Unlocking the Potential of Hydrosols: Transforming Essential Oil Byproducts into Valuable Resources.

The global demand for sustainable and non-toxic alternatives across various industries is driving the exploration of naturally derived solutions. Hydrosols, also known as hydrolates, represent a promising yet underutilised byproduct of the extraction process of essential oils (EOs). These aqueous solutions contain a complex mixture of EO traces and water-soluble compounds and exhibit significant biological activity. To fully use these new solutions, it is necessary to understand how factors, such as distillation time and plant-to-water ratio, affect their chemical composition and biological activity. Such insights are crucial for the standardisation and quality control of hydrosols. Hydrosols have demonstrated noteworthy properties as natural antimicrobials, capable of preventing biofilm formation, and as antioxidants, mitigating oxidative stress. These characteristics position hydrosols as versatile ingredients for various applications, including biopesticides, preservatives, food additives, anti-browning agents, pharmaceutical antibiotics, cosmetic bioactives, and even anti-tumour agents in medical treatments. Understanding the underlying mechanisms of these activities is also essential for advancing their use. In this context, this review compiles and analyses the current literature on hydrosols' chemical and biological properties, highlighting their potential applications and envisioning future research directions. These developments are consistent with a circular bio-based economy, where an industrial byproduct derived from biological sources is repurposed for new applications.

Effect of photostimulation through red LED light radiation on natural fermentation of table olives: An innovative case study with Negrinha the Freixo variety.

In this study, for the first time, red LED light radiation was applied to the fermentation process of table olives using the Negrinha de Freixo variety. Photostimulation using LED light emission (630 ± 10 nm) is proposed to shorten and speed up this stage and reduce time to market. Several physical-chemical characteristics and microorganisms (total microbial count of mesophilic aerobic, molds, yeasts, and lactic acid bacteria) and their sequence during fermentation were monitored. The fermentation occurred for 122 days, with two irradiation periods for red LED light. The nutritional composition and sensory analysis were performed at the end of the process. Fermentation under red LED light increased the viable yeast and lactic acid bacteria (LAB) cell counts and decreased the total phenolics in olives. Even though significant differences were observed in some color parameters, the hue values were of the same order of magnitude and similar for both samples. Furthermore, the red LED light did not play a relevant change in the texture profile, preventing the softening of the fruit pulp. Similarly, LED light did not modify the existing type of microflora but increased species abundance, resulting in desirable properties and activities. The species identified were yeasts - Candida boidinii, Pichia membranifaciens, and Saccharomyces cerevisiae, and bacteria - Lactobacillus plantarum and Leuconostoc mesenteroides, being the fermentative process dominated by S. cerevisiae and L. plantarum. At the end of fermentation (122 days), the irradiated olives showed less bitterness and acidity, higher hardness, and lower negative sensory attributes than non-irradiated. Thus, the results of this study indicate that red LED light application can be an innovative technology for table olives production.

Disclosing the potential of Cupressus leylandii A.B. Jacks & Dallim, Eucalyptus globulus Labill., Aloysia citrodora Paláu, and Melissa officinalis L. hydrosols as eco-friendly antimicrobial agents.

Antimicrobial resistance is a major global health concern, threatening the effective prevention and treatment of infections caused by microorganisms. These factors boosted the study of safe and green alternatives, with hydrosols, the by-products of essential oils extraction, emerging as promising natural antimicrobial agents. In this context, four hydrosols obtained from Cupressus leylandii A.B. Jacks & Dallim, Eucalyptus globulus Labill., Aloysia citrodora Paláu and Melissa officinalis L. were studied. Their chemical composition comprises neral, geranial, 1,8-cineole, terpinen-4-ol, and oplopanonyl acetate, compounds with recognised antimicrobial activity. Concerning antimicrobial activity, significant differences were found using different hydrosol concentrations (10-20% v/v) in comparison to a control (without hydrosol), showing the potential of the tested hydrosols to inhibit the microbial growth of Escherichia coli, Staphylococcus aureus, and Candida albicans. A. citrodora hydrosol was the most effective one, inhibiting 90% of E. coli growth and 80% of C. albicans growth, for both hydrosol concentrations (p < 0.0001). With hydrosol concentration increase, it was possible to observe an improved antimicrobial activity with significant reductions (p < 0.0001). The findings of this work indicate the viability of reusing and valuing the hydrosols, encouraging the development of green applications for different fields (e.g., food, agriculture, pharmaceuticals, and cosmetics).

