全文获取类型
收费全文 | 486篇 |
免费 | 15篇 |
专业分类
化学 | 367篇 |
力学 | 15篇 |
数学 | 42篇 |
物理学 | 77篇 |
出版年
2021年 | 10篇 |
2020年 | 2篇 |
2019年 | 3篇 |
2018年 | 4篇 |
2017年 | 6篇 |
2016年 | 5篇 |
2015年 | 15篇 |
2014年 | 12篇 |
2013年 | 19篇 |
2012年 | 31篇 |
2011年 | 32篇 |
2010年 | 24篇 |
2009年 | 12篇 |
2008年 | 31篇 |
2007年 | 26篇 |
2006年 | 31篇 |
2005年 | 32篇 |
2004年 | 18篇 |
2003年 | 19篇 |
2002年 | 24篇 |
2001年 | 3篇 |
2000年 | 2篇 |
1999年 | 5篇 |
1998年 | 4篇 |
1997年 | 9篇 |
1996年 | 6篇 |
1995年 | 5篇 |
1994年 | 4篇 |
1993年 | 3篇 |
1992年 | 4篇 |
1991年 | 3篇 |
1990年 | 2篇 |
1989年 | 2篇 |
1988年 | 5篇 |
1986年 | 2篇 |
1985年 | 10篇 |
1984年 | 13篇 |
1983年 | 7篇 |
1982年 | 6篇 |
1981年 | 10篇 |
1980年 | 4篇 |
1979年 | 3篇 |
1978年 | 2篇 |
1977年 | 8篇 |
1976年 | 3篇 |
1975年 | 2篇 |
1974年 | 2篇 |
1973年 | 3篇 |
1972年 | 4篇 |
1911年 | 2篇 |
排序方式: 共有501条查询结果,搜索用时 15 毫秒
41.
Leif Arkeryd 《Journal of statistical physics》1983,31(2):347-361
This paper studies the boundedness of solutionsf of the initial-value problem for the space-homogeneous Boltzmann equation for inverse kth power forces, whenk>5, and under angular cutoff. The main result is that if the initial value isf 0 ? 0 with (1 + ¦υ¦2)φ0 εL 1 and (1 + ¦υ¦)s f 0ε L∞ for somes > 2, then (1 + ¦υ¦s'f tεL ∞ fort>0 and essυ,t sup(1 + ¦υ¦)s'f(υ, t,) < ∞ for anys′ ? s whens ? 5, and anys′ ? s ifs > 5. 相似文献
42.
43.
Schröder L Schmitz C Bachert P 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2005,174(1):68-77
NMR spectra of non-weakly coupled spin systems exhibit asymmetries in line intensities known as "roof effect" in 1D spectroscopy. Due to limited spectral resolution, this effect has not been paid much attention so far in in vivo spectroscopy. But when high-quality spectra are obtained, this effect should be taken into account to explain the quantum-mechanical fine structure of the system. Adenosine 5'-triphosphate (ATP) represents a 31P spin system with multiple line splittings which are caused by J-couplings of medium strength at 1.5 T. We analyzed the ATP roof effect in vivo, especially for the beta-ATP multiplet. The intensities of its outer resonances deviate by ca. 12.5% from a symmetrical triplet. As this asymmetry reflects the transition from Paschen-Back to Zeeman effect with total spin that is largely broken up, the Clebsch-Gordan coefficients of the system can be indicated in analogy to the hyperfine structure of hydrogen. Taking the roof effect into account, the chi2 of fitting in vivo ATP resonances is reduced by ca. 9% (p<0.005). 相似文献
44.
Virta P Holmström T Roslund MU Mattjus P Kronberg L Sjöholm R 《Organic & biomolecular chemistry》2004,2(6):821-827
Four novel derivatives of 2-amino-9-(beta-D-ribofuranosyl)purine (1) were synthesised and fully characterised. When 1 was reacted with chloroacetaldehyde (a), 2-chloropropanal (b), bromomalonaldehyde (c) and a mixture of chloroacetaldehyde + malonaldehyde (d), 3-(beta-D-ribofuranosyl)-imidazo-[1,2a]purine (2), 3-(beta-D-ribofuranosyl)-5-methylimidazo-[1,2a]purine (3), 3-(beta-D-ribofuranosyl)-5-formylimidazo-[1,2a]purine (4) and 9-(beta-D-ribofuranosyl)-2-(3,5-diformyl-4-methyl-1,4-dihydro-1-pyridyl)purine (5) were formed, respectively. The products were isolated, purified by chromatography and characterised by MS, complete NMR assignment as well as fluorescence and UV spectroscopy. The yields of these reactions were moderate (14-20%). The fluorescence properties differed from those of the starting compound and the quantum yields were considerably lower. 相似文献
45.
