全文获取类型
收费全文 | 32086篇 |
免费 | 4644篇 |
国内免费 | 3724篇 |
专业分类
化学 | 17760篇 |
晶体学 | 317篇 |
力学 | 1457篇 |
综合类 | 255篇 |
数学 | 2790篇 |
物理学 | 9289篇 |
无线电 | 8586篇 |
出版年
2024年 | 53篇 |
2023年 | 760篇 |
2022年 | 809篇 |
2021年 | 1099篇 |
2020年 | 1233篇 |
2019年 | 1121篇 |
2018年 | 901篇 |
2017年 | 934篇 |
2016年 | 1320篇 |
2015年 | 1321篇 |
2014年 | 1604篇 |
2013年 | 2081篇 |
2012年 | 2615篇 |
2011年 | 2549篇 |
2010年 | 1841篇 |
2009年 | 1886篇 |
2008年 | 2139篇 |
2007年 | 1999篇 |
2006年 | 1915篇 |
2005年 | 1613篇 |
2004年 | 1233篇 |
2003年 | 1068篇 |
2002年 | 948篇 |
2001年 | 756篇 |
2000年 | 767篇 |
1999年 | 852篇 |
1998年 | 714篇 |
1997年 | 595篇 |
1996年 | 609篇 |
1995年 | 517篇 |
1994年 | 473篇 |
1993年 | 403篇 |
1992年 | 351篇 |
1991年 | 303篇 |
1990年 | 277篇 |
1989年 | 180篇 |
1988年 | 141篇 |
1987年 | 105篇 |
1986年 | 113篇 |
1985年 | 88篇 |
1984年 | 41篇 |
1983年 | 43篇 |
1982年 | 41篇 |
1981年 | 23篇 |
1980年 | 9篇 |
1979年 | 6篇 |
1976年 | 1篇 |
1957年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 609 毫秒
981.
Recently,theconformationofthecalixarenehasbeenshowntobeimportantincontrollingtheseIectivityofthereceptor.Forexample,sodiumioncouldbeboundverystronglybyesterderivativesofcalix[4]areneintheconeconformationl.Wehavefoundthatinthepresenceofcertainamountofsodiumion,microamountofReO4-canbequantitativelyextractedintol,2-dichloroethanebytheligandtetraethylp-tert-butylcalix[4]arenetetraacetate(L).ItshowsthatthepresenceofNa inaqueoussolutioncanpromotetheformationofhydrophobiccomplex[NaL] .ReO'-whichc… 相似文献
982.
Rosen MJ Wang H Shen P Zhu Y 《Langmuir : the ACS journal of surfaces and colloids》2005,21(9):3749-3756
The interfacial tension (IFT) between alkanes and several individual surfactants and their mixtures has been investigated, using three kinds of alkyl hydrocarbons: decane, dodecane, and tetradecane. For individual and mixed surfactant systems, critical micelle concentrations and areas per molecule at the hydrocarbon-aqueous solution interface were calculated; for the mixed surfactant systems, betasigma(LL), the molecular interaction parameter at the hydrocarbon-aqueous solution interface, and beta(M), the molecular interaction parameter in mixed micelle formation, were calculated. It was found that IFT in the 10(-3) mN/m (ultralow) range can be obtained at surfactant concentrations below 0.05 wt % and even at concentrations below 0.01 wt %, when mixtures of certain surfactants are used at the proper ratio. Surfactants with branched-chain alkyl groups show a much better IFT reduction effectiveness than those with straight-chain alkyl groups. Contrary to what has been observed at the air-aqueous solution surface, mixtures of two homologues with two hydrophobic groups show significant molecular interactions, with both betasigma(LL) and beta(M) having negative values in the 4-5 range in some cases, with the betasigma(LL) value more negative than beta(M). The relationship between micellar shape and ultralow IFT was investigated by calculating the critical packing parameter of the surfactants. It was found that ultralow IFT between the surfactant mixtures and the three hydrocarbons investigated could reach ultralow (<10(-2) mN/m) values when the critical packing parameter is very close to 1. 相似文献
983.
