2-Cyanoethyl dimethyldithiocarbamate, a new contact allergen found in accelerator-free nitrile gloves.

BACKGROUND: Allergic contact dermatitis (ACD) from rubber glove usage is usually caused by rubber additives such as the accelerators. However, in analyses of the suspected gloves, ordinary rubber allergens are not always found. Accelerator-free rubber gloves are available, but some patients with accelerator allergy do not tolerate them and might also be patch test positive to them. OBJECTIVES: To identify and chemically characterize a new allergen, 2-cyanoethyl dimethyldithiocarbamate (CEDMC), in rubber gloves. We describe two patient cases: patient 1 that led us to the identification of CEDMC and patient 2 with occupational ACD caused by CEDMC. METHODS: The patients were examined with patch testing including baseline and rubber series, and their own rubber gloves. High-performance liquid chromatography (HPLC) was used for chemical analysis of rubber gloves. The allergen was synthesized and identified by nuclear magnetic resonance, mass spectrometry and infrared spectrometry, and tested on patient 2. RESULTS: CEDMC was identified by HPLC in a nitrile glove associated with hand eczema in patient 1. Patient 2 whose nitrile gloves contained CEDMC was patch test positive to CEDMC. CONCLUSIONS: CEDMC is a new contact allergen in nitrile gloves and probably forms during vulcanization from residual monomer acrylonitrile and rubber additives.

Toxicity and Environmental Risk Assessment of Polycarbamate and Its Main Components to Marine Algae and Crustaceans.

Polycarbamate is commonly used as an antifoulant coating on fishing nets in Japan. Although its toxicity to freshwater organisms has been reported, its toxicity to marine organisms is currently unknown. We conducted algal growth inhibition and crustacean immobilization tests to assess the effects of polycarbamate on marine organisms. We also evaluated the acute toxicity of the main components of polycarbamate, namely, dimethyldithiocarbamate and ethylenebisdithiocarbamate, to algae, which are the most sensitive tested organisms to polycarbamate. The toxicities of dimethyldithiocarbamate and ethylenebisdithiocarbamate partially explain that of polycarbamate. To assess the primary risk, we derived the predicted no-effect concentration (PNEC) for polycarbamate in a probabilistic manner using species sensitivity distributions. The 72 h no observed effect concentration (NOEC) of polycarbamate to the alga Skeletonema marinoi-dohrnii complex was 0.45 µg/L. The toxicity of dimethyldithiocarbamate may have contributed up to 72% of the toxicity observed for polycarbamate. The fifth percentile of hazardous concentration (HC5) derived from the acute toxicity values was 0.48 µg/L. Comparison of previously reported environmental polycarbamate concentrations in Hiroshima Bay, Japan, to the PNEC estimated using the minimum NOEC and HC5 suggest that polycarbamate currently poses a high ecological risk. Therefore, reducing the risk by restricting polycarbamate use is necessary.

Factors affecting the durability of dimethyl dithiocarbamate-stabilized air pollution control (APC) residues derived from municipal solid waste incineration.

Sodium dimethyl dithiocarbamate (SDD) is widely used for stabilizing heavy metals to minimize pollution from air pollution control (APC) residues derived from municipal solid waste incineration. However, the effect of environmental conditions on heavy metal leaching from SDD-stabilized APC residues remains unknown. Therefore, this study aimed to evaluate the durability of SDD-stabilized APC residues and determine the relationship between heavy metal leaching and environmental factors, including pH, temperature, and oxygen. The results revealed that accelerated SDD decomposition and the decline in durability of SDD-stabilized APC residues were caused by acidic and aerated conditions and temperatures above 40 °C. A decrease in pH from 12.25 to 4.69 increased the Cd and Pb concentrations in SDD-stabilized APC residue leachate from below detection (0.002 mg/L) to 1.32 mg/L and 0.04 mg/L to 3.79 mg/L, respectively. Heating at 100 °C for 2 d increased the Cd and Pb concentrations from below detection (0.002 mg/L and 0.01 mg/L) to 2.96 mg/L and 0.47 mg/L, respectively. Aeration for 5 d increased the Cd and Pb concentrations from below detection to 0.09 mg/L and 0.49 mg/L, respectively. The decline in durability was attributed to acid hydrolysis, thermal decomposition, and oxidative damage of SDD, resulting in breakage of the chelated sulfur-metal bond, which was confirmed by the decrease in the oxidizable fraction of heavy metals and the SDD content. This study improves the understanding of the factors contributing to the decline in durability of heavy metals in SDD-stabilized APC residues, which is important for ensuring the long-term stabilization and environmental safety of these residues.

