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.

Analysis of Dithiocarbamate Fungicides in Vegetable Matrices Using HPLC-UV Followed by Atomic Absorption Spectrometry.

A simple method combining ion-pair methylation, high-performance liquid chromatography (HPLC) analysis with detection at 272 nm and atomic absorption spectrometry was developed in order to determine 10 dithiocarbamate fungicides (Dazomet, Metam-sodium, Ferbam, Ziram, Zineb, Maneb, Mancozeb, Metiram, Nabam and Propineb) and distinguish ethylenbisdithiocarbamates (EBDTCs) Zineb, Maneb and Mancozeb in diverse matrices. This method associates reverse phase analysis by HPLC analysis with detection at 272 nm, with atomic absorption spectrometry in order to distinguish, with the same extraction protocol, Maneb, Mancozeb and Zineb. The limits of detection (0.4, 0.8, 0.5, 1.25 and 1.97) and quantification (1.18, 2.5, 1.52, 4.2 and 6.52) calculated in injected nanogram, respectively, for Dazomet, Metam-Na, dimethyldithiocarbamates (DMDTCs), EBDTCs and propylenebisdithiocarbamates (PBDTCs) justify the sensitivity of the method used. The coefficients of determination R2 were 0.9985, 0.9978, 0.9949, 0.988 and 0.9794, respectively, for Dazomet, Metam-Na, DMDTCs, EBDTCs and PBDTCs, and the recovery from fortified apple and leek samples was above 90%. Results obtained with the atomic absorption method in comparison with spectrophotometric analysis focus on the importance of the atomic absorption as a complementary specific method for the distinction between different EBDTCs fungicides.

Real-time scattered light dark-field microscopic imaging of the dynamic degradation process of sodium dimethyldithiocarbamate.

Single nanoparticle analysis (SNA) technique with the aid of a dark-field microscopic imaging (iDFM) technique has attracted wide attention owing to its high sensitivity. Considering that the degradation of pesticides can bring about serious problems in food and the environment, and that the real-time monitoring of the dynamic degradation process of pesticides can help understand and define their degradation mechanisms, herein we real-time monitored the decomposition dynamics of sodium dimethyldithiocarbamate (NaDDC) under neutral and alkaline conditions by imaging single silver nanoparticles (AgNPs) under a dark-field microscope (DFM); the localized surface plasmon resonance (LSPR) scattering signals were measured at a single nanoparticle level. As a result, the chemical mechanism of the degradation of NaDDC under neutral and alkaline conditions was proposed, and the inhibition effects of metal ions including Zn(II) and Cu(II) were investigated in order to understand the decomposition process in different environments. It was found that Cu(II) forms the most stable complex with NaDDC with a stoichiometric ratio of 1 : 2, which greatly reduces the toxicity.

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.

Oxidation of dithiocarbamates to yield N-nitrosamines by water disinfection oxidants.

Two most commonly used dithiocarbamate (DTC) pesticides, dimethyldithiocarbamate (DMDTC) and diethyldithiocarbamate (DEDTC), were examined in this study to evaluate their potential to form nitrosamines when in contact with various water disinfection oxidants. Results show that DTCs can serve as nitrosamine precursors, by release of secondary amines through hydrolysis or through reactions with oxidants. The reactions of DTCs with monochloramine and ozone were found to be particularly problematic in the risk of generating nitrosamines, though all four tested oxidants, including free chlorine and chlorine dioxide, formed nitrosamines. NDEA yield from DEDTC was lower, by different degrees, than NDMA yield from DMDTC for all four oxidants, which was attributed to the steric hindrance associated with bulkier reaction intermediate that are more difficult to be further oxidized to form nitrosamine. The yield of nitrosamines increased with the oxidant dosage for both monochloramination and ozonation of DTCs. Results for nitrosamine formation from DTCs at varying pH were found to be consistent with the pH trend of nitrosamine formation from ozonation and monochloramination of secondary amines. Kinetic study results and identification and quantification of reaction products suggest that the DTCs were not significant direct precursors of nitrosamines during monochloramination or ozonation, but rather nitrosamines formed were primarily from reaction of oxidants with the amine which may be generated either through hydrolysis or through oxidation of DTCs.

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.

Highly cytotoxic substitutionally inert rhodium(III) tris(chelate) complexes: DNA binding modes and biological impact on human cancer cells.

