Optimization of the extraction and fractionation of corn bran oil using analytical supercritical fluid instrumentation

Supercritical fluid extraction (SFE) is combined with supercritical fluid chromatography (SFC) in an analytical mode to develop a system for fractionating and enriching high value ferulate-phytosterol esters (FPE) contained in corn bran oil. Corn bran is initially extracted with neat supercritical carbon dioxide (SC-CO2) at various pressures (13.8, 34.5, and 69 MPa) and temperatures (40, 60, and 80 degrees C) to see if the FPE can be enriched in the extracts. These initial studies show the greatest percentage of FPE could be extracted under two sets of conditions: 69 MPa at 80 degrees C and 34.5 MPa at 40 degrees C. Both sets of parameters yield an extract containing approximately 1.25% FPE. A stock supply of corn bran oil is then produced by scaled-up SFE at 34.5 MPa and 40 degrees C for subsequent chromatographic fractionation. The SFE-obtained corn bran oil is then applied to the head of a minichromatographic column containing an amino-propyl sorbent. SFC is than commenced using neat SC-CO2 at 69 MPa and 80 degrees C to remove the majority of the triglyceride-based oil. Pressure and temperature are then lowered to 34.5 MPa and 40 degrees C, respectively, and ethanol is added as a modifier. The modifier is added in an increasing stepwise gradient program, and fractions are collected at equal volume intervals. The resultant fractions are analyzed by analytical high-performance liquid chromatography with evaporative light-scattering detection and show that FPE could be enriched to a 14.5% (w) level.     

High accuracy analysis by isotope dilution mass spectrometry using an iterative exact matching technique

The selection of an appropriate isotope dilution mass spectrometry technique for the practical application of this potentially primary method of analysis is highly important. The NARL approach for the application of the exact matching double isotope dilution mass spectrometry technique developed by Henrion is presented. NARL's approach utilises exact matching to minimise the effect of measurement biases within the method but also includes the thorough examination of all other biasing factors. The approach has been successfully tested in international CCQM intercomparisons with other national metrology institutes.     

Modes of decomposition of silver,lead and mercuric toluenedithiolates. A synthetic and analytical study

The silver, lead and mercuric toluenedithiolates were synthesised and analysed by both conventional chemical methods and thermoanalytical methods. The thermal decomposition was studied by thermogravimetric analysis in air, nitrogen and vacuum. The formulae of the decomposition products were derived using the mole weights and i.r. absorption spectra. The activation energies for the first stage of decomposition were calculated. The volatile products contain mostly carbon and hydrogen while the residues contain the corresponding metals either free or combined with sulfur.

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Zusammenfassung Die Silber-, Blei- und Quecksilber-Toluoldithionate wurden synthetisiert und sowohl mit konventionellen chemischen Methoden als auch thermoanalytisch analysiert. Die thermische Zersetzung wurde durch thermogravimetrische Analyse in Luft, Stickstoff und Vakuum untersucht. Die Formeln der Zersetzungsprodukte wurden aus den Molekulargewichten und den Infrarot-Absorptionsspektren abgeleitet. Die Aktivierungsenergien für den ersten Zersetzungsschritt wurden berechnet. Die flüchtigen Produkte enthalten hauptsächlich Kohlenstoff und Wasserstoff, während die Rückstände die entsprechenden Metalle in freier Form oder in Form von Schwefelverbindungen enthalten.

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Abstracted in part from a thesis submitted by T. Ktenas to the Graduate School of Howard University, in partial fulfillment of the requirements for the degree of Master of Science.     

An improved synthesis of cyclopropanes from stabilized phosphonates and 1,2-dioxines

Addition of stabilized Horner-Wadsworth-Emmons (HWE) phosphonates to substituted 1,2-dioxines leads to diastereomerically pure di- and trisubstituted cyclopropanes in high yields and represents a viable alternative to ylides in the cyclopropanation reaction involving 1,2-dioxines. While yields are comparable, reaction times with these stabilized phosphonates were accelerated and the diastereoselectivity for this cyclopropanation reaction was significantly greater than for the previously reported examples employing ylides.     

Multi-residue method for rapid screening and confirmation of pesticides in crude extracts of fruits and vegetables using isocratic liquid chromatography with electrospray tandem mass spectrometry

A LC-MS-MS method capable of the quantitative determination of a range of pesticide residues present in crude extracts from a variety of fruit and vegetables has been developed. Isocratic LC conditions have been used in conjunction with electrospray ionisation tandem mass spectrometry to detect and identify up to 38 pesticides presented as various mixtures in different matrices. The utility of the method is demonstrated by the analysis of crude extracts, with no sample clean up, from grape, kiwi fruit, strawberry, spinach, lemon, peach and nectarine. Mean recoveries ranging from 63 to 96% with relative standard deviations < 20% were obtained for 30 of the 38 pesticides following analysis of organic produce fortified at concentrations between 0.01 and 0.8 mg/kg. Detected residues were quantified from interpolation against calibration data generated using matrix-matched standards that covered analyte concentration ranges between 0.005 and 0.8 microg/ml. Conditions suitable for the qualitative and quantitative confirmation of residues detected in samples are specified.     

Spectroscopic studies of lewis acid—base complexes: IV. An infrared study of oriented single crystals and normal coordinate analyses of trimethylamine—boron halide adducts

A total of 19 isotopic species of various (CH₃)₃NBX₃ complexes have been prepared and their IR spectra studied in the solid state in the region 40–4000 cm^?1. The isotopes involved are deuterium, boron-10, boron-11, and nitrogen-15 with X = F, CI, Br and I. C_3v symmetry has been preserved in all cases. Symmetry classifications of the fundamental molecular frequencies have been derived from polarized IR measurements on oriented single crystals in the range 250–4000 cm^?1. Errors and inconsistencies in previous studies have been resolved and revised vibrational assignments are proposed on the basis of the new data. Normal coordinate analyses have been carried out utilizing symmetry compliance constants without the assumption of point mass methyl groups. A common potential function containing 22 parameters for the A₁ class and 26 for the E class was utilized. The results support the proposed frequency assignments. B-N force constants obtained by inversion of the compliance matrices vary systematically from the chloro to the iodo complex. However, the B-N force constant for the fluoro complex falls between that for the chloro and bromo species; no systematic trend appears for the B-N compliance constants.     

Synthesis of alpha-fluorosulfonamides by electrophilic fluorination

Alpha-fluorosulfonamides were prepared by electrophilic fluorination of tertiary sulfonamides using N-fluorobenzenesulfonimide as fluorinating agent and utilizing the dimethoxybenzyl group (DMB) as a new sulfonamide protecting group. Removal of the DMB group with TFA/CH(2)Cl(2) gave primary and secondary alpha-fluorosulfonamides.