全文获取类型
收费全文 | 5183篇 |
免费 | 994篇 |
国内免费 | 523篇 |
专业分类
化学 | 3542篇 |
晶体学 | 54篇 |
力学 | 205篇 |
综合类 | 71篇 |
数学 | 451篇 |
物理学 | 2377篇 |
出版年
2024年 | 19篇 |
2023年 | 110篇 |
2022年 | 172篇 |
2021年 | 186篇 |
2020年 | 178篇 |
2019年 | 184篇 |
2018年 | 182篇 |
2017年 | 142篇 |
2016年 | 249篇 |
2015年 | 254篇 |
2014年 | 258篇 |
2013年 | 343篇 |
2012年 | 489篇 |
2011年 | 548篇 |
2010年 | 328篇 |
2009年 | 328篇 |
2008年 | 352篇 |
2007年 | 299篇 |
2006年 | 267篇 |
2005年 | 213篇 |
2004年 | 181篇 |
2003年 | 123篇 |
2002年 | 149篇 |
2001年 | 111篇 |
2000年 | 125篇 |
1999年 | 114篇 |
1998年 | 94篇 |
1997年 | 108篇 |
1996年 | 87篇 |
1995年 | 83篇 |
1994年 | 64篇 |
1993年 | 74篇 |
1992年 | 42篇 |
1991年 | 63篇 |
1990年 | 42篇 |
1989年 | 35篇 |
1988年 | 17篇 |
1987年 | 15篇 |
1986年 | 18篇 |
1985年 | 15篇 |
1984年 | 11篇 |
1983年 | 12篇 |
1982年 | 7篇 |
1981年 | 3篇 |
1979年 | 2篇 |
1976年 | 1篇 |
1942年 | 2篇 |
1919年 | 1篇 |
排序方式: 共有6700条查询结果,搜索用时 0 毫秒
41.
The gas-phase photocatalytic oxidation of aniline on a new kind of porous nano-TiO2 composite films is investigated. The composite film was prepared on glass fiber with the water glass as binders and dilute
H2SO4 solution as solidifying reagent. The surface characters were observed by scanning electron microscope. The photocatalytic
degradation of aniline on the composite films was carried out in a TiO2/UV system. Some important factors affecting the photodegradation, such as the concentration of TiO2, the initial concentration of aniline, and the existing water vapor, are also studied. The product of photocatalytic oxidation
was detected by Fourier transform-Infrared. The partial intermediate products were absorbed on TiO2 surface, which resulted in catalyst deactivation. But when it was irradiated under UV illumination or solar irradiation for
some time, the catalyst could be reused without loss of catalytic activity.
Translated from the Journal of Wuhan University (Natural Science Edition), 2005, 51(2) (in Chinese) 相似文献
42.
Wang YY Dai YH Zhang L Tang K Luo L Gong Q Zhao S Li MZ Wang EJ Yu JY 《Journal of colloid and interface science》2004,280(1):76-82
The interfacial dilational viscoelastic properties of hydrophobically associating block copolymer composed of acrylamide (AM) and a low amount of 2-phenoxylethyl acrylate (POEA) (<1.0 mol%) at the octane-water interfaces were studied by means of the interfacial tension relaxation method. The dependencies of interfacial dilational elasticity and viscous component on the dilational frequency were investigated. The interaction of hydrophobically associating block copolymer [P(AM/POEA)] with sodium dodecyl sulfate (SDS) has been explored. The results show that at lower frequency, the dilational elasticity for different concentration copolymer is close to zero; at higher frequency, the dilational elasticity shows no change with increased frequency; At moderate frequency (10(-3)-1 Hz), the dilational elasticity decreased with a decrease in the dilational frequency. The results show that the hydrophobic groups of [P(AM/POEA)] chains can be associated by inter- or intrachain liaisons in water solution. The dilational viscous component for P(AM/POEA) comes forth a different maximum value at different frequencies when the polymer concentration is different. It is generally believed that the dilational viscous component reflects the summation of the various microscopic relaxation processes at and near the interface and different relaxation processes have different characteristic frequencies. The spectrum of dilational viscous component may appear more than once maximum values at different frequencies. The influence of SDS on the limiting dilational elasticity and viscous component for polymer solution was elucidated. For 5000 ppm polymer solution, the limiting dilational elasticity decreased with an increase in SDS concentration. The dilational viscous component passed through a maximum value with a rise in the dilational frequency, which appeared at different frequency when SDS concentration is different; and the higher is the concentration, the lower is the dilational frequency. It can be explained that macromolecules may be substituted by SDS molecules in the interface and the interaction of molecules decrease, which makes the limiting dilational elasticity decrease. For 200 ppm polymer solution, the limiting dilational elasticity increased firstly and then decreased with SDS concentration increasing. This may be explained that the interfacial polymer concentration is so low that SDS molecules absorbed in the interface dominate dilational properties of the interfacial film even at very low SDS concentration. However, SDS molecules can gradually substitute the polymer molecules in the interface with a rise in SDS concentration, which results in the decrease in the limiting dilational elasticity. 相似文献
43.
