Iron Dithiocarbamates Research Articles

ЕFFECT OF IRON AND NICKEL DITHIOCARBAMATES ON THE PROPERTIES OF MODIFIED POLYURETHANES

The effect of modifiers - nickel bis(N,N-dimethyldithiocarbamate) (DTC-Ni) and iron tris(N, N-dimethyldithiocarbamate) (DTC-Fe) depending on their content on the structural peculiarities of polyurethane matrix based on polyoxytetramethylene glycol-1000 4,4’-diphenylmethane diisocyanate and 1,4-butanediol has been studied. The method of IR spectroscopy according to the results of NH groups’, C = O- and COC fragments’ association has shown the structuring effect of modifiers due to the PU matrix coordination. The processes of photolysis occurred as a result of exposure of PU under the conditions of the climate chamber have been also studied by IR spectroscopy method. The influence of modifiers and their content on the modified polyurethanes density has been investigated. The planar structure of DTC-Ni has shown to contribute to the density increase of modified PU as the result of polymer chain coordination, while the spherical structure of DTC-Fe - causes a density decrease due to steric hindrances in the implementation of H-bonds. Modification of polyurethanes with both nickel bis (N, N-dimethyldithiocarbamate) and iron tris (N, N-dimethyldithiocarbamate) as well as UV irradiation and moisture under the conditions of the climatic chamber contribute to the increase of water absorption. Studies of the strength properties of modified polyurethanes in comparison with the matrix under the conditions of the climate chamber have established the photosensitizing effect of nickel and iron dithiocarbamates. By studying the mass of samples of PU-DTС-Fe/Ni after extraction with dimethylformamide in the Soxhlet apparatus it has been found an increase in the level of gel fraction (0.29 - 1.58%) with increasing the modifier content, which confirms the presence of a network structure of modified PU due to radical processes taking place during destruction with the modifier participation. The influence of alkaline and acidic media on the destruction level of both modified polyurethanes and their analogues depending on the modifier content under the influence of climatic chamber conditions has been studied. Comparative derivatographic studies in air of weight loss of modified polyurethanes have confirmed the structuring and thermostabilizing effect of DTC-Ni on the PU matrix due to the probable difficulty of oxygen diffusion to the polymer volume, while the spatial structure of PU-DTC-Fe reduces the thermal stability.

Fe(ii) and Fe(iii) dithiocarbamate complexes as single source precursors to nanoscale iron sulfides: a combined synthetic and in situ XAS approach.

Nanoparticulate iron sulfides have many potential applications and are also proposed to be prebiotic catalysts for the reduction of CO2 to biologically important molecules, thus the development of reliable routes to specific phases with controlled sizes and morphologies is important. Here we focus on the use of iron dithiocarbamate complexes as single source precursors (SSPs) to generate greigite and pyrrhotite nanoparticles. Since these minerals contain both iron(iii) and iron(ii) centres, SSPs in both oxidation states, [Fe(S2CNR2)3] and cis-[Fe(CO)2(S2CNR2)2] respectively, have been utilised. Use of this Fe(ii) precursor is novel and it readily loses both carbonyls in a single step (as shown by TGA measurements) providing an in situ source of the extremely air-sensitive Fe(ii) dithiocarbamate complexes [Fe(S2CNR2)2]. Decomposition of [Fe(S2CNR2)3] alone in oleylamine affords primarily pyrrhotite, although by careful control of reaction conditions (ca. 230 °C, 40–50 nM SSP) a window exists in which pure greigite nanoparticles can be isolated. With cis-[Fe(CO)2(S2CNR2)2] we were unable to produce pure greigite, with pyrrhotite formation dominating, a similar situation being found with mixtures of Fe(ii) and Fe(iii) precursors. In situ X-ray absorption spectroscopy (XAS) studies showed that heating [Fe(S2CNiBu2)3] in oleylamine resulted in amine coordination and, at ca. 60 °C, reduction of Fe(iii) to Fe(ii) with (proposed) elimination of thiuram disulfide (S2CNR2)2. We thus carried out a series of decomposition studies with added thiuram disulfide (R = iBu) and found that addition of 1–2 equivalents led to the formation of pure greigite nanoparticles between 230 and 280 °C with low SSP concentrations. Average particle size does not vary significantly with increasing concentration, thus providing a convenient route to ca. 40 nm greigite nanoparticles. In situ XAS studies have been carried out and allow a decomposition pathway for [Fe(S2CNiBu2)3] in oleylamine to be established; reduction of Fe(iii) to Fe(ii) reduction triggers substitution of the secondary amide backbone by oleylamine (RNH2) resulting in the in situ formation of a primary dithiocarbamate derivative [Fe(RNH2)2(S2CNHR)2]. This in turn extrudes RNCS to afford molecular precursors of the observed FeS nanomaterials. The precise role of thiuram disulfide in the decomposition process is unknown, but it likely plays a part in controlling the Fe(iii)–Fe(ii) equilibrium and may also act as a source of sulfur allowing control over the Fe : S ratio in the mineral products.

