Discrimination of Olive Oil and Extra-Virgin Olive Oil from Other Vegetable Oils by Targeted and Untargeted HRMS Profiling of Phenolic and Triterpenic Compounds Combined with Chemometrics.

Extra-virgin olive oil (EVOO) and virgin olive oil (VOO) are valuable natural products of great economic interest for their producing countries, and therefore, it is necessary to establish methods capable of proving the authenticity of these oils on the market. This work presents a methodology for the discrimination of olive oil and extra-virgin olive oil from other vegetable oils based on targeted and untargeted high-resolution mass spectrometry (HRMS) profiling of phenolic and triterpenic compounds coupled with multivariate statistical analysis of the data. Some phenolic compounds (cinnamic acid, coumaric acids, apigenin, pinocembrin, hydroxytyrosol and maslinic acid), secoiridoids (elenolic acid, ligstroside and oleocanthal) and lignans (pinoresinol and hydroxy and acetoxy derivatives) could be olive oil biomarkers, whereby these compounds are quantified in higher amounts in EVOO compared to other vegetable oils. The principal component analysis (PCA) performed based on the targeted compounds from the oil samples confirmed that cinnamic acid, coumaric acids, apigenin, pinocembrin, hydroxytyrosol and maslinic acid could be considered as tracers for olive oils authentication. The heat map profiles based on the untargeted HRMS data indicate a clear discrimination of the olive oils from the other vegetable oils. The proposed methodology could be extended to the authentication and classification of EVOOs depending on the variety, geographical origin, or adulteration practices.

Synthesis and Antimicrobial Activity Evaluation of Homodrimane Sesquiterpenoids with a Benzimidazole Unit.

Herein we report a feasible study concerning the synthesis and the in vitro antimicrobial activity of some new homodrimane sesquiterpenoids with a benzimidazole unit. Based on some homodrimane carboxylic acids, on their acyl chlorides and intermediate monoamides, a series of seven N-homodrimenoyl-2-amino-1,3-benzimidazoles and 2-homodrimenyl-1,3-benzimidazoles was synthesized. The syntheses involved the decarboxylative cyclization and condensation of the said acids or acyl chlorides with o-phenylendiamine and 2-aminobenzimidazole, as well as the p-TsOH-mediated cyclodehydration of the said monoacylamides. The structures of the synthesized compounds have been fully confirmed, including by the X-ray diffraction. Their biological activities were evaluated on five species of fungi (Aspergillus niger, Fusarium solani, Penicillium chrysogenum, P. frequentans, and Alternaria alternata) and two strains of bacteria (Bacillus sp. and Pseudomonas aeruginosa). Compounds 7 and 20 showed higher antifungal (MIC = 0.064 and 0.05 µg/mL) and antibacterial (MIC = 0.05 and 0.032 µg/mL) activities compared to those of the standards: caspofungin (MIC = 0.32 µg/mL) and kanamycin (MIC = 2.0 µg/mL), and compounds 4, 10, 14, and 19 had moderate activities.

Synthesis of Homodrimane Sesquiterpenoids Bearing 1,3-Benzothiazole Unit and Their Antimicrobial Activity Evaluation.

Based on some homodrimane carboxylic acids and their acyl chlorides, a series of fourteen 2-homodrimenyl-1,3-benzothiazoles, N-homodrimenoyl-2-amino-1,3-benzothiazoles, 4'-methyl-homodrimenoyl anilides and 4'-methyl-homodrimenthioyl anilides were synthesized and their biological activities were evaluated on five species of fungi (Aspergillus niger, Fusarium solani, Penicillium chrysogenum, P. frequentans, and Alternaria alternata) and two strains of bacteria (Bacillus sp. and Pseudomonas aeruginosa). The synthesis involved the decarboxylative cyclization, condensation and thionation of the said acids, anhydrides or their derivatives with 2-aminothiophenol, 2-aminobenzothiazole, p-toluidine and Lawesson's reagent. As a result, together with the desired compounds, some unexpected products 8, 25, and 27 were obtained, and the structures and mechanisms for their formation have been proposed. Compounds 4, 9, and 25 showed higher antifungal and antibacterial activity compared to the standards caspofungin (MIC = 1.5 µg/mL) and kanamycin (MIC = 3.0 µg/mL), while compound 8 had comparable activities. In addition, compounds 6, 17, and 27 showed selective antifungal activity at MIC = 2.0, 0.25, and 1.0 µg/mL, respectively.

