全文获取类型
收费全文 | 1796篇 |
免费 | 48篇 |
国内免费 | 8篇 |
专业分类
化学 | 1468篇 |
晶体学 | 16篇 |
力学 | 17篇 |
综合类 | 1篇 |
数学 | 96篇 |
物理学 | 254篇 |
出版年
2023年 | 8篇 |
2022年 | 8篇 |
2021年 | 10篇 |
2020年 | 15篇 |
2019年 | 15篇 |
2018年 | 14篇 |
2017年 | 18篇 |
2016年 | 34篇 |
2015年 | 30篇 |
2014年 | 38篇 |
2013年 | 77篇 |
2012年 | 105篇 |
2011年 | 116篇 |
2010年 | 66篇 |
2009年 | 63篇 |
2008年 | 128篇 |
2007年 | 109篇 |
2006年 | 106篇 |
2005年 | 113篇 |
2004年 | 106篇 |
2003年 | 72篇 |
2002年 | 73篇 |
2001年 | 26篇 |
2000年 | 23篇 |
1999年 | 37篇 |
1998年 | 15篇 |
1997年 | 28篇 |
1996年 | 19篇 |
1995年 | 19篇 |
1994年 | 15篇 |
1993年 | 27篇 |
1992年 | 15篇 |
1991年 | 11篇 |
1990年 | 14篇 |
1989年 | 13篇 |
1988年 | 22篇 |
1987年 | 16篇 |
1986年 | 11篇 |
1985年 | 28篇 |
1984年 | 17篇 |
1983年 | 20篇 |
1982年 | 14篇 |
1981年 | 30篇 |
1980年 | 10篇 |
1979年 | 17篇 |
1978年 | 8篇 |
1977年 | 14篇 |
1976年 | 16篇 |
1975年 | 8篇 |
1974年 | 9篇 |
排序方式: 共有1852条查询结果,搜索用时 15 毫秒
71.
Hatano T Shintani Y Aga Y Shiota S Tsuchiya T Yoshida T 《Chemical & pharmaceutical bulletin》2000,48(9):1286-1292
Two new phenolic compounds, glicophenone (1) and glicoisoflavanone (2), were isolated from commercial licorice, and their structures were elucidated on the basis of spectroscopic data. Antibacterial assays of licorice phenolics for Staphylococcus aureus, including four strains of methicillin-resistant S. aureus (MRSA), and also for Escherichia coli K12 and Pseudomonas aeruginosa PAO1, were then examined. Two compounds among them, 8-(gamma,gamma-dimethylallyl)-wighteone (21) and 3'-(gamma,gamma-dimethylallyl)-kievitone (28), showed remarkable antibacterial effects [minimum inhibitory concentrations (MICs), 8 microg/ml on the MRSA strains and methicillin-sensitive S. aureus. Licochalcone A (14), gancaonin G (20), isoangustone A (24), glyasperins C (30) and D (31), glabridin, (32), licoricidin (33), glycycoumarin (34) and licocoumarone (40) showed antibacterial effects on the MRSA strains with MIC values of 16 microg/ml. Effects on the beta-lactam resistance of the MRSA strains were also examined, and licoricidin (33) noticeably decreased the resistance of the MRSA strains against oxacillin, as shown by the reduction in the MICs of oxacillin (lower than 1/128-1/1000 in the presence of 8 microg/ml of 33, and 1/8-1/32 in the presence of 4 microg/ml of 33). Mechanistic study suggested that 33 does not inhibit the formation of penicillin-binding protein 2' (PBP2'), but affects the enzymatic function of PBP2'. 相似文献
72.
Suzuki N Aihara N Takahara H Watanabe T Iwasaki M Saburi M Hashizume D Chihara T 《Journal of the American Chemical Society》2004,126(1):60-61
Five-membered metallacyclic alkynes that have no substituents adjacent to the triple bond have been synthesized, isolated, and structurally characterized. Zirconocene dichlorides, Cp'2ZrCl2 (Cp' = C5H5, C5H4-t-Bu), reacted with 1,4-dichlorobut-2-yne in the presence of magnesium to give 1-zirconacyclopent-3-yne compounds (5 (a) Cp' = C5H5, (b) Cp' = C5H4-t-Bu) that have a -CH2CCCH2- moiety in good yields. They are stable enough to be isolated in a pure form, despite the absence of substituents. 5a reacted with an equimolar amount of Cp2Zr(but-1-ene)(PMe3) to produce a bimetallic complex in which the zirconacyclopentyne coordinates to the other zirconocene moiety as an alkyne. 相似文献
73.
