Search Results (36)

Cannabis (Cannabis sativa L.) contains numerous secondary metabolites with different bioactivities. Extraction methods differ in their efficiency in recovering metabolites from plant material, and thus cannabis extracts vary significantly in their composition and activity. We aimed to develop a repeatable and accurate HPLC-MS method for the determination of nine common cannabinoids and compare two widely used extraction techniques: ultrasound-assisted extraction (UAE) with methanol and supercritical CO₂ extraction (SFE). Inflorescences of the Kompolti cultivar were used as the plant material. On a polar C18 column, more than thirty compounds were well separated within 25 min; thirteen cannabinoids were identified and eight of them were quantified, with cannabidiol and its acidic precursor being the most abundant. Additionally, three spectrophotometric assays were employed for extract characterization: the total phenolic content, total flavonoid content, and DPPH radical scavenging capacity. The SFE extract, obtained using ethanol as a co-solvent under low pressure (<100 bar) and temperature (<45 °C), was more enriched than the UAE extract (181.62 ± 2.90 vs. 140.64 ± 13.24 mg quercetin equivalents/g of dry extract) and cannabinoids (446.29 ± 22.66 vs. 379.85 ± 17.16 mg/g of dry extract), especially cannabinoid acids. However, UAE achieved greater recovery from the plant material (cannabinoids: 83.42 ± 5.15 vs. 68.84 ± 3.49 mg/g of plant material) and showed superior antioxidant capacity (DPPH IC₅₀: 2.50 ± 0.18 vs. 3.37 ± 0.07 mg/mL). Notwithstanding the observed partial decarboxylation, the high repeatability (RSD < 15%, n = 11) of the entire analytical workflow involving UAE extraction and LC-MS analysis renders it suitable for routine analyses. This study contributes to the ongoing efforts toward the quality control and valorization of C. sativa. Full article

Photochemical degradation is a major removal pathway for pharmaceutical pollutants in water, and dissolved organic matter (DOM) in water is an important factor affecting this process. This study investigates the differential effects of seasonally-varied dissolved organic matter (DOM) from Songhua River and Liao River on the photodegradation of pharmaceutical pollutants, using levofloxacin (LFX), sulfamethoxazole (SMZ), and ibuprofen (IBP) as target compounds. The results demonstrated that summer and autumn DOM inhibited the photodegradation of LFX and SMZ through light screening and dynamic quenching effects, with inhibition rates of 35.1% and 55.5%, respectively, whereas winter DOM enhanced degradation through photo-oxidation mechanisms. DOM from Songhua River and Liao River significantly promoted the photodegradation of IBP. Quenching experiments showed differences in the contributions of photochemically reactive intermediates (PPRIs) to the photodegradation of different target pollutants, with hydroxyl radicals (•OH) dominating LFX photodegradation (48.79% contribution), excited triplet states of DOM (³DOM*) dominating SMZ photodegradation (85.20% contribution), and singlet oxygen (¹O₂) dominating IBP photodegradation (79.89% contribution). The photodegradation pathways were elucidated by measuring the photodegradation by-products of the target pollutants: LFX mainly underwent piperazine ring cleavage and oxidative decarboxylation, SMZ underwent isoxazole ring opening and deamination during photodegradation, and IBP underwent photodecarboxylation and oxidation reactions. Under the influence of the DOM from the Songhua River and Liao River, the generation of multiple photodegradation by-products led to an increasing trend in the acute toxicity of target pollutants to luminescent bacteria. This investigation elucidates the dual regulatory mechanisms of natural aquatic DOM on both photo-induced degradation pathways and toxicity evolution dynamics of pharmaceutical contaminants, which is of great significance for understanding the photochemical transformation behavior and risk assessment of pharmaceutical pollutants in aquatic environments. Full article

