Kingsley K. Donkor

Determination of thermodynamic pKa values of benzimidazole and benzimidazole derivatives by capillary electrophoresis.

Thermodynamic pK(a) values for benzimidazole and several substituted benzimidazoles were determined by CE. Electrophoretic mobilities of benzimidazoles were determined by CE at different pH levels and ionic strengths. The dependence of electrophoretic mobilities on pH was used to obtain pK(a) values at different ionic strengths. Extrapolations to zero ionic strength were used to determine the thermodynamic pK(a) values. Using this method the thermodynamic pK(a) values of 15 benzimidazoles were determined and found to range from 4.48 to 7.38. Results from the CE measurements were compared with spectrophotometric measurements which were evaluated at wavelengths where the highest absorbance difference for varying pH was recorded. The two analytical techniques were in good agreement.

Cure from the cave: volcanic cave actinomycetes and their potential in drug discovery

*ncheeptham@tru.ca well understood, hence, there is a need to investigate further (Northup & Welbourn, 1997; Barton et al., 2001; Northup & Lavoie, 2001; Barton & Luiszer, 2005; Barton, 2006; Barton & Jurado, 2007; Barton & Northup, 2007; Snider et al., 2009; Engel, 2010; Lavoie et al., 2010; Bhullar et al., 2012). Antibiotic resistance in pathogens is surfacing at an increasingly alarming rate in hospitals and communities around the world. When dealing with multidrug resistant pathogens, currently available antibiotics have often fallen short for their lack of specific inhibitory activities or with negative side effects. Therefore, there INTRODUCTION

Rapid Determination of Total Conjugated Linoleic Acid Content in Select Canadian Cheeses by 1H NMR Spectroscopy

The application of (1)H nuclear magnetic resonance (NMR) spectroscopy to the measurement of conjugated linoleic acid (CLA) content in the lipid fraction of dairy products is both a novel and inviting alternative to traditional methods such as gas chromatography (GC), which can require time-consuming sample derivatization. In this work, a newly developed, rapid, and reliable lipid extraction protocol was combined with simple, nondestructive (1)H NMR spectroscopic analysis to measure the total CLA content in CLA standards and in various Canadian cheeses from conventional, organic, and grass-fed dairy sources. The total CLA concentrations (mg/g cheese) obtained using these new extraction and analysis methods were consistent with amounts found using the modified Folch extraction and GC analysis (correlation coefficient of 0.948). Results showed that cheeses from exclusively grass-fed dairy cows were significantly higher in total CLA content than either conventional or organic cheese.

Separation and determination of closely related lantibiotics by micellar electrokinetic chromatography

A sensitive micellar electrokinetic chromatography (MEKC) method was developed for the separation and determination of four closely related lantibiotics: gallidermin, cinnamycin, duramycin and nisin. Factors affecting the separation of the lantibiotics such as pH, phosphate buffer concentration, SDS concentration and wavelength for UV detection were investigated. By optimizing these experimental conditions, successful separation was achieved between class 1A lantibiotics (nisin and gallidermin) and class 1B lantibiotics (duramycin and cinnamycin). The four lantibiotics were separated within 12 min in 50 mM phosphate buffer at pH 3.95 +/- 0.1 containing 80 mM SDS with UV detection of 214 nm. The LOD (S/N = 3) were 61 ng/mL for gallidermin, 57 ng/mL for cinnamycin, 55 ng/mL for duramycin and 58 ng/mL for nisin. The method was successfully applied to real samples such as fermentation broth, bovine colostrum and predrop beer. This method yielded satisfactory results, with quantitative recoveries of spiked lantibiotics in the three samples ranging from 86.1 to 99.6%.

Micellar electrokinetic chromatography method development for simultaneous determination of thiabendazole, carbendazim, and fuberidazole

Thiabendazole (TBz), carbendazim (CBz), and fuberidazole (FBz) are systemic benzimidazole-type fungicides used for pre- and post-harvest treatment to control various types of fungal diseases on a variety of crops. Significant levels of these fungicides could alter the composition or flavour of crops, and being possible carcinogens, they could also pose risks for humans and the environment. A mode of capillary electrophoresis called micellar electrokinetic chromatography (MEKC) was investigated for the determination of these three benzimidazole fungicides. The study involved two kinds of surfactants in which several experimental conditions were optimized, i.e., buffer concentration, pH, micelle concentration, and percent organic modifier (methanol). Using the optimum experimental conditions, the fungicides were successfully separated by MEKC. The limits of detection and quantification were in the range of 0.6–0.7 and 2.1–2.5 mg L−1, respectively, and the calibration curves were linear over the range of 5–60 mg L−1 for the three fungicides. The potential of the proposed MEKC method was demonstrated by analyzing water samples which were fortified with the fungicides. The proposed method enabled simultaneous determination of the three benzimidazole fungicides and method validation with spiked water samples yielded satisfactory quantitative recoveries for all the three fungicides.

