A Natural deep eutectic solvent as an effective material for dual debridement and antibiofilm effects in chronic wound treatment.

In chronic wound treatment, the debridement of devitalized tissue and the eradication of the biofilm must balance aggressiveness with care to protect regenerating tissues. In this study, urea, a potent chaotropic molecule, was modulated through the formation of a Natural Deep Eutectic Solvent (NADES) with betaine to develop a new debriding material (BU) suitable for application into injured dermal tissues. To evaluate BU's debriding capacity, along with its antibiofilm effect and biocompatibility, pre-clinical to clinical methods were employed. In vitro determinations using artificial and clinical slough samples indicate that BU has a high debriding capacity. Additionally, BU's de-structuring effects lead to a strong antibiofilm capability, demonstrated by a reduced bacterial load compared to the antiseptic PHMB-Betaine or medical honey, evaluated in artificial slough and ex vivo human skin. Furthermore, BU's efficacy was evaluated in a murine model of diabetic wound, demonstrating significant effects on debriding and antibiofilm capacity, similar to those observed in PHMB-Betaine and medical honey-treated animals. Finally, BU was clinically evaluated in leg ulcers, showing superiority in reduction of bacterial load and wound area compared to honey, with no adverse effects. Thus, BU represents a simple and non-biocidal option that could contributes to chronic wound care.

Synthesis of ultrasmall cerium oxide nanoparticles in deep eutectic solvent and their application in an electrochemical sensor to detect dopamine in biological fluid.

A solvothermal synthesis of ultrasmall cerium oxide nanoparticles (USCeOxNPs) with an average size of 0.73 ± 0.07 nm using deep eutectic solvent (DES) as a stabilizing medium at a temperature of 90 ºC is reported. Transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS) were used to morphologically characterize the USCeOxNPs. These revealed approximately spherical shapes with emission lines characteristic of cerium. Selected area electron diffraction (SAED) was used to determine the crystalline structure of the cerium oxide nanoparticles (CeO2NPs), revealing the presence of crystalline cubic structures. The USCeOxNPs-DES/CB film was characterized by scanning electron microscopy (SEM), which demonstrated the spherical characteristic of CB with layers slightly covered by DES residues. DES was characterized by Fourier transform infrared (FT-IR) and nuclear magnetic resonance (NMR), indicating its formation through hydrogen bonds between the precursors. An electrochemical sensor for dopamine (DA) determination in biological fluids was developed using the USCeOxNPs together with carbon black (CB). An enhanced current response was observed on DA voltammetric determination, and this can be attributed to the USCeOxNPs. This sensor displayed linear responses for DA in the range 5.0 × 10-7 mol L-1 to 3.2 × 10-4 mol L-1, with a limit of detection of 80 nmol L-1. Besides detectability, excellent performances were verified for repeatability and anti-interference. The sensor based on USCeOxNPs synthesized in DES in a simpler and environmentally friendly way was successfully applied to determine DA in biological matrix.

Deep eutectic solvent for the extraction of polycyclic aromatic compounds in fuel, food and environmental samples.

Polycyclic aromatic compounds (PACs) encompass a wide variety of organic analytes that have mutagenic and carcinogenic potentials for human health and are recalcitrant in the environment. Evaluating PACs levels in fuel (e.g., gasoline and diesel), food (e.g., grilled meat, fish, powdered milk, fruits, honey, and coffee) and environmental (e.g., industrial effluents, water, wastewater and marine organisms) samples are critical to determine the risk that these chemicals pose. Deep eutectic solvents (DES) have garnered significant attention in recent years as a green alternative to traditional organic solvents employed in sample preparation. DES are biodegradable, have low toxicities, ease of synthesis, low cost, and a remarkable ability to extract PACs. However, no comprehensive assessment of the use of DESs for extracting PACs from fuel, food and environmental samples has been performed. This review focused on research involving the utilization of DESs to extract PACs in matrices such as PAHs in environmental samples, NSO-HET in fuels, and bisphenols in foods. Chromatographic methods, such as gas chromatography (GC) and high-performance liquid chromatography (HPLC), were also revised, considering the sensibility to quantify these compound types. In addition, the characteristics of DES and advantages and limitations for PACs in the context of green analytical chemistry principles (GAC) and green profile based on metrics provide perspective and directions for future development.

