全文获取类型
收费全文 | 4020篇 |
免费 | 176篇 |
国内免费 | 14篇 |
专业分类
化学 | 2738篇 |
晶体学 | 100篇 |
力学 | 80篇 |
数学 | 466篇 |
物理学 | 826篇 |
出版年
2023年 | 33篇 |
2022年 | 51篇 |
2021年 | 51篇 |
2020年 | 58篇 |
2019年 | 80篇 |
2018年 | 81篇 |
2017年 | 92篇 |
2016年 | 148篇 |
2015年 | 115篇 |
2014年 | 178篇 |
2013年 | 313篇 |
2012年 | 280篇 |
2011年 | 325篇 |
2010年 | 182篇 |
2009年 | 179篇 |
2008年 | 237篇 |
2007年 | 182篇 |
2006年 | 149篇 |
2005年 | 175篇 |
2004年 | 129篇 |
2003年 | 133篇 |
2002年 | 120篇 |
2001年 | 42篇 |
2000年 | 46篇 |
1999年 | 35篇 |
1998年 | 35篇 |
1997年 | 38篇 |
1996年 | 36篇 |
1995年 | 24篇 |
1994年 | 29篇 |
1993年 | 37篇 |
1992年 | 31篇 |
1991年 | 32篇 |
1990年 | 28篇 |
1989年 | 25篇 |
1988年 | 28篇 |
1987年 | 23篇 |
1986年 | 27篇 |
1985年 | 29篇 |
1984年 | 48篇 |
1983年 | 30篇 |
1982年 | 26篇 |
1981年 | 22篇 |
1980年 | 24篇 |
1979年 | 19篇 |
1978年 | 27篇 |
1977年 | 29篇 |
1976年 | 19篇 |
1975年 | 19篇 |
1974年 | 19篇 |
排序方式: 共有4210条查询结果,搜索用时 15 毫秒
21.
Corona-Avendaño S Rojas-Hernández A Romero-Romo MA Pardavé MP Ramírez-Silva MT 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(13-14):3139-3144
Noradrenaline is a catecholamine which has been largely recognised to play a very important role in biological systems. In view of the neurotransmitter's alleged importance, this work aimed at showing the influence of time on its spectral behaviour using different analytical methods and determining its acidity constants through spectrophotometric titration and by the so-called point-by-point analysis, where the samples are freshly prepared for each pH value investigated at the instant required. Because the catecholamines are light-sensitive and likely to react with the oxygen in the surrounding air, both methods used preclude its incidence onto the samples being analysed under the presence of a nitrogen atmosphere maintained over the solutions. The constants obtained through point-by-point analysis were log beta1 = 30.71+/-0.16, log beta2 = 22.00+/-0.15 and log beta3 = 11.69+/-0.16. 相似文献
22.
23.
Rodríguez AD Ramírez C Rodríguez II Barnes CL 《The Journal of organic chemistry》2000,65(5):1390-1398
Four diterpenes and a nor-diterpenoid, all of which possess unusual carbocyclic skeletons, were isolated from the hexane solubles of the West Indian gorgonian Pseudopterogorgia elisabethae. The structures and relative configurations of novel metabolites elisabethin D (2), elisabethin D acetate (3), 3-epi-elisabanolide (5), elisapterosin A (6), and elisapterosin B (7) were elucidated by interpretation of overall spectral data, which included 2D NMR correlation methods, IR, UV, and accurate mass measurements (HREI-MS and HRFAB-MS), chemical reactions, and X-ray diffraction analyses. The tetracyclic carbon skeleton of the elisapterosins is undescribed and constitutes a new class of C(20) rearranged diterpenes. Elisapterosin B displays strong in vitro anti-tuberculosis activity. 相似文献
24.
Ram Parkash S. C. Ahluwalia S. C. Sud R. N. Sahni R. C. Paul 《Monatshefte für Chemie / Chemical Monthly》1981,112(6-7):707-711
Heats solution of someLewis acids and bases in acetic anhydride have been determined and the following order of their relative strengths is proposed: SbCl5>SO3>SnCl4>TiCl4>AsCl3 and piperidine>
n-butylamine>potassium acetate>sodium acetate -picoline>quinoline. Heats neutralization of theseLewis acids and bases in acetic anhydride suggest that the major enthalpy change in these neutralization reactions is due to the combination of a proton and the (CH2COOCOCH3)-ion, resulting in the formation of acetic anhydride.
Lösungs- und Neutralisationswärmen von Lewis-Säuren und-Basen in Essigsäureanhydrid
Zusammenfassung Es wurden die Lösungswärmen einigerLewis-Säuren in Essigsäureanhydrid bestimmt und folgende Reihung nach ihrer relativen Stärke vorgeschlagen: SbCl5>SO3>SnCl4>TiCl4>AsCl3 und Piperidin> n-Butylamin>KAc>NaAc-Picolin>Chinolin. Die Neutralisationswärmen dieserLewis-Säuren und-Basen legen nahe, daß der Hauptanteil daran auf die Reaktion eines Protons mit (CH2–COOCOCH3)-zurückzuführen ist.相似文献
25.
Organic phase conversion of bulk (wurtzite) ZnO to nanophase (wurtzite and zinc blende) ZnO 总被引:1,自引:0,他引:1
Lauren P. Snedeker Aditi S. Risbud Ombretta Masala Jin Ping Zhang Ram Seshadri 《Solid State Sciences》2005,7(12):1500
We describe the all-organic phase conversion of bulk commercial ZnO in the wurtzite modification to sub-30 nm ZnO that we find to be partially in the zinc blende [, a=4.568(3) Å] modification. The conversion involves refluxing ZnO in 2,4-pentanedione (acetylacetone) at 413 K to form the zinc 2,4-pentanedionate, which is decomposed by heating at 573 K in an appropriate high-temperature solvent such as dibenzylether to form nanophase ZnO. This nanophase, partially zinc blende ZnO can also be obtained in a single step by heating commercial zinc 2,4-pentanedionate in refluxing dibenzylether. Thermodiffractometry suggests that the conversion of zinc blende ZnO to wurtzite ZnO commences near 650 K. 相似文献
26.