Study of the impact of vine cultivation technology on the Feteasca Neagra wine phenolic composition and antioxidant properties.

In this work a comparative assessment was performed on individual and total polyphenols and biochemical properties of some Feteasca Neagra red wines obtained from grapes cultivated with different farming technologies (organic vs. conventional). The effect of a 30% cluster thinning treatment in both organic and conventional vineyard, compared to control plots with no thinning, was also monitored. The wines were obtained during two vintages, one with more favourable climatic conditions and one less favourable, in the period 2010-2019. Our results indicate that by applying a 30% cluster thinning treatment in the vineyard it is possible to increase the concentration of total and individual polyphenols of the resulted Feteasca Neagra wines. Furthermore, the differences observed between the phenolic profiles of wines from conventionally and organically produced grapes showed that organic Feteasca Neagra wines have higher phenolic compounds concentrations and antioxidant properties, with some important individual phenols accumulating in larger quantities than in the case of conventional wines. The beneficial effect of the organic cultivation is more evident in years characterised by less favourable climatic conditions. The statistical analysis tools applied to the analytical data allowed a good discrimination of experimental wine variants according to the vine cultivation technology (organic vs. conventional, with and without cluster thinning) and vintage. Thus, the results indicated that the applied cultivation technologies, especially when both organic cultivation and cluster thinning are combined, can greatly improve the polyphenolic content of Feteasca Neagra wines. The absolute value of the increase in polyphenol concentration was higher in favourable years, but the relative increase, in percentages, as compared to control wines, was higher in less favourable years. The combination of both viticultural practices may be thus exploited in order to obtain wines with higher polyphenolic content, which leads to better structure, better ageing potential, enhanced nutritional and antioxidant properties.

Demonstration of Allium sativum Extract Inhibitory Effect on Biodeteriogenic Microbial Strain Growth, Biofilm Development, and Enzymatic and Organic Acid Production.

To the best of our knowledge, this is the first study demonstrating the efficiency of Allium sativum hydro-alcoholic extract (ASE) againstFigure growth, biofilm development, and soluble factor production of more than 200 biodeteriogenic microbial strains isolated from cultural heritage objects and buildings. The plant extract composition and antioxidant activities were determined spectrophotometrically and by HPLC-MS. The bioevaluation consisted of the qualitative (adapted diffusion method) and the quantitative evaluation of the inhibitory effect on planktonic growth (microdilution method), biofilm formation (violet crystal microtiter method), and production of microbial enzymes and organic acids. The garlic extract efficiency was correlated with microbial strain taxonomy and isolation source (the fungal strains isolated from paintings and paper and bacteria from wood, paper, and textiles were the most susceptible). The garlic extract contained thiosulfinate (307.66 ± 0.043 µM/g), flavonoids (64.33 ± 7.69 µg QE/g), and polyphenols (0.95 ± 0.011 mg GAE/g) as major compounds and demonstrated the highest efficiency against the Aspergillus versicolor (MIC 3.12-6.25 mg/mL), A. ochraceus (MIC: 3.12 mg/mL), Penicillium expansum (MIC 6.25-12.5 mg/mL), and A. niger (MIC 3.12-50 mg/mL) strains. The extract inhibited the adherence capacity (IIBG% 95.08-44.62%) and the production of cellulase, organic acids, and esterase. This eco-friendly solution shows promising potential for the conservation and safeguarding of tangible cultural heritage, successfully combating the biodeteriogenic microorganisms without undesirable side effects for the natural ecosystems.

Valorization of Gleditsia triacanthos Invasive Plant Cellulose Microfibers and Phenolic Compounds for Obtaining Multi-Functional Wound Dressings with Antimicrobial and Antioxidant Properties.

