A Convenient Method for Determination of Tetramethylthiuram Disulphide.

Åkerström, Stig; Lindahl, Per Eric; Rasmussen, Svend Erik; Block-Bolten, A.; Toguri, J. M.; Flood, H.

doi:10.3891/acta.chem.scand.16-1206

Cited by 12 publications

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“…Blower and co-workers have prepared bis(phosphonate) derivatives (Figure 2f), incorporating 64 Cu for imaging applications [38] and Wilton-Ely has linked together ruthenium (Figure 2h) and other metal centres through a Cu(II) dithiocarbamate motif [39]. There are reports of Cu(II) complexes containing two different dithiocarbamates [40,41], but no well-characterised examples, and due to the lability of the dithiocarbamate at the Cu(II) centre, it seems likely these are mixtures with the homoleptic dithiocarbamate complexes (see later). Thus a literature report of [Cu(S2CNMe2)(S2CNEt2)], formed upon the addition of tetramethyl thiuram disulfide to the Cu(I) cluster, [Cu(μ3-S2CNEt2)]4 [40], is likely a mixture with [Cu(S2CNMe2)2] and [Cu(S2CNEt2)2].…”

Section: Copper(ii) Bis(dithiocarbamate) Complexesmentioning

confidence: 99%

“…Almost a century passed between the initial synthesis of [Cu(S2CN i Bu2)2] and the elucidation of its structure by single-crystal X-ray diffraction (Figure 3a) [7]. As in all Cu(II) There are reports of Cu(II) complexes containing two different dithiocarbamates [40,41], but no well-characterised examples, and due to the lability of the dithiocarbamate at the Cu(II) centre, it seems likely these are mixtures with the homoleptic dithiocarbamate complexes (see later). Thus a literature report of [Cu(S 2 CNMe 2 )(S 2 CNEt 2 )], formed upon the addition of tetramethyl thiuram disulfide to the Cu(I) cluster, [Cu(µ 3 -S 2 CNEt 2 )] 4 [40], is likely a mixture with [Cu(S 2 CNMe 2 ) 2 ] and [Cu(S 2 CNEt 2 ) 2 ].…”

Section: Copper(ii) Bis(dithiocarbamate) Complexesmentioning

confidence: 99%

“…As in all Cu(II) There are reports of Cu(II) complexes containing two different dithiocarbamates [40,41], but no well-characterised examples, and due to the lability of the dithiocarbamate at the Cu(II) centre, it seems likely these are mixtures with the homoleptic dithiocarbamate complexes (see later). Thus a literature report of [Cu(S 2 CNMe 2 )(S 2 CNEt 2 )], formed upon the addition of tetramethyl thiuram disulfide to the Cu(I) cluster, [Cu(µ 3 -S 2 CNEt 2 )] 4 [40], is likely a mixture with [Cu(S 2 CNMe 2 ) 2 ] and [Cu(S 2 CNEt 2 ) 2 ]. In contrast, isomeric [Cu(S 2 CNMeEt) 2 ] is wellcharacterised [42].…”

Section: Copper(ii) Bis(dithiocarbamate) Complexesmentioning

confidence: 99%

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Copper Dithiocarbamates: Coordination Chemistry and Applications in Materials Science, Biosciences and Beyond

Hogarth

Onwudiwe

2021

Inorganics

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Copper dithiocarbamate complexes have been known for ca. 120 years and find relevance in biology and medicine, especially as anticancer agents and applications in materials science as a single-source precursor (SSPs) to nanoscale copper sulfides. Dithiocarbamates support Cu(I), Cu(II) and Cu(III) and show a rich and diverse coordination chemistry. Homoleptic [Cu(S2CNR2)2] are most common, being known for hundreds of substituents. All contain a Cu(II) centre, being either monomeric (distorted square planar) or dimeric (distorted trigonal bipyramidal) in the solid state, the latter being held together by intermolecular C···S interactions. Their d9 electronic configuration renders them paramagnetic and thus readily detected by electron paramagnetic resonance (EPR) spectroscopy. Reaction with a range of oxidants affords d8 Cu(III) complexes, [Cu(S2CNR2)2][X], in which copper remains in a square-planar geometry, but Cu–S bonds shorten by ca. 0.1 Å. These show a wide range of different structural motifs in the solid-state, varying with changes in anion and dithiocarbamate substituents. Cu(I) complexes, [Cu(S2CNR2)2]−, are (briefly) accessible in an electrochemical cell, and the only stable example is recently reported [Cu(S2CNH2)2][NH4]·H2O. Others readily lose a dithiocarbamate and the d10 centres can either be trapped with other coordinating ligands, especially phosphines, or form clusters with tetrahedral [Cu(μ3-S2CNR2)]4 being most common. Over the past decade, a wide range of Cu(I) dithiocarbamate clusters have been prepared and structurally characterised with nuclearities of 3–28, especially exciting being those with interstitial hydride and/or acetylide co-ligands. A range of mixed-valence Cu(I)–Cu(II) and Cu(II)–Cu(III) complexes are known, many of which show novel physical properties, and one Cu(I)–Cu(II)–Cu(III) species has been reported. Copper dithiocarbamates have been widely used as SSPs to nanoscale copper sulfides, allowing control over the phase, particle size and morphology of nanomaterials, and thus giving access to materials with tuneable physical properties. The identification of copper in a range of neurological diseases and the use of disulfiram as a drug for over 50 years makes understanding of the biological formation and action of [Cu(S2CNEt2)2] especially important. Furthermore, the finding that it and related Cu(II) dithiocarbamates are active anticancer agents has pushed them to the fore in studies of metal-based biomedicines.

