Diethyldithiocarbamate Complexes Research Articles

In situ generation of copper(Ⅱ)/diethyldithiocarbamate complex through tannic acid/copper(Ⅱ) network coated hollow mesoporous silica for enhanced cancer chemodynamic therapy

The Cu2+ complex formed by the coordination of disulfiram (DSF) metabolite diethyldithiocarbamate (DTC), Cu(DTC)2, can effectively inhibit tumor growth. However, insufficient Cu2+ levels in the tumor microenvironment can impact tumor-suppressive effects of DTC. In this study, we proposed a Cu2+ and DSF tumor microenvironment-targeted delivery system. This system utilizes hollow mesoporous silica (HMSN) as a carrier, after loading with DSF, encases it using a complex of tannic acid (TA) and Cu2+ on the outer layer. In the slightly acidic tumor microenvironment, TA/Cu undergoes hydrolysis, releasing Cu2+ and DSF, which further form Cu(DTC)2 to inhibit tumor growth. Additionally, Cu2+ can engage in a Fenton-like reaction with H2O2 in the tumor microenvironment to form OH, therefore, chemodynamic therapy (CDT) and Cu(DTC)2 are used in combination for tumor therapy. In vivo tumor treatment results demonstrated that AHD@TA/Cu could accumulate at the tumor site, achieving a tumor inhibition rate of up to 77.6 %. This study offers a novel approach, circumventing the use of traditional chemotherapy drugs, and provides valuable insights into the development of in situ tumor drug therapies.

Thermoelectric Performance of Tetrahedrite (Cu12Sb4S13) Thin Films: The Influence of the Substrate and Interlayer.

In the present work, tetrahedrite Cu12Sb4S13 thin films were deposited on various substrates via aerosol-assisted chemical vapor deposition (AACVD) using diethyldithiocarbamate complexes as precursors. A buffer layer of Sb2O3 with a small lattice mismatch to Cu12Sb4S13 was applied to one of the glass substrates to improve the quality of the deposited thin film. The buffer layer increased the coverage of the Cu12Sb4S13 thin film, resulting in improved electrical transport properties. The growth of the Cu12Sb4S13 thin films on the other substrates, including ITO-coated glass, a SiO2-coated Si wafer, and mica, was also investigated. Compared to the films grown on the other substrates, the Cu12Sb4S13 thin film deposited on the SiO2-coated Si wafer showed a dense and compact microstructure and a larger grain size (qualities that are beneficial for carrier transport), yielding a champion power factor (PF) of ∼362 μW cm-1 K-2 at 625 K. The choice of substrate strongly influenced the composition, microstructure, and electrical transport properties of the deposited Cu12Sb4S13 thin film. At 460 K, the highest zT value that was obtained for the thin films was ∼0.18. This is comparable to values reported for Cu-Sb-S bulk materials at the same temperature. Cu12Sb4S13 thin films deposited using AACVD are promising for thermoelectric applications. To the best of our knowledge, the first full thermoelectric characterization of the Cu12Sb4S13 thin film is performed in this work.

Coordination chemistry applied to anti-doping analysis: Cobalt quantification as its diethyldithiocarbamate complex by liquid chromatography coupled to high resolution tandem mass spectrometry.

Cobalt was included on the World Anti-Doping Agency Prohibited List in 2015 due to its effect on stimulus of erythropoiesis via stabilization of hypoxia-inducible factor. Although it has proven benefits for performance enhancement, the unavailability of inductively coupled plasma-mass spectrometry on routine of the accredited laboratories is a factor that reduces its applicability in anti-doping analysis. Therefore, an analytical method for quantification of urinary cobalt as its diethyldithiocarbamate complex by liquid chromatography coupled with high-resolution tandem mass spectrometry was developed and validated. Palladium was proposed as internal standard and rhodium as a complexation control. A microwave-assisted acid digestion of the urine samples was essential, not only to eliminate the matrix effect but mainly to avoid the non-specific bond of cobalt to endogenous molecules. A linear method was obtained over the studied range from a negative urine control to a spiked concentration of 25 ng/mL, with an estimated limit of quantification of 2.5ng/mL, and an adequate combined standard uncertainty of 11.4%. Considering that all reagents are commercially available, the proposed strategy is feasible to be included on routine sample preparation. Monitoring urinary cobalt concentrations globally opens the perspective to support the anti-doping system to define a suitable threshold value and to understand its potential misuse by athletes seeking for performance improvement.

