全文获取类型
收费全文 | 489篇 |
免费 | 32篇 |
国内免费 | 59篇 |
专业分类
化学 | 381篇 |
晶体学 | 12篇 |
物理学 | 187篇 |
出版年
2023年 | 4篇 |
2022年 | 3篇 |
2021年 | 5篇 |
2020年 | 13篇 |
2019年 | 8篇 |
2018年 | 7篇 |
2017年 | 6篇 |
2016年 | 16篇 |
2015年 | 13篇 |
2014年 | 16篇 |
2013年 | 37篇 |
2012年 | 18篇 |
2011年 | 34篇 |
2010年 | 31篇 |
2009年 | 34篇 |
2008年 | 20篇 |
2007年 | 36篇 |
2006年 | 30篇 |
2005年 | 34篇 |
2004年 | 17篇 |
2003年 | 33篇 |
2002年 | 26篇 |
2001年 | 23篇 |
2000年 | 18篇 |
1999年 | 12篇 |
1998年 | 14篇 |
1997年 | 20篇 |
1996年 | 8篇 |
1995年 | 8篇 |
1994年 | 10篇 |
1993年 | 4篇 |
1992年 | 6篇 |
1991年 | 2篇 |
1990年 | 2篇 |
1988年 | 2篇 |
1986年 | 4篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1981年 | 2篇 |
排序方式: 共有580条查询结果,搜索用时 171 毫秒
1.
EXAFS study of liposome-encapsulated cisplatin 总被引:1,自引:0,他引:1
《Colloids and surfaces. B, Biointerfaces》2004,33(3-4):199-204
The anticancer agent cisplatin encapsulated in sterically stabilized liposomes is studied with extended X-ray absorption fine structure (EXAFS) method. Analysis of local atomic structure around Pt atoms clearly indicates that the liposome-encapsulated drug is chemically stable and does not hydrolyze. Cisplatin forms a supersaturated solution in the liposome interior at a concentration about eight-fold above its aqueous solubility. 相似文献
2.
S K Deshpande S M Chaudhari Ashok Pimpale A S Nigavekar S B Ogale V G Bhide 《Pramana》1991,37(4):373-385
An automated linear laboratory EXAFS spectrometer of the Johansson type has been indigenously developed. Only two translational
motions are required to achieve the necessary Rowland circle configuration for the (fixed) X-ray source, the dispersing and
focusing bent crystal and the receiving slit. With the available crystals the spectral region from 5 to 25 keV can be scanned.
The linear motions of the crystal and receiving slit including the detector assembly are achieved by employing software-controlled
DC motors and utilizing optical encoders for position sensing. The appropriate rotation of the crystal is achieved by the
geometry of the instrument. There is a facility to place the sample alternately in the path of the X-ray beam and out of the
path to record both the incident X-ray intensityI
0 and the transmitted intensityI employing the scintillation detector. An arrangement with a two-window proportional detector before the sample to measureI
0 and the scintillation detector to recordI is also developed; in this case it is not necessary to oscillate the sample. Fast electronic circuits are employed to minimize
counting errors. The instrument is user-friendly and it is operated through a menu-driven IBM compatible PC. EXAFS spectra
of high resolution have been recorded using the spectrometer and employing the Si(111) reflecting planes; the X-ray source
being a Rigaku 12 kW rotating anode with Cu target. We describe the spectrometer and discuss its performance with a few representative
spectra. 相似文献
3.
Stephan H. Irsen Peter Kroll Richard Dronskowski Thomas E. Weirich Matthias Epple 《无机化学与普通化学杂志》2003,629(10):1751-1759
Tetrasulfur tetranitride, S4N4, reacts with elemental Cu within inert solvents to a black‐blue material of approximate composition Cu7S4N4 which is totally amorphous to X‐rays and which cannot be made crystalline by either thermal treatment or electron radiation. Cu7S4N4 explodes if heated above 234 °C or when subjected to mechanical shock to eventually yield copper(I) sulfide; this together with the characteristic infrared spectrum of Cu7S4N4 indicates the presence of molecular S4N4 units inside the amorphous phase. The metastable nature of Cu7S4N4 is also mirrored by electron microscopy which furthermore allows the structural characterization of its degradation products. Based on experimental EXAFS data offering characteristic Cu—N and Cu—S distances, a theoretical crystalline approximant of Cu7S4N4 was suggested and structurally optimized by density‐functional total‐energy calculations including periodic boundary conditions. This model incorporates a central S4N4 unit bonded to three shells of Cu atoms of different functionalities; in addition, a partial rupture of the S4N4 unit is likely to allow for a lowering of the total energy of the metastable phase. The latter observation supports the impossibility to make Cu7S4N4 crystallize using 4N4 crystallize using whatever kind of measures. 相似文献
4.
