全文获取类型
收费全文 | 1416篇 |
免费 | 61篇 |
国内免费 | 14篇 |
专业分类
化学 | 958篇 |
晶体学 | 14篇 |
力学 | 41篇 |
数学 | 260篇 |
物理学 | 218篇 |
出版年
2024年 | 3篇 |
2023年 | 9篇 |
2022年 | 45篇 |
2021年 | 55篇 |
2020年 | 26篇 |
2019年 | 29篇 |
2018年 | 29篇 |
2017年 | 20篇 |
2016年 | 58篇 |
2015年 | 46篇 |
2014年 | 58篇 |
2013年 | 95篇 |
2012年 | 93篇 |
2011年 | 114篇 |
2010年 | 42篇 |
2009年 | 53篇 |
2008年 | 81篇 |
2007年 | 93篇 |
2006年 | 76篇 |
2005年 | 60篇 |
2004年 | 53篇 |
2003年 | 58篇 |
2002年 | 34篇 |
2001年 | 28篇 |
2000年 | 17篇 |
1999年 | 13篇 |
1998年 | 9篇 |
1997年 | 7篇 |
1996年 | 17篇 |
1995年 | 11篇 |
1994年 | 13篇 |
1993年 | 10篇 |
1992年 | 11篇 |
1991年 | 12篇 |
1990年 | 10篇 |
1989年 | 10篇 |
1988年 | 8篇 |
1987年 | 6篇 |
1986年 | 4篇 |
1985年 | 9篇 |
1984年 | 10篇 |
1983年 | 6篇 |
1982年 | 11篇 |
1981年 | 7篇 |
1980年 | 7篇 |
1979年 | 4篇 |
1978年 | 3篇 |
1977年 | 6篇 |
1973年 | 3篇 |
1972年 | 2篇 |
排序方式: 共有1491条查询结果,搜索用时 0 毫秒
21.
Alan R. Katritzky Amir S. Afridi Wojciech Kuzmierkiewicz 《Helvetica chimica acta》1991,74(8):1931-1935
tert-Alkyl sulfides, with an α-(1H-benzotriazol-1-yl) group 6 and 13 , are readily prepared from N-[(aryl-thio)methyl]-1H-benzotriazoles 3 and N-( 11 ), respectively, by reaction with BuLi and then with the appropriate electrophile. The tert-alkyl sulfides 6 and 13 are smoothly converted by BF3. OEt2 into vinyl sulfides 5, 7 or 12 , respectively, in satisfactory yields. 相似文献
22.
5'-O-DMT-deoxyribonucleoside-3'-O-(2-selena-4,4-pentamethylene-1,3,2-oxathiaphospholane) monomers, derivatives of dA, dC, dG, and T, can be resolved into pure P-diastereomers by silica gel column chromatography. They have been used for DBU-promoted, either solution- or solid-phase synthesis of P-stereodefined phosphoroselenoate analogues of oligodeoxyribonucleotides. Fast- and slow-eluting monomers are precursors of phosphoroselenoate internucleotide linkage of R(P) and S(P) absolute configuration, respectively. [reaction: see text] 相似文献
23.
Wojciech Dmowski 《Journal of fluorine chemistry》1981,18(1):25-30
1-Phenylpentafluoropropene and a number of its para- and ortho-substituted derivatives were prepared in high yields by reaction of hexafluoropropene with etheral solutions of corresponding phenylmagnesium bromides in sealed glass tubes under autogenous pressure. The products were obtained as mixtures of the Z and E isomers, which ratios varied from 1/2 to 1/6 in favour of the E forms. 19F n.m.r. and i.r. spectra and b.p. of the 1-phenylpentafluoropropenes are reported. 相似文献
24.
Flow-injection single-point titration of acids is based on biamperometric measurement of iodine formed quantitatively in the reaction of iodide with iodate. Results are presented for determination of sulphuric, hydrofluoric, monochloroacetic, formic and acetic acids. The slopes of the calibration plots, which are linear for about 1–10 rum acid, depend on the strength of the acid, decreasing from sulphuric acid to acetic acid. With microcomputer on-line data processing, relative standard deviations were about 0.2%. 相似文献
25.
Spontaneous Nef reaction of primary and secondary 3-aryl-2-(diethoxyphosphoryl)-4-nitroalkanoic acids has been observed for the first time. The reaction provides a general and effective, highly diastereoselective synthesis of 3-(diethoxyphosphoryl)-1-hydroxysuccinimides and 2-(diethoxyphosphoryl)-4-oxoalkanoic acids. 相似文献
26.