Pickering Emulsions Based in Inorganic Solid Particles: From Product Development to Food Applications.

Pickering emulsions (PEs) have attracted attention in different fields, such as food, pharmaceuticals and cosmetics, mainly due to their good physical stability. PEs are a promising strategy to develop functional products since the particles' oil and water phases can act as carriers of active compounds, providing multiple combinations potentiating synergistic effects. Moreover, they can answer the sustainable and green chemistry issues arising from using conventional emulsifier-based systems. In this context, this review focuses on the applicability of safe inorganic solid particles as emulsion stabilisers, discussing the main stabilisation mechanisms of oil-water interfaces. In particular, it provides evidence for hydroxyapatite (HAp) particles as Pickering stabilisers, discussing the latest advances. The main technologies used to produce PEs are also presented. From an industrial perspective, an effort was made to list new productive technologies at the laboratory scale and discuss their feasibility for scale-up. Finally, the advantages and potential applications of PEs in the food industry are also described. Overall, this review gathers recent developments in the formulation, production and properties of food-grade PEs based on safe inorganic solid particles.

Microwave-Assisted Lignin Wet Peroxide Oxidation to C4 Dicarboxylic Acids.

Innovative methodologies, such as microwave-assisted reaction, can help to valorize lignin with higher productivity and better energy efficiency. In this work, microwave heating was tested in the wet peroxide oxidation of three lignins (Indulin AT, Lignol, and Eucalyptus globulus lignins) as a novel methodology to obtain C4 dicarboxylic acids. The effect of temperature, time, and catalyst type (TS-1 or Fe-TS1) was evaluated in the production of these acids. The TS-1 catalyst improved succinic acid yield, achieving up to 9.4 wt % for Lignol lignin. Moreover, the microwave heating specifically enhanced Lignol conversion to malic acid (34 wt %), even without catalyst, showing to be an attractive path for the future valorization of organosolv lignins. Overall, compared to conventional heating, microwave heating originated a rapid lignin conversion. Nevertheless, for prolonged times, conventional heating led to better results for some target products, e.g., malic and succinic acids.

Saponins as Natural Emulsifiers for Nanoemulsions.

The awareness of sustainability approaches has focused attention on replacing synthetic emulsifiers with natural alternatives when formulating nanoemulsions. In this context, a comprehensive review of the different types of saponins being successfully used to form and stabilize nanoemulsions is presented, highlighting the most common natural sources and biosynthetic routes. Processes for their extraction and purification are also reviewed altogether with the recent advances for their characterization. Concerning the preparation of the nanoemulsions containing saponins, the focus has been initially given to screening methods, lipid phase used, and production procedures, but their characterization and delivery systems explored are also discussed. Most experimental outcomes showed that the saponins present high performance, but the challenges associated with the saponins' broader application, mainly the standardization for industrial use, are identified. Future perspectives report, among others, the emerging biotechnological processes and the use of byproducts in a circular economy context.

Pickering Emulsions Stabilized with Curcumin-Based Solid Dispersion Particles as Mayonnaise-like Food Sauce Alternatives.