A novel chemical sensor for the colorimetric detection of mercuric salts is described. The sensor is based on a mesoporous nanocrystalline TiO2 film sensitised with a ruthenium dye; immersion of this film in an aqueous solution of Hg2+ results in a rapid colorimetric response, with both a high selectivity and a sub-micromolar sensitivity. 相似文献
27.
K. Babu V. Ganesh Shridhar R. Gadre Nour E. Ghermani 《Theoretical chemistry accounts》2004,111(2-6):255-263
Experimental and theoretical studies of electron densities and the corresponding derived entities such as electrostatic potentials have been the primary means of understanding the chemical nature and electronic properties of crystalline substances. Conventional crystal calculation methods such as the embedded cluster models are capable of performing calculations on small and medium-sized molecules, while periodic ab initio methods can treat crystals with up to 200 atoms per unit cell. A linear scaling method, viz. the molecular tailoring approach, has recently been developed for obtaining ab initio quality one-electron properties. In the present study, the molecular tailoring approach is employed to generate electron density, electrostatic potential and interaction density maps with the ibuprofen crystal as a test case. The interaction density and electrostatic potential maps produced in the present work succinctly bring out the actual crystalline environment around a given reference molecule by including the interactions with atoms in its neighborhood. The results obtained from the molecular tailoring approach may thus be expected to enhance our understanding of the environment in the crystalline material with reasonably small computational effort.Contribution to the Jacopo Tomasi Honorary Issue 相似文献
28.
Treatment of the bis(allylsulfoximine)titanium complexes derived from the beta-methyl-substituted acyclic allylic sulfoximines 13a and 13b with aldehydes gave with high selectivities the corresponding sulfoximine-substituted homoallylic alcohols which were isolated as the silyl ethers 15a-h. Methylation of sulfoximines 15a-h afforded the aminosulfoxonium salts 5a-h which upon treatment with LiN(H)tBu gave in high yields the enantio- and diastereomerically pure silyl-substituted 2,3-dihydrofurans 4a-h. Treatment of the titanium complexes derived from the cyclic allylic sulfoximines 17a, 17b, and ent-17c with p-MeOC(6)H(4)CHO delivered with high selectivities the corresponding sulfoximine-substituted cyclic homoallylic alcohols which were isolated as the silyl ethers 18a, 18b, and ent-18c, respectively. Methylation of sulfoximines 18a, 18b, and ent-18c furnished the aminosulfoxonium salts 8a, 8b, and ent-8c, respectively, whose treatment with LiN(H)t-Bu gave the enantio- and diastereomerically pure fused bicyclic 2,3-dihydrofurans 6a, 6b, and ent-6c, respectively, in good yields. It is proposed that the 1-alkenyl aminosulfoxonium salts 5a-h, 8a, 8b, and ent-8c react with the base under alpha-elimination and formation of the acyclic and cyclic beta-silyloxy alkylidene carbenes 2a-h, 7a, 7b, and ent-7c, respectively, which then undergo a 1,5-O,Si-bond insertion and 1,2-silyl migration. The cyclic aminosulfoxonium salts 8a, 8b, and ent-8c upon treatment with 1,8-diazabicyclo[5.4.0]-7-undecene did not undergo an alpha-elimination but suffered a novel migratory cyclization with formation of the enantio- and diastereomerically pure bicyclic tetrahydrofurans 9a, 9b, and ent-9c, respectively. It is proposed that the 1-alkenyl sulfoxonium salts 8a, 8b, and ent-8c are isomerized to the allylic aminosulfoxonium salts 10a, 10b, and ent-10c, respectively, which then suffer an intramolecular substitution of the (dimethylamino)sulfoxonium group by the silyloxy group followed by a desilylation. The syntheses of the 2,3-dihydrofurans 4a-h, 6a, and 6b and of the tetrahydrofurans 9a and 9b are accompanied by the formation of sulfinamide 16 of >or=98% ee, which can be converted via sulfoxide 28 of >or=98% to the starting sulfoximine 11 of >or=98% ee. 相似文献
29.
[Reaction: see text] Transformation of enantiopure diastereoisomers (2R,1'S)- and (2S,1'S)-2-(1-aminoalkyl)epoxides into the corresponding 4-(1-aminoalkyl)-1,3-dioxolanes is achieved by reaction with different ketones in the presence of BF3.Et2O. The conversion takes place in very high yields, total selectivity, and without epimerization. A mechanism to explain this transformation is proposed. The obtained 1,3-dioxolanes can be deprotected, and (2R,3S)- and (2S,3S)-3-aminoalkano-1,2-diols were isolated. 相似文献
30.
ágnes Zsigmond Ramóna Madácsi Ferenc Notheisz Erzsébet Mernyák and Ferenc Joó 《Reaction Kinetics and Catalysis Letters》2006,87(2):297-304
Summary [RuCl2(PPh3)3], [{RuCl2(TPPMS)2}2] and their heterogenized analogs were applied in the selective hydrogenation of 17-keto- and α,β-unsaturated ketosteroids.
In basic conditions these complexes selectively hydrogenated the C=O bonds, similarly to the results obtained in the case
of α,β-unsaturated aldehydes. A new method was developed for the synthesis of an expensive steroid alcohol, which can be prepared
traditionally in a more complicated way. 相似文献