全文获取类型
收费全文 | 4659篇 |
免费 | 125篇 |
国内免费 | 17篇 |
专业分类
化学 | 3562篇 |
晶体学 | 34篇 |
力学 | 52篇 |
数学 | 483篇 |
物理学 | 670篇 |
出版年
2021年 | 99篇 |
2020年 | 70篇 |
2019年 | 66篇 |
2018年 | 54篇 |
2017年 | 52篇 |
2016年 | 126篇 |
2015年 | 102篇 |
2014年 | 126篇 |
2013年 | 263篇 |
2012年 | 231篇 |
2011年 | 284篇 |
2010年 | 171篇 |
2009年 | 170篇 |
2008年 | 307篇 |
2007年 | 253篇 |
2006年 | 263篇 |
2005年 | 242篇 |
2004年 | 185篇 |
2003年 | 160篇 |
2002年 | 172篇 |
2001年 | 81篇 |
2000年 | 62篇 |
1999年 | 64篇 |
1998年 | 46篇 |
1997年 | 47篇 |
1996年 | 58篇 |
1995年 | 49篇 |
1994年 | 53篇 |
1993年 | 46篇 |
1992年 | 41篇 |
1991年 | 34篇 |
1990年 | 26篇 |
1989年 | 30篇 |
1988年 | 24篇 |
1987年 | 24篇 |
1986年 | 23篇 |
1985年 | 33篇 |
1984年 | 37篇 |
1983年 | 24篇 |
1982年 | 43篇 |
1981年 | 44篇 |
1980年 | 41篇 |
1979年 | 33篇 |
1978年 | 29篇 |
1977年 | 27篇 |
1975年 | 26篇 |
1974年 | 22篇 |
1956年 | 19篇 |
1955年 | 37篇 |
1954年 | 57篇 |
排序方式: 共有4801条查询结果,搜索用时 281 毫秒
81.
J. A. Duffy H. M. Fretwell A. P. Clarke S. B. Dugdale M. A. Alam 《Journal of Radioanalytical and Nuclear Chemistry》1996,211(1):173-179
The phase behaviour of carbon dioxide confined in VYCOR glass at pressures below that of the bulk triple point (0.51 MPa) has been investigated. The temperature at which freezing occurs appears to be pressure dependent below 0.3 MPa. As experiments are performed at successively lower pressures, the confined phase transitions gradually disappear, due to either partial pore filling, or the proximity of the confined triple point. 相似文献
82.
M. A. Alam H. M. Fretwell J. A. Duffy A. P. Clarke S. B. Dugdale 《Journal of Radioanalytical and Nuclear Chemistry》1996,210(2):255-271
In this paper we present a brief review of the current state of positron annihilation research into the phase behaviour of fluids confined within restricted boundaries. We summarise, in the form of selected examples, the work done so far on: (1) fluids confined in the nanometer-size pores of VYCOR glass, with particular emphasis on the confined phase diagram and the mechanisms behind phase transitions compared to bulk. (2) The adsorption/physisorption of gases on internal surfaces of grafoil and the potential of positron technique for revealing physical properties, such as the intricate molecular arrangements during phase transitions of the layered fluid. 相似文献
83.
84.
85.
Bazzicalupi C Bencini A Berni E Bianchi A Ciattini S Giorgi C Maoggi S Paoletti P Valtancoli B 《The Journal of organic chemistry》2002,67(25):9107-9110
The synthesis of three new tris-macrocycles, containing three [12]aneN(4) (L1), [12]aneN(3)O (L2), or [14]aneN(4) (L3) moieties appended to a tren unit, is reported. The crystal structure of the [(Na(ClO(4))(6)) subset L1(2)H(13)]Na(6)Cl(2)(ClO(4))(12) compound shows the anionic cluster [Na(ClO(4))(6)](5)(-) assembled inside the cavity defined by two bowl-shaped polyammonium receptors, held by multiple charge-charge and hydrogen bond interactions. 相似文献
86.
Baciocchi E Bietti M Chiavarino B Crestoni ME Fornarini S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(2):532-537
The gas-phase acidity of ionized benzyl alcohol and of some of its derivatives with selected reference bases has been studied by Fourier Transform Ion Cyclotron Resonance (FT-ICR) mass spectrometry. The aim was to relate the gas-phase reactivity to the behavior in aqueous solution of the radical cations of benzyl alcohols bearing methoxy substituent(s) on the phenyl ring which are known to undergo deprotonation at both the CH2 and OH groups. The dual reactivity behavior is confirmed in the gas phase, in which the prototypical ion, C6H5CH2OH*+, is deprotonated at both the CH2 and OH groups, whereas the ring hydrogens are not involved. An increasing extent of O-deprotonation is shown as the strength of the base increases. Appropriate methyl substitution, as in the radical cations of C6H5C(Me)2OH and C6H5CH2OMe, allows only O- or C-acidity. The two processes are characterized by comparable thermodynamic features with a Gas-phase Basicity (GB) value of 852 kJ mol(-1) for the cumyloxyl radical and 850 kJ mol(-1) for the alpha-methoxybenzyl radical. The possible origin of the observed mechanistic dichotomy is discussed. 相似文献
87.