Pickering emulsions, which are emulsions stabilized by colloidal particles, are being increasingly positioned as novel strategies to develop innovative food product solutions. In this context, the present work aims to develop Pickering emulsions stabilized by natural-based curcumin-loaded particles produced by the solid dispersion technique as promising mayonnaise-like food sauce alternatives. Two particle formulations (KC1 and KC2) were produced using k-carrageenan as the matrix material and different curcumin contents, then employed in the preparation of three Pickering emulsion formulations comprising different oil fractions (φ) and particle concentrations (KC1 φ 0.4 (4.7%), KC2 φ 0.4 (4.7%) and KC2 φ 0.6 (4.0%)). The creaming index tests accompanied by the optical microscopy analysis evidenced the good stability of the developed products for the tested period of 28 days. The final products were tested concerning color attributes, pH, oxidative stability, textural, and nutritional composition, and compared with two commercial mayonnaises (traditional and light products). Overall, the produced emulsions were characterized by a bright yellow color (an appealing attribute for consumers), an acidic pH (similar to mayonnaise), and a considerably improved oxidative stability, implying a foreseeable longer shelf life. The sauce KC1 φ 0.4 (4.7%) showed a similar texture to the light commercial mayonnaise, being a promising alternative to conventional sauces, holding a low-fat content and potentially added benefits due to the curcumin and virgin olive oil intrinsic properties.

Water-in-Oil-in-Water Double Emulsions as Protective Carriers for Sambucus nigra L. Coloring Systems.

The use of natural colorants is needed to overcome consumer concerns regarding synthetic food colorants' safety. However, natural pigments have, in general, poor stability against environmental stresses such as temperature, ionic strength, moisture, light, and pH, among others. In this work, water-in-oil-in-water (W1/O/W2) emulsions were used as protective carriers to improve color stability of a hydrophilic Sambucus nigra L. extract against pH changes. The chemical system comprised water and corn oil as the aqueous and oil phases, respectively, and polyglycerol polyricinoleate (PGPR), Tween 80, and gum Arabic as stabilizers. The primary emulsion was prepared using a W1/O ratio of 40/60 (v/v). For the secondary emulsion, W1/O/W2, different (W1/O)/W2 ratios were tested with the 50/50 (v/v) formulation presenting the best stability, being selected as the coloring system to test in food matrices of different pH: natural yogurt (pH 4.65), rice drink (pH 6.01), cow milk (pH 6.47), and soy drink (pH 7.92). Compared to the direct use of the extract, the double emulsion solution gave rise to higher color stability with pH change and storage time, as corroborated by visual and statistical analysis.

Anthocyanins from Rubus fruticosus L. and Morus nigra L. Applied as Food Colorants: A Natural Alternative.

Given the importance of colour in the general acceptance or rejection of a product, the use of colorants is a widespread practice, particularly in the food industry. At the same time, with the increasing consumers' awareness of the health effects that some artificial colorants can exert, there is a growing tendency to prioritize foodstuffs containing natural additives. In this work, Morus nigra L. and Rubus fruticosus L. fruit juices were characterized in terms of anthocyanins, organic acids, free sugars, and tocopherols, as also regarding their bioactive properties. Given their richness in anthocyanins, this study also aimed to prepare different solid colouring formulations by the spray-drying technique, using as stabilizers maltodextrin and arabic gum. Six free sugars and two organic acids were detected in the fruit juices, as well as the four tocopherol isoforms. Two cyanidin derivatives were found in M. nigra (cyanidin-3-O-glucoside and cyanidin-O-rhamnoside) and other four in R. fruticosus (cyanidin-O-hexoside, cyanidin-3-O-glucoside, cyanidin-O-pentoside, and cyanidin-3-O-dioxaloilglucoside). The developed colouring formulations revealed a good stability over time, in terms of anthocyanin concentration and colour parameters, and revealed to be safe for consumption, either concerning their low microbial load and lack of cytotoxicity. Thus, they represent a promising natural alternative to the massively used artificial colorants.

Development of Chitosan Microspheres through a Green Dual Crosslinking Strategy Based on Tripolyphosphate and Vanillin.

Microencapsulation procedures have recently focused attention on designing novel microspheres via green synthesis strategies. The use of chitosan (CS) as an encapsulating material has increased interest due to its unique bioactive properties and the various crosslinking possibilities offered by their functional groups. The consolidation of the microspheres by physical crosslinking using sodium tripolyphosphate (TPP) combined with chemical crosslinking using vanillin (VA) open new opportunities in the framework of green dual crosslinking strategies. The developed strategy, a straightforward technique based on an aqueous medium avoiding complex separation/washing steps, offers advantages over the processes based on VA, mostly using water-in-oil emulsion approaches. Thus, in this work, the combination of TPP crosslinking (3, 5, and 10 wt.%) via spray-coagulation technique with two VA crosslinking methods (in situ and post-treatment using 1 wt.% VA) were employed in the preparation of microspheres. The microspheres were characterized concerning morphology, particle size, physicochemical properties, thermal stability, and swelling behavior. Results revealed that the combination of 5 wt.% TPP with in situ VA crosslinking led to microspheres with promising properties, being an attractive alternative for natural bioactives encapsulation due to the green connotations associated with the process.

