全文获取类型
收费全文 | 4310篇 |
免费 | 490篇 |
国内免费 | 602篇 |
专业分类
化学 | 3917篇 |
晶体学 | 31篇 |
力学 | 68篇 |
综合类 | 28篇 |
数学 | 275篇 |
物理学 | 1083篇 |
出版年
2024年 | 12篇 |
2023年 | 43篇 |
2022年 | 105篇 |
2021年 | 114篇 |
2020年 | 146篇 |
2019年 | 143篇 |
2018年 | 116篇 |
2017年 | 121篇 |
2016年 | 168篇 |
2015年 | 163篇 |
2014年 | 195篇 |
2013年 | 426篇 |
2012年 | 271篇 |
2011年 | 294篇 |
2010年 | 236篇 |
2009年 | 273篇 |
2008年 | 268篇 |
2007年 | 257篇 |
2006年 | 256篇 |
2005年 | 239篇 |
2004年 | 220篇 |
2003年 | 202篇 |
2002年 | 175篇 |
2001年 | 107篇 |
2000年 | 104篇 |
1999年 | 103篇 |
1998年 | 98篇 |
1997年 | 69篇 |
1996年 | 76篇 |
1995年 | 60篇 |
1994年 | 54篇 |
1993年 | 46篇 |
1992年 | 44篇 |
1991年 | 33篇 |
1990年 | 24篇 |
1989年 | 30篇 |
1988年 | 25篇 |
1987年 | 14篇 |
1986年 | 16篇 |
1985年 | 6篇 |
1984年 | 13篇 |
1983年 | 5篇 |
1982年 | 8篇 |
1981年 | 4篇 |
1980年 | 2篇 |
1979年 | 5篇 |
1978年 | 3篇 |
1977年 | 4篇 |
1976年 | 3篇 |
1975年 | 2篇 |
排序方式: 共有5402条查询结果,搜索用时 15 毫秒
71.
D. N. Kravtsov A. S. Peregudov L. S. Golovchenko E. I. Smyslova 《Russian Chemical Bulletin》1996,45(5):1194-1199
19F NMR spectroscopy was used to study the exchange reactions involving 4-fluorothiophenoxides, 4-nitrophenoxides, chlorides, and acetates of arylmercury and triphenylphosphinegold. The analysis of the data on equilibrium constants allows one to obtain information on the comparative chemical hardness of ArHg+ and Ph3PAu+ cations. The increase in the electron-donating ability of aryl ligands enhances the chemical hardness of ArHg+ cations, their influence being best described by 0 constants of substituted phenyl groups.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1255–1260, May, 1996. 相似文献
72.
Compounds of general formulatrans-ArNi(PR3)2OAr' (R = Et, cyclohexyl; Ar = 2-MeC6H4, 2-FC6H4; Ar' = 4-FC6H4, 4-NO2C6H4) were synthesized by the reaction of Ar'OK with cationic nickel complexes generated by treatment of ArNi(PR3)2Cl with TlBF4. Syntheses of 4-fluorophenoxide complexes, ArNi(PR3)2OC6H4F-4, additionally give some quantities oftrans-[ArNi(PR3)2OC6H4F-4][HOC6H4F-4] adducts. Exchange reactions MeC6H4Ni(PEt3)2OC6H4F-4 + XC6H4OH 2-MeC6H4Ni(PEt3)2OC6H4X + 4-FC6H4OH were studied in THF. The equilibrium is shifted to the right as the acidity of ArOH increases. A linear relationship between lgK
eq and pK
a of XC6H4OH in DMSO was found. A conclusion concerning the strong polarization of the Ni-O bond was made on the basis of an analysis of the chemical shifts of fluorine atoms in 2-MeC6H4Ni(PEt3)2OC6H4F-4.Translated fromIvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2266–2271, November, 1995. 相似文献
73.
Magnetic and structural data for 28 compounds containing the tetrabromocuprate ion are presented. The parameters which affect the strength and sign of the magnetic superexchange interaction via non-bonding contacts between bromide ions are described and a system for describing the topology of the interaction between tetrahedra is proposed. Analysis of the data suggests that the primary factors affecting the magnetic exchange are the Br?Br distance, the Cu-Br?Br angle and the Cu-Br?Br-Cu dihedral angle. 相似文献
74.
The kinetics of ion exchange between Ca2 , Mg2 , Co(Ⅱ), Cu(Ⅱ),Ni(Ⅱ), Fe(Ⅲ), y3 or Sm3 , respectively, in 0.50 mol/L HC1 and H on macrorecticular sulfonic ion exchange resin and the kinetics of the same reactions (M -H exchange) when Mn(Ⅱ) coexisted in resin phase as accelerating ion were studied. The accelerating effect manifested and its rule are consistent with the accelerating effect theory based on the concept concerned with adsorption electrical double layer which has been suggested in a previous paper published. 相似文献
75.