Dzygiel A Rzeszotarska B Masiukiewicz E Cmoch P Kamieński B 《Chemical & pharmaceutical bulletin》2004,52(2):192-198
Methyl 5-amino-1H-[1,2,4]triazole-3-carboxylate hydrochloride (1). and free ester (2). were obtained and 2 was reacted with Ac(2)O to give the acetylated products 3-6. Compounds 1-6 were studied using HPLC, GC-MS, FTIR and multinuclear NMR spectroscopy, including the cross-polarisation magic angle spinning (CPMAS) technique. The results of the acetylation of 2 were compared to those of the acetylation of 5-amino-1H-[1,2,4]triazole, and for 2 a significant decrease in the susceptibility to acetylation was found. The reaction of 2 with Ac(2)O at 20 degrees C, regardless of the amount and the concentration of the latter, including neat Ac(2)O, proceeds fully regioselectively and leads to one product: methyl 1-acetyl-5-amino-1H-[1,2,4]triazole-3-carboxylate (3). In sharp contrast to 5-amino-1H-[1,2,4]triazole, neither an additional monoacetylated isomer, whether annular or exocyclic, nor any diacetylated derivative could be detected. The diacetylation of 2 requires the process to be carried out in neat boiling Ac(2)O and, as in the case of 5-amino-1H-[1,2,4]triazole, gives two diacetylated isomers. These are methyl 1-acetyl-3-(acetylamino)-1H-[1,2,4]triazole-5-carboxylate (4) and 1-acetyl-5-(acetylamino)-1H-[1,2,4]triazole-3-carboxylate (5). Hypothetical pathways of their formation have been suggested. A mixture of 4 and 5 upon hydrolysis of the ring acetyl group gives the monoacetylated derivative methyl 5-(acetylamino)-1H-[1,2,4]triazole-3-carboxylate (6). The spectroscopic, structural and conformational characteristics of compounds 1-6 have been given and methods for their preparation have been provided. 相似文献
88.
Determination of pharmaceuticals, iodinated contrast media and musk fragrances in sludge by LC/tandem MS and GC/MS 总被引:1,自引:0,他引:1
Ternes TA Bonerz M Herrmann N Löffler D Keller E Lacida BB Alder AC 《Journal of chromatography. A》2005,1067(1-2):213-223
Analytical methods have been developed that allow for the determination of antiphlogistics, lipid regulators, the antiepileptic carbamazepine, cytostatic agents, the psychiatric drug diazepam and iodinated contrast media (ICM) as well as two major polycyclic musk fragrances HHCB (galaxolide) and AHTN (tonalide) in activated and digested sludge. The procedures consist of ultrasonic solvent extraction (USE) using methanol/acetone or pressurized liquid extraction (PLE) using 100% methanol. Clean-up was performed with C18ec material and silica gel followed by LC tandem MS (electrospray or atmospheric pressure chemical ionization) detection for pharmaceuticals and iodinated contrast media as well as GC/MS in the SIM mode for musk fragrances. Absolute recoveries from spiked activated sludge in general ranged from 88+/-4 to 119+/-20% for ICM and were 78+/-15 and 87+/-10% for the AHTN and HHCB, respectively. For the pharmaceuticals, absolute recoveries in activated sludge ranged between 43 and 78%. Subsequently, compensation of losses was carried out by using surrogate standards (acidic pharmaceuticals: fenoprop, neutral pharmaceuticals: dihydro-carbamazepine, musk fragrances: AHTN-D3). With one exception the recoveries were also adequate in digested sludge ranging from 43% to 120%. 相似文献
89.
Dunne KS Bisaro F Odell B Paris JM Gouverneur V 《The Journal of organic chemistry》2005,70(26):10803-10809
[reaction: see text] The preparation of phosphorus-containing trienes featuring two diastereotopic vinyl moieties followed by a diastereoselective ring-closing metathesis is described. This methodology allowed for the synthesis of novel highly functionalized P-stereogenic heterocycles featuring both an exo- and an endocyclic double bond. An investigation into the factors influencing the diastereochemical outcome of the ring-closing metathesis is also presented, revealing that the geometry of the double bonds conjugated to phosphorus is important and that 1,3-stereoinduction is superior to 1,4-stereoinduction for these reactions. 相似文献
90.