ADSORPTION OF TRIBENURON-METHYL BY NATURAL AND MODIFIED CLAYS

This work deals with the purification of water containing residues of the herbicide tribenuron-methyl by means of a cleaning system based on a composite organo-clay mineral. Tribenuron-methyl suffers hydrolysis, for this reason it is important to clean the water not only from the mother molecule, but also from the products of its degradation. Experiments on adsorption/desorption of tribenuron-methyl and its metabolites by using natural and organo-micellar montmorillonite were performed. Desorption of the herbicide from the micelle clay-composite was done using acetonitrile

Biological activities of alkaloids: From toxicology to pharmacology

Plants produce many secondary metabolites, which reveal biological activity [...]

An attempt of biocontrol the tomato-wilt disease caused by Verticillium dahliae using Burkholderia gladioli pv. agaricicola and its bioactive secondary metabolites

There is a great interest in discovering new microbial natural biocides such as microbial secondary metabolites to reduce the environmental pollution due to the excessive use of synthetic pesticides. Verticillium wilt, caused by the soil-borne Verticillium dahliae, is a widespread disease in tomato growing in many parts of the world. Burkholderia gladioli pv. agaricicola produces some antimicrobial substances and extracellular hydrolytic enzymes which exhibited promising antimicrobial activity towards several phytopathogens. The aims of the current research are to assess in vitro fungicidal effect of 4 strains of B. gladioli pv. agaricicola (ICMP11096, 11097, 12220 and 12322) against V. dahliae using culture or cell-free culture filtrate. In situ assay was performed to evaluate the biocontrol effect of the most efficient bacterial strain on wilt disease caused by V. dahliae in tomato plants. Results demonstrated that the studied bacterial strain ICMP12322 exerted the highest in vitro antifungal activity against V. dahliae which correlated with its ability to produce extracellular hydrolytic enzymes. Furthermore, in situ results showed that the selected bacterial strain significantly minimized the disease incidence

Simulated ageing of crude oil and advanced oxidation processes for water remediation since crude oil pollution

Crude oil can undergo biotic and abiotic transformation processes in the environment. This article deals with the fate of an Italian crude oil under simulated solar irradiation to understand (i) the modification induced on its composition by artificial aging and (ii) the transformations arising from different advanced oxidation processes (AOPs) applied as oil-polluted water remediation methods. The AOPs adopted were photocatalysis, sonolysis, and, simultaneously, photocatalysis and sonolysis (sonophotocatalysis). Crude oil and its water-soluble fractions underwent analysis using GC-MS, liquid-state1H-NMR, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), and fluorescence. The crude oil after light irradiation showed (i) significant modifications induced by the artificial aging on its composition and (ii) the formation of potentially toxic substances. The treatment produced oil oxidation with a particular effect of double bonds oxygenation. Non-polar compounds present in the water-soluble oil fraction showed a strong presence of branched alkanes and a good amount of linear and aromatic alkanes. All remediation methods utilized generated an increase of C5 class and a decrease of C6-C9 types of compounds. The analysis of polar molecules elucidated that oxygenated compounds underwent a slight reduction after photocatalysis and a sharp decline after sonophotocatalytic degradation. Significant modifications did not occur by sonolysis

Diazepam stability in wastewater and removal by advanced membranes technology, activated carbon and micelle- clay complex

