全文获取类型
收费全文 | 15722篇 |
免费 | 1091篇 |
国内免费 | 1448篇 |
专业分类
化学 | 16721篇 |
晶体学 | 180篇 |
力学 | 11篇 |
综合类 | 44篇 |
数学 | 187篇 |
物理学 | 1118篇 |
出版年
2024年 | 7篇 |
2023年 | 147篇 |
2022年 | 297篇 |
2021年 | 416篇 |
2020年 | 617篇 |
2019年 | 436篇 |
2018年 | 415篇 |
2017年 | 388篇 |
2016年 | 500篇 |
2015年 | 388篇 |
2014年 | 479篇 |
2013年 | 1040篇 |
2012年 | 1487篇 |
2011年 | 663篇 |
2010年 | 610篇 |
2009年 | 810篇 |
2008年 | 866篇 |
2007年 | 1037篇 |
2006年 | 870篇 |
2005年 | 789篇 |
2004年 | 803篇 |
2003年 | 707篇 |
2002年 | 514篇 |
2001年 | 461篇 |
2000年 | 472篇 |
1999年 | 430篇 |
1998年 | 372篇 |
1997年 | 337篇 |
1996年 | 347篇 |
1995年 | 368篇 |
1994年 | 229篇 |
1993年 | 210篇 |
1992年 | 172篇 |
1991年 | 112篇 |
1990年 | 71篇 |
1989年 | 58篇 |
1988年 | 56篇 |
1987年 | 44篇 |
1986年 | 39篇 |
1985年 | 38篇 |
1984年 | 31篇 |
1983年 | 14篇 |
1982年 | 27篇 |
1981年 | 16篇 |
1980年 | 18篇 |
1979年 | 14篇 |
1978年 | 8篇 |
1977年 | 8篇 |
1974年 | 4篇 |
1973年 | 6篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
11.
Padavattan Govindaswamy Patrick J. Carroll Yurij A. Mozharivskyj Mohan Rao Kollipara 《Journal of Chemical Sciences》2006,118(4):319-326
The reaction of [{(η5-C5Me5)M(μ-Cl)Cl}2] {where M = Rh (1), Ir (2)} with functionalized phosphine viz., diphenyl-2-pyridylphosphine (PPh2Py) in dichloromethane solvent yield neutral ϰ1-P-coordinated rhodium and iridium complexes [(η5-C5Me5)RhCl2(κ1-P-PPh2Py)]3 and [(η5-C5Me5) IrCl2(ϰ1-P-PPh2Py)]4. Reaction of complexes 1 and 2 with the ligand PPh2Py in methanol under reflux give bis-substituted complexes such as [(η5-C5Me5)RhCl(ϰ1-P-PPh2Py)2]+
5 and [(η5-C5Me5)IrCl(ϰ1-P-PPh2Py)2]+
6, whereas stirring in methanol at room temperature gives P-, N-chelating complexes of the type [(η5-C5Me5)RhCl(ϰ2-P-N-PPh2Py)]+ 7 and [(η5-C5Me5)IrCl(ϰ2-P-N-PPh2Py)]+
8. Neutral ϰ1-P-coordinated complexes [(η5-C5Me5)RhCl2(ϰ1-P-PPh2Py)]3 and [(η5-C5Me5)IrCl2(ϰ1-P-PPh2Py)]4 easily undergo conversion to the cationic P-, N-chelating complexes [(η5-C5Me5)RhCl(ϰ2-P-N-PPh2Py)]+
7 and [(η5-C5Me5) IrCl(ϰ2-P, N-PPh2Py)]+
8 on stirring in methanol at room temperature. These complexes are characterized by FT-IR and FT-NMR spectroscopy as well as
analytical methods. The molecular structures of the representative complexes [(η5-C5Me5)RhCl2(ϰ1-P-PPh2Py)]3, [(η5-C5Me5)IrCl2(ϰ1-P-PPh2Py)]4 and hexafluorophosphate salt of complex [(η5-C5Me5)IrCl(ϰ2-P-PPh2Py)2]+
6 are established by single-crystal X-ray diffraction methods 相似文献
12.
13.
Reynaldo C. Castells Eleuterio L. Arancibia Angel M. Nardillo 《Journal of solution chemistry》1993,22(1):85-94
The retention behavior of eight halomethanes and four saturated hydrocarbons was measured in gas chromatographic stationary phases consisting in tri-n-octylamine (TOA), squalane (SQ) and six TOA+SQ mixtures, at 55.0, 58.5, 62.5 and 65.0°C. Equlibrium constants for complex formation were extracted from experimental data by using a lattice model developed by Martire. The results may be interpreted in terms of the formation of weak hydrogen-bonded complexes, with sociation constants of about 0.13 L-mol–1 for haloforms and 0.07 L-mol–1 for dihalomethanes at 60°C. 相似文献
14.
The characterization of the clusters formed on alkaline hydrolysis of [PdCl4]2– was performed using17O,23Na,35Cl,133Cs NMR and UV spectroscopy. The chemical composition of the clusters was found to be [Pd(OH)2]
n
·nNaCl. No mononuclear oxo- or hydroxocomplexes were detected. The spatial structure of the clusters is stabilized by alkali metal cations.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 675–679, April, 1993. 相似文献
15.