Structural and gas sensing properties of greigite (Fe3S4) and pyrrhotite (Fe1-xS) nanoparticles

Iron sulfide nanoparticles Fe3S4 and Fe1-xS were synthesized via solvothermal decomposition of piperidine iron(III) dithiocarbamate complex in oleylamine. At a reaction temperature of 230 °C, the cubic Fe3S4 phase (greigite) was obtained whereas at 300 °C, monoclinic Fe1-xS (pyrrhotite) was obtained. In both cases, hexagonal sheet like structures with sizes ranging from 50 to 200 nm were obtained. Powder X-ray diffraction studies reveal that the temperature plays a significant role in determining the crystalline structure and chemical composition of the as-synthesized nanoparticles (NPs). Gas sensing applications further reveal activities which are phase-dependent. The greigite has a higher response to humidity but saturates faster than the pyrrhotite. The pyrrhotite phase however outwits the greigite on response to H2, NO2, NH3 and CH4. In these gases, the greigite displays early saturation as well as noisy and uncoordinated signals.

Principles of supramolecular polymeric chain formation in heteronuclear gold(III)–iron(III) complexes ([Au(S2CNR2)2][FeCl4]) n (R = C3H7, iso-C3H7): Chemisorption synthesis, structural organization, and thermal behavior

Polymeric gold(III)–iron(III) dithiocarbamate–chloride complexes of the ionic type are synthesized by the chemisorption binding of gold(III) with freshly precipitated iron(III) dipropyl and di-iso-propyl dithiocarbamates from solutions of H[AuCl4] in 2 M HCl. Heteropolynuclear complexes of the compositions ([Au{S2CN(C3H7)2}2][FeCl4])n (I) and ([Au{S2CN(iso-C3H7)2}2][FeCl4])n (II) are preparatively isolated as individual forms of gold(III) binding. The structural organization of the complexes is established by X-ray diffraction analysis (CIF files CCDC no. 1480802 (I) and no. 1480806 (II)). The structures of compounds I and II are characterized at the supramolecular level by the presence of two types of polymeric chains, the methods of formation of which differ substantially. Compound I contains the following structural units: four structurally nonequivalent centrosymmetric complex cations [Au{S2CN(C3H7)2}2]+ (A, B, С, and D) and two complex anions [FeCl4]– related to each other as conformers. Two independent cation-cationic linear polymeric chains (···А···В···)n and (···С···D···)n are formed in the structure of complex I due to pair relatively weak secondary interactions Au···S (nonvalent type) between the adjacent complex cations. The structure of compound II is characterized by zigzag cation-anionic chains (···[Au{S2CN(iso-C3H7)2}2]+···[FeCl4]–···)n in the formation of which the secondary interactions Au···Cl play the determining role. The thermal behavior of complexes I and II is studied by simultaneous thermal analysis. The thermal destruction process includes the thermolysis of the dithiocarbamate moiety of the complexes and [FeCl4]− with the reduction of gold(III) to the metal, the liberation of FeCl3, and the partial transformation of the latter into Fe2O3. In both cases, the final products of the thermal transformations of the studied compounds are elemental gold and Fe2O3.

