Efficient Capture of Cannabis Terpenes in Olive Oil during Microwave-Assisted Cannabinoid Decarboxylation.

The development of selective extraction protocols for Cannabis-inflorescence constituents is still a significant challenge. The characteristic Cannabis fragrance can be mainly ascribed to monoterpenes, sesquiterpenes and oxygenated terpenoids. This work investigates the entrapment of Cannabis terpenes in olive oil from inflorescences via stripping under mild vacuum during the rapid microwave-assisted decarboxylation of cannabinoids (MW, 120 °C, 30 min) and after subsequent extraction of cannabinoids (60 and 100 °C). The profiles of the volatiles collected in the oil samples before and after the extraction step were evaluated using static headspace solid-phase microextraction (HS-SPME), followed by gas chromatography coupled to mass spectrometry (GC-MS). Between the three fractions obtained, the first shows the highest volatile content (~37,400 mg/kg oil), with α-pinene, ß-pinene, ß-myrcene, limonene and trans-ß-caryophyllene as the main components. The MW-assisted extraction at 60 and 100 °C of inflorescences using the collected oil fractions allowed an increase of 70% and 86% of total terpene content, respectively. Considering the initial terpene amount of 91,324.7 ± 2774.4 mg/kg dry inflorescences, the percentage of recovery after decarboxylation was close to 58% (mainly monoterpenes), while it reached nearly 100% (including sesquiterpenes) after extraction. The selective and efficient extraction of volatile compounds, while avoiding direct contact between the matrix and extraction solvents, paves the way for specific applications in various aromatic plants. In this context, aromatized extracts can be employed to create innovative Cannabis-based products within the hemp processing industry, as well as in perfumery, cosmetics, dietary supplements, food, and the pharmaceutical industry.

Semi-industrial ultrasound-assisted extraction of grape-seed proteins.

BACKGROUND: To manage industrial waste in accordance with the circular bioeconomy concept it is sometimes necessary to handle grape seeds, an abundant by-product of the wine-making process. This study presents a process based on ultrasound technology for the extraction of grape-seed proteins, due to their nutritional and techno-functional properties. The protein content of extracts obtained under silent and lab-scale conditions was compared with that obtained under semi-industrial ultrasound conditions, and the chemical composition (carbohydrates, total phenols, and lipids) and the elemental profiles of the final, up-scaled downstream extracts were characterized. RESULTS: This work found that the maximum amount of protein in the final product was 378.31 g.kg-1 of the extract. Chemical characterization revealed that each 1 kg of extract had an average content of 326.19 g gallic acid equivalent as total phenols, 162.57 g glucose equivalent as carbohydrates, and 382.76 g of lipophilic compounds. Furthermore, when the extract was checked for hazardous elements, none were found in levels that could be considered a risk for human health. CONCLUSION: The proposed semi-industrial strategy has the potential to contribute greatly to the valorization of grape seeds through the preparation of a protein-rich extract that can be used as an alternative to synthetic wine stabilizers and for the development of novel food and nutraceutical products. © 2024 Society of Chemical Industry.

Valorisation of By-Products from Soybean (Glycine max (L.) Merr.) Processing.

In recent years, increased awareness of the health benefits associated with consuming soy-based foods, knowledge of milk-related allergies and a move towards more sustainable food production have led to an increase in the number of available soy-based products. The biggest producers in the world, the USA, South America and China, are from the Pacific region. This enormous production is accompanied by the accumulation of related by-products, in particular, a substance that is known as okara. Okara is a paste that is rich in fibre (50%), protein (25%), fat (10%), vitamins and trace elements. Its proper use would lead to economic advantages and a reduction in the potential for polluting the environment. Its high fibre content and low production costs mean that it could also be used as a dietary supplement to prevent diabetes, obesity and hyperlipidaemia. Chemical or enzymatic treatment, fermentation, extrusion, high pressure and micronisation can all increase the soluble fibre content, and thus improve nutritional quality and processing properties. However, the product also degrades rapidly due to its high moisture content (70-80%), which makes it difficult to handle and expensive to dry by conventional means. The aim of this paper is therefore to thoroughly study the existing literature on this subject in order to develop a general protocol for okara exploitation and valorisation. A cost/benefit analysis could drive the design of eco-friendly, sustainable protocols for the preparation of high-value nutritional products.