74.
An on-line purification method for catecholamines was studied using a flow system equipped with an alumina microcolumn. The procedure involves catecholamine adsorption, column washing and catecholamine elution steps. The system is designed not to decompose catecholamines under alkaline conditions in the adsorption step. Flow-rates and times for different solutions delivered in each step (alkaline buffer for adsorption, water for washing and an acidic solution for elution), column length and sample volume to be loaded were systematically investigated by liquid chromatography. Under optimum conditions, norepinephrine, epinephrine, dopamine and 3,4- dihydroxybenzylamine (internal standard) can be purified with recoveries of ? 90% within 11 min with manual operation. This method was efficiently applied to urine samples and the results indicate the possibility that catecholamines in biological samples are automatically purified. 相似文献
75.
Ayumi Yoshida Hitoshi Yamauchi Hideki Sakai Norimichi Kawashima Masahiko Abe 《Colloids and surfaces. B, Biointerfaces》1997,8(6):191-342
Molecular interactions between lipid bilayers (liposomes) and chondroitin sulfate C (CS), a water soluble polymer, have been investigated in terms of zeta-potential, particle size, microscopic-viscosity, microscopic-polarity of liposomes and permeability of calcein. Microscopic morphology is dramatically changed by the addition of CS to the positively charged liposomes (Pos.L), while it is not changed by the addition to uncharged liposomes (Unc.L) or negatively charged liposomes (Neg.L). The absolute value of the particle size of Pos.L increases with the addition of CS, while the zeta- potential of Pos.L decreases. Permeability of Pos.L decreases with an increase in the concentration of CS. Phase transition temperature of Pos.L is changed after the addition of CS. These values, however, are not changed for the other liposomes by the addition of CS. The results of gel filtration chromatography show that CS is absorbed on the Pos.L surface. Microscopic viscosity is also increased by the addition of CS to Pos.L due to the adsorption of CS. 相似文献
76.
Nobutaka Takahashi Noboru Murofushi Saburo Tamura Nobuhide Wasada Hiroko Hoshino Toshikazu Tsuchiya Shin-Ichi Sasaki Tetsumi Aoyama Eiji Watanabe 《Journal of mass spectrometry : JMS》1969,2(7):711-722
Based on the element maps of twenty-two gibberellin methyl esters fragmentations are discussed, which are characteristic of the common structural features as well as structural modification in gibberellin homologues. 相似文献
77.
Kazuo Itoh Masahiko Chikuma Hisashi Tanaka 《Fresenius' Journal of Analytical Chemistry》1988,330(7):600-604
Summary The hydride generation/atomic absorption spectrometry (AAS) with an automated flow system is useful for the routine analysis of selenium in environmental samples. This method is, however, subject to interferences from transition metal ions and other hydride forming ions. The conditions to minimize the interferences were established: the concentration of hydrochloric acid 6 mol/l; the concentration of tetrahydroborate 0.5%. Iron(III) chloride released the depression of selenium signals by metal ions such as copper(II) and bismuth(III). Selenium in several standard reference materials including sediment samples was determined by the present method and by fluorimetry with 2,3-diaminonaphthalene. The results obtained by the two methods agreed with an acceptable precision. This means that hydride generation/AAS offers good precision and accuracy in the determination of selenium in sediment samples as well as DAN fluorimetry. However, the former is much simpler in operation. The method was applied to the determination of selenium in estuarine sediments collected in Nagoya harbor and Ise Bay. The results can be used to assess the pollution state of these places.
Selenbestimmung in Sedimenten durch AAS mit Hydriderzeugung. Eliminierung von Störungen相似文献
78.
