全文获取类型
收费全文 | 2258篇 |
免费 | 101篇 |
国内免费 | 10篇 |
专业分类
化学 | 1821篇 |
晶体学 | 28篇 |
力学 | 25篇 |
数学 | 160篇 |
物理学 | 335篇 |
出版年
2023年 | 18篇 |
2022年 | 19篇 |
2021年 | 27篇 |
2020年 | 21篇 |
2019年 | 56篇 |
2018年 | 34篇 |
2017年 | 21篇 |
2016年 | 62篇 |
2015年 | 51篇 |
2014年 | 63篇 |
2013年 | 113篇 |
2012年 | 154篇 |
2011年 | 152篇 |
2010年 | 69篇 |
2009年 | 76篇 |
2008年 | 169篇 |
2007年 | 125篇 |
2006年 | 140篇 |
2005年 | 148篇 |
2004年 | 126篇 |
2003年 | 119篇 |
2002年 | 91篇 |
2001年 | 39篇 |
2000年 | 44篇 |
1999年 | 20篇 |
1998年 | 14篇 |
1997年 | 21篇 |
1996年 | 28篇 |
1995年 | 11篇 |
1994年 | 12篇 |
1993年 | 15篇 |
1992年 | 26篇 |
1991年 | 14篇 |
1990年 | 15篇 |
1989年 | 15篇 |
1988年 | 8篇 |
1987年 | 9篇 |
1986年 | 15篇 |
1985年 | 30篇 |
1984年 | 19篇 |
1983年 | 8篇 |
1982年 | 12篇 |
1981年 | 20篇 |
1980年 | 9篇 |
1979年 | 14篇 |
1978年 | 12篇 |
1977年 | 14篇 |
1976年 | 23篇 |
1975年 | 18篇 |
1974年 | 6篇 |
排序方式: 共有2369条查询结果,搜索用时 93 毫秒
91.
The reaction of ortho-alkynylated benzaldehydes 1 with allyltrimethylsilane under the Pd(OAc)2-CuCl2 catalyst system gave the isochromene derivatives 2 together with the chlorinated products 3. When the reaction was conducted in the presence of half equiv of H2O, the formation of 3 was suppressed and 2 was obtained in good to high yields. When the reaction of 1a was carried out with trimethylsilylcyanide instead of allylsilane, the cyano group-substituted isochromene 9 was obtained in 94% yield. 相似文献
92.
Power-free poly(dimethylsiloxane) microfluidic devices for gold nanoparticle-based DNA analysis 总被引:1,自引:0,他引:1
An extremely simple, power-free pumping method for poly(dimethylsiloxane)(PDMS) microfluidic devices is presented. By exploiting the high gas solubility of PDMS, the energy for the pumping is pre-stored in the degassed bulk PDMS, therefore no additional structures other than channels and reservoirs are required. In a Y-shaped microchannel with cross section of 100 microm width x 25 microm height, this method has provided flow rate of 0.5-2 nL s(-1), corresponding to linear velocity of 0.2-0.8 mm s(-1), with good reproducibility. As an application of the power-free pumping, gold nanoparticle-based DNA analysis, which does not rely on the cross-linking mechanism between nanoparticles, has been implemented in a microchannel with three inlets. Target 15mer DNA has been easily and unambiguously discriminated from its single-base substituted mutant. Instead of colorimetric detection in a conventional microtube, an alternative detection technique suitable for microdevices has been discovered-observation of deposition on the PDMS surfaces. The channel layout enabled two simultaneous DNA analyses at the two interfaces between the three laminar streams. 相似文献
93.
M. Akiyama M. Narita K. Seida T. Osawa 《Journal of polymer science. Part A, Polymer chemistry》1976,14(9):2173-2181
N-Hydroxysuccinimide-type soluble copolymer with styrene and three similar divinylbenzene (3–4 mole-%) crosslinked copolymers with styrene, N-vinylpyrrolidone, and N,N-dimethylacrylamide were prepared from their precursor copolymers of N-acetoxymaleimide. Acylation of these N-hydroxyl polymers with carbobenzoxyoligo-?-aminocaproic acids was conducted in dimethylformamide at room temperature by using dicyclohexylcarbodiimide as condensing agent. The soluble styrene copolymer was acylated in good conversions (76–89%) in every case (n = 1–3), whereas the acylation of the crosslinked copolymers decreased slightly from n = 1 to n = 2, and dropped suddenly to only small conversions (4.7–7.4%) with n = 3, showing a marked inhibitory effect of crosslinking when the acids became longer. The effect of the microenvironment of the polymer did not appear significant. All the acyl polymers, including the precursor polymers, yielded the corresponding cyclohexylamides when treated with cyclohexylamine. 相似文献
94.
Asao N Takahashi K Lee S Kasahara T Yamamoto Y 《Journal of the American Chemical Society》2002,124(43):12650-12651
The reaction of o-alkynylbenzaldehydes 1 and alkynes 2 in the presence of a catalytic amount of AuCl3 in (CH2Cl)2 at 80 degrees C gave naphthyl ketone products in high yields. The AuCl3-catalyzed formal [4 + 2] benzannulation proceeds most probably through the coordination of the triple bond of 1 to AuCl3, the formation of benzo[c]pyrylium auric ate complex via the nucleophilic addition of the carbonyl oxygen atom, the Diels-Alder addition of alkynes 2 to the auric ate complex, and subsequent bond rearrangement. Similarly, the AuCl3-catalyzed reactions of o-alkynylacetophenone and o-alkynylbenzophenone with phenylacetylene afforded the corresponding naphthyl ketone products in good yields. 相似文献
95.
