Thermal Phase Behavior of DMPG Bilayers in Aqueous Dispersions as Revealed by (2)H- and (31)P-NMR

The synthetic lipid 1,2-dimyristoyl-sn-3-phosphoglycerol (DMPG), when dispersed in water/NaCl exhibits a complex phase behavior caused by its almost unlimited swelling in excess water. Using deuterium ((2)H)- and phosphorus ((31)P)-NMR we have studied the molecular properties of DMPG/water/NaCl dispersions as a function of lipid and NaCl concentration. We have measured the order profile of the hydrophobic part of the lipid bilayer with deuterated DMPG while the orientation of the phosphoglycerol headgroup was deduced from the (31)P NMR chemical shielding anisotropy. At temperatures > 30 degrees C we observe well-resolved (2)H- and (31)P NMR spectra not much different from other liquid crystalline bilayers. From the order profiles it is possible to deduce the average length of the flexible fatty acyl chain. Unusual spectra are obtained in the temperature interval of 20-25 degrees C, indicating one or several phase transitions. The most dramatic changes are seen at low lipid concentration and low ionic strength. Under these conditions and at 25 degrees C, the phosphoglycerol headgroup rotates into the hydrocarbon layer and the hydrocarbon chains show larger flexing motions than at higher temperatures. The orientation of the phosphoglycerol headgroup depends on the bilayer surface charge and correlates with the degree of dissociation of DMPG-Na(+). The larger the negative surface charge, the more the headgroup rotates toward the nonpolar region.

Structure and thermal reactivity of Zn(II) salts of isocinchomeronic acid (2,5-pyridinedicarboxylic acid)

The synthesis, an improved refined crystal and molecular structure re-determination, and the thermal decomposition behavior of two Zn(II) derivatives of isocinchomeronic acid (2,5-pyridinedicarboxylic acid or H(2)2,5-pydc) are presented. [Zn(2,5-pydc)(H(2)O)(3)Zn(2,5-pydc)(H(2)O)(2)](2) (1) crystallizes in the triclinic P-1 space group with a = 7.106(2), b = 11.450(2), c = 11.869(1) angstrom, alpha = 107.29(1), beta = 104.08(1), gamma = 90.32(2)degrees, and Z = 2. [Zn(2,5-pydc)(H(2)O)(2)] center dot H(2)O (2) is orthorhombic (P2(1)2(1)2(1) space group), with a = 7.342(1), b = 9.430(1), c = 13.834(2) angstrom, and Z = 4. The structures were refined to agreement R(1)-factors of 0.0315 (1) and 0.0336 (2). Complex (1) is arranged as molecular Zn(4)(2,5-pydc)(4)(H(2)O)(10) tetramers, the cages of which define channels that remain unblocked by anions. Compound (2) is polymeric with Zn(2,5-pydc)(H(2)O)(2) and Zn(2,5-pydc)(H(2)O)(3) units linked through bridging ligands. Both compounds were synthesized under mild conditions in aqueous media, without need to resort to hydrothermal media. Changing the pH from 4.51 to 5.75 suffices to direct the chemical processes toward the orthorhombic compound rather than to the triclinic one.

Crystal structures and thermal behavior of alkaline earth tricyanomethanides

The alkaline earth tricyanomethanides Mg(tcm)(2) center dot 2H(2)O, Ca(tcm)(2), Sr(tcm)(2) - H2O and Ba(tcm)(2) center dot 2H(2)O were prepared from aqueous solutions of the respective chlorides and silver tricyanomethanide. Their IR spectra and thermal behavior are described. The crystal structures of Ca(tcm)(2) and Ba(tcm)(2) center dot 2H(2)O were determined by single crystal X-ray diffraction. The structure of Ca(tcm)(2) is of the type found for several transition metal tricyanomethanides [1], containing two independent interpenetrating networks. Ba(tcm)(2) center dot 2H(2)O has a unique crystal structure corresponding to a three-dimensional coordination polymer with nine fold coordinated Ba atoms connected by water molecules and tricyanomethanide anions.

