Rationalising the retro-Diels-Alder fragmentation pattern of viscutins using electrospray interface-tandem mass spectrometry coupled to theoretical modelling.

RATIONALE: Although mass spectrometry (MS) is a powerful tool in structural elucidation of unknown flavonoids based on their unique fragmentation patterns, proposing the correct fragmentation mechanism is still a challenge from tandem mass spectrometry data only. In recent years, computational tools such as molecular networking and MS2LDA have played a major role in the identification of structurally related compounds through an in-depth survey of their fragmentation patterns. METHODS: Therefore, in this study, three viscutin molecules in Viscum combreticola Engl. crude extracts were characterised using ultra-high-performance liquid chromatography-quadrupole-time-of-flight tandem mass spectrometry and MS2LDA, a computational tool. Ion-trap mass spectrometry and density functional theoretical modelling were used as confirmatory tools to rationalise the unique fragmentation patterns observed for these molecules. RESULTS: Here, MS2LDA revealed the presence of a unique Mass2Motif in all the three viscutin molecules at m/z 137, which was confirmed to be a 1,3 A- RDA (retro-Diels-Alder) fragmentation product using liquid chromatography-ion-trap mass spectrometry and density functional theoretical modelling. Moreover, MS2LDA proved to be useful in differentiating this spectral feature that was specific to viscutin molecules in the presence of other isobaric ions at m/z 137 occurring in compounds in other molecular families. CONCLUSION: Therefore, the results of the current study showed that computational tools such as MS2LDA are essential in uncovering some gas-phase fragmentation reactions of molecules in MS and that theoretical modelling is a powerful tool in rationalising these reactions in metabolite identification.

Biosorption of toxic metal ions (Cr+6, Cd2+) and nutrients (PO43-) from aqueous solution by diatom biomass.

This paper evaluates diatom biomass as a biosorbent for removing Cr+6, Cd2+, and PO43- ions from water. The diatom was characterized by X-ray Diffraction (XRD), Fourier Transform Infrared (FTIR), and Scanning Electron Microscopy (SEM-EDS) for its crystallinity, functional groups, and morphology. A batch sorption study was conducted to evaluate the parameters influencing Cr+6, Cd2+, and PO43- ions adsorption, and the mechanisms were explored. The FTIR spectra revealed Si-O, O-H, N-H, and C-O as the main functional groups present on the surface of the adsorbent. The SEM showed a rough and irregular-shaped morphology, while the EDS indicated that the diatom biomass is an aluminosilicate material. The rate-limiting steps for Cr+6 and Cd2+ were pseudo-first order, and pseudo-second order sorption favored PO43- based on their R2 values. Moreover, the dominant adsorption model that best described the equilibrium data was the Freundlich isotherm. The maximum adsorption capacities obtained for Cr+6 was 5.66 (mg/g), and Cd2+ was 5.27 (mg/g) at 313 K while PO43- was 19.13 (mg/g) at 298 K. The thermodynamic data revealed that the reaction was endothermic for Cd2+ and exothermic for Cr+6 and PO43-, respectively. Diatom biomass was observed to be a promising bio-sorbent for removing Cr6+, Cd2+ and PO42- from wastewater.

Evaluation of a Chaotrope and Kosmotrope in the Multivariate Optimization of PHW-ATPE of Solasodine from Leaves of Solanum mauritianum.

A hyphenated pressurized hot water­aqueous two-phase extraction (PHW-ATPE) method was applied to extract solasodine from Solanum mauritianum (S. mauritianum). A central composite design (CCD) was applied to determine the optimal conditions for the extraction of solasodine. The parameters evaluated included the percentage concentration of salt (NaCl or Na2CO3) and temperature. The fit of the central composite design response surface model for PHW-ATPE to the data generated a model with a good quadratic fit (R2 = 0.901). The statistically significant (p < 0.05) parameters, such as the linear and quadratic effects of the concentration of salt (%) powder, had a significant impact on the extraction of solasodine. The application of multiply charged salts such as Na2CO3 (kosmotrope) was shown to be a comparably better extractant of solasodine than NaCl (chaotrope) due to the salting-out effect. The optimized conditions for extraction of solasodine with NaCl or Na2CO3 were a temperature of 80 °C at a salt concentration of 20%. The maximum extraction of solasodine was 300.79 mg kg−1 and 162.34 mg kg−1 for Na2CO3 and NaCl, respectively.