D.-G. Chen D.-S. Wu H. Zhang Y.-C. Zhang Y.-J. Gong Z.-G. Kan 《Journal of solid state chemistry》2004,177(11):3927-3933
A novel compound Ba2ZnV2O8 has been synthesized in high temperature solution reaction and its crystal structure has been characterized by means of single crystal X-ray diffraction analysis. It crystallizes in monoclinic system and belongs to space group P21/c with a=7.9050(16), b=16.149(3), , β=90.49(3). It builds up from 1-D branchy chains of [ZnV2O84−]∞, and the Ba2+ cations are located in the space among these chains. The IR spectrum, ultraviolet-visible diffuse reflection integral spectrum and fluorescent spectra of this compound have been investigated. The calculated results of energy band structure by the density functional theory method show that the solid-state compound of Ba2ZnV2O8 is an insulator with direct band gap of 3.48 eV. The calculated total and partial density of states indicate that the top valence bands are contributions from the mixings of O-2p, V-3d, and Zn-3d states and low conduction bands mostly originate from unoccupied antibonding states between the V-3d and O-2p states. The V-O bonds are mostly covalence characters and Zn-O bonds are mostly ionic interactions, and the ionic interaction strength is stronger between the Ba-O than between the Zn-O. The refractive index of nx, ny, and nz is estimated to be 1.7453, 1.7469, and 1.7126, respectively, at wavelength of 1060 nm for Ba2ZnV2O8 crystal. 相似文献
44.
2,6-O-diethyl-β-cyclodextrins were prepared and immobilized onto silica gel to develop a fluorosensor for dipyridamole. The
analytical performance characteristics of the proposed sensor for analysis of dipyridamole were as follows: the detection
limit was 0.8 nmol/L with a relative standard deviation of 1.4% for 10 determinations of 50 nmol/L of dipyridamole. The modification
of β-CD improved the sensitivity and selectivity for measuring dipyridamole. The recommended method has been successfully
tested for the determination of dipyridamole in clinical samples (urine and pharmaceutical preparations).
Received: 23 January 1997 / Revised: 14 April 1997 / Accepted: 21 April 1997 相似文献
45.
本文研究在盐酸介质中以三辛胺氮氧化物(分子式为(C_8H)O,简称TOO),萃取金(Ⅲ)的行为及其机理。用等温曲线、斜率、Job法、紫外光谱、摩尔电导、红外和核磁共振等方法确定了萃合物的组成,表明系由两个TOO分子和H~+发生氢键作用,并与AuCl形成离子缔合物,其组成可表述为[TON0…H~+…0NOT]AuCl_4-。 相似文献
46.
A model beta-hairpin dodecapeptide [EFGWVpGKWTIK] was designed by including a favorable D-ProGly Type II' beta-turn sequence and a Trp-zip interaction, while also incorporating a beta-strand unfavorable glycine residue in the N-terminal strand. This peptide is highly folded and monomeric in aqueous solution as determined by combined analysis with circular dichroism and 1H NMR spectroscopy. A peptide representing the folded conformation of the model beta-hairpin [cyclic(EFGWVpGKWTIKpG)] and a linear peptide representing the unfolded conformation [EFGWVPGKWTIK] yield unexpected relative deviations between the CD and 1H NMR spectroscopic results that are attributed to variations in the packing interactions of the aromatic side chains. Mutational analysis of the model beta-hairpin indicates that the Trp-zip interaction favors folding and stability relative to an alternate hydrophobic cluster between Trp and Tyr residues [EFGYVpGKWTIK]. The significance of select diagonal interactions in the model beta-hairpin was tested by rearranging the cross-strand hydrophobic interactions to provide a folded peptide [EWFGIpGKTYWK] displaying evidence of an unusual backbone conformation at the hydrophobic cluster. This unusual conformation does not appear to be a result of the glycine residue in the beta-strand, as replacement with a serine results in a peptide [EWFSIpGKTYWK] with a similar and seemingly characteristic CD spectrum. However, an alternate arrangement of hydrophobic residues with a Trp-zip interaction in a similar position to the parent beta-hairpin [EGFWVpGKWITK] results in a folded beta-hairpin conformation. The differences between side chain packing of these peptides precludes meaningful thermodynamic analysis and illustrates the caution necessary when interpreting beta-hairpin folding thermodynamics that are driven, at least in part, by aromatic cross strand interactions. 相似文献
47.
The hexamolybdenum cluster complex [Mo6(3-Cl)8(O2CMe)6]2–, 1 was isolated as the Bu4N+ salt in 71% yield from the reaction of (Bu4N)2[Mo6(3-Cl)8Cl6] with AgO2CMe in CH2Cl2 solvent. The compound was characterized by single crystal X-ray diffraction analysis. The cluster contains an octahedral arrangement of six molybdenum atoms with eight chloride ligands bridging the eight trianglar faces and six carboxylate ligands terminally coordinated through one oxygen atom to each of the six molybdenum atoms. Crystal data: space group =P21/n,a=10.713(3)Å,b=14.43(1)Å,c=21.919(4)Å, =94.37(2)°,Z=2, 1965 reflections,R=0.036. 相似文献
48.
Ning GL Li XC Munakata M Gong WT Maekawa M Kamikawa T 《The Journal of organic chemistry》2004,69(4):1432-1434
Phenyl-substituted cyclopentadienes are proved to form phenylated pyrylium cations in the presence of silver(I) perchlorate by insertion of an oxygen atom into the cyclopentadiene-ring. Three phenylated pyrylium compounds, [(Ph(5)C(5)O(+))(ClO(4)(-))](2)(CH(2)Cl(2)) (1), Ag(ClO(4))(H(2)O)(Ph(4)HC(5)O(+)) (ClO(4)(-)) (2), and (Ph(3)H(2)C(5)O(+))(ClO(4)(-)) (3) have been synthesized and characterized. A possible reaction pathway and formation mechanism of the pyrylium cation are proposed and discussed. 相似文献
49.
Ni^2—交换蒙脱石中的镍物种及焙烧温度影响研究 总被引:2,自引:0,他引:2
对一组自制Ni^2+交换蒙脱石样品中镍物种的存在在形及焙烧温度影响进行了TPR和XRD考察结果表明,样品中镍负载量等于或小于Ni^2+的交换量时,镍主要以难还原听可交换性阳离子Ni(OH)^q+x和易还原的自由态镍Ni(OH)2或NiO两种形式存在。 相似文献
50.