Electrocatalytic Poly(3,4-ethylenedioxythiophene) for Electrochemical Conversion of 5-Hydroxymethylfurfural.

This study investigates the utilization of the conductive polymer poly(3,4-ethylenedioxythiophene) (PEDOT) as a catalytic material for the 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA). PEDOT films doped with different counterions were electrodeposited on graphite foil. In particular, the mobile anion perchlorate and the polymeric ionomers polystyrenesulfonate, Nafion, and Aquivion were used. The electrocatalytic properties of PEDOT films were evaluated toward the TEMPO redox mediator in the absence and the presence of HMF as a substrate for oxidation reactions. The electrocatalytic HMF oxidation was confirmed to occur at PEDOT electrodes, and it was also found that the chemical nature of PEDOT counterions controls the electrocatalytic conversion of HMF by modulating the kinetics of the electrochemical generation of the oxoammonium cation TEMPO(+). Potentiostatic electrolysis experiments showed that both the reference graphite electrode and PEDOT substrates were able to convert HMF to FDCA with an 80% faradaic efficiency (FE) and a >90% yield (FDCA), but, compared to graphite, the complete conversion of HMF to FDCA required a ca. 30% shorter time when using PEDOT electrodes doped with perchlorate or Aquivion, thanks to their ability to sustain a higher current density in the initial phase of the electrolysis. In addition, while all PEDOT films were chemically stable under the electrochemical conditions herein described, only PEDOT films doped with Aquivion were also mechanically robust and stable against delamination. Thus, the new PEDOT/Aquivion composite may represent the best choice for the implementation of PEDOT-based electrodes in TEMPO-mediated electrocatalytic applications.

Sustainable cannabinoids purification through twin-column recycling chromatography and green solvents.

In the present study, twin-column recycling chromatography has been employed for the purification of a Cannabis extract by using a green solvent, ethanol, as the mobile phase. In particular, the complete removal of the psychoactive tetrahydrocannabinol (THC) from a Cannabis extract rich in cannabidiol (CBD) was achieved under continuous conditions. The performance of the method, in terms of compound purity, recovery, productivity and solvent consumption, was compared to that of traditional batch operations showing the potential of the twin-column recycling approach. The employment of a theoretical model to predict the band profiles of the two compounds during the recycling process has facilitated method development, thus further contributing to process sustainability by avoiding trial and error attempts or at least decreasing the number of steps significantly.

Enhancing the purification of crocin-I from saffron through the combination of multicolumn countercurrent chromatography and green solvents.

Crocin-I, a valuable natural compound found in saffron (Crocus sativus L.), is the most abundant among the various crocin structures. Developing a cost-effective and scalable purification process to produce high-purity crocin-I is of great interest for future investigations into its biological properties and its potential applications in the treatment of neurological disorders. However purifying crocin-I through single-column preparative chromatography (batch) poses a yield-purity trade-off due to structural similarities among crocins, meaning that the choice of the collection window sacrifices either yield in benefit of higher purity or vice versa. This study demonstrates how the continuous countercurrent operating mode resolves this dilemma. Herein, a twin-column MCSGP (multicolumn countercurrent solvent gradient purification) process was employed to purify crocin-I. This study involved an environmentally friendly ethanolic extraction of saffron stigma, followed by an investigation into the stability of the crocin-I within the feed under varying storage conditions to ensure a stable feed composition during the purification. Then, the batch purification process was initially designed, optimized, and subsequently followed by the scale-up to the MCSGP process. To ensure a fair comparison, both processes were evaluated under similar conditions (e.g., similar total column volume). The results showed that, at a purity grade of 99.7%, the MCSGP technique demonstrated significant results, namely + 334% increase in recovery + 307% increase in productivity, and - 92% reduction in solvent consumption. To make the purification process even greener, the only organic solvent employed was ethanol, without the addition of any additive. In conclusion, this study presents the MCSGP as a reliable, simple, and economical technique for purifying crocin-I from saffron extract, demonstrating for the first time that it can be effectively applied as a powerful approach for process intensification in the purification of natural products from complex matrices.

Novel insights into the dependence of adsorption-desorption kinetics on particle geometry in chiral chromatography.