Evaluation of the stability of heavy metal-containing sediments obtained in the wastewater treatment processes with the use of various precipitating agents.

The article presents the results of research on the leachability of selected heavy metals (cadmium, nickel, chromium, cobalt, lead, and copper) from solid waste obtained in laboratory processes involved in the industrial treatment of wastewater generated in metal surface treatment plants. The test sludges were precipitated using sodium hydroxide solution, calcium hydroxide suspension, 45% solution sodium trithiocarbonate (Na2CS3), 15% solution trimercapto-s-triazine, sodium salt (TMT), and 40% solution sodium dimethyldithiocarbamate (DMDTC). The precipitates were treated with artificial acid rain and artificial salt water. After 1, 7, 14, and 21 days of leaching, the concentration of Cd, Co, Cr, Cu, Pb, and Ni in the leachate was determined. Artificial acid rain leached Ni and Cd to a maximum concentration of 724 mg/L and 1821 mg/L, respectively, from the sludge obtained after the application of Na2CS3, while artificial salt water leached Ni in the maximum amount of 466 mg/L and Cd-max. 1320 mg/L. When Ca(OH)2/NaOH was used, the leaching of Cr reached a similar level for both leaching agents, i.e., the maximum for artificial acid rain was 72.2 mg/L and the maximum for artificial salt water 71.8 mg/L. The use of Na2CS3 or Ca(OH)2/NaOH poses a risk of some heavy metals entering the environment, which may have a negative impact on living organisms, whereas the sludges obtained with the use of DMDTC and TMT as precipitants were the most stable under the experimental conditions and did not pose a potential environmental hazard.

N,N-Dimethyldithiocarbamate Elicits Pneumococcal Hypersensitivity to Copper and Macrophage-Mediated Clearance.

Streptococcus pneumoniae is a Gram-positive, encapsulated bacterium that is a significant cause of disease burden in pediatric and elderly populations. The rise in unencapsulated disease-causing strains and antimicrobial resistance in S. pneumoniae has increased the need for developing new antimicrobial strategies. Recent work by our laboratory has identified N,N-dimethyldithiocarbamate (DMDC) as a copper-dependent antimicrobial against bacterial, fungal, and parasitic pathogens. As a bactericidal antibiotic against S. pneumoniae, DMDC's ability to work as a copper-dependent antibiotic and its ability to work in vivo warranted further investigation. Here, our group studied the mechanisms of action of DMDC under various medium and excess-metal conditions and investigated DMDC's interactions with the innate immune system in vitro and in vivo. Of note, we found that DMDC plus copper significantly increased the internal copper concentration, hydrogen peroxide stress, nitric oxide stress, and the in vitro macrophage killing efficiency and decreased capsule. Furthermore, we found that in vivo DMDC treatment increased the quantity of innate immune cells in the lung during infection. Taken together, this study provides mechanistic insights regarding DMDC's activity as an antibiotic at the host-pathogen interface.

Synthesis of Water-Soluble Copolymers of N-vinylpyrrolidone with N-vinyldithiocarbamate as Multidentate Polymeric Chelation Systems and Their Complexes with Indium and Gallium.

Dithiocarbamate (DTC) derivatives of N-vinylpyrrolidone-N-vinylamine (VP-VA) copolymers were synthesized via reaction between the copolymers and carbon disulfide in alkaline medium; molecular masses of the products were 12 and 29 kDa; the VP:VDTC ratios were 94:6 and 83:17 mol.%. Complexation between the obtained DTC derivatives and metal ions (indium and gallium) was investigated. It was demonstrated that metal-DTC ligand complexes with 1:3 ratio between components were formed. Gallium metal-polymer complexes (MPC) were unstable in solution. Individual indium MPC were isolated and characterized by spectral and chromatographic methods. Unlike similar gallium MPC, they appeared to be stable in histidine challenge reaction.