Effectiveness of wetlands to phytoremediate zinc, lead and chromium.

This study was conducted to assess the levels of zinc, chromium and lead in the Mvudi River, located in Thohoyandou in the Limpopo Province, South Africa. Enlighten with the recent developments of plant species as remediates, plants were sampled for this study to assess their phytoremediation efficiency. The surface water and plant samples were collected before, within and after a wetland near a cement brick making factory. The samples were analyzed to determine the concentration of zinc, lead and chromium. The results showed that zinc was the most concentrated metal in plants and water reaching a concentration levels of up to 4.52 mg kg-1 in the leaves of Bidens pilosa and 0.77 mg L-1 within the wetland. Chromium and lead were easily absorbed by the roots of the plants as showed by the significant decrease in concentration while moving into the wetland. The highest concentrations of chromium in plants was 0.41 mg kg-1 in Xanthium strumarium (stem). The amounts of zinc, chromium and lead in plants samples were found to be higher as compared to that of water samples and this shows that plants were absorbing large amounts of metals. Novelty Statement: Several studies that have been conducted in Mvudi River focused primarily on analyzing heavy metals in water. The aim of the present study was to assess the effectiveness of selected wetland plants as remediates of heavy metals contaminating Mvudi River in Thohoyandou, South Africa. This was done by measuring the concentration of heavy metals of selected plants before, within and after the wetland area. If high level of heavy metals in the Mvudi River are not remediated, this will affect the quality of potable water and pose serious health effect to the people. This investigation exhibited an important role the wetland plants play of accumulating heavy metals in contaminated water.

Response Surface Optimization of Oil Removal Using Synthesized Polypyrrole-Silica Polymer Composite.

The severity of oil pollution, brought about by improper management, increases daily with an increase in the exploration and usage of oil, especially with an increase in industrialization. Conventional oil treatment methods are either expensive or time consuming, hence the need for new technologies. The aim of this research is to synthesize polypyrrole-modified silica for the treatment of oily wastewater. Pyrrole was copolymerized with silica in the presence of ferric chloride hexahydrate by adding 23 mL of 117.4 g/dm3 ferric chloride hexahydrate drop wise to a silica-pyrrole mixture (1:2.3). The mixture was stirred for 24 h, filtered and dried at 60 °C for 24 h. The composite was then characterized using FTIR and SEM/EDX. A central composite model was developed in design expert software to describe the efficiency of oil removal using the polypyrrole-modified silica under the influence of initial oil concentration, adsorbent dosage and contact time. The synthesized adsorbent had FTIR bands at 3000-3500 cm-1 (due to the N-H), 1034 cm-1 (attributed to the Si-O of silica), 1607 cm-1 and 1615 cm-1 (due to the stretching vibration of C=C of pyrrole ring). The adsorption capacity values predicted by the central composite model were in good agreement with the actual experimental values, indicating that the model can be used to optimize the removal of oil from oily wastewater in the presence of polypyrrole-modified silica. The adsorbent showed excellent oil uptake when compared with similar materials. The optimum conditions for oil removal were 7091 mg/L oil concentration, 0.004 g adsorbent dosage and contact time of 16 h. Under these conditions, the percentage of oil adsorption was 99.3% and adsorption capacity was 8451 mg/g. As a result of the low optimum dosage and the lack of agitation, the material was found to be applicable in the remediation of field wastewater.

Green pre-concentration techniques during pesticide analysis in food samples.