Stability and removal of the anti-anxiety drug diazepam (valium) from spiked wastewater samples were studied. An advanced wastewater treatment plant (WWTP), utilizing ultrafiltration (UF), activated charcoal (AC), and reverse osmosis (RO) after the secondary biological treatment showed that UF and RO were relatively sufficient in removing spiked diazepam to a safe level. Kinetic studies in both pure water (abiotic degradation) and in sludge (biotic degradation) at room temperature were investigated. Diazepam showed high chemical stability toward degradation in pure water, and underwent faster biodegradation in sludge providing two main degradation products. The degradation reactions in sludge and pure water showed first-order kinetics with rate constant values of 2.6 × 10−7 s−1 and 9.08 × 10−8 s−1, respectively (half-life = 31 and 88 d, respectively). Adsorption of diazepam by activated carbon and composite micelle–clay (octadecyltrimethylammonium montmorillonite) complex was studied using both Langmuir and Freundlich isotherms. Based on the determination coefficient, Langmuir isotherm was found to better fit the data, indicating the retention of diazepam monolayer on both adsorbents. Filtration of 100 mg L−1 solutions of diazepam by micelle–clay filter yielded almost complete removal at flow rates of 2 mL min−1

Hemp chemotype definition by cannabinoids characterization using lc-esi(+)-ltq-fticr ms and infrared multiphoton dissociation

The development and application of advanced analytical methods for a comprehensive analysis of Cannabis sativa L. extracts plays a pivotal role in order to have a reliable evaluation of their chemotype definition to guarantee the efficacy and safety in pharmaceutical use. This paper deals with the qualitative and quantitative determination of cannabidiol (CBD), tetrahydro-cannabinol (THC), cannabinol (CBN), tetrahydrocannabivarin (THCV), cannabidivarin (CBDV), and cannabigerol (CBG) based on a liquid chromategraphy-mass spectrometry (LC-MS) method using electrospray ionization in positive mode (ESI+), coupled with a hybrid quadrupole linear ion trap (LTQ) and Fourier transform ion cyclotron resonance mass spectrometer (FTICR-MS). For the first time, structural information of phytocannabinoids is available upon precursor ions’ isolation within the FTICR trapping cell and subsequent fragmentation induced by infrared multiphoton dissociation (IRMPD). Such fragmentation and accurate mass measurement of product ions, alongside collision-induced dissociation (CID) within LTQ, was advantageous to propose a reliable fragmentation pattern for each compound. Then, the proposed LC-ESI(+)-LTQ-FTICR MS method was successfully applied to the hemp chemotype definition of three registered Italian accessions of hemp C. sativa plants (Carmagnola C.S., Carmagnola, and Eletta Campana), thus resulting in the Eletta Campana accession being the best one for cannabis product manufacturing

Detection of Eight Cannabinoids and One Tracer in Wastewater and River Water by SPE-UPLC–ESI-MS/MS

The consumption of illicit drugs represents a global social and economic problem. Using suitable analytical methods, monitoring, and detection of different illegal drugs residues and their metabolites in wastewater samples can help combat this problem. Our article defines a method to develop, validate, and practically applicate a rapid and robust analytical process for the evaluation of six naturally occurring cannabinoids (CBG, CBD, CBDV, CBN, THC, THCV), two cannabinoids in acidic form (CBDA, THCA-A), and the major cannabis-related human metabolite (THC-COOH). After SPE offline enrichment, we used a UPLC–ESI-MS/MS system, which permitted the determination of several by-products. Studied matrices were samples of different origins: (i) effluent water from a wastewater treatment plant in the Porto urban area; (ii) environmental water from Febros River, the last left-bank tributary of the Douro River. The multi-residue approach was substantiated and successfully employed to analyze the water samples collected in the above locations. The rapid and precise quantification of nine different cannabinoids in different water samples occurred within nine minutes at the ng L−1 level. The appearance of dozens of ng L−1 of some cannabis secondary metabolites, such as CBD, CBDA, CBN, THCA-A, indicates this plant species’ widespread usage among the general population in the considered area