Technology and Process Design for Phenols Recovery from Industrial Chicory (Chicorium intybus) Leftovers.

Vegetal leftovers from the agro-food industry represent a huge source of primary and secondary metabolites, vitamin, mineral salts and soluble as well as insoluble fibers. Economic reports on the growth in the polyphenol market have driven us to focus our investigation on chicory (Chicorium intybus L.), which is one of the most popular horticultural plants in the world and a rich source of phenolic compounds. Ultrasound-assisted extraction (UAE), microwave-assisted extraction (MAE) and their simultaneous combination, using either ethanol/water or water alone (also sub-critical), have been investigated with the aim of designing a green and efficient extraction process. Higher total-polyphenol yields as well as dramatic reductions in extraction times and solvent consumption have been obtained under these conditions. ANOVA test for analyses of variance followed by the Tukey honestly significant difference (HSD) post-hoc test of multiple comparisons was used in the statistical analysis. MAE experiments performed with sub-critical water, and MW/US experiments with an ethanol solution have shown polyphenol recovery values of up to ~3 g of gallic acid equivalents (GAE) per kg of fresh material in only 15 min, while conventional extraction required 240 min to obtain the same result.

Antiproliferative, Proapoptotic, Antioxidant and Antimicrobial Effects of Sinapis nigra L. and Sinapis alba L. Extracts.

High Brassicaceae consumption reduces the risk of developing several cancer types, probably due to high levels of glucosinolates. Extracts from Sinapis nigra L. (S. nigra) and Sinapis alba L. (S. alba) have been obtained from leaves and seeds under different conditions using ethanol/water mixtures because their glucosinolates are well accepted by the food industry. The EtOH/H2O 8:2 mixture gives better yields in glucosinolate amounts from ground seeds, mainly, sinalbin in S. alba and sinigrin in S. nigra. The highest antiproliferative activity in both non-tumor and tumor cell lines was induced by S. alba seeds extract. To evaluate whether the effect of Sinapis species (spp) was only due to glucosinolate content or whether it was influenced by the extracts' complexity, cells were treated with extracts or glucosinolates, in the presence of myrosinase. Pure sinigrin did not modify cell proliferation, while pure sinalbin was less effective than the extract. The addition of myrosinase increased the antiproliferative effects of the S. nigra extract and sinigrin. Antiproliferative activity was correlated to Mitogen-Activated Protein Kinases modulation, which was cell and extract-dependent. Cell-cycle analysis evidenced a proapoptotic effect of S. alba on both tumor cell lines and of S. nigra only on HCT 116. Both extracts showed good antimicrobial activity in disc diffusion tests and on ready-to-eat fresh salad. These results underline the potential effects of Sinapis spp in chemoprevention and food preservation.

The unveiling of a dynamic duo: hydrodynamic cavitation and cold plasma for the degradation of furosemide in wastewater.

The degradation in water of furosemide (FUR), a widely used diuretic drug, was herein reported. The method entails an integrated approach based on the hybridisation of hydrodynamic cavitation (HC) with electrical discharge (ED) plasma technology. This dynamic duo could increase the production of oxidising compounds in water, in particular hydroxyl radicals (OH radicals), by triggering the rapid homolytic decomposition of water molecules and avoiding the addition of external oxidants. This study clearly emphasises the effectiveness of an integrated approach to improve the degradation of pollutants in wastewater originating from active pharmaceutical ingredients (APIs). The results of HC/ED-assisted FUR degradation in the presence of radical scavengers highlight the predominant role of the radical oxidation mechanism at the gas-liquid interface of the cavitation bubble during HC/ED treatment. A comparative analysis of the three technologies-HC alone, HC/ED and UV alone-emphasised the promising potential of hybrid HC/ED as a scalable industrial technology. This is demonstrated by the higher degradation rates (100%, 10 min) when treating large volumes (5L) of wastewater contaminated with FUR (50 mg/L), even in the presence of other APIs.