Chitosan-based Pickering emulsions and their applications: A review.

Pickering emulsions, which are emulsions stabilized by solid particles, have gained increased research interest owing to their eco-friendliness and high stability. Among a wide range of solid particles, chitosan particles and chitosan-based particles have become attractive candidates as Pickering stabilizers due to their biodegradable, biocompatible and nontoxic properties. This review aims to provide an insight into the recent advances in the production and physicochemical properties of these systems. Moreover, this paper highlights the research progress in employing chitosan-based Pickering emulsions in different application areas, such as food and cosmetic applications, and environmental research. Chitosan-based Pickering emulsions have opened new avenues for the designing and production of innovative materials. The review also sheds light on the novel materials that are synthesized from these Pickering emulsion systems. Future research directions and opportunities on these promising Pickering systems are also addressed.

Betacyanins from Gomphrena globosa L. flowers: Incorporation in cookies as natural colouring agents.

A betacyanin rich extract was obtained from the flowers of Gomphrena globosa L. by ultrasound-assisted extraction and dried either by lyophilization or spray-drying, was tested as a natural colourant in cookies and compared to a commercial colourant. The extracts were characterized in terms of betacyanin content and antioxidant potential. The effects of the colourants incorporation in the cookies were assessed through proximate composition, soluble sugars, fatty acids, color, texture and microbial load, over a shelf life of 30 days. Considering all the assays and analyzing the results through a 2-way analysis of variance, the cookies incorporated with spray-dried colourant showed the most intense pink coloration while cookies incorporated with lyophilized extract lost less color intensity over time. Thus, betacyanin extracts have potential as pink natural alternatives to synthetic colourants in the food industry.

Formulation and Optimization of Nanoemulsions Using the Natural Surfactant Saponin from Quillaja Bark.

Replacing synthetic surfactants by natural alternatives when formulating nanoemulsions has gained attention as a sustainable approach. In this context, nanoemulsions based on sweet almond oil and stabilized by saponin from Quillaja bark with glycerol as cosurfactant were prepared by the high-pressure homogenization method. The effects of oil/water (O/W) ratio, total surfactant amount, and saponin/glycerol ratio on their stability were analyzed. The formation and stabilization of the oil-in-water nanoemulsions were analyzed through the evaluation of stability over time, pH, zeta potential, and particle size distribution analysis. Moreover, a design of experiments was performed to assess the most suitable composition based on particle size and stability parameters. The prepared nanoemulsions are, in general, highly stable over time, showing zeta potential values lower than -40 mV, a slight acid behavior due to the character of the components, and particle size (in volume) in the range of 1.1 to 4.3 µm. Response surface methodology revealed that formulations using an O/W ratio of 10/90 and 1.5 wt% surfactant resulted in lower particle sizes and zeta potential, presenting higher stability. The use of glycerol did not positively affect the formulations, which reinforces the suitability of preparing highly stable nanoemulsions based on natural surfactants such as saponins.

The Role of Bioactive Compounds and other Metabolites from Mushrooms against Skin Disorders- A Systematic Review Assessing their Cosmeceutical and Nutricosmetic Outcomes.

