Entropy-weighted water quality index, hydrogeochemistry, and Monte Carlo simulation of source-specific health risks of groundwater in the Morava River plain (Serbia).

Population growth, urbanization, industry, floods, and agriculture globally degrade groundwater in river plains, necessitating action for its quality assessment and management. Hence, a comprehensive methodology, including hydrogeochemical facies (Piper, Gibbs), irrigation indices (SAR, Wilcox), entropy-weighted water quality index (EWQI), positive matrix factorization (PMF), and Monte Carlo simulation of source-specific health risks was used in this study to analyze groundwater in the Morava river plain (Serbia). The results revealed a prevalent Ca-Mg-HCO3 groundwater type, influenced by water-rock interactions. Although groundwater was found suitable for irrigation, only 66.7 % of the samples were considered drinkable. Agricultural activities, natural processes, and municipal wastewater were identified as primary pollution sources. The incremental lifetime cancer risk (ILCR) and hazard index (HI) threshold exceedance for adults and children ranged from 8.5 % to 39 % of the samples, with arsenic identified as the most risk-contributing contaminant. These findings provide valuable insights for researchers studying groundwater vulnerability in river plains.

Ionic liquids in green analytical chemistry-are they that good and green enough?

The widespread use of ionic liquids (ILs) as greener solvents in analytical sciences, especially in sample pretreatment, has focused attention on exploiting their enormous potential, not only on eliminating and improving the drawbacks faced by scientists. These ionic compounds with unique physicochemical properties can be tuned through smart synthesis, combining cations and anions, so that the compound exhibits excellent properties for its intended purpose. Ionic liquids are rightly referred to as designer solvents. Validation of a newly proposed analytical methods using ionic liquids, either in sample preparation or in further analysis, is a critical process to demonstrate that a particular analytical method is fit for purpose and provides reliable and accurate results. In addition, this article specially addressed the potential toxicity of ionic liquids with the modest goal of assisting researchers in this field by expanding their target areas.

Greener chemistry in analytical sciences: from green solvents to applications in complex matrices. Current challenges and future perspectives: a critical review.

More environment-friendly solvents in analytical chemistry are almost inevitable in both sample preparation and analysis to meet the high standards of sustainable chemistry and human welfare. In this review paper, a critical look at the advantages and still unsolved problems of most potential classes of green solvents is presented to give an overview of the current state-of-the-art in this field. Replacing volatile organic compounds (VOCs) by ecofriendly and benign solvents in extractions/separations in sample preparation, as the most tedious and demanding step in analysis, is one of roads toward sustainable chemistry. Water under sub- and supercritical conditions, carbon-dioxide, ionic liquids (ILs), deep eutectic solvents (DESs), and those of natural origin (NADES) belong to the most promising classes of solvents in green analytical chemistry. Basic theory and mechanisms of their use illustrated by representative but not exhaustive list of examples related to complex matrices (environmental and natural food products) from analytical practice are presented in this review. Perspectives of QuEChERS, in line with GAC principles, are highlighted, in line with current trends of "going green" for quick, easy, cheap, effective, rugged, and safe analytical methods. Compliance with green chemistry (GC), especially green analytical chemistry (GAC) principles, is not a fashionable issue but, more the trend toward a sustainable future with greener chemistry; thus, green metrics are an unavoidable tool to measure how green the applied method or procedure is. Herein, the most common tools will be presented and discussed, such as national environmental method index (NEMI), analytical ecoscale, green analytical procedure index (GAPI), analytical greenness calculator (AGREE), complementary green analytical procedure index (ComplexGAPI), and analytical greenness metric for sample preparation (AGREEprep). The future trends for research and development in this still expanding field are presented in a critical view of advantages and disadvantages as well as improvement of the validation of analytical procedures. The creation of new certified reference materials (CRMs) and validated methods for specified analytes in complex matrices is a demanding task in the coming years. Tailor-made solvents with physicochemical properties for intended use are required for the selective extraction and separation and open numerous possibilities and huge potential for future research and industrial applications.

Deep Eutectic Solvent Based Reversed-Phase Dispersive Liquid-Liquid Microextraction and High-Performance Liquid Chromatography for the Determination of Free Tryptophan in Cold-Pressed Oils.