The existence of slow adsorption-desorption kinetics in chiral liquid chromatography is common knowledge. This may significantly contribute to worsening the efficiency and kinetic performance of a chromatographic run, especially when high flow rates are employed. Many attempts and protocols have been proposed to access this term, the so-called c ads , but they are based on different (theoretical) assumptions. As a consequence, no official method is available for the estimation of the adsorption-desorption kinetics term. In this work, a novel approach to access c ads is presented. This procedure combines experimental results obtained with kinetic and thermodynamic measurements. The investigations have been performed on two zwitterionic teicoplanin chiral stationary phases (CSPs) based on 1.9 µ m fully porous and 2.0 µ m superficially porous particles (FPPs and SPPs), using Z-D,L-Methionine as probe molecule. Kinetic studies have been performed through the combination of both stop-flow and dynamic measurements, while adsorption isotherms have been calculated through Inverse Method. This study has confirmed that, on both particle formats, analyte diffusion on the surface of the particle is negligible, meaning that adsorption is localized, and it has been demonstrated that adsorption-desorption kinetics is strongly dependent on particle geometry and, in particular, on the loading of chiral selector. These findings are fundamental not only to unravel novel aspects of the complex enantiorecognition mechanism but also to optimize the employment of CSPs for ultra-fast and preparative applications.

The influence of drying and storage conditions on the volatilome and cannabinoid content of Cannabis sativa L. inflorescences.

The increasing interest in hemp and cannabis poses new questions about the influence of drying and storage conditions on the overall aroma and cannabinoids profile of these products. Cannabis inflorescences are subjected to drying shortly after harvest and then to storage in different containers. These steps may cause a process of rapid deterioration with consequent changes in precious secondary metabolite content, negatively impacting on the product quality and potency. In this context, in this work, the investigation of the effects of freeze vs tray drying and three storage conditions on the preservation of cannabis compounds has been performed. A multi-trait approach, combining both solid-phase microextraction (SPME) two-dimensional gas chromatography coupled to mass spectrometry (SPME-GC × GC-MS) and high-performance liquid chromatography (HPLC), is presented for the first time. This approach has permitted to obtain the detailed characterisation of the whole cannabis matrix in terms of volatile compounds and cannabinoids. Moreover, multivariate statistical analyses were performed on the obtained data, helping to show that freeze drying conditions is useful to preserve cannabinoid content, preventing decarboxylation of acid cannabinoids, but leads to a loss of volatile compounds which are responsible for the cannabis aroma. Furthermore, among storage conditions, storage in glass bottle seems more beneficial for the retention of the initial VOC profile compared to open to air dry tray and closed high-density polyethylene box. However, the glass bottle storage condition causes formation of neutral cannabinoids at the expenses of the highly priced acid forms. This work will contribute to help define optimal storage conditions useful to produce highly valuable and high-quality products.

miRNAs as Biomolecular Markers for Food Safety, Quality, and Traceability in Poultry Meat-A Preliminary Study.

In this study, the expression and abundance of two candidate chicken (Gallus gallus; gga) microRNAs (miRNAs, miR), gga-miR-21-5p (miR-21) and gga-miR-126-5p (miR-126), have been analyzed in order to identify biomarkers for the traceability and quality of poultry meat. Two breeds of broiler chickens were tested: the most common Ross308 (fast-growing) and the high-quality Ranger Gold (slow-growing). A preliminary analysis of the two miRNAs expressions was conducted across various tissues (liver, lung, spleen, skeletal muscle, and kidney), and the three tissues (lung, spleen, and muscle) with a higher expression were chosen for further analysis. Using quantitative reverse transcription polymerase chain reaction (RT-qPCR), the expression of miRNAs in the three tissues of a total of thirteen animals was determined. The results indicate that miR-126 could be a promising biomarker for the lung tissue in the Ranger Gold (RG) breed (p < 0.01), thus suggesting a potential applicability for tracing hybrids. RG exhibits a significantly higher miR-126 expression in the lung tissue compared to the Ross308 broilers (R308), an indication of greater respiratory capacity and, consequently, a higher oxidative metabolism of the fast-growing hybrid. During sampling, two R308 broilers presented some anomalies, including airsacculitis, hepatic steatosis, and enlarged spleen. The expression of miR-126 and miR-21 was compared in healthy animals and in those presenting anomalies. Chickens with airsacculitis and hepatic steatosis showed an up-regulation of miR-21 and miR-126 in the most commercially valuable tissue, the skeletal muscle or breast (p < 0.05).

Understanding the Transition from High-Selective to High-Efficient Chiral Separations by Changing the Organic Modifier with Zwitterionic-Teicoplanin Chiral Stationary Phase.

