Dithiocarbamate Research Articles

Synthesis of 1,3-thiazolidine-2-thiones using CS2 and epoxy amines

An efficient method for the synthesis of 5-(hydoxymethyl)-1,3-thiazolidine-2-thiones is developed via the reaction of carbon disulfide with N-alkyl(aryl) epoxy amines. The reaction proceeds via intramolecular epoxide ring opening with in situ prepared dithiocarbamic acid. The products were obtained in good to high yields.

Synthesis of bisnitroepoxides and their applications in the synthesis of bis(thiazolidine-2-thiones), bis(dithiocarbamates), bis(xanthates) and bis(thiazoles)

Novel bis(nitroepoxides) were prepared based on terephthaldehyde and isophthaladehyde and their reactions with diversities of nucleophiles such as primary and secondary amine-based dithiocarbamic acids, xanthates, and ammonia-based dithiocarbmamates were investigated for the synthesis of bis(thiazolidine-2-thiones), bis(dithiocarbamates), bis(xanthates) and bis(thiazoles), respectively. It provides simple access to complex molecules in one step in high to excellent yields.

Intra-amniotic delivery of tropomodulin 3 rescues cell apoptosis induced by miR-200b-3p upregulation via non-canonical nuclear factor kappa B pathways in ethylene thiourea induced anorectal malformations fetal rat

Ethylene thiourea (ETU), a metabolite of the fungicide ethylene bisdithiocarbamate (EBDC), has received great concern because of its harmful effects. ETU-induced anorectal malformations (ARMs) in rat models have been reported and widely used in the study of ARMs embryogenesis. Dysplasia of the lumbosacral spinal cord (LSSC), pelvic floor muscles (PFMs), and hindgut (HG) during intrauterine life affects postoperative defecation in patients with ARMs. However, the underlying toxic effects of ETU and pathological mechanisms in the three defecation-related tissues of fetuses with ARMs have not been reported. Thus, this study aimed to elucidate the molecular mechanisms involved in ARMs, with a focus on the dysregulation of miR-200b-3p and its downstream target tropomodulin 3 (TMOD3). The mRNA and protein levels of miR-200b-3p and TMOD3 in LSSC, PFMs, and HG of fetal rats with ARMs were evaluated by reverse transcription quantitative polymerase chain reaction and Western blotting (WB) on embryonic day 17 (E17). Further, a dual-luciferase reporter assay confirmed their targeting relationship. Gene silencing and overexpression of miR-200b-3p and TMOD3 were performed to verify their functions in HEK-293 T cells. Fetal rats with ARMs also received intra-amniotic microinjection of Ad-TMOD3 on E15, and key molecules in nuclear factor kappa (NF-κB) signaling and apoptosis were evaluated by WB on E21. Abnormally high levels of miR-200b-3p inhibited TMOD3 expression by binding with its 3′-untranslated region, leading to the activation of the non-canonical NF-κB signaling pathway, which is critical in the maldevelopment of LSSC, PFMs, and HG in ARMs rats. Furthermore, miR-200b-3p triggered apoptosis by directly targeting TMOD3. Notably, intra-amniotic Ad-TMOD3 microinjection revealed that the upregulation of TMOD3 expression mitigates the effects of miR-200b-3p on the activation of non-canonical NF-κB signaling and apoptosis in fetal rat model of ARMs. A novel miR-200b-3p/TMOD3/non-canonical NF-κB signaling axis triggered the massive apoptosis in LSSC, PFMs, and HG of ARMs, which was restored by the intra-amniotic injection of Ad-TMOD3 during embryogenesis. Our results indicate the potential of TMOD3 as a treatment target to restore defecation.

In-Situ Investigation of Surface Modifiers Dithiocarbamates on Au Electrodes for Electrochemical CO2 Reduction

Molecular functionalization of metal electrodes via self-assembled monolayers (SAMs) can introduce synthetically tunable properties to metal surfaces and has exhibited great potential in electrocatalysis. Alkanethiols are commonly used organic ligands because of their strong affinity to Au but they are prone to desorption at negative potentials. Alternatively, dithiocarbamates (DTC) show superior electrochemical stability. In this study, a series of DTCs, differing in hydrophobicity, size, and steric bulk, were synthesized to prepare SAM-functionalized Au electrodes. The properties of the resulting surfaces (e.g. wettability, surface coverage, and reductive stability) were investigated by analytical and electrochemical techniques. Particularly, in-situ approaches such as surface-enhanced infrared absorption spectroscopy (SEIRAS) are employed to characterize the molecularly modified interface. The novel catalyst platforms were explored for electrochemical CO2 reduction.

