全文获取类型
收费全文 | 124篇 |
免费 | 1篇 |
专业分类
化学 | 97篇 |
数学 | 14篇 |
物理学 | 14篇 |
出版年
2022年 | 1篇 |
2021年 | 1篇 |
2015年 | 1篇 |
2014年 | 1篇 |
2013年 | 2篇 |
2012年 | 4篇 |
2011年 | 3篇 |
2010年 | 1篇 |
2009年 | 1篇 |
2008年 | 8篇 |
2007年 | 11篇 |
2006年 | 3篇 |
2005年 | 4篇 |
2004年 | 4篇 |
2003年 | 1篇 |
2002年 | 7篇 |
2001年 | 7篇 |
2000年 | 6篇 |
1999年 | 3篇 |
1998年 | 2篇 |
1997年 | 2篇 |
1996年 | 2篇 |
1995年 | 4篇 |
1994年 | 2篇 |
1993年 | 1篇 |
1992年 | 4篇 |
1991年 | 2篇 |
1990年 | 1篇 |
1988年 | 2篇 |
1987年 | 4篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1983年 | 3篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1979年 | 2篇 |
1978年 | 5篇 |
1977年 | 2篇 |
1976年 | 1篇 |
1975年 | 2篇 |
1973年 | 5篇 |
1972年 | 1篇 |
1966年 | 1篇 |
1928年 | 2篇 |
1896年 | 1篇 |
排序方式: 共有125条查询结果,搜索用时 31 毫秒
91.
H. A. Claessens C. A. Cramers J. W. de Haan F. A. H. den Otter L. J. M. van de Ven P. J. Andree G. J. de Jong N. Lammers J. Wijma J. Zeeman 《Chromatographia》1985,20(10):582-586
Summary Laboratory use of HPLC columns packed with C8 and C18 bonded phases leads to changes in selectivities and retention volumes. FTIR,1H NMR of hydrolysed bonded phases and solid state13C- and29Si NMR were applied to characterize the materials. The results of the various techniques are in fair agreement except solid state NMR. Loss of silane and hydrolysis of surface siloxane groups have been observed for the C8 bondes phase, while for the C18 material the latter process seems to dominate. The solid state NMR results have been tentatively explained in terms of changing chain arrangements and mobilities.Dedicated to Professor J. F. K. Huber on the occasion of his 60th birthday. 相似文献
92.
Mengerink Y Peters R deKoster CG van der Wal S Claessens HA Cramers CA 《Journal of chromatography. A》2001,914(1-2):131-145
The linear and cyclic structures of polyamide-6 were separated by liquid chromatography at critical conditions (LCCC) and identified with different mass spectrometric (MS) techniques and quantitated by LCCC with evaporative light-scattering detection (ELSD). Electrospray ionization MS was not suitable to identify the higher cyclic structures. For this purpose, matrix-assisted laser desorption ionization time-of-flight MS performed better and cyclic and linear structures were oligomerically resolved and separately identified in the mass spectrometer. The highest cyclic structure present and detected was the cyclic pentacontamer. It could be demonstrated that cyclic and linear oligomers follow different ionization and fragmentation routes/patterns. Quantification with ELSD of the components separated by LCCC using a universal calibration curve or an iterative procedure was developed. An area correction to account for different peak widths of coeluting components improves precision and accuracy of the calibration curve and improves quantitation accuracy for the samples analyzed. With these corrected values, no molecular mass dependency was observed for the cyclic and linear structures. Under critical conditions, the linear and cyclic structures of polyamide-6 were separated, identified and quantified. 相似文献
93.
Successful packing of high quality HPLC columns is dependent upon a number of parameters. Especially when using slurry packing techniques, the absence of conglomerates of particles in the slurry and the wettability of the particles are important. The method described in this paper fulfills these conditions, imparting a ξ potential to the 5 and 10 μm silica particles by applying a pH gradient. This results in repulsive forces between the particles and hence leads to a well-controlled monodisperse situation. Water is used as a slurry and displacement liquid; it combines the advantages of excellent wetting properties and non-toxicity. 相似文献
94.
Vervoort RJ Ruyter E Debets AJ Claessens HA Cramers CA de Jong GJ 《Journal of chromatography. A》2002,964(1-2):67-76
This paper describes the characterisation of reversed-phase liquid chromatography (RPLC) columns using thermodynamic measurements. Retention versus 1/T data were used to construct Van't Hoff plots. The slope of these plots indicates the standard enthalpy of transfer of the analyte from the mobile to the stationary phase. The standard entropy can be calculated from the intercept. Van't Hoff plots were linear for the investigated RPLC columns, meaning that for basic analytes over the temperature range studied no changes in the retention mechanism occurred. Enthalpies and entropies of transfer of basic analytes from the mobile to the stationary phase revealed information about the types of interaction of protonated and neutral compounds with the stationary phases. However, a clear view using the present set of basic compounds on how these thermodynamic data may explain the observed substantial differences in peak symmetry cannot be given. It is considered that addition of N,N-dimethyloctylamine (DMOA) to the eluent will results in a dynamically coating of the stationary phase. Addition of DMOA to the eluent resulted for protonated basic compounds in a reduction of both enthalpy and entropy. In practice, with DMOA in the eluent symmetrical peaks were obtained. It is assumed that this is due to blocking residual silanols and/or ion exclusion effects. 相似文献
95.