Bioactive compounds derived from mushrooms have been shown to present promising potential as cosmeceutical or nutricosmetic ingredients. Scientific data reviewed herein showed that extracts prepared from medicinal and edible mushrooms and their individual metabolites presented antiinflammatory, antioxidant, photoprotective, antimicrobial, anti-tyrosinase, anti-elastase, and anticollagenase activities. These metabolites can be utilised as ingredients to suppress the severity of Inflammatory Skin Diseases, offer photoprotection to the skin, and correct Hyperpigmentation. However, studies regarding the molecular mechanism behind the mentioned bioactivities are still lacking. Challenges associated with the use of mushroom extracts and their associated metabolites as cosmeceutical and nutricosmetic ingredients include several steps from the fruiting bodies to the final product: extraction optimization, estimation of the efficacy and safety claims, the use of micro and nanocarriers to allow for controlled release and the pros and cons associated with the use of extracts vs individual compounds. This systematic review highlights that mushrooms contain diverse biomolecules that can be sustainably used in the development of nutricosmetic and cosmeceutical formulations. Reports regarding stability, compatibility, and safety assessment, but also toxicological studies are still needed to be considered. Furthermore, some of the constraints and limitations hindering the development of this type of ingredients still require long-term studies to achieve major breakthroughs.

Enhancing trans-resveratrol topical delivery and photostability through entrapment in chitosan/gum Arabic Pickering emulsions.

The surfactant-free nature and higher stability of Pickering emulsions make them preferable solutions over conventional emulsions for skin applications. In this work, Pickering emulsions stabilized by chitosan/gum Arabic (CH/GA) nanoparticles were tested as vehicles for trans-resveratrol topical delivery. Skin absorption was examined ex vivo using Franz diffusion cells and porcine skin. Pickering emulsions allowed higher cutaneous retention and lower permeation of resveratrol, in comparison with a control solution based on a 20% v/v ethanol. The total amount of resveratrol retained in the skin, 24 h after the application, was 11.60% and 10.82% of the applied dose for the tested Pickering emulsion-based formulations prepared with 0.5% and 1.5% w/v CH/GA nanoparticles, respectively. In contrast, resveratrol skin retention from the control solution was only 2.86%. Confocal laser scanning microscopy revealed enhanced skin deposition of Nile Red to deeper layers from the Pickering emulsion-based formulations. Moreover, Pickering emulsions led to trans-resveratrol photostability increase, as measured after exposure to UV for 4 h. These results show that the CH/GA Pickering emulsions are promising solutions for the topical delivery of trans-resveratrol and have the potential to be used as green cosmetic products.

Araucaria angustifolia (Bertol.) Kuntze extract as a source of phenolic compounds in TPS/PBAT active films.

There is growing interest in the development of biodegradable packaging materials containing natural antioxidant extracts. In this sense, the use of extracts obtained from agro-industrial byproducts has proved to be a sustainable alternative. In this study, Pinhão extract, a byproduct of Pinhão (Araucaria angustifolia (Bertol.) Kuntze) seed consumption, was characterized by HPLC-DAD-ESI/MSn, demonstrating the presence of eight phenolic compounds, (+)-catechin and (-)-epicatechin being the most abundant molecules. TPS/PBAT films containing Pinhão extract were produced by blown extrusion and their properties (tensile properties, thermal characteristics and microstructure) were evaluated in order to determine the effect of the presence of extracts. Results suggested that the interaction between the phenolic compounds of the extract and the polymeric matrix caused the reduction in the crystallinity degree, and an increase in the starch glass transition temperature. The presence of Araucaria angustifolia (Bertol.) Kuntze extract significantly (p < 0.05) affected the color and opacity of the film. Regarding water vapor permeation, no significant difference (p > 0.05) was detected. However, the water solubility and the contact angle with water (polar solvent) and diiodomethane (non-polar solvent) significantly changed due to the extract addition. Moreover, the Pinhão extract conferred significant antioxidant capacity to the TPS/PBAT films as determined by DPPH, suggesting that this material can be applied as an active packaging material.

Preparation of chitosan/gum Arabic nanoparticles and their use as novel stabilizers in oil/water Pickering emulsions.