A 5,5’‐Thiobis(thiazol‐2‐amine)‐based dithiocarbamate polymer: Straightforward synthesis and application in PVC membrane modification to enhance cadmium and dye removal

AbstractA novel dithiocarbamate polymer (TTDP) derived from bis(2‐aminothiazole) sulfide was synthesized through a straightforward process. The synthesis involved the initial conversion of 2‐aminothiazole into its bis(sulfide), subsequent reaction with chloroacetyl chloride, and final copolymerization with disodium ethylene bisdithiocarbamate. TTDP boasts a high percentage of functional groups containing sulfur, nitrogen, and oxygen, contributing to its hydrophilicity, strong chelation capacity with metal cations, and compatibility with other polymers. Therefore, it was used as a strong candidate for making membranes in water media. According to this, TTDP was blended in ratios 1, 2, 5, and 10 wt% with polyvinyl chloride (PVC; 15 wt%), 2 wt% of polyethylene glycol 4000 in N,N‐dimethylacetamide as polymeric membranes for water‐based applications. The blended membranes were prepared using the casting and immersion precipitation method. The blended membrane showed high fluxes, up to 1052 L/m2 h for 2 wt% of TTDP (in comparison to the bare membrane's 459 L/m2h). Notably, they demonstrated an excellent protein solution flux of 222–269 L/m2 h at 3 bar with 96%–98% bovine serum albumin rejection. Furthermore, these membranes showed remarkable efficacy in removing cadmium ions (up to 98.96% for 5 and 10 wt% TTDP) and synthetic dye methyl orange (up to 84.03% for 2 wt% TTDP).

Genome sequencing, annotation and application of a strain of Microbacterium paraoxydans – A bacterium with arsenic bioremediation and plant growth promoting potential

A heavy metal hypertolerant plant growth-promoting bacterium was isolated from the arsenic-contaminated garden soil of Bhagobangola I block (Murshidabad district). Metagenomic classification identified the bacterial isolate as a member of the genus Microbacterium. Taxonomic assessment of the isolated strain revealed its maximum average nucleotide identity (89.99 %) with the Microbacterium paraoxydans strain DSM 15019. Prokaryotic genome annotation was performed by Prokka, DFAST and RAST. The entire genome consisted of 3365911 bases with 69.90 % GC content. Prokka detected 3216 coding sequences (1461 hypothetical sequences), 3283 genes, 10 miscellaneous RNAs, 3 rRNAs, 53 tRNAs and 1 tmRNA in the bacterial genome. DFAST detected 3257 coding sequences (1217 hypothetical sequences), 3 rRNA sequences and 53 tRNA sequences in the bacterial genome. RAST detected 3285 coding sequences and 49 RNAs in the genome. Only 25 % of these coding sequences could be categorised in the RAST subsystems. In RAST, 789 and 32 coding sequences were considered as non-hypothetical and hypothetical, respectively. The genes and gene clusters responsible for arsenic resistance (arsR, arsB, arsC, acr1, acr2 and acr3), tolerance to other heavy metals (copper, manganese, zinc, etc.) and plant growth promotion (auxin biosynthesis, siderophore-mediated iron acquisition, phosphate and polyphosphate metabolism, trehalose biosynthesis, etc.) were also identified in the Microbacterium paraoxydans genome. The bioremediation potential and plant growth-promoting nature of the bacterium were confirmed by silver diethyl dithio carbamate (SDDC) method and pot experiments, respectively. The aforementioned traits point towards potential of the bacterium as a bioremediation tool and biofertilizer for reducing arsenic toxicity and promoting plant growth.