The retention behavior of small molecules and N-protected amino acids on a zwitterionic teicoplanin chiral stationary phase (CSP), prepared on superficially porous particles (SPPs) of 2.0 µm particle diameter, has shown that efficiency and enantioselectivity, and so enantioresolution, dramatically change depending on the employed organic modifier. In particular, it was found that while methanol permits the boost of enantioselectivity and resolution of the amino acids, at the cost of efficiency, acetonitrile allows for the ability to reach extraordinary efficiency even at high flow rates (with reduced plate height <2 and up to 300,000 plates/m at the optimum flow rate). To understand these features, an approach based on the investigation of mass transfer through the CSP, the estimation of the binding constants of amino acids on the CSP, and the assessment of compositional properties of the interfacial region between bulk mobile phase and solid surface has been adopted.

Development and validation of a GC × GC-ToFMS method for the quantification of pesticides in environmental waters.

Water is a fundamental resource for living things, which is why its control is necessary. The widespread use of pesticides for agricultural and non-agricultural purposes has resulted in the presence of their residues in surface water and groundwater resources. Their presence in water is regulated through different directives, such as the Groundwater Directive, the Drinking Water Directive, and the Water Framework Directive, modified later several times, setting a maximum concentration of 0.1 µg.L-1 for individual pesticides and their degradation products, and 0.5 µg.L-1 for total pesticide residues present in a sample. There are different kinds of pesticides (e.g., organophosphorus and organochlorine pesticides, triazines, chloroacetamides, triazoles, (thio)carbamates) that have diverse chemical structures. Their determination and monitoring in a single analytical procedure are possible through multiresidue methods. In this study, 53 pesticides belonging to different chemical classes and their metabolites were selected based on their local occurrence and investigated in surface water and groundwater from agricultural areas susceptible to pesticide contamination. The methodology consisted of a classical solid-phase extraction (SPE) for the purification and enrichment of the pesticides, with a subsequent analysis in multidimensional gas chromatography coupled to mass spectrometry (GC×GC-MS). The quantification method was validated according to the Eurachem Guide in terms of linearity, precision, accuracy, limit of detection, and limit of quantification. After validation, the method was applied to 34 real-world water samples, and the results were compared with those obtained by a GC-QMS routine method.

The contribution of high-resolution GC separations in plastic recycling research.

One convenient strategy to reduce environmental impact and pollution involves the reuse and revalorization of waste produced by modern society. Nowadays, global plastic production has reached 367 million tons per year and because of their durable nature, their recycling is fundamental for the achievement of the circular economy objective. In closing the loop of plastics, advanced recycling, i.e., the breakdown of plastics into their building blocks and their transformation into valuable secondary raw materials, is a promising management option for post-consumer plastic waste. The most valuable product from advanced recycling is a fluid hydrocarbon stream (or pyrolysis oil) which represents the feedstock for further refinement and processing into new plastics. In this context, gas chromatography is currently playing an important role since it is being used to study the pyrolysis oils, as well as any organic contaminants, and it can be considered a high-resolution separation technique, able to provide the molecular composition of such complex samples. This information significantly helps to tailor the pyrolysis process to produce high-quality feedstocks. In addition, the detection of contaminants (i.e., heteroatom-containing compounds) is crucial to avoid catalytic deterioration and to implement and design further purification processes. The current review highlights the importance of molecular characterization of waste stream products, and particularly the pyrolysis oils obtained from waste plastics. An overview of relevant applications published recently will be provided, and the potential of comprehensive two-dimensional gas chromatography, which represents the natural evolution of gas chromatography into a higher-resolution technique, will be underlined.

Investigating the effect of polarity of stationary and mobile phases on retention of cannabinoids in normal phase liquid chromatography.

This work reports about a screening of four adsorbents with different polarity employed for the separation of the main phytocannabinoids contained in Cannabis sativa L., under normal phase liquid chromatography (NPLC). The effect of polarity and type of interaction mechanisms of the adsorbents (namely Si-, CN-, Diol-, and NH2-based SPs) on retention has been investigated under a variety of conditions either by using different combinations of apolar solvents (heptane or hexane) and alcohols (ethanol or isopropanol). The columns have also been employed for the separation of a real cannabis sample. Graphical Abstract Investigating the effect of polarity of stationary and mobile phases on retention of cannabinoids in normal phase liquid chromatography.

Therapeutic Potential of Allicin and Aged Garlic Extract in Alzheimer's Disease.

Garlic, Allium sativum, has long been utilized for a number of medicinal purposes around the world, and its medical benefits have been well documented. The health benefits of garlic likely arise from a wide variety of components, possibly working synergistically. Garlic and garlic extracts, especially aged garlic extracts (AGEs), are rich in bioactive compounds, with potent anti-inflammatory, antioxidant and neuroprotective activities. In light of these effects, garlic and its components have been examined in experimental models of Alzheimer's disease (AD), the most common form of dementia without therapy, and a growing health concern in aging societies. With the aim of offering an updated overview, this paper reviews the chemical composition, metabolism and bioavailability of garlic bioactive compounds. In addition, it provides an overview of signaling mechanisms triggered by garlic derivatives, with a focus on allicin and AGE, to improve learning and memory.

