全文获取类型
收费全文 | 220篇 |
免费 | 10篇 |
国内免费 | 1篇 |
专业分类
化学 | 169篇 |
晶体学 | 7篇 |
力学 | 3篇 |
数学 | 33篇 |
物理学 | 19篇 |
出版年
2021年 | 2篇 |
2020年 | 3篇 |
2019年 | 5篇 |
2018年 | 3篇 |
2017年 | 4篇 |
2016年 | 4篇 |
2015年 | 8篇 |
2014年 | 5篇 |
2013年 | 12篇 |
2012年 | 18篇 |
2011年 | 16篇 |
2010年 | 12篇 |
2009年 | 9篇 |
2008年 | 9篇 |
2007年 | 9篇 |
2006年 | 6篇 |
2005年 | 18篇 |
2004年 | 4篇 |
2003年 | 8篇 |
2002年 | 16篇 |
2001年 | 3篇 |
1999年 | 2篇 |
1996年 | 2篇 |
1995年 | 3篇 |
1994年 | 2篇 |
1993年 | 2篇 |
1992年 | 5篇 |
1990年 | 4篇 |
1989年 | 2篇 |
1987年 | 1篇 |
1986年 | 2篇 |
1985年 | 2篇 |
1983年 | 2篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1978年 | 3篇 |
1977年 | 3篇 |
1975年 | 5篇 |
1974年 | 4篇 |
1970年 | 2篇 |
1969年 | 2篇 |
1960年 | 1篇 |
1956年 | 1篇 |
排序方式: 共有231条查询结果,搜索用时 15 毫秒
101.
Three methods of obtaining asymmetric diaryloxy complexes of titanium (h5-Cp)(h5-Cp′)Ti(OAr)(OAr′) are proposed.Each of these methods leads to secondary products, selective substitution of the ligand (OAr) or (OAr′) by chlorine atom occurs by the action of hydrochloric acid in C6H6 solution. 相似文献
102.
Colette C Denier Andrée A Brisson-Lougarre Ghislaine G Biasini Jean J Grozdea Didier D Fournier 《BMC biochemistry》2002,3(1):2-8
Background
In humans, there are four alkaline phosphatases, and each form exibits a characteristic pattern of tissue distribution. The availability of an easy method to reveal their activity has resulted in large amount of data reporting correlations between variations in activity and illnesses. For example, alkaline phosphatase from neutrophils of mothers pregnent with a trisomy 21 fetus (Down's syndrome) displays significant differences both in its biochemical and immunological properties, and in its affinity for some specific inhibitors. 相似文献103.
The reaction of the lanthanide salts LnI3(thf)4 and Ln(OTf)3 with tris(2-pyridylmethyl)amine (tpa) was studied in rigorously anhydrous conditions and in the presence of water. Under rigorously anhydrous conditions the successive formation of mono- and bis(tpa) complexes was observed on addition of 1 and 2 equiv of ligand, respectively. Addition of a third ligand equivalent did not yield additional complexes. The mono(tpa) complex [Ce(tpa)I3] (1) and the bis(tpa) complexes [Ln(tpa)2]X3 (X = I, Ln = La(III) (2), Ln = Ce(III) (3), Ln = Nd(III) (4), Ln = Lu(III) (5); X = OTf, Ln = Eu(III) (6)) were isolated under rigorously anhydrous conditions and their solid-state and solution structures determined. In the presence of water, 1H NMR spectroscopy and ES-MS show that the successive addition of 1-3 equiv of tpa to triflate or iodide salts of the lanthanides results in the formation of mono(tpa) aqua complexes followed by formation of protonated tpa and hydroxo complexes. The solid-state structures of the complexes [Eu(tpa)(H2O)2(OTf)3] (7), [Eu(tpa)(mu-OH)(OTf)2]2 (8), and [Ce(tpa)(mu-OH)(MeCN)(H2O)]2I4 (9) have been determined. The reaction of the bis(tpa) lanthanide complexes with stoichiometric amounts of water yields a facile synthetic route to a family of discrete dimeric hydroxide-bridged lanthanide complexes prepared in a controlled manner. The suggested mechanism for this reaction involves the displacement of one tpa ligand by two water molecules to form the mono(tpa) complex, which subsequently reacts with the noncoordinated tpa to form the dimeric hydroxo species. 相似文献
104.
105.
Schaniel D Woike T Delley B Boskovic C Güdel HU 《Physical chemistry chemical physics : PCCP》2008,10(36):5531-5538
Photogeneration of side-on N2 linkage isomers in [Ru(NH3)5N2]2+ and [Os(NH3)5N2]2+ is achieved by irradiation with lambda = 325 nm of powder samples at T = 80 K and detected by the downshift of the nu(N-N) vibration and by the heat release at elevated temperature due to the back switching of the side-on configuration to the ground state. The concentration of the transferred molecules is evaluated by the decrease of the area of the nu(N-N) or 2nu(N-N) vibrational bands. All characteristic changes between the linear Ru-N-N and side-on configuration are predicted by DFT calculations: the structure of the anion, shifts of the vibrations, electronic excitation energy, energetic position and sequence of the electronic orbitals, the potentials of the ground and relaxed metastable state with the activation energy, saddle points and energetic position of the minimum. 相似文献
106.
Alley KG Mukherjee A Clérac R Boskovic C 《Dalton transactions (Cambridge, England : 2003)》2008,(1):59-63
The reaction of Cu(OAc)2 and Ln(OAc)3 (Ln = Gd, Tb and Dy) with 2-amino-2-methyl-1,3-propanediol (ampdH2) under solvothermal conditions has afforded a new family of isostructural octanuclear Cu4Ln4 complexes with the formula [Cu4Ln4(OAc)12(ampdH)8(OH2)2] (Ln = Gd (1), Tb (2) and Dy(3)) in good yield. Variable temperature magnetic susceptibility measurements reveal weak intramolecular exchange interactions for 1 and 2. Ferromagnetic coupling is observed for 1 and attributed to Cu...Gd interactions. In contrast, the magnetic susceptibility behaviour of 2 arises from a combination of intramolecular exchange interactions and the crystal field splitting of the (7)F6 ground state of the Tb(III) ions. 相似文献
107.
108.
109.
Poling influence on the mechanical properties and molecular mobility of highly piezoelectric P(VDF‐TrFE) copolymer 下载免费PDF全文
Aurélien Roggero Eric Dantras Colette Lacabanne 《Journal of Polymer Science.Polymer Physics》2017,55(18):1414-1422
The calorimetric, dielectric, and mechanical responses of highly piezoelectric 70/30 P(VDF‐TrFE) displaying homogenous d33 of ?19 pC N?1 are studied. This work aims at better understanding the influence of poling on the mechanical properties of this copolymer. To explain the one decade mechanical modulus drop observed across the Curie transition, a stiffening process of the amorphous phase due to the local electric fields in the ferroelectric crystals is proposed. In poled P(VDF‐TrFE), these fields are preferentially aligned resulting in a more stable and higher modulus below the Curie transition. This hypothesis accounts for the lower dielectric signals obtained with the poled sample. Through the Curie transition, the vanishing of these local electric fields, stemming from progressive disorientation and conversion of ferroelectric crystals to paraelectric ones, releases the constraints on the amorphous phase, leading to a storage modulus drop typical of a viscoelastic transition. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55 , 1414–1422 相似文献
110.