Ibuprofen (IBF), as a representative emerging contaminant, poses urgent environmental and ecological risks that demand efficient removal technologies. This study employed an O₃/H₂O₂ catalytic oxidation process to degrade IBF in aqueous systems and systematically investigated the effects of reactant ratios, pH, and reactive species on the degradation efficiency. The results demonstrated that O₃-dominated oxidation significantly outperformed H₂O₂ alone in IBF removal, with an optimal dosage ratio of c(O₃):c (H₂O₂) = 6:1 and a removal efficiency of 94.75% at pH > 7. Radical quenching experiments confirmed that •OH served as the dominant reactive species, the concentration and stability of which directly governed the degradation kinetics. Combined density functional theory (DFT) calculations and mass spectrometry analysis revealed that the benzene ring and carboxyl groups in IBF were vulnerable to radical attack, with degradation pathways involving hydroxylation, decarboxylation, and ring-opening reactions, yielding 13 intermediate products. The toxicity assessment indicated that over 70% of these intermediates exhibited low or negligible toxicity. Remarkably, IBF removal efficiencies exceeded 99.4% in real water matrices (raw, filtered, and finished water), validating the robust anti-interference capability of the O₃/H₂O₂ system. This process, characterized by high efficiency and low ecological risk, provides a feasible solution for eliminating trace emerging contaminants in advanced drinking water treatment. Full article

Lignin is a natural aromatic macromolecule present in wood and an abundant resource on Earth, yet it is hardly used. In this study, an aqueous solution plasma treatment was investigated for the catalyst-free production of valuable chemicals from lignin. To elucidate the decomposition mechanism, the aqueous solution plasma treatment was applied to the fundamental lignin aromatic model compounds—phenol, guaiacol, and syringol. The results showed that the decomposition rate followed the order syringol > guaiacol > phenol, indicating that electron-donating methoxy groups enhance reactivity. These aromatic model compounds underwent hydroxylation at the ortho and para positions, oxidative ring cleavage, and fragmentation, leading to the formation of various dicarboxylic acids, primarily oxalic acid. All these reactions were promoted by hydroxyl radicals generated from water. Ultimately, decarbonylation and decarboxylation of carboxyl groups resulted in gasification, mainly producing H₂, CO, and CO₂. These results provide fundamental insights into lignin decomposition and demonstrate that aqueous solution plasma is a promising method for producing dicarboxylic acids from lignin under mild conditions without catalysts. Full article

Malaria remains a major global health problem that has been exacerbated by the impact of the COVID-19 pandemic on health systems. To combat this, the World Health Organization (WHO) has set a target of driving forward research into innovative treatment methods such as new drugs and vaccines. Quinones, particularly 1,4-naphthoquinones, have been identified as promising candidates for the development of antiprotozoal drugs. Herein, we report several methods for the preparation of 2-benzyl-1,4-naphthoquinones. In particular, the silver-catalyzed Kochi–Anderson radical decarboxylation is well suited for the preparation of these compounds. The antiprotozoal activity of all synthesized compounds was evaluated against Plasmodium falciparum NF54 and Trypanosoma brucei rhodesiense STIB900. Cytotoxicity towards L6 cells was also determined, and the respective selectivity indices (SI) were calculated. The synthesized compounds exhibited good antiplasmodial activity against the P. falciparum (NF54) strain, particularly (2-fluoro-5-trifluoromethylbenzyl)-menadione 2e, which showed strong efficacy and high selectivity (IC₅₀ = 0.006 µM, SI = 7495). In addition, these compounds also displayed favorable physicochemical properties, suggesting that the benzylnaphthoquinone scaffold may be a viable option for new antiplasmodial drugs. Full article

The presence of drugs in wastewater effluent is of concern due to their effects on the aquatic fauna and flora and there are growing efforts for their removal from the environment. In this paper, we study the photocatalytic visible-light degradation of naproxen, an over-the-counter anti-inflammatory drug, using 5% copper-doped TiO₂. The photocatalyst was characterized by XRD and BET surface area measurements. The optimal conditions for the degradation of 1 × 10⁻³ M of naproxen were found to be 3 h, with a catalyst loading of 50 mg/100 mL of the drug solution, and an acidic pH of 4.55. The degradation followed pseudo-first order kinetics and achieved a photodegradation efficiency of 44.8%. HPLC was used to separate the degradation products and their structures were determined using MS/MS data. A pathway for the degradation of naproxen is proposed along with degradation mechanisms. The major degradation events involve the formation of hydroxyl radicals, hydroxylation, keto-enol tautomerism, and decarboxylation. Full article