The analytical performance of a glow discharge quadrupole mass spectrometer is demonstrated using sintered tungsten as an example. The inherent problem of molecular interferences in glow discharge mass Spectrometry has been considerably reduced using neon as a complementing discharge gas. Particular attention has been paid to time dependences. Analytical figures of merit are presented. 相似文献
27.
Wojciech Dmowski 《Journal of fluorine chemistry》1990,50(3):319-325
The title compound, CF3CF2CF2(CF3)2CCH2CH2CH2CF(CF3)2, was synthesised in high yield by a free radical addition of heptafluoroisopropyl iodide to 3-(perfluoro-1, 1-dimethylbutyl)-1- propene followed by reduction of the adduct. Physical properties and solubilities for oxygen, nitrogen, carbon dioxide and air of the new fluorohydrocarbon have been determined. 相似文献
28.
Fastyn P Kornacki W Gierczak T Gawłowski J Niedzielski J 《Journal of chromatography. A》2005,1078(1-2):7-12
The water uptake by carbon molecular sieves (CMS) and graphitized carbons, all of which are used to determine volatile organic compounds in air, was investigated using a direct experimental approach. CMS, e.g. Carboxen 1002, Carboxen 1003 and Anasorb CMS adsorb substantial amounts of water, in the range 400 to 450 mg per gram of adsorbent. Graphitized carbons, e.g. Carbrogaph 5TD and Carbopack X show low water trapping, less than 30 mg g(-1) and Carbopack Y as little as 5 mg g(-1) or less. The water sorption capacity for graphitized carbons is strongly dependent on the relative humidity (RH). The change of RH from 95 to 90% decreases the amount of adsorbed water by more than a factor of 2. Two different water adsorption mechanisms are operative: adsorption on polar centers and micropore volume filling. For graphitized carbons and CMS at low RH, adsorption on polar centers is involved. For CMS, once the threshold value of relative humidity (RHth) is surpassed, micropore volume filling becomes predominant. RHth is 44 +/- 3 and 42 +/- 3% for Carboxen 1002 and 1003, respectively, and 32 +/- 3% for Anasorb CMS. The CMS mass in the trap was found not to affect the mass of retained water under condition of incomplete saturation of adsorbent bed with water. Thus, the restrictions commonly imposed on the CMS mass are not necessary. The dry purging technique is suggested to remove adsorbed water. Carbograph 5TD and Carbopack X require only a few hundred ml of dry air to remove adsorbed water entirely. Water can also be purged out from CMS; however, much larger volumes of dry air are needed. 相似文献
29.
Analysis of selected ionic liquid cations by ion exchange chromatography and reversed-phase high performance liquid chromatography 总被引:1,自引:0,他引:1
The chromatographic behavior of 8 ionic liquids - 7 homologues of 1-alkyl-3-methylimidazolium and 4-methyl-N-butylpyridinium - has been investigated with a strong cation exchange adsorbent. In particular, the dependence of the retention properties of these solutes on mobile phase composition, pH, and buffer concentration was evaluated with the aim of optimizing and improving the selectivity and retention of solute separation. While using the SCX stationary phase, several interactions occurred with varying strengths, depending on the mobile phase composition. Cation exchange, nonspecific hydrophobic interactions, and adsorption chromatography behavior were observed. Reversed phase chromatography occurred at low concentrations of acetonitrile, electrostatic and adsorption interactions at higher organic modifier concentrations. Elevated buffer concentrations lowered the retention factors without affecting the selectivity of ionic liquids. Obtained results were further compared to the chromatographic behaviour of ionic liquids in the reversed phase system. All analyzed ionic liquids follow reversed-phase behavior while being separated. Much lower selectivity in the range of highly hydrophilic compounds is obtained. This suggests preferred use of ion chromatography for separation and analysis of compounds below 4 carbon atoms in the alkyl side chain. 相似文献
30.
Bathoferroine can be used for anion determinations by a method based on selective ion-pair extraction if the selectivity of extraction has been enhanced by addition of nonelectrolyte to the water phase. The method of perchlorate and perrhenate determinations characterizes parameters similar to those obtained by methods in which other cation complexes have been used. The advantage of the proposed method is the possibility of considerable concentration of ion association compound extracts by nitromethane reextraction. 相似文献