Synthesis of In : SnO2/La4NiS7 via Diethyldithiocarbamate‐Assisted Spin Coating: A Promising Route for High‐Performance Transparent Photoelectrochemical Energy Storage and Generation

AbstractConstructing nanostructures that fully boost the performance of all metals while offering a positive inter‐particle effect among frameworks is an efficient approach for enhancing electrochemical effectiveness. Elongated In : SnO2/La4NiS7 structure is created using diethyl dithiocarbamate complex. Investigations were done on the material‘s surficial, crystallographical and electrochemical characters. The direct optical band gap as determined by UV‐visible analysis was 2.9 eV. X‐ray photoelectron spectroscopy presented La3d and Ni2p core level. Electrical investigations of the transparent photoactive electrode in a photoelectrochemical cell showed an exceptional specific capacity of 906 F ⋅ g−1 at 5 mV ⋅ s−1 under illumination. Transient chronoamperometric response of the photoelectrode presented 35.3 mA photocurrent generation. Greater photocurrents were achieved at all scan rates in the existence of light indicating that the exposure to light positively impacted the electrode's performance. Undoubtedly, this work proposed a beneficial photoelectrode that‘s applicable to systems that generate electricity from renewable sources.

Green synthesis of antimony sulphide (Sb2S3) nano-rods in plant oils and study of photocatalytic activity

This study reports the green synthesis of antimony sulphide (Sb2S3) nano-rods synthesized by thermolysis of antimony diethyldithiocarbamate (Sb [S2CNEt2]) complex as a single source precursor in various plants oils acting as capping agents through their carboxylic acid functionality. The reported method reflects a facile and single-step fabrication of antimony sulphide nanorods and reveales their orthorhombic stibinite phase characterized by p-XRD. The quantification of energy dispersive X-ray spectrometric (EDS) analysis depicted an atomic ratio of approximately 2:3 for Sb: S. The morphology of nano-rods was confirmed by scanning electron microscopy (SEM) analysis and crystallize size was observed ranging 8.09–8.27 nm. The band gap calculated from absorption spectra was found to be 1.93 eV to 2.01 eV for all studied samples. The photocatalytic efficiency of synthesized nanorods evaluated by photocatalysis of Janus Green and Rose Bengal showed the dye degradation up to 99.9% in the presence of biosynthesized catalysts at different times.

Dispersive Liquid Phase Microextraction (DLPME) as a Strategy for CdII Separation and Determination in High-Salinity Produced Waters by Graphite Furnace Atomic Absorption Spectrometry

In this study, we propose a microextraction method for the determination of CdII in produced waters. The process is based on the conversion of CdII ions into a hydrophobic diethyldithiocarbamate (DDTC) complex with its subsequent dispersive liquid phase microextraction (DLPME) from the aqueous medium with chloroform. The organic phase was then diluted with ethanol and Cd absorbance was measured by graphite furnace atomic absorption spectrometry (GF AAS). The experimental conditions related to the DLPME process were investigated, and the best microextraction conditions were achieved at pH = 6.0 (acetate buffer), 7.5 × 10-6 mol L-1 of DDTC, and when using 200 µL of chloroform as the extracting solvent. No dispersing solvent was needed, which allowed the recovery of approximately 140 µL of chloroform extract. Pyrolysis and atomization temperatures of the GF AAS program were determined through the construction of the respective curves. The estimated limits of detection (LOD) and quantification (LOQ) were 5 and 17 ng L-1, respectively, whereas the enrichment factor for the method was 17. Six samples of seawater and five samples of produced waters with salinities between 30 and 270‰ were analyzed as well as two certified reference materials of saline waters.

Co-delivery of a tumor microenvironment-responsive disulfiram prodrug and CuO2 nanoparticles for efficient cancer treatment.