Dithiocarbamate‐Based Solution Processing for Cation Disorder Engineering in AgBiS2 Solar Absorber Thin Films

AbstractCation disorders refer to the phenomenon where cations are randomly distributed in multi‐cation systems. These disorders have emerged as an effective strategy for tailoring material properties across diverse applications. Notably, engineering cation disorder in AgBiS2 has garnered attention, owing to its remarkable enhancement of light absorption coefficients, which are crucial for efficient solar energy conversion in ultrathin light absorber layers. In this study, a novel dithiocarbamate (DTC)‐based solution processing method designed to control cation disorder is presented in AgBiS2 thin films. Unlike conventional approaches that rely on heat treatment, the strategy is based on molecular coordination dynamics between DTC and metal cations. By adjusting the ratio of DTC to the metal cations, the formation of cation‐disordered AgBiS2 thin films is demonstrated. Notably, the order‐to‐disorder transition is solely dependent on the DTC‐metal coordination and independent of the annealing temperature. These disordered films exhibit a high light absorption coefficient (>5 × 105 cm−1), mirroring the characteristics of thermally‐treated cation‐disordered AgBiS2 nanocrystals reported previously. The disordered AgBiS2 thin‐film photodetector exhibited a higher photocurrent density and responsivity compared to its ordered counterpart. The approach establishes a novel platform for cation disorder engineering, paving the way for advancements in cation‐disordered materials with diverse applications.

Solid-State Fluorescent Organic Polymers for Visual Detection and Elimination of Heavy Metals in Water.

Selective sensing and removal of toxic heavy metals from water are highly essential since their presence poses significant health and environmental hazards. Herein, we designed and synthesized a novel fluorescent nonconjugated organic polymer by strategically incorporating two key functional groups, namely, a dansyl fluorophore and dithiocarbamate (DTC). Different characterization techniques, including 1H nuclear magnetic resonance (NMR), scanning electron microscopy (SEM), X-ray diffraction (XRD), energy-dispersive X-ray analysis (EDAX), Fourier transform infrared (FTIR), and fluorescence spectroscopy, were performed to understand its structure and material properties. The quantum yield of 4.72% and its solid-state fluorescence indicate that it has potential for various applications in several technological and scientific domains. In this study, we investigated a specific application involving the detection and elimination of heavy metals from water. Interestingly, the presence of dansyl and DTC moieties demonstrated remarkable selectivity toward Cu2+, Co2+, Ni2+, Fe3+, and Fe2+ sensing, displaying distinct color changes specific to each metal. Cu2+ resulted in a yellow color, Co2+ showed a green color, Ni2+ displayed a pale yellowish-green color, and Fe2+/Fe3+ exhibited a brown color. The LOD (limit of detection) for each metal was obtained in the nanomolar range by using a fluorescence spectrometer and the micromolar range from UV-visible spectra: 13.27 nM and 0.518 μM for Cu2+, 8.27 nM and 0.581 μM for Co2+, 14.36 nM and 0.140 μM for Ni2+, 14.95 nM and 0.174 μM for Fe2+, and 15.54 nM and 0.33 μM for Fe3+. Moreover, the DTC functionality on its backbone facilitates effective interaction with the aforementioned heavy metals, subsequently removing them from water (except Fe2+ and Fe3+), validating its dual functionality as both an indicator and a purifier for heavy metals in water. The polymer exhibited a maximum adsorption capacity of 192.30 mg/g for Cu2+, 159.74 mg/g for Co2+, and 181.81 mg/g for Ni2+. Furthermore, this approach exhibits versatility in crafting fluorescent polymers with adjustable attributes that are suitable for a wide range of applications.

Development of a novel HPLC-CDCL method utilizing nitrogen-doped carbon dots for sensitive and selective detection of dithiocarbamate pesticides in tea

In this study, S-methyl derivatives of dithiocarbamates (DTCs) were shown to significantly enhance chemiluminescence (CL) between Ce(IV) and efficient and environmentally friendly nitrogen-doped carbon dots (NCDs). Based on the elucidation of the CL mechanisms, an innovative approach involving high-performance liquid chromatography coupled with N-CDs and CL detection (HPLC-CDCL) was proposed. The developed method was successfully applied to the highly sensitive detection of three DTC fungicides (dimethyl dithiocarbamate, ethylene bisdithiocarbamate, and propylene bisdithiocarbamate) in tea. The recovery of the established method ranged 70.51–116.45%, with relative standard deviations (RSD) of <9.40%. The limit of detection (S/N = 3) was as low as 0.19 μg/L (as CS2), which is superior to the previous methods and comparable to UPLC-tandem mass spectrometry (MS/MS). Moreover, the proposed approach does not require solid-phase extraction and offers excellent selectivity. This study proposes a novel method for the detection of DTCs in the food safety and environmental fields.

