Sorption Capacity of Polydimethylsiloxane Foams Filled with Thermal-Treated Bentonite-Polydimethylsiloxane Composite Foams for Oil Spill Remediation.

The spillage of oil causes severe and long-lasting impacts on both the environment and human life. It is crucial to carefully reconsider the methods and techniques currently employed to recover spilled oil in order to prevent any possible secondary pollution and save time. Therefore, the techniques used to recover spilled oil should be readily available, highly responsive, cost-effective, environmentally safe, and, last but not least, they should have a high sorption capacity. The use of sorbents obtained from natural materials is considered a suitable approach for dealing with oil spills because of their exceptional physical characteristics that support sustainable environmental protection strategies. This article presents a novel sorbent material, which is a composite siloxane foam filled with bentonite clay, aimed at enhancing the hydrophobic and oleophilic behavior of the material. The thermal treatment of bentonite optimizes its sorption capacity by eliminating water, and increasing the surface area, and, consequently, its interaction with oils. In particular, the maximum sorption capacity is observed in kerosene and naphtha for the bentonite clay thermally treated at 600 °C, showing an uptake at saturation of 496.8% and 520.1%, respectively. Additionally, the reusability of the composite foam is evaluated by squeezing it after reaching its saturation point to determine its sorption capacity and reusability.

Selected fungi of the genus Lactarius - screening of antioxidant capacity, antimicrobial activity, and genotoxicity.

It is well-known that mushrooms of the genus Lactarius constitute a natural food resource providing health benefits as a nutritient. This genus contains 4 mushrooms identified as L. deliciosus, L. volemus, L. sanguifluus, L. semisanguifluus and L. piperatus which were collected in Serbia. The aim of this study aimed was to identify and characterize the content of phenolic compounds and examine the antioxidant potential of 5 wild edible mushrooms. L. sanguifluus contained the highest content of total phenol compounds (75.25 mg gallic acid equivalents (GAE) per g dry extract weight (GAE/g DE) and exhibited the greatest antioxidant activity through the ability to remove radicals as evidenced by ABTS assay (8.99 mg of trolox equivalents (TE) per g dry extract weight (mg TE/g DE); total reducing power (TRP) assay mg ascorbic acid equivalents per mg of dry extract weight (0.42 mg AAE/g DE) and CUPRAC (14.23 mg TE /g DE). L. deliciosus methanolic extract produced greatest scavenging of the DPPH radical (46%). The methanol mushroom extracts were screened for in vitro antimicrobial activity against a panel of pathogenic bacterial strains using the microdilution method. Of all the extracts tested, L. sanguifluus extract showed the best antibacterial properties. The cytokinesis block micronucleus assay results for the examined mushrooms demonstrated that extracts at a concentration of 3 µg/ml decreased the number of micronuclei (MN) in the range of 19-49% which is significant bearing in mind that radioprotectant amifostine reduced the frequency of MN by only 16.3%. Data thus demonstrate that the 5 wild edible mushrooms of genus Lactarius contain constituents that are beneficial not only as nutrients but also have the potential as antioxidants, antibacterial and antigenotoxic properties.

Mineral Composition of Herbaceous Species Seseli rigidum and Seseli pallasii: a Chemometric Approach.

Nutrients play an essential role in many metabolic processes whose deficiency or excess can be harmful to the plant itself and through the food chain to both animals and humans. Medicinal plants used in the food and pharmaceutical industries can be contaminated with increased concentrations of heavy metals. The plant species Seseli rigidum and Seseli pallasii from the Balkan Peninsula are used in traditional medicine and spices in the diet, so it was necessary to determine the mineral composition to ensure their safe application. In this work, the mineral composition was determined in medicinal species of the genus Seseli using inductively coupled plasma with optical emission spectrometry (ICP-OES). Two multivariate statistic methods -principal component analysis (PCA) and hierarchical cluster analysis (HCA) were applied to distinguish samples regarding their mineral composition. The mineral composition of both studied species is following the literature data. The results obtained using multivariate statistics methods agree and distinguish certain parts of the tested plants based on the highest content of micro, macro, or trace elements.