Ziram and sodium N,N-dimethyldithiocarbamate inhibit ubiquitin activation through intracellular metal transport and increased oxidative stress in HEK293 cells.

Ubiquitin activating enzyme E1 plays a pivotal role in ubiquitin based protein signaling through regulating the initiating step of the cascade. Previous studies demonstrated that E1 is inhibited by covalent modification of reactive cysteines contained within the ubiquitin-binding groove and by conditions that increase oxidative stress and deplete cellular antioxidants. In this study, we determined the relative contribution of covalent adduction and oxidative stress to E1 inhibition produced by ziram and sodium N,N-dimethyldithiocarbamate (DMDC) in HEK293 cells. Although no dithiocarbamate-derived E1 adducts were identified on E1 using shotgun LC/MS/MS for either ziram or DMDC, both dithiocarbamates significantly decreased E1 activity, with ziram demonstrating greater potency. Ziram increased intracellular levels of zinc and copper, DMDC increased intracellular levels of only copper, and both dithiocarbamates enhanced oxidative injury evidenced by elevated levels of protein carbonyls and expression of heme oxygenase-1. To assess the contribution of intracellular copper transport to E1 inhibition, coincubations were performed with the copper chelator triethylenetetramine hydrochloride (TET). TET significantly protected E1 activity for both of the dithiocarbamates and decreased the associated oxidative injury in HEK293 cells as well as prevented dithiocarbamate-mediated lipid peroxidation assayed using an ethyl aracidonate micelle system. Because TET did not completely ameliorate intracellular transport of copper or zinc for ziram, TET apparently maintained E1 activity through its ability to diminish dithiocarbamate-mediated oxidative stress. Experiments to determine the relative contribution of elevated intracellular zinc and copper were performed using a metal free incubation system and showed that increases in either metal were sufficient to inhibit E1. To evaluate the utility of the HEK293 in vitro system for screening environmental agents, a series of additional pesticides and metals was assayed, and eight agents that produced a significant decrease and five that produced a significant increase in activated E1 were identified. These studies suggest that E1 is a sensitive redox sensor that can be modulated by exposure to environmental agents and can regulate downstream cellular processes.

Analysis of silver nanoparticles in antimicrobial products using surface-enhanced Raman spectroscopy (SERS).

Silver nanoparticles (AgNPs) are the most commonly used nanoparticles in consumer products. Concerns over human exposure to and risk from these particles have resulted in increased interest in novel strategies to detect AgNPs. This study investigated the feasibility of surface-enhanced Raman spectroscopy (SERS) as a method for the detection and quantification of AgNPs in antimicrobial products. By using ferbam (ferric dimethyl-dithiocarbamate) as an indicator molecule that binds strongly onto the nanoparticles, AgNPs detection and discrimination were achieved based on the signature SERS response of AgNPs-ferbam complexes. SERS response with ferbam was distinct for silver ions, silver chloride, silver bulk particles, and AgNPs. Two types of AgNPs with different coatings, citrate and polyvinylpirrolidone (PVP), both showed strong interactions with ferbam and induced strong SERS signals. SERS was effectively applicable for detecting Ag particles ranging from 20 to 200 nm, with the highest signal intensity in the 60-100 nm range. A linear relationship (R(2) = 0.9804) between Raman intensity and citrate-AgNPs concentrations (60 nm; 0-20 mg/L) indicates the potential for particle quantification. We also evaluated SERS detection of AgNPs in four commercially available antimicrobial products. Combined with ICP-MS and TEM data, the results indicated that the SERS response is primarily dependent on size, but also affected by AgNPs concentration. The findings demonstrate that SERS is a promising analytical platform for studying environmentally relevant levels of AgNPs in consumer products and related matrices.

Elucidating the removal mechanism of N,N-dimethyldithiocarbamate in an anaerobic-anoxic-oxic activated sludge system.

