Search Results (175)

Glucosinolate-derived metabolites play central roles in plant defense and are increasingly recognized for their pharmacological importance. Barbarea vulgaris produces a structurally diverse set of such compounds, yet their biological activities remain insufficiently explored. In this study, natural metabolites and their synthetic analogues were evaluated for antimicrobial, antibiofilm, antioxidant, and anti-inflammatory properties. Antimicrobial activity was assessed against human and plant pathogens by determining minimum inhibitory and minimum microbicidal concentrations, antibiofilm potential was examined using microplate assays, and radical scavenging activity was measured by DPPH and ABTS assays. In addition, the compounds were screened for inhibitory effects on lipoxygenase (LOX) and cyclooxygenase-2 (COX-2). Phenolic derivatives, particularly methyl-4-hydroxyphenylethyl dithiocarbamate (2) and 2-(4-hydroxyphenyl)ethyl isothiocyanate (8), exhibited notable in vitro antibacterial activity (MIC 0.312–1.25 mg mL⁻¹ against E. coli ATCC 25922 and S. aureus ATCC 25923) and detectable antibiofilm effects. Racemic barbarin (4) preferentially inhibited LOX, underscoring its potential as an anti-inflammatory scaffold, whereas COX-2 inhibition was weak across all tested compounds. None of the metabolites showed radical scavenging activity, suggesting that their effects rely on enzyme inhibition or microbial interactions rather than nonspecific antioxidant mechanisms. This study provides an integrated evaluation of B. vulgaris metabolites, highlighting their ecological role in plant defense and their potential as scaffolds for novel antimicrobial and anti-inflammatory agents. Full article

With the increasing demand for nickel, relentless efforts have been made to find alternative and highly selective collectors for recovering pentlandite. This study employed density functional theory (DFT) with dispersion correction to examine the interactions of iron-rich pentlandite (Fe₅Ni₄S₈) mineral surface with various collectors: S-allyl-N-diethyl-dithiocarbamate (ADEDTC), O-isopropyl-N-diethyl-thionocarbamate (IPDETC), sodium mercaptobenzothiazole (SMBT), and sodium-2,6-dithio-4-butylamino-1,3,5-triazine (SDTBAT). The plane surface of (311) proved to be the most stable surface with a surface energy of 1.48 J.m⁻², aligning well with the experimental X-ray diffraction (XRD) results and morphology. Adsorption simulations were performed on both Ni and Fe atoms of the plane surface of (311). ADEDTC exhibited the most exothermic adsorption energy of −460.58 kJ.mol⁻¹, compared to SMBT (−249.59 kJ.mol⁻¹), IPDETC (−161.01 kJ.mol⁻¹), and SDTBAT (−352.48 kJ.mol⁻¹). The adsorption strengths followed the order ADEDTC > SMBT > SDTBAT > IPDETC. Importantly, these collectors showed a preferential adsorption on the Ni atoms over Fe atoms, indicating selectivity towards Ni sites on the pentlandite mineral surface. These findings suggested that ADEDTC was the most effective collector for flotation applications involving pentlandite. As such, ADEDTC could potentially replace commonly used collectors or be used as a co-collector in the recovery of pentlandite minerals. Full article

Based on the need for safe disposal of hazardous waste incineration fly ash (HFA), this study evaluated the solidification/stabilization (S/S) performance of silicate cement, sodium dihydrogen phosphate (NaH₂PO₄), and sodium dimethyl dithiocarbamate (SDD) used individually and in combination. The raw HFA failed the leaching test for Pb, Zn, Cd, and Ni, with their concentrations exceeding the GB16889-2024 limits by factors of 3.1, 2.45, 1.67, and 1.1, respectively. While cement (150% dosage) effectively immobilized Pb, and Cd with >90% leaching reduction, it resulted in significant volume expansion (2.7-fold). NaH₂PO₄ excelled in Pb stabilization (100% efficiency at 20% dosage) via insoluble phosphate formation but required high doses. SDD effectively chelated Zn (63.4% efficiency at 5% dosage) but was less effective for Pb and costly. A synergistic combination of 5% cement, 15% SDD, and 10% NaH₂PO₄ was identified as the possible optimal formulation, successfully immobilizing all heavy metals within regulatory limits. This combined approach minimized dosage, controlled volume expansion ratio (R_VE) (~1.31), and reduced cost. The low initial dioxin content (7.6 ng TEQ/kg) was unaffected by S/S treatments and remained compliant. Mechanistic analyses (XRD, FTIR, SEM-EDS) confirmed the formation of C-S-H gels from cement, insoluble phosphates from NaH₂PO₄, and metal chelates from SDD, collectively transforming the HFA into a compact, low-porosity matrix conducive to safe disposal. This stabilization and solidification strategy not only achieves the safe disposal of hazardous waste incineration fly ash but also contributes to the goals of sustainable waste management by reducing the environmental footprint of treatment processes and minimizing the final disposal volume. Full article

