Phenolic compounds,essential oil composition,and antioxidant activity of Angelica purpurascens (Avé-Lall.) Gill

In this study, methanol extracts (MEs) and essential oil (EO) of Angelica purpurascens (Avé-Lall.) Gill obtained from different parts (root, stem, leaf, and seed) were evaluated in terms of antioxidant activity, total phenolics, compositions of phenolic compound, and essential oil with the methods of 2,2-azino-bis(3ethylbenzo-thiazoline-6-sulfonic acid (ABTS•⁺), 2,2-diphenyl-1-picrylhydrazil (DPPH•) radical scavenging activities, and ferric reducing/antioxidant power (FRAP), the Folin–Ciocalteu, liquid chromatography−tandem mass spectrometry (LC−MS/MS), and gas chromatography-mass spectrometry (GC−MS), respectively. The root extract of A. purpurascens exhibited the highest ABTS•⁺, DPPH•, and FRAP activities (IC₅₀: 0.05 ± 0.0001 mg/mL, IC₅₀: 0.06 ± 0.002 mg/mL, 821.04 ± 15.96 µM TEAC (Trolox equivalent antioxidant capacity), respectively). Moreover, EO of A. purpurascens root displayed DPPH• scavenging activity (IC₅₀: 2.95 ± 0.084 mg/mL). The root extract had the highest total phenolic content (438.75 ± 16.39 GAE (gallic acid equivalent), µg/mL)). Twenty compounds were identified by LC−MS/MS. The most abundant phenolics were ferulic acid (244.39 ± 15.64 μg/g extract), benzoic acid (138.18 ± 8.84 μg/g extract), oleuropein (78.04 ± 4.99 μg/g extract), and rutin (31.21 ± 2.00 μg/g extract) in seed, stem, root, and leaf extracts, respectively. According to the GC−MS analysis, the major components were determined as α-bisabolol (22.93%), cubebol (14.39%), α-pinene (11.63%), and α-limonene (9.41%) among 29 compounds. Consequently, the MEs and EO of A. purpurascens can be used as a natural antioxidant source.     

The Effect of Fermentation with Kefir Grains on the Physicochemical and Antioxidant Properties of Beverages from Blue Lupin (Lupinus angustifolius L.) Seeds

Plant derived fermented beverages have recently gained consumers’ interest, particularly due to their intrinsic functional properties and presence of beneficial microorganisms. Three variants containing 5%, 10%, and 15% (w/w) of sweet blue lupin (Lupinus angustifolius L. cv. “Boregine”) seeds were inoculated with kefir grains and incubated at 25 °C for 24 h. After processing, beverages were stored in refrigerated conditions (6 °C) for 21 days. Changes in microbial population, pH, bioactive compounds (polyphenolics, flavonoids, ascorbic acid), reducing sugars, and free amino acids were estimated. Additionally, viscosity, firmness, color, and free radicals scavenging properties were determined. Results showed that lactic acid bacteria as well as yeast were capable of growing well in the lupin matrix without any supplementation. During the process of refrigeration, the viability of the microorganisms was over the recommended minimum level for kefir products. Hydrolysis of polysaccharides as well as increase of free amino acids was observed. As a result of fermentation, the beverages showed excellent DPPH, ABTS^+·, ^·OH, and O₂⁻ radicals scavenging activities with a potential when considering diseases associated with oxidative stress. This beverages could be used as a new, non-dairy vehicle for beneficial microflora consumption, especially by vegans and lactose-intolerant consumers.     

The Influence of Ripeness on the Phenolic Content,Antioxidant and Antimicrobial Activities of Pumpkins (Cucurbita moschata Duchesne)

Cucurbita moschata Duchesne (Cucurbitaceae) is a plant food highly appreciated for the content of nutrients and bioactive compounds, including polyphenols and carotenoids, which contribute to its antioxidant and antimicrobial capacities. The purpose of this study was to identify phenolic acids and flavonoids of Cucurbita moschata Duchesne using high-performance liquid chromatography–diode array detection–electrospray ionization tandem mass spectrometry (HPLC–DAD–ESI-MS) at different ripening stages (young, mature, ripened) and determine its antioxidant and antimicrobial activities. According to the results, phenolic acids and flavonoids were dependent on the maturity stage. The mature fruits contain the highest total phenolic and flavonoids contents (97.4 mg GAE. 100 g⁻¹ and 28.6 mg QE. 100 g⁻¹).A total of 33 compounds were identified. Syringic acid was the most abundant compound (37%), followed by cinnamic acid (12%) and protocatechuic acid (11%). Polyphenol extract of the mature fruits showed the highest antioxidant activity when measured by DPPH (0.065 μmol TE/g) and ABTS (0.074 μmol TE/g) assays. In the antimicrobial assay, the second stage of ripening had the highest antibacterial activity. Staphylococcus aureus was the most sensitive strain with an inhibition zone of 12 mm and a MIC of 0.75 mg L⁻¹. The lowest inhibition zone was obtained with Salmonella typhimurium (5 mm), and the MIC value was 10 mg L⁻¹.     