The ever-increasing demand for determining pesticides at low concentration levels in different food matrices requires a preliminary step of pre-concentration which is considered a crucial stage. Recently, the parameter of "greenness" during sample pre-concentration of pesticides in food matrices is as important as selectivity in order to avoid using harmful organic solvents during sample preparation. Developing new green pre-concentration techniques is one of the key subjects. Thus, to reduce the impact on the environment during trace analysis of pesticides in food matrices, new developments in pre-concentration have gone in three separate directions: the search for more environmentally friendly solvents, miniaturization and development of solvent-free pre-concentration techniques. Eco-friendly solvents such as supercritical fluids, ionic liquids and natural deep eutectic solvents have been developed for use as extraction solvents during pre-concentration of pesticides in food matrices. Also, miniaturized pre-concentration techniques such as QuEChERS, dispersive liquid-liquid micro-extraction and hollow-fiber liquid-phase micro-extraction have been used during trace analysis of pesticides in food samples as well as solvent-free techniques such as solid-phase micro-extraction and stir bar sorptive extraction. All these developments which are aimed at ensuring that pesticide pre-concentration in different food matrices is green are critically reviewed in this paper.

Status of pharmaceuticals in African water bodies: Occurrence, removal and analytical methods.

In this review paper, the milestones and challenges that have been achieved and experienced by African Environmental Scientists regarding the assessment of water pollution caused by the presence of pharmaceutical compounds in water bodies are highlighted. The identification and quantification of pharmaceuticals in the African water bodies is important to the general public at large due to the lack of information. The consumption of pharmaceuticals to promote human health is usually followed by excretion of these drugs via urine or fecal matter due to their slight transformation in the human metabolism. Therefore, large amounts of pharmaceuticals are being discharged continuously from wastewater treatment plants into African rivers due to inefficiency of employed sewage treatment processes. Large portions of African communities do not even have proper sanitation systems which results in direct contamination of water resources with human waste that contains pharmaceutical constituents among other pollutants. Therefore, this article provides the overview of the recent studies published, mostly from 2012 to 2016, that have focused on the occurrence of different classes of pharmaceuticals in African aqueous systems. Also, the current analytical methods that are being used in Africa for pharmaceutical quantification in environmental waters are highlighted. African Scientists have started to investigate the materials and remediation processes for the elimination of pharmaceuticals from water.

Investigation of As(V) removal from acid mine drainage by iron (hydr) oxide modified zeolite.

In this work, the synthesis of iron (hydr) oxide modified zeolite was achieved through precipitation of iron on the zeolite. The structure and surface morphology of iron (hydr) oxide modified zeolite (IHOMZ) was studied by scanning electron microscopy (SEM), coupled with an energy-dispersive X-ray spectroscopy (EDX), and Fourier transform infrared (FT-IR) spectra. The efficiency of IHOMZ was then investigated through batch technique for the extraction of As(V) from mine waste water. The optimum parameters for maximum As(V) adsorption were: an initial As(V) concentration (10 mg L-1), adsorbent dosage (3.0 g), contact time (90 min) and temperature (53 °C). The initial pH of the solution had no compelling effect on As(V) adsorption by IHOMZ. However, adsorption capacity was significantly affected by the solution temperature with 53 °C registering the maximum removal efficiency. The thermodynamic parameters: Entropy (ΔS° = 0.00815 kJ (K mol)-1), variation of the Gibbs free energy (ΔG°) and enthalpy (ΔH° = 9.392 kJ mol-1) of As(V) adsorption onto IHOMZ system signified a non-spontaneous and endothermic process. It was noted that Freundlich isotherm model exhibited a better fit to the equilibrium experimental data, implying that the adsorption process occurred on a heterogeneous surface. The kinetic data from As(V) adsorption experiments was depicted by the pseudo-second-order kinetic model (R2 > 0.999), suggesting a chemisorption adsorption process. The experimental batch equilibrium results indicated that IHOMZ could be used as an effective sorbent for As(V) ion extraction from acid mine drainage.

Sorption of uranium(VI) onto hydrous ferric oxide-modified zeolite: Assessment of the effect of pH, contact time, temperature, selected cations and anions on sorbent interactions.