Preparation of a New Heavy Metal Chelating Agent and Its Removal of Copper Ions in Wastewater

In this study, a new type of dithiocarbamate (DTCs) heavy metal chelating agent MF-DTC was prepared by carbon disulfide modified melamine formaldehyde resin prepolymer, and the structure of the chelating agent and chelating products was characterized by infrared, ultraviolet, elemental analysis, thermogravimetry, scanning electron microscopy and other means: the process of chelating agent Cu was studied, and the results showed that MF-DTC chelating agent had a higher adsorption capacity, and compared with the traditional chelating agent SDD and Na2S, it had higher chelating capacity under acidic conditions, it can be directly used to treat heavy metals in acidic wastewater. Moreover, the environmental stability of heavy metals after chelation is high. Heavy metals are not easy to be leached again after treatment.

Solidification and Release Characteristics of Heavy Metals in Gypsum from Coal-Fired Power Plants

Heavy metals in flue gas desulfurization (FGD) gypsum from coal-fired power plants are at risk of releaching during the processes of stockpiling and resource utilization. In this study, the effects of organosulfur chelators dithiocarbamate (DTC) and trisodium trithiocyanate-15 (TMT-15) on the solidification characteristics of heavy metals in desulphurized gypsum under different mass fractions, pH values, water contents and reaction times were investigated. The chemical composition and morphology were analyzed by inductively coupled plasma atomic emission spectrometer (ICP-AES) and scanning electron microscope (SEM). The experiments showed that both DTC and TMT-15 were effective at stabilizing the heavy metals in the FGD gypsum, with more than a 50% curing effect for all the heavy metals except Pb. DTC showed a better stabilization for Pb, Hg, Cu, Zn, and Cr, and TMT-15 showed a better curing effect for Cd. The solidified gypsum had good heavy metal stability in low-water-content environments. Increasing the mass fraction, reaction time, and pH decreased the heavy metal leaching, and the mass fraction had the greatest effect on the total heavy metal leaching concentration, followed by the reaction time and pH value.

Synthesis and antitumor activity of gold(I) N-heterocyclic carbene with dithiocarbamate and alkynyl complexes

A series of new type gold(I) N-heterocyclic carbene (NHC) complexes bearing a paeonol ligand in the side chain of NHC and bearing dithiocarbamate or alkynyl groups as a second ligand have been synthesized and structurally characterized by spectroscopic methods. The structure of Pa-NHC-Au-Cl has been established by X-ray crystallography. Their antitumor activities in vitro were investigated by CCK8 assay against two tumor cell lines (A549 and Hela). The gold(I) NHC with dithiocarbamate (DTC) complexes showed good to excellent antiproliferative activity and strongly inhibited the selenoenzyme thioredoxin reductase (TrxR).

Biomonitoring Equivalents for ethylene thiourea

Ethylene thiourea, or ETU, is used in the rubber industry and is a degradation product and impurity in some fungicides. The general public may be exposed to low concentrations of residues of ETU in a variety of ways, including food treated with ethylene bis-dithiocarbamate (EBDC) fungicides or migration from rubber products. Biomonitoring of ETU in urine is useful for an assessment of integrated exposures to ETU across different sources and routes of exposure. In this evaluation, we review available health-based risk assessments and toxicological reference values (TRVs) for ETU and derive Biomonitoring Equivalent (BE) values for interpretation of population biomonitoring data. BEs were derived based on existing TRVs derived by Health Canada, yielding a BE of 27 μg of total ETU/L in urine associated with the Acceptable Daily Intake (ADI) and 6.7 μg/L associated with a 1e-6 cancer risk. These BEs are based on an analytical method that involves a digestion step to liberate conjugated ETU, thus producing ‘total’ ETU in urine. The BE values derived in this manuscript can serve as a guide to help public health officials and regulators interpret population based ETU biomonitoring data in a public health risk context.

