全文获取类型
收费全文 | 2743篇 |
免费 | 100篇 |
国内免费 | 13篇 |
专业分类
化学 | 2079篇 |
晶体学 | 33篇 |
力学 | 18篇 |
数学 | 188篇 |
物理学 | 538篇 |
出版年
2023年 | 20篇 |
2022年 | 27篇 |
2021年 | 32篇 |
2020年 | 39篇 |
2019年 | 55篇 |
2018年 | 27篇 |
2017年 | 21篇 |
2016年 | 57篇 |
2015年 | 50篇 |
2014年 | 62篇 |
2013年 | 133篇 |
2012年 | 160篇 |
2011年 | 188篇 |
2010年 | 106篇 |
2009年 | 88篇 |
2008年 | 182篇 |
2007年 | 153篇 |
2006年 | 135篇 |
2005年 | 166篇 |
2004年 | 154篇 |
2003年 | 134篇 |
2002年 | 101篇 |
2001年 | 52篇 |
2000年 | 41篇 |
1999年 | 20篇 |
1998年 | 16篇 |
1997年 | 23篇 |
1996年 | 39篇 |
1995年 | 30篇 |
1994年 | 20篇 |
1993年 | 29篇 |
1992年 | 22篇 |
1991年 | 21篇 |
1990年 | 18篇 |
1989年 | 14篇 |
1988年 | 18篇 |
1987年 | 21篇 |
1986年 | 25篇 |
1985年 | 43篇 |
1984年 | 42篇 |
1983年 | 17篇 |
1982年 | 27篇 |
1981年 | 30篇 |
1980年 | 28篇 |
1979年 | 39篇 |
1978年 | 21篇 |
1977年 | 36篇 |
1976年 | 22篇 |
1975年 | 12篇 |
1973年 | 16篇 |
排序方式: 共有2856条查询结果,搜索用时 109 毫秒
31.
The d.c. polarographic current-potential curves of Cd(II)-EDTA complexes were examined in the pH range 0.5–10.0, to elucidate the mechanism of their electrode processes and to determine the relevant electrochemical kinetic parameters. It was shown that the first wave observed below pH 3 at ?0.58 to ?0.65 V vs. SCE is the reversible reduction wave of Cd(II) aquo-ion with kinetically-controlled limiting current, and the second wave observed above pH 1.5 at ?0.75 to ?1.21 V vs. SCE corresponds to the simultaneous irreversible reduction of four complex species, CdH3L+, CdH2L, CdHL? and CdL2?, where CdHpL(p?2)+ and L4? denote the protonated complex species with p protons and the unprotonated EDTA ion, respectively. Analysis of the dependence of limiting current on the hydrogen ion concentration led to the conclusion that the preceding reaction determining the behaviour of limiting current is CdH3L+?Cd2++H3L? with k3d=6.3×102 s?1 and k3f=3.3×106 s?1M?1, where k3d and k3f are the dissociation and formation rate constants, respectively. On the other hand, from analysis of the dependence of half-wave potentials of the second wave on the hydrogen ion concentration, the kinetic parameters of the four complex species were evaluated, and are given in Table 1. Further, it was shown that the cathodic rate constants of these four charge transfer processes at some reference potential together with those of Cd(II)-HEDTA complexes fulfil the linear free energy relationship. 相似文献
32.
33.
Tanaka M Nakamura M Ikeda T Ikeda K Ando H Shibutani Y Yajima S Kimura K 《The Journal of organic chemistry》2001,66(21):7008-7012
Synthetic procedures for monoazathiacrown ethers were explored, and monoazatrithia-12-crown-4, monoazatetrathia-15-crown-5, and monoazapentathia-18-crown-6 were obtained in moderate yields by the reaction of bis(2-chloroethyl)amine with the appropriate dithiols in the presence of lithium hydroxide in THF. To evaluate metal-ion binding properties of the monoazathiacrown ethers by solvent extraction, lipophilic dodecyl and dodecanoyl groups were incorporated onto the monoazathiacrown ethers. The solvent extraction experiments suggested that monoazathiacrown ethers have Ag(+) and Hg(2+) selectivities and that the relative selectivity between Ag(+) and Hg(2+) depends on their nitrogen atom properties and numbers of sulfur atoms reflecting the respective affinities of nitrogen and sulfur atoms to Hg(2+) and Ag(+). An interesting ability to bind Mg(2+) was observed in the case of N-dodecyl monoazatrithia-12-crown-4. 相似文献
34.
Pyrene-azacrown ether hybrid: cation-π interaction 总被引:1,自引:0,他引:1
A pyrene-modified lariat ether was synthesized in order to observe the cation-π interaction in solution. 相似文献
35.