Coumarin derivatives, whether natural or synthetic, have attracted considerable interest from medicinal chemists due to their versatile biological properties. Their appealing pharmacological activities—such as anticancer, anti-inflammatory, neuroprotective, anticoagulant, and antioxidant effects—combined with the ease of their synthesis and the ability to introduce chemical modifications at multiple positions have made them a widely explored class of compounds. In the scientific literature, there are many examples. On the other hand, dithiocarbamates, originally employed as pesticides and fungicides in agriculture, have recently emerged as potential therapeutic agents for the treatment of serious diseases such as cancer and microbial infections. Moreover, dithiocarbamates bearing diverse organic functionalities have demonstrated significant antifungal properties against resistant phytopathogenic fungi, presenting a promising approach to combat the growing global issue of fungal resistance. Dithiocarbamates linked to coumarin derivatives have been shown to exhibit cytotoxic activity against various human cancer cell lines, including MGC-803 (gastric), MCF-7 (breast), PC-3 (prostate), EC-109 (esophageal), H460 (non-small cell lung), HCCLM-7 (hepatocellular carcinoma), HeLa (cervical carcinoma), MDA-MB-435S (mammary adenocarcinoma), SW480 (colon carcinoma), and Hep-2 (laryngeal carcinoma). Numerous studies have revealed that the inclusion of a dithiocarbamate moiety can provide central nervous system (CNS) activity, particularly through inhibitory potency and selectivity toward acetylcholinesterase (AChE) and monoamine oxidases (MAO-A and MAO-B). Recently, it has been reported that coumarin–dithiocarbamate derivatives exhibit α-glucosidase inhibitory effects and also possess promising antimicrobial activity. This study presents an overview of recent progress in the chemistry of coumarin–dithiocarbamate derivatives, with a focus on their biological activity. Previous review papers focused on coumarin derivatives as multitarget compounds for neurodegenerative diseases and described various types of compounds, with dithiocarbamate derivatives representing only a small part of them. Our work deals exclusively with coumarin dithiocarbamates and their biological activity. Full article

Despite the widespread use of dithiocarbamate fungicides such as maneb, mancozeb, metiram, propineb, thiram, and ziram detected, according to EU legislation, via common degradation product carbon disulfide (CS₂), recent and comprehensive reviews on analytical methods for their determination in plant-based foods are lacking. Given the well-documented toxicity shown by the experimental model for these pesticides, including neurotoxicity and endocrine disruption, harmonized and reliable analytical protocols are crucial for food safety monitoring and regulatory compliance. Dithiocarbamates, beyond CS₂ release, have been associated with immunotoxicity, thyroid dysfunction, and potential carcinogenicity, raising further concern regarding chronic dietary exposure. Their metabolites may disrupt enzymatic activity and oxidative balance, enhancing systemic toxicity. Early methods, had limited sensitivity, poor reproducibility, and relied on hazardous solvents, reducing practical value. Although later advancements improved detection limits, modern procedures, including those proposed by the European Union Reference Laboratory (EURL), still show limitations. The EURL-recommended protocol involves acid hydrolysis using concentrated HCl, extraction with isooctane, heating to 85 °C, and rapid ice-bath cooling, which poses environmental concerns. Recovery efficiency remains inconsistent in some cases, and reproducibility within commodity groups is poor. This review discusses the status of methods for determining dithiocarbamates as individual compounds and via CS₂ moiety. Full article

