Etude thermocinetique des phenomenes de dissolution par calorimetrie Calvet a haute temperature dissolution d'alumines dans la cryolithe

Although the thermal curves given by a Calvet calorimeter can be considered representative of the thermogenesis of slow phenomena, this is not the case for the brief thermal effects of dissolution, for example, which need typically no more than twenty minutes. At high temperatures, a numerical method of deconvolution of the recorded signal was applied in order to obtain the proper thermogenesis of the phenomenon. The time constants of the calorimeter were determined from thermal effects due to the dropping into the bath of small quantities of silver and platinum. The method was applied to the dissolution of a-alumina and industrial aluminas in cryolithic baths at 1290 K. The different kinds of alumina could be classified according to their time of dissolution. The dependence of the alumina concentration of the bath on the dissolution rate was also investigated.

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Zusammenfassung Die mittels eines Calvet-Kalorimeters erhaltenen thermischen Kurven sind zwar repräsentativ für langsame Phänomene der Thermogenese, nicht jedoch für kurzzeitige thermische Effekte wie z. B. ein Inlösunggehen, das im allgemeinen nicht mehr als 20 Minuten dauert. In solchen Fällen wurde für hohe Temperaturen eine numerische Methode zur Zerlegung des registrierten Signals angewandt, um die reine Thermogenese der Phänomens zu erhalten. Zeitkonstanten des Kalorimeters wurden aus den thermischen Effekten bestimmt, die beim Einwerfen kleiner Silber- und Platinmengen in das Bad auftraten. Die Methode wurde zur Untersuchung der Auflösung von -Aluminiumoxid und industriellen Aluminiumoxidproben in Kryolithbädern bei 1290 K herangezogen. Die verschiedenen Aluminiumoxidarten konnten nach der zur Auflösung notwendigen Zeit klassifiziert werden. Die Abhängigkeit der Auflösungsgeschwindigkeit von der Aluminiumoxidkonzentration des Bades wurde ebenfalls untersucht.

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Aging of a medical device surface following cold plasma treatment: Influence of low molecular weight compounds on surface recovery

The surface of medical devices is of great importance for biocompatibility. Surface properties can evolve with a material treatment, time, and storage conditions. In this work, poly(urethane) catheters sterilised by cold nitrogen plasma treatment, were subjected to air and temperature aging in order to evaluate the influence of humidity and temperature on surface recovery. The surface of catheters was analysed by contact angle measurements and XPS. Faster surface changes upon aging were observed at high temperature (45 °C) and relative humidity (90%). For the commercial poly(urethane) catheters analysed in this work, the importance of the nature and polymorphism of additives added to the polymer (lubricant, antioxidant) in the recovery process was demonstrated. Indeed, DSC and TSC showed that additive transitions (relaxation, melting…) could govern the aging process.     

Structural and physico-chemical studies on modification of polypropylene and its polyphenolic antioxidant by electron beam irradiation

As polypropylene (PP) is widely used in medical and pharmaceutical fields, the effect of sterilization on both the polymer and its additives must be taken into account. In this study, PP and its antioxidants Irganox 1010 and 1076 were electron beam irradiated in order to evaluate by Fourier transform infrared spectroscopy, differential scanning calorimetry and size exclusion chromatography, their structural and physico-chemical modifications. A good correlation between those analytical techniques has indicated the formation of oxidation products, chain scissions as well as crosslinking. The effect of the absorbed dose is underlined.     

Liquid chromatography with tandem mass spectrometry for the simultaneous identification and quantification of cardiovascular drugs applied to the detection of substandard and falsified drugs