Synthesis, spectral, single crystal X-ray structural, CShM and BVS characterization of iron(III) cyclohexyl dithiocarbamates and their solvothermal decomposition to nano iron(II) sulphide

[Fe(chmdtc)3] (1), [Fe(chedtc)3] (2), [Fe(achdtc)3] (3) and [Fe(chpdtc)3] (4) (where chmdtc = cyclohexylmethylcarbodithioate, chedtc = cyclohexylethylcarbodithioate, achdtc = allylcyclohexylcarbodithioate and chpdtc = cyclohexylpiperazinecarbodithioate) have been prepared and characterisized by elemental analysis, electronic, IR spectral, magnetic susceptibility, thermogravimetric analysis. The single crystal X-ray crystal structures of [Fe(chedtc)3] (2)and [Fe(chpdtc)3] (4) have been determined. Characteristic thioureide IR bands occur at 1483, 1477, 1454 and 1479 cm−1 for (1), (2), (3) and (4) respectively. Electronic spectral bands at 514,512,510 and 510 nm for (1), (2), (3) and (4) respectively are due to dxy → dx2 − y2 transition. One electron quasi reversible reductions due to Fe(III)/Fe(II) redox process are observed in CV. Magnetic susceptibility measurements exhibit a temperature dependent variation. Final residue obtained in thermal processes is FeS, which indicates the reduction of Fe(III) → Fe(II). Single crystal X-ray structures of [Fe(chedtc)3] (2)and [Fe(chpdtc)3] (4) show that the central atom is in a distorted octahedral environment. The CShM values have been calculated from the structural data as 2.5807 and 3.2329 for (2) and (4) respectively in a scale of zero to hundred. The observed values show that compound (4) is relatively more distorted than (2) in its octahedral coordination due to the steric demands of the cyclohexyl ring attached to piperazine. Both of them prefer octahedral coordination environment over trigonal prism. Bond Valence Sum (BVS) calculations confirmed the oxidation state of iron as +3. A non conventional solvothermal formation of FeS nano particles is reported with iron dithiocarbamates as single source precursors. Morphology and composition of the nano product have been characterized by PXRD and EDX analysis.

New Types of CO-Releasing Molecules (CO-RMs), Based on Iron Dithiocarbamate Complexes and [Fe(CO)3I(S2COEt)

New CO-releasing molecules, [Fe(CO)3X(S2CNR2)] and [Fe(CO)3I(S2COEt)], are reported. [Fe(CO)3X(S2CNR2)] releases the first two carbonyls rapidly to myoglobin (t1/2 24 h) and is not observed from [Fe(CO)2(S2COEt)2]. The mechanism of CO loss was investigated using Gaussian 09 calculations for [Fe(CO)3Br(S2CNMe2)] and [Fe(CO)2(S2CNMe2)2]. The X-ray structures of [Fe(CO)3Br(S2CNMe2)] and [Fe(CO)3I(S2CNEt2)]2I2 were determined.

Nitric Oxide Switches on the Photoluminescence of Molecularly Engineered Quantum Dots

The photoluminescence of nonfluorescent molecularly engineered quantum dots (QDs) with iron(III) dithiocarbamates was selectively switched on by nitric oxide. Such functional QDs consisted of CdSe-ZnS nanocrystals as fluorophores and surface bound tris(N-(dithiocarboxy)sarcosine)iron(III) as reactive centers for nitric oxide. The fluorescence of the QDs was quenched by energy transfer between the excited QD cores and the surface bound iron(III) dithiocarbamates due to their optical energy overlapping. Nitric oxide restored the fluorescence of the QDs through reduction of the surface bound iron(III) complexes to iron(I)-NO adducts and thus shutting down the energy transfer pathway. The fluorescence of the iron(III) complex engineered QDs was selectively and quantitatively restored by nitric oxide but not by other reactive oxygen species. Such a property of the functional QDs could be used for sensing nitric oxide based on the fluorescence "turn on" mechanism.

NO spin trapping in biological systems

The most recent data on mechanisms of spin trapping of nitric oxide (NO) by iron dithiocarbamate complexes in animal and plant cells and tissues are considered. The rationale is as follows: 1 In the absence of NO in cells and tissues, iron binds primarily to compounds others than dithiocarbamate ligands, e.g., tricarbonic acids. 2. Predominant binding of iron to dithiocarbamate ligands takes place only after its binding to NO, since nitrosylated iron manifests much higher affinity for these ligands that for any non-thiol compounds. 3.Within the composition of mononitrosyl dithiocarbamate complexes, iron exists predominantly in the oxidized (Fe3+) form, i.e., these complexes are originally diamagnetic. Their subsequent single-electron reduction to the paramagnetic, EPR -detectable form is mediated by endogenous or exogenous (e.g., dithionite) reducing agents. 4.Superoxide-mediated transition of paramagnetic mononitrosyl dithiocarbamate iron complexes into EPR-silent state can be accompanied by significant reduction of EPR-detectable complexes. This defect can be overcome through the use of the so-called ABC method. 5. In contrast to hydrophobic complexes fast decomposition of water-soluble mononitrosyl iron complexes in animal organisms testifies to low efficiency of these complexes in determination of NO content in animal cells and tissues.