Disulfiram (DSF) has been used as a hangover drug for more than seven decades and was found to have potential in cancer treatment, especially mediated by copper. However, the uncoordinated delivery of disulfiram with copper and the instability of disulfiram limit its further applications. Herein, we synthesize a DSF prodrug using a simple strategy that could be activated in a specific tumor microenvironment. Poly amino acids are used as a platform to bind the DSF prodrug through the B-N interaction and encapsulate CuO2 nanoparticles (NPs), obtaining a functional nanoplatform Cu@P-B. In the acidic tumor microenvironment, the loaded CuO2 NPs will produce Cu2+ and cause oxidative stress in cells. At the same time, the increased reactive oxygen species (ROS) will accelerate the release and activation of the DSF prodrug and further chelate the released Cu2+ to produce the noxious copper diethyldithiocarbamate complex, which causes cell apoptosis effectively. Cytotoxicity tests show that the DSF prodrug could effectively kill cancer cells with only a small amount of Cu2+ (0.18 μg mL-1), inhibiting the migration and invasion of tumor cells. In vitro and in vivo experiments have demonstrated that this functional nanoplatform could kill tumor cells effectively with limited toxic side effects, showing a new perspective in DSF prodrug design and cancer treatment.

Synthesis and characterisation of Ga- and In-doped CdS by solventless thermolysis of single source precursors.

We report a facile and low temperature synthesis of Ga- and In-doped CdS nanoparticles from molecular precursors. Diethyldithiocarbamate complexes of Cd(II), Ga(III), and In(III), were synthesised and decomposed in tandem through solventless thermolysis, producing Ga- or In-doped CdS. The resultant MxCd1-xS1+0.5x (where M = Ga/In at x values of 0, 0.02, 0.04, 0.06, 0.08 and 0.1) particulate powder was analysed by powder X-ray diffraction, which showed that both Ga (through all doping levels) and In (at doping levels <8 mol%) were successfully incorporated into the hexagonal CdS lattice without any impurities. Raman spectroscopy also showed no significant change from CdS. Scanning electron microscopy and energy dispersive X-ray spectroscopy were used to investigate the morphology and elemental dispersion through the doped CdS materials, showing homogenous incorporation of dopant. The optical and luminescent properties of the doped MxCd1-xS1+0.5x materials were examined by UV-Vis absorption and photoluminescence spectroscopies respectively. All materials were found to exhibit excitonic emission, corresponding to band gap energies between 2.7 and 2.9 eV and surface defect induced emission which is more prominent for Ga than for In doping. Additionally, moderate doping slows down charge carrier recombination by increasing the lifetimes of excitonic and surface state emissions, but particularly for the latter process.

Speciation of tin ions in oxide glass containing iron oxide through solvent extraction and inductively coupled plasma atomic emission spectrometry after the decomposition utilizing ascorbic acid.

Determining the concentrations of different Sn ions in glass containing iron oxide by wet chemical analysis is a challenge because a redox reaction occurs between Sn2+ and Fe3+. A chemical analysis method for determining the concentrations of Sn2+ and Sn4+ in soda lime glass containing iron oxide was proposed. A mixture of ascorbic acid, hydrochloric acid, and hydrofluoric acid was used to decompose the sample in a vessel with nitrogen flow. Ascorbic acid functioned as a reductant for Fe3+. Subsequently, the Sn2+ were separated as a diethyldithiocarbamate complex. Furthermore, inductively coupled plasma atomic emission spectroscopy was used to determine the concentrations of Sn4+ and total Sn, from which the concentration of Sn2+ can be calculated. The results were validated by comparing ratios of Sn2+ to total Sn to results obtained using Mössbauer spectroscopy. The results were in agreement, thereby validating the use of the proposed approach.

