全文获取类型
收费全文 | 1526篇 |
免费 | 35篇 |
国内免费 | 2篇 |
专业分类
化学 | 830篇 |
晶体学 | 13篇 |
力学 | 65篇 |
数学 | 142篇 |
物理学 | 513篇 |
出版年
2023年 | 8篇 |
2020年 | 12篇 |
2019年 | 16篇 |
2018年 | 8篇 |
2016年 | 27篇 |
2015年 | 35篇 |
2014年 | 27篇 |
2013年 | 61篇 |
2012年 | 80篇 |
2011年 | 82篇 |
2010年 | 55篇 |
2009年 | 54篇 |
2008年 | 68篇 |
2007年 | 72篇 |
2006年 | 84篇 |
2005年 | 78篇 |
2004年 | 62篇 |
2003年 | 56篇 |
2002年 | 43篇 |
2001年 | 23篇 |
2000年 | 36篇 |
1999年 | 16篇 |
1998年 | 13篇 |
1997年 | 20篇 |
1996年 | 22篇 |
1995年 | 27篇 |
1994年 | 23篇 |
1993年 | 34篇 |
1992年 | 29篇 |
1991年 | 12篇 |
1990年 | 23篇 |
1989年 | 13篇 |
1988年 | 8篇 |
1987年 | 14篇 |
1986年 | 8篇 |
1985年 | 11篇 |
1984年 | 12篇 |
1983年 | 11篇 |
1982年 | 15篇 |
1980年 | 8篇 |
1979年 | 12篇 |
1978年 | 11篇 |
1977年 | 12篇 |
1976年 | 7篇 |
1975年 | 10篇 |
1974年 | 9篇 |
1943年 | 7篇 |
1934年 | 6篇 |
1933年 | 11篇 |
1931年 | 8篇 |
排序方式: 共有1563条查询结果,搜索用时 15 毫秒
91.
Conrad T. Pfeiffer Justin D. Northrup Jae Eun Cheong Melody A. Pham Matthew F.L. Parker Christian E. Schafmeister 《Tetrahedron letters》2018,59(30):2884-2888
Spiroligomers are a class of peptidomimetics that connect interchangeable, stereochemically pure, cyclic monomers through pairs of amide bonds to form diketopiperazines between the monomers. This enables them to adopt predictable and programmable structure due to the rigidity of the final molecule. We present a new method for the solid phase synthesis of highly functionalized spiroligomers that incorporates the use of the p-nitrobenzyloxycarbonyl (pNZ) as a temporary amine protecting group and the pentafluorophenyl ester for monomer activation. This new method allows for the synthesis of spiroligomers with higher purity and increased yields when compared to previous methods. This improved method of synthesis of functionalized spiroligomers will facilitate the development of applications as catalysts, therapeutics and membrane channels. 相似文献
92.
Cyclization of 4‐Phenylthiosemicarbazide with Phenacylbromide Revisited. Formation of 1,3,4‐Thiadiazines and of Isomeric 1,3‐Thiazoles 下载免费PDF全文
Wolf‐Diethard Pfeiffer Dieter Junghans Ashot S. Saghyan Peter Langer 《Journal of heterocyclic chemistry》2014,51(4):1063-1067
The cyclization of 4‐phenylthiosemicarbazide with phenacylbromide, carried out in refluxing ethanol, afforded 1,3,4‐thiadiazine 1 as the major product. In contrast to a previous report, 2‐phenylimino‐4‐phenyl‐2,3‐dihydro‐1,3‐thiazol‐3‐amine ( 2 ) and not 2‐hydrazono‐3,4‐diphenyl‐2,3‐dihydro‐1,3‐thiazole ( 8 ) was formed as a side‐product. This product is the main product when the reaction is carried out in concentrated hydrochloric acid. Our findings were independently confirmed by independent syntheses of the isomeric products and by a thorough study of their reactivity. It is important to note that the product distribution of the cyclization of thiosemicarbazides with haloketones strongly depends on the substitution pattern and on the reaction conditions. 相似文献
93.
Siddappa Patil Anthony Deally Brendan Gleeson Helge Müller‐Bunz Francesca Paradisi Matthias Tacke 《应用有机金属化学》2010,24(11):781-793
From the reaction of 1H‐imidazole ( 1a ), 4,5‐dichloro‐1H‐imidazole ( 1b ) and 1H‐benzimidazole ( 1c ) with p‐cyanobenzyl bromide ( 2 ), symmetrically substituted N‐heterocyclic carbene (NHC) [( 3a–c )] precursors, 1‐methylimidazole ( 5a ), 4,5‐dichloro‐1‐methylimidazole ( 5b ) and 1‐methylbenzimidazole ( 5c ) with benzyl bromide ( 6 ), non‐symmetrically substituted N‐heterocyclic carbene (NHC) [( 7a–c )] precursors were synthesized. These NHC? precursors were then reacted with silver(I) acetate to yield the NHC‐silver complexes [1,3‐bis(4‐cyanobenzyl)imidazole‐2‐ylidene] silver(I) acetate ( 4a ), [4,5‐dichloro‐1,3‐bis(4‐cyanobenzyl)imidazole‐2‐ylidene] silver(I) acetate ( 4b ), [1,3‐bis(4‐cyanobenzyl)benzimidazole‐2‐ylidene] silver(I) acetate ( 4c ), (1‐methyl‐3‐benzylimidazole‐2‐ylidene) silver(I) acetate ( 8a ), (4,5‐dichloro‐1‐methyl‐3‐benzylimidazole‐2‐ylidene) silver(I) acetate ( 8b ) and (1‐methyl‐3‐benzylbenzimidazole‐2‐ylidene) silver(I) acetate ( 8c ) respectively. The four NHC‐precursors 3a–c, 7c and four NHC–silver complexes 4a–c and 8c were characterized by single crystal X‐ray diffraction. The preliminary antibacterial activity of all the compounds was studied against Gram‐negative bacteria Escherichia coli, and Gram‐positive bacteria Staphylococcus aureus using the qualitative Kirby‐Bauer disc‐diffusion method. All NHC–silver complexes exhibited medium to high antibacterial activity with areas of clearance ranging from 4 to 12 mm at the highest amount used, while the NHC‐precursors showed significantly lower activity. In addition, all NHC–silver complexes underwent preliminary cytotoxicity tests on the human renal‐cancer cell line Caki‐1 and showed medium to high cytotoxicity with IC50 values ranging from 53 ( ± 8) to 3.2 ( ± 0.6) µM. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
94.