Methyl ethyl ketone (MEK) is among the most extensively utilized solvents in various industrial applications. In this study, we present a highly efficient synthesis route for MEK via the decarboxylation of biomass-derived levulinic acid, using potassium persulfate (K₂S₂O₈) and silver nitrate (AgNO₃) as key reagents. The specific roles of AgNO₃ and K₂S₂O₈ were thoroughly investigated. Additional silver species, such as Ag₂O and AgO, were also detected during the reaction. X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) analyses provided evidence of the evolution of solid phases throughout the reaction. Based on these findings, we propose a radical decarboxylation mechanism initiated by the generation of sulfate radicals (SO₄•⁻) through the catalytic breakdown of K₂S₂O₈ by AgNO₃. This mechanistic understanding, combined with a parametric study, enabled us to achieve an unprecedented level of levulinic acid conversion (97.9%) and MEK yield (86.6%) with this system, surpassing all previously reported results in the literature. Full article

Magnetic CuFe₂O₄ was prepared with the modified sol–gel method and used for enhanced peroxymonosulfate (PMS) activation and ofloxacin (OFL) degradation. The OFL could almost degrade within 30 min at a catalyst dosage of 0.66 g/L, PMS concentration of 0.38 mM, and initial pH of 6.53 without adjustment, using response surface methodology (RSM) with Box-Behnken design (BBD). In the CuFe₂O₄/PMS system, the coexisting substances, including CO₃²⁻, NO₃⁻, SO₄²⁻, Cl⁻ and humic acid, have little effect on the OFL degradation. The system also performs well in actual water, such as tap water and surface water (Mei Lake), indicating the excellent anti-interference ability of the system. The cyclic transformation between Cu(II)/Cu(I) and Fe(III)/Fe(II) triggers the generation of active radicals including SO₄^•−, •OH, •O₂⁻ and ¹O₂. The OFL degradation pathway, mainly involving the dehydrogenation, deamination, hydroxylation, decarboxylation and carboxylation processes, was proposed using mass spectroscopy. Moreover, the toxicity assessment indicated that the end intermediates are environmentally friendly. This study is about how the CuFe₂O₄/PMS system performs well in PMS activation for refractory organic matter removal in wastewater. Full article

Ketones are ubiquitous patterns found in various biological molecules and natural products. In recent years, a number of acylation methods have been developed based on the use of α-oxocarboxylic acids as acyl-transfer reagents, with particular emphasis on the photoinduced decarboxylative acylation of α-keto acids. This review focuses on the latest advancements in acylation methodologies through the decarboxylation of α-keto acids over the past several years, highlighting their product diversity, selectivity, and applicability. Where possible, the mechanistic rationale is presented, providing a positive outlook for the promising future of this field. Full article

The photoredox-catalyzed decarboxylative cross-coupling reaction of aryl acetic acids and aryl nitriles has been achieved under an argon atmosphere in high yields. This method provides a fast way to obtain prevalent aryl acetic acids from an abundant natural source. A tentative radical mechanism has been proposed. Full article

Herein, we present the first examples of amino acid decarboxylation via photochemically activated carbonyl sulfide (COS) elimination of the corresponding thioacids. This method offers a mild approach for the decarboxylation of amino acids, furnishing N-alkyl amino derivatives. The methodology was compatible with amino acids displaying both polar and hydrophobic sidechains and was tolerant towards widely used amino acid-protecting groups. The compatibility of the reaction with continuous-flow conditions demonstrates the scalability of the process. Full article

The incorporation of amide groups into biologically active molecules has been proven to be an efficient strategy for drug design and discovery. In this study, we present a simple and practical method for the synthesis of amide-containing quinazolin-4(3H)-ones under transition-metal-free conditions. This is achieved through a carbamoyl-radical-triggered cascade cyclization of N3-alkenyl-tethered quinazolinones. Notably, the carbamoyl radical is generated in situ from the oxidative decarboxylative process of oxamic acids in the presence of (NH₄)₂S₂O₈. Full article