Detection of basal NO production in rat tissues using iron–dithiocarbamate complexes

We probe endogenous NO production in WKY rats by trapping NO with iron–dithiocarbamate complexes. The aim was to detect non-stimulated NO production in small organs like kidneys of juvenile rats. The yields of mononitrosyl Fe–dithiocarbamate complexes are small and difficult to quantify in the presence of strong contaminating signals from Cu 2+–DETC complexes. We evaluate four methods to improve the detection of mononitrosyl Fe–dithiocarbamate adducts: progressive microwave saturation, tissue perfusion, spectral subtraction, and finally, reduction of the tissue with sodium dithionite. While the first three were only moderately useful, reduction was very helpful for quantification of the mononitrosyl Fe–dithiocarbamate yield. The increase in sensitivity allows the detection of non-stimulated NO release in small organs of juvenile rats.

Why iron–dithiocarbamates ensure detection of nitric oxide in cells and tissues

The in vivo mechanism of NO trapping by iron–dithiocarbamate complexes is considered. Contrary to common belief, we find that in biological systems the NO radicals are predominantly trapped by ferric iron–dithiocarbamates. Therefore, the trapping leads to ferric mononitrosyl complexes which are diamagnetic and cannot be directly detected with Electron Paramagnetic Resonance spectroscopy. The ferric mononitrosyl complexes are far easily reduced to ferrous state with l-cysteine, glutathione, ascorbate or dithiocarbamate ligands than their non-nitrosyl counterpart. When trapping NO in oxygenated biological systems, the majority of trapped nitric oxide is found in diamagnetic ferric mononitrosyl iron complexes. Only a minority fraction of NO is trapped in the form of paramagnetic ferrous mononitrosyl iron complexes with dithiocarbamate ligands. Subsequent ex vivo reduction of biological samples sharply increases the total yield of the paramagnetic mononitrosyl iron complexes. Reduction also eliminates the overlapping EPR spectrum from Cu 2+–dithiocarbamate complexes. This facilitates the quantification of yields from NO trapping.

Application of electron spin resonance spin-trapping technique for evaluation of substrates and inhibitors of nitric oxide synthase

The electron spin resonance (ESR) spin-trapping technique coupled with iron–dithiocarbamate complexes is one of the most specific methods for nitric oxide (NO) detection. In this study, we applied this method for the evaluation of the substrate and the inhibitors of NO synthase (NOS). A three-line ESR signal was detected from the mixture of inducible NOS (iNOS), l-arginine (Arg), nicotinamide adenine dinucleotide phosphate (NADPH), tetrahydrobiopterin, dithiothreitol, and Fe 2+- N-(dithiocarboxy) sarcosine (DTCS–Fe), and the signal intensity increased time-dependently. The signal was not observed by excluding either Arg or NADPH, and it was decreased by the addition of hemoglobin, which is an NO scavenger, and N G-monomethyl- l-arginine ( l-NMMA), N G-nitro- l-arginine ( l-NAME), and aminoguanidine (AG), which are NOS inhibitors, depending on the concentration. In comparison with l-NAME and AG, l-NMMA strongly inhibited iNOS activity. By using this method, the K m value of Arg and the K i value of l-NMMA for iNOS were determined to be 12.6 and 6.1 μM, respectively. These values are consistent with the reported values measured by the oxyhemoglobin and citrulline assays. These results suggest that the ESR spin-trapping technique coupled with the iron–dithiocarbamate complex can be applied for the evaluation of substrates and inhibitors of NOS, and it would be a powerful tool due to its simplicity and high specificity to NO.