Phytochemistry, Toxicology and Therapeutic Value of Petasites hybridus Subsp. Ochroleucus (Common Butterbur) from the Balkans.

Petasites hybridus (Common butterbur) is extensively used in traditional medicine, and is currently gaining interest and popularity as a food supplement and for its medicinal properties. It contains a large number of active compounds of potential therapeutic activity, but also toxic pyrrolizidine alkaloids. Science-based information is needed to support the developing modern use of this plant, and to direct continued safe practice in traditional medicine. The present study focused on the essential oils from leaves and rhizomes of the understudied P. hybridus ssp. ochroleucus from the Balkans, and evaluated its phytochemistry and potential therapeutic activities (antimicrobial, antioxidant, anti-cholinesterase and anti-inflammatory), as well its toxicology potential (acute toxicity in insects and mice). We studied the essential oils, which are not commonly used in traditional practices, but have a potential for safe use since the toxic pyrrolizidine alkaloids, which are non-volatiles, are usually not present in the distilled essential oils. Pyrrolizidine alkaloids were indeed not detected in the essential oils; ingestion of the essential oils did not induce toxicity signs in mice, and topical application did not elicit skin irritation in humans. The essential oils had no antimicrobial properties against 20 pathogenic bacterial strains, but demonstrated good local anti-inflammatory activity in a Carrageenan-induced paw edema test. An insect toxicity test demonstrated that the leaf essential oil is an efficient insect repellent, and the demonstrated anti-cholinesterase activity suggests a potential for the treatment of neurological conditions. Isopetasin, a sesquiterpene found in plants of the genus Petasites, known to have anti-inflammatory effects, was present only in the rhizomes essential oil (3.9%), and sesquiterpene lactones concentrations were high, likely contributing to the antioxidant activity.

Volatiles composition and antioxidant activity Inula oculus-christi L. from Serbia.

The chemical composition of the essential oil and the volatiles obtained by static headspace (HS) of Inula oculus-christi L. is presented. The GC-MS analysis of the hydrodistilled oil resulted in the identification of 90 components, representing 92.7% of the oil. The most abundant compounds were: caryophyllene oxide (9.8%), trans-longipinocarveol (9.2%), eucalyptol (7.3%) and intermedeol (6.2%). The major constituent of I. oculus-christi L. HS volatiles was eucalyptol (87.4%). The antioxidant activity was evaluated by four different methods: 2,2-diphenyl-1-picryl-hydrazylhydrate free radical assay (DPPH), 2,2-azino-bis-3-ethylbenzothiazoline-6-sulfonic acid (ABTS) method, total reducing power (TRP), ferric reducing antioxidant power (FRAP), and cupric reducing antioxidant capacity (CUPRAC). Total phenolic content in (TPC) examined oil was 177.95 µg GAE/mg oil. Radical scavenging potential of the oil was promising RSC-DPPH was 57.4% and RSC-ABTS was 82.7%.[Formula: see text].

Chemical profile and biological activities of Peltigera horizontalis (Hudson) Baumg. thallus and apothecia extracts.

The aim of this study was to determine, for the first time, the chemical composition of Peltigera horizontalis thallus and apothecia extracts (ether, ethyl acetate, dichloromethane and acetone) by HPLC-UV and GC-MS, and evaluate activity of genotoxic, anticholinesterase, antioxidant and antibacterial potential of acetone extracts. Major constituents of thallus extracts were gyrophoric acid, and methyl gyrophorate while dominant component of apothecia extracts was tenuiorin. The predominant volatile compounds in extracts were methyl orsellinate, dodecyl acrylate, orcinol and orcinol monomethyl ether. The thallus acetone extract at concentration of 2.0 µg mL-1 gave the greatest decrease in the micronuclei frequency (22.4%) of all tested extracts. Apothecia extract showed stronger antioxidant activity as compared to thallus extract. Tested extracts at concentration of 10 mg mL-1 exhibited inhibitory effect (16.5% for thallus and 12.8% for apothecia) on pooled human serum cholinesterase. P. horizontalis acetone extracts had no activity against the tested five bacteria strains.

