Assessment of Enzymatically Derived Blackcurrant Extract as Cosmetic Ingredient-Antioxidant Properties Determination and In Vitro Diffusion Study.

Blackcurrant is an anthocyanin-rich berry with proven antioxidant and photoprotective activity and emerging prebiotic potential, widely applied in cosmetic products. Hereby, highly efficient enzyme-assisted extraction of blackcurrant polyphenols was performed, giving extract with very high antioxidant activity. Obtained extract was characterized in terms of anthocyanin composition, incorporated into three different cosmetic formulations and subjected to Franz cell diffusion study. Experimental values obtained using cellulose acetate membrane for all four dominant anthocyanins (delphinidin 3-glucoside, delphinidin 3-rutinoside, cyanidin 3-glucoside and cyanidin 3-rutinoside) were successfully fitted with the Korsmeyer-Peppas diffusion model. Calculated effective diffusion coefficients were higher for hydrogel compared to oil-in-water cream gel and oil-in-water emulsion, whereas the highest value was determined for cyanidin 3-rutinoside. On the other hand, after a 72 h long experiment with transdermal skin diffusion model (Strat-M® membrane), no anthocyanins were detected in the receptor fluid, and only 0.5% of the initial quantity from the donor compartment was extracted from the membrane itself after experiment with hydrogel. Present study revealed that hydrogel is a suitable carrier system for the topical delivery of blackcurrant anthocyanins, while dermal and transdermal delivery of these molecules is very limited, which implies its applicability for treatments targeting skin surface (i.e., prebiotic, photoprotective).

In vitro assessment of skin permeation properties of enzymatically derived oil-based fatty acid esters of vitamin C.

Current topical formulations containing vitamin C face limitations in therapeutic effectiveness due to the skin's selective properties that impede drug deposition. Consequently, the widespread use of toxic and irritating chemical permeation enhancers is common. Hereby, we investigated enzymatically derived fatty acid ascorbyl esters (FAAEs) obtained using natural oils for their skin permeation properties using the Strat-M® skin model in a Franz cell diffusion study. By evaluating various cosmetic formulations without added enhancers, we found that emulgel is most suitable for enhancing the cutaneous and transdermal delivery of FAAEs. Furthermore, medium-chain coconut oil-derived FAAEs exhibited faster diffusion rates compared to sunflower oil-based FAAEs with long-side acyl residues, including the commonly applied ascorbyl palmitate. Experimental data were successfully fitted using the Peppas and Sahlin model, which accounted for a lag phase and the combined effect of Fickian diffusion and polymer relaxation. In the case of long-chain esters, the lag phase was prolonged, and the calculated effective diffusion coefficients (Deff) were lower compared to medium-chain FAAEs. Accordingly, the highest Deff value was observed for ascorbyl caprylate, being even 60 times higher than for ascorbyl palmitate. These results suggest the emerging potential of emulgel with incorporated coconut oil-derived FAAEs for efficiently delivering vitamin C into the skin.

Liposomal Encapsulation of Ascorbyl Palmitate: Influence on Skin Performance.

L-ascorbic acid represents one of the most potent antioxidant, photoprotective, anti-aging, and anti-pigmentation cosmeceutical agents, with a good safety profile. However, the main challenge is the formulation of stable topical formulation products, which would optimize the penetrability of L-ascorbic acid through the skin. The aim of our research was to evaluate the performance of ascorbyl palmitate on the skin, incorporated in creams and emulgels (2%) as carriers, as well as to determine the impact of its incorporation into liposomes on the penetration profile of this ingredient. Tape stripping was used to study the penetration of ascorbyl palmitate into the stratum corneum. In addition, the sensory and textural properties of the formulations were determined. The liposomal formulations exhibited a better penetration profile (p < 0.05) of the active substance compared to the non-liposomal counterpart, leading to a 1.3-fold and 1.2 fold-increase in the total amount of penetrated ascorbyl palmitate in the stratum corneum for the emulgel and cream, respectively. Encapsulation of ascorbyl palmitate into liposomes led to an increase in the adhesiveness and density of the prepared cream and emulgel samples. The best spreadability and absorption during application were detected in liposomal samples. The obtained results confirmed that liposomal encapsulation of ascorbyl palmitate improved dermal penetration for both the cream and emulgel formulations.