Environmental organo bentonite synthesis using curcumin-derived chemicals is used as catalyst support for zinc with a Zn-pillaring structure (Zn@CU/BEN). The obtained composite was assessed as an affordable, highly effective, and multifunctional photocatalyst for enhanced oxidation of ibuprofen (IBU) residuals in water supplies. The Zn@CU/BEN composite (0.4 g/L) displayed significant catalytic activities, resulting in the complete oxidation of IBU (25 mg/L) after 80 min. Then, the complete mineralization based on the full elimination of TOC content was recognized after 160 min, with significant indications about the formed intermediates. The identified intermediates, together with the identification of hydroxyl radicals as the essential oxidizing agent, declared an oxidation pathway of IBU over Zn@CU/BEN that involved three steps: hydroxylation, decarboxylation/demethylation, and ring-opening processes. The toxic properties of raw pollutants as well as the oxidizing product at different durations were assessed based on the cell viability results of kidney (HEK293T) and liver (HepG2) cell lines. The partially oxidized sample in the initial duration displayed a higher toxicity impact than the raw IBU. However, the treated sample after 160 min reflected high biosafety and non-toxic properties (cell viability > 97%). The synergetic impact of bentonite and bentonite organo-modified by curcumin extract reflects enhancements in the adsorption as well as the oxidation performance of pillared zinc as a catalyst. Full article

Alkali-activated persulfate (PS) is widely used in situ in chemical oxidation processes; however, studies on the innovation of the alkali activation process are very limited. Two supported solid superbases, namely KNO₃/γ-Al₂O₃ (KAl) and KNO₃/SBA-15/MgO (KSM), respectively, were prepared and used to activate persulfate to degrade DCF in this work. The results showed that the superbases elevated the solution pH once added and thus could catalyze persulfate to degrade diclofenac efficiently above pH 10.5. The catalytic efficiency of KAl was close to that of sodium hydroxide, and that of KSM was the highest. The mechanism might be that, in addition to raising the solution pH, some potassium existed as K₂O₂, which had a strong oxidizing effect and was conducive to DCF removal. Hydroxyl, sulfate and superoxide radicals were all found in the reaction system, among which hydroxyl might play the most important role. The material composition ratio, common anion and humic acid all had some influences on the catalytic efficiency. A total of five intermediates were found in the KSM/PS oxidation system, and six oxidation pathways, which were hydroxylation, dehydrogen, dechlorination, dehydration, decarboxylation, and C-N bond breakage, might be involved in the reaction process. Several highly toxic oxidation products that should be paid attention to were also proposed. Full article

Oxidative degradation of 2,4-dinitrotoluenes in aqueous solution was executed using persulfate combined with semiconductors motivated by ultrasound (probe type, 20 kHz). Batch-mode experiments were performed to elucidate the effects of diverse operation variables on the sono-catalytic performance, including the ultrasonic power intensity, dosage of persulfate anions, and semiconductors. Owing to pronounced scavenging behaviors caused by benzene, ethanol, and methanol, the chief oxidants were presumed to be sulfate radicals which originated from persulfate anions, motivated via either the ultrasound or sono-catalysis of semiconductors. With regard to semiconductors, the increment of 2,4-dinitrotoluene removal efficiency was inversely proportional to the band gap energy of semiconductors. Based on the outcomes indicated in a gas chromatograph–mass spectrometer, it was sensibly postulated that the preliminary step for 2,4-dinitrotoluene removal was denitrated into o-mononitrotoluene or p-mononitrotoluene, followed by decarboxylation to nitrobenzene. Subsequently, nitrobenzene was decomposed to hydroxycyclohexadienyl radicals and converted into 2-nitrophenol, 3-nitrophenol, and 4-nitrophenol individually. Nitrophenol compounds with the cleavage of nitro groups synthesized phenol, which was sequentially transformed into hydroquinone and p-benzoquinone. Full article