全文获取类型
收费全文 | 1611篇 |
免费 | 49篇 |
国内免费 | 8篇 |
专业分类
化学 | 1232篇 |
晶体学 | 24篇 |
力学 | 20篇 |
数学 | 84篇 |
物理学 | 308篇 |
出版年
2022年 | 14篇 |
2021年 | 13篇 |
2020年 | 24篇 |
2019年 | 21篇 |
2018年 | 13篇 |
2017年 | 16篇 |
2016年 | 26篇 |
2015年 | 41篇 |
2014年 | 48篇 |
2013年 | 94篇 |
2012年 | 83篇 |
2011年 | 101篇 |
2010年 | 47篇 |
2009年 | 50篇 |
2008年 | 103篇 |
2007年 | 101篇 |
2006年 | 97篇 |
2005年 | 117篇 |
2004年 | 94篇 |
2003年 | 92篇 |
2002年 | 77篇 |
2001年 | 29篇 |
2000年 | 17篇 |
1999年 | 26篇 |
1998年 | 15篇 |
1997年 | 14篇 |
1996年 | 16篇 |
1995年 | 18篇 |
1994年 | 12篇 |
1993年 | 13篇 |
1992年 | 15篇 |
1991年 | 5篇 |
1990年 | 13篇 |
1989年 | 12篇 |
1988年 | 9篇 |
1987年 | 9篇 |
1986年 | 6篇 |
1985年 | 14篇 |
1984年 | 19篇 |
1983年 | 15篇 |
1982年 | 12篇 |
1981年 | 17篇 |
1980年 | 7篇 |
1979年 | 13篇 |
1978年 | 10篇 |
1977年 | 9篇 |
1976年 | 10篇 |
1975年 | 8篇 |
1974年 | 11篇 |
1973年 | 7篇 |
排序方式: 共有1668条查询结果,搜索用时 15 毫秒
21.
It was confirmed that the rhenium complex, ReBr(CO)5, catalyzed the allylation of aldehydes with allyltributylstannane to give the corresponding homoallylic alcohols in moderate to good yields. Similarly, the reaction of aldehydes with enol silyl ether was efficiently promoted by the rhenium catalyst to afford the corresponding β-hydroxy carbonyl compounds. 相似文献
22.
A novel lignan: sphaerophyside SC was isolated from ethanolic extract of the seeds of Sphaerophysa salsula (Pall.) DC. The structure of the compound was elucidated mainly on the basis of the 1D NMR and 2D NMR data. 相似文献
23.
Alfred Trautwein Yutaka Maeda Frank E. Harris Helmuth Formanek 《Theoretical chemistry accounts》1974,36(1):67-76
Experimental Mössbauer spectra of the Fe57-enriched CO complex of sperm whale myoglobin (MbCO) at T= 4.2 K with and without applied magnetic field (H⊥γ) were measured to derive the sign of the electric field gradient (EFG), the quadrupole splitting ΔE Q, and the isomer shift δ of the heme iron. We find a positive EFG, δE Q = 0.363 mm/sec, and δ + 0.266 mm/sec. Molecular orbital calculations were carried out to obtain theoretical estimates of EFG and ΔE Q for several steric arrangements of the CO ligand relative to the heme group. Our results are most consistent with the conclusion that the iron is situated in the heme plane, and that a bent geometry with a Fe-C-O angle of about 135 ° is more favorable than a more symmetric structure with a linear Fe-C-O geometry. 相似文献
24.
Yutaka Hiramine 《Geometriae Dedicata》1993,48(2):139-189
In this paper we consider finite nets of orderq
2 and degreeq + 1 which admit GL(2,q). Our main result says that if a net
of orderq
2 and degreeq + 1 admits a collineation group with a point-regular normal subgroupT such that /T GL(2,q), then
is isomorphic to a regulus net, a twisted regulus net, a Hering net, or
. Except in the last one, each of them corresponds to a surface in PG(3,q) obtained from a homogeneous polynomial in two variables. 相似文献
25.
[reaction: see text] Diphenylphosphine oxide and related P(O)H compounds react with propargyl alcohols at room temperature in the presence of a catalytic amount of Ni(0) complex and Ph(2)P(O)OH to produce high yields of phosphinoyl 1,3-dienes though an efficient in situ dehydration process. 相似文献
26.
Cao B Wakahara T Tsuchiya T Kondo M Maeda Y Aminur Rahman GM Akasaka T Kobayashi K Nagase S Yamamoto K 《Journal of the American Chemical Society》2004,126(30):9164-9165
A new metallofullerene, La2@C78, has been synthesized by DC arc discharge method, isolated by high-performance liquid chromatography, and characterized by laser desorption time-of-flight mass spectrometry, UV-vis-NIR absorption, differential pulse voltammetry, 13C NMR spectroscopy, and theoretical calculations. The La2@C78/CS2 solution is dark violet and presents several characteristic absorption features at 647, 561, 533, and 386 nm, with an onset around 1000 nm. With respect to empty D3-C78, the capability of La2@C78 as an electron acceptor or donor is stronger. Addition of 1,1,2,2-tetrakis(2,4,6-trimethylphenyl)-1,2-disirane to La2@C78 photochemically, as well as thermally, affords bis- and mono-adducts. Theoretical studies and 13C NMR spectroscopic analysis of La2@C78 indicate that it possesses a D3h-C78 cage (78:5). 相似文献
27.
