Recent advances in thermal analysis and calorimetry presented at the 2nd Journal of Thermal Analysis and Calorimetry Conference and 7th V4 (Joint Czech–Hungarian–Polish–Slovakian) Thermoanalytical Conference (2019)

Journal of Thermal Analysis and Calorimetry - At present, miniaturization of the devices in order to make them for effective performance, reliability and ease at cost is the primary need of any...     

Ammonium bis(salicylaldehyde thiosemicarbazonato)ferrate(III), a supramolecular material containing low‐spin FeIII

The synthesis and crystal structure (100 K) of the title compound, ammonium bis[salicylaldehyde thiosemicarbazonato(2?)‐κ³O,N¹,S]iron(III), NH₄[Fe(C₈H₇N₃OS)₂], is reported. The asymmetric unit consists of an octahedral [Fe^III(thsa)₂]^? fragment, where thsa^2? is salicylaldehyde thiosemicarbazonate(2?), and an NH₄⁺ cation. Each thsa^2? ligand binds via the thiolate S, the imine N and the phenolate O donor atoms, resulting in an Fe^IIIS₂N₂O₂ chromophore. The ligands are orientated in two perpendicular planes, with the O and S atoms in cis and the N atoms in trans positions. The Fe^III ion is in the low‐spin state at 100 K. The crystal structure belongs to a category I order–disorder (OD) family. It is a polytype of a maximum degree of order (MDO). Fragments of the second MDO polytype lead to systematic twinning by pseudomerohedry.     

Evaluation of the Synthetic Scope and the Reaction Pathways of Proton-Coupled Electron Transfer with Redox-Active Guanidines in C−H Activation Processes

Proton-coupled electron transfer (PCET) is currently intensively studied because of its importance in synthetic chemistry and biology. In recent years it was shown that redox-active guanidines are capable PCET reagents for the selective oxidation of organic molecules. In this work, the scope of their PCET reactivity regarding reactions that involve C−H activation is explored and kinetic studies carried out to disclose the reaction mechanisms. Organic molecules with potential up to 1.2 V vs. ferrocenium/ferrocene are efficiently oxidized. Reactions are initiated by electron transfer, followed by slow proton transfer from an electron-transfer equilibrium.     

Tris-{hydridotris(1-pyrazolyl)borato}actinide Complexes: Synthesis,Spectroscopy, Crystal Structure,Bonding Properties and Magnetic Behaviour

The isostructural compounds of the trivalent actinides uranium, neptunium, plutonium, americium, and curium with the hydridotris(1-pyrazolyl)borato (Tp) ligand An[η³-HB(N₂C₃H₃)₃]₃ (AnTp₃) have been obtained through several synthetic routes. Structural, spectroscopic (absorption, infrared, laser fluorescence) and magnetic characterisation of the compounds were performed in combination with crystal field, density functional theory (DFT) and relativistic multiconfigurational calculations. The covalent bonding interactions were analysed in terms of the natural bond orbital (NBO) and quantum theory of atoms in molecules (QTAIM) models.     

Determination of binding constants of multiple charged cyclodextrin complexes by ACE using uncorrected and ionic strength corrected actual mobilities of the species involved

In this study, the apparent binding constants and limiting mobilities of the multiply charged complexes of the Δ− and Λ−enantiomers of Ru(II)- and Fe(II)-polypyridyl associates ([Ru(2,2′-bipyridine)₃]²⁺, [Ru(1,10-phenanthroline)₃]²⁺, and [Fe(1,10-phenanthroline)₃]²⁺) with single-isomer 2,3-diacetylated-6-sulfated-cyclodextrins (CDs) (12Ac-6S-α-CD, 14Ac-7S-β-CD, and 16Ac-8S-γ-CD) were determined by ACE using uncorrected and ionic strength corrected actual mobilities of the species involved. Two limiting models were tested for the ionic strength correction of the actual mobilities based on an empirical relation for the ionic strength correction of multivalent ionic species. In model 1, the nominal values of the charge numbers (z_S,nom) and analytical concentrations (c_S,nom) of the above CD selectors in the BGEs were applied for calculation of the BGE ionic strength, as usual. In model 2, the CD selectors were considered as singly charged species (z_S = −1) with |z_S,nom|-times higher concentrations in the BGE than their analytical concentrations (c_S = |z_S,nom| × c_S,nom) in the calculation of the BGE ionic strength. In all three cases–with uncorrected actual mobilities as well as with actual mobilities corrected according to the two limiting models–the measured effective mobilities of the above enantiomers fit well the theoretical curves of their mobility dependences on the CD selectors concentrations in the BGE, with high average coefficients of determination (R² = 0.9890–0.9995). Nevertheless, the best physico-chemically meaningful values of the apparent binding constants and the limiting mobilities of the enantiomer-CDs complexes with low RSDs were obtained using the actual mobilities of the species involved corrected according to model 2.     