Recently, there has been a renewed interest in Pickering emulsions owing to their surfactant-free nature, and the use of natural-based particles as stabilizers became a priority due to the applications they can enable. In this work, chitosan/gum Arabic (CH/GA) nanoparticles were synthesized and tested as novel stabilizers. Among the tested CH/GA weight ratios, the particles prepared using 1:1 ratio exhibited near-neutral wettability, an average size of 108.6 nm and a zeta potential of 56.3 mv. Pickering emulsions prepared from these particle dispersions (1.5% w/v), and high oil volume fractions (φ = 0.6, 0.7), have shown high storage stability. Moreover, confocal laser scanning microscopy confirmed the o/w type and the effective adsorption of the nanoparticles at the oil/water interface forming a barrier against droplets coalescence. The emulsions have shown shear-thinning and elastic-like behavior. These findings open new avenues for using these emulsions as novel delivery systems, e.g. in cosmetic and food applications.

Promising Antioxidant and Antimicrobial Food Colourants from Lonicera caerulea L. var. Kamtschatica.

Lonicera caerulea L. (haskap) berries are widely known for their richness in anthocyanins. In this study, such fruits were assessed for their nutritional and chemical composition, but also as sources of anthocyanins with great colouring properties to be applied in foodstuff. Haskap presented high levels of water, four free sugars (mainly fructose and glucose), five organic acids (mainly citric, malic, and quinic), α- and γ-tocopherol, twenty fatty acids (with prevalence of linoleic acid), and eight phenolic compounds, among which six were anthocyanins (mainly cyanidin-3-O-glucoside). The extract presented great antioxidant properties, evaluated through TBARS and OxHLIA assays, as well as antimicrobial capacity against six bacteria and six fungi. Two colourants were obtained by spray-drying haskap juice with maltodextrin and a mixture of maltodextrin and arabic gum. These formulations were stable over 12 weeks of storage at room and refrigerated temperature, without significant variations in colour parameters and in anthocyanins concentration. They were considered safe for consumption once neither microbial contamination nor cytotoxicity in non-tumour cells were detected. The results obtained allow for the consideration of haskap as a promising source of colourants to be applied not only in the food industry, but also in other fields that rely on artificial colourants.

Tailoring swelling of alginate-gelatin hydrogel microspheres by crosslinking with calcium chloride combined with transglutaminase.

Alginate-based hydrogels can find uses in a wide range of applications, including in the encapsulation field. This type of hydrogels is usually ionically crosslinked using calcium sources giving rise to products with limited internal crosslinking. In this work, it is hypothesized that the combination of alginate crosslinked by calcium chloride (external crosslinking; ionic mechanism) with gelatin crosslinked by transglutaminase (internal crosslinking; enzymatic induced mechanism) can be used to tailor the swelling behavior of alginate-based hydrogel microspheres. A systematic study was conducted by covering process variables such as gelatin content, TGase concentration, and CaCl2 contact time, added by statistic tools as central composite rotatable design (CCRD), principal component analysis (PCA) and multiobjective optimization, to map their effect on the resulting water content after production (expressed as swelling ratio), and swelling properties at pH 3 and 7. Among the studied variables, particle's swelling was mostly affected by the gelatin content and transglutaminase concentration.

Ultrasound as a Rapid and Low-Cost Extraction Procedure to Obtain Anthocyanin-Based Colorants from Prunus spinosa L. Fruit Epicarp: Comparative Study with Conventional Heat-Based Extraction.

An ultrasound rapid and low-cost procedure for anthocyanin-based colorants from Prunus spinosa L. fruit epicarp was developed, and the advantages were compared with conventional heat-based extraction. To obtain the conditions that maximize anthocyanins' extraction, a response surface methodology was applied using the variables of time, temperature, and ethanol content, in the case of heat extraction, whereas for ultrasound assisted extraction, temperature was replaced by ultrasound power. Two anthocyanin compounds were identified by HPLC-DAD-ESI/MS-namely, cyanidin 3-rutinoside and peonidin 3-rutinoside. The responses used were the extraction yield and the content of the identified anthocyanins. Ultrasound extraction was the most effective method at 5.00 ± 0.15 min, 400.00 ± 32.00 W, and 47.98% ± 2.88% of ethanol obtaining 68.60% ± 2.06% of extracted residue, with an anthocyanin content of 18.17 mg/g (extract-basis) and 11.76 mg/g (epicarp-basis). Overall, a viable green process was achieved that could be used to support pilot-scale studies for industrial production of anthocyanin-based colorants from P. spinosa fruit epicarp.