Dynamics of Phloridzin and Related Compounds in Four Cultivars of Apple Trees during the Vegetation Period

Apple trees (Malus domestica Borgh) are a rich source of dihydrochalcones, phenolic acids and flavonoids. Considering the increasing demand for these phytochemicals with health-benefitting properties, the objective of this study was to evaluate the profile of the main bioactive compounds—phloridzin, phloretin, chlorogenic acid and rutin—in apple tree bark, leaves, flower buds and twigs. The variety in the phenolic profiles of four apple tree cultivars was monitored during the vegetation period from March to September using chromatography analysis. Phloridzin, the major glycoside of interest, reached the highest values in the bark of all the tested cultivars in May (up to 91.7 ± 4.4 mg g⁻¹ of the dried weight (DW), cv. ‘Opal’). In the leaves, the highest levels of phloridzin were found in cv. ‘Opal’ in May (82.5 ± 22.0 mg g⁻¹ of DW); in twigs, the highest levels were found in cv. ‘Rozela’ in September (52.4 ± 12.1 mg g⁻¹ of DW). In the flower buds, the content of phloridzin was similar to that in the twigs. Aglycone phloretin was found only in the leaves in relatively low concentrations (max. value 2.8 ± 1.4 mg g⁻¹ of DW). The highest values of rutin were found in the leaves of all the tested cultivars (10.5 ± 2.9 mg g⁻¹ of DW, cv. ‘Opal’ in September); the concentrations in the bark and twigs were much lower. The highest content of chlorogenic acid was found in flower buds (3.3 ± 1.0 mg g⁻¹ of DW, cv. ‘Rozela’). Whole apple fruits harvested in September were rich in chlorogenic acid and phloridzin. The statistical evaluation by Scheffe’s test confirmed the significant difference of cv. ‘Rozela’ from the other tested cultivars. In conclusion, apple tree bark, twigs, and leaves were found to be important renewable resources of bioactive phenolics, especially phloridzin and rutin. The simple availability of waste plant material can therefore be used as a rich source of phenolic compounds for cosmetics, nutraceuticals, and food supplement preparation.     

Highly Porous Carbons Synthesized from Tannic Acid via a Combined Mechanochemical Salt-Templating and Mild Activation Strategy

Highly porous activated carbons were synthesized via the mechanochemical salt-templating method using both sustainable precursors and sustainable chemical activators. Tannic acid is a polyphenolic compound derived from biomass, which, together with urea, can serve as a low-cost, environmentally friendly precursor for the preparation of efficient N-doped carbons. The use of various organic and inorganic salts as activating agents afforded carbons with diverse structural and physicochemical characteristics, e.g., their specific surface areas ranged from 1190 m²·g⁻¹ to 3060 m²·g⁻¹. Coupling the salt-templating method and chemical activation with potassium oxalate appeared to be an efficient strategy for the synthesis of a highly porous carbon with a specific surface area of 3060 m²·g⁻¹, a large total pore volume of 3.07 cm³·g⁻¹ and high H₂ and CO₂ adsorption capacities of 13.2 mmol·g⁻¹ at −196 °C and 4.7 mmol·g⁻¹ at 0 °C, respectively. The most microporous carbon from the series exhibited a CO₂ uptake capacity as high as 6.4 mmol·g⁻¹ at 1 bar and 0 °C. Moreover, these samples showed exceptionally high thermal stability. Such activated carbons obtained from readily available sustainable precursors and activators are attractive for several applications in adsorption and catalysis.     

Construction of Two Stable Co(II)-Based Hydrogen-Bonded Organic Frameworks as a Luminescent Probe for Recognition of Fe3+ and Cr2O72− in H2O

