Brendan J. Holland

Screening of cannabinoids in industrial-grade hemp using two-dimensional liquid chromatography coupled with acidic potassium permanganate chemiluminescence detection

Widely known for its recreational use, the cannabis plant also has the potential to act as an antibacterial agent in the medicinal field. The analysis of cannabis plants/products in both pharmacological and forensic studies often requires the separation of compounds of interest and/or accurate identification of the whole cannabinoid profile. In order to provide a complete separation and detection of cannabinoids, a new two-dimensional liquid chromatography method has been developed using acidic potassium permanganate chemiluminescence detection, which has been shown to be selective for cannabinoids. This was carried out using a Luna 100 Å CN column and a Poroshell 120 EC-C18 column in the first and second dimensions, respectively. The method has utilized a large amount of the available separation space with a spreading angle of 48.4° and a correlation of 0.66 allowing the determination of more than 120 constituents and mass spectral identification of ten cannabinoids in a single analytical run. The method has the potential to improve research involved in the characterization of sensitive, complex matrices.

Chemiluminescence detection of cannabinoids and related compounds with acidic potassium permanganate

This is the first report of chemiluminescence from the reaction of cannabinoids with acidic potassium permanganate, which we have applied to the high performance liquid chromatography (HPLC) determination of cannabidiol (CBD) in industrial-grade hemp. The intensities of the light-producing reactions with two commercially available cannabinoid standards were compared to that of seven model phenolic analytes. Resorcinol, representing the parent phenolic moiety of the cannabinoid class, was shown to react with the permanganate reagents in a manner more similar to phenol than to its hydroxyphenol positional isomers, pyrocatechol and hydroquinone. Alkyl substituents on the phenolic ring, however, have a considerable impact on emission intensity that is dependent upon the position of the groups and the composition of the permanganate reagent. This analytical approach has potential for the determination of other cannabinoids including Δ(9) -tetrahydrocannabinol in drug-grade cannabis.

Electro-catalytic biodiesel production from canola oil in methanolic and ethanolic solutions with low-cost stainless steel and hybrid ion-exchange resin grafted electrodes

Biodiesel is a growing alternative to petroleum fuels and is produced by the catalysed transesterification of fats in presence of an alcohol base. Transesterification processes using homogeneous catalysts are considered to be amongst the most efficient methods but rely on the feedstock quality and low water content in order to avoid undesirable saponification reactions. In this work, the electro-catalytic conversion of canola oil to biodiesel in a 1% aqueous methanolic and ethanolic reaction mixture was performed without the addition of external catalyst or co-solvent. An inexpensive stainless steel electrode and a hybrid stainless steel electrode coated with an ion-exchange resin catalyst were used as cathode materials while the anode was composed of a plain carbon paper. The cell voltages were varied from 10 to 40 V and the reaction temperature maintained at 20 or 40°C. The canola oil conversion rates were found to be superior at 40°C without saponification reactions for cell voltages below 30 V. The conversion rates were as high as 87% for the hybrid electrode and 81% for the plain stainless steel electrode. This work could inspire new process development for the conversion of high water content feedstock for the production of second-generation biodiesel.

The importance of chain length for the polyphosphate enhancement of acidic potassium permanganate chemiluminescence

Sodium polyphosphate is commonly used to enhance chemiluminescence reactions with acidic potassium permanganate through a dual enhancement mechanism, but commercially available polyphosphates vary greatly in composition. We have examined the influence of polyphosphate composition and concentration on both the dual enhancement mechanism of chemiluminescence intensity and the stability of the reagent under analytically useful conditions. The average chain length (n) provides a convenient characterisation, but materials with similar values can exhibit markedly different distributions of phosphate oligomers. There is a minimum polyphosphate chain length (∼6) required for a large enhancement of the emission intensity, but no further advantage was obtained using polyphosphate materials with much longer average chain lengths. Providing there is a sufficient average chain length, the optimum concentration of polyphosphate is dependent on the analyte and in some cases, may be lower than the quantities previously used in routine detection. However, the concentration of polyphosphate should not be lowered in permanganate reagents that have been partially reduced to form high concentrations of the key manganese(III) co-reactant, as this intermediate needs to be stabilised to prevent formation of insoluble manganese(IV).