The counterfeiting of pharmaceuticals has been detected since about 1990 and has alarmingly continued to pick up steam. We have been recently involved in an evaluation program of some of the most commonly prescribed cardiovascular drugs in Africa, for analysing an important number of tablets or capsules obtained from different places in seven African countries. A reversed‐phase high‐performance liquid chromatography with tandem mass spectrometry method was developed and validated to simultaneously control the identity and the quantity of acenocoumarol, amlodipine, atenolol, captopril, furosemide, hydrochlorothiazide and simvastatin in tablets. Their separation was performed on a Kinetex® C₁₈ (100 mm × 2.1 mm inside diameter, 2.6 μm) column using a gradient elution of 20 mM ammonium formate buffer and acetonitrile (90:10 10:90 v/v) at a flow rate of 0.5 mL/min. The analytes were detected using electrospray ionisation tandem mass spectrometry in both positive and negative modes with multiple reaction monitoring. Tandem mass spectrometry fragmentation patterns of captopril, furosemide and acenocoumarol, up to now not detailed in the literature, were also studied to assist in the selection of the most relevant transitions towards the objectives. The developed method was validated as per International Conference on Harmonisation guidelines with respect to specificity, linearity, trueness, precision, limits of detection and quantification. It has been successfully applied to the control of oral forms of seven cardiovascular drugs collected in African countries.     

SEC with UV and ELSD detection for analysis of gamma-irradiated PS-radiation-grafted P(VDF/HFP) films

Summary Thin poly(vinylidene fluoride/hexafluoropropylene) (P(VDF/HFP)) films ahve been irradiated with gammarays to induce the initiation of styrene grafting by the indirect method. To obtain a better understanding of the radiation-grafting process we have used size exclusion chromatography (SEC) to study the effect of irradiation of this polymer and the evolution of the molecular weights of the polystyrene (PS) grafted chains as a function of the grafting time. Pristine, irradiated and PS radiation-grafted samples have been compared. We present evidence that the gamma irradiation induces both scission and crosslinking of the P(VDF/HFP) chains. We show that the average molecular weights of the PS grafted chains increase with grafting time and that the asymmetry of the chromatographic peak increases also. These grafted chains have molecular weights much higher than those of pristine P(VDF/HFP) and they cannot be confused with PS homopolymer chains, which have higher molecular weights as both, pristine and radiation-grafted P (VDF/HFP). Reversed-phase high-performance liquid chromatography (RPHPLC) has shown the absence of additives in pristine P(VDF/HFP) and has provided evidence of the presence of oligomers.     

Synthesis and characterization of Ni (II), Cu (II), Fe (II) and Fe3O4 nanoparticle complexes with tetraaza macrocyclic Schiff base ligand for antimicrobial activity and cytotoxic activity against cancer and normal cells

This work describes a simple synthesis of complexes of the type [M(C₃₂H₂₈N₄)Cl₂], where M = Ni (II), Cu (II) and Fe (II) and a novel complex of magnetite nanoparticle (Fe₃O₄NP) inside (INS) tetraaza macrocyclic Schiff base ligand (C₃₂H₂₈N₄): [Fe₃O₄NP‐INS‐(C₃₂H₂₈N₄)], which was prepared by using a novel co‐precipitation method of coordinated ferric ion (Fe³⁺) in the complex [Fe(C₃₂H₂₈N₄)Cl₂] under mild conditions. The synthesized compounds were characterized and compared with a various physic‐chemical techniques like: Fourier transform infrared (FT‐IR), ultraviolet–visible spectroscopic techniques (UV–Vis), 1‐dimensional (1D) ¹H‐NMR, ¹³C‐NMR spectroscopic techniques, mass spectra, Powder X‐ray diffraction (PXRD), Vibrating sample magnetometer (VSM), Scanning electron microscopy (SEM), elemental analysis and molar conductance measurements. Furthermore, the highest saturation magnetization was 26.56 emu.g^?1 obtained from [Fe₃O₄NP‐INS‐(C₃₂H₂₈N₄)] (diameter of Fe₃O₄NPs~20.87 nm) that prove easy separation by an external magnetic field. In vitro screening of all the compounds against different species of bacteria and fungi shows that [Fe₃O₄NP‐INS‐(C₃₂H₂₈N₄)] is effective against the tested strains as compared to the tetraaza macrocyclic ligand and selected complexes. The cytotoxic activity of the all compounds was also examined in 3 human tumor cell lines as U87, MDA‐MB‐231 and LS‐174. The complex [Fe₃O₄NP‐INS‐(C₃₂H₂₈N₄)] shows moderate and strong cytotoxic activity against brain cancer, colon cancer and breast cancer (U87, MDA‐MB‐231 and LS‐174 respectively), without showing cytotoxicity towards peripheral blood mononucleocyte (PBMC) cells.     