Mass spectrometry application on the detection of Sildenafil in aqueous phases

Sildenafil, the active ingredient of Viagra (Figure n.1), is a drug helpful in solving erectile dysfunction problems and recently entered the list of emerging contaminants. The use of these pharmaceuticals is increasingly widespread among perfectly healthy young people (20 or 30 years old) who make them a dangerous abuse for "recreational" purposes together with ecstasy: the result is a synergistic amplification of their final effects, such as the feeling of euphoria, confusion, disorientation, hallucinations, tremors or, in severe cases, irregular heartbeat and even coma. According to the 2018 annual report prepared by the Italian Medicines Agency (AIFA), this compounds’ consumption had increased over time from 2.9 DDD (Defined Daily Dose assumed per 1000 inhabitants in the referred year) in 2014 to 3.6 DDD in 2018. Unfortunately, it is impossible to detect the actual quantity used from the population (young and patients) because the internet network is becoming a way of purchasing to avoid medical prescriptions. Indeed, some researchers [1] report that illicit trading with pharmaceuticals products from the Internet is not wholly conscious of the risks for health concerning the quality of these products, such as the possible presence of toxic impurities [2]. The increase in demand is powering the illegal trade via the web, and, consequently, the risk of using an ineffective/harmful to health drug is very high [3,4]. The human body does not fully utilize these drugs. An unknown quantity, probably transformed, is excreted with urine and faeces. The high consumption of this substance, globally accomplished by legal and illegal ways, and the fact that Wastewater treatment plants (WWTP) cannot remove all types of contaminants that enter the sewer legitimates thinking that they can pose a severe threat to ecosystems and human health [5]. The unambiguous analytical determination of the active parent drug and the identification of its transformation products are therefore indispensable to try understanding if the quantity found of this drug in wastewater and surface water is linked to actual medical use and to verify whether tertiary purification treatments of wastewater are effective in the removal. In this work, the identification and quantification of this pharmaceutical product in water and synthetic wastewater were performed by LC-ESI-LTQ/MS and confirmed by CID-MSn. Thanks to high mass precision and MS/MS capability, determination and structural interpretation of sildenafil and its transformation products were achieved

Classification, Toxicity and Bioactivity of Natural Diterpenoid Alkaloids

Diterpenoid alkaloids are natural compounds having complex structural features with many stereo-centres originating from the amination of natural tetracyclic diterpenes and produced primarily from plants in the Aconitum, Delphinium, Consolida genera. Corals, Xenia, Okinawan/Clavularia, Alcyonacea (soft corals) and marine sponges are rich sources of diterpenoids, despite the difficulty to access them and the lack of availability. Researchers have long been concerned with the potential beneficial or harmful effects of diterpenoid alkaloids due to their structural complexity, which accounts for their use as pharmaceuticals as well as their lousy reputation as toxic substances. Compounds belonging to this unique and fascinating family of natural products exhibit a broad spectrum of biological activities. Some of these compounds are on the list of clinical drugs, while others act as incredibly potent neurotoxins. Despite numerous attempts to prepare synthetic products, this review only introduces the natural diterpenoid alkaloids, describing 'compounds' structures and classifications and their toxicity and bioactivity. The purpose of the review is to highlight some existing relationships between the presence of substituents in the structure of such molecules and their recognized bioactivity

SECONDARY METABOLITES: APPLICATIONS ON CULTURAL HERITAGE

Biological sciences and related bioͲtechnology play a very important role in research projects concerning protection and preservation of cultural heritage for future generations. In this work secondary metabolites of Burkholderia gladioli pv. agaricicola (Bga) ICMP 11096 strain and crude extract of glycoalkaloids from Solanaceae plants, were tested against a panel of microorganisms isolated from calcarenite stones of two historical bridges located in Potenza and in Campomaggiore (Southern Italy). The isolated bacteria belong to Bacillus cereus and Arthrobacter agilisspecies, while fungi belong to Aspergillus, Penicillium, Coprinellus, Fusarium, Rhizoctonia and Stemphylium genera. Bga broth (unfiltered) and glycoalkaloids extracts were able to inhibit the growth of all bacterial isolates. Bga culture was active against fungal colonies, while Solanaceae extract exerted bioͲactivity against Fusarium and Rhizoctonia gener