Synthesis of ternary copper antimony sulfide via solventless thermolysis or aerosol assisted chemical vapour deposition using metal dithiocarbamates

Copper antimony sulfide (Cu-Sb-S) has recently been proposed as an attractive alternative photovoltaic material due to the earth-abundant and non-toxic nature of the elements, high absorption coefficients and band gaps commensurate with efficient harvesting of solar photonic flux across multiple phases of Cu-Sb-S. These materials are therefore highly desirable and sustainable and scalable deposition techniques to produce them are of interest. In this paper, we demonstrate two facile, low-temperature and inexpensive techniques (solventless thermolysis and aerosol-assisted chemical vapor deposition (AACVD)) for the preparation of binary digenite (Cu1.8S), chalcocite (Cu2S) and stibnite (Sb2S3) and several phases of ternary copper-antimony-sulfide (Cu2xSb2(1−x)Sy, where 0 ≤ x ≤ 1). It was found that by utilising these different techniques and varying the ratio of Cu:Sb, pure phases of ternary chalcostibite (CuSbS2), fematinite (Cu3SbS4) and tetrahedrite (Cu12Sb4S13) can be achieved. Two single-source precursors were investigated for this purpose, namely the diethyldithiocarbamate (DTC) complexes of copper and antimony Cu(DTC)2 and Sb(DTC)3. These were decomposed both individually (to produce binary materials) and combined (to produce ternary materials) at different ratios. From the solventless thermolysis and AACVD methods, either particulate or thin film material was formed, respectively. These materials were then characterised by powder XRD, SEM, EDX and Raman spectroscopies to determine the crystalline phase, material morphology and uniformity of elemental composition. This analysis demonstrated that as the Cu-content increases, the phase of the ternary material changes from chalcostibite (CuSbS2) and fematinite (Cu3SbS4) at a low Cu:Sb ratio to tetrahedrite (Cu12Sb4S13) at a high Cu:Sb ratio.

Synthesis and Characterization of Manganese Dithiocarbamate Complexes: New Evidence of Dioxygen Activation.

(1) Background: Metal dithiocarbamate compounds have long been the subject of research due to their ease of formation, excellent properties and potential applications. However, manganese complexes with dithiocarbamates, to our knowledge, have never been used for medical imaging applications. With the aim of developing a new class of mononuclear manganese(II)-based agents for molecular imaging applications, we performed a specific investigation into the synthesis of mononuclear bis-substituted Mn(II) complexes with dithiocarbamate ligands. (2) Methods: Synthesis in either open or inert atmosphere at different Mn(II) to diethyldithiocarbamate molar ratios were performed and the products characterized by IR, EA, ESI-MS and XRD analysis. (3) Results: We found that only under oxygen-free atmospheric conditions the Mn(II) complex MnL2, where L = diethyldithiocarbamate ligand, is obtained, which was further observed to react with dioxygen in the solid state to form the intermediate superoxo Mn(III) complex [MnL2(η2-O2)]. The existence of the superoxo complex was revealed by mass spectroscopy, and this species was interpreted as an intermediate step in the reaction that led the bis-substituted Mn(II) complex, MnL2, to transform into the tris-substituted Mn(III) complex, MnL3. A similar result was found with the ligand L’ (= bis(N-ethoxyethyl)dithiocarbamate). (4) Conclusions: We found that in open atmosphere and in aqueous solution, only manganese(III) diethyldithiocarbamate complexes can be prepared. We report here a new example of a small-molecule Mn(II) complex that efficiently activates dioxygen in the solid state through the formation of an intermediate superoxide adduct.

Novel nanoformulated diethyldithiocarbamate complexes with biosynthesized or green chemosynthesized copper oxide nanoparticles: An in vitro comparative anticancer study

Developing more soluble and stable nanoformulation for the potent anticancer complex of copper diethyldithiocarbamate (CD) is extremely desired. Herein, for the first time, CD nanoparticles (NPs) were formulated by chelating diethyldithiocarbamate to bacterially and green chemically prepared copper oxide NPs (Bio CO NPs and Chemo CO NPs, respectively). Chemo CO NPs were produced in simpler and less time-consuming manner with higher NPs homogeneity. These CO NPs were identified, by X-ray diffractometer, as CuO and Cu2O, respectively. The nanoformulated CD complexes (Bio CD NPs and Chemo CD NPs) which have nanosizes (215.7 nm and 148.1 nm, respectively) with negative zeta potentials (∼−20 mv), exhibited not only high serum stability and solubility but also a potent anticancer effect. More importantly, Chemo CD NPs outperformed Bio CD NPs in the terms of synergistic anticancer index, apoptosis induction (>81% and <54%, respectively) and anti-migration efficacy (≥80% and <71%, respectively). This could be attributed to smaller nanosize and Cu2O of Chemo CD NPs causing higher cellular uptake with stronger inhibition of aldehyde dehydrogenase 1A1 and more free radical generation in Chemo CD NPs-treated cancer cells than Bio CD NPs. This distinct anticancer efficacy of novel Chemo CD NPs deserves further investigation using animal models.