Zeolites are commonly used as adsorbents for metal removal in most applications e.g. in wastewater. However, the ubiquity of iron in such systems may, in the long-term, distort the true interactions and mechanisms of contaminant removal as a result of modification of the zeolite surface. In this study, this potential phenomenon was assessed for the removal of uranium(VI) from aqueous solution by hydrous ferric oxide-modified zeolite (HFOMZ). This was prepared by precipitating iron hydroxide (the common precipitate of iron in aqueous systems) onto zeolite. The prepared HFOMZ was characterised by the scanning electron microscope (SEM), and Fourier transform infrared spectroscopy (FTIR). Batch adsorption experiments were performed to assess the effect of: pH, initial uranium(VI) concentration, adsorbent dosage, contact time, temperature, presence of cations (Pb2+, Cr3+, Cu2+, Mn2+ and Co2+) and anions ( [Formula: see text] , [Formula: see text] and [Formula: see text] ) on the adsorption of uranium(VI). Kinetic studies under these conditions indicated that the pseudo second-order kinetic model (R2 > 0.99) best described the adsorption behaviour, implying that this could be proceeding through a chemisorption process. The experimental data was best described by the Freundlich isotherm model (R2 > 0.93), an implication that the adsorption surface was heterogeneous. The thermodynamic parameters calculated from the experimental data suggested that the adsorption of U(VI) onto HFOMZ was spontaneous and exothermic in nature. The adsorption of U(VI) onto HFOMZ was dominated by complexation with strong ionizable hydroxyl sites on the hydrous ferric oxide surfaces and the edge sites of the zeolite. At pH values from 2 to 6, increased adsorption was observed and this decreased at higher pH values (above 6). This corresponded with the changes in speciation as determined by the PHREEQC modelling code. The presence of the cations (Pb2+, Cr3+, Cu2+, Mn2+ and Co2+) and anions ( [Formula: see text] and [Formula: see text] ) resulted in a significant decrease in the adsorption capacity of U(VI) by HFOMZ, implying that in a system where these anions and cations are present in high concentrations over time, U(VI) will adsorb less onto the material.

Miniaturized pipette-tip-based electrospun polyacrylonitrile nanofibers for the micro-solid-phase extraction of nitro-based explosive compounds.

In this study, a self-assembly of miniaturized pipette-tip-based solid-phase extraction for the simultaneous extraction of nitroaromatic compounds was developed, with electrospun polyacrylonitrile nanofibers used as sorbents. The electrospun polyacrylonitrile nanofibers were characterized by scanning electron microscopy, FTIR analysis and surface area analysis. Good linearities for the four nitroaromatic compounds (2,6-dinitrotoluene, 2-nitrotoluene, 3-nitrotoluene, and 4-nitrotoluene) were obtained in a range of 250-1000 µg/L with coefficients of determination > 0.99. The limits of detection of these analytes were between 21 and 38 µg/L. The results showed that the pipette-tip-based solid-phase extraction was effective in extracting nitrotoluenes in the pH regime of environmental interest (≈ 6). The investigation also revealed that the optimum mass of electrospun polyacrylonitrile nanofibers sorbent was 15 mg and 20 aspirating/dispensing cycles gave the maximum recovery of nitrotoluenes with 200 µL acetonitrile as the best eluting solvent. Moreover, the performance of the present method was studied for the extraction and determination of nitroaromatic compounds in real environmental water samples and good recoveries ranging from 70 to 115% were found, and respective relative standard deviations of <12% were obtained.

A Relook into the Flavonoid Chemical Space of Moringa oleifera Lam. Leaves through a Combination of LC-MS and Molecular Networking.

