BIS(CYCLO-HEXAMETHYLENEDITHIOCARBAMATO)GOLD(III) HYDRODINITRATE: PREPARATION, SUPRAMOLECULAR SELF-ASSEMBLY OF A THREE-DIMENSIONAL PSEUDO-POLYMERIC ARCHITECTURE AND THERMAL BEHAVIOR

Investigation on caloric requirement of biomass pyrolysis using TG–DSC analyzer

Vibrational and thermal characterization of Nafion ® membranes substituted by alkaline earth cations

Thermal analysis techniques play a key role to determine and characterize solid phase thermal decomposition. In this sense, Simultaneous Thermal Analysis (STA, i.e. TGA and DSC tests carried out simultaneously) are widely employed, since it provides information about how mass is lost and energy released while the temperature of the sample increases. Fire computer models combined with methods numerical methods are widely used to represent the results from tests and to achieve the values of the kinetic and thermal parameters.Previous works looked forward achieving those parameters using, as unique optimization target, the mass loss curve (TGA) or its derivative (DTGA). As the study of heat release rate is a decisive element to characterize the material properly, most recent works were adding additional measures. These extra measurements concern the heat transfer and the energy required or released during temperature programmed heating, such as heat rate release, heat of gasification, or the surface temperatures of the samples. The information about the energy is provided by the Differential Scanning Calorimetry curve (DSC).Despite of the employment of the information provided by the DSC, this information usually is not used as a target to approach the DSC simulated curve to the experimental one as TGA does. Based on the lack of use of the DSC curve as numerical approaching process to set the kinetic properties, we decide to explore the possibility of adding this as a new target in the process. Therefore, kinetic and thermal properties might be achieved fitting experimental and simulated curves simultaneously, which should allow us to take into account the decomposition process and their energy released.Results obtained in the present work reveal the major challenge of getting a set of parameters, which can fit DSC curve. The level of accuracy reached when only TGA is utilized as target to approach is higher than the level of accuracy of DSC curve. This fact makes increase the value of the errors when both curves are used as targets to approach. In other words, an approach to both curves simultaneously cannot be directly made. With this consideration in mind, this paper proposes an alternative methodology in order to fit TGA curve considering the optimization of the DSC curve.The methodology proposed in the present work is applied to the analysis of poly(methyl methacrylate) (PMMA).

For freshly precipitated zinc complex with cyclic morpholinedithiocarbamate (MfDtc) ligand, the ability to extract gold(III) from solutions in 2 M HCl was studied. The hydrated ionic type polymeric complexes, ([Au{S2CN(CH2)4O}2]2[ZnCl4] · 2H2O) n (I) and ([Au{S2CN(CH2)4O}2]Cl · 2H2O) n (II), were preparatively isolated as individual gold-binding forms. The molecular and supramolecular structures of compounds I and II were established from single-crystal X-ray diffraction data; the thermal behavior was studied by simultaneous thermal analysis (STA). The structures of both compounds contain polymeric chains formed by the complex cations [Au{S2CN(CH2)4O}2]+ through secondary non-valence Au⋯S bonds. The anionic part of the complexes is presented by structurally disordered tetrahedral [ZnCl4]2− ions (in I) and polymeric chains involving water molecules and Cl− anions (in II). The multistage thermal decomposition process comprises dehydration of the complexes, thermolysis of the cationic and anionic moieties with gold(III) reduction to the metal, release of zinc chloride, and partial formation of ZnS.

The capability of silver(I) cyclo-hexamethylenedithiocarbamate to concentrate gold(III) from solutions characterized by a high level of salinity (5.15 M NaCl) into the solid phase has been established. The double chloroform-solvated Au(III)–Ag(I) complex [Au{S2CN(CH2)6}2]2[AgCl2]Cl·2CHCl3 (I) was preparatively isolated as an individual form of binding of [AuCl4]– anions. The composition of the ionic structural units of compound I indicates that gold(III) binding from a solution to the solid phase is accompanied by the complete redistribution of the HmDtc ligands between the coordination spheres of Ag(I) and Au(III). Complex I characterized by IR spectroscopy, simultaneous thermal analysis, and X-ray structure analysis (CIF file CCDC no. 2051654) exhibits the supramolecular structure containing two oppositely charged pseudo-polymeric subsystems. Complex cations [Au{S2CN(CH2)6}2]+ and anions [AgCl2]– (in a ratio of 2 : 1) form a complicatedly organized cation-anionic pseudo-polymeric ribbon ({[Au(HmDtc)2]⋅⋅⋅[AgCl2]⋅⋅⋅[Au(HmDtc)2]}+)n due to secondary interactions Ag⋅⋅⋅S (3.2613 Å) and Au⋅⋅⋅Cl (3.2765 Å). The pseudo-polymeric ribbon consists of two rows of cations and a row of anions. The outer-sphere chloride ions combine the solvate chloroform molecules by two equivalent hydrogen bonds Cl⋅⋅⋅H–C yielding anion-molecular triads [Cl3CH⋅⋅⋅Cl⋅⋅⋅HCCl3]–, which are involved in the formation of the supramolecular ribbon due to the secondary Cl⋅⋅⋅Cl interactions (3.4058 Å) between the nonequivalent chlorine atoms of the nearest solvate molecules. The study of the thermal behavior of complex I makes it possible to determine the character of thermolysis and conditions for the quantitative regeneration of bound gold.