Recent Advances in Repurposing Disulfiram and Disulfiram Derivatives as Copper-Dependent Anticancer Agents.

Copper (Cu) plays a pivotal role in cancer progression by acting as a co-factor that regulates the activity of many enzymes and structural proteins in cancer cells. Therefore, Cu-based complexes have been investigated as novel anticancer metallodrugs and are considered as a complementary strategy for currently used platinum agents with undesirable general toxicity. Due to the high failure rate and increased cost of new drugs, there is a global drive towards the repositioning of known drugs for cancer treatment in recent years. Disulfiram (DSF) is a first-line antialcoholism drug used in clinics for more than 65 yr. In combination with Cu, it has shown great potential as an anticancer drug by targeting a wide range of cancers. The reaction between DSF and Cu ions forms a copper diethyldithiocarbamate complex (Cu(DDC)2 also known as CuET) which is the active, potent anticancer ingredient through inhibition of NF-κB and ubiquitin-proteasome system as well as alteration of the intracellular reactive oxygen species (ROS). Importantly, DSF/Cu inhibits several molecular targets related to drug resistance, stemness, angiogenesis and metastasis and is thus considered as a novel strategy for overcoming tumour recurrence and relapse in patients. Despite its excellent anticancer efficacy, DSF has proven unsuccessful in several cancer clinical trials. This is likely due to the poor stability, rapid metabolism and/or short plasma half-life of the currently used oral version of DSF and the inability to form Cu(DDC)2 at relevant concentrations in tumour tissues. Here, we summarize the scientific rationale, molecular targets, and mechanisms of action of DSF/Cu in cancer cells and the outcomes of oral DSF ± Cu in cancer clinical trials. We will focus on the novel insights on harnessing the immune system and hypoxic microenvironment using DSF/Cu complex and discuss the emerging delivery strategies that can overcome the shortcomings of DSF-based anticancer therapies and provide opportunities for translation of DSF/Cu or its Cu(DDC)2 complex into cancer therapeutics.

Testing the Efficacy of the Synthesis of Iron Antimony Sulfide Powders from Single Source Precursors

The antimony-iron sulfide system in general does not produce alloys below 540 °C from traditional solid-state methods. However, single source precursors have been known to produce unexpected products that arise from kinetically trapped polymorphs. In this paper, we test the efficacy of this approach toward the Fe-Sb-S system. Antimony and iron diethyldithiocarbamate complexes of the form Sb[S2CN(Et2)]3 (1) and Fe[S2CN(Et2)]3 (2) were synthesised, characterised, and used as single-source precursors for the preparation of Sb2S3, FexSy, and mixed iron antimony sulfide Sb2(1−x)Fe2xS3 (0 ≥ x ≥ 1) powders using the solvent-less thermolysis method at different temperatures ranging from 300 to 475 °C. The effect of different mole fractions of the iron precursor was evaluated on morphology, shape, and optical and magnetic properties of Sb2(1−x)Fe2xS3 (0 ≥ x ≥ 1). The obtained powders were characterized by X-ray diffraction (XRD), Raman spectroscopy scanning electron microscopy (SEM), energy dispersive X-ray (EDX) spectroscopy, magnetometer measurement, and UV/vis/NIR spectroscopy. The results demonstrated that the crystalline structure, morphology, and elemental composition of the samples changed with the mole fraction of the precursor. There was significant phase separation between Sb and Fe sulfides noted from EDX spectroscopic mapping, yet an optoelectronic study monitoring the direct band gap energy of antimony sulfide shows that the band gap energy increases as a function of Fe content, which suggests limited alloying is possible from the single source route.

