全文获取类型
收费全文 | 683篇 |
免费 | 8篇 |
国内免费 | 3篇 |
专业分类
化学 | 603篇 |
晶体学 | 13篇 |
力学 | 3篇 |
数学 | 10篇 |
物理学 | 65篇 |
出版年
2022年 | 7篇 |
2021年 | 9篇 |
2020年 | 11篇 |
2019年 | 11篇 |
2018年 | 5篇 |
2017年 | 5篇 |
2016年 | 13篇 |
2015年 | 11篇 |
2014年 | 12篇 |
2013年 | 30篇 |
2012年 | 35篇 |
2011年 | 38篇 |
2010年 | 29篇 |
2009年 | 14篇 |
2008年 | 40篇 |
2007年 | 39篇 |
2006年 | 32篇 |
2005年 | 39篇 |
2004年 | 32篇 |
2003年 | 27篇 |
2002年 | 25篇 |
2001年 | 6篇 |
2000年 | 10篇 |
1999年 | 8篇 |
1998年 | 7篇 |
1997年 | 9篇 |
1996年 | 8篇 |
1995年 | 5篇 |
1994年 | 9篇 |
1993年 | 14篇 |
1992年 | 8篇 |
1991年 | 5篇 |
1990年 | 11篇 |
1989年 | 9篇 |
1988年 | 7篇 |
1987年 | 9篇 |
1986年 | 14篇 |
1985年 | 8篇 |
1984年 | 7篇 |
1983年 | 3篇 |
1982年 | 7篇 |
1981年 | 9篇 |
1980年 | 9篇 |
1979年 | 11篇 |
1978年 | 6篇 |
1977年 | 11篇 |
1976年 | 3篇 |
1975年 | 3篇 |
1974年 | 7篇 |
1971年 | 2篇 |
排序方式: 共有694条查询结果,搜索用时 0 毫秒
1.
2.
3.
Thiraporn Charoenraks Suchada Chuanuwatanakul Kensuke Honda Yoko Yamaguchi Orawon Chailapakul 《Analytical sciences》2005,21(3):241-245
The analysis of tetracycline, oxytetracyline, chlortetracycline and doxycycline by high-performance liquid chromatography with pulsed amperometric detection using an anodized boron-doped diamond thin film (BDD) electrode is originally reported. The analyses were carried out using the mobile phase, phosphate buffer (0.01 M, pH 2.5)-acetonitrile (80:20; v/v), on a C18 column (250 x 4.6 mm i.d., 5 microm) at a flow rate of 1.0 mL/min. The optimal PAD waveform parameters at the anodized BDD were 1.5 V (versus Ag/AgCl) detection potential (E(det)) for 290 ms (200 ms delay time and 90 ms integration time), 2.0 V (versus Ag/AgCl) oxidation potential (E(oxd)) for 200 ms oxidation time (t(oxd)) and 0.4 V (versus Ag/AgCI) reduction potential (E(red)) for 200 ms reduction time (t(red)). The proposed method showed the simultaneous determination of tetracycline, oxytetracyline, chlortetracycline and doxycycline with a linear range of 0.1 - 100 microg/mL, detection limits of 0.05 - 0.1 microg/mL and recoveries of 70.8 - 96.0%. The application of this method to real samples was demonstrated and validated using a shrimp sample. 相似文献
4.
Nishimiya N Yamaguchi Y Ohrui Y Suzuki M 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2004,60(3):493-504
The mirror gap of a Fabry-Perot interferometer was stabilized with two laser diodes; one locked to the line frequency 385,243,555.14445 MHz of the F=3<--1 in 5D(3/2)<--5S(1/2) (87Rb) and the other to the 385,284,566.3663 MHz of the F=4<--2 in 5D(5/2)<--5S(1/2) (87Rb) [Opt. Commun. 102 (1993) 432]. The length of the mirror gap was adjusted to generate the zero-cross points simultaneously at both of the two line positions. The fringe signals obtained from an interferometer thus stabilized can be used as frequency markers having accuracies of the order of 10(10) depending on the finesse of the interferometer used. Based on measurement using Cs D1 hyperfine lines reported by Udem et al. [Phys. Rev. Lett. 82 (1999) 3568], the uncertainty of markers in the region 50 THz apart from the reference lines is +/- 5 MHz. 相似文献
5.
Shin-ichi Hirano Toshinobu Yogo Wataru Sakamoto Seiji Yamada Tomoyuki Nakamura Tomoe Yamammto Hiroyuki Ukai Kouichi Banno Tomoko Nakafuku Yukari Ando 《Journal of Sol-Gel Science and Technology》2003,26(1-3):35-41
Nano sized crystalline particles/polymer hybrids were synthesized form designed metal-organic precursors. The newly developed method is composed of the synthesis of organic matrix by polymerization and the in situ nucleation and growth of crystalline oxide particles in the organic matrix below 100°C. The design of metal-organic precursor modified with polymerizable ligand and the selection of reaction conditions does influence the size and crystallinity of ceramic particles in organic matrix. The nano-sized magnetic particle/polymer hybrid exhibits the interesting feature of superparamagnetism and quantum size effect. The crystalline particles of BaTiO3/, PbTiO3/, and KNbO3/polymer hybrids behave to be dielectric and show the typical electro-rheological behavior. 相似文献
6.
Kiyoshi Tanemura Yoko Nishida Tsuneo Suzuki Koko Satsumabayashi Takaaki Horaguchi 《Journal of heterocyclic chemistry》1997,34(2):457-460
1,3-Dithianes 1 , 1,3-dithiolanes 2 , and diphenyl dithioacetals 3 derived from cinnamaldehydes reacted with 2,3-dichloro-5,6-dicyano-p-benzoquinone in aqueous solvents to give benzaldehydes 4 . Hydride transfer from 1–3 to 2,3-dichloro-5,6-dicyano-p-benzoquinone followed by hydrolysis and oxidative carbon-carbon bond cleavage would produce benzaldehydes 4 . 相似文献
7.