A fixation mode of gold from solutions using heterogeneous reaction of cadmium dicyclohexyl dithiophosphate with H[AuCl4]. Structural and (13C, 31P) CP/MAS NMR studies and thermal behaviour of crystalline polymeric gold(I) dicyclohexyl dithiophosphate and bis(dicyclohexylthiophosphoryl) disulphide

The surface of Fe3O4 nanoparticles is very reactive and can oxidize to γ-Fe2O3 (maghemite) and α-Fe2O3 (hematite) structures. Based on this, the oxidation process of Fe3O4 nanoparticles must be prevented, and one of the strategies is surface functionalization with organic or inorganic molecules. Thus, this study analyzed the thermal behavior of Fe3O4 and Fe3O4-EDTA nanoparticles using X-ray diffraction (XRD), simultaneous thermogravimetry-differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC). Results showed that γ- Fe2O3 was obtained as an intermediate in Fe3O4 and Fe3O4-EDTA decomposition, as confirmed by TG-DTA and DSC curves. Moreover, Fe3O4-EDTA exhibited a temperature peak (Tp = 573.5°C) of phase transformation (γ-Fe2O3 → α-Fe2O3) higher than that of Fe3O4 (Tp = 533.0°C), confirming that EDTA molecules stabilized the nanoparticles efficiently. The kinetic behavior of samples changed, and the activation energy for functionalized samples decreased.

Double pseudo-polymeric complexes of [Au(S2CNBu2)2][AgCl2] and [Au(S2CNHm)2]3[AgCl2][Ag0.59Au0.41Cl2]2: Preparation, supramolecular self-assembly, thermal behaviour and anti-mycobacterial activity

Two structural types of dithiocarbamato-chlorido complexes of mercury(II): Preparation, supramolecular self-assembly, solid-state 13C and 15N NMR characterisation and thermal behaviour of pseudo-polymeric compounds of [Hg2(S2CNBu2)2Cl2] and [Hg4(S2CNiBu2)6][Hg2Cl6

Gold-based compounds are of great interest in the field of medicinal chemistry as novel therapeutic (anticancer) agents due to their peculiar reactivity and mechanisms of action with respect to organic drugs. Despite their promising pharmacological properties, the possible toxic effects of gold compounds need to be carefully evaluated in order to optimize their design and applicability. This study reports on the potential toxicity of three experimental gold-based anticancer compounds featuring lansoprazole ligands (1-3) studied in an ex vivo model, using rat precision cut kidney and liver slices (PCKS and PCLS, respectively). The results showed a different toxicity profile for the tested compounds, with the neutral complex 2 being the least toxic, even less toxic than cisplatin, followed by the cationic complex 1. The dinuclear cationic gold complex 3 was the most toxic in both liver and kidney slices. This result correlated with the metal uptake of the different compounds assessed by ICP-MS, where complex 3 showed the highest accumulation of gold in liver and kidney slices. Interestingly compound 1 showed the highest selectivity towards cancer cells compared to the healthy tissues. Histomorphology evaluation showed a similar pattern for all three Au(i) complexes, where the distal tubular cells suffered the most extensive damage, in contrast to the damage in the proximal tubules induced by cisplatin. The binding of representative gold compounds with the model ubiquitin was also studied by ESI-MS, showing that after 24 h incubation only 'naked' Au ions were bound to the protein following ligands' loss. The mRNA expression of stress response genes appeared to be similar for both evaluated organs, suggesting oxidative stress as the possible mechanism of toxicity. The obtained results open new perspectives towards the design and testing of bifunctional gold complexes with chemotherapeutic applications.