The antiproliferative properties and cellular impact of novel substitutionally inert rhodium(III) complexes of the types [Rh{(CH3)2 NCS2}2(pp)]Cl 3-5 (pp=5,6-Me2phen, dpq, dppz) and OC-6-23-[Rh(2-S-py)2(pp)]Cl 6 and 7 (2-S-py=pyridine-2-thiolate; pp=dpq, dppz) have been investigated for the adherent human cancer cell lines MCF-7 and HT-29 and for non-adherent Jurkat cells. Whereas CD and viscosity measurements indicate that the polypyridyl ligands of 4 and 5 intercalate into CT DNA, this is not the case for the analogous pyridine-2-thiolate complexes 6 and 7. Complexes 3-7 all exhibit a high antiproliferative activity towards MCF-7 and HT-29 cells, with IC(50) values in the range 0.055-0.285 µM. As established by online monitoring with a cell-based sensor chip, the highly cytostatic complex 6 (IC(50)=0.059 and 0.078 µM) invokes an immediate concentration-dependent reduction of MCF-7 cell respiration and a time-delayed decrease in cellular impedance, which can be ascribed to the induction of cell death. Annexin V/PI assays demonstrated that 6 also has a pronounced antiproliferative activity towards Jurkat cells and that it invokes extensive apoptosis and high concentrations of reactive oxygen species in these leukemia cells. The observation of a dose-dependent inhibition of the oxygen consumption of isolated mice mitochondria indicates the involvement of an intrinsic mitochondrial pathway in this process.

Adsorption performances and mechanisms of the newly synthesized N,N'-di (carboxymethyl) dithiocarbamate chelating resin toward divalent heavy metal ions from aqueous media.

N,N'-di (carboxymethyl) dithiocarbamate chelating resin (PSDC) was synthesized by anchoring the chelating agent of N,N'-di (carboxymethyl) dithiocarbamate to the chloromethylated PS-DVB (Cl-PS-DVB) matrix, as a new adsorbent for removing divalent heavy metal ions from waste-stream. The physicochemical structures of Cl-PS-DVB and PSDC were elaborately characterized using Fourier transform infrared spectroscopy (FT-IR), elemental analysis (EA), and were further morphologically characterized using BET and BJH methods. The adsorption performances of PSDC towards heavy metals such as Cu(II), Pb(II) and Ni(II) were systematically investigated, based upon which the adsorption mechanisms were deeply exploited. For the above target, the classic batch adsorption experiments were conducted to explore the kinetics and isotherms of the removal processes with pH-value, initial concentration, temperature, and contact time as the controlling parameters. The kinetic and isotherm data could be well elucidated with Lagergren-second-order equation and Langmuir model respectively. The strong affinity of PSDC toward these target soft acids could be well demonstrated with the electrostatic attraction and chelating interaction caused by IDA moiety and sulphur which were namely soft bases on the concept of hard and soft acids and bases (HASB). Thermodynamic parameters, involving DeltaH(o), DeltaS(o) and DeltaG(o) were also calculated from graphical interpretation of the experimental data. The standard heats of adsorption (DeltaH(o)) were found to be endothermic and the entropy change values (DeltaS(o)) were calculated to be positive for the adsorption of Cu(II), Pb(II) and Ni(II) ions onto the tested adsorbents. Negative values of DeltaG(o) indicated that adsorption processes for all tested metal ions onto PSDC were spontaneous.

Preliminary chemico-biological studies on Ru(III) compounds with S-methyl pyrrolidine/dimethyl dithiocarbamate.

[RuCl(3).nH(2)O] and Na(trans-[RuCl(4)(DMSO)(2)]) were reacted with 1-pyrrolidinedithiocarbamate (PDT), its S-methyl ester (PDTM), and N,N-dimethylcarbamodithioic acid methyl ester (DMDTM) in water or methanol in order to obtain the corresponding Ru(III) derivatives. Once isolated and purified, the complexes were characterized by means of elemental analysis, conductivity measurements, FT-IR and (1)H NMR spectroscopy, ion electrospray mass spectrometry (ESI-MS), and thermal analyses. The crystal structure of mer-[Ru(DMDTM)(DMSO)Cl(3)] has been also determined by X-ray crystallography. In vitro cytotoxic activity of all the synthesized complexes was eventually evaluated on some selected human tumor cell lines.