Redox cycling of iron complexes of N-(dithiocarboxy)sarcosine and N-methyl- d-glucamine dithiocarbamate

Iron(II)–dithiocarbamate complexes are used to trap nitrogen monoxide in biological samples, and the resulting nitrosyliron(II)–dithiocarbamate is detected and quantified by ESR. As the chemical properties of these compounds have been little studied, we investigated whether iron dithiocarbamate complexes can redox cycle. The electrode potentials of iron complexes of N -(dithiocarboxy)sarcosine (dtcs) and N -methyl - d -glucamine dithiocarbamate (mgd) are 56 and −25 mV at pH 7.4, respectively, as measured by cyclic voltammetry. The autoxidation and Fenton reaction of iron(II)–dtcs and iron(II)–mgd were studied by stopped-flow spectrophotometry with both iron(II) complexes and dioxygen or hydrogen peroxide in excess. In the case of excess iron(II)–dtcs and –mgd complexes, the rate constants of the autoxidation and the Fenton reaction are (1.6–3.2) × 10 4 and (0.7–1.1) × 10 5 M −1 s −1, respectively. In the presence of nitrogen monoxide, the oxidation of iron(II)–dtcs and iron(II)–mgd by hydrogen peroxide is significantly slower (ca. 10–15 M −1 s −1). The physiological reductants ascorbate, cysteine, and glutathione efficiently reduce iron(III)–dtcs and iron(III)–mgd. Therefore, iron bound to dtcs and mgd can redox cycle between iron(II) and iron(III). The ligands dtcs and mgd are slowly oxidized by hydrogen peroxide with rate constants of 5.0 and 3.8 M −1 s −1, respectively.

Pharmacokinetics of 1-nitrosomelatonin and detection by EPR using iron dithiocarbamate complex in mice

The N-nitroso-derivative of melatonin, NOM (1-nitrosomelatonin), which has been demonstrated to be a NO* [oxidonitrogen*] donor in buffered solutions, is a new potential drug particularly in neurological diseases. The advantage of NOM, a very lipophilic drug, is its ability to release both melatonin and NO*, an easily diffusible free radical. In order to evaluate the distribution and the pharmacokinetics of NOM, [O-methyl-3H]NOM was administered to and followed in mice. A complementary method for monitoring NOM, EPR, was performed in vitro and ex vivo with (MGD)2-Fe2+ (iron-N-methyl-D-glucamine dithiocarbamate) complex as a spin trap. The behaviour of NOM was compared with that of GSNO (S-nitrosoglutathione), a hydrophilic NO* donor. In the first minutes following [O-methyl-3H]NOM intraperitoneal injection, the radioactivity was found in organs (6% in the liver, 1% in the kidney and 0.6% in the brain), but not in the blood. In both liver and brain, the radioactivity content decreased over time with similar kinetics reflecting the diffusion and metabolism of NOM and of its metabolites. Based on the characterization and the quantification of the EPR signal in vitro with NOM or GSNO using (MGD)2-Fe2+ complex in phosphate-buffered solutions, the detection of these nitroso compounds was realized ex vivo in mouse tissue extracts. (MGD)2-Fe2+-NO was observed in the brain of NOM-treated mice in the first 10 min following injection, revealing that NOM was able to cross the blood-brain barrier, while GSNO was not.

Spin trapping nitric oxide from neuronal nitric oxide synthase: A look at several iron–dithiocarbamate complexes

The free radical, nitric oxide (√NO), is responsible for a myriad of physiological functions. The ability to verify and study √NO in vivo is required to provide insight into the events taking place upon its generation and in particular the flux of √NO at relevant cellular sites. With this in mind, several iron-chelates (Fe2+(L)2) have been developed, which have provided a useful tool for the study and identification of √NO through spin-trapping and electron paramagnetic resonance (EPR) spectroscopy. However, the effectiveness of √NO detection is dependent on the Fe2+(L)2 complex. The development of more efficient and stable Fe2+(L)2 chelates may help to better understand the role of √NO in vivo. In this paper, we present data comparing several proline derived iron–dithiocarbamate complexes with the more commonly used spin traps for √NO, Fe2+-di(N-methyl-D-glutamine-dithiocarbamate) (Fe2+(MGD)2) and Fe2+-di(N-(dithiocarboxy)sarcosine) (Fe2+(DTCS)2). We evaluate the apparent rate constant (kapp) for the reaction of √NO with these Fe2+(L)2 complexes and the stability of the corresponding Fe2+(NO)(L)2 in presence of NOS I.

Spontaneous formation of thiuram disulfides in solutions of iron(III) dithiocarbamates.