The adsorption of (R)- and (S)-2-phenylpropionamide (PPA, C(9)H(11)ON) molecules on a Cu(111) surface has been investigated using the density functional method with supercell models. The adsorption orientations of both (R)- and (S)-PPA molecules on the surface are the same: the phenyl rings are approximately parallel to the Cu(111) surface and positioned in the hollow sites, the amino and methyl groups occupy two-bridge sites, and the carbonyl occupies the top site. After the adsorption, the bond lengths in the two enantiomers are almost unchanged, but the changes for two dihedral angles show differences, especially for (R)-PPA molecule. The first angles between the (N,C9,C7) plane and the (C9,C7,C6) plane are 19.4 and 0.7 degrees for (R)- and (S)-PPA molecules, respectively, and the second angles between the (C8,C7,C6) plane and the (C7,C6,C5) plane are 74.8 and 0.4 degrees for (R)- and (S)-PPA molecules, respectively. The adsorption energies of (R)- and (S)-PPA molecules are calculated to be -34 and -26 kJ mol(-1), respectively. The simulated scanning tunneling microscopy (STM) images of (R)- and (S)-PPA molecules on the Cu(111) surface display different features and are coincident with the experimental ones. The interaction between the adsorption molecule and the metal surface is found to be responsible for the discrimination of (R)- and (S)-PPA molecules on the surface. 相似文献
984.
采用双股并流共沉淀方法制备了SnO2含量从10%至90%的锡锆体系DeNOx催化剂,用XRD、微区电子衍射、FT-Raman及FT-IR等技术深入研究了锡锆体系氧化物的结构及其随组成的变化规律.结果表明,由于Sn4+与Zr4+离子半径接近,SnO2与ZrO2易于形成固溶体,并随组成变化表现出不同的结构特征.纯ZrO2为单斜相,当少量Sn4+(SnO2 ≤ 20%)进入ZrO2晶格时形成四方相富锆固溶体,Sn4+起到稳定ZrO2四方相的作用;随着SnO2含量的增大,结构从无定形或微晶态的富锆固溶体(含SnO2 30~50%)经富锆固溶体与金红石结构的富锡固溶体在55% SnO2含量的共存状态变化到具有金红石结构的富锡固溶体(SnO2 ≥ 60%).FT-Raman和FT-IR光谱测试证明,Zr进入SnO2晶格使得Sn-O键的结合减弱,Sn离子上的有效正电荷减小,降低了SnO2对丙烯的燃烧能力,从而提高了对NO的还原活性. 相似文献
985.
The enthalpies of mixing of glycine, l-α-alanine, l-γ-aminobutyric acid, l-α-valine, l-α-serine and l-α-threonine with cyclohexanone in aqueous solutions and their respective enthalpies of dilution have been measured by calorimetry at 298.15 K. Experimental enthalpies of dilution and mixing have been correlated with the virial expansion equation that was obtained with the McMillan-Mayer theory. The enthalpic interaction parameters hxy, hxxy and hxyy of the amino acids studied with cyclohexanone in aqueous solutions have been evaluated, and the heterotactic enthalpic pair interaction coefficients (hxy) are discussed in terms of solute-solute interactions. 相似文献
986.
稀土元素对人肝癌细胞SMMC-7721增殖的影响 总被引:7,自引:3,他引:7
用MTT法研究了14种稀土元素(La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb和Lu)对人肝癌细胞SMMC-7721增殖的影响。他们对肝癌细胞的生长作用可分为3类。其中La^3 、Ce^3 和Eu^3 对肝癌细胞的增殖有剂量依赖性正效应,能够在一定浓度范围内刺激细胞生长;Sm^3 ,Gd^3 ,Ho^3 ,Er^3 ,Yb^3 对肝癌细胞生长的刺激作用没有剂量依赖性特征;而Pr^3 ,Nd^3 ,Tb^3 ,Dy^3 ,Tm^3 和Lu^3 则表现出对肝癌细胞的增殖具有不用程度的抑制。推测14种稀土元素作用方式的不同与他们的原子结构有一定的关系,它们对肝癌细胞的相对增殖率随着原子序数的增加呈现出一定的规律性。 相似文献
987.