Solvothermal synthesis of Bi2S3 nanoparticles for active photocatalytic and energy storage device applications

High edge energy storage with large life-span stable materials have become the most significant and major requirement in near future. Bismuth sulfide (Bi2S3) nanoparticles (NPs) was effectively synthesized by utilizing bismuth diethyldithiocarbamate (Bi[DTC]3) complex as single-source antecedent. The synthesized Bi2S3 NPs were affirmed by structural, morphological and thermal analysis with various analytical studies. The electrochemical performance of Bi2S3 NPs reveals that, exhibit redox behavior from cyclic voltammetry analysis, the charge–discharge analysis was examined by the galvanostatic chronopotentiometry. Bi2S3 NPs exhibit excellent supercapacitor behavior with value of the specific capacitance 470 Fg−1 at current density 0.5 Ag−1 and the retentivity of 79% after 1000 cycles. The Bi2S3 NPs were further utilized as photocatalytic discoloration of Congo Red (CR) dye in aqueous medium under UV light irradiation. Which shows, excellent catalytic behaviour, up to 98% of CR dye degrade within 150 min and it is exhibit good catalytic stability and reusability.

Solid-state fabrication of CNT-threaded Fe1-S@N-doped carbon composite as high-rate anodes for sodium-ion batteries and hybrid capacitors

Abstract Metal sulfide/carbon composites have emerged as promising sodium-storage anode materials because of their decent theoretical capacities and low cost. Nevertheless, conventional metal sulfide/carbon nanocomposites are generally prepared via wet-chemical methods such as solvothermal routes, which is fussy and hard to scale up for mass production. Herein, we develop a facile solid-state method, in which a Fe1−xS@N-doped carbon composite threaded by CNTs (FS@NC@CNT) is prepared by directly annealing a ball-milled mixture containing iron (III) diethyldithiocarbamate complex and graphitized multi-walled CNTs. Highly dispersed Fe1-xS nanophase in N-doped carbon together with the highly conductive graphitized CNT networks greatly facilitate ion transport and electron transfer and thus promote the conversion reaction kinetics. The FS@NC@CNT composite exhibits competitive reversible capacity (440 mAh g−1 at 0.05 A g−1), excellent rate capacity (330 mAh g−1 at 10 A g−1), and good cyclic stability (86.5% capacity retention after 450 cycles at 7 A g−1). Coupled with Na3(VO0.5PO4) 2F2 @GO cathode, the full sodium-ion battery (SIBs) exhibits a high capacity retention of 98% after 80 cycles at 0.2 A g−1. Inspired by such excellent sodium storage performance in both half and full SIBs, the potential application of the composite in sodium-ion hybrid capacitors (SIHCs) is further studies by coupling with zeolite-templated carbon as a cathode. The SIHC device can maintain 80% capacity after 4500 cycles at 1 A g−1.

Copper(II)-disulfiram loaded melanin-dots for cancer theranostics

Copper(II) diethyldithiocarbamate complex (CuET), the metabolite of disulfiram complexed with copper, is the component responsible for cancer treatment efficacy of disulfiram. But the hydrophobic property of CuET limits its use in vivo, and an appropriate drug delivery system needs to be developed. Ultrasmall melanin nanoparticle (M-Dot) with excellent biosafety and biocompatibility properties has been synthesized in our previous studies. Herein we prepared CuET loaded with M-Dots through hydrophobic interaction, which could enhance the water solubility significantly. After the administration of M-Dots-CuET in mice tumor models, the nanoparticles showed good tumor accumulation as evidenced by the enhanced photoacoustic signal in tumor regions. M-Dots-CuET also displayed excellent tumor inhibition capability, and the tumor growth inhibition value (TGI) was 45.1%. When combined with photothermal therapy, the TGI reached up to 78.6%. In summary, M-Dots-CuET provide a new potential strategy for cancer theranostics.