Gleditsia triacanthos is an aggressive invasive species in Eastern Europe, producing a significant number of pods that could represent an inexhaustible resource of raw material for various applications. The aim of this study was to extract cellulose from the Gleditsia triacanthos pods, characterize it by spectrophotometric and UHPLC-DAD-ESI/MS analysis, and use it to fabricate a wound dressing that is multi-functionalized with phenolic compounds extracted from the leaves of the same species. The obtained cellulose microfibers (CM) were functionalized, lyophilized, and characterized by ATR-FTIR and SEM. The water absorption and retention capacity as well as the controlled release of phenolic compounds with antioxidant properties evaluated in temporal dynamics were also determined. The antimicrobial activity against reference and clinical multi-drug-resistant Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, Acinetobacter baumannii, Enterobacter cloacae, Candida albicans, and Candida parapsilosis strains occurred immediately after the contact with the tested materials and was maintained for 24 h for all tested microbial strains. In conclusion, the multi-functionalized cellulose microfibers (MFCM) obtained from the reproductive organs of an invasive species can represent a promising alternative for the development of functional wound dressings with antioxidant and antimicrobial activity, as well as being a scalable example for designing cost-effective, circular bio-economy approaches to combat the accelerated spread of invasive species.

Comparison of the Polyphenolic Profile of Medicago sativa L. and Trifolium pratense L. Sprouts in Different Germination Stages Using the UHPLC-Q Exactive Hybrid Quadrupole Orbitrap High-Resolution Mass Spectrometry.

Identification and quantification of polyphenols in plant material are of great interest since they make a significant contribution to its total bioactivity. In the present study, an UPLC-Orbitrap-MS/MS approach using the variable data acquisition mode (vDIA) was developed and applied for rapid separation, identification, and quantification of the main polyphenolic compounds in Medicago sativa L. and Trifolium pratense L. sprouts in different germination stages. Based on accurate MS data and fragment ions identification strategy, a total of 29 compounds were identified by comparing their accurate masses, fragment ions, retention times, and literatures. Additionally, a number of 30 compounds were quantified by comparing to the reference standards. Data were statistically analysed. For both plant species, the sprouts of the third germination day are valuable sources of bioactive compounds and could be used in phytotherapy and nutrition. Although Trifolium pratense L. (Red Clover) is considered to be a reference for natural remedies in relieving menopause disorders, alfalfa also showed a high level of biological active compounds with estrogenic activity.

Phenolic compounds profile and biochemical properties of honeys in relationship to the honey floral sources.

INTRODUCTION: Honey has been considered to have therapeutic properties since ancient times and among the factors responsible for such activity are phenolic compounds including phenolic acids and flavonoids from different natural sources. OBJECTIVE: This study investigated the phenolic compounds profile and bioactive properties of different honey types from Romanian flora in order to develop reliable tools for honey floral origin, thus contributing to the honey traceability in the European Union context. MATERIAL AND METHODS: Thirty-three honey samples were examined, including unifloral (acacia and rape), polyfloral, honeydew honeys and mixture honeys. Phenolic acids and flavonoids were isolated from the water soluble honey matrix using a solid-phase extraction (SPE) method and analysed by ultra-high-performance liquid chromatography diode array detector electrospray ionisation mass spectrometry (UHPLC-DAD-ESI/MS). Honey bioactive properties were measured in honey dissolved in 80% ethanol using UV-visible spectrophotometric methods. Multivariate statistical tools (principal component analysis and hierarchical clustering analysis) were used for honey classification. RESULTS: The results of this study confirm that honey samples had similar, but quantitatively different, phenolic acids and flavonoids profiles and bioactive properties, related with honey floral source. Coloured honeys, such as honeydew honey, show high phenolic composition and bioactive properties and implicitly a high therapeutic potential compared with the other floral honeys. CONCLUSION: Distinctive clusters obtained by principal component analysis enabled us to consider that honeydew and polyfloral honeys could be distinguished from acacia and rape honey with the analytical methods developed. Based on this study, the methods might be promising tools for honey traceability, which needs to be explored on a larger set of samples with different regional floral origins in future studies.

Application of Spectroscopic UV-Vis and FT-IR Screening Techniques Coupled with Multivariate Statistical Analysis for Red Wine Authentication: Varietal and Vintage Year Discrimination.