First Report about Mineral Content, Fatty Acids Composition and Biological Activities of Four Wild Edible Mushrooms.

The goal of this research was a comprehensive analysis of four wild edible mushroom species, Cantharellus cinereus, Clavariadelphus pistillaris, Clitocybe nebularis and Hygrocybe punicea, which have not been analyzed so far. Extracts of different polarities have been prepared and evaluated for their antioxidant activities by DPPH, ABTS, FRAP, TRP and CUPRAC methods. For all extracts, total phenolic content was determined. Based on the analysis, it was shown that solvent type had a significant effect on the antioxidant capacities of mushroom extracts, so water extracts showed the highest activity. Furthermore, the analysis includes determination of mineral composition, fatty acid profiles and antimicrobial activity. Unsaturated fatty acids, which are very important for human health, are dominant in the studied mushroom species. Linoleic and oleic acid consist of over 50 % of the total fatty acid composition. Seventeen biologically important and toxic elements have been analyzed by ICP-OES and ICP-MS and results showed that the element concentrations were species-dependent. Also, it has been found that analyzed mushrooms did not show any antimicrobial activity. Chemometric analysis was used to understand the connection between the extracts of different polarities.

Dispersive micro-solid phase extraction of 16 priority polycyclic aromatic hydrocarbons from water by using thermally treated clinoptilolite, and their quantification by GC-MS.

The authors report on a novel sorbent (thermally treated natural zeolite; clinoptilolite) for use in dispersive micro-solid phase extraction (D-µ-SPE) of polycyclic aromatic hydrocarbons (PAHs) from water samples. The method was applied to the D-µ-SPE of 16 priority PAHs which then were quantified by gas chromatography with mass spectrometric detection (GC-MS). The method was validated in terms of specificity and selectivity, linearity and linear range, accuracy, precision, uncertainty, limits of detection and quantification. Figures of merit include (a) linear analytical ranges between 2.08 and 208 ppb, and (b) detection limits in the range from 0.01 to 0.92 ppb. The method was successfully applied to the determination of PAHs in river waters. Graphical abstract Schematic representation of dispersive micro-solid phase extraction (D-µ-SPE) of trace levels of PAHs in water samples by using thermally treated clinoptilolite as sorbent prior to gas chromatography-mass spectrometry analysis (GC-MS).

Hypogymnia tubulosa extracts: chemical profile and biological activities.

This study reports for the first time in the chemical composition of acetone, ether, ethyl acetate and dichloromethane extracts of Hypogymnia tubulosa determined by HPLC-UV, GC-FID and GC-MS as well as effect of H. tubulosa acetone extract on micronucleus distribution on human lymphocytes and on cholinesterase activity. Additionally, antioxidant (estimated via DPPH, ABTS, TRP, CUPRAC and TPC assays) and antibacterial activity against two Gram-positive and three Gram-negative bacteria were also determined. The HPLC-UV analysis revealed the presence of depsidones, 3-hydroxyphysodic, 4-O-methyl physodic acid, physodic and physodalic acid together with two depsides, atranorin and chloroatranorin. GC-FID and GC-MS analyses enabled the identification of atranol, chloroatranol, atraric acid, olivetol, olivetonide and 3-hydroxyolivetonide as the main components. The results of present study show that H. tubulosa acetone extract is a promising candidate for in vivo experiments considering antioxidant activity.

Comparative Study of Fatty Acids Profile in Eleven Wild Mushrooms of Boletacea and Russulaceae Families.

Eleven species of wild mushrooms which belong to Boletaceae and Russulaceae families were examined by gas chromatography (GC) and gas chromatography-mass spectrometry (GC/MS) analysis for the presence of fatty acids. As far as we know, the fatty acid profiles of B. purpureus and B. rhodoxanthus were described for the first time. Twenty-six fatty acids were determined. Linoleic (19.5 - 72%), oleic (0.11 - 64%), palmitic (5.9 - 22%) and stearic acids (0.81 - 57%) were present in the highest contents. In all samples, unsaturated fatty acids dominate. Agglomerative hierarchical clustering was used to display the correlation between the fatty acids and their relationships with the mushroom species. Based on the fatty acids profile in the samples, the mushrooms can be divided into two families: Boletaceae and Russulaceae families, using cluster analysis.