Valorisation of Raspberry Seeds in Cosmetic Industry-Green Solutions.

The fruit processing industry generates large quantities of by-products well known to be rich in bioactive compounds with numerous nutritional properties and beneficial effects for human health. We developed a strategy to valorise raspberry seeds and obtain valuable ingredients with potential application in cosmetic skincare formulas. Cold press extraction technology was applied to extract oil, and the remaining defatted raspberry seed cake was treated with three proline based deep eutectic solvents (DES) to extract polyphenols. The most potent was proline/citric acid extract, with free and total ellagic acid content (52.4 mg/L and 86.4 mg/L), total phenolic content (TPC, 550.1 mg GAE/L) and radical scavenging activity (RSA, 4742.7 mmol TE/L). After the direct mixing of the extract and after encapsulation with starch as a carrier, the skincare emulsion and microemulsion were characterised by irritation potential (Zein test), transepidermal water loss (TEWL), red blood cell (RBC), and DPPH antioxidant test. The resulting preparations were of improved quality in comparison to the control hand cream, with a low skin irritation effect, lower TEWL, and higher antioxidant potential. This work complies with circular economy principles and green technology standards, and represents the efficient model on how to reuse natural resources through waste minimization.

Derivatives of L-Ascorbic Acid in Emulgel: Development and Comprehensive Evaluation of the Topical Delivery System.

The dual controlled release of emulgels makes them efficient drug delivery systems of increasing interest. The framework of this study was to incorporate selected L-ascorbic acid derivatives into emulgels. From the formulated emulgels, the release profiles of actives were evaluated considering their different polarities and concentrations, and consequently their effectiveness on the skin via a long-term in vivo study that lasted for 30 days was determined. Skin effects were assessed by measuring the electrical capacitance of the stratum corneum (EC), trans-epidermal water loss (TEWL), melanin index (MI) and skin pH. In addition, the sensory and textural properties of emulgel formulations were compared with each other. The changes in the rate of the release of the L-ascorbic acid derivatives were monitored using the Franz diffusion cells. The obtained data were statistically significant, and indicated an increase in the degree of hydration of the skin and skin whitening potential, while no significant changes in TEWL and pH values were detected. The consistency, firmness and stickiness of the emulgels were estimated by volunteers applying the established sensory evaluation protocol. In addition, it was revealed that the difference in hydrophilic/lipophilic properties of L-ascorbic acid derivatives influenced their release profiles without changing their textural characteristics. Therefore, this study highlighted emulgels as L-ascorbic acid suitable carrier systems and one of the promising candidates as novel drug delivery systems.

Recovery of Polyphenolic Compounds and Vitamins from the Stinging Nettle Leaves: Thermal and Behavior and Biological Activity of Obtained Extracts.

Stinging nettle (SN) is an extraordinary plant from the Urticaceae botanical family. It is well-known and widely used in food and folk medicine to treat different disorders and diseases. This article aimed to study the chemical composition of SN leaves extracts, i.e., polyphenolic compounds and vitamins B and C, because many studies ascribed high biological potency to these compounds and their significance in the human diet. Besides the chemical profile, the thermal properties of the extracts were studied. The results confirmed presence of many polyphenolic compounds and vitamins B and C. It also showed that the chemical profile closely correlated with the applied extraction technique. The thermal analysis showed that analyzed samples were thermally stable up to about 160 °C. Thermal degradation of samples UAE, MAE, and MAC took place in four steps, and sample SE in three steps. Altogether, results confirmed the presence of health-beneficial compounds in stinging nettle leaves and indicated the possible application of its extract in pharmaceutical and food industries as both a medicinal and food additive.

The Effects of rGO Content and Drying Method on the Textural, Mechanical, and Thermal Properties of rGO/Polymer Composites.