N,N-Dimethyldithiocarbamate (DMDTC) is a typical precursor of N-nitrosodimethylamine (NDMA). Based on separate hydrolysis, sorption and biodegradation studies of DMDTC, a laboratory-scale anaerobic-anoxic-oxic (AAO) system was established to investigate the removal mechanism of DMDTC in this nutrient removal biological treatment system. DMDTC hydrolyzed easily in water solution under either acidic conditions or strong alkaline conditions, and dimethylamine (DMA) was the main hydrolysate. Under anaerobic, anoxic or oxic conditions, DMDTC was biodegraded and completely mineralized. Furthermore, DMA was the main intermediate in DMDTC biodegradation. In the AAO system, the optimal conditions for both nutrient and DMDTC removal were hydraulic retention time 8 hr, sludge retention time 20 day, mixed-liquor return ratio 3:1 and sludge return ratio 1:1. Under these conditions, the removal efficiency of DMDTC reached 99.5%; the removal efficiencies of chemical organic demand, ammonium nitrogen, total nitrogen and total phosphorus were 90%, 98%, 81% and 93%, respectively. Biodegradation is the dominant mechanism for DMDTC removal in the AAO system, which was elucidated as consisting of two steps: first, DMDTC is transformed to DMA in the anaerobic and anoxic units, and then DMA is mineralized to CO2 and NH3 in the anoxic and oxic units. The mineralization of DMDTC in the biological treatment system can effectively avoid the formation of NDMA during subsequent disinfection processes.

Exposure to dithiocarbamate fungicide Ziram results in hepatic and renal toxicity in Long Evan rats.

Ziram is a dimethyldithiocarbamate fungicide that is complexed to the metal zinc. The focus of this study is to examine the effects of dimethyldithiocarbamate exposure on metal homeostasis, glutathione levels, and the physiological parameters of the kidney and liver in Long-Evan rats. Our results indicate significant accumulation of copper or zinc, and changes in total GSH or GSH/GSSG ratio in the liver and kidneys of animals treated with Ziram only. Histopathological examination of liver and kidney sections indicate the presence of infiltrates in the liver of animals treated with Ziram only, whereas protein aggregates, sloughing of cells and increased KIM-1 positive cells, an indicator of tubule deterioration, are seen in the kidneys of animals treated with Ziram and sodium-dimethyldithiocarbamate, the salt form of the dimethyldithiocarbmate backbone. These findings suggest that the overall toxicological effect of Ziram is mediated by an intrinsic property rather than to dimethyldithiocarbamate backbone or metal moiety.

Gold nanorods as surface enhanced Raman spectroscopy substrates for sensitive and selective detection of ultra-low levels of dithiocarbamate pesticides.

We report the use of gold nanorods as solution-based SERS substrates for the detection of ultralow-levels of three different dithiocarbamate fungicides: thiram, ferbam and ziram. Gold nanorods are attractive to use as SERS substrates due to the ability to tune the surface plasmon resonance of the nanoparticles to the laser excitation wavelength of the Raman spectrometer equipped with a 785 nm diode laser. The gold nanorods are synthesized using a seed-mediated growth method and characterized using UV-Visible spectroscopy, zeta potential, and TEM. The gold nanorods have an aspect ratio of 2.19 ± 0.21 and have an average length of 37.81 ± 4.83 nm. SERS spectra are acquired at different concentrations of each fungicide and calibration curves are obtained by monitoring the intensity of the band arising from the ν(C-N) stretching mode coupled to the symmetric δ(CH(3)) motion. The limits of detection and limits of quantitation are obtained for each fungicide. The limits of detection are 11.00 ± 0.95 nM, 8.00 ± 1.01 nM, and 4.20 ± 1.22 nM for thiram, ferbam, and ziram respectively. The limits of quantitation are 34.43 ± 0.95 nM, 25.61 ± 1.01 nM, and 12.94 ± 1.22 nM for thiram, ferbam, and ziram respectively. It can be seen that the three different dithiocarbamates can be detected in the low nM range based on the limits of detection that are achieved.

Chemical treatment of chelated metal finishing wastes.