A pair of cobalt(II)-based hydrogen-bonded organic frameworks (HOFs), [Co(pca)₂(bmimb)]_n (1) and [Co₂(pca)₄(bimb)₂] (2), where Hpca = p-chlorobenzoic acid, bmimb = 1,3-bis((2-methylimidazol-1-yl)methyl)benzene, and bimb = 1,4-bis(imidazol-1-ylmethyl)benzene were hydrothermally synthesized and characterized through infrared spectroscopy (IR), elemental and thermal analysis (EA), power X-ray diffraction (PXRD), and single-crystal X-ray diffraction (SCXRD) analyses. X-ray diffraction structural analysis revealed that 1 has a one-dimensional (1D) infinite chain network through the deprotonated pca⁻ monodentate chelation and with a μ₂-bmimb bridge Co(II) atom, and 2 is a binuclear Co(II) complex construction with a pair of symmetry-related pca⁻ and bimb ligands. For both 1 and 2, each cobalt atom has four coordinated twisted tetrahedral configurations with a N₂O₂ donor set. Then, 1 and 2 are further extended into three-dimensional (3D) or two-dimensional (2D) hydrogen-bonded organic frameworks through C–H···Cl interactions. Topologically, HOFs 1 and 2 can be simplified as a 4-connected qtz topology with a Schläfli symbol {6⁴·8²} and a 4-connected sql topology with a Schläfli symbol {4⁴·6²}, respectively. The fluorescent sensing application of 1 was investigated; 1 exhibits high sensitivity recognition for Fe³⁺ (K_sv: 10970 M⁻¹ and detection limit: 19 μM) and Cr₂O₇²⁻ (K_sv: 12960 M⁻¹ and detection limit: 20 μM). This work provides a feasible detection platform of HOFs for highly sensitive discrimination of Fe³⁺ and Cr₂O₇²⁻ in aqueous media.     

Synthesis and Structural Characterization of a Silver(I) Pyrazolato Coordination Polymer

Coinage metal(I)···metal(I) interactions are widely of interest in fields such as supramolecular assembly and unique luminescent properties, etc. Only two types of polynuclear silver(I) pyrazolato complexes have been reported, however, and no detailed spectroscopic characterizations have been reported. An unexpected synthetic method yielded a polynuclear silver(I) complex [Ag(μ-L1Clpz)]_n (L1Clpz⁻ = 4-chloride-3,5-diisopropyl-1-pyrazolate anion) by the reaction of {[Ag(μ-L1Clpz)]₃}₂ with (ⁿBu₄N)[Ag(CN)₂]. The obtained structure was compared with the known hexanuclear silver(I) complex {[Ag(μ-L1Clpz)]₃}₂. The Ag···Ag distances in [Ag(μ-L1Clpz)]_n are slightly shorter than twice Bondi’s van der Waals radius, indicating some Ag···Ag argentophilic interactions. Two Ag–N distances in [Ag(μ-L1Clpz)]_n were found: 2.0760(13) and 2.0716(13) Å, and their N–Ag–N bond angles of 180.00(7)° and 179.83(5)° indicate that each silver(I) ion is coordinated by two pyrazolyl nitrogen atoms with an almost linear coordination. Every five pyrazoles point in the same direction to form a 1-D zig-zag structure. Some spectroscopic properties of [Ag(μ-L1Clpz)]_n in the solid-state are different from those of {[Ag(μ-L1Clpz)]₃}₂ (especially in the absorption and emission spectra), presumably attributable to this zig-zag structure having longer but differently arranged intramolecular Ag···Ag interactions of 3.39171(17) Å. This result clearly demonstrates the different physicochemical properties in the solid-state between 1-D coordination polymer and metalacyclic trinuclear (hexanuclear) or tetranuclear silver(I) pyrazolate complexes.     

A QuEChERS-HPLC-MS/MS Method with Matrix Matching Calibration Strategy for Determination of Imidacloprid and Its Metabolites in Procambarus clarkii (Crayfish) Tissues

We developed a method for determination of imidacloprid and its metabolites 5-hydroxy imidacloprid, olefin imidacloprid, imidacloprid urea and 6-chloronicotinic acid in Procambarus clarkii (crayfish) tissues using quick, easy, cheap, effective, rugged, and safe (QuEChERS) and high-performance liquid chromatography-triple quadrupole mass spectrometry. Samples (plasma, cephalothorax, hepatopancrea, gill, intestine, and muscle) were extracted with acetonitrile containing 0.1% acetic acid and cleaned up using a neutral alumina column containing a primary secondary amine. The prepared samples were separated using reverse phase chromatography and scanned in the positive and negative ion multiple reaction-monitoring modes. Under the optimum experimental conditions, spiked recoveries for these compounds in P. clarkii samples ranged from 80.6 to 112.7% with relative standard deviations of 4.2 to 12.6%. The limits of detection were 0.02–0.5 μg·L⁻¹, the limits of quantification were 0.05–2.0 μg·L⁻¹ and the method of quantification was 0.05–2.0 μg·kg⁻¹. The method is rapid, simple, sensitive and suitable for rapid determination and analysis of imidacloprid and its metabolites in P. clarkii tissues.     