One of the most important issues in the wine sector and prevention of adulterations of wines are discrimination of grape varieties, geographical origin of wine, and year of vintage. In this experimental research study, UV-Vis and FT-IR spectroscopic screening analytical approaches together with chemometric pattern recognition techniques were applied and compared in addressing two wine authentication problems: discrimination of (i) varietal and (ii) year of vintage of red wines produced in the same oenological region. UV-Vis and FT-IR spectra of red wines were registered for all the samples and the principal features related to chemical composition of the samples were identified. Furthermore, for the discrimination and classification of red wines a multivariate data analysis was developed. Spectral UV-Vis and FT-IR data were reduced to a small number of principal components (PCs) using principal component analysis (PCA) and then partial least squares discriminant analysis (PLS-DA) and linear discriminant analysis (LDA) were performed in order to develop qualitative classification and regression models. The first three PCs used to build the models explained 89% of the total variance in the case of UV-Vis data and 98% of the total variance for FR-IR data. PLS-DA results show that acceptable linear regression fits were observed for the varietal classification of wines based on FT-IR data. According to the obtained LDA classification rates, it can be affirmed that UV-Vis spectroscopy works better than FT-IR spectroscopy for the discrimination of red wines according to the grape variety, while classification of wines according to year of vintage was better for the LDA based FT-IR data model. A clear discrimination of aged wines (over six years) was observed. The proposed methodologies can be used as accessible tools for the wine identity assurance without the need for costly and laborious chemical analysis, which makes them more accessible to many laboratories.

¹H-NMR Profiling and Carbon Isotope Discrimination as Tools for the Comparative Assessment of Walnut (Juglans regia L.) Cultivars with Various Geographical and Genetic Origins-A Preliminary Study.

：The aim of the study was to investigate the differences between walnut genotypes of various geographical and genetic origins grown under the same or different environmental conditions. The biological material analyzed consisted in walnut kernels of 34 cultivars, nine advanced selections, and six hybrids harvested in 2015 and 2016, summing up to a total of 64 samples. The walnuts, walnut oil, and residue were characterized in respect to their chemical (proximate composition-fat, protein, nutritional value, fatty acids profile by ¹H-NMR) and carbon-13 isotopic composition. The data was used to statistically discriminate the cultivars according to composition, geographical area of origin, and year of harvest, comparing the Romanian cultivars, selections, and hybrids with the internationally available ones.

Electrochemical Detection of Glyphosate in Surface Water Samples Based on Modified Screen-Printed Electrodes.

This study addresses the necessity to monitor the presence of glyphosate (Gly) in waters, highlighting the need for on-site detection of Gly by using electrochemical sensors in environmental and agricultural monitoring programs. Two approaches were employed: (1) modification with graphene decorated with gold nanoparticles (AuNPs-Gr) and dispersed in either dimethylformamide (DMF) or a solution containing Nafion and isopropanol (NAF), and (2) molecularly imprinted polymers (MIPs) based on polypyrrole (PPy) deposited on gold SPEs (AuSPE). Electrochemical characterization revealed that sensors made of AuNPs-Gr/SPCE exhibited enhanced conductivity, larger active area, and improved charge transfer kinetics compared to unmodified SPEs and SPEs modified with graphene alone. However, the indirect detection mechanism of Gly via complex formation with metallic cations in AuNPs-Gr-based sensors introduces complexities and compromises sensitivity and selectivity. In contrast, MIPPy/AuSPE sensors demonstrated superior performance, offering enhanced reliability and sensitivity for Gly analysis. The MIPPy/AuSPE sensor allowed the detection of Gly concentrations as low as 5 ng/L, with excellent selectivity and reproducibility. Moreover, testing in real surface water samples from the Olt River in Romania showed recovery rates ranging from 90% to 99%, highlighting the effectiveness of the detection method. Future perspectives include expanding the investigation to monitor Gly decomposition in aquatic environments over time, providing insights into the decomposition's long-term effects on water quality and ecosystem health, and modifying regulatory measures and agricultural practices for mitigating its impact. This research contributes to the development of robust and reliable electrochemical sensors for on-site monitoring of Glyphosate in environmental and agricultural settings.

Bee Bread: A Promising Source of Bioactive Compounds with Antioxidant Properties-First Report on Some Antimicrobial Features.