Downstream Processing of Therapeutic Peptides by Means of Preparative Liquid Chromatography.

The market of biomolecules with therapeutic scopes, including peptides, is continuously expanding. The interest towards this class of pharmaceuticals is stimulated by the broad range of bioactivities that peptides can trigger in the human body. The main production methods to obtain peptides are enzymatic hydrolysis, microbial fermentation, recombinant approach and, especially, chemical synthesis. None of these methods, however, produce exclusively the target product. Other species represent impurities that, for safety and pharmaceutical quality reasons, must be removed. The remarkable production volumes of peptide mixtures have generated a strong interest towards the purification procedures, particularly due to their relevant impact on the manufacturing costs. The purification method of choice is mainly preparative liquid chromatography, because of its flexibility, which allows one to choose case-by-case the experimental conditions that most suitably fit that particular purification problem. Different modes of chromatography that can cover almost every separation case are reviewed in this article. Additionally, an outlook to a very recent continuous chromatographic process (namely Multicolumn Countercurrent Solvent Gradient Purification, MCSGP) and future perspectives regarding purification strategies will be considered at the end of this review.

Modern trends in downstream processing of biotherapeutics through continuous chromatography: The potential of Multicolumn Countercurrent Solvent Gradient Purification.

Single-column (batch) preparative chromatography is the technique of choice for purification of biotherapeutics but it is often characterized by an intrinsic limitation in terms of yield-purity trade-off, especially for separations containing a larger number of product-related impurities. This drawback can be alleviated by employing multicolumn continuous chromatography. Among the different methods working in continuous mode, in this paper we will focus in particular on Multicolumn Countercurrent Solvent Gradient Purification (MCSGP) which has been specifically designed for challenging separations of target biomolecules from their product-related impurities. The improvements come from the automatic internal recycling of the impure fractions inside the chromatographic system, which results in an increased yield without compromising the purity of the pool. In this article, steps of the manufacturing process of biopharmaceuticals will be described, as well as the advantages of continuous chromatography over batch processes, by particularly focusing on MCSGP.

Investigation of mass transfer properties and kinetic performance of high-efficiency columns packed with C18 sub-2 µm fully and superficially porous particles.

Three columns packed with 2.0 µm superficially porous particles, 1.7 µm fully porous particles, and monodisperse 1.9 µm fully porous particles with narrow particle size distribution have been deeply characterized from a kinetic point of view. The 1.9 µm column showed excellent kinetic performance, comparable to that of the superficially porous one. These two columns also exhibit flatter c-branches of the van Deemter curve compared to the 1.7 µm fully porous particles column, resulting in smaller loss of efficiency when they are operated at higher flow rates than the optimal ones. The independent evaluation of each contribution to band broadening has revealed that the difference in kinetic performance comes from the very small eddy dispersion contribution on the 1.9 µm column, surprisingly even lower than that of the superficially porous one. This finding suggests a very good packing of the monodisperse 1.9 µm column. On the other hand, the potential of 1.7 µm fully porous particles is completely broken down by the strong frictional heating effect already arising at relatively low flow rates.

High-Silica Zeolites as Sorbent Media for Adsorption and Pre-Concentration of Pharmaceuticals in Aqueous Solutions.

The present work focused on the use of high-silica commercial zeolites as sorbent media for pharmaceuticals in an aqueous matrix. As drug probes, ketoprofen, hydrochlorothiazide, and atenolol were selected, because of their occurrence in surface waters and effluents from wastewater treatment plants. Pharmaceuticals adsorption was evaluated for two Faujasite topology zeolites with Silica/Alumina Ratio 30 and 200. The selected zeolites were demonstrated to be efficient sorbents towards all investigated pharmaceuticals, thanks to their high saturation capacities (from 12 to 32% w/w) and binding constants. These results were corroborated by thermal and structural analyses, which revealed that adsorption occurred inside zeolite's porosities, causing lattice modifications. Finally, zeolites have been tested as a pre-concentration media in the dispersive-solid phase extraction procedure. Recoveries higher than 95% were gained for ketoprofen and hydrochlorothiazide and approximately 85% for atenolol, at conditions that promoted the dissolution of the neutral solute into a phase mainly organic. The results were obtained by using a short contact time (5 min) and reduced volume of extraction (500 µL), without halogenated solvents. These appealing features make the proposed procedure a cost and time saving method for sample enrichment as well as for the regeneration of exhausted sorbent, rather than the more energetically expensive thermal treatment.