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Section: Copper(ii) Bis(dithiocarbamate) Complexesmentioning

confidence: 99%

Section: Copper(ii) Bis(dithiocarbamate) Complexesmentioning

confidence: 99%

Section: Copper(ii) Bis(dithiocarbamate) Complexesmentioning

confidence: 99%

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Copper Dithiocarbamates: Coordination Chemistry and Applications in Materials Science, Biosciences and Beyond

Hogarth

Onwudiwe

2021

Inorganics

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“…Thus Fe(III) SSPs actually convert to formation of Fe(II) species in the decomposition media. Since thiuram disuldes are oxidising agents, adding to low valent metal centres as two dithiocarbamate ligands via an oxidativeaddition process, [67][68][69][70][71][72] we considered that an equilibrium was operating. Hu and Zhang previously considered the role of thiuram disuldes in the solvothermal synthesis of CdS 73 and we have also recently shown that addition of tetra-isobutylthiuram disulde (3) to the oleylamine solutions of [Ni(S 2 CN i Bu 2 ) 2 ] can have a signicant effect on the nanomaterials generated.…”

Section: (V) Decomposition Of [Fe(s 2 Cnr 2 ) 3 ] With Added Thiuram mentioning

confidence: 99%

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

et al. 2019

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“…Rates DIECA in the suspending medium was determined by measuring the absorbance of a copper (II) DIECA complex at 433 nm (1).…”

Section: Methodsmentioning

confidence: 99%

Disulfiram Metabolism in Isolated Mesophyll Cells and Inhibition of Photosynthesis and Cyanide-Resistant Respiration

Bown¹,

Pullen²,

Shadeed³

1984

Plant Physiol.

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Disulfiram (tetraethylthiuram disulfide) is a potent inhibitor of cyanide-resistant respiration in isolated mitochondria (7) or intact mesophyll cells of Asparagus sprengeri Regel (17). In addition, disulfiram and other thiuram disulfides inhibit photosynthesis (13,14). The mechanisms by which disulfiram inhibits these processes are not understood. Inhibition in both cases may result from a reaction between the disulfide component of disulfiram and enzyme thiol groups essential for the cyanide-resistant pathway or photosynthesis (7,14,16). Another possible mechanism of inhibition involves chelation by disulfiram of transition metals located in enzyme systems (14). Inhibition may also be mediated by disulfiram's ability to function as a free radical scavenger and react with fatty acid peroxy radicals (18). In the present paper, the ability of isolated Asparagus mesophyll cells to rapidly reduce disulfiram to DIECA2 is demonstrated. The possible involvement of DIECA production in inhibition of either process is investigated. MATERIALS AND METHODSAsparagus sprengeri Regel was grown and mesophyll cells isolated using previously described methods (3,4). Chl content of cell suspensions was determined by the method of Amon (2) DIECA in the suspending medium was determined by measuring the absorbance of a copper (II) DIECA complex at 433 nm (1).Rates of 02 production in the light or 02 consumption in the dark were determined with a calibrated 02 electrode (YSI 4004) using cells suspended in 7.5 ml of a 30'C buffered medium contained witin a closed system (3). A concentration of NaHCO3 saturating for photosynthesis (4) was added to the cell suspension immediately after illumination with a 300-w reflector lamp (Sylvania) began. Irradiance at the surface of the vessel was 1200 x 10-5 w cm-2. Rates were corrected for consumption by the 02 electrode and expressed as Mmol 02/mg Chl -h or Mmol 02/106 cells h.Stock solutions of DIECA and disulfiram were made using 80% (v/v) ethanol and volumes of KCN, ethanol, DIECA, or disulfiram were dispensed with Hamilton syringes to give the concentrations indicated. RESULTS Measurements of net rates of H' efflux were initiated by the addition of 9 to 12 x 106 cells suspended in 3 ml unbuffered salt solution to 7 ml of similar medium. The resulting 10 ml cell suspension was stirred and aerated. The initial value for the net rate of H' efflux varied between 0.3 and 1.8 nmol H'/I06 cellsmin and the mean value expressed on a Chl basis was 31.6 nmol H'/mg Chl min. Disulfiram stimulated acidification with no apparent lag (Fig. 1). In the light, 0.4 mM disulfiram stimulated acidification to a mean value of 18 nmol H'/I06 cells min and the overall decline in pH was equivalent to 396 + 83 (SD) nmol H'. The molar ratio ofH+ appearing in the medium to disulfiram added was 0.1. In the dark, 0.4 mm disulfiram stimulated the acidification rate to 8.6 nmol H+/I06 cells-min and the pH decrease was equivalent to 210 + 64 (SD) nmol H+ (Fig. 1)

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A Convenient Method for Determination of Tetramethylthiuram Disulphide.

Cited by 12 publications

References 0 publications

Copper Dithiocarbamates: Coordination Chemistry and Applications in Materials Science, Biosciences and Beyond

Copper Dithiocarbamates: Coordination Chemistry and Applications in Materials Science, Biosciences and Beyond

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

Disulfiram Metabolism in Isolated Mesophyll Cells and Inhibition of Photosynthesis and Cyanide-Resistant Respiration

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