全文获取类型
收费全文 | 1266篇 |
免费 | 41篇 |
国内免费 | 2篇 |
专业分类
化学 | 1043篇 |
晶体学 | 16篇 |
力学 | 5篇 |
数学 | 23篇 |
物理学 | 222篇 |
出版年
2023年 | 8篇 |
2022年 | 14篇 |
2021年 | 10篇 |
2020年 | 26篇 |
2019年 | 34篇 |
2018年 | 17篇 |
2017年 | 11篇 |
2016年 | 28篇 |
2015年 | 36篇 |
2014年 | 29篇 |
2013年 | 54篇 |
2012年 | 67篇 |
2011年 | 68篇 |
2010年 | 42篇 |
2009年 | 41篇 |
2008年 | 104篇 |
2007年 | 81篇 |
2006年 | 94篇 |
2005年 | 87篇 |
2004年 | 73篇 |
2003年 | 34篇 |
2002年 | 46篇 |
2001年 | 25篇 |
2000年 | 21篇 |
1999年 | 22篇 |
1998年 | 14篇 |
1997年 | 14篇 |
1996年 | 15篇 |
1995年 | 10篇 |
1994年 | 7篇 |
1993年 | 10篇 |
1992年 | 10篇 |
1991年 | 10篇 |
1990年 | 12篇 |
1989年 | 10篇 |
1988年 | 10篇 |
1987年 | 7篇 |
1986年 | 6篇 |
1985年 | 10篇 |
1984年 | 9篇 |
1982年 | 8篇 |
1981年 | 4篇 |
1980年 | 7篇 |
1979年 | 7篇 |
1978年 | 5篇 |
1975年 | 8篇 |
1973年 | 6篇 |
1972年 | 5篇 |
1971年 | 9篇 |
1968年 | 4篇 |
排序方式: 共有1309条查询结果,搜索用时 15 毫秒
91.
Shotaro Hayashi Minami Sakamoto Fumitaka Ishiwari Takanori Fukushima Shin-ichi Yamamoto Toshio Koizumi 《Tetrahedron》2019,75(8):1079-1084
Here we report the facile derivatization of a cyano-substituted stilbene into higher π-extended analogues. The cyano-substituted stilbene, which serves as a synthetic scaffold, has a bromo group and a formyl group on its 4- and 4′-position of the phenylene rings and thus readily undergoes selective transformation into other functional groups using various simple organic reactions. The resultant π-conjugated molecules that contain a cyano-substituted stilbene skeleton exhibit fluorescence in solution and in the solid state. 相似文献
92.
Miyashita T Baba M Shigeta S Mori K Shinozuka K 《Chemical & pharmaceutical bulletin》2003,51(6):630-634
A series of novel 10-thiaisoalloxazine derivatives bearing an alkoxymethyl or benzyloxymethyl moiety at the N-1 position has been synthesized through the bromination of 1-substituted-5-hydroxyuracils and subsequent condensation with aminobenzenethiol in a one-pot reaction. Contrary to the previous report, the formation of intermediary 5,6-diethoxy-5-hydroxy-5,6-dihydrouracil seems to be not the necessary factor for the formation of the thiaisoalloxazines, since the reaction proceeds in tetrahydrofuran (THF) or acetonitrile far more smoothly than in ethanol. The anti-human immunodeficiency virus (HIV)-1 activity of the resulted thiaisoalloxazine derivatives was evaluated in lymphocyte cells based on the inhibitory activity against the viral-induced cytopathic activity. Among the derivatives, compounds 6, 7, and 8 bearing an alkoxymethyl moiety at the N-1 position exhibited modest inhibitory activity towards the cytotopathic effect of HIV-1. 相似文献
93.
Summary An emission-spectrometric method is described for the quantitative determination of traces of non-rare earth elements in yttrium oxide, employing addition of AgF-Ga2O3 mixed carrier. This addition effects an increase of the rate of evaporation of the analytical elements and of the number of atoms in the arc plasma. It enhances the sensitivity of the analytical elements to a larger extent than other carriers and permits the determination of microquantities of the elements (Mg, Ca, Mn, Co, Fe, Pb, Cu, Cd, Al, B, Sn, As, Bi) within limits of detection from 0.1 to 13 ppm in high-purity yttrium oxide. The coefficients of variation are less than 20%.
Emissionsspektrometrische Bestimmung von nicht zu den Seltenen Erden gehörenden Elementspuren in Yttriumoxid mit Hilfe eines AgF-Ga2O3 -Trägergemisches
Zusammenfassung Das Trägergemisch bewirkt eine Erhöhung der Verdampfungsgeschwindigkeit der zu bestimmenden Elemente und der Anzahl der Atome im Bogenplasma. Es verbessert mehr als andere Träger die Empfindlichkeit und ermöglicht die Bestimmung von Mikromengen der Elemente (Mg, Ca, Mn, Co, Fe, Pb, Cu, Cd, Al, B, Sn, As, Bi) in hochreinem Yttriumoxid mit Nachweisgrenzen von 0,1–13 ppm. Die Variationskoeffizienten liegen unter 20%.相似文献
94.