Mustafa Barri George K. El Khoury Helge I. Andersson Bjrnar Pettersen 《国际流体数值方法杂志》2010,64(7):777-792
Direct numerical simulation (DNS) has been performed to study the channel flow over a backward‐facing step at a Reynolds number Reb=5600 based on the step height h and the inflow bulk velocity Ub. A dynamic method has been used in order to generate realistic turbulent inflow conditions. The results upstream of the step compared well with the fully developed channel flow. Downstream of the step our results show excellent agreement with experimental data. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
95.
We develop an analog of classical oscillation theory for Sturm–Liouville operators which, rather than measuring the spectrum
of one single operator, measures the difference between the spectra of two different operators.
This is done by replacing zeros of solutions of one operator by weighted zeros of Wronskians of solutions of two different
operators. In particular, we show that a Sturm-type comparison theorem still holds in this situation and demonstrate how this
can be used to investigate the number of eigenvalues in essential spectral gaps. Furthermore, the connection with Krein’s
spectral shift function is established.
Research supported by the Austrian Science Fund (FWF) under Grant No. Y330. 相似文献
96.
97.
We observe density-induced 90 degrees rotations of the anisotropy axes in transport measurements at half-filled high Landau levels in the two dimensional electron system, where stripe states are proposed ( nu = 9/2, 11/2, etc.). Using a field effect transistor, we find the transition density to be 2.9x10(11) cm(-2) at nu = 9/2. Hysteresis is observed in the vicinity of the transition. We construct a phase boundary in the filling factor magnetic field plane in the regime 4.4相似文献
98.
Kolbitsch C Lorenz IH Hörmann C Hinteregger M Löckinger A Moser PL Kremser C Schocke M Felber S Pfeiffer KP Benzer A 《Magnetic resonance imaging》2002,20(7):535-541
Conflicting results reported on the effects of hyperoxia on cerebral hemodynamics have been attributed mainly to methodical and species differences. In the present study contrast-enhanced magnetic resonance imaging (MRI) perfusion measurement was used to analyze the influence of hyperoxia (fraction of inspired oxygen (FiO2) = 1.0) on regional cerebral blood flow (rCBF) and regional cerebral blood volume (rCBV) in awake, normoventilating volunteers (n = 19). Furthermore, the experiment was repeated in 20 volunteers for transcranial Doppler sonography (TCD) measurement of cerebral blood flow velocity in the middle cerebral artery (CBFV(MCA)). When compared to normoxia (FiO2 = 0.21), hyperoxia heterogeneously influenced rCBV (4.95 +/- 0.02 to 12.87 +/- 0.08 mL/100g (FiO2 = 0.21) vs. 4.50 +/- 0.02 to 13.09 +/- 0.09 mL/100g (FiO2 = 1.0). In contrast, hyperoxia diminished rCBF in all regions (68.08 +/- 0.38 to 199.58 +/- 1.58 mL/100g/min (FiO2 = 0.21) vs. 58.63 +/- 0.32 to 175.16 +/- 1.51 mL/100g/min (FiO2 = 1.0)) except in parietal and left frontal gray matter. CBFV(MCA) remained unchanged regardless of the inspired oxygen fraction (62 +/- 9 cm/s (FiO2 = 0.21) vs. 64 +/- 8 cm/s (FiO2 = 1.0)). Finding CBFV(MCA) unchanged during hyperoxia is consistent with the present study's unchanged rCBF in parietal and left frontal gray matter. In these fronto-parietal regions predominantly fed by the middle cerebral artery, the vasoconstrictor effect of oxygen was probably counteracted by increased perfusion of foci of neuronal activity controlling general behavior and arousal. 相似文献
99.
100.
Coherent anti-Stokes Raman scattering (CARS) spectra of excited molecules as well as Shpolskii spectra provide information about geometry changes between ground and excited states. Vibrational frequencies and relative intensities from recently obtained CARS spectra of the chrysene S1 and T1 state and earlier observed Shpolskii spectra are interpreted in terms of molecular geometry and force-field changes by means of quantum-chemical consistent force field (QCFF) and Franck-Condon factor calculations. The comparison of observed and calculated relative intensities indicates a coupling between the S1 and S2 state enhancing some of the vibrational radiative singlet transitions both in absorption and fluorescence spectra whereas within the phosphorescence spectra proportionality to calculated Franck-Condon factors is obeyed. The T1 state is the more loosely bound state and its geometry change is different from that of the S1 state. The resonance CARS transitions in the S1 state are assigned to totally symmetric vibrations getting their intensity by a coupling scheme analogous to the A term of the resonance Raman effect: the relative intensity of a transition is shown to be proportional to the Franck-Condon factor to the higher excited state and to the squared vibrational frequency. Using this relation this state can be identified by means of its finger-print-like intensity pattern. 相似文献