Perovskite-type barium lithium fluoride (BaLiF3) was synthesized by pyrolysis of metal trifluoroacetates. The reaction temperature necessary for producing a single-phase material was found to be 600°C, which was lower than that for a conventional solid-state reaction or a melting method. Eu-doped BaLiF3 was also prepared and characterized to examine the suitability of trifluoroacetates for precursors in synthesizing homogeneous complex metal fluoride materials. It was demonstrated that trivalent Eu3+, which was used as acetate for a starting material, was reduced to divalent Eu2+ in the pyrolysis process of BaLiF3, as indicated by a broad blue emission due to an allowed 4f65d→4f7 transition at 408 nm with a ultraviolet excitation at 254 nm. The concentration quenching of the blue emission occurred at 5 at% of Eu in BaLiF3, indicating that Eu was homogeneously dispersed in the BaLiF3 host lattice. Mechanisms of the formation and reduction process of BaLiF3 were discussed based on pertinent chemical reactions. 相似文献
8.
The hydrogenolysisof 1-phenylbicyclo[4.1.0]heptane (1a), cis-1-phenyl-2-methylbicyclo[4.1.0]heptane (1b), 1-phenyl-7-azabicyclo[4.1.0]heptane (2) and 1-phenyl-7-oxabicyclo[4.1.0]heptane (3) was studied using Ni, Pd, Rh and Pt as catalysts. The hydrogenolysis of the C1C7 bond of 1a and 1b led to the selective formation of trans-1-phenyl-2-methylcyclohexane (4a) with retention of configuration. Compound 1a gave not only 4a but also phenylcycloheptane (6a), which is the product of C1C6 bond fission, and the ratio of 6a to 4a increased in the sequence: Ni ? Pd, Rh < Pt. No C1C6 bond fission was observed in the hydrogenolysis of 1b. These results can be explained by a mechanism involving the formation of the π-benzyl complex.trans-2-Phenylcyclohexylamine (8) was obtained stereoselectively in the hydrogenolysis of 2 over Raney Ni. This selective formation can be ascribed to the competition of “SN i” and “radical” processes. The Pd catalysed hydrogenolysis gave cis-2-phenylcyclohexylamine (9) as the main product, while the presence of sodium hydroxide promoted the formation of 8.Raney Ni catalysed hydrogenolysis of 3 yielded a mixture of phenylcyclohexane (13) and 2-phenylcyclohexanols (10 and 11). trans-2-Phenylcyclohexanol (10) was the dominant isomer; the hydrogenolysis resulted in the predominant configurational retention. Compound 13 was confirmed to be produced via 1-phenylcyclohexene (12). This deoxygenation may be explained by a mechanism involving the radical cleavage reaction of 3. The presence of sodium hydroxide led to the formation of cis-2-phenylcyclohexanol (11). The Pd catalysed hydrogenolysis also gave mainly 11.The difference in behaviour of cyclopropane, azidirine and epoxide we ascribe to the differences in the affinity for the catalyst and differences in the electronegativity between C, N and O atoms. 相似文献
9.
Yoko Nambu Takeshi Endo Makoto Okawara 《Journal of polymer science. Part A, Polymer chemistry》1981,19(8):1937-1943
Reductive S-monoacylation of lipoamide with some carboxylic acids and tri-n-butylphosphine was carried out in acetonitrile to obtain the corresponding S-monoacylated compounds in excellent yield. This method was applied to the preparation of S-monoacylated dihydrolipoyl polymer with a neighboring thiol group. The acyl transfer from the polymer to cyclohexylamine was enhanced as much as 64 times by adding silver perchlorate. 相似文献
10.
The molecular mechanism for 5-bromo-2'-deoxyuridine (BrdU) photosensitization was studied in thymine-requiring wild-type and uracil-DNA glycosylase (UDG)-deficient ung mutant cells of Escherichia coli K-12. Wild-type cells were more sensitive to BrdU photosensitiLation than ung mutant cells. IJV induced the identica/ numbers of alkaline sucrose single-strand breaks (SSB) in 5-bromouracil-DNA (BrU-DNA) of both the wild type and ung mutant. The ung mutant cells repaired SSB almost completely, whereas the wild-type cells with UDG produced more adverse SSB by 90 min after UV. Neutral agarose gel electrophoresis of minipreps indicated that UV induced (1) more smears of host BrU-DNA possibly by more double-strand breaks (DSB) and (2) a greater decline of pBR322 Form I BrU-DNA in the wild-type cells than the ung cells. These results indicated a greater induction of SSB by apyrimidinic (AP) endonucleases in wild-type cells. The ung/ wild ratios (=1.7–1.9) for cellular and plasmid BrdU sensitizations aftcr growth in 50% BrdU were similar. The extents of UDG-dependent and UDG-independent sensitizations in wild-type cells were ∼40 and ∼60%, respectively. The xth nfo double mutant defective in both exonuclcase III and endonucleasc IV was more sensitive to BrdU photosensitization than the wild type, indicating that an excess of AP sites remaining after uracil excision in the xth nfo mutant causes a greater BrdU photosensitization than SSB by AP endonucleases in wild-type cells. Conversely, the xth rfo ung triple mutant was more resistant to BrdU photosensitization than the xth nfo double mutant, so that UV-induced uracil residues in the BrU-DNA are tolerated and do not appear to be directly responsible for BrdU photosensitization. 相似文献