This study evaluated two chemical approaches for treatment of commingled cadmium-cyanide (Cd-CN) and zinc-nickel (Zn-Ni) wastewaters. The first approach, which involved application of sodium hypochlorite (NaOCl), focused on elimination of chelating substances. The second approach evaluated the use of sodium dimethyldithiocarbamate (DMDTC) to specifically target and precipitate regulated heavy metals. Results demonstrated that by maintaining a pH of 10.0 and an oxidation-reduction potential (ORP) value of +600 mV, NaOCl treatment was effective in eliminating all chelating substances. Cadmium, chromium, nickel, and zinc solution concentrations were reduced from 0.27, 4.44, 0.06, and 0.10 ppm to 0.16, 0.17, 0.03, and 0.06 ppm, respectively. Similarly, a 1% DMDTC solution reduced these same metal concentrations in commingled wastewater to 0.009, 1.142, 0.036, and 0.320 ppm. Increasing the DMDTC concentration to 2% improved the removal of all regulated heavy metals except zinc, the removal of which at high pH values is limited by its amphotericity.

Electrical conductivity and thermodynamic studies on Sodium Dimethyldithiocarbamate in non aqueous solvents Dimethylformamide (DMF), at different temperatures.

This paper threw some light on the behavior of Sodium N,N-Dimethyldithiocarbamate as an electrolyte. The effect of solvents on the conductance of this salt would be discussed via measurements of Λo, ao and KA, since it can be assumed that the different solvents have a little chance to impose great variations on the solvation processes. The conductance method was chosen as a tool to illustrate the electrolyte-solvent interactions. Fuoss-Onsager equation would be tested using Sodium Dimethyldithiocarbamate in presence of dimethylformamide solvent at different temperatures. The conductance of dilute solutions of Sodium N,N-Dimethyldithiocarbamate is measured in Dimethylformamide, at different temperatures (25, 30, 35 and 40 °C). Accurate values of Λo were obtained by applying the (Fuoss-Kraus-Shedlovsky) equation. Finally, the (Fuoss-Onsager) equation was solved to give the correct values of the constants Λo, J, KA and a° (the closest distance of approach) for Sodium N,N-Dimethyldithiocarbamate salt in Dimethylformamide solvent. Λo and a° (solvation) increase with increasing temperatures. Thermodynamic parameters (∆G°, ∆H°, ∆S° and ∆Es) of Sodium N,N-Dimethyldithiocarbamate in Dimethylformamide were calculated from conductance measurements, the activation energy (∆Es), the enthalpy change (heat of association) (∆H°) and the entropy change (∆S°) are positive, however The free energy change (∆G°) values was negative for Sodium N,N-Dimethyl dithiocarbamate in DMF systems studied with increasing the temperature.

Sensitive detection of ferbam by coupling solid phase microextraction with surface enhanced Raman spectroscopy based on Au nano-glass capillary.

In this study, we developed an innovative approach that combines solid phase microextraction (SPME) with surface-enhanced Raman spectroscopy (SERS) to detect pesticide ferbam rapidly. An Au nano-glass capillary was fabricated by coating template-freely synthesized three-dimensional network Au nanostructures (3D-NW AuNSs) on the roughened surface of glass capillary and used for SPME and SERS respectively. Significant Raman signals were obtained by the SPME-SERS method, followed by detection of ferbam in water and orange juice samples with only 1 min SPME process. Results showed that Au nano-glass capillaries could achieve the detection of ferbam with limit of detection of 0.05 µg/L, and coefficient of determination (R2) of 0.9913. The recovery of predicted results was in the range of 88.46-103.29% and the relative standard deviation (RSD) was 3.5-8.2%. This study demonstrated potential capability of the SPME-SERS method for rapid (within 1 min) and sensitive detection of organic compounds in complex matrices. The SERS-active Au nano-glass capillary is easy to carry and operate, and is expected to play a role in the detection of trace pollutants.

PCDD/Fs and heavy metals in the vicinity of landfill used for MSWI fly ash disposal: Pollutant distribution and environmental impact assessment.