Adsorption of Acid Red 73 on copper dithiocarbamate precipitate-type solid wastes.

Three solid wastes, copper N,N'-bis(dithiocarboxy)piperazine ([CuBDP](n)), copper diethyldithiocarbamate (Cu(DDTC)(2)) and copper dimethyldithiocarbamate (Cu(DMTC)(2)), were prepared and tested as adsorbents to remove Acid Red 73 from wastewater. It was found that the three precipitates all could effectively adsorb the dye but their adsorption abilities were rather different. The maximum adsorption amounts of the coordination polymer precipitate [CuBDP](n) reached as high as 364mg g(-1), much greater than those of Cu(DDTC)(2) and Cu(DMTC)(2) (42.9 and 37.8mg g(-1), respectively). The investigation of adsorption models showed these adsorption processes followed the pseudo-second-order kinetic equation and the adsorption balances could be described with both Langmuir and Freundlich isotherms, but the latter seemed to be more suitable. Their adsorption nature was inferred to be physical adsorption and mainly depended on the hydrophobic interaction between these precipitates and Acid Red 73. This is the first example for the reutilization of metal dithiocarbamate precipitates as solid wastes to date.

Dithiocarbamates have a common toxic effect on zebrafish body axis formation.

We previously determined that the dithiocarbamate pesticide sodium metam (NaM) and its active ingredient methylisothiocyanate (MITC) were developmentally toxic causing notochord distortions in the zebrafish. In this study, developing zebrafish were exposed to isothiocyanates (ITCs), dithiocarbamates (DTCs) and several degradation products to determine the teratogenic relationship of these chemical classes at the molecular level. All dithiocarbamates tested elicited notochord distortions with notochord NOELs from <4 to 40 ppb, while none of the ITCs caused notochord distortions with the exception of MITC. Carbon disulfide (CS(2)), a common DTC degradate, also caused distortions at concentrations >200 times the DTCs. Whole mount in situ hybridization of developmental markers for collagen (collagen2a1), muscle (myoD), and body axis formation (no tail) was perturbed well after cessation of treatment with pyrolidine-DTC (PDTC), dimethyl-DTC (DMDTC), NaM, MITC, and CS(2). Therefore, distinct albeit related chemical classes share a common toxic effect on zebrafish notochord development. To test the responsiveness of the distortion to metal perturbation, five metal chelators and 2 metals were studied. The membrane permeable copper chelator neocuproine (NCu) was found to cause notochord distortions similar to DTC-related molecules. DMDTC and NCu treated animals were protected with copper, and collagen 2a1 and no tail gene expression patterns were identical to controls in these animals. PDTC, NaM, MITC, and CS(2) were not responsive to copper indicating that the chelation of metals is not the primary means by which these molecules elicit their developmental toxicity. Embryos treated with DMDTC, NaM, and NCu were rescued by adding triciaine (MS-222) which abolishes the spontaneous muscle contractions that begin at 18 hpf. In these animals, only collagen 2a1 expression showed a similar pattern to the other notochord distorting molecules. This indicates that the perturbation of no tail expression is in response to the muscle contractions distorting the notochord, while collagen 2a1 is associated with the impact of these molecules on much earlier developmental processes.

Spectrophotometric determination of ziram in a commercial sample and wheat by extraction of its copper dimethyldithiocarbamate complex into molten naphthalene.

A method was developed for the determination of zinc(II) dimethyldithiocarbamate by converting it into the copper(II) dithiocarbamate complex, which is then extracted into molten naphthalene. The absorbance is measured at 430 nm versus a reagent blank. Beer's law is obeyed for concentrations of 0.63 x 10(-3) to 17.2 x 10(-3) g/L in the final solution. The method is sensitive and was applied to the determination of ziram in a commercial sample and in wheat grain.

Experimental and theoretical vibrational study of bis(N,N-dimethylthiocarbamoylthio)acetic acid.

Harmonic vibrational analysis at HF/3-21G level is performed on the ab initio optimized molecular structure of bis(N,N-dimethylthiocarbamoylthio)acetic acid, and the outcome used in assigning the infrared spectrum of the acid. The calculated spectrum compares well with the experimental solid-state FT IR spectrum recorded at 298 and at 77 K.