Moringa oleifera Lam. is a functional tree that is known to produce a variety of metabolites with purported pharmacological activities. It is frequently called the "miracle tree" due to its utilization in numerous nutraceutical and pharmacological contexts. This study was aimed at studying the chemical space of M. oleifera leaf extracts through molecular networking (MN), a tool that identifies metabolites by classifying them based on their MS-based fragmentation pattern similarities and signals. In this case, a special emphasis was placed on the flavonoid composition. The MN unraveled different molecular families such as flavonoids, carboxylic acids and derivatives, lignin glycosides, fatty acyls, and macrolactams that are found within the plant. In silico annotation tools such as network annotation propagation (NAP) and DEREPLICATOR, an unsupervised substructure identification tool (MS2LDA), and MolNet enhancer were also explored to further compliment the classic molecular networking output within the Global Natural Product Social (GNPS) site. In this study, common flavonoids found within Moringa oleifera were further annotated using MS2LDA. Utilizing computational tools allowed for the discovery of a wide range of structurally diverse flavonoid molecules within M. oleifera leaf extracts. The expansion of the flavonoid chemical repertoire in this plant arises from intricate glycosylation modifications, leading to the creation of structural isomers that manifest as isobaric ions during mass spectrometry (MS) analyses.

Advances in the application of chitosan-based metal organic frameworks as adsorbents for environmental remediation.

Chitosan is a bio-adsorbent with many amino and hydroxyl groups. The physicochemical properties of chitosan can be greatly enhanced by the formation of composites with other adsorbents. Thus, some researchers have incorporated metal-organic frameworks (MOFs) such as MIL (Materials Institute Lavoisier), UiO (University of Oslo), ZIF (Zeolitic Imidazolate Frameworks) and, HKUST (Hong Kong University of Science and Technology) series into the chitosan structure resulting in the formation of adsorbents with better adsorptive properties and mechanical stability. The advances in the application of these chitosan/MOF composites during the adsorption of environmental contaminants are the main aim of this current review. The review showed that composites of chitosan and MOFs are versatile adsorbents of a variety of environmental pollutants, and most of them can be easily regenerated and recycled. In addition, the challenges associated with the use of these composites and future prospects are explored in detail in this review.

Recyclable polysaccharide/stimuli-responsive polymer composites and their applications in water remediation.

The use of composites of stimuli-responsive polymers with polysaccharides during water remediation has gained impetus in recent years. The applications of composites of polysaccharides (chitosan, cellulose and cyclodextrin) with stimuli-responsive polymers (CO2-, thermo-, light-, and pH-responsive polymers) were reviewed in this paper. These smart composites have tuneable physicochemical properties that enable them to form tailor-made adsorbents for the adsorption of pollutants from water. Adsorption and desorption of pollutants can be switched on and off by adjusting appropriate stimuli without the use of toxic organic solvents. The polysaccharide/stimuli-responsive polymer-based adsorbents, therefore, can be easily recovered during water remediation by adjusting the stimuli, and this makes them to be eco-friendly and recyclable. These attributes of the polysaccharide/stimuli-responsive polymer-based composites were explored in detail in this review. In addition, the challenges associated with the use of these smart composites as well as their future prospects were also articulated in this paper.

Application of polysaccharide-based metal organic framework membranes in separation science.

Polysaccharide/MOF composite membranes have captured the interests of many researchers during decontamination of polluted environments. Their popularity can be attributed to the relatively high chemical and thermal stabilities of these composite membranes. Chitosan is among the polysaccharides extensively used during the synthesis of hybrid membranes with MOFs. The applications of chitosan/MOF composite membranes in separation science are explored in detail in this paper. Researchers have also synthesised mixed matrix membranes of MOFs with cellulose and cyclodextrin that have proved to be effective during separation of a variety of materials. The uses of cellulose/MOF and cyclodextrin/MOF membranes for the removal of environmental pollutants are discussed in this review. In addition, the challenges associated with the use of these mixed matrix membranes are explored in this current paper.

Diverse chemical modifications of the chlorogenic acid composition of Viscum combreticola Engl.: A premise for the state of readiness against excessive sunlight exposure.

