全文获取类型
收费全文 | 2122篇 |
免费 | 69篇 |
国内免费 | 5篇 |
专业分类
化学 | 1416篇 |
晶体学 | 9篇 |
力学 | 84篇 |
数学 | 217篇 |
物理学 | 470篇 |
出版年
2023年 | 12篇 |
2022年 | 20篇 |
2021年 | 23篇 |
2020年 | 44篇 |
2019年 | 30篇 |
2018年 | 13篇 |
2017年 | 16篇 |
2016年 | 61篇 |
2015年 | 30篇 |
2014年 | 42篇 |
2013年 | 94篇 |
2012年 | 97篇 |
2011年 | 116篇 |
2010年 | 61篇 |
2009年 | 62篇 |
2008年 | 118篇 |
2007年 | 98篇 |
2006年 | 91篇 |
2005年 | 91篇 |
2004年 | 105篇 |
2003年 | 67篇 |
2002年 | 48篇 |
2001年 | 37篇 |
2000年 | 44篇 |
1999年 | 29篇 |
1998年 | 17篇 |
1997年 | 24篇 |
1996年 | 35篇 |
1995年 | 30篇 |
1994年 | 22篇 |
1993年 | 26篇 |
1992年 | 28篇 |
1991年 | 49篇 |
1990年 | 30篇 |
1989年 | 31篇 |
1988年 | 24篇 |
1987年 | 20篇 |
1986年 | 20篇 |
1985年 | 28篇 |
1984年 | 41篇 |
1983年 | 36篇 |
1982年 | 27篇 |
1981年 | 18篇 |
1980年 | 24篇 |
1979年 | 20篇 |
1978年 | 27篇 |
1977年 | 15篇 |
1976年 | 20篇 |
1975年 | 17篇 |
1972年 | 10篇 |
排序方式: 共有2196条查询结果,搜索用时 10 毫秒
21.
Burkhard Schmidt Ingo Franke Franz-Josef Witteler Michael Binder 《Helvetica chimica acta》1983,66(8):2564-2571
The novel cannabinoids (6aR, 10aR)-N-ethyl-Δ8-tetrahydrocannabinol-18-amide (15) and (6aR, 10aR, 17 RS)-N-ethyl-17-methyl-Δ8- tetrahydrocannabinol-18-amide (16) , designed as cannabinoid affinity ligands, were synthesized from the corresponding acids 11 and 12 via the N-hydroxysuccinimide esters. Amide 16 was tested in the rat and was generalized to Δ9-tetrahydrocannabinol, being 5 times less potent than the training drug. An improved synthesis of (6aR, 10aR)-17,18-didehydro-Δ8-tetrahydrocannabinol (23) is reported. As model reaction for the preparation of a tritiated Δ8-tetrahydrocannabinol, compound 23 was selectively deuterated at C(17) and C(18) in benzene/Et3N using [(C6H5)3P]3RuCl2 as catalyst. 相似文献
22.
23.
Arisaka K Auerbach LB Axelrod S Belz J Biery KA Buchholz P Chapman MD Cousins RD Diwan MV Eckhause M Ginkel JF Guss C Hancock AD Heinson AP Highland VL Hoffmann GW Horvath J Irwin GM Joyce D Kaarsberg T Kane JR Kenney CJ Kettell SH Kinnison WW Knibbe P Konigsberg J Kuang Y Lang K Lee DM Margulies J Mathiazhagan C McFarlane WK McKee RJ Melese P Milner EC Molzon WR Ouimette DA Riley PJ Ritchie JL Rubin P Sanders GH Schwartz AJ Sivertz M Slater WE Urheim J Vulcan WF Wagner DL Welsh RE Whyley RJ 《Physical review letters》1993,71(24):3910-3913
24.
25.
The synthesis and structure of an acetal protected 10-membered cyclic enediyne-1,2-diol rac-10 is reported. The conformational constrain of the unsaturated macrocycle by the acetal protection group prevents the thermal cyclization reaction of the endiyne during synthesis and purification. 相似文献
26.
A practicable and selective liquid chromatography-mass spectrometry assay for the determination of two cyclooxygenase-2 inhibitors, etoricoxib and valdecoxib, in human plasma is presented. The analytical technique is based on reversed-phase high-performance liquid chromatography (HPLC) coupled to atmospheric pressure chemical ionisation (APCI) mass spectrometry (Finnigan Mat LCQ ion trap). Mass analysis was performed in the positive ion mode. The ion trap was operated in the tandem MS mode (MS2) and the transitions of etoricoxib (m/z 359.2 --> 280.3) and valdecoxib (m/z 315.1 --> 235.1) were followed by selected reaction monitoring. Retention times of etoricoxib and valdecoxib were 1.05 and 1.08 min, respectively. The method was validated over a linear range 10-2500 and 5-1000 microg/L using the other substrate as internal standard. After validation, the method was used to study the pharmacokinetic pro fi le of etoricoxib or valdecoxib in a healthy volunteer after administration of a single oral dose (valdecoxib, 20 mg; etoricoxib, 90 mg). The presented method was suf fi cient to cover more than 90% of the area under the plasma concentration time curve. 相似文献
27.