A fast and straightforward reversed-phase dispersive liquid-liquid microextraction (RP-DLLME) using a deep eutectic solvent (DES) procedure to determine free tryptophan in vegetable oils was developed. The influence of eight variables affecting the RP-DLLME efficiency has been studied by a multivariate approach. A Plackett-Burman design for screening the most influential variables followed by a central composite response surface methodology led to an optimum RP-DLLME setup for a 1 g oil sample: 9 mL hexane as the diluting solvent, vortex extraction with 0.45 mL of DES (choline chloride-urea) at 40 °C, without addition of salt, and centrifugation at 6000 rpm for 4.0 min. The reconstituted extract was directly injected into a high-performance liquid chromatography (HPLC) system working in the diode array mode. At the studied concentration levels, the obtained method detection limits (MDL) was 11 mg/kg, linearity in matrix-matched standards was R2 ≥ 0.997, relative standard deviations (RSD) was 7.8%, and average recovery was 93%. The combined use of the recently developed DES -based RP-DLLME and HPLC provides an innovative, efficient, cost-effective, and more sustainable method for the extraction and quantification of free tryptophan in oily food matrices. The method was employed to analyze cold-pressed oils from nine vegetables (Brazil nut, almond, cashew, hazelnut, peanut, pumpkin, sesame, sunflower, and walnut) for the first time. The results showed that free tryptophan was present in the range of 11-38 mg/100 g. This article is important for its contributions to the field of food analysis, and for its development of a new and efficient method for the determination of free tryptophan in complex matrices, which has the potential to be applied to other analytes and sample types.

An application of the standardised reference extract quantification strategy in the quality control of ginseng infusions by liquid chromatography with mass spectrometric detection.

INTRODUCTION: Limited availability of individual standards is a bottleneck for quality control of functional foods and natural medicines. The use of standard mixtures or secondary standards is a possible alternative in this case. Earlier, an approach known as standardised reference extract (RE) strategy was introduced for HPLC-UV analysis of different plant materials; however, its application in HPLC-MS analysis has not been investigated. OBJECTIVE: To establish an HPLC-MS-based RE method for determination of ginsenoside content in ginseng infusions using commercially available extract reference material of Panax quinquefolius L. RESULTS: The developed HPLC-MS method was validated as precise (1.1%-9.4% intra-day variation; 1.6%-12.8% inter-day variation) and highly sensitive [limit of detection (LOD): 1-40 ng/mL; limit of quantification (LOQ): 4-120 ng/mL]. The stability of samples was satisfactory (5.7%-16.3%). The RE quantification method was compared with the external standard method, and the obtained difference was not significant, mostly in the range of 5%-10%. Matrix effects for the diluted samples of RE and ginseng infusions, determined via the standard addition method, were in the range of 85%-115% and 80%-126%, respectively, and were also positively correlated with the ginsenoside concentration. Eleven batches of ginseng infusions from different manufacturers were analysed using the established method. CONCLUSION: The method for HPLC-MS-based ginsenoside quantification using RE as a secondary standard was established for the first time. The results of this study demonstrate that the application of the standardised RE strategy in HPLC-MS can minimise the matrix effect-related error in addition to the cost-effective quality control of herbal products, foods, and traditional medicines.

Is a Lead Isotope Ratios in Wine Good Marker for Origin Assessment?

Lead isotope ratio pattern (206Pb/207Pb, 208Pb/206Pb, 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb) was analyzed in 59 samples of Serbian wine, from four geographical regions. By utilization of powerful inductively coupled plasma mass spectrometry (ICP-QMS), lead isotope ratios were used as unique "fingerprint", when combined with multivariate methods of analysis (Principal Component Analysis), provided information on the geographical origin of wine. In validation of ICP- QMS method and quantitative analysis, the certified reference material NIST SRM 981 was employed to test the mass-bias correction and thallium isotopes 203Tl and 205Tl (NIST SRM 997) as an internal standard. The obtained results were discussed in correlation with the corresponding values of LIRs of different European and Australian wines. In addition, the impact of anthropogenic Pb from different sources on the total Pb isotopic composition in Serbian wines was analyzed too. On the other side, the obtained values of Pb content were compared with the applicable health safety standards, according to the International Code of Oenological Practices.

