Synthesis, characterization and thermal behaviour of solid 4-methoxybenzoates of heavier trivalent lanthanides

Solid-state Ln-4-MeO-Bz compounds, where Ln stands for trivalent Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y and 4-MeO-Bz is 4-methoxybenzoate, have been synthesized. Simultaneous thermogravimetry and differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), X-ray powder diffractometry, infrared spectroscopy and complexometry were used to characterize and to study the thermal behaviour of these compounds. The results led to information about the composition, dehydration, phase transition, coordination mode, structure, thermal behaviour and thermal decomposition of the isolated compounds. The phase transition observed in the some compounds has been reported for the first time. (C) 2006 Elsevier B.V. All rights reserved.

Preparation and thermal behavior of mixture of basic carbonate and 4-dimethylaminocinnamylidenepyruvate with lanthanides (III) and yttrium (III) in the solid state

Solid Ln-OKCO3-DMCP compounds, where Ln represents lanthanides (III) and yttrium (III) ions and DMCP is the anion 4-dimethyiaminocinnamylidenepyruvate, have been prepared. Thermogravimetry, derivative thermogravimetry (TG, DTG), differential scanning calorimetry (DSC), X-ray diffraction powder patterns and elemental analysis have been used to characterize the compounds. The thermal stability as well as the thermal decomposition of these compounds were studied using an alumina crucible in an air atmosphere.

Synthesis, characterisation and thermal behaviour of solid state compounds of 4-methylbenzylidenepyruvate with some bivalent metal ions

Solid state M-4-Me-BP compounds, where M stands for bivalent Mn, Fe, Co, Ni, Cu, Zn, Pb and 4-Me-BP is 4-methylbenzylidenepyruvate, have been synthesized. Simultaneous thermogravimetry-differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), X-ray powder diffractometry, infrared spectroscopy, elemental analysis, and complexometry were used to characterise and to study the thermal behaviour of these compounds. The results led to information about the composition, dehydration, thermal stability and thermal decomposition of the isolated complexes. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Photoluminescence in amorphous PLZ

Amorphous and crystalline powder of PLZ was prepared by using the polymeric precursor method. TGA-DSC (Thermal analysis and Differential Scanning Calorimetry) shows the decomposition of polymeric resin, an amorphous phase and the crystallization of powder. Raman scattering of powder shows an amorphous and semicrystalline phase at 450 and 550 degreesC, respectively. XRD (X-ray diffraction pattern) of powder shows high crystallinity at 700 degreesC/3 h. PL (Photoluminescence) analysis of powder at 300 degreesC/3 h shows a broad asymmetric peak at 585 nm and increases of calcining time led to intense peaks of PL at 300 degreesC/6 h. This emission could be attributed to Zr --> O from the oxygen-2p orbitals to the zirconate-3d orbitals. (C) 2003 Elsevier Ltd and Techna S.r.l. All rights reserved.

Influence of preparation methods and thermal treatment in melt-solidified and cast films of poly(vinylidene fluoride-trifluorethylene) copolymers

This paper is aimed at addressing the differences observed in film properties when poly(vinylidene fluoride-trifluorethylene) P(VDF-TrFE) films are fabricated using distinct methods. Samples were obtained either from casting a solution or by compression molding from a molten phase and characterized by differential scanning calorimetry (DSC). It is shown that the main differences between melt-solidified and cast films arise from the thermal treatment inherent in the former samples.

Structural studies of NaPO3-MoO3 glasses by solid-state nuclear magnetic resonance and raman spectroscopy