Essential oil composition of Erica spiculifolia Salisb - first report.

The essential oil isolated from Erica spiculifolia Salisb. by hydrodistillation was analysed by GC-MS. One hundred compounds representing 92.6% of total oil were identified. Among the detected compounds 38 were monoterpenoids (46.2%), 30 were sesquiterpenoids (31.7%), 2 diterpene (0.4%) and 30 compounds (14.3%) were with various non-terpenoid structures. Oxygenated monoerpenes were by far the main class (45.3%) with α-terpineol (7.5%) endo-borneol (7.2%), pinocarveol (5.9%) and thymol (3.7%) as the major compounds. The predominant components of sesquiterpenes were caryophyllene oxide (5.0%), caryophyllene (4.2%), τ -murrolol (3.5%), spathulenol (2.9) and α-cadinol (2.3%).

Phytochemical analysis of Saponaria officinalis L. shoots and flowers essential oils.

Phytochemical analysis by GC and GC/MS of the essential oil samples obtained from fresh shoots and flowers of Saponaria officinalis L. allowed the identification of 96 components in total, comprising 94.7% and 86.0% of the total oils compositions, respectively. Regarding the shoots essential oil, the major of 87 identified volatile compounds were phytol (14.1%), tricosane-6,8-dione (13.4%), patchouli alcohol (7.9%) and tricosane (7.2%), whereas patchouli alcohol (20.0%), heneicosane (11.5%) and tricosane (8.4%) were dominant among the 66 volatiles in the flower oil. Nonterpenoid compounds had the highest contribution in S. officinalis shoots essential oil (53.7%), while in the flower oil, constituents were almost evenly distributed between the oxygenated sesquiterpenoid (41.2%) and nonterpenoid compounds (39.5%).

Ramalina capitata (Ach.) Nyl. acetone extract: HPLC analysis, genotoxicity, cholinesterase, antioxidant and antibacterial activity.

In the present investigation, effects of Ramalina capitata acetone extract on micronucleus distribution on human lymphocytes, on cholinesterase activity and antioxidant activity (by the CUPRAC method) were examined, for the first time as well as its HPLC profile. Additionally, total phenolic compounds (TPC), antioxidant properties (estimated via DPPH, ABTS and TRP assays) and antibacterial activity were determined. The predominant phenolic compounds in this extract were evernic, everninic and obtusatic acids. Acetone extract of R. capitata at concentration of 2 µg mL-1 decreased a frequency of micronuclei (MN) for 14.8 %. The extract reduces the concentration of DPPH and ABTS radicals for 21.2 and 36.1 % (respectively). Values for total reducing power (TRP) and cupric reducing capacity (CUPRAC) were 0.4624 ± 0.1064 µg ascorbic acid equivalents (AAE) per mg of dry extract, and 6.1176 ± 0.2964 µg Trolox equivalents (TE) per mg of dry extract, respectively. The total phenol content was 670.6376 ± 66.554 µg galic acid equivalents (GAE) per mg of dry extract. Tested extract at concentration of 2 mg mL-1 exhibited inhibition effect (5.2 %) on pooled human serum cholinesterase. The antimicrobial assay showed that acetone extract had inhibition effect towards Gram-positive strains. The results of manifested antioxidant activity, reducing the number of micronuclei in human lymphocytes, and antibacterial activity recommends R. capitata extract for further in vivo studies.

The effect of multiple contamination of soil on LMW and MMW PAHs accumulation in the roots of Rubus fruticosus L. naturally growing near The Copper Mining and Smelting Complex Bor (East Serbia).