Spatial distribution of multielements including lanthanides in sediments of Iron Gate I Reservoir in the Danube River.

Recent studies show that lanthanides (Ln) are becoming emerging pollutants due to their wide application in new technologies, but their environmental fate, transport, and possible accumulation are still relatively unknown. This study aims to determine major and trace elements including Ln in the Danube River sediment which either belong or close to the Iron Gate Reservoir. The Iron Gate Reservoir is characterized by accumulation of sediments as an effect of building hydropower dam Iron Gate I. The surface sediments were collected on the Danube River-1141 to 864 km and three tributaries along this waterway. Two samples of deep sediments were used for comparison. The results indicate the significant upward enrichment of Zn, Sb, Cr, Nd, and Dy in sediments belongs to the Iron Gate Reservoir. The sample 4-Smed is labelled as a hot spot of contamination with Zn, Cr, As, Sb, Nd, and Dy. Also, a trend of increasing concentration in the time period from 1995 to 2016 was found for elements Zn, Cr, and Ni in sediment samples in the Iron Gate Reservoir. Chemometric analysis shows the grouping of sample sites into clusters characterized by the following properties: (i) increased concentration of all measured elements (samples within the Iron Gate Reservoir); (ii) increased Cu concentration (11-Pek); and (iii) lower concentrations of the measured elements (deep sediments). The data presented hereby contribute to the monitoring of pollution of the River Danube sediments and give the first view of Ln profile in the studied sediments.

Chemometric Approach to a Rapid Attenuated Total Reflection Fourier Transform Infrared Analysis of Complex Heroin-Based Mixtures.

Heroin is one of the most frequently seized drugs in Southeastern Europe. Due to the position in the Balkan route, the Republic of Serbia keeps important role in suppression of the trafficking of heroin for domestic and foreign illegal market. This research is aimed to provide a good scientific approach in the field of seized heroin analysis. Two different forms of heroin are present in the illegal market, mostly in mixtures with typical "cutting" agents: caffeine, paracetamol, and sugars. It was observed that the quantity of pure heroin in seized samples slightly increases from year to year. The aim of this study was to produce a reliable and fast procedure for classification of illicit heroin samples and determination of the concentration range of heroin in the samples. For that purpose, the attenuated total reflection Fourier transform infrared spectroscopy (ATR FT-IR) technique was used and combined with such chemometric methods as principal component analysis, cluster analysis, and partial least squares. Principal component analysis (PCA) as an unsupervised model was used for exploratory purposes to identify trends, similarities, and differences between samples by reducing the dimensionality of the data. The cluster classification of examined samples turned out to be extremely useful to evaluate the possibilities of the ATR FT-IR technique to classify the samples appropriately into the patterns, the constituted clusters. Additionally, partial least square was the suitable method for the purpose of determination of the heroin hydrochloride concentration range in examined samples. It is proved that the joined application of spectroscopy and chemometrics can be extremely convenient and useful for forensic and drugs control laboratories.

Lead isotope ratios as tool for elucidation of chemical environment in a system of Macrolepiota procera (Scop.) Singer - soil.

The analysis of isotope ratios of lead in the mushrooms and soil, where they were grown, assisted with a principal component analysis, offered a new perspective for understanding possible chemical environment in a real setup of those compartments. The content of lead and its isotope compositions were determined in soil samples and mushroom Macrolepiota procera from unpolluted area of Mountain Goc, Serbia. Sequential extraction procedure based on the Commission of the European Community Bureau of Reference (BCR) was applied on soil samples in order to determine the distribution of lead in the labile and un-labile fractions of the soil. Caps and stipes of mushrooms were subjected to microwave acid-assisted digestion prior to measurements by inductively coupled plasma quadrupole mass spectrometer for determination of lead content and lead isotope ratios. Information about the chemical fractionation of Pb in soil, Pb isotopic data from soil fractions and fruiting bodies allowed a more detailed insight on the uptake mechanisms. Lead was predominantly associated with reducible fraction (~ 60%). Only its small portion (∼ 1%) was present in the exchangeable and acid-extractable fractions suggesting the low mobility of Pb. Lead isotope analysis revealed the presence of anthropogenic lead in the surface soil. Significant lower 206Pb/207Pb compared with other fractions was found in exchangeable and acid-soluble fraction (1.331 ± 0.010), which corresponds to the isotope ratio of European gasoline. The highest 206Pb/207Pb ratio was observed in reducible fraction (1.162 ± 0.007), while in oxidizable and residual fraction, those values were similar (1.159 ± 0.006 and 1.159 ± 0.004, respectively). Distinction of exchangeable and acid-extractable fractions from others was also confirmed, for the first time, by principal component analysis. The analysis of four isotope ratios (206Pb/207Pb, 208Pb/206Pb, 206Pb/204Pb, and 207Pb/204Pb) indicated that the analyzed M. procera accumulates lead from the first two fractions of topsoil layers.