Improving the Composition and Bioactivity of Cocoa (Theobroma cacao L.) Bean Shell Extract by Choline Chloride-Lactic Acid Natural Deep Eutectic Solvent Extraction Assisted by Pulsed Electric Field Pre-Treatment.

An environmentally friendly method for the release of cocoa bean shell (CBS) extracts is proposed in this paper. This work aims to investigate the effect of pulsed electric field (PEF) pre-treatment on subsequent solid-liquid extraction (SLE) of metabolites with choline chloride-lactic acid natural deep eutectic solvent (NaDES) and bioactivity of cocoa bean shell (CBS) extract. Two different media for PEF application were evaluated: water and chlorine chloride-lactic acid. Total polyphenols (TPC), total flavonoids (TFC), individual major compounds, and antioxidant and antibacterial activity of CBS extracts were assessed. The performance of PEF-assisted extraction was compared with SLE and ultrasound-assisted extraction (UAE). The proposed method improved the release of TPC up to 45% and TFC up to 48% compared with the conventional extraction. The CBS extract showed medium growth inhibition of Escherichia coli and high growth inhibition of Salmonella sp, Listeria monocytogenes, and Staphylococcus aureus. Thus, an extract with enhanced antioxidant and antibacterial properties was obtained.

Natural deep eutectic solvents (NADES)-Extracted Anthocyanins: Bioaccessibility in electrospun PEO microfibers.

Anthocyanins extracted with deep eutectic solvent (NADES) (chlorine-chloride: xylitol, 5:2) were used to produce polyethylene oxide (PEO) composites through electrospinning technique, analyzing their microscopic and physical characteristics. The coated anthocyanins were then subjected to in vitro gastrointestinal digestion to evaluate their bioaccessibility compared to lyophilized jussara pulp. The remaining total anthocyanin content (TAC) after intestinal in vitro digestion did not change significantly among the assessed samples, and both showed around 30% recovery. The TAC recovery after the gastric phase, on the other hand, showed a major difference (70.84% vs. 48.13%), revealing that the composites fabricated by the electrospinning technique can significantly maintain anthocyanins NADES-extracted stability during the gastric phase of digestion, potentially allowing better absorption trough stomach wall. The results can be considered a first step to applying anthocyanins-encapsulated in foodstuff as a natural pigment.

Deep eutectic solvents as a green alternative for trace element analysis in food and beverage samples: Recent advances and challenges.

Metals and metalloids have different effects on human health even at trace levels. Some of them are essential for living organisms while others can be toxic. Therefore, the determination of trace elements in food and beverage is highly important to understand their impact in human health. A new generation of solvents named deep eutectic solvents (DES) has emerged as a green alternative for trace element analysis, owing to their low toxicity, biodegradability, and high extraction capacity. In recent years, the application of DES in extraction techniques for trace element analysis in food and beverage samples has increased significantly. This review summarizes recent advances and challenges on the application of DES to develop microextraction techniques useful for the analysis of samples with complex matrices. The importance of the use of biodegradable substances instead of classic organic solvents, which are toxic, volatile, and flammable in methods for elemental analysis with a positive environmental impact is also highlighted. Finally, conclusions and future challenges arising from the use of DES in microextraction techniques are discussed.

Effect of choline chloride-based deep eutectic solvents on polyphenols extraction from cocoa (Theobroma cacao L.) bean shells and antioxidant activity of extracts.