N Kubodera K Miyamoto M Akiyama M Matsumoto T Mori 《Chemical & pharmaceutical bulletin》1991,39(12):3221-3224
Three vitamin D3 analogues, 1 alpha,25-dihydroxy-23-oxavitamin D3 (3), 1 alpha,25-dihydroxy-23-thiavitamin D3 (4) and 1 alpha,25-dihydroxy-23-azavitamin D3 (5) were synthesized. In the differentiation-inducing activity of human myeloid leukemia cells into macrophages in vitro, the 23-aza analogue (5) showed the least activity, while no remarkable differences were observed between the 23-oxa analogue (3) and the 23-thia analogue (4), which were less active than 1 alpha,25-dihydroxyvitamin D3 (1). 相似文献
96.
J. Koarashi K. Akiyama T. Asano T. Yokota 《Journal of Radioanalytical and Nuclear Chemistry》2005,262(3):771-774
The effects of incorporating tritiated water into a 14C-sampling system in sample preparation and 14C activity measurement by liquid scintillation counting were investigated. Experiments derived the limit of water content in the prepared sample, and also demonstrated that 14C activity can be determined without any interference from 3H contamination for a clear-sample solution. The results enabled us to estimate the permissible relative humidity of air required for accomplishing sample preparation and 14C activity measurement. These showed that for sampling of air with less than the permissible relative humidity, total 14C activity in airborne effluent can be evaluated accurately without dehumidification of air.The authors would like to thank T. Kozawa, K. Isaka and Y. Adachi of Inspection Development Company Ltd., Y. Hiyama of Zuihou Sangyou Company Ltd., and T. Mizutani, H. Watanabe, M. Takeishi and K. Shinohara of Japan Nuclear Cycle Development Institute for their valuable assistance. 相似文献
97.
Michiya Itoh Kenji Murata Kunihiro Tokumura Koichi Shudo Naoki Miyata Toshihiko Okamoto 《Tetrahedron》1979,35(9):1059-1063
Photorearrangement reactions of K-region arene oxides, 9,10-epoxy-9,10-dihydrophenanthrene (1a), 3-acetyl-9,10-epoxy-9,10-dihydrophenanthrene (1b), and 3,4-epoxy-3,4-dihydropyrene (1c) in dichloroethane (DCE) solution were investigated by steady irradiation and nanosecond transient spectroscopy. Photorearrangements producing substituted oxepins, 2 occur via the singlet excited state of these compounds, while the phenolic products, 9-hydroxyphenanthrene (3a), 3-acetyl-9-hydroxyphenanthrene (3b), and 4-hydroxypyrene (3c) are formed via the triplet state. Phenol 3 formation from the triplet 1 sensitized by the triplet 3 (i.e. product sensitization) is proposed for the photorearrangement reactions of 1a and 1c, and this process is the only way phenol (3a) is formed because of the negligible intersystem crossing probability of 1a. No product sensitization occurs in the photorearrangement reaction of 1b. 相似文献
98.
A slab optical waveguide (SOWG) has been used for study of adsorption of both methylene blue (MB) and new methylene blue (NMB) in liquid–solid interface. Adsorption characteristics of MB and NMB on both bare SOWG and silanized SOWG by octadecyltrichlorosilane (ODS) were compared. Effect of pH on adsorption on MB and NMB was investigated. Binding rate constant analysis showed that both MB and NMB on bare SOWG demonstrates larger association constants than those on ODS-SOWG. Interactions of MB and NMB on bare SOWG and ODS-SOWG were analyzed by molecular mechanics calculation method. The binding energy change was in the following order: ENMB–bare > EMB–bare > ENMB–ODS > EMB–ODS. 相似文献
99.
Possible use of room temperature ionic liquids (RTILs) as chelate extraction solvent was evaluated by using 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]), 1-hexyl-3-methylimidazolium hexafluorophosphate ([hmim][PF6]) and 1-octyl-3-methylimidazolium hexafluorophosphate ([omim][PF6]). These RTILs showed high extraction performance for divalent metal cations with 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione (Htta). The extracted metals were back-extracted into 1 mol dm−3 nitric acid quantitatively. Furthermore, the extracted species were estimated as neutral hydrated complexes M(tta)2(H2O)n (n= 1 or 2) for M = Ni, Cu and Pb and anionic complexes M(tta)3− for M = Mn, Co, Zn and Cd. 相似文献
100.
Oxidations of alkanes, alkenes, and aromatic rings with pyridine N-oxides are efficiently catalyzed by ruthenium porphyrins under mild conditions. We show here that the oxidation of N-acyl cyclic amines with RuIVtetraarylporphyrin dichloride-2,6-substituted pyridine N-oxides directly gives N-acyl amino acids in modest to good yield via oxidative C-N bond cleavage. N-Acylpyrrolidines and N-acylpiperidines were converted to N-acyl-gamma-aminobutyric acids and N-acyl-delta-aminovaleric acids, respectively. This type of reaction is a novel one in which the C-N bond is cleaved selectively at the less substituted carbon. Notably, the proline residue in proline-containing peptides was selectively converted to glutamate. A large intramolecular kinetic isotope effect (kH/kD = 9.8) was observed in the oxidation of N-benzoyl[2,2,-d2]pyrrolidine, indicating that the reaction should involve an alpha-hydrogen atom abstraction process as the rate-determining step. N-Acylcarbaldehyde, the putative intermediate ring-opened form of alpha-hydroxylated N-acyl cyclic amine, was readily oxidized with the oxidizing system to afford the corresponding N-acylamino acid in good yield. Further, lactams (1-methyl-2-pyrrolidone and 1-methyl- 2-piperidone) were also oxidized to give the corresponding imides (1-methylsuccinimide and 1-methylpiperidine-2,6-dione). 相似文献