Mistletoe plants that are positioned on the canopy of their hosts are more susceptible to UV radiation exposure. These aerial plants are resistant to damage by UV radiation due the presence of epidermal constituents such as the cuticle, cork layer, trichomes and antioxidant secondary metabolites. In response to the photo-oxidative stress associated with UV exposure, plants generally deploy photo-protective responsive mechanisms that involve the biosynthesis of UV absorbing phenolic compounds such as chlorogenic acids (CGAs). The hydroxycinnamic acid moieties of these CGAs are predominantly in the trans configuration, naturally. However, excessive sunlight exposure of plants containing these compounds can result in geometrical isomerisation, characterized by the formation of cis isomers. Therefore, in this study, the effect of UV light radiation on the CGA composition of Viscum combreticola Engl. (Santalacaeae) plants using an in vitro model was unravelled through UHPLC-q-TOF-MS-based metabolic profiling. Interestingly, the findings of this study revealed that this plant has a diverse chemical composition of CGAs that is characterized by epimerization, monoacylation, homodiacylation and heterodiacylation of the quinic acid (QA), thereby, contributing to the state of readiness in these plants against sunlight or UV exposure. In addition to the commonly reported cinnamoyl containing heterodiacylated CGAs, hydroxybenzoyl containing heterodiacylated CGAs were also reported in this study. Moreover, cis isomers (24 in total) of some CGAs were identified in the non-irradiated samples and the formation of these compounds has been reported to help plants in the mitigation of photo-oxidative stress. An additional 28 cis isomers of CGAs and HCA derivatives were observed in the UV-irradiated samples, hence, further increasing the complexity of the metabolome of this plant, with a total of 108 compounds identified in this study. The presence of epimers, positional and geometrical isomers of these compounds could be a biochemical strategy to maximize the chemical arsenal of this plant to withstand the photo-oxidative stress posed by UV radiation from the sunlight. Due to purported pharmacological properties associated with the identified compounds these parasitic plants can be a rich source of prospective therapeutic compounds that can be employed as drug discovery leads. Moreover, UV radiation might be essential in future to produce potent drugs since plants naturally produce these compounds in low quantities.

Switchable solvent-based micro-extraction of pesticides in food and environmental samples.

Switchable solvents are new generation solvents that are environmentally friendly and can be used for the effective pre-concentration of pesticide residues in food and environmental matrices. They have physico-chemical properties that can be switched abruptly and reversibly between two opposite forms. The common switchable solvents used commonly during pesticide pre-concentration involve polarity switch. Such solvent switch between hydrophobic and hydrophilic forms during pesticide pre-concentration. Secondary and tertiary amines are typical switchable hydrophilicity solvents. The amines are hydrophobic but they abruptly and reversibly switch to their hydrophilic forms on addition of CO2 to them. The application of amine-based switchable solvents during pre-concentration of pesticide residue in food and environmental samples are discussed in this paper. Medium-chain fatty acids can also be used as switchable solvents. Their switch between hydrophobic and hydrophilic forms is usually triggered by pH changes. Applications of fatty acid-based switchable solvents during pre-concentration of pesticide residues are reviewed in this paper. Switchable solvent-based micro-extraction can be combined with other pre-concentration techniques to enhance selectivity resulting in clean chromatograms. This paper has a section dedicated to the application of hyphenated switchable solvent-based micro-extraction techniques during pre-concentration of pesticides in food and environmental samples. In addition, the challenges associated with the use of switchable solvents during micro-extraction of pesticide residues are also discussed.

Supramolecular solvent-based micro-extraction of pesticides in food and environmental samples.

Supramolecular solvent-based micro-extraction is a very important green technique for the isolation and pre-concentration of pesticide residues in food and environmental samples prior to their chromatographic analysis. The attractive features of supramolecular solvent-based micro-extraction include its simplicity, high pre-concentration factor, fastness, accuracy, low cost, less consumption of chemical reagents and environmental friendliness. The supramolecular solvent is generated from a ternary mixture of amphiphiles, water and a water miscible dispersion and coacervating solvent. Tehydrofuran is one of the solvents commonly used as both a dispersion solvent and a coacervating agent. This paper gives a recent comprehensive review on the application of alkanols as amphiphiles during supramolecular solvent-based micro-extraction of pesticide residues in food and environmental samples. Other researchers used long chain fatty acids as amphiphiles during pesticide analysis in food and environmental samples using supramolecular solvent-based micro-extraction, and this is discussed in this paper. The incorporation of ferrofluids in supramolecular solvents enables phase separation using a magnet instead of the time-consuming centrifugation technique. This paper also gives a detailed review of the application of ferrofluid-based supramolecular solvent micro-extraction of pesticide residues in food and environmental samples.