This study focused on the syngenetic control of polychlorinated-ρ-dibenzodioxins and dibenzofurans (PCDD/Fs) and heavy metals by field stabilization/solidification (S/S) treatment for municipal solid waste incineration fly ash (MSWIFA) and multi-step leachate treatment. Modified European Community Bureau of Reference (BCR) speciation analysis and risk assessment code (RAC) revealed the medium environment risk of Cd and Mn, indicating the necessity of S/S treatment for MSWIFA. S/S treatment significantly declined the mass/toxic concentrations of PCDD/Fs (i.e., from 7.21 to 4.25 µg/kg; from 0.32 to 0.20 µg I-TEQ/kg) and heavy metals in MSWIFA due to chemical fixation and dilution effect. The S/S mechanism of sodium dimethyldithiocarbamate (SDD) and cement was decreasing heavy metals in the mild acid-soluble fraction to reduce their mobility and bioavailability. Oxidation treatment of leachate reduced the PCDD/F concentration from 49.10 to 28.71 pg/L (i.e., from 1.60 to 0.98 pg I-TEQ/L) by suspension absorption or NaClO oxidation decomposition, whereas a so-called "memory effect" phenomena in the subsequent procedures (adsorption, press filtration, flocculating settling, slurry separation, and carbon filtration) increased it back to 38.60 pg/L (1.66 pg I-TEQ/L). Moreover, the multi-step leachate treatment also effectively reduced the concentrations of heavy metals to 1-4 orders of magnitude lower than the national emission standards. Furthermore, the PCDD/Fs and heavy metals in other multiple media (soil, landfill leachate, groundwater, and river water) and their spatial distribution characteristics site were also investigated. No evidence showed any influence of the landfill on the surrounding liquid media. The slightly higher concentration of PCDD/Fs in the soil samples was ascribed to other waste management processes (transportation and unloading) or other local source (hazardous incineration plant). Therefore, proper management of landfills and leachate has a negligible effect on the surrounding environment.

Au@Ag-TGANPs based SERS for facile screening of thiabendazole and ferbam in liquid milk.

Surface-enhanced Raman spectroscopy based on thioglycolic acid (TGA) functionalized silver-coated gold nanoparticles (Au@Ag-TGANPs) was developed for the facile screening of thiabendazole (TBZ) and ferbam (0.025-10 ppm) in liquid milk for the first time. Results showed that silver-coated gold nanoparticles (Au@AgNPs) with a core size of 32 nm and a shell thickness of 5 nm was successfully modified with 3 nm TGA. The sensitive Au@Ag-TGANPs could enhance TBZ and ferbam signals by factors of 6.4 × 104 and 9.8 × 104, respectively, and achieved the detection of TBZ and ferbam with limits of detection of 0.12 and 0.003 ppm, R2 of 0.988 and 0.9821, percent recoveries of 88-103% and of 87.2-103.5%, and relative standard deviations of 4.1-9.2% and 3.5-8.3%, respectively. The current simple and green method could thus be used to detect other unsafe chemicals in future studies.

Synthesis of bimetallic core-shelled nanoparticles modified by 2-mercaptoethanol as SERS substrates for detecting ferbam and thiabendazole in apple puree.

Modification of surface-enhanced Raman spectroscopy (SERS) substrates with thiol ligands is an emerging approach in enhancing the stability and sensitivity of metal substrates due to their good affinity with metals such as Au, Ag, and Cu. Thus, in the current study, 2-mercaptoethanol was used to modify the surface of silver-coated gold nanoparticles to develop a novel SERS substrate for the rapid assessment of fungicide residues in fruit samples. Results showed that the substrate could achieve the detection of ferbam and thiabendazole residues in apple puree with limits of detection of approximately 0.0042 and 0.0064 ppm, high coefficients of determination of 0.9946 and 0.9968, good recoveries ranging from 80 to 105 and 81 to 107% and relative standard deviations of 3.5-7.5 and 3.8-7.9 %, respectively. Therefore, the substrate developed could potentially be utilised to assess other toxic agrochemicals in future.

Demonstration of N,N-Dimethyldithiocarbamate as a Copper-Dependent Antibiotic against Multiple Upper Respiratory Tract Pathogens.