Bee bread has received attention due to its high nutritional value, especially its phenolic composition, which enhances life quality. The present study aimed to evaluate the chemical and antimicrobial properties of bee bread (BB) samples from Romania. Initially, the bee bread alcoholic extracts (BBEs) were obtained from BB collected and prepared by Apis mellifera carpatica bees. The chemical composition of the BBE was characterized by Fourier Transform Infrared Spectroscopy (FTIR) and the total phenols and flavonoid contents were determined. Also, a UHPLC-DAD-ESI/MS analysis of phenolic compounds (PCs) and antioxidant activity were evaluated. Furthermore, the antimicrobial activity of BBEs was evaluated by qualitative and quantitative assessments. The BBs studied in this paper are provided from 31 families of plant species, with the total phenols content and total flavonoid content varying between 7.10 and 18.30 mg gallic acid equivalents/g BB and between 0.45 and 1.86 mg quercetin equivalents/g BB, respectively. Chromatographic analysis revealed these samples had a significant content of phenolic compounds, with flavonoids in much higher quantities than phenolic acids. All the BBEs presented antimicrobial activity against all clinical and standard pathogenic strains tested. Salmonella typhi, Candida glabrata, Candida albicans, and Candida kefyr strains were the most sensitive, while BBEs' antifungal activity on C. krusei and C. kefyr was not investigated in any prior research. In addition, this study reports the BBEs' inhibitory activity on microbial (bacterial and fungi) adhesion capacity to the inert substratum for the first time.

Status of different anthropogenic organic pollutants accumulated in sediments from Olt River Basin, Romania: From distribution and sources to risk assessment.

Some organic pollutants including organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) have been banned from production worldwide, but due to their toxicity and persistence are still of concern. Also, unintentional by-products of combustion and industrial processes such as polycyclic aromatic hydrocarbons (PAHs), represent a permanent threat to the safety of the environment and the population. In this study, surface sediment samples from the middle and lower Olt River Basin (ORB), Romania, including dams, the main tributaries and the confluence with Danube River were collected during seasonal sampling campaigns in 2019 and analyzed for 13 OCPs, 12 PCBs and 15 PAHs in order to evaluate the impact of the main anthropogenic activities in the area (industrial activities and agriculture) and the ecological status of the ORB. The registered levels of OCPs, PCBs and PAHs in surface sediments varied from low to significantly polluted environments, indicating a clear spatial distribution between sites based on concentrations and congener profiles correlated with the influence of anthropogenic activities in the surrounding area. Based on some molecular diagnostic ratio and multivariate statistical analysis, both non-point sources and point sources deposition by surface runoff or atmospheric deposition were identified. Overall, the contamination profile of the study area reveals significant amounts of organochlorine compounds, resulting from the industrial production of chlorinated products, including lindane, but also from the long-term agricultural use of both HCHs and DDTs, more than half of the sites having levels that pose a potential risk for benthic organisms. Therefore, levels of POPs in the hot-spots sampling locations raise numerous concerns about the safety of the environment and the population in the region, requiring immediate actions.

Distribution, sources and ecological risk assessment of polycyclic aromatic hydrocarbons in waters and sediments from Olt River dam reservoirs in Romania.

This study provides important data on the distribution, sources and ecological risks of polycyclic aromatic hydrocarbons (PAHs), in surface waters and sediments collected from dam reservoirs on middle and lower course of the Olt River, the main tributary of the Danube, until the discharge into the Black Sea. A wide variation range of total PAHs concentrations in water (from 1.3 to 46.2 ng/L) and sediment (from 1.78 to 614.04 µg/kg) samples was emphasized by the results. The highest average PAHs concentration in water was recorded in the cold season and the lowest in the summer. In sediments, no differences were observed depending on the sampling period. Spatial distribution of PAHs in waters and sediments was correlated with the main anthropogenic activities along the river course. Regardless of the method used to attribute PAH sources (diagnostic ratios of specific PAHs, principal component analysis and hierarchical cluster analysis), it was confirmed that the potential anthropogenic sources of PAHs were both pyrogenic (incomplete combustion of biomass and coal) and pyrolytic (incomplete combustion of liquid fossil fuels and vehicle exhaust emissions), with a dominant pyrolytic input. Ecological risk assessment based on environmental quality standards, mean effect range-median quotient (m-ERM-Q), toxic equivalency factors (TEFs) and risk quotient (RQ) methods indicated potentially low ecological risks from PAHs. The ecological status of the Olt river waters poses no potential risk, and pollution of surface sediments can be classified as low polluted, except for two sites near industrial activities classified as moderately polluted. Therefore, a regular monitoring of PAHs concentration in the waters and sediments should be performed to prevent further contamination of PAHs in the studied area, especially in densely populated industrial areas.