Composite hydrogels samples consisting of poly(methyl methacrylate/butyl acrylate/2-hydroxyethylmethacrylate) (poly-OH) and up to 60% reduced graphene oxide (rGO) containing rGO were synthesized. The method of coupled thermally induced self-assembly of graphene oxide (GO) platelets within a polymer matrix and in situ chemical reduction of GO was applied. The synthesized hydrogels were dried using the ambient pressure drying (APD) and freeze-drying (FD) methods. The effects of the weight fraction of rGO in the composites and the drying method on the textural, morphological, thermal, and rheological properties were examined for the dried samples. The obtained results indicate that APD leads to the formation of non-porous xerogels (X) of high bulk density (D), while FD results in the formation of highly porous aerogels (A) with low D. An increase in the weight fraction of rGO in the composite xerogels leads to an increase in D, specific surface area (SA), pore volume (Vp), average pore diameter (dp), and porosity (P). With an increase in the weight fraction of rGO in A-composites, the D values increase while the values of SP, Vp, dp, and P decrease. Thermo-degradation (TD) of both X and A composites takes place through three distinct steps: dehydration, decomposition of residual oxygen functional group, and polymer chain degradation. The thermal stabilities (TS) of the X-composites and X-rGO are higher than those of the A-composites and A-rGO. The values of the storage modulus (E') and the loss modulus (E") of the A-composites increase with the increase in their weight fraction of rGO.

Indigo Carmine in a Food Dye: Spectroscopic Characterization and Determining Its Micro-Concentration through the Clock Reaction.

Indigo carmine is a commonly used industrial blue dye. To determine its concentration in a commercially available food dye composed of a mixture of indigo carmine and D-glucose, this paper characterizes it through (ATR, KBr) FTIR micro-Raman as well as UV/Vis and clock: Briggs-Rauscher (BR) oscillatory reaction methods. The indigo carmine was detected in the bulk food dye only by applying micro-Raman spectroscopy, indicating a low percentage of the indigo carmine present. This research provides an improvement in the deviations from the experimental Raman spectrum as calculated by the B97D/cc-pVTZ level of theory one, resulting in a better geometrical optimization of the indigo carmine molecule compared to data within the literature. The analytical curves used to determine indigo carmine concentrations (and quantities) in an aqueous solution of food dye were applied by means of UV/Vis and BR methods. BR yielded significantly better analytical parameters: 100 times lower LOD and LOQ compared to commonly used UV/Vis. The remarkable sensitivity of the BR reaction towards indigo carmine suggests that not only does indigo carmine react in an oscillatory reaction but also its decomposition products, meaning that the multiple oxidation reactions have an important role in the BR's indigo carmine mechanism. The novelty of this research is the investigation of indigo carmine using a clock BR reaction, opening new possibilities to determine indigo carmine in other complex samples (pharmaceutical, food, etc.).

The effect of various extraction techniques on the quality of sage (Salvia officinalis L.) essential oil, expressed by chemical composition, thermal properties and biological activity.

In this study, influence of the extraction techniques on the quality of the sage essential oil was investigated. Obtained samples were analyzed for chemical composition by GC/MS, thermal properties by thermogravimetric analysis (TGA), and for biological activity: antioxidant (DPPH, CUPRAC, FRAP, ABTS, HRSA and TBARS), microbiological (Staphylococcus aureus, Escherichia coli, Bacillus subtilis, Pseudomonas aeruginosa, Candida albicans, and Aspergillus niger), and cytotoxic (HeLa, LS-174, A549 and MRC-5) activities. Chemical composition showed that viridiflorol was principal compound in all samples followed by camphor, thujones, and verticiol. MWD 400 W was the most potent antioxidant agent, D 200 W and MWD 400 W antimicrobial agents, while hydrodistallates (D 200 W and D 400 W) were the most potent cytotoxic agents. An artificial neural network model was developed for the antioxidant activity anticipation of analyzed samples. These models showed good prediction properties (the r2 value during training cycle for output variables was 0.998).

Recovery of biologically active compounds from stinging nettle leaves part I: Supercritical carbon dioxide extraction.

Stinging nettle is annual plant from Urticaceae family used as food and medicine. Due to the nonsufficient data, this work aimed to isolate the bioactive compounds from the stinging nettle leaves by supercritical carbon dioxide. Extracts were analyzed and assessed for antioxidant and cytotoxic activities. Main fatty acids were α-linolenic (31.06-58.42 mg/g E), palmitic (9.17-13.12 mg/g E), and linoleic (10.93-16.51 mg/g E) acids. Chlorophylls (33.00-7365.11 mg/100 g E) and carotenoids (166.88-722.62 mg/100 g E) were also found in all samples. Four empirical kinetic equations were effectively utilized for kinetic modeling of supercritical fluid extraction. As per proper statistical features, empirical models show good concurrence with experimental data. The numerical modeling of a process is gainful to foresee the process conduct and furthermore extend the methodology from laboratory to industrial scales. The principal component analysis was used to visualize the fatty acids profile, antioxidant capacity, and cytotoxic activity of extract.