Transition metals are necessary cofactors and structural elements in living systems. Exposure to high concentrations of biologically important transition metals, such as zinc and copper, results in cell toxicity. At the infection site, the immune system deploys metal sorbent proteins (e.g., lactoferrin and calprotectin) to starve pathogens of necessary metals (such as iron), while phagocytes expose engulfed pathogens to high levels of other metals, such as copper and zinc. The opportunistic pathogen Streptococcus pneumoniae (the pneumococcus) encounters macrophages during initial and protracted infections. The pneumococcus employs a copper export pathway, which improves colonization and persistent infection of the nasopharynx and the upper respiratory tract. Because copper is tightly regulated in the host, we instead sought to leverage the localized power of nutritional immunity by identifying small molecules with copper-dependent toxicity (CDT) through a targeted screen of compounds for antibiotic efficacy. We chose to include dithiocarbamates, based on the copper synergy observed in other organisms with 1-(diethylthiocarbamoyldisulfanyl)-N,N-diethyl-methanethioamide (tetraethylthiuram disulfide, disulfiram). We observed CDT of some dithiocarbamates in S. pneumoniae. Only N,N-dimethyldithiocarbamate (DMDC) was consistently toxic across a range of concentrations with copper both in vitro and in vivo against the pneumococcus. We also observed various degrees of CDT in vitro using DMDC in Staphylococcus aureus, Coccidioides posadasii, and Schistosoma mansoni. Collectively, we demonstrate that the compound DMDC is a potent bactericidal compound against S. pneumoniae with antimicrobial efficacy against bacterial and fungal pathogens. IMPORTANCE With the rise of antibiotic resistance, approaches that add new antimicrobials to the current repertoire are vital. Here, we investigate putative and known copper ionophores in an attempt to intoxicate bacteria and use ionophore/copper synergy, and we ultimately find success with N,N-dimethyldithiocarbamate (DMDC). We show that DMDC has in vitro efficacy in a copper-dependent manner and kills pathogens across three different kingdoms, Streptococcus pneumoniae, Coccidioides posadasii, and Schistosoma mansoni, and in vivo efficacy against S. pneumoniae. As such, dithiocarbamates represent a new potential class of antimicrobials and thus warrant further mechanistic investigation.

Development of cellulose Nanofiber-based substrates for rapid detection of ferbam in kale by Surface-enhanced Raman spectroscopy.

This study developed a novel surface-enhanced Raman spectroscopy (SERS) method coupled with cellulose nanofiber (CNF)-based SERS wipers that were fabricated on quartz papers coated with a mixture of silver nanoparticle (AgNP) and gold nanostar (AuNS). A "drop-wipe-test" protocol was developed for rapid detection of pesticide residues in vegetables by SERS. Tremendously enhanced Raman scattering signals were obtained from the quartz/CNF/mixture (AgNP + AuNS) substrate, which were much higher than the paper/mixture (AgNP + AuNS) substrate. This method was used to detect ferbam on kale leaves within a few minutes and the detection limit was 50 µg/kg based on the PLS models (R2 = 0.89). The enhancement factor of the SERS substrate was calculated to be ~ 104 with satisfactory reproducibility. Satisfactory SERS performance could be achieved within 1-month storage period. These results demonstrate that this CNF-based SERS/wiper method is a practical approach for rapid detection of chemical contaminants in fresh produce.

Ecotoxicity assessment of sodium dimethyldithiocarbamate and its micro-sized metal chelates in Caenorhabditis elegans.

Sodium dimethyldithiocarbamate (SDDC) is a widely used heavy metal chelating agent in harmless treatment of wastewater and hazardous waste, but SDDC and its heavy metal chelates may leak into the environment and bring potential ecological risks. In this study, the model organism Caenorhabditis elegans was used to evaluate the toxic effect of SDDC and its heavy metal Cu, Pb chelates. Multiple endpoints were investigated by subacute exposure to SDDC (0.01-100 mg/L) and micro-sized Cu, Pb chelates of SDDC (1-100 mg/L). Our data indicated that the LC50 value of SDDC was 139.39 mg/L (95% Cl: 111.03, 174.75 mg/L). In addition, SDDC was found that concentration of 1 mg/L is a safe limit value for nematode C. elegans, and concentration above 1 mg/L caused adverse effects on the survival, growth, locomotion behaviors and reactive oxygen species (ROS) production of exposed nematodes. Furthermore, all tested SDDC-Cu and SDDC-Pb chelates had obviously lower toxic effect than untreated Cu, Pb metals. These two chelates also had a lower toxic effect than SDDC agent due to its more stable structure. Moreover, SDDC-Cu had a higher toxic effect than SDDC-Pb at the same concentration. Thus, our results suggest that SDDC as a kind of chelating agent applied in harmless treatment of heavy metals, the safe addition limit should not be exceeded.