Juraj Bunta Martin Dahlberg Leif Eriksson Nikolai Korolev Aatto Laaksonen Raimo Lohikoski Alexander Lyubartsev Miroslav Pinak Patric Schyman 《International journal of quantum chemistry》2007,107(2):279-291
This work highlights four different topics in modeling of DNA: (i) the importance of water and ions together with the structure and function of DNA; the hydration structure around the ions appears to be the determining factor in the ion coordination to DNA, as demonstrated in the results of our MD simulations; (ii) how MD simulations can be used to simulate single molecule manipulation experiments as a complement to reveal the structural dynamics of the studied biomolecules; (iii) how damaged DNA can be studied in computer simulations; and (iv) how repair of damaged DNA can be studied theoretically. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
46.
Lomoth R Häupl T Johansson O Hammarström L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(1):102-110
Quenching of the 3MLCT excited state of [Ru(bpy)3]2+ (bpy=bipyridine) by the reduction products (MV*+ and MV0) of methyl viologen (MV2+) was studied by a combination of electrochemistry with laser flash photolysis or femtosecond pump-probe spectroscopy. Both for the bimolecular reactions and for the reactions in an Ru(bpy)3(2+)-MVn+ dyad, quenching by MV*+ and MV0 is reductive and gives the reduced ruthenium complex [Ru(bpy)3]+, in contrast to the oxidative quenching by MV2+. Rate constants of quenching (kq), and thermal charge recombination (krec) and cage escape yields (phi(ce)) were determined for the bimolecular reactions, and rates of forward (kf) and backward (kb) electron transfer in the dyad were measured for quenching by MV2+, MV*+, and MV0. The reactions in the dyad are very rapid, with values up to kf = 1.3 x 10(12) s(-1) for *Ru(bpy)3(2+)-MV*+. In addition, a long-lived (tau = 15 ps) vibrationally excited state of MV*+ with a characteristically structured absorption spectrum was detected; this was generated by direct excitation of the MV*+ moiety both at 460 and 600 nm. The results show that the direction of photoinduced electron transfer in a Ru(bpy)3-MV molecule can be switched by an externally applied bias. 相似文献
47.
Ban F Lundqvist MJ Boyd RJ Eriksson LA 《Journal of the American Chemical Society》2002,124(11):2753-2761
DNA-protein cross-linking is one of the many DNA lesions mediated by hydroxyl radicals, the most damaging among the reactive oxygen species in biological systems. Density functional theory methods are employed to investigate the complex reaction mechanisms of the formation of cytosine-tyrosine cross-links as observed in gamma-irradiated aqueous solutions of cytosine and tyrosine, as well as in gamma-irradiated nucleohistone. The majority of the radical addition mechanisms considered are found to have significant barriers and therefore to be thermodynamically unfavorable for the formation of the initial cross-linked product. Our calculated reaction potential energy surfaces suggest that a feasible complete mechanism consists of radical combination forming the initial cross-linked product, a hydrogen shuffle within the initial cross-linked product, and an acid-catalyzed dehydration reaction. Water and hydrogen-bonding interactions are suggested to play a key role in catalyzing the hydrogen-transfer step of the reaction. 相似文献
48.
Leif Anderson 《Analytica chimica acta》1979,110(1):123-128
The flow injection principle is used in the photometric determination of nitrite and nitrate with sulfanilamide and N-(1-naphthyl)ethylenediamine as reagents. An on-line copper-coated cadmium reductor reduces nitrate to nitrite. The detection limit is 0.05 μM for nitrite and 0.1 mM for nitrate at a total sample volume of 200 μM. Up to 30 samples can be analyzed per hour with a relative precision of ca. 1%. 相似文献
49.
Rapid prototyping of polymer microsystems via excimer laser ablation of polymeric moulds 总被引:1,自引:0,他引:1
Jensen MF McCormack JE Helbo B Christensen LH Christensen TR Geschke O 《Lab on a chip》2004,4(4):391-395
This study presents a novel method for rapid prototyping of polymer microsystems. The method is based on excimer laser ablation of a thermally and mechanically stable polymer, such as PEEK (poly-ether-ether-ketone). A negative of the desired microsystem is laser machined in PEEK, which can then be used directly for hot embossing or injection moulding of a series of prototypes. This approach is very rapid and considerably cheaper than more traditional approaches to toolmaking, while still performing well in terms of reproduction of tool dimensions. The reduction in time and cost for a master tool using this method opens up new possibilities for testing small series in the R&D phase of a microsystem. Finally, two particular applications of the technique are presented. 相似文献
50.