylic anhydride, 5-norbornene-2-methyl-2,3-dicarboxylic anhydride, and 5-norbornen-2-endo-carboxylic acid, lactonization occurs to give a trans-oxythallation adduct having a lactone ring, no introduction of either methoxy or acetoxy groups being observed. 1H and/or 13C NMR data for several new oxythallation adducts are provided. The alkaline sodium borohydride reduction of adducts in methanol affords mainly the parent olefin together with 10–16% yields of the corresponding exo-alcohol. 相似文献
7.
Toshio Takido Sachiko Tamura Kenji Sato Haruo Kamijo Toshikatsu Nakazawa Manabu Seno Tadashi Hata 《Journal of heterocyclic chemistry》1998,35(2):437-443
The synthesis of hexahydrooxoepithiopyridinedicarboxyimide (5: X2 = N-Ph) by the reaction of thioamides 1 with N-substituted maleimide ( 2a ) was examined. The reaction of primary thioamides, such as thiobenzamide and p-toluthioamide with N-phenylmaleimide gives compounds 5 together with corresponding 4-hydroxy-1,3-thiazoles 4 . However, a similar reaction of secondary thioamides, such as N-methylthioacetamide, thiobenzanilide, with N-phenylmaleimide did not provide compounds 5 without addition of acid. The reaction pathway and the configuration of 5 were also investigated. 相似文献
8.
The reaction of conjugated dienes such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2,5-dimethyl-2,4-hexadiene, 1,3-cyclopentadiene, and 1,3-cyclohexadiene, with thallium(III)acetate in acetic acid at 10–65° for 0.5–15 hr affords an isomeric mixture of the corresponding diacetoxyalkenes (1,2- and 1,4-addition products) in 10–92% yields. The 1,2-addition products are predominantly formed in all cases examined except the case of 1,3-cyclopentadiene. The reaction is assumed to proceed through acetoxythallation and dethallation steps, the latter step being accompanied and/or followed by an attack of acetoxyl group. An initial attack of thallium moiety is proposed to occur mainly at C-1 and C-2 carbons in the cases of linear terminal dienes and cyclic dienes, respectively. 相似文献
9.
Yamaguchi T Sunatsuki Y Kojima M Akashi H Tsuchimoto M Re N Osa S Matsumoto N 《Chemical communications (Cambridge, England)》2004,(9):1048-1049
Dinuclear [(NiL)Gd(hfac)(2)(EtOH)](H(3)L = 1,1,1-tris(N-salicylideneaminomethyl)ethane, Hhfac = hexafluoroacetylacetone), trinuclear [(NiL)(2)Gd(NO(3))], and tetranuclear [(NiL)Gd(CH(3)CO(2))(2)(MeOH)](2) complexes, were prepared by treating [Ni(HL)] with [Gd(hfac)(3)(H(2)O)(2)], Gd(NO(3))(3).6H(2)O, and Gd(CH(3)CO(2))(3).4H(2)O, respectively, in the presence of Et(3)N. All the complexes show that ferromagnetic interactions occur between the Ni(II) and Gd(III) ions. 相似文献
10.
Talukder MM Takeyama T Hayashi Y Wu JC Kawanishi T Shimizu N Ogino C 《Applied biochemistry and biotechnology》2003,110(2):101-112
The activity and stability of Chromobacterium viscosum lipase (glycerolester hydrolase, EC 3.1.1.3)-catalyzed olive oil hydrolysis in sodium bis (2-ethyl-1-hexyl)sulfosuccinate (AOT)/isooctane reverse micelles is increased appreciably when low molecular weight polyethylene
glycol (PEG 400) is added to the reverse micelles. To understand the effect of PEG 400 on the phase behavior of the reverse
micellar system, the phase diagram of AOT/PEG 400/water/isooctane system was studied. The influences of relevant parameters
on the catalytic activity in AOT/PEG 400 reverse micelles were investigated and compared with the results in the simple AOT
reverse micelles. In the presence of PEG 400, the linear decreasing trend of the lipase activity with AOT concentration, which
is observed in the simple AOT reverse micelles, disappeared. Enzyme entrapped in AOT/PEG reverse micelles was very stable,
retaining>75% of its initial activity after 60 d, whereas the half-life in simple AOT reverse micelles was 38 d. The kinetics
parameter maximum velocity (V
max)exhibiting the temperature dependence and the activation energy obtained by Arrhenius plot was suppressed significantly by
the addition of PEG 400. 相似文献