Poly (ε-caprolactone) microspheres for prolonged release of selenium nanoparticles.

Poly (ε-caprolactone) (PCL) microspheres as a carrier for sustained release of antibacterial agent, selenium nanoparticles (SeNPs), were developed. The obtained PCL/SeNPs microspheres were in the range 1-4 µm with the encapsulation efficiency of about 90%. The degradation process and release behavior of SeNPs from PCL microspheres were investigated in five different degradation media: phosphate buffer solution (PBS), a solution of lipase isolated from the porcine pancreas in PBS, 0.1 M hydrochloric acid (HCl), Pseudomonas aeruginosa PAO1 cell-free extract in PBS and implant fluid (exudate) from the subcutaneously implanted sterile polyvinyl sponges which induce a foreign-body inflammatory reaction. The samples were thoroughly characterized by SEM, TEM, FTIR, XRD, PSA, DSC, confocal microscopy, and ICP-OES techniques. Under physiological conditions at neutral pH, a very slow release of SeNPs occurred (3 and 8% in the case of PBS or PBS + lipase, respectively and after 660 days), while in the acidic environment their presence was not detected. On the other hand, the release in the medium with bacterial extract was much more pronounced, even after 24 h (13%). After 7 days, the concentration of SeNPs reached a maximum of around 30%. Also, 37% of SeNPs have been released after 11 days of incubation of PCL/SeNPs in the implant exudate. These results suggest that the release of SeNPs from PCL was triggered by Pseudomonas aeruginosa PAO1 bacterium as well as by foreign body inflammatory reaction to implant. Furthermore, PCL/SeNPs microspheres were investigated in terms of their biocompatibility. For this purpose, cytotoxicity, the formation of reactive oxygen species (ROS), and genotoxicity were evaluated on HepG2 cell line. The interaction of PCL/SeNPs with phagocytic cell line (Raw 264.7 macrophages) was monitored as well. It was found that the microspheres in investigated concentration range had no acute cytotoxic effects. Finally, SeNPs, as well as PCL/SeNPs, showed a considerable antibacterial activity against Gram-positive bacteria: Staphylococcus aureus (ATCC 25923) and Staphylococcus epidermidis (ATCC 1228). These results suggest that PCL/SeNPs-based system could be an attractive platform for a prolonged prevention of infections accompanying implants.

Comparative in vitro studies of the biological potential and chemical composition of stems, leaves and berries Aronia melanocarpa's extracts obtained by subcritical water extraction.

Preparation of functional products as well as natural-based products requires non-toxic but effective extraction techniques. In this study, subcritical water extraction was used for the extraction of different aronia parts in order to explore their potential. Stems, leaves and berries of Aronia melanocarpa were extracted under the following conditions: temperature 130 °C; pressure 35 bar; time 20 min. The total phenols and flavonoid contents of the produced extracts were evaluated by conventional spectrophotometric methods. Additionally, the main phenolic compounds were also identified and quantified by high performance liquid chromatography with diode array detection (HPLC-DAD). The biological potential of the extracts was evaluated by determining their antioxidant (DPPH, ABTS and lipid peroxidation assays), antimicrobial, enzyme inhibitory (cholinesterase and elastase) and cytotoxic effects (HeLa, A-549, LS-174T, MRC-5 cell lines). The results indicate that leaves and berries extracts exhibited stronger antioxidant action when compared with stems. The strongest cholinesterase and elastase inhibitory activity was also found in berries extract. Similarly, the extracts obtained from leaves and berries showed considerable cytotoxic effects against tested cell lines. A moderate antimicrobial effects was observed too. Demonstrated biological potential of all three aronia parts can trace a new road map for developing newly designed functional products.