Dithiocarbamate fungicides, including benomyl (methyl 1-butylcarbamoyl-2-benzimidazolecarbamate), share a common mechanism of toxicity by inhibiting aldehyde dehydrogenases (ALDHs), enzymes essential for detoxifying reactive aldehydes. One such aldehyde, 3,4-dihydroxyphenylacetaldehyde (DOPAL), a dopamine metabolite, is implicated in the catecholaldehyde hypothesis of Parkinson’s disease. This study examines ALDH inhibition as the molecular initiating event (MIE) within an adverse outcome pathway (AOP) leading to neurotoxicity. Caenorhabditis elegans at the L4 stage were exposed for 24 h to 10 or 100 μM benomyl. While 10 μM had no significant effect on lethality, growth, or reproduction, 100 μM induced adverse effects, albeit with low lethality. Both doses inhibited ALH activity, an effect mitigated by Alda-1, a selective ALDH activator. Alda-1 alone increased ALH-1 protein levels but did not alter benomyl-induced protein localization and relative abundance. Benomyl exposure also elevated oxidative stress markers—superoxide dismutase, catalase, and lipid peroxidation—which Alda-1 reduced. Neurotoxicity was evidenced by dopaminergic dysfunction, including impaired basal slowing response, neuronal morphological abnormalities, and reduced locomotion upon optogenetic activation. Fluorescent reporter assays confirmed ALH-1 presence in dopaminergic neurons. These results identify ALH inhibition as the MIE in benomyl-induced neurotoxicity, linking dopaminergic degeneration and redox imbalance to the catecholaldehyde hypothesis, and providing mechanistic insights into an AOP relevant to neurodegenerative disorders. Full article

Food safety concerns related to pesticide residues in fruits and vegetables have increased globally, particularly in regions where monitoring programs are scarce or inconsistent. This study provides the first multi-year evaluation of pesticide contamination and associated dietary risks in Cape Verde, an African island nation increasingly reliant on imported produce. A total of 570 samples of fruits and vegetables—both locally produced and imported—were collected from major markets across the country between 2017 and 2020 and analyzed using validated multiresidue methods based on gas chromatography coupled to Ion Trap mass spectrometry (GC-IT-MS/MS), and both gas and liquid chromatography coupled to triple quadrupole tandem mass spectrometry (GC-QqQ-MS/MS and LC-QqQ-MS/MS). Residues were detected in 63.9% of fruits and 13.2% of vegetables, with imported fruits showing the highest contamination levels and diversity of compounds. Although only one sample exceeded the maximum residue limits (MRLs) set by the European Union, 80 different active substances were quantified—many of them not authorized under the current EU pesticide residue legislation. Dietary exposure was estimated using median residue levels and real consumption data from the national nutrition survey (ENCAVE 2019), enabling a refined risk assessment based on actual consumption patterns. The cumulative hazard index for the adult population was 0.416, below the toxicological threshold of concern. However, when adjusted for children aged 6–11 years—taking into account body weight and relative consumption—the cumulative index approached 1.0, suggesting a potential health risk for this vulnerable group. A limited number of compounds, including omethoate, oxamyl, imazalil, and dithiocarbamates, accounted for most of the risk. Many are banned or heavily restricted in the EU, highlighting regulatory asymmetries in global food trade. These findings underscore the urgent need for strengthened residue monitoring in Cape Verde, particularly for imported products, and support the adoption of risk-based food safety policies that consider population-specific vulnerabilities and mixture effects. The methodological framework used here can serve as a model for other low-resource countries seeking to integrate analytical data with dietary exposure in a One Health context. Full article

Cuproptosis, a newly discovered copper-dependent programmed cell death pathway, represents a promising approach for anticancer therapy. However, the efficacy of cuproptosis critically depends on intracellular copper accumulation. Traditional copper ionophores have limited therapeutic efficacy due to their reliance on serum copper levels. Therefore, the development of novel copper ionophores to enhance intracellular copper levels is urgently needed. In this study, we targeted a melanoma model and pioneered the application of Bis(2-hydroxyethyl)dithiocarbamic acid copper(II) [Cu(HEDTC)₂] as a highly efficient copper ionophore for inducing cuproptosis in B16 melanoma cells. Compared to conventional copper ionophores, Cu(HEDTC)₂ exhibits superior intracellular copper delivery efficiency, thereby enhancing the induction of cuproptosis. We further constructed a Cu(HEDTC)₂@Soluplus-nanomicelle (CS NM) system designed to disrupt copper ion homeostasis in tumor cells and amplify cuproptosis. In this system, Cu(HEDTC)₂, as a novel copper ionophore, significantly enhanced the copper level in B16 melanoma cells. Upon cellular internalization, CS NM underwent degradation and released copper ions, which subsequently triggered cuproptosis by causing abnormal aggregation of mitochondrial lipoylated proteins. This study provides a new experimental foundation and potential therapeutic strategy for cuproptosis-based cancer treatment. Full article