Paramagnetic metal ions bound to proteins generate a dipolar field that can be accurately probed by pseudocontact shifts (PCS) displayed by the protein's nuclear spins. PCS are highly useful for determining the coordinates of individual spins in the molecule and for rapid structure determinations of entire protein-protein and protein-ligand complexes. However, PCS measurements require reliable resonance assignments for the molecule in its paramagnetic state and in a diamagnetic reference state. This article discusses different approaches for pairwise resonance assignments, with emphasis on a strategy which exploits chemical exchange between the two states. 相似文献
76.
电位法测定异价阳离子通过阳离子交换膜时的选择透过性 总被引:2,自引:0,他引:2
从理论上导出了不等价的两种阳离子在通过阳离子交换膜时的选择透过性与膜电位的关系,并用电位法对一些不等价阳离子组合在两种商品膜中的选择透过性进行了测定。本方法测定结果与电渗析实际分离效果相符。 相似文献
77.
Quantitative study on La~(3+) influx mediated by sodium-calcium exchanger in human lymphocytes 总被引:2,自引:0,他引:2
Whether La3+ can enter human peripheral blood lymphocytes by the Na+/Ca2+ exchanger or not and the effect of La3+on the Na+/Ca2+ exchanger activity are examined by fura-2 technique. And that whether La3+ is sequestered by intracellular organelles (mainly endoplasmic reticulum and mitochondria) is studied by this method. La3+uptake is obviously stimulated by pre-treating the cells with ouabain and by removing extracellular Na+, and intracellular La3+concentration ([La3+]i) is directly proportional to its extracellular concentration ([La3+]o). But when [La3+]o exceeds 0.4 mmol/L, the 340/380 nm ratio of fluorescence is no longer varied and the maximum [La3+], is 1.5×10-12 mol · L-1. The higher concentration of La3+ (0.1 mmol/L) increases Na+/Ca2+ exchange-mediated calcium influx, but lower concentration (10 μmol/L) appears to block calcium influx. The results also suggest that cytosolic La3+ is transported by the ATP-dependent Ca2+ pump. Intracellular Ca2+ stores are depleted by ionomycin, and then ion 相似文献
78.
Experimental and numerical results for binding Aedes aegypti densonucleosis virus (AeDNV) using anion and cation exchange membranes are presented. AeDNV particles are adsorbed by anion and cation exchange membranes providing the virus particles and membranes are oppositely charged. Q membranes which are strongly basic anion exchangers were the most effective. Dynamic and static capacities for Q membranes were found to be similar. A numerical model is proposed which assumes a log normal pore size distribution. By estimating the required parameters from static binding experiments, the model may be used to calculate the breakthrough curve for virus adsorption. 相似文献
79.
Kinetic parameters of interphase exchange of oxygen in high-temperature proton conductors BaCe0.95Nd0.05O3- and SrCe0.95Y0.05O3- are determined using an isotope exchange method in the temperature range 630-820°C at oxygen pressures of 2.7-13.3 gPa and diffusion coefficients for oxygen are calculated. Effective energies of activation of oxygen exchange and diffusion coefficients for oxygen are calculated. Dependence of exchange characteristics and the diffusion coefficients on the oxygen pressure in the gas phase is investigated. The oxygen exchange on the surface of studied oxides is shown to proceed only with the participation of oxygen of the oxides, which causes high rates of interphase exchange of oxygen of studied cerates of barium and strontium. It is shown that the obtained data satisfactorily agree with those found in the relevant literature. 相似文献
80.
A variety of biomolecules and their variants, which have previously been problematic to separate, have been analysed using a novel anion-exchange resin based on a non-porous polystyrene polymeric support with a hydrophilic coating and grafted tentacular quaternary ammonium functional groups. The hydrophilic coating results in minimal interaction between the support and the biomolecule, while the highly flexible tentacular-like anion-exchange groups increase the ionic interaction potential and act as an umbrella to hold the proteins away from the surface. Because of the removal of silanophilic interactions, minimisation of hydrophobic interactions, and the highly flexible nature of the tentacle-like ion exchangers, ionic interactions can therefore dominate the separation. As such this phase is highly suited to the separation of highly charged biomolecules and their variants. This polymeric strong anion-exchange (SAX) support was packed into a fused-silica capillary column and, using a salt concentration gradient, various recombinant proteins were analysed by -HPLC resulting in baseline resolution.Awarded a poster prize on the occasion of the Euranalysis XIII conference, Salamanca, Spain, 5–10 September 2004 相似文献