Samples of roots and spatial soils of native Rubus fruticosus L. were collected from the spots positioned at different distances from the copper smelter and city heating plants in the industrial zone of the town of Bor (Serbia) and subjected to chemical analyses in order to determine the content of several heavy metals, and 15 priority polycyclic aromatic hydrocarbons (PAHs). In this study, the results for 9 low and medium molecular weight PAHs (LMW and MMW PAHs) are represented and processed using the calculation of bio-concentration factors and statistical methods such as hierarchical cluster analysis and Pearson's correlation study with the aim of investigating the plant capabilities for their uptake from the soil and later accumulation into the root tissue, under the hostile circumstances of multiple contamination. The obtained data revealed different accumulation rates for the investigated PAHs and showed that in several cases, the contents of root PAHs were under the strong influence of present contaminants such as soil copper and some soil PAHs, indicating at the same time that R. fruticosus can regulate the processes of LMW and MMW PAHs extraction/accumulation using different mechanisms, depending on the existing environmental circumstances. The used mechanisms could be exploited in phytoremediation methods based not only on the extraction and concentration of PAHs in plant roots but also on PAH degradation or stabilization in the soil. Also, the results of this study confirmed that, except in the case of naphthalene and fluoranthene, there was no PAH pollution, which originated solely from the industrial zone.

Comparative Study of Composition, Antioxidant, and Antimicrobial Activities of Essential Oils of Selected Aromatic Plants from Balkan Peninsula.

The objective of the present study to perform a comparative analysis of the chemical composition, antioxidant, and antimicrobial activities of the essential oils of plant species Hyssopus officinalis, Achillea grandifolia, Achillea crithmifolia, Tanacetum parthenium, Laserpitium latifolium, and Artemisia absinthium from Balkan Peninsula. The chemical analysis of essential oils was performed by using gas chromatography and gas chromatography-mass spectrometry. Monoterpenes were dominant among the recorded components, with camphor in T. parthenium, A. grandifolia, and A. crithmifolia (51.4, 45.4, and 25.4 %, respectively), 1,8-cineole in H. officinalis, A. grandifolia, and A. crithmifolia (49.1, 16.4, and 14.8 %, respectively), and sabinene in L. latifolium and A. absinthium (47.8 and 21.5 %). The antiradical and antioxidant activities were determined by using 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) and 2,2-diphenyl-1-picrylhydrazyl radical scavenging methods. The essential oil of A. grandifolia has shown the highest antioxidant activity [IC50 of 33.575 ± 0.069 mg/mL for 2,2-diphenyl-1-picrylhydrazyl and 2.510 ± 0.036 mg vitamin C/g for the 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) assay]. The antimicrobial activity against 16 multiresistant pathogenic bacteria isolated from human source material was tested by the broth microdilution assay. The resulting minimum inhibitory concentration/minimum bactericidal concentration values ranged from 4.72 to 93.2 mg/mL. Therefore, the essential oils of the plant species included in this study may be considered to be prospective natural sources of antimicrobial substances, and may contribute as effective agents in the battle against bacterial multiresistance.

Dittrichia graveolens (L.) Greuter Essential Oil: Chemical Composition, Multivariate Analysis, and Antimicrobial Activity.

The chemical composition and in vitro antimicrobial activities of Dittrichia graveolens (L.) Greuter essential oil was studied. Moreover, using agglomerative hierarchical cluster (AHC) and principal component analyses (PCA), the interrelationships of the D. graveolens essential-oil profiles characterized so far (including the sample from this study) were investigated. To evaluate the chemical composition of the essential oil, GC-FID and GC/MS analyses were performed. Altogether, 54 compounds were identified, accounting for 92.9% of the total oil composition. The D. graveolens oil belongs to the monoterpenoid chemotype, with monoterpenoids comprising 87.4% of the totally identified compounds. The major components were borneol (43.6%) and bornyl acetate (38.3%). Multivariate analysis showed that the compounds borneol and bornyl acetate exerted the greatest influence on the spatial differences in the composition of the reported oils. The antimicrobial activity against five bacterial and one fungal strain was determined using a disk-diffusion assay. The studied essential oil was active only against Gram-positive bacteria.

Chemical composition of the essential oil of Laserpitium latifolium from Serbia.

The essential oil of aerial parts ofLaserpitium latifolium L. from Serbia, obtained by hydro distillation, was analyzed by GC-MS and GC-FID applying liquid injection mode; thirty-four compounds were registered (99.9% of the total oil). The essential oil clearly belongs to the monoterpenoid chemotype, with monoterpenoids constituting 99.8% of the total oil. Sabinene (47.8%), α-pinene (25.0%) and ß-pinene (7.1%) were the major constituents.