Emerging green solvents and their applications during pesticide analysis in food and environmental samples.

Green solvents reduce secondary pollution of the environment during pesticide pre-concentration in food and environmental matrices. Ionic liquids are among the green solvents that are widely used during pesticides analysis. Their physico-chemical properties can be easily modified by changing the cation/anion combinations in their structures. This paper critically reviews the application of ionic liquids during pre-concentration of pesticides in food and environmental samples. Another group of green, designer solvents is composed of deep eutectic solvents. They are synthesised simply by mixing hydrogen bond donors and hydrogen bond acceptors. Their contributions during pesticide pre-concentration are reviewed critically in this paper. The use of supramolecular solvents during pesticide pre-concentration is gaining popularity among researchers. They are green, water-immiscible solvents composed of three-dimensional amphiphilic aggregates and their applications during pesticide pre-concentration are reviewed in this paper. The amount of chemicals used during pesticide analysis can be reduced by using switchable solvents. This paper also gives a critical review of the applications of switchable solvents during micro-extraction of pesticides in food and environmental samples. In addition, the challenges associated with the use of these green solvents are discussed in this review as well as the future prospects.

Deep eutectic solvent-based dispersive liquid-liquid micro-extraction of pesticides in food samples.

Deep eutectic solvents are versatile, green and new generation solvents that can be used during dispersive liquid-liquid micro-extraction techniques for pesticides. They have tunable physico-chemical properties that can be easily changed by varying the ratios of hydrogen bond donors and hydrogen bond acceptors in their structures. Deep eutectic solvents are non-flammable, chemically and thermally stable solvents with low vapour pressure. Thus, they have characteristics that are similar to those of ionic liquids. However, they have simpler synthetic procedures, less expensive and are more biodegradable than ionic liquids. One of the limitations of deep eutectic solvents is their toxicity to the environment but they are less toxic than ionic liquids. This paper gives a focused and comprehensive recent review on the applications of deep eutectic solvents during dispersive liquid-liquid micro-extraction of pesticides in food samples for the period starting from 2016 to 2020. Emphasis was placed on the modifications done to the deep eutectic solvent-based dispersive liquid-liquid micro-extraction techniques in order to enhance their greenness during pesticide pre-concentration in food samples. In addition, hyphenated dispersive liquid-liquid micro-extraction techniques were also reviewed and lastly, the paper outlined the challenges associated with the use of DESs during the DLLME techniques.

Advances in the development of biopolymeric adsorbents for the extraction of metabolites from nutraceuticals with emphasis on Solanaceae and subsequent pharmacological applications.

Biopolymers are renowned for their sustainable, biodegradable, biocompatible and most of them have antitoxic characteristics. These versatile naturally derived compounds include proteins, polynucleotides (RNA and DNA) and polysaccharides. Cellulose and chitosan are the most abundant polysaccharides. Proteins and polysaccharides have been applied as emulsifiers. Additional applications of proteins and polysaccharides include cosmetics, food and wastewater treatment for adsorption of dyes and pesticides. However, more interesting applications of biopolymers are emerging, such as use in transport systems for delivery of plant derived nutraceuticals to sites of inflammation, due to its inherent ability to immobilize different biological and chemical systems. This review aims to give a summary on new trends and complement what is already known in the development of polysaccharides and proteins as adsorbents of nutraceutical compounds. The application of polysaccharides/protein containing the adsorbed Solanum derived nutraceutical compounds for drug deliveryis also reviewed.