Rosemary Essential Oils as a Promising Source of Bioactive Compounds: Chemical Composition, Thermal Properties, Biological Activity, and Gastronomical Perspectives.

Rosemary (Rosmarinus officinalis L.) is a plant worldwide cultivated mainly for essential oils, extracts, and as a spice. Up-to-date results showed diversity in composition of the essential oils, which may influence their quality, biological activity, and thermal properties. Therefore, the aim of this study was to investigate the chemical composition, antimicrobial activity, and thermal properties of the rosemary essential oils originating from Serbia and Russia. Additionally, oils were added to the sunflower oils in order to investigate possible antioxidant activity during the frying. Investigation of the chemical profile marked α-pinene, eucalyptol, and camphor as the most abundant compounds in both oils. However, overall composition influenced in such manner that Russian oil showed significantly higher antimicrobial activity, while Serbian oil proved to be better antioxidant agent in case of frying of sunflower oil. This would significantly influence possible application of the oils, which could be used as an antioxidant agent for extension of the food shelf life, or antimicrobial agent for protection against different microbial strains.

Distribution of polyphenolic and sugar compounds in different buckwheat plant parts.

The aim of this study was to provide information on the phenolic and sugar profiles of different parts of the buckwheat plant, which can define that buckwheat is a functional food, with a high nutritional value and very useful for human health. Therefore, the extracts of buckwheat leaf, stem, and flower, as well as buckwheat grain were analysed for the content of polyphenol and antioxidant tests. The identification of a notable number of phenolic compounds and quantification of sugars in different parts of buckwheat indicates that buckwheat is a highly valuable plant. A total of 60 phenolic compounds were identified (18 cinnamic acid derivatives, 14 flavonols, 13 flavan-3-ols (including proanthocyanidins), 10 hydroxybenzoic acid derivatives, and 5 flavones) using ultra-high-performance liquid chromatography (UHPLC), coupled with a hybrid mass spectrometer which combines the Linear Trap Quadrupole (LTQ) and OrbiTrap mass analyzer. The highest number of phenolic compounds was found in the analysed buckwheat flower sample, and then in the leaf, followed by the grain and the stem. In addition, the sugar profile of buckwheat leaf, stem, flower and grain, as well as the buckwheat pollen and the nectar was analysed. Hence, 16 sugars and 5 sugar alcohols were detected by the high-performance anion exchange chromatography (HPAEC) with a pulsed amperometric detector (PAD). Sucrose was found in a significant amount with the highest content in buckwheat leaf. Trisaccharides had similar accumulation in the sample extracts, while disaccharides dominated in buckwheat leaf, followed by nectar and pollen. The sugar alcohols showed the highest content in buckwheat grain, where erythritol was predominant. The obtained results show that buckwheat is very rich in phenolic compounds and sugars. In addition to grain, the other parts of the buckwheat plant can be used as a very good source of different classes of phenolic compounds. This study provides useful information on the distribution of phytochemicals in different parts of the buckwheat plant, which contribute to the maintaining of the status of buckwheat as a functional food.

Chemical composition and antimicrobial activity of Osage orange (Maclura pomifera) leaf extracts.

The main goal of this study was to establish the chemical profile of Osage orange (Maclura pomifera) leaf extracts, obtained by conventional maceration technique, and to examine its antimicrobial activity. The identification and quantification of the extract compounds were done using ultra-high-performance liquid chromatography, with a diode array detector coupled with triple-quadrupole mass spectrometer and gas chromatography-mass spectrometry techniques. Thirty-one polyphenolic compounds were detected and identified in the ethanolic extracts, whereby 5-O-caffeoylquinic acid was found to be the dominant compound. Among other compounds, pentacosane and palmitic acid were the most abundant compounds in the dichloromethane extract. The preliminary antimicrobial activity screening shows that Gram-positive bacteria tend to be more sensitive to the investigated extracts. The highest antimicrobial activity was determined against Enterococcus faecalis ATCC 19433 and Listeria monocytogenes ATCC 35152. From these results, Osage orange leaves can be considered as plant material with significant antimicrobial properties.