Takahiro Hosokawa Takanori Kono Toru Shinohara Shun-Ichi Murahashi 《Journal of organometallic chemistry》1989,370(1-3):C13-C16
The oxidative cyclization of 2-(3-pentenyl)phenol catalyzed by [(η3-pinene)PdOAc]2 gives optically active (+)-2-vinylchroman (25% e.e.), while (−)-2-(1-hydroxyethyl)chroman (56% e.e.) is formed as a single diastereomer upon treatment with t-BuOOH in the presence of Ti(OiPr)4 and
-(+)-diethyl tartrate. 2-(2-Butenyl)phenol also undergoes the Ti-promoted asymmetric cyclization to give (2S,1′R)-(−)-2-(1-hydroxyethyl)-2,3-dihydrobenzofuran (29% e.e.). 相似文献
95.
T. Suzuki T. Hatsushika M. Miyake 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4)
Abstract The cation-exchange characteristics between Pb2+ ions of aqueous solutions containing counter-anions (F?, C1?) and Ca2+ ions of synthetic hydroxyapatite samples have been investigated in detail under the conditions of low pH values (3.0, 4.0 and 5.0) by a normal batch method. Even at the low pH value of 3.0 the apatite structure in a solution containing F? or C1? ions was maintained via a concurrent ion-exchange effect of Pb2+ ions together with F? or C1?ions, which are known to be exchangeable with OH- ions of the apatite. Moreover, it was found that Ca2+ ions in the apatite sample can easily be exchanged for Pb2+ ions almost without distinction between MI and M2 sites, assisted by the loosening effect of protons even at room temperature. Next, it was found that the hydroxyapatite samples are transformed into amorphous states by the reactions between Ca 2+ ions in the samples and Sn 2+ ions in the SnC12 acidic aqueous solutions with pH of 3.0 or below with a molar ratio of Sn2+/Ca2+ -1.0. The existence of hydroxyapatite as amorphism in acidic aqueous solutions such as SnC12 is quite interesting, because in general the hydroxyapatite has been found to be dissolved in acidic aqueous solutions. Moreover, the obtained amorphism are found to be stable up to at least 500 to 6OO°C but to be unstable in alkaline solutions. The characteristics of Sn2+ ions are found to have been found to form crystalline Pb 2+ apatite even in be quite different from those of homologous Pb2+ ions which have been found to form crystalline pb2+ apatite even in such an acidic atmosphere. 相似文献
96.
Kimura T Takahashi S Akiyama S Uzawa T Ishimori K Morishima I 《Journal of the American Chemical Society》2002,124(39):11596-11597
The helix formation dynamics of poly-L-glutamic acids (PGAs) were observed by the microsecond-resolved Fourier transform infrared (FTIR) and circular dichroism (CD) spectroscopies. The helix formation of 34-residue PGA from random coil at pH (or pD for FTIR) 8.0 was initiated by a pH jump to 4.9 using the rapid solution mixer whose mixing dead time is 50 micros. The amide I' line in the time-resolved FTIR spectra exhibited the fast (<100 micros) increase of the total helical content. The time-resolved CD spectra of the same process also showed the fast (<150 micros) formation of short helical segments (5 +/- 1 residues), which was followed by the slower (<1 ms) elongation of the short helices to longer helices (>10 residues). Similar dynamics were observed for the same pH jump of approximately 190-residue PGA, although there were additional steps that made the helix formation of approximately 190-residue PGA more complex. The observed multistep helix formation is likely caused by the strong hydrogen-bonding interactions between the protonated side chains of PGAs. 相似文献
97.
Controlled Dynamic Helicity of a Folded Macrocycle Based on a Bisterephthalamide with a Twofold Z‐Shaped Structure 下载免费PDF全文
Dr. Ryo Katoono Keiichi Kusaka Prof. Dr. Kenshu Fujiwara Prof. Dr. Takanori Suzuki 《化学:亚洲杂志》2014,9(11):3182-3187
Dynamic helicity in a folded macrocycle and control of the helical preference are described. We designed macrocycle 1 with a dual mode of folding through the integration of two flexible units that are arranged twice to form a cyclic structure. As a folding unit, we used a terephthalamide skeleton and a Z‐shaped hydrocarbon: the former acted as a control unit to induce a preference of a particular sense of dynamic helicity and the latter was just a spacer. A terephthalamide unit provided a binding site for capturing a ditopic hydrogen‐bonding guest when it adopted helically folded syn forms (M/P). Thus, only the terephthalamide unit controlled the helical sense of dynamic helicity in a folded macrocycle through the supramolecular transmission of chirality upon complexation with a chiral ditopic guest. In addition, chirality on a host could also contribute to the control of the helical preference in a folded macrocycle, which led to exceptionally enhanced chiroptical signals. 相似文献
98.
99.
Ohkita M Kawano M Suzuki T Tsuji T 《Chemical communications (Cambridge, England)》2002,(24):3054-3055
The crystallization of 2,4,6-triethynyl-1,3,5-triazine (2) leads to a pi-stacked layered structure of a C(sp)-H...N hydrogen-bonded unique hexagonal network structure, which may be regarded as a supramolecular analogue of a hitherto unknown graphyne network: in-plane intermolecular interactions are short and linear H...N contacts (2.31 and 2.34 A) and the interlayer separation is 3.23 A. 相似文献
100.
[reaction: see text]. Rhodium complex-catalyzed carbonylative alkene-alkyne coupling proceeds using aldehydes as a CO source. Cinnamaldehyde is the best CO donor, and various cyclopentenones were provided in high isolated yields by a solvent-free system. 相似文献