Hanioka N Jinno H Nishimura T Ando M Ozawa S Sawada J 《Biomedical chromatography : BMC》2001,15(5):328-333
A simple and sensitive assay for glucuronidation activity of 7-ethyl-10-hydroxycamptothecin (SN-38), the active metabolite of irinotecan (CPT-11), in human liver microsomes by high-performance liquid chromatography (HPLC) with fluorescence detection is reported. The method was validated for the determination of SN-38 glucuronide (SN-38G) with respect to specificity, linearity, recovery, stability, precision, accuracy, and limits of detection and quantitation. There was no interference from matrix and non-enzymatic reactions. The calibration curve for SN-38G was linear from 5 to 500 nM. Average recoveries ranged from 98 to 100% in spiked human liver microsome samples, and the SN-38G was stable at 4 degrees C for at least 72 h. The newly developed method was found to be more sensitive and selective than previous methods using thin layer chromatography and HPLC. The limit of quantitation for SN-38G was 5 nM (2.5 pmol/assay). The intra- and inter-day precision and accuracy were less than 7 and 4%, respectively. The intra- and inter-day precision of enzyme assay for UDP-glucuronosyltransferase (UGT) activity toward SN-38 in human liver microsomes was less than 4%. With this improved sensitivity, the kinetics of SN-38 glucuronidation in human liver microsomes could be determined more precisely. Therefore, this method is applicable to in vitro study on the side effects and drug interactions of CPT-11 using small amounts of biological sample. 相似文献
36.
Sachiko Yamada Keiko Nakayama Hiroaki Takayama Toshimasa Shinki Tatsuo Suda 《Tetrahedron letters》1984,25(30):3239-3242
(25)-25,26-Dihydroxy-23-oxovitamin D3 was synthesized efficiently and stereoselectively, and it was converted enzymatically to (25)-1α,25,26-trihydroxy-23-oxovitamin D3, a putative metabolite of 1α,25-dihydroxyvitamin D3. The spectral and chemical properties of (25)-25,26-dihydroxy-23-oxovitamin D3 and its 1α,hydroxylated derivative disagree with those reported for the isolated metabolite. 相似文献
37.
38.
To examine the reason for the formation and the structure of cubic ice in a restricted space, we measured the powder x-ray diffraction patterns of cubic ice formed within the mesopores of porous silicas as a function of pore size (4-70 nm). The results strongly suggest that cubic ice formed in the mesopores does not take a cubic structure as envisaged by Konig. It may be actually composed of very small crystallites of hexagonal ice that contains a large amount of growth faults depending on the crystallite size, that is, ice with disordered stacking sequence. Suppression of crystal growth of ice in the mesopores seems to be a vital factor for the formation and the stability of cubic ice. 相似文献
39.
Aldehyde-2,4-dinitrophenylhydrazones exist as (E)- and (Z)-geometrical isomers, and adventitious isomerization during sample preparation can cause analytical errors. Purified alkenal-2,4-dinitrophenylhydrazone derivatives comprise only the (E)-isomer. However, partial isomerization to the (Z)-isomer occurs upon addition of acid to attain an equilibrium isomer ratio. The UV-visible spectral properties of the isomers differ; the (Z)-isomer exhibiting a 6-10 nm lower absorption maximum compared to the (E)-isomer. Alkenal-2,4-dinitrophenylhydrazones having a CC double bond at the 2- or 3-position of the alkenal exhibited similar absorption maxima with an equilibrium isomer ratio (0.035) that was much lower than those of other alkenals. The CC double bond at the 3-position migrates to a position of conjugation with the CN double bond during hydrazone synthesis to form a stabilized molecular structure. Alkenal-2,4-dinitrophenylhydrazones having a double bond at the 4-position or greater exhibited a similar absorption maxima equilibrium isomer ratio (0.14) to alkanal-2,4-dinitrophenylhydrazones. The quantitative analysis of carbonyl compounds in air or water using DNPH is usually conducted in the presence of an acid catalyst. Consequently, the solution of the direct extract prepared for HPLC or GC analysis contains both (E)- and (Z)-isomers. 相似文献
40.
Takaaki Horaguchi Hiroaki Yagoh Kiyoshi Tanemura Tsuneo Suzuki 《Journal of heterocyclic chemistry》1986,23(3):657-663
4,5-Dihydro-3H-naphtho[1,8-bc]furans 4 and 6 which have various substituents (R1 and R2) have been synthesized from 8-oxo-5,6,7,8-tetrahydro-1-naphthyloxyacetic acids 1 and 3 or their ethyl esters 2 . The reaction of acids 1 and 3 with sodium acetate in acetic anhydride gave a mixture of furans 4 and 6 and lactones 5 and 7 . The ratios of the products were varied according to the types of substituents (R1 and R2) in acids 1 and 3 . As the substituent R1 (R2 = hydrogen) in acids 1 was changed from hydrogen to a methyl, ethyl or isopropyl group, production of furans 4 became more difficult. However, when a phenyl group was used as the substituent, furan 4 was obtained in good yield. Similarly, as the substituent R2 (R1 = hydrogen) in acids 1 was changed from hydrogen to a methyl, ethyl or isopropyl group, furan formation was more difficult. In contrast, acids 3 which had electron-withdrawing substituents such as chlorine, bromine or a nitro group at the 4-position afforded furans 6 in good yield. 4,5-Dihydro-3H-naphtho[1,8-bc]furans 4 and 4,5-dihydro-3H-naphtho[1,8-bc]furan-2-carbocylic acids 8 were synthesized from the reaction of esters 2 and potassium hydroxide in dioxane. When the substituents R1 or R2 in esters 2 were varied from hydrogen to a methyl, ethyl or isopropyl group the total yields of furans 4 and furancarboxylic acids 8 were reduced. 相似文献