Dinitrosyl Iron Complexes with Thiol-Containing Ligands Exist in Living Organisms Mainly in the Binuclear Form

The levels of the mononitrosyl iron complex with diethyldithiocarbamate that form in the liver of mice in vivo and in vitro after intraperitoneal injection of binuclear dinitrosyl iron complexes with N-acetyl-L-cysteine or glutathione, S-nitrosoglutathione, sodium nitrite, or the vasodilating drug isosorbide dinitrate (Isoket®) have been assessed by electron paramagnetic resonance (EPR). The levels of the complex in mice that received binuclear dinitrosyl iron complexes with thiol-containing ligands or S-nitrosoglutathione do not change after the treatment of liver preparations with the strong reducing agent dithionite, in contrast to those formed after nitrite or isosorbide dinitrate administration, whose levels sharply increase after the same treatment. It is inferred that in the latter case an EPR-active mononitrosyl iron complex with diethyldithiocarbamate is produced with the absence or presence of dithionite in the reaction of NO formed from nitrite with Fe2+-diethyldithiocarbamate and Fe3+-diethyldithiocarbamate complexes, respectively. In the former case, the mononitrosyl iron complex with diethyldithiocarbamate is produced by transition of iron-mononitrosyl fragments from already present iron-dinitrosyl groups of binuclear dinitrosyl complexes, whose content is three to four times higher than the content of the mononuclear form of these complexes in the tissue. The results we obtained indicate that when dinitrosyl iron complexes with thiol-containing ligands, either introduced into the body or produced with the participation of endogenous NO, appear in animal tissues in vivo, these complexes are presented in these tissues mainly in their diamagnetic, EPR-silent binuclear form.

Synthesis of palladium diethyldithiocarbamate complexes as precursor for the deposition of un-doped and copper sulfide doped thin films by a facile physical vapour deposition technique

Palladium sulfide thin films have been effectively prepared through a physical vapour deposition technique. Metal diethyldithiocarbamate complexes have been synthesized and used as precursors for the deposition of un-doped and copper sulfide doped palladium sulfide thin films. XRD analysis confirmed that the complex deposited pure cubic palladium sulfide films. The incorporation of copper in palladium sulfide changed the lattice parameters of palladium sulfide in thin films. The purity of thin films and copper doping was confirmed by the commencing of new peaks. FTIR analysis also validates the presence of respective metal complexes. UV–vis studies revealed the peak shift from 431−393 nm showing the variance in transmittance and reflectance from 80−69% and 20–35 % with the band gap 1.57 eV–1.64 eV. Study of surface morphology of the films by SEM showed the cauliflower-like structure of metal sulfide particles. The elemental composition of the films by EDX spectroscopy confirmed the presence of respective metal sulfide on the thin film. To the best of our knowledge, these complexes are the first in their class to be used as single source precursors to deposit CuxPd1-xS2 thin films.

ДИНИТРОЗИЛЬНЫЕ КОМПЛЕКСЫ ЖЕЛЕЗА C ТИОЛСОДЕРЖАЩИМИ ЛИГАНДАМИ ПРЕДСТАВЛЕНЫ В ЖИВЫХ ОРГАНИЗМАХ В ОСНОВНОМ ИХ БИЯДЕРНОЙ ФОРМОЙ

The number of mononitrosyl iron complexes with diethyldithiocarbamate, formed in the liver of mice in vivo and in vitro after intraperitoneal injection of binuclear dinitrosyl iron complexes with N-acetyl-L-cysteine or glutathione, S-nitrosoglutathione, sodium nitrite or the vasodilating drug Isoket® was assessed by electron paramagnetic resonance (EPR). The number of the said complexes, in contrast to the complexes, formed after nitrite or Isoket administration, the level of which sharply increased after treatment of liver preparations with a strong reducing agent - dithionite, did not change in the presence of dithionite. It was concluded that, in the first case, EPR-detectable mononitrosyl iron complexes with diethyldithiocarbamate in the absence and presence of dithionite appeared as a result of the reaction of NO formed from nitrite with Fe2+-dieth- yldithiocarbamate and Fe3+-diethyldithiocarbamate complexes, respectively. In the second case, mononitrosyl iron complexes with diethyldithiocarbamate appeared as a result of the transition of iron-mononitosyl fragments from ready-made iron-dinitrosyl groups of binuclear dinitrosyl complexes, which is three to four times higher than the content of the mononuclear form of these complexes in the tissue...