Industrial Multiple-Effect Fractional Condensation under Vacuum for the Recovery of Hop Terpene Fractions in Water.

The inflorescences of Humulus lupulus L. are the most valuable ingredient in the brewing industry. Only female cones are used as their bitterness and aroma, much associated with beer, are granted by the production of resins and essential oils, respectively. The traditional brewing process for the extraction of the organic volatiles in hops is called dry hopping. It consists of extended maceration at low temperature after the fermentation phase. New extraction technologies can improve extraction rates and product quality while saving time and money. This article proves that multiple-effect fractional condensation under a vacuum is suitable for flavouring applications and especially for performing dry hopping without contamination risks and reductions in hop amounts. This technique leads to the recovery of aqueous aromatic fractions that are very rich in hop sesquiterpenes and monoterpenes. These suspensions are extremely stable when stored at 5-8 °C and avoid degradation even after several months. This feature is crucial for the marketing of non-alcoholic beverages, where the dilution of essential oils is otherwise problematic.

Determination of trace antibiotics in water and milk via preconcentration and cleanup using activated carbons.

CPAC-SPE-HPLC (coconut powdered activated carbon -SPE- HPLC) has been developed for the determination of antibiotic (ABX), sulfamonomethoxine sodium (SMM), oxytetracycline (OTC), ceftiofur hydrochloride (CEF) and marbofloxacin (MAR), in water and milk. Over 99.0% SMM and OTC were recovered from 20 mL of 0.5 µg/mL ABX solution using 10 mg-CPAC for adsorption and 2 mL of 30% NH4OH/EtOH (1/19 v/v) for elution. Similarly, over 99.0% CEF and MAR were recovered using 15 mg-CPAC and 2 mL of 30% NH4OH/n-PrOH (1/19 v/v). Moreover, the recovery efficiencies of various ABX from 5 to 80 mL of 0.02-2.00 µg/mL medicated milk containing 10 mM EDTA are ordered as follows: OTC (99.3%), SMM (99.1%) > CEF (68.9%) > MAR (61.4%). No interference towards HPLC analysis were observed with elution using 2 mL of 30% NH4OH/EtOH (1/19 v/v). Furthermore, much lower limit of detections (0.02 µg/mL) than the maximum residual limits from European Commission (0.075-0.100 µg/mL) were obtained.

Combined Ultrasound and Pulsed Electric Fields in Continuous-Flow Industrial Olive-Oil Production.

The aim of the present study is to develop a new industrial process for the continuous-flow extraction of virgin olive oil (VOO) using the non-thermal ultrasound (US) and pulsed electric field (PEF) treatments. These technologies have been tested both separately and in combination, with the aim of making the malaxation step unnecessary. The ultrasound-assisted extraction (UAE) and PEF treatments are both effective technologies for VOO production and have been well documented in the literature. The present study combines a new continuous-flow set-up, with four US units and PEF treatment. The industrial-plant prototype is able to improve VOO yields, thanks to powerful non-thermal physical effects (acoustic cavitation and electroporation), from 16.3% up to 18.1%. Moreover, these technologies increased the content of nutritionally relevant minor components, which, in turn, improves VOO quality and its commercial value (overall tocopherols and tocotrienols improved from 271 mg/kg under the conventional process to 314 mg/kg under the US process). The combined UAE and US-PEF process also increased the extraction yield, while overcoming the need for kneading in the malaxation step and saving process water (up to 1512 L per working day). Continuous-flow US and PEF technologies may be a significant innovation for the VOO industry, with benefits both for oil millers and consumers. The VOO obtained via non-thermal continuous-flow production can satisfy the current trend towards healthier nutrient-enriched products.

Batch and Flow Ultrasound-Assisted Extraction of Grape Stalks: Process Intensification Design up to a Multi-Kilo Scale.

