全文获取类型
收费全文 | 132篇 |
免费 | 3篇 |
国内免费 | 1篇 |
专业分类
化学 | 103篇 |
力学 | 5篇 |
数学 | 8篇 |
物理学 | 20篇 |
出版年
2020年 | 1篇 |
2019年 | 1篇 |
2018年 | 2篇 |
2017年 | 2篇 |
2016年 | 5篇 |
2015年 | 5篇 |
2014年 | 4篇 |
2013年 | 6篇 |
2012年 | 8篇 |
2011年 | 10篇 |
2010年 | 5篇 |
2009年 | 4篇 |
2008年 | 7篇 |
2007年 | 6篇 |
2006年 | 14篇 |
2005年 | 7篇 |
2004年 | 3篇 |
2003年 | 7篇 |
2002年 | 6篇 |
2000年 | 2篇 |
1999年 | 2篇 |
1998年 | 1篇 |
1997年 | 3篇 |
1994年 | 1篇 |
1993年 | 1篇 |
1992年 | 2篇 |
1990年 | 1篇 |
1988年 | 1篇 |
1987年 | 3篇 |
1986年 | 1篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1970年 | 1篇 |
1897年 | 1篇 |
排序方式: 共有136条查询结果,搜索用时 15 毫秒
81.
A novel type of retention indices for alkylphenols and related compounds are proposed. The alkylphenol retention indices (APRI) use para-substituted n-alkylphenols as reference series. APRI for para-n-alkylphenols are per definition equal to the number of carbon atoms in the alkyl substituent; the value for phenol is zero. Application of the APRI system with different types of derivatisation of the phenolic hydroxy group showed that the derivatisation has limited influence on these indices. Especially para-substituted alkylphenols gave APRI values that could be transferred with high accuracy from one type of derivative to another. By comparing results obtained with different gradients in temperature-programmed GC, it was also shown that APRI is less affected by chromatographic conditions than retention indices based on n-alkanes. 相似文献
82.
Nachtigallová D Bludský O Otero Areán C Bulánek R Nachtigall P 《Physical chemistry chemical physics : PCCP》2006,8(42):4849-4852
Based on theoretical calculations, and a survey of infrared spectra of CO adsorbed on different cation exchanged zeolites, a model is proposed to explain the influence of the zeolite framework on the vibrational behaviour of CO confined into small void spaces (zeolite channels and cavities). The concepts developed should help to understand a number of details relevant to both, precise interpretation of IR spectra and a better understanding of the vibrational dynamics of small molecules in a confined space. 相似文献
83.
Prof. Edoardo Garrone Prof. Carlos Otero Areán Prof. Montserrat Rodríguez Delgado Prof. Barbara Bonelli 《ChemistryOpen》2020,9(5):599-606
Detailed analysis of recently reported variable-temperature IR (VTIR) spectra of carbon monoxide adsorbed in alkaline zeolites shows how, not only the corresponding values of standard adsorption enthalpy ( ) and entropy ( ) can be obtained, but also the thermodynamic values of molar entropy and enthalpy which characterize the adsorbed gas phase. In addition, it is shown that the so obtained molar entropy data can lead to new insights into soft molecular modes, which would be hardly accessible by conventional IR spectroscopic techniques. 相似文献
84.
85.
Svein Morgenlie 《Journal of carbohydrate chemistry》2013,32(4):661-671
Abstract Hydroxides of various alkali and alkaline earth metals have been investigated as catalysts in the triose aldol condensation and the aldol condensation between glyceraldehyde and glycolaldehyde. The proportions of diastereomers are very similar in the different product mixtures. Mechanistic models, previously suggested for other aldol condensations, have been considered for the reaction, and the observed diastereoselectivity is in accordance with a pericyclic transition state formed from a cis-enediolate-attack on the aldehyde. 相似文献
86.
Hnyk D Wann DA Holub J Samdal S Rankin DW 《Dalton transactions (Cambridge, England : 2003)》2011,40(21):5734-5737
The molecular structure of 1-thia-closo-decaborane(9), 1-SB(9)H(9), has been determined by the concerted use of gas electron diffraction and quantum-chemical calculations. Assuming C(4v) symmetry, the cage structure was distorted from a symmetrically bicapped square antiprism (D(4d) symmetry) mainly through substantial expansion of the tetragonal belt of boron atoms adjacent to sulfur. The S-B and (B-B)(mean) distances are well determined with r(h1) = 193.86(14) and 182.14(8) pm, respectively. Geometrical parameters calculated using the MP2(full)/6-311++G** method and at levels reported earlier [MP2(full)/6-311G**, B3LYP/6-311G** and B3LYP/cc-pVQZ], as well as calculated vibrational amplitudes and (11)B NMR chemical shifts, are in good agreement with the experimental findings. In particular, the so-called antipodal chemical shift of apical B(10) (71.8 ppm) is reproduced well by the GIAO-MP2 calculations and its large magnitude is schematically accounted for, as is the analogous antipodal chemical shift of B(12) in the twelve-vertex closo-1-SB(11)H(11). 相似文献
87.
