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.

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.

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.

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.

Polyphenolics profile effects upon the antioxidant and antimicrobial activity of propolis extracts.

Propolis, a complex bee product, is a source of numerous bioactive principles, beneficial for human health, therefore it is intensively studied. In the present work, extracts of propolis from Bihor Romanian County were studied to identify the relationship between the polyphenolic derivatives profile and their antioxidant and antimicrobial activity. Extracts were obtained using water and 25%, 50%, and 70% ethanolic solutions (w/w), at 2:1, 4:1, and 6:1 liquid: solid ratios (w/w). 21 polyphenolic derivatives were quantified by UHPLC-MS, proving that the extracts composition strongly depends on the solvent. The sum of quantified polyphenolics extracted varied between 1.5 and 91.2 mg/g propolis. The antioxidant capacity was evaluated using the free radicals 2,2'-azino-bis (3-ethylbenzothiazoline-6 sulfonic acid) diammonium salt (ABTS) and 1-diphenyl-2-picryl-hydrazyl (DPPH) scavenging methods. Antimicrobial efficiency was tested against Gram-positive (B. subtilis), Gram-negative bacteria (E. coli), and fungi (C. albicans) by disc-diffusion method. All extracts, even the aqueous ones, demonstrated antibacterial and antifungal activity. Chemometric methods (partial least squares) and a saturation-type model were used to evaluate the contribution of various bioactive principles in building the antioxidant capacity of extracts. Both experimental and modelling results show that 50% ethanolic extracts provide a rich polyphenolics profile and ensure a good antioxidant capacity.

Profiling of Phenolic Compounds and Triterpene Acids of Twelve Apple (Malus domestica Borkh.) Cultivars.

Apple (Malus domestica Borkh.), a popular and widely cultivated fruit world-wide, contains bioactive compounds responsible for their health benefits. Here we report the amounts of some bioactive compounds: two major triterpenes (oleanolic and ursolic acids) and polyphenols (phenolic acids, flavan-3-ols, flavonoids and t-resveratrol), together with bioactive properties of twelve apple cultivars measured by chromatographic and spectrophotometric methods. Significant variations were found comparing the bioactive potential of the investigated cultivars. High contents of phenolic acids were identified in the Montuan, Golden Delicious and Cretesc cultivars, while the most flavonoid dominant was the Richard cultivar. Starkrimson, Jonatan, Beliy Naliv and Richard cultivars present higher antioxidant capacity. Oleanolic acid ranged from 11 to 83 mg/g apple extract, while ursolic acid ranged from 55 to 436 mg/g apple extract, with higher amounts in Richard and Montuan cultivars. Principal component analysis (PCA) and hierarchical cluster analysis (HCA) allowed the discrimination of apple cultivars depending on polyphenolic and triterpene acids composition. Caffeic acid, gallic acid and epicatechin were identified as the main bioactive compounds in Starkrimson, Jonathan, Beliy Naliv and Richard cultivars, while ursolic and oleanolic acids were identified in high amounts in Richard, Montuan, Golden Delicious, Idared and Beliy Naliv apple cultivars. The results obtained in this study will contribute to the understanding of the bioactive composition of apples as well as the importance of their capitalization to obtain value-added products that promote human health.

Establishing authenticity of honey via comprehensive Romanian honey analysis.

Assessing the authenticity of honey is a serious problem that has gained much interest internationally because honey has frequently been subject to various fraudulent practices, including mislabelling of botanical and geographical origin and mixing with sugar syrups or honey of lower quality. To protect the health of consumers and avoid competition, which could create an unstable market, consumers, beekeepers and regulatory bodies are interested in having reliable analytical methodologies to detect non-compliant honey. This paper gives an overview of the different approaches used to assess the authenticity of honey, specifically by the application of advanced instrumental techniques, including spectrometric, spectroscopic and chromatographic methods coupled with chemometric interpretation of the data. Recent development in honey analysis and application of the honey authentication process in the Romanian context are highlighted, and future trends in the process of detecting and eliminating fraudulent practices in honey production are discussed.

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.

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.