(1) Background: Asomate, as a dithiocarbamate compound, is moderately toxic to the human body; thus, it is necessary to develop a rapid and efficient method for detection. To meet this need, this study introduced a rapid, non-destructive, and efficient method for detecting asomate residues on the surface of apples based on surface-enhanced Raman spectroscopy (SERS) combined with flexible substrates. (2) Methods: Concave Au nanorods (AuCNAs) were synthesized in advance. Then, the AuCNAs were loaded on an electrostatically spun film to generate a flexible TiO₂/ZrO₂/AuCNAs substrate for detection. (3) Results: The flexible substrate exhibited strong SERS activity, with an enhancement factor (EF) up to 9.40 × 10⁷ for 4-MBA. Meanwhile, the finite-difference time-domain (FDTD) simulation showed that the localized surface plasmon resonance (LSPR) effects related to the enhancement of the SERS signal are mainly generated from the ‘hot spots’ in AuCNAs. The density functional theory (DFT) simulation detailedly revealed that the SERS peaks could be generated by the interaction among asomate molecules, disassociated Au atoms, and Au facets. Moreover, the asomate in apple peel was analyzed with the limit of detection (LOD) as low as below 10 nM, allowing for the rapid detection of asomate directly on apple peels. (4) Conclusions: The flexible TiO₂/ZrO₂/AuCNAs film can be used for the in situ detection of asomate in apple peel at low concentrations. Moreover, the simulation methods, including FDTD and DFT, explained the mechanism of SERS from the flexible substrates. Full article

Selective separation of gold-bearing pyrite from gold-free pyrite through flotation to improve the gold-to-sulfur ratio in the feed can significantly enhance the throughput of autoclaves, thus achieving efficient and clean processing of refractory pyritic gold ores. To achieve this expectation, this study examined the surface physicochemical differences between gold-bearing and gold-free pyrite under flotation conditions using cyclic voltammetry, polarization curve testing, electrochemical impedance spectroscopy (EIS), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) simulations. Electrochemical tests showed higher reactivity in gold-bearing pyrite, with reactivity positively correlated to gold content. XPS results indicated more oxidation products on gold-bearing pyrite surfaces under identical conditions. DFT simulations revealed that the presence of gold reduced the oxygen adsorption energy on the pyrite surface while enhancing interactions between oxygen atoms and sulfur and iron atoms. Based on these findings, the selective separation of gold-bearing and gold-free pyrite in the flotation process can be explored through pulp aeration pre-oxidation combined with collectors demonstrating selectivity toward barren pyrite (e.g., dithiocarbamate collectors). This study provides theoretical foundations for the efficient exploitation and utilization of refractory gold-bearing pyrite resources. Full article

The antioxidant properties of novel diiodo-substituted 3-dithiocarbamic flavanones were investigated. The three frameworks that proved to be the most active ones in our previous studies were selected. By varying the nature of the substituent at the para position of flavanone ring B, a structure–activity relationship study on radical scavenging properties was performed. The influence of these substituents (F, Cl, Br and H) was investigated against DPPH and ABTS^+•. The results indicate that the presence of the halogen substituents induces better antioxidant properties than ascorbic acid and BHT. The highest radical scavenging activity was found in the case of morpholine carbodithioates. Regarding the ABTS^+• assay, all investigated flavanones exhibited better antioxidant properties than BHT. Full article

This review provides a comprehensive analysis of the role of chemical agents in enhancing the performance of geopolymers for the stabilization and adsorption of heavy metals. Geopolymers, synthesized from aluminosilicate sources activated under alkaline conditions, are recognized for their versatile structural and environmental benefits, including low carbon emissions and high chemical resistance. Their unique Si-O-Al framework supports both stabilization/solidification (S/S) and adsorption processes, making them an ideal polymeric matrix for the immobilization of hazardous heavy metals in contaminated environments. The review categorizes the heavy metal immobilization mechanisms into physical encapsulation, ion exchange, hydroxide precipitation, and chemical complexation, depending on the specific metal species and geopolymer formulation. The introduction of chemical stabilizing agents, such as dithiocarbamate, sodium sulfide, and trimercaptotriazine, significantly improves the encapsulation efficacy of geopolymers by promoting targeted reactions and stable metal complexes. These agents enable the effective S/S of metals, such as lead, cadmium, and chromium, reducing their leachability and environmental impact. In addition to solid waste management applications, geopolymers have shown promising adsorption capabilities for aqueous contaminants, with chemical modifications further increasing their affinity for specific heavy metals. This review evaluates the impact of different agents and synthesis conditions on the overall performance of geopolymers in heavy metal immobilization, highlighting advances in environmental applications and future research directions for sustainable hazardous waste treatment. Full article