Pressurized Extraction as an Opportunity to Recover Antioxidants from Orange Peels: Heat treatment and Nanoemulsion Design for Modulating Oxidative Stress

Orange peel by-products generated in the food industry are an important source of value-added compounds that can be potentially reused. In the current research, the effect of oven-drying (50–70 °C) and freeze-drying on the bioactive compounds and antioxidant potential from Navelina, Salustriana, and Sanguina peel waste was investigated using pressurized extraction (ASE). Sixty volatile components were identified by ASE-GC-MS. The levels of terpene derivatives (sesquitenenes, alcohols, aldehydes, hydrocarbons, and esters) remained practically unaffected among fresh and freeze-dried orange peels, whereas drying at 70 °C caused significative decreases in Navelina, Salustriana, and Sanguina peels. Hesperidin and narirutin were the main flavonoids quantified by HPLC-MS. Freeze-dried Sanguina peels showed the highest levels of total-polyphenols (113.3 mg GAE·g⁻¹), total flavonoids (39.0 mg QE·g⁻¹), outstanding values of hesperedin (187.6 µg·g⁻¹), phenol acids (16.54 mg·g⁻¹ DW), and the greatest antioxidant values (DPPH•, FRAP, and ABTS^•+ assays) in comparison with oven-dried samples and the other varieties. Nanotechnology approaches allowed the formulation of antioxidant-loaded nanoemulsions, stabilized with lecithin, starting from orange peel extracts. Those provided 70–80% of protection against oxidative UV-radiation, also decreasing the ROS levels into the Caco-2 cells. Overall, pressurized extracts from freeze-drying orange peel can be considered a good source of natural antioxidants that could be exploited in food applications for the development of new products of commercial interest.     

Bioprospecting of Coralline Red Alga Amphiroa rigida J.V. Lamouroux: Volatiles,Fatty Acids and Pigments

Due to the lack of phytochemical composition data, the major goals of the present study on Amphiroa rigida J.V. Lamouroux were to: (a) investigate and compare volatilome profiles of fresh and air-dried samples obtained by headspace solid-phase microextraction (HS-SPME) and hydrodistillation (HD) followed by gas chromatography and mass spectrometry (GC/MS) analysis; (b) determine fatty acids profile by gas chromatography with flame ionization detector (GC-FID); (c) obtain the pigment profiles of semipurified extracts by high performance liquid chromatography (HPLC) and (d) evaluate the antioxidant and antimicrobial activities of its less polar fractions. The comparison of headspace of fresh (FrAr) and air-dried (DrAr) samples revealed many similarities regarding the presence and abundance of the major (heptadecane and pentadecane) and minor compounds. The hydrodistillate (HD) of DrAr profile was quite different in comparison to HD-FrAr. The predominant compound in HD-FrAr was (E)-phytol. In HD-DrAr, its percentage was approximately one-half reduced, but the abundance of its degradation product phytone and of unsaturated and oxygenated compounds increased indicating more intense fatty acid decomposition and oxidation during drying. The fatty acid determination revealed that the most dominant was palmitic acid (42.86%) followed by eicosapentaenoic acid (19.14%) and stearic acid (11.65%). Among the pigments, A. rigida contained fucoxanthin (0.63 mg g⁻¹ of dry fraction), lutein (5.83 mg g⁻¹), β-carotene (6.18 mg g⁻¹) and chlorophyll a (13.65 mg g⁻¹). The analyzed less polar fractions of A. rigida exhibited antioxidant scavenging activity with diammonium salt of 2,2′-azino-bis (3-ethylbenzthiazolin-6-yl) sulfonic acid (ABTS) assay up to 3.87 mg g⁻¹ trolox equivalents (TE), and with the oxygen radical absorbance capacity (ORAC) assay up to 825.63 μmol g⁻¹ TE (with carotenoids as the major contributors).     

Absolute Antioxidant Activity of Five Phenol-Rich Essential Oils

Essential oils (EOs) have promising antioxidant activities which are gaining interest as natural alternatives to synthetic antioxidants in the food and cosmetic industries. However, quantitative data on chain-breaking activity and on the kinetics of peroxyl radical trapping are missing. Five phenol-rich EOs were analyzed by GC-MS and studied by oxygen-uptake kinetics in inhibited controlled autoxidations of reference substrates (cumene and squalene). Terpene-rich Thymus vulgaris (thymol 4%; carvacrol 33.9%), Origanum vulgare, (thymol 0.4%; carvacrol 66.2%) and Satureja hortensis, (thymol 1.7%; carvacrol 46.6%), had apparent k_inh (30 °C, PhCl) of (1.5 ± 0.3) × 10⁴, (1.3 ± 0.1) × 10⁴ and (1.1 ± 0.3) × 10⁴ M⁻¹s⁻¹, respectively, while phenylpropanoid-rich Eugenia caryophyllus (eugenol 80.8%) and Cinnamomum zeylanicum, (eugenol 81.4%) showed apparent k_inh (30 °C, PhCl) of (5.0 ± 0.1) × 10³ and (4.9 ± 0.3) × 10³ M⁻¹s⁻¹, respectively. All EOs already granted good antioxidant protection of cumene at a concentration of 1 ppm (1 mg/L), the duration being proportional to their phenolic content, which dictated their antioxidant behavior. They also afforded excellent protection of squalene after adjusting their concentration (100 mg/L) to account for the much higher oxidizability of this substrate. All investigated EOs had k_inh comparable to synthetic butylated hydroxytoluene (BHT) were are eligible to replace it in the protection of food or cosmetic products.     