Nowadays, approximately 1 billion kg/y of grape stalks, with a remarkable polyphenols content, are produced worldwide. In this paper, the extraction process intensification of polyphenols in water was achieved under ultrasound-assisted recovery, focusing on kinetics and scaling-up factors. Immersion and cup-horn systems were exploited as acoustic cavitation sources, and the total phenolic content (TPC) was chosen to assess the process efficiency. The kinetics were evaluated by Peleg's hyperbolic model, and the effect of both the initial feedstock granulometry and ultrasound size-reduction were determined. The results were compared with conventional extraction methods (data analysis by ANOVA). The best polyphenols yield was obtained after 45 min of sonication, giving between 29.71 and 31.89 mg/g (gallic acid equivalents over the dry matter). The extracts were characterized using HPLC-DAD, UPLC-ESI-MS/MS, DPPH• assay (2,2-diphenyl-1-picrylhydrazyl), TEAC assay (Trolox equivalent antioxidant capacity), and proanthocyanidin content determination. The flow-mode extraction procedure of grape stalks (2 kg) was carried out in a 15 L reactor. A semi-industrial decanter unit and a bag-filter were the keys units of the downstream operations. The resulting particle-free solution underwent nanofiltration on a membrane pilot skid, providing a final polyphenols-enriched stream concentrated up to 355.91%, as shown by the antioxidant activity and TPC.

Analytical dataset of Ecuadorian cocoa shells and beans.

Full analytical data of Ecuadorian cocoa wastes (raw shells) and beans (as benchmark), are herein reported. A detailed characterization of production residues may pave the road to a zero-waste strategy for the cocoa industry. Multiple analytical techniques have been exploited to define the composition of the matrices, among them: elemental analyses, FTIR, Py-GC/MS/FID and UHPLC-ESI-MS/MS. Quali-quantitative data of carbohydrates, lipids, lignin, polyphenols, alkaloids and proteins have been obtained by Py-GC/MS/FID and UHPLC-ESI-MS/MS. Assignations are fully supported by literature references. The FAMEs composition of lipophilic UAE extract is also reported for sake of comparison with cocoa butter. This data collection completes a wider valorization work, "Cocoa bean shell waste valorisation; extraction from lab to pilot-scale cavitational reactors" (Grillo et al., 2018).

Cocoa bean shell waste valorisation; extraction from lab to pilot-scale cavitational reactors.

The use of zero-waste processes to integrate food-waste valorisation into the circular economy equation is currently one of the hottest topics in sustainability research. This goal is still far from being fully achieved despite the release of a number of patents and papers that deal with the topic. The present work aims to valorise cocoa shells, one of the main by-product of the roasting process, in order to enhance the effective extraction of high added value compounds by means of green protocols. The high potential added value of the residual waste has been demonstrated via a direct analytical comparison of extracts and bean composition. A range of raw matrix extraction procedures have been investigated in order to define the best solvent and technology; ultrasound (US) and hydrodynamic cavitation (HC) were compared with conventional methods. The high-energy microenvironments generated by cavitation substantially promote fast biomass deconstruction with low energy consumption. The optimized protocol couples a HC reactor with a ternary water/ethanol/hexane mixture, simultaneously providing a hydrophilic product, which is rich in methylxanthines and polyphenols, and a lipid layer. Sequential milling and sieving pretreatment provided an enriched shell fraction via the partial removal of husk fibres (54.45 vs. 81.36 w/w % total fibres). The disposal of the latter reduces mass balance, but is rerouted into animal feedstock components and crop mulching. The protocols herein reported produce valuable extracts, which are rich in antioxidant flavanols (catechins and epicatechins), theobromine (32.7 ±â€¯0.12 mg/g shells), caffeine (1.76 ±â€¯0.08 mg/g shells) and cocoa butter, in a simple and easy manner. This new valorisation process afforded 20.5 w/w % and 15.8 w/w % hydrophilic and lipophilic fractions, respectively, when scaled up to function in a pilot flow reactor. The fatty acids, obtained in remarkable yield (forming the 96.4 w/w % of the total light part) well match the commercial cocoa butter profile. The antioxidant extract shows an impressive total phenolic content of 197.4 mg/g extract (gallic acid eq.), with a radical scavenging activity of 62.0 ±â€¯3.1 µg/mL (expressed in DPPH EC50). This work should facilitate industrial design for the convenient recovery of cocoa by-products as part of a zero-waste strategy.