Winter B Ivanco J Netzer FP Ramsey MG Salzmann I Resel R 《Langmuir : the ACS journal of surfaces and colloids》2004,20(18):7512-7516
A combination of in situ surface sensitive-techniques, UV photoemission and low energy electron diffraction, with ex situ bulk sensitive X-ray diffraction reveals the formation of epitaxial thin films of sexiphenyl on Al(111) starting from the first monolayer. For room temperature growth, highly ordered films are formed with a unique alignment of the sexiphenyl molecules with the long axes of all molecules aligned parallel to both the surface and the <10> azimuthal directions of Al(111). This is related to a densely packed highly commensurate first monolayer, which acts as a template for the unique (21) crystallite orientation observed. 相似文献
28.
The radical yields and rate constants in the quenching reaction of thionine triplet with the complete series of monohalogen substituted anilines as electron donors were determined by flash spectroscopy. Whereas the quenching rate constants show little and unsystematic variation, the radical yields decrease with increasing spin—orbit coupling constant of the halogen substituent. This effect is very sensitive to the position of the halogen in the donor. The results are explained in terms of a heavy atom effect on the intersystem crossing rate constant in a triplet exciplex. 相似文献
29.
Kraineva J Narayanan RA Kondrashkina E Thiyagarajan P Winter R 《Langmuir : the ACS journal of surfaces and colloids》2005,21(8):3559-3571
We investigated the effect of incorporation of a small aqueous peripheral membrane protein (cyt c) into the three-dimensional periodic nanochannel structures formed by the lipid monoolein (MO) on its rich phase behavior as a function of temperature, pressure, and protein concentration using synchrotron X-ray small-angle diffraction. By simultaneous use of the pressure-jump relaxation technique and time-resolved synchrotron X-ray diffraction, we also studied the kinetics of various lipid mesophase transformations of the system for understanding the mechanistic pathways of their formation influenced by the protein-lipid interactions. Cyt c incorporated into the bicontinuous cubic phase Ia3d of MO has a significant effect on the lipid structure and the pressure stability of the system already at low protein concentrations. Concentrations higher than 0.2 wt % of cyt c led to an increase in interfacial curvature due to interaction of the protein with the lipid headgroups. This promotes the formation of a new, probably partially micellar cubic phase of crystallographic space group P4(3)32. Upon pressurization, the P4(3)32 phase undergoes a phase transition to a cubic Pn3m phase with smaller partial specific volume. Increase in protein concentration increases the pressure stability of the P4(3)32 phase. The formation of this phase from the cubic phase Pn3m is a slow process taking many seconds and having a time lag in the beginning. It seems to occur as a two-state process without ordered intermediate states. At temperatures above 60 degrees C, the P4(3)32 phase is unable to accommodate the unfolded protein and transforms to a bicontinuous cubic Ia3d phase. Time-resolved small-angle X-ray scattering studies show that the L(alpha) --> Ia3d transition in pure MO dispersions under limited hydration conditions occurs within a time interval of 1 s at 35 degrees C preceded by a lag phase of 1.5 s. The Ia3d cubic phase initially forms with a much larger lattice constant due to hydration and experiences an initially lower curvature that relaxes within about 1 s. Interestingly, no other cubic phases are involved as intermediates in the transition, i.e., the gyroid cubic phase is able to form directly from the L(alpha) phase. The mechanism behind the L(alpha) --> Ia3d transition in pure MO dispersions has been discussed within the framework of recent stalk models for membrane fusion. In the presence of cyt c, the L(alpha) --> Ia3d transition is much slower. The rather long relaxation times of the order of seconds are probably due to a kinetic trapping of the system and limitation by the transport and redistribution of water and lipid in the evolving new lipid phases. We also studied the transition from the pure lamellar L(alpha) phase to the Ia3d-P4(3)32 two phase region and observed a rather complex transition behavior with transient lamellar and cubic intermediate states. 相似文献
30.
Alkylation of 1-dimethylamino-1-cyanomethanephosphonic acid diethyl ester (8), easily obtainable from diethyl phosphite and the 0,N-acetal 9, yields 1-alkyl derivatives 14. Elimination of HCN converts 14 into 1-phosphonoenamines 6. Carbonyl compounds react with 8 to give 1-cyanoenamines 15 which may be hydrolyzed to from the homologous carboxylic acid. Alternatively, deprotonation of 15 yields the homoenolate anions 17 which can be alkylated or hydroxyalkylated, permitting chain extension of carbonyl compounds through introduction of an α-carboxyl and a β-alkyl group. Acid catalyzed hydrolysis of 8 results in cleavage of the PC bond, leading to the corresponding α-dimethylamino alkanoic acids. A phosphonic acid 11 can be obtained from 8 by application of the silylester method. An unambigous assignment of E/Z-isomers of the cyanoenamines 15 has been derived from 13C-NMR spectroscopy. 相似文献