The effective extraction of natural compounds from cocoa bean shells using deep eutectic solvents could contribute to the sustainable valorization of this waste material. The objective of this study was to: (1) analyze the extraction kinetics of polyphenols released from cocoa (Theobroma cacao L.) bean shells (CBS) by the solid-liquid extraction method using choline chloride-based deep eutectic solvents (ChCl-DES) and their aqueous solutions; (2) investigate the effect of choline chloride-based deep eutectic solvents (ChCl-DES) aqueous solutions on in-vitro antioxidant capacity and the main individual compounds of the extracts. ChCl-DES were prepared with lactic acid, glycerol, and ethylene glycol in a 1:2 ratio. Aqueous solutions (30%, 40%, and 50% water) to obtain solvents with different physicochemical properties were performed. The total phenolic content (TPC) was determined by the Folin-Ciocalteu method. The solution of Fick's law model for plate geometry particles was applied to fit the experimental data and calculate the effective diffusivity coefficient (De). The antioxidant capacity of the extracts was analyzed by a combination of 2,2-diphenyl-1-(2,4,6-trinitrophenyl) hydrazyl (DPPH) free radical scavenging capacity and ferric-reducing antioxidant power (FRAP) assays. The main bioactive compounds were quantified by high-performance liquid chromatography. The results showed that the type of hydrogen bond donor influences the total phenolic content, antioxidant activity and the main individual compounds in the extracts. Moreover, the washing/diffusion mechanism adequately depicts the extraction kinetics data for total phenolic content. However, the influence of an additional mechanism that enhanced the extraction capacity of deep eutectic solvents compared with organic solvent was confirmed.

From capillaries to microchips, green electrophoretic features for enantiomeric separations: A decade review (2013-2022).

Enantioseparation by the electromigration-based method is well-established and widely discussed in the literature. Electrophoretic strategies have been used to baseline resolve complex enantiomeric mixtures, typically using a selector substance into the background electrolyte (BGE) from capillaries to microchips. Along with developing new materials/substances for enantioseparations, it is the concern about the green analytical chemistry (GAC) principles for method development and application. This review article brings a last decade's update on the publications involving enantioseparation by electrophoresis for capillary and microchip systems. It also brings a critical discussion on GAC principles and new green metrics in the context of developing an enantioseparation method. Chemical and green features of native and modified cyclodextrins are discussed. Still, given the employment of greener substances, ionic liquids and deep-eutectic solvents are highlighted, and some new selectors are proposed. For all the mentioned selectors, green features about their production, application, and disposal are considered. Sample preparation and BGE composition in GAC perspective, as well as greener derivatization possibilities, were also addressed. Therefore, one of the goals of this review is to aid the electrophoretic researchers to look where they have not.

Improved Antioxidant and Mechanical Properties of Food Packaging Films Based on Chitosan/Deep Eutectic Solvent, Containing Açaí-Filled Microcapsules.

The development of biobased antioxidant active packaging has been valued by the food industry for complying with environmental and food waste concerns. In this work, physicochemical properties for chitosan composite films as a potential active food packaging were investigated. Chitosan films were prepared by solution casting, plasticized with a 1:2 choline chloride: glycerol mixture as a deep eutectic solvent (DES) and incorporated with 0-10% of optimized açaí oil polyelectrolyte complexes (PECs). Scanning electron microscopy and confocal laser scanning microscopy revealed that the chitosan composite films were continuous and contained well-dispersed PECs. The increased PECs content had significant influence on the thickness, water vapor permeability, crystallinity (CrD) and mechanical and dynamic behavior of the films, as well as their antioxidant properties. The tensile strength was reduced in the following order: 11.0 MPa (control film) > 0.74 MPa (5% DES) > 0.63 MPa (5% DES and 5% PECs). Films containing 2% of PECs had an increased CrD, ~6%, and the highest elongation at break, ~104%. Films with 1% of PECs displayed the highest antioxidant properties against the ABTS and DPPH radicals, ~6 and ~17 mg TE g-1, respectively, and highest equivalent polyphenols content (>0.5 mg GAE g-1). Films with 2% of particles were not significantly different. These results suggested that the chitosan films that incorporated 1-2% of microparticles had the best combined mechanical and antioxidant properties as a potential material for food packaging.