Overcoming solvent mismatch limitations in 2D-HPLC with temperature programming of isocratic mobile phases

This work describes a method for two-dimensional high performance liquid chromatography (2D-HPLC) that uses an isocratic mobile phase with a temperature gradient in the first dimension. Temperature programming was used to manipulate solvent elution strength in place of a mobile phase concentration gradient. This ensured that all eluent fractions transferred into the second dimension were of an identical solvent composition, i.e. the second dimension injection solvent did not increase during the course of the analysis. When applied to a complex natural product extract of coffee, the separation was completed in 35 min and had an orthogonality of 35% (calculated using the bins method) and a spreading angle of 52° as determined via a geometric approach to factor analysis. This approach, incorporating a temperature gradient in the first dimension, compared favourably to previously reported 2D-HPLC separations of coffee, with similar or shorter analysis times.

Coacervation Technique as an Encapsulation and Delivery Tool for Hydrophobic Biofunctional Compounds

Abstract Coacervation between proteins and other polymers such as polyphosphates and polysaccharides is of interest for both research and industrial applications due to the increasing demands of the consumers for the food products prepared using natural ingredients. Consequently, coacervation technology has been investigated and used for the stabilization of susceptible biofunctional food ingredients against oxidation and/or degradation, with the benefit of masking undesired flavors and enhancing their controlled-release behavior. Compared with spray drying which is the most widely used microencapsulation technique, complex coacervation has advantages including high encapsulation efficiency (up to 99%), high loading of the “core” material (>50%) and significantly improved controlled-release characteristics. This chapter focuses on the utilization of coacervation techniques for encapsulating and stabilizing various oxidatively unstable biofunctional food ingredients. Discussion will center upon factors affecting the entire preparation of microencapsulation products, from the design of the delivery system, selection of the appropriate “shell” material to the crosslinking of the encapsulant. Characterization of the final microcapsules and applications of coacervation technology in the food industry will also be discussed.

Effects of Different Pretreatments to Fresh Fruit on Chemical and Thermal Characteristics of Crude Palm Oil

This study selected 5 methods, including boiling, hot air drying, high-pressurized steam, freezing, and microwave radiation to pretreat fresh oil palm fruit before solvent extraction of the oil. Using fresh fruit as a control, the pretreatment methods were compared for the effects on the activity of the 2 main enzymes in the fruit and some physicochemical properties of the crude palm oil. The results indicated, although all the 5 pretreatments could inactivate lipase and peroxidase in the treated flesh significantly (P < 0.05), the high-pressurized steam was the most effective. There were also differences in the unsaturated fatty acid contents of the 6 oils. The crude oil from frozen fruit contained significantly more vitamin E (37829.33 ppm) than previously reported. Microwave radiation was shown to significantly decrease the free fatty acid content and the peroxide value, while increasing the oxidative stability index. Thermal behaviors of the oils were significantly different to each other with the exception a few parameters (P < 0.05).

Bioprocessing of plant-derived bioactive phenolic compounds

This chapter describes the bioprocessing, health, and biotechnological applications of plant-derived polyphenolic compounds. Isolation of these compounds from plants and their by-products using conventional and greener emerging technologies, including sample preparation techniques, is highlighted. Routinely applied techniques for the quantitative and qualitative analysis of plant-based phenolics are reviewed. Also highlighted are emerging technologies and recent trends in the use of in silico “omic” techniques to aid screening and extraction of bioactive phenolic compounds from plants. We also include a discussion of the health-promoting bioactivity of plant-derived polyphenols and their incorporation into food products for human consumption.