Optimization of crystal packing in semiconducting spin-crossover materials with fractionally charged TCNQδ− anions (0 < δ < 1)

Co-crystallization of the prominent Fe(ii) spin-crossover (SCO) cation, [Fe(3-bpp)₂]²⁺ (3-bpp = 2,6-bis(pyrazol-3-yl)pyridine), with a fractionally charged TCNQ^δ− radical anion has afforded a hybrid complex [Fe(3-bpp)₂](TCNQ)₃·5MeCN (1·5MeCN, where δ = −0.67). The partially desolvated material shows semiconducting behavior, with the room temperature conductivity σ_RT = 3.1 × 10⁻³ S cm⁻¹, and weak modulation of conducting properties in the region of the spin transition. The complete desolvation, however, results in the loss of hysteretic behavior and a very gradual SCO that spans the temperature range of 200 K. A related complex with integer-charged TCNQ⁻ anions, [Fe(3-bpp)₂](TCNQ)₂·3MeCN (2·3MeCN), readily loses the interstitial solvent to afford desolvated complex 2 that undergoes an abrupt and hysteretic spin transition centered at 106 K, with an 11 K thermal hysteresis. Complex 2 also exhibits a temperature-induced excited spin-state trapping (TIESST) effect, upon which a metastable high-spin state is trapped by flash-cooling from room temperature to 10 K. Heating above 85 K restores the ground-state low-spin configuration. An approach to improve the structural stability of such complexes is demonstrated by using a related ligand 2,6-bis(benzimidazol-2′-yl)pyridine (bzimpy) to obtain [Fe(bzimpy)₂](TCNQ)₆·2Me₂CO (4) and [Fe(bzimpy)₂](TCNQ)₅·5MeCN (5), both of which exist as LS complexes up to 400 K and exhibit semiconducting behavior, with σ_RT = 9.1 × 10⁻² S cm⁻¹ and 1.8 × 10⁻³ S cm⁻¹, respectively.

Co-crystallization of the cationic complex [Fe(3-bpp)2]²⁺ with fractionally charged TCNQ^δ− anions (0 < δ < 1) affords semiconducting spin-crossover (SCO) materials. The abruptness of SCO is strongly dependent on the interstitial solvent content.     

Copper coordination polymers from cavitand ligands: hierarchical spaces from cage and capsule motifs,and other topologies

The cyclotriveratrylene-type ligands (±)-tris(iso-nicotinoyl)cyclotriguaiacylene L1 (±)-tris(4-pyridylmethyl)cyclotriguaiacylene L2 and (±)-tris{4-(4-pyridyl)benzyl}cyclotriguaiacylene L3 all feature 4-pyridyl donor groups and all form coordination polymers with Cu^I and/or Cu^II cations that show a remarkable range of framework topologies and structures. Complex [Cu^I ₄Cu^II _1.5(L1)₃(CN)₆]·CN·n(DMF) 1 features a novel 3,4-connected framework of cyano-linked hexagonal metallo-cages. In complexes [Cu₃(L2)₄(H₂O)₃]·6(OTf)·n(DMSO) 2 and [Cu₂(L3)₂Br₂(H₂O)(DMSO)]·2Br·n(DMSO) 3 capsule-like metallo-cryptophane motifs are formed which linked through their metal vertices into a hexagonal 2D network of (4³.12³)(4².12²) topology or a coordination chain. Complex [Cu₂(L1)₂(OTf)₂(NMP)₂(H₂O)₂]·2(OTf)·2NMP 4 has an interpenetrating 2D 3,4-connected framework of (4.6².8)(6².8)(4.6².8²) topology with tubular channels. Complex [Cu(L1)(NCMe)]·BF₄·2(CH₃CN)·H₂O 5 features a 2D network of 6³ topology while the Cu^II analogue [Cu₂(L1)₂(NMP)(H₂O)]·4BF₄·12NMP·1.5H₂O 6 has an interpenetrating (10,3)-b type structure and complex [Cu₂(L2)₂Br₃(DMSO)]·Br·n(DMSO) 7 has a 2D network of 4.8² topology. Strategies for formation of coordination polymers with hierarchical spaces emerge in this work and complex 2 is shown to absorb fullerene-C₆₀ through soaking the crystals in a toluene solution.     