以均苯三甲酸为配体,水热条件下合成了均苯三甲酸铕及铕镧系列发光配合物LaxEu1-x(BTC)·nH2O(x=0,0.1,0.3,0.5,0.7,0.9),通过元素分析及化学滴定法测定了配合物的组成。用红外光谱对其进行了表征,确定了该系列配合物的组成为LaxEu1-x(BTC)·nH2O。研究了系列配合物的荧光性质,荧光光谱表明:该类配合物均能发出强的铕离子的特征荧光,并且镧元素的掺入能增强铕配合物的发光强度,但发射峰的位置基本上没有变化;其中5D0→7F1和5D0→7F2的跃迁发射较强,且均劈裂为两个峰(587,593nm)和(611,618nm),这是由于铕离子所处的配位环境引起的。 相似文献
16.
S. J. Cheng W. Sheng P. Hawrylak S. Raymond S. Studenikin A. Sachrajda Z. Wasilewski A. Babinski M. Potemski G. Ortner M. Bayer 《Physica E: Low-dimensional Systems and Nanostructures》2004,21(2-4):211
We present results of calculations and experiments on electron–hole complexes in InGaAs/GaAs self-assembled quantum dots in high magnetic field (B). Due to hidden symmetries, the chemical potential of an N-exciton system at special B fields becomes insensitive to the exciton number as well as the magnetic field. This results in plateau regions of high intensity in measured magneto-PL spectrum. Theoretical calculations using exact diagonalization techniques successfully explain the measured magneto-photoluminescence spectrum with B fields up to 28 T. 相似文献
17.
Jeroen J. L. M. Cornelissen W. Sander Graswinckel Alan E. Rowan Nico A. J. M. Sommerdijk Roeland J. M. Nolte 《Journal of polymer science. Part A, Polymer chemistry》2003,41(11):1725-1736
The conformational properties of polymers derived from isocyanodipeptides have been investigated with a combination of model calculations, X‐ray diffraction, and circular dichroism spectroscopy. Depending on the configuration of the side chains, defined arrays of hydrogen bonds along the polymeric backbone are formed. This leads to a well‐defined conformation as, for example, expressed in the formation of lyotropic liquid‐crystalline phases and increased helical stability. Upon the disruption of the hydrogen bonds by a strong acid, a less well‐defined macromolecular conformation is observed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1725–1736, 2003 相似文献
18.
Marcelino Maneiro Manuel R. Bermejo M. Isabel Fernndez Ana M. Gonzlez‐Noya Alexei M. Tyryshkin Robin G. Pritchard 《无机化学与普通化学杂志》2003,629(2):285-290
A new MnIII‐Schiff base complex, [MnL(OH2)](ClO4) ( 1 ) (H2L = N, N′‐bis‐(3‐Br‐5‐Cl‐salicylidene)‐1, 2‐diimino‐2‐methylethane), an inorganic model of the catalytic center (OEC, Oxygen Evolving Complex) in photosystem II (PSII), has been synthesized and characterized by elemental analysis, IR and EPR spectroscopy, mass spectrometry, magnetic susceptibility measurement and the study of its redox properties by cyclic and normal pulse voltammetry. This complex mimics reactivity (showing a relevant photolytic activity), and also some structural characteristics (parallel‐mode MnIII EPR signal from partially assembled OEC cluster) of the natural OEC. The complex 1 was found to rearrange in solution into a crystallographically solved square‐pyramidal complex, [MnLL′] ( 2 ) (HL′ = 6‐bromo‐4‐chloro‐2‐cyanophenol), through a process, which probably liberates radical species (detected by EPR), and provokes a C—N bond cleavage in the ligand. A photo‐radical mechanism is discussed to explain this rearrangement. 相似文献
19.
Non-isothermal short-range-order kinetics of binary alloys as influenced by solute-vacancy complexes
A model describing the roles of bound and unbound vacancies is proposed in order to predict defect decay and short-range-order
kinetics of quenched binary alloys during linear heating experiments. This is an alternative treatment of a previous approach.
The model has been applied to the differential scanning calorimetry (DSC) curves of Cu-5 at.% Zn quenched from different temperatures.
An expression to calculate the activation energy for migration of solute-vacancy complexes was also developed which make use
of DSC trace data. A value of 89.12±0.32 kJ mol-1 was obtained for the above alloy. The relative contribution of bound and unbound vacancies to partition of effective activation
energy corresponding to the ordering process as influenced by quenching temperature was also assessed.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
20.
Xinjiang Chen Goh Matsuo Bunsho Ohtani Kaoru Tsujii 《Journal of polymer science. Part A, Polymer chemistry》2007,45(21):4891-4900
A racemic amphiphilic monomer, n‐dodecyl glyceryl itaconate (DGI), forms bilayer membranes in water in the presence of small amount of ionic cosurfactant and shows iridescent color. A chiral DGI, S‐DGI, also shows an iridescent property, but with a rather red shift in the color, which can be ascribed to the increased packing density of the monomer in the bilayer membranes. Chrial DGI has a more compact packing density than racemic one owing to closer distance between the monomer molecules; the conversion rate, however, is slower than that of racemic one when H2O2 is used as an initiator. When the initiator is changed to an amphiphilic one, 4‐(2‐hydroxyethoxy) phenyl‐(2‐hydroxy‐2‐propyl) ketone (Irgacure 2959), the chiral DGI shows even a little faster conversion rate than that of racemic one. The NMR chemical shift results of protons in benzene ring show that the molecules of Irgacure 2959 insert into the bilayer membranes. The molecular weights of the corresponding polymers prove that the initiation by H2O2 is restricted compared to that by Irgacure 2959. It is concluded that the decelerated polymerization behavior of chiral DGI initiated by H2O2 is a result of limited diffusion of the initiator into the lamellar bilayer structures. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4891–4900, 2007 相似文献