全文获取类型
收费全文 | 213篇 |
免费 | 9篇 |
专业分类
化学 | 128篇 |
晶体学 | 1篇 |
数学 | 32篇 |
物理学 | 61篇 |
出版年
2023年 | 3篇 |
2021年 | 1篇 |
2020年 | 3篇 |
2019年 | 3篇 |
2018年 | 6篇 |
2017年 | 4篇 |
2016年 | 9篇 |
2015年 | 5篇 |
2014年 | 10篇 |
2013年 | 20篇 |
2012年 | 12篇 |
2011年 | 23篇 |
2010年 | 14篇 |
2009年 | 13篇 |
2008年 | 14篇 |
2007年 | 10篇 |
2006年 | 5篇 |
2005年 | 10篇 |
2004年 | 5篇 |
2003年 | 7篇 |
2002年 | 5篇 |
2000年 | 3篇 |
1999年 | 2篇 |
1998年 | 5篇 |
1997年 | 3篇 |
1996年 | 2篇 |
1995年 | 1篇 |
1994年 | 2篇 |
1991年 | 2篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1981年 | 4篇 |
1980年 | 1篇 |
1979年 | 2篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有222条查询结果,搜索用时 26 毫秒
31.
32.
Mouad Arrad Mehriban Aliyeva Sérgio M. Vilas-Boas Mohammed Kaddami Hannu Sippola Pekka Taskinen Simão P. Pinho 《Journal of solution chemistry》2018,47(4):774-786
The water activities of manganese nitrate solutions were measured using a humidity sensor instrument up to almost the saturation molality at 298.15 K; the thermodynamic properties of the system were described by the Pitzer model and specific interaction theory (SIT). The evaluation of the ion interaction parameters for the Pitzer model and SIT were carried out using experimental freezing points and osmotic coefficients of manganese nitrate aqueous solutions, collected from the open literature, and the water activity data measured in this work. A set of Pitzer and SIT parameters were estimated using a temperature dependency, that enables us to cover wider temperature ranges, and consequently calculate system properties to higher molalities. Both approaches represent very satisfactorily, and with similar accuracy, the experimental data and the calculated manganese nitrate molal activity coefficients are comparable to those already published for analogous systems. Additionally, the Pitzer model was also able to calculate the ice curve and the solubility branch of manganese nitrate hexahydrate up to a salt solution 6.5 mol·kg?1. 相似文献
33.
Amrita Chakraborty Ann Candice Fernandez Dr. Anirban Som Biswajit Mondal Dr. Ganapati Natarajan Dr. Ganesan Paramasivam Dr. Tanja Lahtinen Prof. Hannu Häkkinen Dr. Nonappa Prof. Thalappil Pradeep 《Angewandte Chemie (International ed. in English)》2018,57(22):6522-6526
The self‐assembled structures of atomically precise, ligand‐protected noble metal nanoclusters leading to encapsulation of plasmonic gold nanorods (GNRs) is presented. Unlike highly sophisticated DNA nanotechnology, this strategically simple hydrogen bonding‐directed self‐assembly of nanoclusters leads to octahedral nanocrystals encapsulating GNRs. Specifically, the p‐mercaptobenzoic acid (pMBA)‐protected atomically precise silver nanocluster, Na4[Ag44(pMBA)30], and pMBA‐functionalized GNRs were used. High‐resolution transmission and scanning transmission electron tomographic reconstructions suggest that the geometry of the GNR surface is responsible for directing the assembly of silver nanoclusters via H‐bonding, leading to octahedral symmetry. The use of water‐dispersible gold nanoclusters, Au≈250(pMBA)n and Au102(pMBA)44, also formed layered shells encapsulating GNRs. Such cluster assemblies on colloidal particles are a new category of precision hybrids with diverse possibilities. 相似文献
34.
Ochsenbein ST Tuna F Rancan M Davies RS Muryn CA Waldmann O Bircher R Sieber A Carver G Mutka H Fernandez-Alonso F Podlesnyak A Engelhardt LP Timco GA Güdel HU Winpenny RE 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(17):5144-5158
We report the synthesis and structural characterisation of a family of finite molecular chains, specifically [{[R(2)NH(2)](3)[Cr(6)F(11)(O(2)CCMe(3))(10)]}(2)] (in which R=nPr 1, Et 2, nBu 3), [{Et(2)NH}(2){[Et(2)NH(2)](3)[Cr(7)F(12)(O(2)CCMe(3))(12)][HO(2)CCMe(3)](2)}(2)] (4), [{[Me(2)NH(2)](3)[Cr(6)F(11)(O(2)CCMe(3))(10)]2.5 H(2)O}(4)] (5) and [{[iPr(2)NH(2)](3)[Cr(7)F(12)(O(2)CCMe(3))(12)]}(2)] (6). The structures all contain horseshoes of chromium centres, with each Cr...Cr contact within the horseshoe bridged by a fluoride and two pivalates. The horseshoes are linked through hydrogen bonds to the secondary ammonium cations in the structure, leading to di- and tetra-horseshoe structures. Through magnetic measurements and inelastic neutron scattering studies we have determined the exchange coupling constants in 1 and 6. In 1 it is possible to distinguish two exchange interactions, J(A)=-1.1 meV and J(B)=-1.4 meV; J(A) is the exchange interactions at the tips of the horseshoe and J(B) is the exchange within the body of the horseshoe (1 meV=8.066 cm(-1)). For 6 only one interaction was needed to model the data: J=-1.18 meV. The single-ion anisotropy parameters for Cr(III) were also derived for the two compounds as: for 1, D(Cr)=-0.028 meV and |E(Cr)|=0.005 meV; for 6, D(Cr)=-0.031 meV. Magnetic-field-dependent inelastic neutron scattering experiments on 1 allowed the Zeeman splitting of the first two excited states and level crossings to be observed. For the tetramer of horseshoes (5), quantum Monte Carlo calculations were used to fit the magnetic susceptibility behaviour, giving two exchange interactions within the horseshoe (-1.32 and -1.65 meV) and a weak inter-horseshoe coupling of +0.12 meV. Multi-frequency variable-temperature EPR studies on 1, 2 and 6 have also been performed, allowing further characterisation of the spin Hamiltonian parameters of these chains. 相似文献
35.