Catalyst/Metal/Solvent-Free Markovnikov Hydrothiolation of Unactivated Alkenes with Dithiocarbamic Acids.

Catalyst-free Markovnikov-selective hydrothiolation of unactivated alkenes still remains a great challenge. Herein, we develop a catalyst/metal/solvent-free methodology for the Markovnikov hydrothiolation of unactivated alkenes with in situ prepared dithiocarbamic acids, providing a wide array of alkyl dithiocarbamates. A variety of terminal, internal, cyclic, and acyclic unactivated alkenes were applied successfully in this protocol. This three-component thiol-ene reaction can be considered as a new family of click reactions.

Apoptosis and Paraptosis Induced by Disulfiram-Loaded Ca2+/Cu2+ Dual-Ions Nano Trap for Breast Cancer Treatment.

Regarded as one of the hallmarks of tumorigenesis and tumor progression, the evasion of apoptotic cell death would also account for treatment resistance or failure during cancer therapy. In this study, a Ca2+/Cu2+ dual-ion "nano trap" to effectively avoid cell apoptosis evasion by synchronously inducing paraptosis together with apoptosis was successfully designed and fabricated for breast cancer treatment. In brief, disulfiram (DSF)-loaded amorphous calcium carbonate nanoparticles (NPs) were fabricated via a gas diffusion method. Further on, the Cu2+-tannic acid metal phenolic network was embedded onto the NPs surface by self-assembling, followed by mDSPE-PEG/lipid capping to form the DSF-loaded Ca2+/Cu2+ dual-ions "nano trap". The as-prepared nanotrap would undergo acid-triggered biodegradation upon being endocytosed by tumor cells within the lysosome for Ca2+, Cu2+, and DSF releasing simultaneously. The released Ca2+ could cause mitochondrial calcium overload and lead to hydrogen peroxide (H2O2) overexpression. Meanwhile, Ca2+/reactive oxygen species-associated mitochondrial dysfunction would lead to paraptosis cell death. Most importantly, cell paraptosis could be further induced and strengthened by the toxic dithiocarbamate (DTC)-copper complexes formed by the Cu2+ combined with the DTC, the metabolic products of DSF. Additionally, the released Cu2+ will be reduced by intracellular glutathione to generate Cu+, which can catalyze the H2O2 to produce a toxic hydroxyl radical by a Cu+-mediated Fenton-like reaction for inducing cell apoptosis. Both in vitro cellular assays and in vivo antitumor evaluations confirmed the cancer therapeutic efficiency by the dual ion nano trap. This study can broaden the cognition scope of dual-ion-mediated paraptosis together with apoptosis via a multifunctional nanoplatform.

Stabilization of heavy metals in municipal solid waste incineration fly ash using organic chelating agents: Insight into risk assessment and function mechanism

Landfill treatment of municipal solid waste incineration fly ash (MSWI FA) after stabilization is the primary disposal technology. However, only few studies have assessed the stability of MSWI-FA-chelated products in different landfill scenarios. In this study, three commonly used dithiocarbamate (DTC)-based organic chelating agents (CAs) (TS-300, SDD, and PD) were selected to stabilize heavy metals (HMs) in MSWI FA. In addition, the leaching toxicity and environmental risks of the chelated products were assessed in different disposal environments. The results demonstrate that the HM leaching concentrations of the chelated products met the concentration limits of the sanitary landfill standard (GB16889–2008; mixed Landfill Scenario) for the three CAs at a low additive level (0.3 %). However, in the compartmentalized landfill scenario (the leaching agent was acid rain), the leaching of HMs from the chelated products met the standard when TS-300, SDD, and PD were added at 1.5 %, 6.0 %, and 8.0 %, respectively. Additionally, Pb, Zn, and Cd in the chelated products from the 1.5 %-TS-300 and 6.0 %-SDD groups met the leaching limits within the pH ranges 6–12 and 7–12, 6–12 and 7–12, and 8–12 and 8–12, respectively. This was primarily due of TS-300's multiple DTC groups forming stable chain-like macromolecular chelates with Pb. However, although the environmental risks associated with Pb, Zn, and Cd in the initial (0-d) chelated products of the 1.5 %-TS-300 and 6.0 %-SDD groups were minimized to low and negligible levels, there was a significant increase in the leaching of the three HMs after 28 d of storage. Therefore, with appropriate CA addition, although the leaching concentration of HMs in the chelated product may comply with the GB16889–2008 standards, it remains essential to consider its environmental risk, particularly in highly acidic or alkaline environments and during prolonged storage of the product.