A typical solid propellant gas generator upon ignition will generate gas-phase combustion products and particulates that leave the generator through an exhaust line. The combustion products are at high pressure and temperature that can be tapped from the gas chamber to control the actuator system. This paper aims to investigate the Ammonium Nitrate (AN)-based gas generator propellants which are most suitable for low flame temperature and chlorine-free combustion products. Ammonium Nitrate is useful for slower burning rate and low flame temperature. Hydroxyl Terminated Polybutadiene (HTPB) was used as a binder and fuel, added to the oxidizer (AN). The ignitability of the propellants is increased by adding certain additives such as Ammonium Dichromate (ADC) and Guanidine Nitrate (GN) in the propellants, which have been studied. Five different propellant compositions were made and analyzed the effect of ammonium dichromate on propellants. Adiabatic flame temperature for the compositions has been determined by using C PROP-SHELL and it was obtained for a constant chamber pressure of 40 bar. For thermal analysis, STA (Simultaneous Thermal Analysis) was used to determine decomposition temperature from the DSC curve and mass loss from the TG curve. Each sample was heated from 30 °C to 600 °C at a heating rate of 27 K/min, and initial decomposition temperature and exothermic peak values were found. The change in mass of a sample with respect to temperature and time in the controlled atmosphere was measured by TGA. The influence of ADC and GN on the decomposition and thermal behavior of propellants has been investigated through this work.KeywordsHydroxyl Terminated Polybutadiene (HTPB)Ammonium Nitrate (AN)Ammonium Dichromate (ADC)Guanidine Nitrate (GN)Toluene Diisocyanate (TDI)Dioctyladipate (DOA)Differential Scanning calorimetry (DSC)Thermogravimetric Analysis (TGA)

Reliable interpretation of the changes occurring in the samples during their heating is ensured by using more than one measurement technique. This is related to the necessity of eliminating the uncertainty resulting from the interpretation of data obtained by two or more single techniques based on the study of several samples analyzed at different times. Accordingly, the purpose of this paper is to briefly characterize thermal analysis techniques coupled to non-thermal techniques, most often spectroscopic or chromatographic. The design of coupled thermogravimetry (TG) with Fourier transform infrared spectroscopy (FTIR), TG with mass spectrometry (MS) and TG with gas chromatography/mass spectrometry (GC/MS) systems and the principles of measurement are discussed. Using medicinal substances as examples, the key importance of coupled techniques in pharmaceutical technology is pointed out. They make it possible not only to know precisely the behavior of medicinal substances during heating and to identify volatile degradation products, but also to determine the mechanism of thermal decomposition. The data obtained make it possible to predict the behavior of medicinal substances during the manufacture of pharmaceutical preparations and determine their shelf life and storage conditions. Additionally, characterized are design solutions that support the interpretation of differential scanning calorimetry (DSC) curves based on observation of the samples during heating or based on simultaneous registration of FTIR spectra and X-ray diffractograms (XRD). This is important because DSC is an inherently non-specific technique. For this reason, individual phase transitions cannot be distinguished from each other based on DSC curves, and supporting techniques are required to interpret them correctly.

Thermogravimetry (TG), differential scanning calorimetry (DSC), polarized light thermal microscopy (PLTM), as well as X-ray powder diffraction (XRD) and Fourier transformed infrared spectroscopy (FTIR) were used to study the thermal behavior and the chemical structure of cimetidine, famotidine, ranitidine-HCl, and nizatidine. The TG–DSC curves show that the famotidine and ranitidine-HCl suffer decomposition during melting and they are thermally less stable in comparison with cimetidine and nizatidine, the latter being the most stable of all the drugs studied in this study. The DSC curves of famotidine and ranitidine-HCl show exothermic peaks immediately after the melting, confirming the occurrence of thermal decomposition. The DSC curves also show that the cimetidine and nizatidine have some thermal stability after melting. The thermal events shown in the PLTM images are consistent with the results shown in the TG–DSC and DSC curves. The XRD patterns show that the cimetidine and famotidine are less crystalline compared with ranitidine-HCl and nizatidine. The theoretical FTIR bands are in agreement with those obtained experimentally, and in some cases, no difference is observed between the theoretical and experimental values, even being identical in one of the cases.

Perchloratobis(pentafluorophenyl)triphenylphosphinegold(III) as a precursor of new gold complexes

Manganese ferrite nanopowder was prepared by a new solvothermal method, using 1,2 propanediol as solvent and KOH as precipitant. The as-synthesized powder, by solvothermal treatment in autoclave at 195 °C, for 12 h, consisted of fine manganese ferrite nanoparticles. The further thermal treatment of the initial manganese ferrite powder to higher temperature resulted in manganese ferrite decomposition due to Mn(II) oxidation to Mn(III), as observed by X-ray diffraction. FT-IR spectroscopy has evidenced that the oxidation takes place even at 400 °C. The oxidation of Mn(II) to Mn(III) was studied by TG/DSC simultaneous thermal analysis. It was shown that Mn(II) oxidation takes place in a very small extent up to 400 °C. The main oxidation step occurs around 600 °C, when a clear mass gain is registered on TG curve, associated with a sharp exothermic effect on DSC curve. The exothermic effect is smaller in case of the powder annealed at 400 °C, confirming the superficial oxidation of Mn(II) up to 400 °C. In order to avoid Mn(II) oxidation, the powder obtained at 400 °C was further annealed at 800 °C in argon atmosphere, without degassing, when manganese ferrite MnFe2O4 was obtained as major crystalline phase (69 %). All manganese ferrite powders showed a superparamagnetic behavior, with maximum magnetization of 51 emu g−1 in case of the as-synthesized powder, characteristic of magnetic ferrite nanopowders.