Vitreous samples were prepared in the (100 - x)% NaPO3-x% MoO3 (0 <= x <= 70) glass-forming system by a modified melt method that allowed good optical quality samples to be obtained. The structural evolution of the vitreous network was monitored as a function of composition by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FT-IR), Raman scattering, and solid-state nuclear magnetic resonance (NMR) for P-31, Na-23, and Mo-95 nuclei. Addition of MoO3 to the NaPO3 glass melt leads to a pronounced increase in the glass transition temperatures up to x = 45, suggesting a significant increase in network connectivity. For this same composition range, vibrational spectra suggest that the Mo6+ ions are bonded to some nonbridging oxygen atoms (Mo-O- or Mo=O bonded species). Mo-O-Mo bond formation occurs only at MoO3 contents exceeding x = 45. P-31 magic-angle spinning (MAS) NMR spectra, supported by two-dimensional J-resolved spectroscopy, allow a clear distinction between species having two, one, and zero P-O-P linkages. These sites are denoted as Q(2Mo)((2)), Q(1Mo)((2)), and Q(0Mo)((2)), respectively. For x < 0.45, the populations of these sites can be described along the lines of a binary model, according to which each unit of MoO3 converts two Q(nMo)((2)) sites into two Q((n+1)Mo)((2)) sites (n = 0, 1). This structural model is consistent with the presence of tetrahedral Mo(=O)(2)(O-1/2)(2) environments. Indeed, Mo-95 NMR data suggest that the majority of the molybdenum species are four-coordinated. However, the presence of additional six-coordinate molybdenum in the MAS NMR spectra indicates that the structure of these glasses may be more complicated and may additionally involve sharing of network modifier oxide between the network formers phosphorus and molybdenum. This latter hypothesis is further supported by Na-23{P-31} rotational echo double resonance (REDOR) data, which clearly reveal that the magnetic dipole-dipole interactions between P-31 and Na-23 are increasingly diminished with increasing molybdenum content. The partial transfer of modifier from the phosphate to the molybdate network former implies a partial repolymerization of the phosphate species, resulting in the formation of Q(nMo)((3)) species and accounting for the observed increase in the glass transition temperature with increasing MoO3 content that is observed in the composition range 0 <= x <= 45. Glasses with MoO3 contents beyond x = 45 show decreased thermal and crystallization stability. Their structure is characterized by isolated phosphate species [most likely of the P(OMo)(4) type] and molybdenum oxide clusters with a large extent of Mo-O-Mo connectivity.

Thermal Characterization and Cytotoxicity of Complexes Formed by Papain and Cyclodextrin

Papain is a proteolytic enzyme with restricted applications due to its limited stability. Cyclodextrins are widely used in pharmaceutical formulations once they are able to form complexes with other molecules, improving their stability and bioavailability. The purpose of the present paper was to analyze complexes formed by papain/hydroxypropyl-beta-cyclodextrin and papain/beta-cyclodextrin by thermal analysis and cytotoxicity tests to verify their possible interactions and toxicological behavior. Complex solutions were prepared at different molar ratios and collected as a function of time to be lyophilized and analyzed. Results showed changes in endothermic events and cytotoxicity profiles. A complex formation for both complexes is observed; nevertheless, beta-cyclodextrin was able to change the enzyme characteristics more efficiently.

Effects of cardiomyopathic mutations on the biochemical and biophysical properties of the human alpha-tropomyosin

Mutations in the protein alpha-tropomyosin (Tm) can cause a disease known as familial hypertrophic cardiomyopathy. In order to understand how such mutations lead to protein dysfunction, three point mutations were introduced into cDNA encoding the human skeletal tropomyosin, and the recombinant Tms were produced at high levels in the yeast Pichia pastoris. Two mutations (A63V and K70T) were located in the N-terminal region of Tm and one (E180G) was located close to the calcium-dependent troponin T binding domain. The functional and structural properties of the mutant Tms were compared to those of the wild type protein. None of the mutations altered the head-to-tail polymerization, although slightly higher actin binding was observed in the mutant Tm K70T, as demonstrated in a cosedimentation assay. The mutations also did not change the cooperativity of the thin filament activation by increasing the concentrations of Ca2+. However, in the absence of troponin, all mutant Tms were less effective than the wild type in regulating the actomyosin subfragment 1 Mg2+ ATPase activity. Circular dichroism spectroscopy revealed no differences in the secondary structure of the Tms. However, the thermally induced unfolding, as monitored by circular dichroism or differential scanning calorimetry, demonstrated that the mutants were less stable than the wild type. These results indicate that the main effect of the mutations is related to the overall stability of Tm as a whole, and that the mutations have only minor effects on the cooperative interactions among proteins that constitute the thin filament.

Aqueous solution behavior of thermosensitive (N-isopropylacrylamide-acrylic acid-ethyl methacrylate) terpolymers

A series of N-isopropylacrylamide (NIPAM)-acrylic acid-ethyl methacrylate terpolymers with varied monomer compositions was prepared by radical polymerization. The solution behavior of these polymers was studied in dilute aqueous solution using spectrophotometry, fluorescence spectroscopy and high-sensitivity differential scanning calorimetry. The results obtained revealed that the lower critical solution temperatures depend strongly on the copolymer composition, solution pH and ionic strength. At a high pH, the ionization of acrylic acid (AA) units leads to an increase in solution cloud points (T-c). Solutions of polymers containing 10% or less of AA display a constant T-c for pH above 5.5, with 15% there is a continuous increase in T-c with pH and, for higher AA contents, no clouding was observed within the studied temperature range. Fluorescence probe studies were conducted by following the I (1)/I (3) ratio of pyrene vibronic bands and the emission of anilinonaphtalene sulfonic acid, sodium salt (ANS), both approaches revealing the existence of hydrophobic domains for polymers with higher ethyl methacrylate content at temperatures lower than T-c, suggesting some extent of aggregation and/or a coil-to-globule transition. Scanning calorimetry measurements showed an endothermic transition at temperatures agreeing with the previously detected cloud points. Moreover, the transition curves became broader and with a smaller transition enthalpy, as both the AA content and the solution pH were increased. These broader transitions were interpreted to be the result of a wider molecular distribution upon polymer ionization, hence, displaying varied solution properties. The decrease in transition enthalpy was rationalized as a consequence of reminiscent hydration of NIPAM units, even after phase separation, owing to the presence of electric charges along the polymer chain.