Akola J Walter M Whetten RL Häkkinen H Grönbeck H 《Journal of the American Chemical Society》2008,130(12):3756-3757
Density functional theory is used to explore the structure of Au25(RS)18. The preferred structure consists of an icosahedral Au13 core protected by 6 RS-Au-RS-Au-RS units. The enhanced stability of the structure as an anion is found to originate from closure of an eight-electron shell for delocalized Au(6s) electrons. The evaluated XRD pattern and optical spectra are in good agreement with experimental data. 相似文献
36.
37.
Bokwon Yoon Dr. Pekka Koskinen Dr. Bernd Huber Oleg Kostko Bernd von Issendorff Prof. Hannu Häkkinen Prof. Michael Moseler Dr. Uzi Landman Prof. 《Chemphyschem》2007,8(1):157-161
Ground-state structures and other experimentally relevant isomers of Au(15) (-) to Au(24) (-) clusters are determined through joint first-principles density functional theory and photoelectron spectroscopy measurements. Subsequent calculations of molecular O(2) adsorption to the optimal cluster structures reveal a size-dependent reactivity pattern that agrees well with earlier experiments. A detailed analysis of the underlying electronic structure shows that the chemical reactivity of the gold cluster anions can be elucidated in terms of a partial-jellium picture, where delocalized electrons occupying electronic shells move over the ionic skeleton, whose geometric structure is strongly influenced by the directional bonding associated with the highly localized "d-band" electrons. 相似文献
38.
The versatile characterization of organic material and especially of the significant aliphatic hydroxy acids in black liquor is of great importance, for example, in monitoring the progress of the kraft pulping process. This paper describes a simple high-performance liquid chromatographic separation method with atmospheric-pressure chemical ionization mass spectrometry (HPLC-APCI-MS) which was developed for the rapid quantitative analysis of these acids, mainly formed as the alkaline degradation products of feedstock carbohydrates. The fraction of carbohydrate degradation products is mainly composed of hydroxy monocarboxylic and volatile acids (formic and acetic acids) along with lesser amounts of various dicarboxylic acids. This method was thoroughly tested and validated to determine the most abundant nonvolatile low-molecular-mass aliphatic mono- and dicarboxylic acids present in softwood (pine and spruce) and hardwood (birch and aspen) kraft black liquors. This straightforward technique provides, compared to the conventional gas chromatographic methods, some important advantages such as simple sample preparation and a faster analysis time, thus enabling almost real-time monitoring of these acids. 相似文献
39.
Mohammad‐Ali Shahbazi Patrick V. Almeida Ermei Mkil Alexandra Correia Mnica P. A. Ferreira Martti Kaasalainen Jarno Salonen Jouni Hirvonen Hlder A. Santos 《Macromolecular rapid communications》2014,35(6):624-629
Currently, developing a stable nanocarrier with high cellular internalization and low toxicity is a key bottleneck in nanomedicine. Here, we have developed a successful method to covalently conjugate poly(methyl vinyl ether‐co‐maleic acid) (PMVE‐MA) copolymer on the surface of (3‐aminopropyl)triethoxysilane‐functionalized thermally carbonized porous silicon nanoparticles (APSTCPSi NPs), forming a surface negatively charged nanovehicle with unique properties. This polymer conjugated NPs could modify surface smoothness, charge, and hydrophilicity of the developed NPs, leading to considerable improvement in the colloidal and plasma stabilities via enhanced suspensibility and charge repulsion. Furthermore, despite the surface negative charge of the polymer‐conjugated NPs, the cellular internalization was increased in both MDA‐MB‐231 and MCF‐7 breast cancer cells. These results provide a proof‐of‐concept evidence that such polymer‐based PSi nanocomposite can be extensively used as a promising candidate for intracellular drug delivery.
40.
We report on the electronic structure of Ge(9)[Si(SiMe(3))(3)](3)(-). Systematic density functional theory analysis of the electronic shell structure of the cluster and its derivatives reveals that the Ge(9)[Si(SiMe(3))(3)](3)(-) and its neutral counterpart have electronic shells that can be explained using the superatom model. The ligand-core interaction of these complexes is distinctly different from previously identified gold, gallium, and aluminium superatom complexes, indicating an electron-donating rather than electron-withdrawing ligand. We modify the electron-counting rule for this case and introduce a simple picture for superatom and superantiatom complexes. Discussions comparing shell models, Zintl clusters, the superhalogen Al(13) and superatom complexes to Ge(9)[Si(SiMe(3))(3)](3)(-) are presented. 相似文献