Improved extraction of vegetable oils under high-intensity ultrasound and/or microwaves.

Ultrasound-assisted extraction (UAE) and microwave-assisted extraction (MAE) techniques have been employed as complementary techniques to extract oils from vegetable sources, viz, soybean germ and a cultivated marine microalga rich in docosahexaenoic acid (DHA). Ultrasound (US) devices developed by ourselves, working at several frequencies (19, 25, 40 and 300 kHz), were used for US-based protocols, while a multimode microwave (MW) oven (operating with both open and closed vessels) was used for MAE. Combined treatments were also studied, such as simultaneous double sonication (at 19 and 25 kHz) and simultaneous US/MW irradiation, achieved by inserting a non-metallic horn in a MW oven. Extraction times and yields were compared with those resulting from conventional procedures. With soybean germ the best yield was obtained with a 'cavitating tube' prototype (19 kHz, 80 W), featuring a thin titanium cylinder instead of a conventional horn. Double sonication, carried out by inserting an immersion horn (25 kHz) in the same tube, improved the yield only slightly but halved the extraction time. Almost comparable yields were achieved by closed-vessel MAE and simultaneous US/MW irradiation. Compared with conventional methods, extraction times were reduced by up to 10-fold and yields increased by 50-500%. In the case of marine microalgae, UAE worked best, as the disruption by US of the tough algal cell wall considerably improved the extraction yield from 4.8% in soxhlet to 25.9%. Our results indicate that US and MW, either alone or combined, can greatly improve the extraction of bioactive substances, achieving higher efficiency and shorter reaction times at low or moderate costs, with minimal added toxicity.

Preparation of second generation ionic liquids by efficient solvent-free alkylation of N-heterocycles with chloroalkanes.

Non-conventional techniques, such as microwave (MW) and power ultrasound (US) as well as combined MW/US irradiation, have been used to promote one-pot synthesis of second-generation ionic liquids (ILs), cutting down reaction times and improving yields. However, the use of chloroalkanes in the alkylation of N-heterocycles requires more drastic conditions if results are to match those obtained with more reactive alkyl halides. The present paper describes a series of MW- or MW/US-promoted IL preparations starting from chloroalkanes and classic heterocycles (1-methylimidazole, pyridine and 1-methylpyrrolidine). When reactions were carried out under conventional heating in an oil bath they required longer reaction times and gave poorer yields. (1)H-NMR analysis and ion-exchange chromatography showed that the present solventless procedure afforded ILs of satisfactory purity. The observed high yields (usually 70-98% isolated), and short reaction times showed that a straightforward access to ILs can be also achieved with the use of alkyl chlorides, resulting in a considerable reduction of costs.

Effects of ultrasonic and hydrodynamic cavitation on the treatment of cork wastewater by flocculation and Fenton processes.

This paper reports that ultrasonic (US) and hydrodynamic cavitation (HC) are efficient strategies for the environmental remediation of cork wastewater (CW). It is necessary to remove toxic, inhibitory or refractory organic matter from CW using physical and chemical techniques (pre-treatment) prior to performing conventional biological treatment. After this biological treatment, it is also critical to further decontaminate (post-treatment) in order to meet the discharge limitation. The pre-treatment of diluted CW using Fenton oxidation (FE) alone led to COD and polyphenol (PP) removal values of 30% and 61%, respectively, while HC and US resulted in 83-90% increases in COD reduction and 26-33% increases in PP reduction. Whereas 55% and 91% COD and PP removal were achieved using flocculation (Floc) alone, COD elimination was increased by a further 7-18% under HC and US. No noticeable improvement in PP elimination was observed. US did not enhance the Floc decontamination of the original concentrated CW, however, considerable quantities of white biofilm were surprisingly generated on the CW surface after the pre-treatment, thus indicating the improvement of biodegradability of the resulting liquid. In fact, the post-treatment stage, using FE alone after having filtered the biofilms, led to reductions of 53% in COD and 90% in PP. The HC and US protocols resulted in 26-34% increases in COD elimination. HC further enhanced PP elimination caused by FE, while US resulted in lower levels of PP elimination.