J. L. Gardea-Torresdey K. J. Tiemann J. R. Peralta-Videa J. G. Parsons M. Delgado 《Microchemical Journal》2004,76(1-2):65
Traditional treatment methods used to clean-up heavy metal contamination of soils and waters are cost intensive whereas more cost effective methods need to be developed. The use of plant materials to remediate heavy contamination has been studied for the past two decades. This technique has shown much promise for many of the common heavy metal contaminants, but few studies have focused on the lanthanide series elements. By investigating the binding and interactions of the lanthanide elements to alfalfa biomass, a more complete understanding of the binding mechanisms and the interactions of heavy metals with biomaterials can be obtained. Different chemical functional groups on the alfalfa biomass, carboxyl, amino, sulfur, and ester groups, were modified to investigate the binding mechanisms of erbium(III) and holmium(III). Batch experiments were performed with native and chemically modified alfalfa biomass suggesting that the carboxyl groups play a major role in the binding of erbium(III) and holmium(III) to the alfalfa biomass. In addition, X-ray absorption spectroscopy (XAS) studies corroborated the data obtained from the batch experiments. 相似文献
5.
Structural studies were performed on catalytically active ruthenium(II) complexes used in interphases, by means of XAFS spectroscopy. The EXAFS investigations indicate that the complexes retain their structural integrity when they are embedded on polysiloxane matrices to form stationary phase materials. The AXAFS studies reveal that the variations in the catalytic activity of the complexes with different ligands can be correlated to the differences in the electronic structure around the active ruthenium center. The EXAFS investigations show that, in asymmetric transfer hydrogenation reactions catalysed by ruthenium(II) complexes, the co‐catalyst plays a crucial role not only in enhancing the catalytic activity, but also in determining the structure of the intermediate species. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
6.
S. Yu. Troitskii A. L. Chuvilin D. I. Kochubei B. N. Novgorodov V. N. Kolomiichuk V. A. Likholobov 《Russian Chemical Bulletin》1995,44(10):1822-1826
The structure of polynuclear PdII hydroxocomplexes (PHC) formed as a result of alkaline hydrolysis of PdII chloride complexes was studied by EXAFS, SAXS, and TEM methods. It is established that in aqueous solutions a hydroxocomplex particle is a filament curled into a ball containing about 100 Pd atoms. The filament consists of planar coordination squares of PdO4 units linkedvia one or two oxygen bridges of different geometry. Aging of samples results in an increase in the number of single bridging ligands and a decrease in the diameter of particles. Interatomic distances around palladium atoms were determined.Translated fromIzvestiya Akademii Nauk. Seriya Khimlcheskaya, No. 10, pp. 1901–1905, October, 1995. 相似文献
7.
Studies were performed to determine the effect of pH on chromium (Cr) binding by native, esterified, and hydrolyzed saltbush (Atriplex canescens) biomass. In addition, X-ray absorption spectroscopy studies were performed to determine the oxidation state of Cr atoms bound to the biomass. The amounts of Cr adsorbed by saltbush biomass were determined by inductively coupled plasma-optical emission spectroscopy (ICP-OES). For Cr(III), the results showed that the percentages bound by native stems, leaves, and flowers at pH 4.0 were 98%, 97%, and 91%, respectively. On the other hand, the Cr(VI) binding by the three tissues of the native and hydrolyzed saltbush biomass decreased as pH increased. At pH 2.0 the stems, leaves, and flowers of native biomass bound 31%, 49%, and 46%, of Cr(VI), respectively. The results of the XAS experiments showed that Cr(VI) was reduced in some extend to Cr(III) by saltbush biomass at both pH 2.0 and pH 5.0. The XANES analysis of the Cr(III) reaction with the saltbush biomass parts showed an octahedral arrangement of oxygen atoms around the central Cr(III) atom. The EXAFS studies of saltbush plant samples confirmed these results. 相似文献
8.
9.
Amorphous precursors for PbZrO3 and PbTiO3 ceramics were prepared from lead acetate and the transition metaln-propoxide inn-propanol orn-butoxide inn-butanol and hydrolysed with an excess of water.
According to GLC and TGA/EGA analyses, the type of alkoxide group influences distinctly the structure of heterometallic precursors,
i.e., oxo or acetate bridging, and the amounts of hydroxyl and organic groups bound to the metal network.
The local environments of metal atoms in the amorphous precursors were also studied by EXAFS. The analysis reveals that in
Pb−Zr precursors alkoxide groups modify the coordination spheres of the zirconium atoms. Conversely, local environments of
both lead and titanium atoms within the analysed range of 3.4 A depend weakly on the type of alkoxide used. 相似文献
10.
用延伸X射线吸收精细结构(EXAFS),测定了标题化合物中两个铜原子的配位结构。两个铜原子有相同的配位,确认每个铜原子均与一个氮原子,三个氧原子形成四配位结构。一氧一氮源于HSB,而另两个氧由乙酸提供。 相似文献