88.
Jean-Raphaël Martinez Chris E. Mohn Svein Stlen Neil L. Allan 《Journal of solid state chemistry》2007,180(12):3388-3392
The structure of Ba2In2O4(OH)2 is analysed by the explicit full optimization of a large number of possible proton arrangements using periodic density functional theory. It is shown that the experimental assignments in which protons appear to be located at high symmetry positions with unphysical bond lengths do not correspond to minima on the potential energy hypersurface. The apparent sites are averages of a number of possible proton locations involving a set of possible local structural environments in which the internuclear separations are more realistic. Such problems with structural refinements are common where profile refinement programs place the atoms at the average position due to dynamic and/or static disorder. Thus while the calculations support a previous neutron diffraction analysis of the structure in that the average structure contains two different proton sites, they also reveal substantial information about the local environments of the protons. In all optimizations, the protons moved from the average positions suggested in the neutron diffraction study with calculated O–H and OHO distances consistent with those observed in other oxides. The energies of different proton distributions vary significantly so the protons are not randomly distributed. We also present an analysis of the vibrational properties of the O–H bonds. Since the strength of the hydrogen bonds is closely related to the local structural environments of the protons, a range of vibrational frequencies is obtained providing a prediction of the vibrational spectra. In O–HO linkages, O–H stretching modes soften with increasing HO hydrogen bond strength, while the in-plane and out-of-plane bending or libration modes stiffen. Together, our results show how modern theoretical methods can provide a clearer understanding of the structure and dynamics of a complex inorganic material. 相似文献
89.
Mahan Mj 《Geometric And Functional Analysis》2014,24(1):297-321
In earlier work, we had shown that Cannon–Thurston maps exist for Kleinian surface groups without accidental parabolics. In this paper we prove that pre-images of points are precisely end-points of leaves of the ending lamination whenever the Cannon–Thurston map is not one-to-one. 相似文献
90.
Bjørge Westereng Jane Wittrup Agger Svein J. Horn Gustav Vaaje-Kolstad Finn L. Aachmann Yngve H. Stenstrøm Vincent G.H. Eijsink 《Journal of chromatography. A》2013,1271(1):144-152
We present an evaluation of HPLC-based analytical tools for the simultaneous analysis of native and oxidized cello-oligosaccharides, which are products of enzymatic cellulose degradation. Whereas cello-oligosaccharides arise from cellulose depolymerization by glycoside hydrolases, oxidized cello-oligosaccharides are produced by cellobiose dehydrogenase and the recently identified copper dependent lytic polysaccharide monooxygenases (LPMOs) currently classified as CBM33 and GH61. The latter enzymes are wide-spread and expected to play crucial roles in further development of efficient enzyme technology for biomass conversion. Three HPLC approaches with well documented performance in the field of oligosaccharide analysis have been investigated: high-performance anion-exchange chromatography (HPAEC), hydrophilic interaction chromatography (HILIC) and porous graphitized carbon liquid chromatography (PGC-LC). HPAEC with pulsed amperometric detection (PAD) was superior for analysis of oxidized oligosaccharides, combining the best separation with superior sensitivity for oligosaccharide species with a degree of polymerization (DP) ranging from 1 to 10. Furthermore, the HPAEC method can be optimized for operation in a high-throughput manner (run time 10 min). Both PGC-LC and HILIC allow reasonable run times (41 and 25 min, respectively), with acceptable separation, but suffer from poor sensitivity compared to HPAEC-PAD. On the other hand, PGC-LC and HILIC benefit from being fully compatible with online mass spectrometry. Using an LC–MS setup, these methods will deliver much better sensitivity than what can be obtained with conventional detectors such as ultraviolet-, charged aerosol-, or evaporative light scattering and may reach sensitivities similar to or even better than what is obtained in HPAEC-PAD. Pure oxidized cello-oligosaccharide standards, ranging from DP2 to DP5, were obtained by semi-preparative PGC and characterized by MS and NMR analysis. 相似文献