Determination of Cd,Pb, and Cu in the Atmospheric Aerosol of Central East Antarctica at Dome C (Concordia Station)

Trace heavy metals Cd, Pb, and Cu were determined (by square wave anodic stripping voltammetry) in aerosol samples collected at Dome C (the Italo-French Station Concordia), a remote site of the Central East Antarctic plateau, for which no data are available until now. During the Austral Summer 2005–2006, three PM10 high-volume impactors were installed in two locations nearby of Concordia station: the first one very close and downwind of the station (about 50 m north), the other two (very close to each other) in a ‘distant’ site, upwind of the station and close to the astrophysics tent (not used in that expedition) at ~800 m south of Station Concordia. For each sample, the availability of the mass of the aerosol collected (obtained by differential weighing carried out on site), in addition to the volume of the filtered air, allowed us to express results both in terms of metal mass fractions in the aerosol and in the usual way of metal atmospheric concentrations. Metal contents increased in the order Cd < Pb < Cu with the following ranges of values: Cd 1.0–8.4 µg g⁻¹ (0.09–3.1 pg m⁻³), Pb 96–470 µg g⁻¹ (12–62 pg m⁻³), and Cu 0.17–20 mg g⁻¹ (0.027–2.4 ng m⁻³). From the metal temporal profiles obtained we estimated the following background values for the area of Dome C, expressed both in mass fractions and in atmospheric concentrations: Cd 1.2 ± 0.2 µg g⁻¹ (0.24 ± 0.13 pg m⁻³), Pb (here fixed as upper limit) 113 ± 13 µg g⁻¹ (21 ± 8 pg m⁻³), and Cu 0.91 ± 0.48 mg g⁻¹ (0.12 ± 0.07 ng m⁻³). The highest values were observed in the first part of the season, and particularly for the site close to the station, possibly related to sample contamination linked to intense activity at the Concordia station connected with the beginning of the expedition, including aircraft arrivals/departures. Increments of up to 10 times (and even 20 times for Cu) were recorded with respect to the background values. The metal excesses of the contaminated over background samples were found approximately, except for Cu, in the same proportion of the metal contents of the special Antarctic blend (SAB) diesel fuel, which is used almost exclusively at Concordia Station. The effect of the wind direction was also observed. Thus in the intermediate period of the campaign, when the wind direction reversed for several days with respect to the prevailing one, Cd and Pb metal contents decreased at the sampling point installed close to the station, now upwind of Concordia station, and increased at the ‘clean’ site astrophysics tent, turned downwind at the main station. No simple and easily interpretable effect of the wind direction was observed for Cu, which suggests that some other extemporaneous and not clearly identified factor may have intervened in this case. These results suggest that the human impact at Dome C influences mainly the zone very close to the station, but also the area in the neighborhood, including the supposed clean site of the astrophysics tent (about 800 m far from the station), when the wind direction reverses with respect to the prevailing one, leaving the site downwind of the station Concordia. Since no other data are reported for the Dome C area, our results are compared with literature data referred to the South Pole Station (the only other plateau site for which data are available) and several other coastal Antarctic sites, observing that our results (excluding Cu) are the lowest ever observed for Antarctic aerosol.     

Determination of 77 Multiclass Pesticides and Their Metabolitesin Capsicum and Tomato Using GC-MS/MS and LC-MS/MS

A quick, sensitive, and reproducible analytical method for the determination of 77 multiclass pesticides and their metabolites in Capsicum and tomato by gas and liquid chromatography tandem mass spectrometry was standardized and validated. The limit of detection of 0.19 to 10.91 and limit of quantification of 0.63 to 36.34 µg·kg⁻¹ for Capsicum and 0.10 to 9.55 µg·kg⁻¹ (LOD) and 0.35 to 33.43 µg·kg⁻¹ (LOQ) for tomato. The method involves extraction of sample with acetonitrile, purification by dispersive solid phase extraction using primary secondary amine and graphitized carbon black. The recoveries of all pesticides were in the range of 75 to 110% with a relative standard deviation of less than 20%. Similarly, the method precision was evaluated interms of repeatability (RSDr) and reproducibility (RSD_wR) by spiking of mixed pesticides standards at 100 µg·kg⁻¹ recorded anRSD of less than 20%. The matrix effect was acceptable and no significant variation was observed in both the matrices except for few pesticides. The estimated measurement uncertainty found acceptable for all the pesticides. This method found suitable for analysis of vegetable samples drawn from market and farm gates.     