Separation of dietary omega‐3 and omega‐6 fatty acids in food by capillary electrophoresis

A lower dietary omega-6/omega-3 (n-6/n-3) fatty acid ratio (<4) has been shown to be beneficial in preventing a number of chronic illnesses. Interest exists in developing more rapid and sensitive analytical methods for profiling fatty acid levels in foods. An aqueous CE method was developed for the simultaneous determination of 15 n-3 and n-6 relevant fatty acids. The effect of pH and concentration of buffer, type and concentration of organic modifier, and additive on the separation was investigated in order to determine the best conditions for the analysis. Baseline separations of the 15 fatty acids were achieved using 40 mM borate buffer at pH 9.50 containing 50 mM SDS, 10 mM β-cyclodextrin, and 10% acetonitrile. The developed CE method has LODs of <5 mg/L and good linearity (R(2) > 0.980) for all fatty acids studied. The proposed method was successfully applied to the determination of n-3 and n-6 fatty acids in flax seed, Udo® oils and a selection of grass-fed and grain-fed beef muscle samples.

Analysis of Athabasca oil sand by near-infrared–diffuse reflectance spectroscopy

A near-infrared–diffuse reflectance spectroscopy (NIR–DR) method is described for the measurement of the bitumen and solids content in Athabasca oil sand over a 15 m vertical transect of a 7 cm diameter core at a sampling resolution of 1 cm. Principal component regression and partial least squares statistical techniques were evaluated as tools for optimizing the calibration models. The two techniques were found to be comparable and satisfactory for this application. Surface roughness was found to exhibit a significant effect on bitumen results. Sampling frequency studies showed that to attain a target precision of 5% for bitumen and solids, and to reduce errors arising from heterogeneity, measurements should be made on areas larger than 1 cm2.

Determination of sulfate and chloride ions in highly saline oilfield water by capillary electrophoresis using bilayer-coated capillaries and indirect absorption detection

Analysis of highly saline oilfield waters for anions presents challenges. Traditional analytical techniques used for such analysis tend to suffer from both poor sensitivity and selectivity due to the high concentrations of salt present in the samples. A capillary electrophoresis method was developed for the simultaneous determination of chloride and sulfate anions which is relevant to the oilfield analysis industry and of economic value. Due to the extremely high concentrations of chloride in highly saline oilfield waters, it is difficult to achieve baseline electrophoretic separation necessary for accurate quantitation. By using a capillary with a noncovalently bound bilayer coating using Polybrene, a cationic polymer and sodium dodecyl sulfate (SDS), an anionic surfactant and a buffer consisting of 50 mM TRIS, 30 mM SDS, 5% methanol and 26 mM chromium trioxide (CrO3) at pH 6.7, baseline separation (Rs > 1.5) of chloride and sulfate was achieved. To mimic possible oilfield water samples, model water solutions of 5%, 10%, 15% and 20% chloride containing low ppm sulfate were prepared and successfully analysed using the method developed. In addition, the method was applied to determine chloride and sulfate anions in highly saline oilfield water samples. The accuracy of the method developed was verified by analysing NIST certified standards of chloride and sulfate. The results obtained for chloride and sulfate with the indirect CE-UV method were in close agreement (94–100% accuracy; <2.5% relative standard deviations) with those of the certified standard analysed by ion chromatography.

Comparison of fatty acids in beef tissues from conventional, organic and natural feeding systems in western Canada

Turner, T. D., Jensen, J., Pilfold, J. L., Prema, D., Donkor, K. K., Cinel, B., Thompson, D. J., Dugan, M. E. R. and Church, J. S. 2015. Comparison of fatty acids in beef tissues from conventional, organic and natural feeding systems in western Canada. Can. J. Anim. Sci. 95: 49-58. The effect of production system on intramuscular and associated trim fatty acid (FA) profiles of retail ribeye steaks from conventional and niche market organic and natural (grain- or grass-fed) beef were compared. Meat from organic grain- and grass-fed systems was leaner, containing greater proportions of polyunsaturated FA, i.e., 18:3n-3, 20:5n-3, 22:5n-3, 22:6n-3. Correspondingly, the n-6/n-3 ratios of organic grain- and grass-fed systems were 3:1, while conventional and natural grain systems had ratios of 8:1. High forage-to-grain ratio production systems increased proportions of desirable biohydrogenation intermediates (BI), including t11-18:1 and c9,t11-18:2, whereas conventional and natural grain systems elevated t10-18:1. Trim fat was similarly affected by production system, and was a relatively richer source of BI. Overall, proportions of desirable FAs, including n-3 and BI, were greater for organic grain- and grass-fed systems, emphasizing the importance of a high forage-to-grain ratio to enhance the healthfulness of beef, whereas conventional and natural grain-fed systems were largely equivalent.

Rapid determination of n-6 and n-3 fatty acid ratios in cereal grains and forages by 1H NMR spectroscopy

Abstract: Herein we describe a new method to rapidly determine the n-6/n-3 fatty acid ratios in cereal grains and forages (hydroponically-grown cereal sprouts and haylage) using 1H nuclear magnetic resonance (NMR) spectroscopy. This NMR method was found to be consistent with more established but time-consuming gas chromatographic methods (R = 0.994).