The A1−xUNbO6−x/2 compounds (x=0, A=Li, Na, K, Cs and x=0.5, A=Rb, Cs): from layered to tunneled structure

Attempts to prepare alkaline metal uranyl niobates of composition A_1−xUNbO_6−x/2 by high-temperature solid-state reactions of A₂CO₃, U₃O₈ and Nb₂O₅ led to pure compounds for x=0 and A=Li (1), Na (2), K (3), Cs (4) and for x=0.5 and A=Rb (5), Cs (6). Single crystals were grown for 1, 3, 4, 5, 6 and for the mixed Na_0.92Cs_0.08UNbO₆ (7) compound. Crystallographic data: 1, monoclinic, P2₁/c, a=10.3091(11), b=6.4414(10), c=7.5602(5) Å, β=100.65(1), Z=4, R₁=0.054 (wR₂=0.107); 3, 5 and 7 orthorhombic, Pnma, Z=8, with a=10.307(2), 10.272(4) and 10.432(3) Å, b=7.588(1), 7.628(3) and 7.681(2) Å, c=13.403(2), 13.451(5) and 13.853(4) Å, R₁=0.023, 0.046 and 0.036 (wR₂=0.058, 0.0106 and 0.088) for 3, 5 and 7, respectively; 6, orthorhombic, Cmcm, Z=8, and a=13.952(3), b=10.607(2) Å, c=7.748(2) Å, R₁=0.044 (wR₂=0.117).The crystal structure of 1 is characterized by layers of uranophane sheet anion topology parallel to the (100) plane. These layers are formed by the association by edge-sharing of chains of edge-shared UO₇ pentagonal bipyramids and chains of corner-shared NbO₅ square pyramids alternating along the [010] direction. The Li⁺ ions are located between two consecutive layers and hold them together; the Li⁺ ions and two layers constitute a neutral “sandwich” {(UNbO₆)⁻-(Li)₂²⁺-(UNbO₆)⁻}. In this unusual structure, the neutral sandwiches are stacked one above another with no formal chemical bonds between the neutral sandwiches.The homeotypic compounds 3, 5, 6, 7 have open-framework structures built from the association by edge-sharing in two directions of parallel chains of edge-shared UO₇ pentagonal bipyramids and ribbons of two edge-shared NbO₆ octahedra further linked by corners. In 3, 5 and 7, the mono-dimensional large tunnels created in the [001] direction by this arrangement can be considered as the association by rectangular faces of two columns of triangular face-shared trigonal prisms of uranyl oxygens. In 3 and 7, all the trigonal prisms are occupied by the alkaline metal, in 5, they are half-occupied. In 6, the polyhedral arrangement is more symmetric and the tunnels created in the [010] direction are built of face-sharing cubes of uranyl oxygens totally occupied by the Cs atoms. This last compound well illustrates the structure-directing effect of the conterion.     

Etude calorimetrique de l'enthalpie de dissolution d'alumines industrielles dans des bains cryolithiques

The partial molar enthalpies of dissolution in cryolitic baths of two different industrial aluminas were measured by calorimetry at 1290 K. The influence of the physico-chemical properties of the aluminas and of additions of excess AlF₃ in the bath were examined.The effects of the presence in the solvent of NaF and LiF (F^– donors) and of AlF₃ in excess (F^– acceptor) agree well with the proposed mechanism of dissolution of alumina in cryolite.

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Zusammenfassung Mittels Kalorimetrie wurden die partiellen molaren Lösungsenthalpien bei 1290 K für zwei verschiedene industrielle Tonerden in Kryolith-Bädern bestimmt. Der Einfluß der physikalischen Eigenschaften der Tonerden und des Zusatzes von AlF₃ im Überschluß wurde untersucht. Die durch die Gegenwart von NaF, LiF (F^–-Donoren) bzw. überschüssigem AlF₃ (F^–-Akzeptor) im Bad verursachten Effekte stimmen gut mit dem für die Lösung von Tonerde in Kryolith vorgeschlagenem Mechanismus überein.