FtsZ Reorganization Facilitates Deformation of Giant Vesicles in Microfluidic Traps**

The geometry of reaction compartments can affect the local outcome of interface-restricted reactions. Giant unilamellar vesicles (GUVs) are commonly used to generate cell-sized, membrane-bound reaction compartments, which are, however, always spherical. Herein, we report the development of a microfluidic chip to trap and reversibly deform GUVs into cigar-like shapes. When trapping and elongating GUVs that contain the primary protein of the bacterial Z ring, FtsZ, we find that membrane-bound FtsZ filaments align preferentially with the short GUV axis. When GUVs are released from this confinement and membrane tension is relaxed, FtsZ reorganizes reversibly from filaments into dynamic rings that stabilize membrane protrusions; a process that allows reversible GUV deformation. We conclude that microfluidic traps are useful for manipulating both geometry and tension of GUVs, and for investigating how both affect the outcome of spatially-sensitive reactions inside them, such as that of protein self-organization.     

Versatile Inclusion Behaviour of a Dinitrocalix[4]arene Having Two Ester Pendants – Preparation and X-ray Crystal Structures of Complexes

An upper-rim dinitro-substituted calix[4]arene possessing two lower-rim ethyl ester pendant groups (1) has been shown to form solid inclusion compounds with acetone (1:1) (1a), DMF (1:1) (1b), DMSO (1:1) (1c) and n-BuOH (2:1) (1d). X-ray crystal structures of the four complexes 1a–d are reported and comparatively discussed, including isostructurality calculations. Although the solid-state conformation of the dinitrocalix[4]arene moiety, stabilized by two intramolecular O–H…O bonds, is maintained in the four inclusion compounds, and all four co-crystals have similar unit cell dimensions and identical space group symmetries, only three of them (1a–c) are homostructural. Depending on the nature of the guest molecule, either the upper or the lower rim site of the calixarene is involved in the complexation, demonstrating either cavitate- or clathrate-type of supramolecular interactions, respectively. Moreover, due to the different guest recognition modes, the calixarene host in 1d is rotated through a non-crystallographic virtual rotation of 180° within the unit cell, in relation to the host molecules in each of the other three homostructural compounds 1a–c, thus giving rise to supramolecular morphotropism – to our knowledge the first case ever described.     

Anatase–rutile transformation at the synthesis of rutile pigments (Ti,Cr,Nb)O2 and their color properties

Synthesis of rutile pigments is based on solid state reaction and on Hedvall effect, i.e., phase transformation from anatase to rutile. Therefore, it is important to know the thermal behavior of these compounds (the temperature of this change). The goal was to prepare rutile pigments of type Ti_1?3xCr_xNb_2xO_2+x/2 by conventional solid state method from titanium dioxide TiO₂ (AV-01, anatase), to determine an influence of composition (x = 0, 0.05, 0.10, 0.20, 0.30, 0.50) and calcination temperature (850; 900; 950; 1,000; 1,050; 1,100; 1,150 °C) on color properties of these compounds and to analyze other starting compounds of titanium (hydrated anatase paste TiO₂·nH₂O, titanyl sulfate dihydrate TiOSO₄·2H₂O (VKR 611), hydrated sodium titanium oxide paste Na₂Ti₄O₉·nH₂O) and their reaction mixtures for x = 0.05 by simultaneous TG–DTA analysis. According to the highest chroma C of color, the optimal conditions for synthesis of these pigments are concentration x = 0.05 and calcination temperature 1,050 °C and higher. It was observed that initial temperature 760–830 °C is needful for a formation of rutile structure. This temperature is the lowest for hydrated Na₂Ti₄O₉ paste (760 °C) and similar for other starting compounds of titanium.     

Experimental study of Fe–C–O based system below 1000 °C

The paper deals with the study of phase transformation temperatures of Fe (Fe–C–O) based metallic alloys. Six model alloys with graded carbon and oxygen content were used for experimental investigation. Low-temperature region (<1000 °C) was the investigated area. Phase transformation temperatures were obtained using Differential thermal analysis and Setaram Setsys 18_TM laboratory system. Controlled heating was conducted at the rates of 2, 4, 7, 10, 15, 20 °C min^?1. Region of eutectoid transformation (Fe_α(C) + Fe₃C → Fe_γ(C)), alpha–gamma (Fe_α(C) → Fe_γ(C)) and transformation Fe_α(O) + Fe_0.92O → Fe_γ(O) + Fe_0.92O was studied. New original data (phase transformation temperatures) were obtained in this study. The relationship between shift of phase transformation temperatures and chemical composition (mainly carbon and oxygen content) is investigated in this paper. To achieve good approximation to the equilibrium conditions, the extrapolation of the obtained phase transformation temperatures to the zero heating rate was performed. The influence of experimental conditions (heating rate) on temperatures of phase transformations was studied as well. Comparison of the obtained experimental data with the data presented in the accessible literature and IDS calculations (Solidification Analysis Package) was carried out. It follows from literature search that there is a lack of thermo-physical and thermo-dynamical data on Fe–C–O system.