Regio- and stereoselective reductions of dehydrocholic acid.

Dehydrocholic acid (DHCA), an unnatural bile acid, is manufactured by oxidation of cholic acid. Its biotransformation by two basidiomycetes (Trametes hirsuta and Collybia velutipes) is reported. These mycelia showed different affinities for the substrate and selectivities of attack: T. hirsuta in particular regio- and stereoselectively reduced the 3-keto group to yield 3 alpha-hydroxy-7,12-diketo-5 beta-cholan-24-oic acid (7,12-diketolithocolic acid) as the main product. A number of different chemical reductions were carried out on DHCA; among them hydrogenation with Raney Nickel in water under high-intensity ultrasound proved highly regio- and stereoselective, yielding 7,12-diketolithocolic acid exclusively. (1)H and (13)C resonances were assigned in details thanks to a series of 1D and 2D NMR runs including DEPT, NOESY, H-H COSY, gHSQC and gHMBC.

Chemical modifications of bile acids under high-intensity ultrasound or microwave irradiation.

High-intensity ultrasound (HIU) and microwave (MW) irradiation, having emerged as effective promoters of organic reactions, were exploited for the synthesis of bile acids derivatives. Esterification, amidation, hydrolysis, oxidation, and reduction were investigated. Compared to conventional methods, both techniques proved much more efficient, increasing product yields and dramatically cutting down reaction times. Scaled-up studies are now under way.

Efficient H2O2/CH3COOH oxidative desulfurization/denitrification of liquid fuels in sonochemical flow-reactors.

The oxidative desulfurization/denitrification of liquid fuels has been widely investigated as an alternative or complement to common catalytic hydrorefining. In this process, all oxidation reactions occur in the heterogeneous phase (the oil and the polar phase containing the oxidant) and therefore the optimization of mass and heat transfer is of crucial importance to enhancing the oxidation rate. This goal can be achieved by performing the reaction in suitable ultrasound (US) reactors. In fact, flow and loop US reactors stand out above classic batch US reactors thanks to their greater efficiency and flexibility as well as lower energy consumption. This paper describes an efficient sonochemical oxidation with H2O2/CH3COOH at flow rates ranging from 60 to 800 ml/min of both a model compound, dibenzotiophene (DBT), and of a mild hydro-treated diesel feedstock. Four different commercially available US loop reactors (single and multi-probe) were tested, two of which were developed in the authors' laboratory. Full DBT oxidation and efficient diesel feedstock desulfurization/denitrification were observed after the separation of the polar oxidized S/N-containing compounds (S≤5 ppmw, N≤1 ppmw). Our studies confirm that high-throughput US applications benefit greatly from flow-reactors.

Alkyne-azide click reaction catalyzed by metallic copper under ultrasound.

This protocol is for the ultrasound (US)-assisted 1,3-dipolar cycloaddition reaction of azides and alkynes using metallic copper (Cu) as the catalyst. The azido group is a willing participant in this kind of organic reaction and its coupling with alkynes is substantially improved in the presence of Cu(I). This protocol does not require additional ligands and proceeds with excellent yields. The Cu-catalyzed azide-alkyne cycloaddition (CuAAC) is generally recognized as the most striking example of 'click chemistry'. Reactions involving metals represent the favorite domain of sonochemistry because US favors mechanical depassivation and enhances both mass transfer and electron transfer from the metal to the organic acceptor. The reaction rate increases still further when simultaneous US and microwave irradiation are applied. The US-assisted click synthesis has been applied for the preparation of a wide range of 1,4-disubstituted 1,2,3-triazole derivatives starting both from small molecules and oligomers such as cyclodextrins (CDs). Using this efficient and greener protocol, all the adducts can be synthesized in 2-4 h (including work-up and excluding characterization). Click chemistry has been shown to be able to directly link chemistry to biology, thus becoming a true interdisciplinary reaction with extremely wide applicability.