John R. Sowa

Reaction calorimetry as an in-situ kinetic tool for characterizing complex reactions☆

Abstract Due to its ability to provide directly reaction rate data and its in-situ nature, reaction calorimetry has become one of the most powerful probes of reaction pathways and mechanisms of chemical reactions by virtue of providing high-quality kinetic data. In this paper, examples of enantioselective hydrogenation and selective consecutive hydrogenation reactions are presented to demonstrate the high quality of kinetic data obtainable from the reaction calorimetry. They are also used to illustrate the use of reaction calorimetry for elucidating reaction pathways and mechanisms from detailed kinetic and thermodynamic information about individual step involved in multi-step reactions that is otherwise difficult to obtain without calorimetry.

Detection of polycyclic aromatic hydrocarbons (PAHs) in raw menhaden fish oil using fluorescence spectroscopy: Method development

Raw menhaden fish oil was developed for biomonitoring polycyclic aromatic hydrocarbons (PAHs) using fluorescence spectroscopy. Menhaden (Genus Brevoortia) were collected in 2010 and/or 2011 from Delaware Bay, New Jersey, USA; James River, Virginia, USA; Vermillion Bay, Louisiana, USA (VBLA); and Barataria Bay, Louisiana, USA (BBLA). Barataria Bay, Louisiana received heavy oiling from the Deepwater Horizon oil spill. Method development included determining optimal wavelengths for PAH detection, fish oil matrix interferences, and influence of solvent concentration on extraction. Results showed that some fish oils contained high molecular weight PAH-like compounds in addition to other fluorescent compounds such as albumin and vitamin A and vitamin E. None of these naturally occurring compounds interfered with detection of high molecular weight PAHs. However, data suggested that the lipid component of fish oil was altering fluorescence spectra by supporting the formation of PAH excimers. For example, the most intense excitation wavelength for hydroxypyrene shifted from Ex285/Em430 to Ex340/Em430. Comparison of Deepwater Horizon crude oil and fish oil spectra indicated that some fish oils contained crude oil-like PAHs. Using wavelengths of Ex360/Em430, fish oil concentrations were calculated as 3.92 μg/g, 0.61 μg/g, and 0.14 μg/g for a Delaware Bay sample, BBLA 2011, and VBLA 2011, respectively. Overall, these results supported using menhaden fish oil to track PAH exposures spatially and temporally.

Gas-phase generation of trifluoromethyl cyclopentadienides

Tetramethyltrifluoromethylcyclopentadienide 1 a is unstable in solution but it can be readily generated in the gas phase. The proton affinities and fluoride binding energies of la and several other trifluoromethyl substituted cyclopentadienides are measured. The data is found to fit an additivity scheme, which suggests that pentakis(trifluoromethyl)cyclopentadiene is an exceptionally strong gas-phase acid, and indicates that substituted trifluoromethylcyclopentadienides may be accessible in solution under the appropriate reaction conditions.

Quantitative Analysis of Polycyclic Aromatic Hydrocarbons at Part Per Billion Levels in Fish Oil by Headspace Solid-Phase Microextraction and Gas Chromatography-Mass Spectrometry (HS-SPME–GC–MS)

Headspace solid-phase microextraction (HS-SPME) was used in combination with gas chromatography-mass spectrometry (GC-MS) for the analysis of polycyclic aromatic hydrocarbons (PAH) at part per billion levels in fish oil samples collected from menhaden fish. The method was initially developed using fish oil from capsules spiked with a standard PAH mixture. The final HS-SPME-GC-MS method presented a linear range from 3 to 1,500 ng/g, with precision for most analytes <10% relative standard deviation. The limits of detection varied from 1 to 7 ng/g depending on the analyte. Real sample analysis was done on menhaden fish oil extracted from fish collected off the coasts of New Jersey and Louisiana. Naphthalene, fluorene, fluoranthene, pyrene, anthracene were detected at low levels of 70-180 ng/g in the real samples. The concentrations of PAHs detected in the real samples were well below established levels of concern for PAHs in finfish.

Polyol-induced partitioning of essential oils in water/acetonitrile solvent mixtures

ABSTRACT Polyol-induced extraction (PIE) is applied to the extraction of essential oils, using glycerol as a mass separating agent. In 1:1 acetonitrile (ACN)/water solvent mixtures, two immiscible phases can be generated. PIE as an alternative extraction technique was assessed by the extraction of the main flavor and fragrance compounds that comprise six essential oils. In the extraction of eugenol (4-allyl-2-methoxyphenol) from clove buds, the partition coefficients were determined and the % recovery and thermodynamic data in the temperature range of −20 to 20°C were calculated. The main components present in each essential oil extract were identified through gas chromatography/mass spectrometry (GC/MS) and the compositional profile was compared to traditional extraction techniques. The optimized extraction conditions (−10°C, 1:1 ACN/water (v/v), 20% glycerol) for eugenol at −10°C give a partition coefficient (KPC) of 87 and an extraction efficiency of 97% in the acetonitrile-rich phase. The eugenol migration to the organic phase is a spontaneous process (ΔG° = −9.3 kJ/mol) and an endothermic process (ΔH° = 9.2 kJ/mol) with entropy being the driving force behind the reaction (ΔS° = 70 J/K, TΔS° = 18.4 kJ). The technique was applied to five other essential oils (cinnamon bark, caraway seed, spearmint leaf, peppermint leaf, and anise seed oils) with similar results. GRAPHICAL ABSTRACT