Unmatched Kinetic Performance in Enantioselective Supercritical Fluid Chromatography by Combining Latest Generation Whelk-O1 Chiral Stationary Phases with a Low-Dispersion in-House Modified Equipment.

This proof-of-concept work investigates the ultimate kinetic limits reachable in chiral supercritical fluid chromatography (SFC) with modern columns and advanced technological solutions. A commercial equipment (Waters Acquity UPC2) has been in-house modified to minimize its overall extra-column variance through a series of technical adjustments including low-volume connecting tubings, reduced-volume flow cell, an in-house made external column oven, external low-dispersion injection system, and electronic temperature controller. Compared to the original (as-shipped) configuration, the extra-column variance on the low-dispersion equipment was reduced by more than 97%, from about 85 to slightly more than 2 µL2 (measured at 2.0 mL/min). This was mainly achieved thanks to the occurrence of fully developed turbulent regime with a proper selection of capillary i.d. at significantly smaller flow rates (1.5-4 mL/min; CO2/methanol 80/20, v/v; 35 °C; back pressure regulator (BPR), 105 bar) than in entry-1 configuration. Ultrahigh efficiency columns of different geometries in-house packed with latest generation sub-2 µm UHPC-FPP-Whelk-O1 Chiral Stationary Phase (CSP) have been employed under sub- and supercritical fluid conditions. By carefully modulating the length and the internal diameter of connecting tubings in the function of column geometry, state of the art efficiencies (estimated in roughly 300 000 theoretical plates/m with reduced HETP of roughly 1.85) have been obtained on 4.6 mm i.d. chiral columns. Remarkably, for 3.0 mm × 100 mm (i.d. × length) columns, the efficiency gain on the fully modified SFC system (compared to an instrumental configuration where only the standard injector was replaced by the low-dispersion one) was greater than 90% for compounds with a retention factor of 1 and as large as 25% for retention factors of 2.5.

Formation of Supramolecular Clusters at the Interface of Zeolite X Following the Adsorption of Rare-Earth Cations and Their Impact on the Macroscopic Properties of the Zeolite.

The adsorption behavior of neodymium (Nd3+ ) and yttrium (Y3+ ) cations on synthetic FAU zeolite X in its sodium form (NaX) has been investigated by means of macroscopic (adsorption isotherm determination and thermal analysis) and microscopic measurements (including solid-state NMR spectroscopy and X-ray powder diffraction). The multidisciplinary study reveals some unexpected features. Firstly, adsorption constants of cations are not correlated to their ionic radii or hydration enthalpy. The adsorption constant of Y3+ on NaX was indeed about twice that of Nd3+ , which is the opposite of what could be expected based on the size of the cations. In addition, adsorption was accompanied by partial dealumination of the zeolite framework. The extent of dealumination changed depending on the exchanged cations, with the extent being more significant on the Nd-exchanged zeolite than on the Y-exchanged one. The most interesting finding of this study, however, is the presence of supramolecular clusters composed of water, Nd3+ , residual sodium ions, and extra-framework aluminum at the interface of Nd-exchanged zeolite. The hypothesis that these host-guest complexes are responsible of the significantly different behavior exhibited by NaX towards the adsorption/desorption of Nd3+ and Y3+ has been formulated.

New frontiers and cutting edge applications in ultra high performance liquid chromatography through latest generation superficially porous particles with particular emphasis to the field of chiral separations.

About ten years after their introduction to the market (happened in 2006), the so-called second generation superficially porous particles (SPPs) have undoubtedly become the benchmark as well as, very often, the preferred choice for many applications in liquid chromatography (LC), when high efficiency and fast separations are required. This trend has interested practically all kinds of separations, with the only exception of chiral chromatography (at least so far). The technology of production of base SPPs is advanced, relatively simple and widely available. The deep investigation of mass transfer mechanisms under reversed-phase (RP) and normal-phase (NP) conditions for achiral separations has shown the advantages in the use of these particles over their fully porous counterparts. In addition, it has been demonstrated that SPPs are extremely suitable for the preparation of efficient packed beds through slurry packing techniques. However, the research in this field is in continual evolution. In this article, some of the most advanced concepts and modern applications based on the use of SPPs, embracing in particular ultrafast chiral chromatography and the design of SPPs with engineered pore structures or very reduced particle diameter, are revised. We describe modern trends in these fields and focus on those aspect where further innovation and research will be required. Graphical Abstract Word cloud of cutting edge applications of superficially porous particles in liquid chromatography.