THERMAL BEHAVIOR STUDY AND DECOMPOSITION KINETICS OF SALBUTAMOL UNDER ISOTHERMAL AND NON-ISOTHERMAL CONDITIONS

The thermal decomposition of salbutamol (beta(2) - selective adrenoreceptor) was studied using differential scanning calorimetry (DSC) and thermogravimetry/derivative thermogravimetry (TG/DTG). It was observed that the commercial sample showed a different thermal profile than the standard sample caused by the presence of excipients. These compounds increase the thermal stability of the drug. Moreover, higher activation energy was calculated for the pharmaceutical sample, which was estimated by isothermal and non-isothermal methods for the first stage of the thermal decomposition process. For isothermal experiments the average values were E(act) = 130 kJ mol(-1) (for standard sample) and E(act) = 252 kJ mol(-1) (for pharmaceutical sample) in a dynamic nitrogen atmosphere (50 mL min(-1)). For non-isothermal method, activation energy was obtained from the plot of log heating rates vs. 1/T in dynamic air atmosphere (50 mL min(-1)). The calculated values were E(act) = 134 kJ mol(-1) (for standard sample) and E(act) (=) 139 kJ mol(-1) (for pharmaceutical sample).

Thin films of carbohydrate based surfactants and carboxymethylcellulose acetate butyrate mixtures: Morphology and thermal behavior

Thin films of mixtures containing carboxymethylcellulose acetate butyrate (CMCAB) and carbohydrate based surfactant, namely, sorbitan monopalmitate (Span 40) or poly(oxyethylene) sorbitan monopalmitate (Tween 40) were spin-coated onto silicon wafers. The effect of surfactant concentration on resulting film morphology and surface toughness Was Studied by atomic force microscopy (AFM). Upon increasing the concentration of Span 40 in the mixture, films became rougher and more heterogeneous, indicating surface enrichment by Span 40 molecules. In the case of mixtures composed by CMCAB and Tween 40, the increase of Tween 40 in the mixture led to smoother and more homogeneous films, indicating compatibility between both components. Differential scanning calorimetry (DSC) revealed that Span 40 and Tween 40 act as plasticizers for CMCAB, leading to dramatic reduction of glass transition temperature of CMCAB, namely, Delta T(g) = -158 degrees C and Delta T(g)=-179 degrees C. respectively. (C) 2008 Elsevier B.V. All rights reserved.

Thermal behavior and stability of biodegradable spray-dried microparticles containing triamcinolone

Thermal analysis has been widely used for obtaining information about drug-polymer interactions and for pre-formulation studies of pharmaceutical dosage forms. In this work, biodegradable microparticles Of Poly (D,L-lactide-co-glycolide) (PLGA) containing triamcinolone (TR) in various drug:polymer ratios were produced by spray drying. The main purpose of this study was to study the effect of the spray-drying process not only on the drug-polymer interactions but also on the stability of microparticles using differential scanning calorimetry (DSC), thermogravimetry (TG) and derivative thermogravimetry (DTG), X-ray analysis (XRD), and infrared spectroscopy (IR). The evaluation of drug-polymer interactions and the pre-formulation studies were assessed using the DSC, TG and DTG, and IR. The quantitative analysis of drugs entrapped in PLGA microparticles was performed by the HPLC method. The results showed high levels of drug-loading efficiency for all used drug: polymer ratio, and the polymorph used for preparing the microparticles was the form B. The DSC and TG/DTG profiles for drug-loaded microparticles were very similar to those for the physical mixtures of the components. Therefore, a correlation between drug content and the structural and thermal properties of drug-loaded PLGA microparticles was established. These data indicate that the spray-drying technique does not affect the physico-chemical stability of the microparticle components. These results are in agreement with the IR analysis demonstrating that no significant chemical interaction occurs between TR and PLGA in both physical mixtures and microparticles. The results of the X-ray analysis are in agreement with the thermal analysis data showing that the amorphous form of TR prevails over a small fraction of crystalline phase of the drug also present in the TR-loaded microparticles. From the pre-formulation studies, we have found that the spray-drying methodology is an efficient process for obtaining TR-loaded PLGA microparticles. (C) 2008 Elsevier B.V. All rights reserved.

Thermal behavior and structural properites of plant-derived eugenyl acetate

Eugenol is an allyl chain-substituted guaiacol in the biosynthesized phenylpropanoid compound class derived from Syzygium aromaticum L. and widely used in folk medicine. Nonetheless, its pharmacological use is limited by some problems, such as instability when exposed to light and high temperature. In order to enhance stability, the eugenol molecule was structurally modified, resulting in eugenyl acetate. The eugenyl acetate`s thermal behavior and crystal structure was then characterized by differential scanning calorimetry (DSC) and X-ray diffraction (XRD) and compared to a commercial sample.

THERMAL BEHAVIOR OF IN VITRO MINERALIZED ANIONIC COLLAGEN MATRICES

In the present study porcine skin and bovine pericardium were used as a source of type I collagen. Both were submitted to an alkaline treatment and mineralized by the alternate soaking method. Thermal stability and extent of mineralization have been investigated using DSC and TG. After alkaline hydrolysis there is a decrease in thermal stability but mineralization stabilizes collagen structure. Thermogravimetric data have shown that the amount of hydroxyapatite present in bovine pericardium matrix (45%) was greater than on porcine skin matrix (20%). Presence of hydroxyapatite was confirmed by EDX.

