Influence of Polarity and Activation Energy in Microwave–Assisted Organic Synthesis (MAOS)

The aim of this work was to determine the parameters that have decisive roles in microwave-assisted reactions and to develop a model, using computational chemistry, to predict a priori the type of reactions that can be improved under microwaves. For this purpose, a computational study was carried out on a variety of reactions, which have been reported to be improved under microwave irradiation. This comprises six types of reactions. The outcomes obtained in this study indicate that the most influential parameters are activation energy, enthalpy, and the polarity of all the species that participate. In addition to this, in most cases, slower reacting systems observe a much greater improvement under microwave irradiation. Furthermore, for these reactions, the presence of a polar component in the reaction (solvent, reagent, susceptor, etc.) is necessary for strong coupling with the electromagnetic radiation. We also quantified that an activation energy of 20–30 kcal mol⁻¹ and a polarity (μ) between 7–20 D of the species involved in the process is required to obtain significant improvements under microwave irradiation.     

Selectivity changes towards steroids in packed column supercritical fluid chromatography (SFC) induced by temperature and pressure variation

Summary Pressure/temperature variation in SFC was shown to influence selectivity towards steroids. Major changes were observed for polar column packings compared to non-polar packings and variation of the amount of modifier showed that this is valid over the whole investigated range. The effect is underlined by a fall in resolution in the low density range (low pressure/high temperature) for polar stationary phases and appears to be significantly larger than for non-polar phases. Major selectivity shifts induced by variation of the physical properties of the mobile phase are considered to be due to the greater effect of polar modifiers on the nature of polar stationary phases than on non-polar phases.     

溴酸钾-亚甲蓝催化光度法测定硝酸盐和亚硝酸盐

用镉柱将NO-3 还原为NO-2 ,利用在磷酸介质中NO-2 对溴酸钾氧化亚甲蓝这一褪色反应具有强烈的催化作用而建立了同时测定痕量硝酸盐和亚硝酸盐的新方法。本方法简便、快速、灵敏 ,对亚硝酸盐和硝酸盐测定的线性范围分别为 0～ 2 0 0 μg·L-1和 0 0 0 3～ 310 μg·L-1,用于测定各种水样中痕量NO-2 和NO-3 的含量均获得满意结果     

Measurement of elastin hydrolysis by reverse-phase HPLC with on-line post-colum derivatization

Summary Excessive breakdown of elastin, a structural protein, may be related to aortic disease and emphysema. Since L-valyl-L-proline occurs in high concentrations in elastin, a rapid and sensitive method using HPLC with post-column on-line derivatization was used to measure the dipeptide from swine aortic tissue, and the amount of elastin present was determined. Elastin was extracted by alkaline hydrolysis. After neutralization and filtration, the sample was injected onto a ODS-2 gel column, and the dipeptide was eluted by a linear gradient of 0 to 10% of 1-propanol in 50 mM heptafluorobutyrate, pH 3, at a flow rate of 1 ml/min. The eluent was reacted with fluorescamine at pH 8.6, and fluorescence was detected at an excitation wavelength of 395 nm and a 455 nm cutoff emission filter.Presented at the 17th International Symposium on Chromatography, September 25–30, 1988, Vienna, Austria.     

High performance liquid chromatographic separation of polar and non-polar chlorophyll pigments from algae using a wide pore polymeric octadecylsilica column

A method employing a wide pore polymeric reversed phase column has been developed for the separation of most of the chlorophylls and related compounds previously described as occurring in marine microalgae. The high selectivity toward molecular shape of this kind of stationary phase has enabled compounds of very similar structure, such as chlorophylls c₁, c₂ and Mg-divinylpheoporphyrin a₅ monomethyl ester, and chlorophyll a and the phytol-substituted chlorophyll c-like pigments, which commonly coelute on monomeric bonded phases, to be resolved in a single run. Some of these pigments, formerly thought to be a single compound, have, in fact, been demonstrated to be groups of two or more. The method has been successfully applied to both algal cultures and natural sea water samples. When visible light absorbance detection was used, the method proved suitable for separation of various carotenoids.     

A generic view of Dantzig-Wolfe decomposition in mixed integer programming

The Dantzig-Wolfe reformulation principle is presented based on the concept of generating sets. The use of generating sets allows for an easy extension to mixed integer programming. Moreover, it provides a unifying framework for viewing various column generation practices, such as relaxing or tightening the column generation subproblem and introducing stabilization techniques.     

New HPLC-chiral stationary phases for enantiomeric resolution of sulfoxides and selenoxides

Summary Enantiomers of several sulfoxides and some selenoxides can be easily separated by using a new chiral stationary phase (CSP-DACH-DNB) containing the 3,5-dinitrobenzoyl derivative of R,R-(-)1,2-diamino-cyclohexane as selector, covalently bonded to the siliceous matrix. The easy operative conditions and the high enantioselectivity values (α) allow a direct transfer of the analytical separations to a semi-preparative and preparative scale.     

High-Throughput Screening of Ten Microcystins and Nodularins, Cyanobacterial Peptide Hepatotoxins, by Reversed-Phase Liquid Chromatography-Electrospray Ionisation Mass Spectrometry

Liquid chromatography-electrospray ionisation mass spectrometry was evaluated in the high-throughput analysis of microcystins and nodularins, cyanobacterial peptide hepatotoxins. Extracts originating from cyanobacterial strains and field material were separated on a 30 mm × 4 mm I.D. Merck Purospher STAR RP-18e column using a rapid gradient of aqueous formic acid and acetonitrile, ionised by electrospray technique and analysed on a Micromass Quattro II triple-quadrupole mass spectrometer operated in the selected ion recording (SIR) mode. The total analysis time per sample was 2.8 min corresponding to 514 samples a day. The system showed good robustness during a series of 320 repetitive injections of a field sample containing three major microcystins.     

Chromatographic investigations of furocoumarins fromHeracleum genus fruits

Summary Furocoumarins from extracts ofHeracleum genus fruits were separated using normal and reversed phase TLC and HPLC and isolated in the milligram scale using overloaded systems of column chromatography. Binary or ternary solvents containing a polar modifier (methanol, diisopropyl ether or acetonitrile) were used as the mobile phases. Preliminary report on this work was presented at the 47th International Congress of Pharmaceutical Sciences of F.I.P. in Amsterdam. The Netherlands, 30 August–5 September 1987.     

Buckling of sandwich wide columns

The paper deals with the theoretical prediction of buckling loads for sandwich columns with metallic and laminated facings and foam or honeycomb core. The loading is a uniform axial compression, applied statically (very slowly) and suddenly with constant magnitude and infinite duration (step loading). The effect of length and boundary conditions is assessed and results are presented for the following cases: for a cantilever column, a simply supported column and a clamped column, for several lengths. Several fiber materials are used in the laminated facings. Two types of core were examined: alloy-foam or hexagonal glass/phenolic honeycomb. The facings are Boron/Epoxy, Graphite/Epoxy and Kevlar/Epoxy laminates with 0° orientation with respect to the column axis and a metallic one made out of aluminum. These various materials are employed to provide comparative data that can be used in design. Results, for the static case are generated by computer codes as well as by the use of closed form theoretical solutions. For the dynamic case, results are generated by the DYNA3D code.