Hybrid nanomaterial-based indirect electrochemical sensing of glyphosate in surface water: a promising approach for environmental monitoring.

Glyphosate (GLY), a widely utilized pesticide, poses a significant threat to human health even at minute concentrations. In this study, we propose an innovative electrochemical sensor for the indirect detection of GLY in surface water samples. The sensor incorporates a nanohybrid material composed of multi-layer graphene decorated with gold nanoparticles (AuNPs), synthesized in a single-step electrochemical process. To ensure portability and on-site measurements, the sensor is developed on a screen-printed electrode, chosen for its integration and miniaturization capabilities. The proposed sensor demonstrates remarkable sensitivity and selectivity for GLY detection in surface water samples, with an exceptional limit of detection (LOD) of 0.03 parts per billion (ppb) in both buffer and surface water matrices. Moreover, it exhibits a remarkably high sensitivity of 0.15 µA ppb-1. This electrochemical sensor offers a promising approach for accurate GLY monitoring, addressing the urgent need for reliable pesticide detection in environmental samples. The proposed sensor showed high selectivity towards GLY, when analysed in the presence of other pesticides such as phosmet, chlorpyrifos and glufosinate-ammonium. The recovery percentages of GLY from spiked surface water samples were between 93.8 and 98.9%. The study's broader implications extend to revolutionizing the way environmental chemistry addresses pesticide contamination, water quality assessment, and sustainable management of environmental pollutants. By pushing the boundaries of detection capabilities and offering practical solutions, this research contributes to the advancement of knowledge and practices that are essential for preserving and protecting our environment.

Antioxidant and Wound Healing Bioactive Potential of Extracts Obtained from Bark and Needles of Softwood Species.

Interest in the extraction of phytochemical bioactive compounds, especially polyphenols from biomass, has recently increased due to their valuable biological potential as natural sources of antioxidants, which could be used in a wide range of applications, from foods and pharmaceuticals to green polymers and bio-based materials. The present research study aimed to provide a comprehensive chemical characterization of the phytochemical composition of forest biomass (bark and needles) of softwood species (Picea abies L., H. Karst., and Abies alba Mill.) and to investigate their in vitro antioxidant and antimicrobial activities to assess their potential in treating and healing infected chronic wounds. The DPPH radical-scavenging method and P-LD were used for a mechanistic explanation of the biomolecular effects of the investigated bioactive compounds. (+)-Catechin, epicatechin, rutin, myricetin, 4 hydroxybenzoic and p-cumaric acids, kaempherol, and apigenin were the main quantified polyphenols in coniferous biomass (in quantities around 100 µg/g). Also, numerous phenolic acids, flavonoids, stilbenes, terpenes, lignans, secoiridoids, and indanes with antioxidant, antimicrobial, anti-inflammatory, antihemolytic, and anti-carcinogenic potential were identified. The Abies alba needle extract was more toxic to microbial strains than the eukaryotic cells that provide its active wound healing principles. In this context, developing industrial upscaling strategies is imperative for the long-term success of biorefineries and incorporating them as part of a circular bio-economy.

Recent progresses in compound specific isotope analysis of halogenated persistent organic pollutants. Assessing the transformation of halogenated persistent organic pollutants at contaminated sites.

Compound specific isotope analysis was extensively used to characterise the environmental processes associated with the abiotic and biotic transformation of persistent halogenated organic pollutants including those of contaminants of emerging concern (CECs). In the last years, the compound specific isotope analysis was applied as tool to evaluate the environmental fate and was expanded to larger molecules like brominated flame retardants and polychlorinated biphenyls. Multi-element (C, H, Cl, Br) CSIA methods have been also employed both in laboratory and field experiments. Nevertheless, despite the instrumental advances of isotope ratio mass spectrometers systems, the instrumental detection limit for gas chromatography-combustion-isotope ratio mass spectrometer (GC-C-IRMS) systems is challenging, especially when it is utilized to δ13C analysis. Liquid chromatography-combustion isotope ratio mass spectrometry methods are challenging, taking into consideration the chromatographic resolution required when analysing complex mixtures. For chiral contaminants, enantioselective stable isotope analysis (ESIA) has turned up as alternative approach but, up to now, it has been used for a limited number of compounds. Taking into consideration the occurrence of new emerging halogenated organic contaminants, new GC and LC methods for non-target screening using high resolution mass spectrometry are needed to be developed prior to the compound specific isotope analysis (CSIA) methods.