Enzymatic Extraction and Characterization of Pectin from Cocoa Pod Husks (Theobroma cacao L.) Using Celluclast® 1.5 L

Cocoa pod husks are a waste generated during the processing of cocoa beans. We aimed to explore the enzymatic extraction of pectin using cellulases. The extraction process was optimized using a central composite design (CCD) and analyzed by response surface methodology (RSM). The parameters optimized were feedstock concentration (%), enzyme dosage (µL/g), and time (h). Three dependent variables were studied: pectin yield (g/100 g dry husk) (R² = 97.02), galacturonic acid content (g/100 g pectin) (R² = 96.90), and galacturonic acid yield (g/100 g feedstock) (R² = 95.35). The optimal parameters were 6.0% feedstock concentration, 40 µL g⁻¹ of enzyme, and 18.54 h, conditions that produced experimentally a pectin yield of 10.20 g/100 g feedstock, 52.06 g galacturonic acid/100 g pectin, and a yield 5.31 g galacturonic acid/100 g feedstock. Using the chemical extraction method, a yield of 8.08 g pectin/100 g feedstock and a galacturonic acid content of 60.97 g/100 g pectin were obtained. Using assisted sonication, a pectin yield of 8.28 g/100 g feedstock and a galacturonic acid content of 42.77 g/100 g pectin were obtained. Enzymatically optimized pectin has rheological and physicochemical features typical of this biomaterial, which provides an interesting alternative for the valorization of cocoa husks.     

Synthesis,Characterization and Assessment of the Antioxidant Activity of Cu(II), Zn(II) and Cd(II) Complexes Derived from Scorpionate Ligands

Seeking to enrich the yet less explored field of scorpionate complexes bearing antioxidant properties, we, here, report on the synthesis, characterization and assessment of the antioxidant activity of new complexes derived from three scorpionate ligands. The interaction between the scorpionate ligands thallium(I) hydrotris(5-methyl-indazolyl)borate (TlTp^4Bo,5Me), thallium(I) hydrotris(4,5-dihydro-2H-benzo[g]indazolyl)borate (TlTp^a) and potassium hydrotris(3-tert-butyl- pyrazolyl)borate (KTp^tBu), and metal(II) chlorides, in dichloromethane at room temperature, produced a new family of complexes having the stoichiometric formula [M(Tp^4Bo,5Me)₂] (M = Cu, 1; Zn, 4; Cd, 7), [M(Tp^a)₂] (M = Cu, 2; Zn, 5; Cd, 8), [Cu(Hpz^tBu)₃Cl₂] (3), [Zn(Tp^tBu)Cl] (6) and [Cd(Bp^tBu)(Hpz^tBu)Cl] (9). The obtained metal complexes were characterized by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance and elemental analysis, highlighting the total and partial hydrolysis of the scorpionate ligand Tp^tBu during the synthesis of the Cu(II) complex 3 and the Cd(II) complex 9, respectively. An assessment of the antioxidant activity of the obtained metal complexes was performed through both enzymatic and non-enzymatic assays against 1,1-diphenyl-2-picryl- hydrazyl (DPPH^·), 2,2′-Azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS^+·), hydroxyl (HO^·), nitric oxide (NO^·), superoxide (O₂⁻) and peroxide (OOH^·) radicals. In particular, the complex [Cu(Tp^a)₂]⋅0.5H₂O (2) exhibited significant antioxidant activity, as good and specific activity against superoxide (O₂^−·), (IC50 values equal to 5.6 ± 0.2 μM) and might be identified as auspicious SOD-mimics (SOD = superoxide dismutase).     

Six New Phenylpropanoid Derivatives from Chemically Converted Extract of Alpinia galanga (L.) and Their Antiparasitic Activities

Chemical conversion of the extract of natural resources is a very attractive way to expand the chemical space to discover bioactive compounds. In order to search for new medicines to treat parasitic diseases that cause high morbidity and mortality in affected countries in the world, the ethyl acetate extract from the rhizome of Alpinia galanga (L.) has been chemically converted by epoxidation using dioxirane generated in situ. The biological activity of chemically converted extract (CCE) of A. galanga (L.) significantly increased the activity against Leishmania major up to 82.6 ± 6.2 % at 25 μg/mL (whereas 2.7 ± 0.8% for the original extract). By bioassay-guided fractionation, new phenylpropanoids (1–6) and four known compounds, hydroquinone (7), 4-hydroxy(4-hydroxyphenyl)methoxy)benzaldehyde (8), isocoumarin cis 4-hydroxymelein (9), and (2S,3S,6R,7R,9S,10S)-humulene triepoxide (10) were isolated from CCE. The structures of isolated compounds were determined by spectroscopic analyses of 1D and 2D NMR, IR, and MS spectra. The most active compound was hydroquinone (7) with IC₅₀ = 0.37 ± 1.37 μg/mL as a substantial active principle of CCE. In addition, the new phenylpropanoid 2 (IC₅₀ = 27.8 ± 0.34 μg/mL) also showed significant activity against L. major compared to the positive control miltefosine (IC₅₀ = 7.47 ± 0.3 μg/mL). The activities of the isolated compounds were also evaluated against Plasmodium falciparum, Trypanosoma brucei gambisense and Trypanosoma brucei rhodeisense. Interestingly, compound 2 was selectively active against trypanosomes with potent activity. To the best of our knowledge, this is the first report on the bioactive “unnatural” natural products from the crude extract of A. galanga (L.) by chemical conversion and on its activities against causal pathogens of leishmaniasis, trypanosomiasis, and malaria.     