96.
Iglesias RS Claessens CG Torres T Herranz MA Ferro VR de la Vega JM 《The Journal of organic chemistry》2007,72(8):2967-2977
Subphthalocyanine (SubPc)-fused dimers and trimers bearing fluorine, iodine, and thioether peripheral substituents were synthesized and characterized. Absorption spectroscopy and electrochemical studies revealed (i) that the substituents have a strong effect on the electronic properties of the macrocycles and (ii) that there is good communication between the subphthalocyaninic moieties within the oligomeric structures. Theoretical calculations at DFT/6-31G(d,p) computational level and electron density studies support the experimental findings. The frontier orbitals in the dimers and trimers were also shown to be significantly altered with respect to those of SubPcs as a consequence of the extension of the conjugation associated with symmetry breaking. Time-dependent density functional theory calculations reproduced the differences observed in the UV-vis spectra of the fused dimers and the monomeric SubPcs. 相似文献
97.
Claessens MM Leermakers FA Hoekstra FA Stuart MA 《The journal of physical chemistry. B》2007,111(25):7127-7132
We correlate the molecularly realistic self-consistent field predictions for the mean bending modulus kc of charged lipid vesicles with experimental observations of the size R of corresponding vesicles that are produced by the freeze-thaw method. We elaborate on the Ansatz that the bending modulus is related to the membrane persistence length and that this length scale sets the radius of the vesicles. Alkali cations have a remarkable effect on the mean bending modulus and thus on the equilibrium radius of negatively charged entropically stabilized dioleoylphosphatidylglycerol (DOPG) vesicles. Where cation hydration typically results in thicker and thus stiffer membranes, specific adsorption to the bilayer surface results in a decrease of the surface charge density and the thickness of the membrane-associated electric double layer. As a result of these opposing effects on kc and R, the largest DOPG vesicles are found in the presence of K+, which combines an intermediate hydration enthalpy and PG-binding affinity. 相似文献
98.
Rodríguez-Morgade MS Claessens CG Medina A González-Rodríguez D Gutiérrez-Puebla E Monge A Alkorta I Elguero J Torres T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(4):1342-1350
A new and general synthetic method for the preparation of fluoro-substituted subazaporphyrins is reported that involves the treatment of the corresponding chloro- or aryloxy-substituted subazaporphyrins (SubAPs) with BF(3).OEt(2). The strategy has been applied to both subphthalocyanines (SubPcs) and subporphyrazines (SubPzs). The yields were high for the latter, although low yields were obtained for the benzo derivatives. In contrast to the corresponding chloro derivatives, fluorosubazaporphyrins are quite robust towards hydrolysis. All of the new compounds were characterized by several spectroscopic techniques, which included (1)H, (13)C, (19)F, (15)N, and (11)B NMR spectroscopy, IR spectroscopy, UV/Vis spectrophotometry, and mass spectrometry (both high and low resolution). In addition, DFT calculations provided theoretical NMR spectroscopy values that are in good agreement with the experimental ones. The high dipole moments exhibited by the fluorosubazaporphyrins as a result of the presence of a fluorine atom in an axial position are responsible for the spontaneous and singular supramolecular aggregation of the macrocycles in the crystalline state. The molecular and crystal structures of two one-dimensional fluorine SubAPs, namely, a SubPc and a SubPz, are discussed. Molecules of the same class stack in alternating configurations along the c axis, which gives rise to columns that contain large numbers of monomers. SubPz 3 c forms aggregates with the macrocycles arranged in a parallel fashion with the B-F bonds perfectly aligned within a column, whereas with SubPc 3 b the neighboring columns cause a commensurate sinusoidal distortion along the columns in the c direction, which prevents the alignment of the B-F bonds. However, the most remarkable feature, common to both crystalline architectures, is the extremely short and unusual intermolecular F...N distances of the contiguous molecules, which are shorter than the sum of the corresponding van der Waals radii. Theoretical calculations have shown that these short distances can be explained by the existence of a cooperativity effect as the number of monomers included in the cluster increases. 相似文献
99.
100.
R J Vervoort E Ruyter A J Debets H A Claessens C A Cramers G J de Jong 《Journal of chromatography. A》2001,931(1-2):67-79
The reversed-phase liquid chromatographic analysis of basic pharmaceuticals can be problematic. Both the properties of the eluent and the stationary phase can influence the chromatographic performance. Therefore selection of suitable experimental conditions for the analysis of basic compounds can be difficult. This paper shows that the organic modifier and the nature of the buffer influence the eluent properties. Moreover, the nature and amount of modifier also influence the basicity of the analytes. Investigations showed that the nature of the buffer can have a significant influence on retention and peak shape of basic compounds. Test procedures using basic analytes as test probes provided relevant information with respect to selecting columns to analyse basic pharmaceutical compounds. Test procedures using compounds like aniline, phenol and benzene were found to be less suitable. 相似文献