Do ultrasonic field effects upon the polyphenolics profile of propolis extracts improve their antioxidant and antimicrobial activity?

Ultrasound-assisted extraction (UAE) was applied for polyphenols extraction from Romanian propolis, followed by comparison with previous maceration work. The effects consisted not only in time reduction and extraction yield increase, but also in polyphenolics profile modification in terms of flavonoids / polyphenolic acids ratio. The operating parameters were ultrasounds (US) field exposure time (10-100 min), solvent composition (water, 25 % and 50 % ethanolic solutions, w/w), and liquid:solid ratio (2:1, 4:1 and 6:1, w:w), while keeping temperature constant. 24 polyphenolic derivatives were quantified by UHPLC-HRMS. UAE favored the extraction of pinocembrin, isorhamnetin and chrysin in water and 25 % ethanol, leading to different profiles than maceration, and further influences upon the antioxidant and antimicrobial activity. All extracts demonstrated increased antibacterial and antifungal activity compared to maceration, particularly the 50 % ethanolic extracts, which presented a three-times larger antioxidant capacity. Chemometric methods (Principal Component Analysis - PCA and Partial Least Squares Regression - PLS) and a saturation type model were used to correlate the polyphenolics profiles and antioxidant capacity. Experimental and modelling results concluded that 50 % ethanolic solutions and UAE represent the favorable operating conditions in terms of yield and extracts quality.

Bee Pollen Extracts: Chemical Composition, Antioxidant Properties, and Effect on the Growth of Selected Probiotic and Pathogenic Bacteria.

This paper evaluated the chemical and biological properties of bee pollen samples from Romania. Firstly, the bee pollen alcoholic extracts (BPEs) were obtained from raw bee pollen harvested by Apis mellifera carpatica bees. The chemical composition of BPE was obtained by determination of total phenol content and total flavonoid content, UHPLC-DAD-ESI/MS analysis of phenolic compounds, and GC-MS analysis of fatty acids, esters, and terpenes. Additionally, the antioxidant activity was evaluated by the Trolox Equivalent Antioxidant Capacity method. Furthermore, the biological properties of BPE were evaluated (antimicrobial and cytotoxic activity). The raw BP samples studied in this paper had significant phenolic acid and flavonoid content, and moderate fatty acid, ester, and terpene content. P1, P2, and P4 have the highest TPC and TFC levels, and the best antioxidant activity. All BPEs studied had antimicrobial activity on pathogenic strains isolated from the clinic or standard strains. A synergistic antimicrobial effect of the BPEs was observed along with the soluble compounds of L. rhamnosus MF9 and E. faecalis 2M17 against some pathogenic (clinical) strains and, considering the tumour proliferation inhibitory activity, makes BP a potential prebiotic and antitumour agent for the gut environment.

Wound Healing and Anti-Inflammatory Effects of a Newly Developed Ointment Containing Jujube Leaves Extract.

Ziziphus jujuba Mill. (jujube) is a well-known medicinal plant with pronounced wound healing properties. The present study aimed to establish the chemical composition of the lyophilized ethanolic extract from Romanian Ziziphus jujuba leaves and to evaluate the healing and anti-inflammatory properties of a newly developed lipophilic ointment containing 10% dried jujube leaves extract. The ultra-High-Performance Liquid Chromatography Electrospray Ionization Tandem Mass Spectrometry method was used, and 47 compounds were detected, among them the novel epicatechin and caffeic acid. The extract contains significant amounts of rutin (29.836 mg/g), quercetin (15.180 mg/g) and chlorogenic acid (350.96 µg/g). The lipophilic ointment has a slightly tolerable pH, between 5.41-5.42, and proved to be non-toxic in acute dermal irritation tests on New Zealand albino rabbits and after repeated administration on Wistar rats. The ointment also has a healing activity comparable to Cicatrizin (a pharmaceutical marketed product) on Wistar rats and a moderate anti-inflammatory action compared to the control group, but statistically insignificant compared to indomethacin in the rat-induced inflammation test by intraplantar administration of kaolin. The healing and anti-inflammatory properties of the tested ointment are due to phenolic acids and flavonoids content, less because of minor components as apocynin, scopoletin, and isofraxidin.