Food safety is essential to ensure that food is safe for human consumption, particularly in light of the growing global and environmental changes, including population growth and climate variations. Meeting the increasing demand for food requires enhancing and protecting agricultural systems. A common strategy is the use of pesticides, which serve to protect cultivated plants from pests, diseases, and weeds. However, improper and excessive use of these products can lead to negative impacts, spanning economic, environmental, and human health aspects. Concerns about pesticide residues in food are global, as their effects on human health vary depending on exposure and quantity. The main objective of this study was to estimate the potential residual consumption (PRC) of pesticides present in food consumed by Brazilian households. Using a specific methodology, it was identified that pineapple had the highest average PRC (121.01 mg), primarily due to the high residue of the active ingredient ethephon. On the other hand, Dithiocarbamates showed the highest residual quantity. Tebuconazole was the most repeated in the samples. It was observed that the insecticide class was responsible for the highest average PRC in households, estimated at 142.45 mg annually, while higher-income families and those located in rural areas showed a greater propensity for potential residual pesticide consumption due to the higher consumption of fruits and vegetables. Additionally, it was found that households where the head of the family is male, highly educated, and older than 40 years present a higher risk of potential residual pesticide consumption. These results highlight the need for public policies focused on sanitary inspection, the training of professionals in the field, the rational use of pesticides by producers, and proper hygiene practices by consumers to mitigate health risks. Full article

Diaryldithiocarbamate complexes, [Fe(S₂CNAr₂)₃], have been prepared and their structure, reactivity, and thermal degradation to afford iron sulfide nanomaterials have been investigated. The addition of three equivalents of LiS₂CNAr₂ to FeCl₂·4H₂O in water-air affords dark red [Fe(S₂CNAr₂)₃] in high yields. All show magnetic measurements consistent with a predominantly high-spin electronic arrangement at room temperature. The molecular structure of [Fe{S₂C(N-p-MeOC₆H₄)₂}₃] reveals the expected distorted octahedral geometry, but Fe-S distances are more consistent with a low-spin electronic configuration, likely a result of the low temperature (120 K) of the data collection. The thermal stability of [Fe{S₂C(N-p-MeC₆H₄)₂}₃] has been investigated. TGA shows that it begins to decompose at a significantly lower temperature (ca. 160 °C) than previously observed for [Fe(S₂CNEt₂)₃], and this is further lowered (to ca. 100 °C) in oleylamine. The decomposition of [Fe{S₂C(N-p-MeC₆H₄)₂}₃] in oleylamine, via either a heat-up or hot injection process, affords nanoparticles of Fe₃S₄ (greigite), while in contrast, dry heating at 450 °C affords FeS (troilite) as large agglomerates. Full article

The strive to reduce harmful emissions from transport has resulted in an increased emphasis on minimising friction in lubricated contacting components to improve the energy efficiency of automotive engines. In this sense, it is of particular interest to investigate whether a synergistic tribological performance could be achieved by combining two or more friction modifier additives with nanoparticles. This study conducts a comprehensive investigation into the tribological characteristics of lubricant formulations enriched with nanodiamonds (NDs), combined with organic (Glycerol Monooleate, GMO) and inorganic (molybdenum dithiocarbamate, MoDTC) friction modifiers and a low-concentration anti-wear additive (Zinc dialkyl dithio-phosphate, ZDDP). The interaction between NDs and MoDTC has been evaluated using reciprocal sliding tests at two different temperatures. The outcomes of the tribological experiments revealed that the interaction of NDs and MoDTC can enhance the friction and wear performance of steel pairs. However, this enhanced performance is shown to highly depend on other additives present in the lubricant mixture. Analysis of wear scars using High-Resolution Transmission Electron Microscopy (HRTEM), Atomic Force Microscopy (AFM) and Raman spectroscopy reveals that when NDs are fully entrapped into the formed tribofilm that contains the MoDTC-derived MoS₂ layer, the lowest friction coefficient can be achieved. Full article