Polyphenol profile of buckwheat honey, nectar and pollen.

A focus of research in recent years is the comparison of honey as the final product of bees with pollen and nectar of the plant from which the honey originates, as the main food source for bees. Buckwheat honey is recognized as a nutritionally valuable product, which provides a scientifically proven health benefit and is confirmed as a functional food. The quality of this type of honey is attributed to high levels of phytochemicals in buckwheat. The purpose of this study was the examination of similarity between buckwheat honey and buckwheat nectar and pollen, as well as simultaneous investigation of their chemical profiles and the origin of the honey. The phenolic profile of buckwheat pollen showed a lower number of flavonoids and phenolic acids than those of nectar and honey samples, but confirmed the presence of the most characteristic polyphenols derived from the buckwheat plant. The notable difference was found to be the presence of (epi)catechin units, its galloylated derivatives and procyanidin dimers, which were not present in honey. Honey polyphenols displayed a pronounced correlation with those of nectar, but not with those of pollen. Finally, by comparing the polyphenolic profiles of honey, nectar and pollen sharing the same geographical origin, new data could be provided for a potential assessment of the botanical origin of buckwheat honey.

Physicochemical analysis and phenolic profile of polyfloral and honeydew honey from Montenegro.

The research subject of this paper was a detail physicochemical analysis of 28 honey samples from the northern part of Montenegro. The honey from Montenegro has not been previously studied in such detail. Differentiation between samples, such as honeydew honey and polyfloral honey, was based on electrical conductivity, which was higher than 0.8 mS cm-1 for honeydew honey, as was expected. Other investigated physicochemical parameters (water content, free acids, diastase activity, hydroxymethylfurfural (HMF) content and sugar content) have shown great similarity for all honey samples. The main interest of this study was the identification and quantification of phenolic compounds using ultra-high performance liquid chromatography (UHPLC) with mass spectrometry detection. The results show that honey samples are very rich in phenolic compounds, especially quercetin. Among the 31 quantified phenolic compounds, the most dominant were phenolic acids. The highlight was based on p-hydroxybenzoic acid, p-coumaric acid, caffeic acid and ferulic acid. Considering polyphenolic compounds and sugar content, a high nutritional value can be observed in all samples, with an emphasis on polyfloral honeys, as was confirmed with principal component analysis (PCA). In addition, all honey samples were tested for total phenolic content (TPC) and radical scavenging activity (RSA). The results indicate the higher antioxidant ability of honeys from Montenegro in comparison to some honey samples from other countries in the region.

Rhamnolipid inspired lipopeptides effective in preventing adhesion and biofilm formation of Candida albicans.

Rhamnolipids are biodegradable low toxic biosurfactants which exert antimicrobial and anti-biofilm properties. They have attracted much attention recently due to potential applications in areas of bioremediation, therapeutics, cosmetics and agriculture, however, the full potential of these versatile molecules is yet to be explored. Based on the facts that many naturally occurring lipopeptides are potent antimicrobials, our study aimed to explore the potential of replacing rhamnose in rhamnolipids with amino acids thus creating lipopeptides that would mimic or enhance properties of the parent molecule. This would allow not only for more economical and greener production but also, due to the availability of structurally different amino acids, facile manipulation of physico-chemical and biological properties. Our synthetic efforts produced a library of 43 lipopeptides revealing biologically more potent molecules. The structural changes significantly increased, in particular, anti-biofilm properties against Candida albicans, although surface activity of the parent molecule was almost completely abolished. Our findings show that the most active compounds are leucine derivatives of 3-hydroxy acids containing benzylic ester functionality. The SAR study demonstrated a further increase in activity with aliphatic chain elongation. The most promising lipopeptides 15, 23 and 36 at 12.5 µg/mL concentration allowed only 14.3%, 5.1% and 11.2% of biofilm formation, respectively after 24 h. These compounds inhibit biofilm formation by preventing adhesion of C. albicans to abiotic and biotic surfaces.