Inferring the origin of rare fruit distillates from compositional data using multivariate statistical analyses and the identification of new flavour constituents.

BACKGROUND: In Serbia, delicatessen fruit alcoholic drinks are produced from autochthonous fruit-bearing species such as cornelian cherry, blackberry, elderberry, wild strawberry, European wild apple, European blueberry and blackthorn fruits. There are no chemical data on many of these and herein we analysed volatile minor constituents of these rare fruit distillates. Our second goal was to determine possible chemical markers of these distillates through a statistical/multivariate treatment of the herein obtained and previously reported data. RESULTS: Detailed chemical analyses revealed a complex volatile profile of all studied fruit distillates with 371 identified compounds. A number of constituents were recognised as marker compounds for a particular distillate. Moreover, 33 of them represent newly detected flavour constituents in alcoholic beverages or, in general, in foodstuffs. With the aid of multivariate analyses, these volatile profiles were successfully exploited to infer the origin of raw materials used in the production of these spirits. It was also shown that all fruit distillates possessed weak antimicrobial properties. CONCLUSION: It seems that the aroma of these highly esteemed wild-fruit spirits depends on the subtle balance of various minor volatile compounds, whereby some of them are specific to a certain type of fruit distillate and enable their mutual distinction.

Chemical composition of Angelica pancicii essential oil determined by liquid and headspace GC-MS techniques.

The essential oil of the Balkan endemic species, Angelica pancicii, obtained by hydrodistillation, was analyzed by GC and GC-MS, applying the liquid injection mode. These results were compared with the chemical composition of volatiles achieved by the "headspace" injection mode, followed by GC and GC-MS (HS-GC-MS). A total of 40 compounds were identified in the essential oil (98.8% of the total oil) and 44 by HS-GC-MS (99.8% of the total oil). The most abundant class of compounds in both cases was monoterpenoids, which formed 92.7% of the essential oil (97.7% by HS-GC-MS) of total identified compounds. The major components in both cases were beta-phellandrene (54.9% and 60.1%, respectively), alpha-pinene (14.5% and 20.1%, respectively) and alpha-phellandrene (4.5% and 4.3%, respectively).

Distinctive gas-phase fragmentation pathway of the mitorubramines, novel secondary metabolites from Hypoxylon fragiforme.

RATIONALE: Azaphilones, belonging to the class of mitorubrins usually produced in Hypoxylon fragiforme, react easily with amino groups, giving amine derivatives, mitorubramines. These secondary metabolites exhibit a wide range of biological activities. Finding new secondary metabolites from fungi is important, and electrospray ionization (ESI) high-resolution mass spectrometry (HRMS) coupled with sequential MS(n) experiments has become a method of choice for the chemotaxonomic classification of fungi. METHODS: High-performance liquid chromatography of methanol extracts coupled to positive electrospray ionization, high resolving power for accurate mass measurements and resonant excitation for selective ion collision-induced dissociation (CID) have been conducted with the aim of resolving the structures of possible novel compounds. RESULTS: Soft desolvation conditions in the ESI source enabled the detection of intact mitorubramines present in the extract. HRMS provided unambiguous information about the elemental composition of the mitorubramines and their product ions, while sequential MS(3) experiments were essential for the structural discernment of already reported mitorubrins and newly discovered mitorubramines. Indeed, specifically from the latter, a series of consecutive dissociations takes place under CID conditions that are useful for structural elucidation. CONCLUSIONS: A distinctive method for two families of secondary metabolites has been developed. Information observed using HRMS and sequential MS(n) experiments gave unambiguous information about the structure of mitorubramines, especially the position of the nitrogen atom, which was strengthened by proposed unusual fragmentation mechanisms, such as the rearrangement yielding the release of CO(2) from the hydroxyl-diketone structures. These experiments demonstrated that the fragmentations are facilitated by the nitrogen electron lone-pair in mitorubramines, which does not occur in mitorubrins.