Antioxidant Capacity, Vitamin C and Polyphenol Profile Evaluation of a Capsicum chinense By-Product Extract Obtained by Ultrasound Using Eutectic Solvent.

Habanero pepper leaves and stems (by-products) have been traditionally considered waste; however, bioactive compounds such as polyphenols, vitamin C and carotenoids have been identified that can be used for formulation of nutraceuticals or functional foods. Furthermore, the extraction of these bioactive compounds by using environmentally friendly methods and solvents is desirable. Thus, the aim of this study was to assess the antioxidant capacity, total polyphenol content (TPC), the phenolic profile and vitamin C content in extracts obtained from by-products (stems and leaves) of two varieties (Mayapan and Jaguar) of habanero pepper by ultrasound-assisted extraction (UAE) using natural deep eutectic solvents (NADES). The results showed that NADES leads to extracts with significantly higher TPC, higher concentrations of individual polyphenols (gallic acid, protocatechuic acid, chlorogenic acid, cinnamic acid, coumaric acid), vitamin C and, finally, higher antioxidant capacity (9.55 ± 0.02 eq mg Trolox/g DM) than UAE extraction performed with methanol as the solvent. The association of individual polyphenols with NADES was confirmed by principal component analysis (PCA). Overall, NADES is an innovative and promising "green" extraction technique that can be applied successfully for the extraction of phenolic compounds from habanero pepper by-products.

Boosting cell proliferation in three-dimensional polyacrylates/nanohydroxyapatite scaffolds synthesized by deep eutectic solvent-based emulsion templating.

Among three-dimensional (3D) scaffold fabrication methods, porous polymers templated using high internal phase emulsions (HIPEs) have emerged as an attractive method due to the facile generation of interconnected porosity through a variety of synthetic routes. These include a bottom-up approach to selectively incorporate nanomaterials onto the inner walls in a nonaqueous environment. In this work, novel nonaqueous HIPEs made of different (meth)acrylate monomers and a deep eutectic solvent (DES) were formulated with nonfunctionalized nanohydroxyapatite (NHA), which also played the role of cosurfactant. Free radical polymerization of HIPEs yielded free-standing nanocomposites with 3D interconnected macroporosity and nonfunctionalized NHA selectively decorating the scaffolds' inner surface. The influence of different polymer functionalities, acrylate or methacrylate, their alkyl tail length, and the presence of NHA on MC3T3-E1 preosteoblast cell proliferation in vitro, reactive oxygen species (ROS) production and alkaline phosphatase (ALP) activity were evaluated. All materials presented promising biocompatibility, non-hemolytic activity, negligible inflammatory response along to remarkably enhanced cell proliferation (e.g., up to 160-fold cell proliferation increase compared with polystyrene plate) in vitro, which open the path for the development of scaffolds in regenerative medicine. It is noteworthy that polyHIPEs studied here were obtained using a green synthetic protocol where nonfunctionalized nanoparticles can be selectively incorporated into a scaffolds' inner walls. This versatile technique allows for the simple construction of 3D bioactive nanocomposite scaffolds with varied compositions for cell culture.

Performance of Choline Geranate Deep Eutectic Solvent as Transdermal Permeation Enhancer: An In Vitro Skin Histological Study.

In the present research work, we addressed the changes in skin by which deep eutectic solvents (DES) enhanced transdermal permeation of bioactive compounds and propose a rationale for this mechanism. Several studies showed that these unusual liquids were ideal solvents for transdermal delivery of biomolecules, but to date, no histological studies relating the action of DES to changes in the structure of the outer skin barrier have been reported. In the research effort described herein, we presented an in-depth analysis of the changes induced in the skin by choline geranate DES, a compound with proven capabilities of enhancing transdermal permeation without deleterious impacts on the cells. The results obtained showed that a low percentage of DES acted as a transient disruptor of the skin structure, facilitating the passage of bioactive compounds dissolved in it.