Oseki Y Fujitsuka M Hara M Cai X Ie Y Aso Y Majima T 《The journal of physical chemistry. B》2005,109(21):10695-10698
Photophysical properties of oligo(2,3-thienyleneethynylene)s (nTE, n denotes the number of thiophene rings, n = 2, 3) in benzene were investigated using steady-state, time-resolved fluorescence, and transient absorption spectroscopies. For 2TE, generation of the radiative S2 and nonradiative S1 states was confirmed. Upon excitation, the S2 state was initially generated and deactivated to the S1 state within 10 ps. The S1 state exhibited the transient absorption band at 470 nm, of which the lifetime was estimated to be 5.3 ns. In the case of 3TE, on the other hand, it was revealed that the radiative S1 state with a transient absorption peak at 650 nm was generated upon excitation. The T1 states of nTE were generated from the S1 states. The quantum yields were estimated to be 0.52 and 0.54 for 2TE and 3TE, respectively. Extremely fast reactions in the higher triplet excited state were indicated for both 2TE and 3TE. 相似文献
28.
Ishii Y Iwahama T Sakaguchi S Nakayama K Nishiyama Y 《The Journal of organic chemistry》1996,61(14):4520-4526
A novel class of catalysts for alkane oxidation with molecular oxygen was examined. N-Hydroxyphthalimide (NHPI) combined with Co(acac)(n)() (n = 2 or 3) was found to be an efficient catalytic system for the aerobic oxidation of cycloalkanes and alkylbenzenes under mild conditions. Cycloalkanes were successfully oxidized with molecular oxygen in the presence of a catalytic amount of NHPI and Co(acac)(2) in acetic acid at 100 degrees C to give the corresponding cycloalkanones and dicarboxylic acids. Alkylbenzenes were also oxidized with dioxygen using this catalytic system. For example, toluene was converted into benzoic acid in excellent yield under these conditions. Ethyl- and butylbenzenes were selectively oxidized at their alpha-positions to form the corresponding ketones, acetophenone, and 1-phenyl-1-butanone, respectively, in good yields. A key intermediate in this oxidation is believed to be the phthalimide N-oxyl radical generated from NHPI and molecular oxygen using a Co(II) species. The isotope effect (k(H)/k(D)) in the oxidation of ethylbenzene and ethylbenzene-d(10) with dioxygen using NHPI/Co(acac)(2) was 3.8. 相似文献
29.
Large-scale separation of metallic and semiconducting single-walled carbon nanotubes 总被引:6,自引:0,他引:6
Maeda Y Kimura S Kanda M Hirashima Y Hasegawa T Wakahara T Lian Y Nakahodo T Tsuchiya T Akasaka T Lu J Zhang X Gao Z Yu Y Nagase S Kazaoui S Minami N Shimizu T Tokumoto H Saito R 《Journal of the American Chemical Society》2005,127(29):10287-10290
In the applications of single-walled carbon nanotubes (SWNTs), it is extremely important to separate semiconducting and metallic SWNTs. Although several methods have been reported for the separation, only low yields have been achieved at great expense. We show a separation method involving a dispersion-centrifugation process in a tetrahydrofuran solution of amine, which makes metallic SWNTs highly concentrated to 87% in a simple way. 相似文献
30.
Nishimura K Suzuki T Momchilova S Miyashita K Katsura E Itabashi Y 《Journal of chromatographic science》2005,43(9):494-499
A simple and highly sensitive method for determining the fatty acid composition of food lipids containing conjugated linoleic acid (CLA) is described. The method is based on the separation of the 9-anthrylmethyl ester derivatives of saturated and unsaturated (conjugated and non-conjugated) fatty acids by reversed-phase high-performance liquid chromatography with fluorescence detection. Just like the other fatty acids, CLA reacts readily with 9-anthryldiazomethane at room temperature to produce 9-anthrylmethyl esters without isomerization and decomposition of the conjugated double bonds. Clear resolution of the individual fatty acids as their 9-anthrylmethyl esters is achieved on a highly efficient octadecylsilylated silica column (150- x 3-mm i.d., 3-microm particle size) using a stepwise gradient elution with methanol-water. The method is standardized with commercially available CLA isomers (cis-9, trans-11 and trans-10, cis-12-octadecadienoic acids, and their cis,cis and trans,trans isomers) and applied for determination of the fatty acid compositions of milk and sdairy products. 相似文献