Dithiocarbamates are used as pesticides and rubber additives. Dithiocarbamates are the reduced forms of thiuram disulfides and both of these groups of substances induce allergic contact dermatitis. The allergic cross-reactivity pattern between dithiocarbamates and thiurams is unclear. The aim of this study was to investigate why these cross-reactions occur sometimes but not always. HPLC-analysis of buffer solutions of iron(III) dithiocarbamates demonstrated that thiuram disulfides were formed spontaneously and rapidly in high yield. No such oxidation was observed in solutions of copper(II), zinc(II), or sodium dithiocarbamates. However, sodium diethyldithiocarbamate and zinc diethyldithiocarbamate were oxidized in buffer solution when ferric salt was added. The influence of different metal ions on the oxidation reaction is probably an explanation for the cross-reactivity patterns seen between dithiocarbamates and thiurams. These findings also show that careful handling is necessary in analytical and biological studies with solutions of iron(III) dithiocarbamates. Oxidation of dithiocarbamates in aqueous buffer at physiological pH has not been shown before.

42] Analytical implications of iron dithiocarbamates for measurement of nitric oxide

Publisher Summary The chapter summarizes factors known to affect sensitivity and reliability of the dithiocarbamate electron paramagnetic resonance (EPR)-trapping technique and discusses approaches to address these problems that enable reliable use of these traps for the quantitative detection of nitric oxide (NO) in biological systems. The following reagents are used: sodium DETC, L-ascorbic acid, and sodium dithionite, all from Sigma; ammonium iron (II) sulfate hexahydrate, hydroquinone, ferric chloride, and dimethyl sulfoxide (DMSO). Using the ferric form of the water-soluble trap can significantly minimize interference with nitrite, whereas the water-insoluble iron dithiocarbamates can completely exclude the unwanted effect. Advantages and disadvantages of applications of different redox states of water-soluble and water-insoluble traps are presented. Dithiocarbamate complexes of iron can be used successfully for the measurement of NO production in a variety of chemical and biological systems. With careful consideration of the chemical and physical properties of these traps and their NO adducts, this EPR method of NO detection provides a unique and powerful tool for the measurement of NO in a broad range of applications, ranging from enzymatic to cellular systems. The technique also enables in vivo or ex vivo measurement and imaging of NO formation and the metabolic pathways by which it is formed.

Iron dithiocarbamate as spin trap for nitric oxide detection: Pitfalls and successes

Iron dithiocarbamate as spin trap for nitric oxide detection: Pitfalls and successes

In vivo nitric oxide transfer of a physiological NO carrier, dinitrosyl dithiolato iron complex, to target complex

Dinitrosyl dithiolato iron complex (DNIC) has been identified as an endogenous NO carrier, yet in vivo mechanisms of NO donation remain undefined. Transnitrosylation, in which a coordinated NO group is transferred to another metal complex, has been observed in transition-metal-nitrosyl chemistry. In this study, we used three kinds of iron dithiocarbamate complexes (Fe-DTCs) as NO acceptors to elucidate in vivo transnitrosylation of diglutathionyl dinitrosyl iron complex [DNIC-(GS) 2]. Fe-DTCs were administered to mice after the injection of DNIC-(GS) 2 and electron paramagnetic resonance (EPR) spectra were measured both in the resected organs and in the upper abdomen of living mice. The spectral feature gradually changed from an initial DNIC-(GS) 2 signal to mononitrosyl iron dithiocarbamate one, suggesting that NO-Fe-DTC was formed through in vivo reaction of DNIC-(GS) 2 with Fe-DTC. The spectral results in in vitro and in vivo systems indicate that NO-Fe-DTCs can be formed not only by the transfer of coordinated NO-group(s) in DNIC-(GS) 2 but also by the abstraction of Fe-NO group in DNIC-(GS) 2 by free DTC ligands. Transnitrosylation proceeded more rapidly in blood than in liver and kidney; and more efficiently in kidney than in liver. Further, the ability to accept NO from DNIC was dependent on water-solubility of Fe-DTCs. Thus, in vivo transnitrosylation from DNIC to exogenous iron complex could be observed and this reaction was influenced by biological constituents and properties of iron complex. These results demonstrate that the transnitrosylation from DNIC to intrinsic NO acceptors like metalloproteins has a probable significance in in vivo NO transfer process.

ChemInform Abstract: The Reaction of Copper and Iron Species with Thiuram Sulfides: Copper and Iron Dithiocarbamate Derivatives

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6A1g ⇌ 2T2g spin-crossover in iron(III) dithiocarbamates

Literature on 6 A 1 g ⇄ 2 T 2 g spin-crossover in iron(III) dithiocarbamates for the last three decades has been reviewed, and kinetics and mechanism of spin-crossover in these systems have been discussed.