Development and Validation of Liquid Chromatography-Tandem Mass Spectrometry Methods for the Quantification of Cefquinome,Ceftiofur, and Desfuroylceftiofuracetamide in Porcine Feces with Emphasis on Analyte Stability

Cefquinome and ceftiofur are β-lactam antibiotics used for the treatment of bacterial infections in swine. Although these antimicrobials are administered intramuscularly, the exposure of the gut microbiota to these cephalosporins is not well described. This exposure can contribute to the emergence and spread of antimicrobials in the environment and to the possible spread of antimicrobial resistance genes. To assess the impact of drug administration on the intestinal excretion of these antimicrobials it is essential to measure the amounts of native compound and metabolites in feces. Two (ultra)-high-performance liquid chromatography-tandem mass spectrometry ((U)HPLC–MS/MS) methods were developed and validated, one for the determination of cefquinome and ceftiofur and the other for the determination of ceftiofur residues, measured as desfuroylceftiofuracetamide, in porcine feces. The matrix-based calibration curve was linear from 5 ng g⁻¹ to 1000 ng g⁻¹ for cefquinome (correlation coefficient (r) = 0.9990 ± 0.0007; goodness of fit (gof) = 3.70 ± 1.43) and ceftiofur (r = 0.9979 ± 0.0009; gof = 5.51 ± 1.14) and quadratic from 30 ng g⁻¹ to 2000 ng g⁻¹ for desfuroylceftiofuracetamide (r = 0.9960 ± 0.0020; gof = 7.31 ± 1.76). The within-day and between-day precision and accuracy fell within the specified ranges. Since β-lactam antibiotics are known to be unstable in feces, additional experiments were conducted to adjust the sampling protocol in order to minimize the impact of the matrix constituents on the stability of the analytes. Immediately after sampling, 500 µL of an 8 µg mL⁻¹ tazobactam solution in water was added to 0.5 g feces, to reduce the degradation in matrix.     

Phytochemical Composition,Antioxidant Activity,and Enzyme Inhibitory Activities (α-Glucosidase,Xanthine Oxidase,and Acetylcholinesterase) of Musella lasiocarpa

In this study, we aimed to investigate the chemical components and biological activities of Musella lasiocarpa, a special flower that is edible and has functional properties. The crude methanol extract and its four fractions (petroleum ether, ethyl acetate, n-butanol, and aqueous fractions) were tested for their total antioxidant capacity, followed by their α-glucosidase, acetylcholinesterase, and xanthine oxidase inhibitory activities. Among the samples, the highest total phenolic and total flavonoid contents were found in the ethyl acetate (EtOAc) fraction (224.99 mg GAE/g DE) and crude methanol extract (187.81 mg QE/g DE), respectively. The EtOAc fraction of Musella lasiocarpa exhibited the strongest DPPH· scavenging ability, ABTS·⁺ scavenging ability, and α-glucosidase inhibitory activity with the IC₅₀ values of 22.17, 12.10, and 125.66 μg/mL, respectively. The EtOAc fraction also showed the strongest ferric reducing antioxidant power (1513.89 mg FeSO₄/g DE) and oxygen radical absorbance capacity ability (524.11 mg Trolox/g DE), which were higher than those of the control BHT. In contrast, the aqueous fraction demonstrated the highest acetylcholinesterase inhibitory activity (IC₅₀ = 10.11 μg/mL), and the best xanthine oxidase inhibitory ability (IC₅₀ = 5.23 μg/mL) was observed from the crude methanol extract as compared with allopurinol (24.85 μg/mL). The HPLC-MS/MS and GC-MS analyses further revealed an impressive arsenal of compounds, including phenolic acids, fatty acids, esters, terpenoids, and flavonoids, in the most biologically active EtOAc fraction. Taken together, this is the first report indicating the potential of Musella lasiocarpa as an excellent natural source of antioxidants with possible therapeutic, nutraceutical, and functional food applications.