Thermal behavior of alpha-(Cu-Al-Ag) alloys

Thermal behavior of alpha-(Cu-Al-Ag) alloys, i.e. alloys with composition less than about 8.5 mass% Al, was studied using differential scanning calorimetry (DSC), differential thermal analysis (DTA), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and X-ray diffractometry (XRD). The results indicated that the presence of silver introduces new thermal events ascribed to the formation of a silver-rich phase and, after addition higher amounts than 8 mass% Ag to the Cu-8 mass% Al alloy it is possible to observe the formation of the gamma(1) phase (Al4Cu9), which is only observed in alloys containing minimum of 9 mass% Al. These results may be attributed to some Ag characteristics and its interaction with Cu and Al.

Antimony oxide based glasses

Glass formation has been investigated in binary systems based on antimony oxide as the main glass former: (100-x)Sb2O3-xWO3, (5 < x < 65), (100 - x)Sb2O3-xSbPO(4), (5 < x < 80) and (100 - x)Sb2O3-x[Sb(PO3)(3)](n), (10 < x < 40). Ternary systems derived from the Sb2O3-WO3 binary glass have also been studied: Sb2O3-WO3-BaF2 Sb2O3-WO3-NaF and Sb2O3-WO3-[Sb(PO3)(3)](n). Glass transition temperature ranges from 280 degreesC to 380 degreesC. It increases as the concentration in tungsten oxide or antimony phosphate increases. Refractive index is larger than 2. Tungsten-containing glasses are yellow in transmission and turn green at the largest WO3 content. Optical transmission and temperatures of glass transition, T-g, onset of the crystallization. T-x, and maximum of crystallization, T-p, have been measured using differential scanning calorimetry (DSC). These glasses have potential photonic applications. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Thermal and photochemical stability of poly(vinyl alcohol)/modified lignin blends

A kraft lignin derivative (KLD) obtained by reaction with p-aminobenzoic acid/phthalic anhydride was blended with poly(vinyl alcohol) (PVA) by solution casting from DMSO. PVA and PVA/KLD films were exposed to ultraviolet radiation (24, 48, and 96 h) and analyzed by thermogravimetry (TG), differential scanning calorimetry (DSC), infrared spectroscopy (FTIR), hydrogen nuclear magnetic resonance (H-1 NMR) spectroscopy, and scanning electron microscopy (SEM). PVA films show a loss of thermal stability due to irradiation. PVA/KLD reveals greater thermal stability than PVA and an increase in thermal stability after irradiation. These results suggest that the incorporation of KLD into PVA provides a gain in thermal and photochemical stability. FTIR, H-1 NMR, DSC, and TG results obtained for the blends suggest that intermolecular interactions between PVA and KLD chains are present. SEM micrographs revealed blend miscibility for a KLD blend content of up to 15 wt%, as observed at magnification of 1000 times. (c) 2005 Elsevier Ltd. All rights reserved.

Sufentanil-2-hydroxypropyl-beta-cyclodextrin inclusion complex for pain treatment: Physicochemical, cytotoxicity, and pharmacological evaluation

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Effect of Ag concentration on the thermal behavior of the Cu-10 mass% Al and Cu-11 mass% Al alloys

In this work the effect of Ag concentration on the thermal behavior of the Cu-10 mass% Al and Cu-11 mass% Al alloys with additions of 4, 6, 8 and 10 mass% Ag was studied using differential scanning calorimetry (DSC), in situ X-ray diffractometry (XRD) and scanning electron microscopy (SEM). The results showed that for the Cu-10 mass% Al alloy Ag addition induce the beta'(1) phase formation and for the Cu-11 mass% Al alloy these additions increase the amount of martensite formed on quenching and decrease the stability range of this phase on heating.

Thermal behavior of the Cu-22.55 at.%Al alloy with small Ag additions

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)