Determination of ethylene-bis-dithiocarbamates and their degradation product ethylenethiourea in dry herbs by UHPLC-MS/MS.

Dithiocarbamates are a class of fungicides widely used in many countries. In this study, methods for determining the ethylene-bis-dithiocarbamate (EBDC) subclass, and their degradation product ethylenethiourea (ETU) were validated by UHPLC-MS/MS in different types of dry herbs, which can be used as food and/or medicinal purposes. Mancozeb was used in the validation of the EBDC method, where it was initially complexed with EDTA, derivatized, extracted with dimethyl sulfate in acetonitrile, magnesium sulfate (MgSO4), and sodium chloride (NaCl), and then purified using primary secondary amine (PSA). In the ETU method, L-cysteine hydrochloride monohydrate was added to the samples before extraction with acetonitrile, MgSO4, and NaCl, followed by purification with PSA. A pesticide-free blend of seven herbs (boldo, artichoke, "espinheira-santa", cat's claw, senna, chamomile, and cascara buckthorn) comprising distinct parts of the plants (leaves, bark, flowers and/or stems) was used as a control for method validation. Recoveries ranged from 79 to 113% for EBDC and 81 to 109% for ETU. Repeatability and intermediate precision were <20% for both methods. The limit of quantification was 0.03 mg kg-1 for EBDC (0.02 mg kg-1 of CS2) and ETU. The limit of detection (LOD) was set at 1/3 of the LOQ (0.01 mg kg-1 for both analytes). In total, 103 samples of 33 different dry herbs were analyzed, of which 19.4% were positive for EBDC (≥LOD), but no ETU residues were found in any of the analyzed samples. Given the absence of registered dithiocarbamates for use in the investigated herbs in Brazil, the positive results suggest potential illegal pesticide use or cross-contamination, especially considering the low concentrations detected in most samples. Although exposure to EBDC through the consumption of medicinal herbs from positive samples did not indicate a health risk to consumers, these plants must be monitored to prevent illicit pesticide usage, particularly when the herbs are intended for therapeutic purposes.

Regioselective Markovnikov hydrothiolation of 1-aryl-1,3-butadienes with dithiocarbamic acid to allyl dithiocarbamates.

A metal, ligand and solvent-free three component reaction of 1-aryl-1,3-butadienes, CS2 and amine has been developed. In this process, readily available CS2 and secondary amines were used for C-N and C-S bonds giving allyl dithiocarbamates with notable Markovnikov selectivity, mild reaction conditions, simple operation and compatibility with various functional groups (37 examples). This is first case of dithiocarbamic acid addition to an unsymmetrical 1,3-diene system.

Facile synthesis of tetrahydroquinoline containing dithiocarbamate derivatives via one-pot sequential multicomponent reaction.

An efficient sequential multi-component method for the synthesis of tetrahydroquinoline containing dithiocarbamates has been developed. This reaction involved a boronic acid-catalysed reduction of quinolines to tertrahydroquinolines, followed by nucleophilic addition reaction with carbon disulphide to form dithiocarbamic acids and subsequent S-arylation via external base-free Chan-Evans-Lam coupling in a one-pot operation. The methodology is compatible with a wide variety of functional groups and also useful in the late-stage functionalization of pharmaceuticals. The dual role of the boronic acid as a catalyst (in the reduction of quinolines) and as a reagent (in the S-arylation) has been demonstrated for the first time herein.

Ts2O mediated deoxygenative C2-dithiocarbamation of quinoline N-oxides with CS2 and amines.

A general, efficient and practical protocol for Ts2O promoted deoxygenative dithiocarbamation of quinoline N-oxides with in situ generated dithiocarbamic acids from CS2 and amines is reported. The reaction proceeded well under transition-metal free conditions to obtain a variety of novel quinoline-dithiocarbamate compounds with wide functional group tolerance and good to high yields.