Analytical Approaches to the Characterization of Solid Drug Delivery Systems with Porous Adsorbent Carriers.

A large variety of analytical techniques are available to meet the needs of characterization of solid samples. But, when solid drug delivery systems are concerned we are faced with demanding methodologies which have to compile capabilities of analytical techniques in regard to large diversity of structures and surface functionality of analyzed adsorbent carriers. In this review, the most commonly used analytical techniques are presented with their basic principles, advantages and disadvantages in applications of interest. Adsorbent carriers are widely used today as ingredients in the formulation of pharmaceutical forms, for increasing the dissolution rate of the drug and hence the bioavailability. They are also used in the formulation of substances with modified or target drug release into a specific tissue. Methods of thermal analysis (Thermogravimetry - TGA, Differential Scanning Calorimetry - DSC and Thermal microscopy - TM), spectroscopic methods (Infrared Spectroscopy - IR, especially Fourier Transform Infrared Spectroscopy - FTIR and Raman spectroscopy), crystallographic methods (Powder X-Ray Diffraction - PXRD) and finally Scanning Electron Microscopy (SEM) are the most powerful in the characterization of modern therapeutic systems with porous adsorbents. The problem-solving power of each particular analytical method is often enhanced by using simultaneous methods rather than a single technique.

Accumulation of heavy metals from soil in medicinal plants.

Medicinal plants accumulate heavy metals from contaminated soil, and their consumption can cause poisoning. Our objective was to determine the levels of Pb, Cd, Zn, Cu, Fe, and Mn in four medicinal plant species (Achillea millefolium, Hypericum perforatum, Plantago lanceolata, and Urtica dioica) and their native soil, all sampled at a former smelter. The highest soil Cd, Pb, and Zn levels surpassed the maximum allowed limit 75-fold, 48-fold, and 14-fold, respectively. Their soil levels correlated with those in the plants, but this was not the case with Cu, Fe, and Mn. Heavy metal accumulation seems to depend on the plant species, yet even so, medicinal herbs should be cultivated and gathered only from controlled (uncontaminated) areas. Polluted areas should be monitored on a regular basis, while further research should investigate the connection between the heavy metal levels in the soil, their levels available for plants, and the levels extractable from plants.

Sex as a determinant of age-related changes in rat spinal cord inflammation-oxidation state.

To close the gap in our knowledge of sex influence on age-related changes in inflammation-oxidation state in spinal cord (SC) relevant to inflammation/oxidative-stress associated neuropathologies, 2-3 month-old (young) and 18-20 month-old (old) rats, exhibiting increased level of IL-6, a commonly used marker of inflamm-aging, were examined for inflammatory/redox status, and the underlying regulatory networks' molecules expression. With age, rat SC microglia became sensitized ("primed"), while SC tissue shifted towards mild inflammatory state, with increased levels of proinflammatory IL-1ß (key marker of microglial systemic inflammation-induced neurotoxicity), which was more prominent in males. This, most likely, reflected age- and sex-related impairment in the expression of CX3CR1, the receptor for fractalkine (CX3CL1), the soluble factor which regulates microglial activation and diminishes production of IL-1ß (central for fractalkine neuroprotection). Considering that (i) age-related changes in SC IL-1ß expression were not followed by complementary changes in SC IL-6 expression, and (ii) the reversal in the direction of the sex bias in circulating IL-6 level and SC IL-1ß expression, it seems obvious that there are tissue-specific differences in the proinflammatory cytokine profile. Additionally, old male rat SC exhibited greater oxidative damage than female, reflecting, most likely, their lower capacity to maintain the pro-oxidant-antioxidant balance. In conclusion, these findings, apart from highlighting the significance of sex for age-associated changes in SC inflammation-oxidation, may be relevant for understating sex differences in human inflammation/oxidative-stress related SC diseases, and consequently, for optimizing their prevention/therapy.