Komeda S Lutz M Spek AL Yamanaka Y Sato T Chikuma M Reedijk J 《Journal of the American Chemical Society》2002,124(17):4738-4746
The reactions of the dinuclear platinum(II) complexes, [[cis-Pt(NH(3))(2)](2)(mu-OH)(mu-pz)](NO(3))(2) (1, pz = pyrazolate), [[cis-Pt(NH(3))(2)](2)(mu-OH)(mu-1,2,3-ta-N1,N2)](NO(3))(2) (2, 1,2,3-ta = 1,2,3-triazolate), and a newly prepared [[cis-Pt(NH(3))(2)](2)(mu-OH)(mu-4-phe-1,2,3-ta-N1,N2)](NO(3))(2) (3, 4-phe-1,2,3-ta = 4-phenyl-1,2,3-triazolate), whose crystal structure was determined, with 9-ethylguanine (9EtG) have been monitored in aqueous solution at 310 K by means of (1)H NMR spectroscopy. The dinuclear platinum(II) complexes 1-3 each react with 9EtG in a bifunctional way to form 1:2 complexes, [[cis-Pt(NH(3))(2)(9EtG-N7)](2)(mu-pz)](3+) (4), [[cis-Pt(NH(3))(2)(9EtG-N7)](2)(mu-1,2,3-ta-N1,N3)](3+) (5), and [[cis-Pt(NH(3))(2)(9EtG-N7)](2)(mu-4-phe-1,2,3-ta-N1,N3)](3+) (6). The reactions of 2 and 3 involve a novel isomerization, in which the Pt atom, initially bound to N2 on the 1,2,3-ta, migrates to N3 after the first substitution by N7 of 9EtG. This isomerization reaction has been unambiguously characterized by 1D and 2D NMR spectroscopy and pH titration. The reactions of 2 and 3 with 9EtG show faster kinetics, and the second-order rate constants (k) for the reactions of 1-3are 1.57 x 10(-4), 2.53 x 10(-4), and 2.56 x 10(-4) M(-1) s(-1), respectively. The pK(a) values at the N1H site of 9EtG were determined for 4-6 from the pH titration curves. Cytotoxicity assays of 1-3 were performed in L1210 murine leukemia cell lines, respectively sensitive and resistant to cisplatin. In the parent cell line, 2 and 3 exhibit higher cytotoxicity compared to cisplatin, especially, 2 is 10 times as active as cisplatin. 1 was found to be less cytotoxic than cisplatin, but still in the active range and more active than cisplatin in a cisplatin-resistant cell line. 相似文献
79.
Norio Yoshino Munetoshi Morita Atsushi Ito Masahiko Abe 《Journal of fluorine chemistry》1995,70(2):187-191
Anionic surfactants having two polyfluoroalkyl chains per molecule, i.e. the sodium salt of bis(1H, 1H, 2H,2H-heptadeca-fluorodecyl)-2-sulfosuccinate, CF3(CF2)7(CH2)2OCOCH2CH(SO3Na)COO(CH2)2(CF2)7CF3, the sodium salt of bis(1H, 1H, 2H, 2H-tridecafluoro-octyl)-2-sulfosuccinate, CF3(CF2)5(CH2)2OCOCH2CH(SO3Na)COO(CH2)2(CF2)5CF3, and the sodium salt of bis(1H, 1H, 2H, 2H-nonafluorohexyl)-2-sulfosuccinate, CF3(CF2)3(CH2)2OCOCH2CH(SO3Na)COO(CH2)2(CF2)3CF3, have been prepared from maleic anhydride, the corresponding alcohols possessing a polyfluoroalkyl chain and sodium hydrogen sulfite. The flocculation and redispersion abilities of these surfactants for dispersed magnetic particles in water have been examined to investigate the effect of the chain length. It was found that this ability was enhanced by an increase in the chain length. The contact angles for water for pelleted surface-modified magnetite have been measured. In order to compare this ability and the contact angles, data for other fluorinated surfactant have been obtained. The Kraff point, the surface tension and the pNa of the aqueous surfactant solutions have also been measured. 相似文献
80.
Enantioselective copper-catalyzed 1,4-additions of dialkylzincs to enones were carried out in the presence of 1 mol % of Cu(OTf)2 and 2.5 mol % of an N,N,P-ligand possessing a tert-butyl group at the adjacent position of the nitrogen of pyridine to afford the corresponding 1,4-adducts in up to 98% ee. 相似文献