Shuhui Yu Kui Yao Francis Eng Hock Tay 《Journal of Sol-Gel Science and Technology》2007,42(3):357-364
The preferential formation of a pyrochlore structure is a knotty problem in the preparation of Pb(Zn1/3Nb2/3)O3 (PZN)-based thin film materials and its presence is significantly detrimental to the dielectric and piezoelectric properties.
In this study, 40 mol% of PZN was replaced with Pb(Mg1/3Nb2/3)O3 (PMN) for obtaining a perovskite composition around a morphotropic phase boundary (MPB), (1−x)(0.6PZN-0.4PMN)-xPT ((1−x)PZMN-xPT, PT: PbTiO3) where x = 0.23. The thin films with this composition were prepared with a polyethylene glycol (PEG) modi-fied sol-gel method on LaAlO3 substrates. The microstructural evolution of the films on heat treatment was examined with X-ray diffraction. With the aid
of PEG, the formation of the pyrochlore phase was suppressed and the perovskite phase formed directly from the amorphous gel
film. The multilayer films with a thickness around 0.25 μm showed a single perovskite phase without any detectable pyrochlore
structure. Microscopic images showed uniform grain size of a few tens of nanometers. The role of the polymer dramatically
promoting the perovskite phase was investigated with the aid of X-ray photoelectron spectroscopy and thermal analysis. The
dielectric constant of the obtained film was 4160 at 1 kHz. The film demonstrated typical ferroelectric hysteresis loops and
exhibited excellent piezoelectric performance. 相似文献
988.
Xueliang Zhu Xiangyang Qi Jing Wang Jingnian Yue Zhida Sun Wenjun Lei 《Chromatographia》2007,65(9-10):625-628
A rapid method based on matrix solid-phase dispersion (MSPD) was developed for the determination of procymidone, pentachloroaniline and methyl-pentachloro-phenylsulfide in wine. After the optimisation of different parameters such as the type of adsorbent, the extraction solvent, and the extraction assistance by sonication. The analysis of samples was accomplished using gas chromatography with electron-capture detector (GC-ECD). Spiked blank samples were used as standards to counteract the matrix effect observed in the chromatographic determination. The recovery of the method was in the range 82.4–93.7% and a good linear relationship (R 2 ≥ 0.9992) with relative standard deviations lower than 8%. The limits of detection (LOD) ranged from 0.1 to 0.4 μg L?1. The proposed method was applied to the analysis of these compounds in commercial wine samples. 相似文献
989.
聚N,N-二乙基丙烯酰胺溶液粘度的温度依赖性 总被引:2,自引:0,他引:2
通过自由基聚合,合成了线型聚N,N-二乙基丙烯酰胺(PDEA),用乌氏粘度计测定并考察了该聚合物在四氢呋喃(THF)、H2O以及THF-H2O混合溶剂中粘度的温度依赖性.实验结果表明,PDEA 在上述三种溶剂中粘度的温度依赖性不同,PDEA-THF体系的相对粘度随温度升高而增大;PDEA-H2O体系以及PDEA-THF-H2O体系的相对粘度随温度升高而减小,且THF体积分数φTHF < 0.7时具有透明-白浊转变现象;对PDEA-THF-H2O体系,φTHF增加,透明-白浊转变温度升高,而当φTHF=0.7时,则观察不到透明-白浊转变现象. 相似文献
990.
The second member of the single-isomer, sulfated gamma-cyclodextrin family, the sodium salt of octa(6-O-sulfo)-gamma-cyclodextrin (OS) has been synthesized, characterized and used to separate the enantiomers of nonelectrolyte, acidic, basic, and ampholytic analytes by capillary electrophoresis in acidic aqueous background electrolytes. The anionic effective mobilities of the nonelectrolyte and anionic analytes increased with increasing concentration of OS. The effective mobilities of strongly complexing cationic analytes became anionic with very low OS concentrations and passed local anionic effective mobility maxima as the OS concentration, and along with it, the ionic strength, of the background electrolyte increased. The effective mobilities of the weakly binding cationic analytes became only slightly anionic at high OS concentration values and did not show the local anionic effective mobility maxima. For nonelectrolyte analytes, separation selectivities decreased with increasing OS concentration. For cationic analytes, separation selectivities were highest where the effective mobilities of the less mobile enantiomers approached zero. OS proved to be a broadly applicable chiral resolving agent. 相似文献