Evaluation of thermal simulation of households in the metropolitan region of So Paulo, Brazil

This paper aims at assessing the performance of a program of thermal simulation (Arquitrop) in different households in the city of Sao Paulo, Brazil. The households were selected for the Wheezing Project which followed up children under 2 years old to monitor the occurrence of respiratory diseases. The results show that in all three study households there is a good approximation between the observed and the simulated indoor temperatures. It was also observed a fairly consistent and realistic behavior between the simulated indoor and the outdoor temperatures, describing the Arquitrop model as an efficient estimator and good representative of the thermal behavior of households in the city of Sao Paulo. The worst simulation is linked to the poorest type of construction. This may be explained by the bad quality of the construction, which the Architrop could not simulate adequately.

Film forming solutions based on gelatin and poly(vinyl alcohol) blends: Thermal and rheological characterizations

The objective of this work was to study the theological and thermal properties of film forming solutions (FFS) based on blends of gelatin and poly(vinyl alcohol) (PVA). The effect of the PVA concentration and plasticizer presence on the flow behavior, and viscoelastic and thermal properties of FFS was studied by steady-shear flow and oscillatory experiments, and also, by microcalorimetry. The FB presented Newtonian behavior at 30 degrees C, and the viscosity was not affected neither by the PVA concentration nor by the plasticizer. All FFS presented a phase transition during tests applying temperature scanning. It was verified that the PVA affected the viscoelastic properties of FFS by dilution of gelatin. This behavior was confirmed by microcalorimetric analysis. The behaviors of the storage (G`) and loss (G ``) moduli as a function of frequency of FFS obtained at 5 degrees C were typical of physical gels; with the G` higher than the G ``. The strength of the gels was affected by the PVA concentration. (C) 2009 Elsevier Ltd. All rights reserved.

Evaluation of mechanical, physical and thermal performance of cement-based tiles reinforced with vegetable fibers

The objective of this work was to analyze mechanical, physical and thermal performance of roofing tiles produced with several formulations of cement-based matrices reinforced with sisal and eucalyptus fibers. The physical properties of the tiles were more influenced by the fiber content of the composite than by the type of reinforcement. The type of the fiber was the main variable for the achievement of the best results of mechanical properties. Exposure to tropical climate has caused a severe reduction in the mechanical properties of the composites. After approximately four months of age under external weathering the toughness of the vegetable fiber-cement fell to 53-68% of the initial toughness at 28 days of age. The thermal performance showed that roofing tiles reinforced with vegetable fiber are acceptable as substitutes of asbestos-cement sheets. (c) 2006 Elsevier Ltd. All rights reserved.

Thermal and structural properties of commercial dental resins light-cured with blue emitting diodes (LEDs)

We have investigated the thermal and structural properties of different commercial dental resins: Filtek(TM) Z-350, Grandio(A (R)), Tetric Ceram(A (R)), and TPH Spectrum(A (R)). The purpose of the present study was to evaluate quantitatively the photo-polymerization behavior and the effect of filler contents on the kinetic cures of the dental resins by using Differential Scanning Calorimetry (DSC) and Fourier Transform Infrared Spectroscopy (FT-IR) techniques. We have successfully obtained the low and high glass transition T (g) values of the dental composite resins from DSC curves. It was also observed a good agreement between the both T (g) values, activation energies from thermal degradation, and the degree of conversion obtained for all samples. The results have shown that Tetric Ceram(A (R)) dental resin presented the higher T (g) values, activation energy of 215 +/- A 6 KJ mol(-1), and the higher degree of conversion (63%) when compared to the other resins studied herein.

High specific surface area LaFeCo perovskites-Synthesis by nanocasting and catalytic behavior in the reduction of NO with CO

LaFe(1-x)CO(x)O(3) perovskites were conventionally or nanocasting synthesized. The nanocasting involved the preparation of a micro-mesoporous carbon mould using a Silica Aerosil 200 and a carbon source. Then, perovskites were carbon cast at 800 degrees C. The solids were characterized by XRD, N(2) sorption, FTIR, TGA/DTG, SEM and TEM. N(2) sorption evidenced that the nanocast perovskites did not show significant intraparticle porosity in despite of their enhanced (30-50 m(2)/g) specific surface area (SSA). Nevertheless, TEM images, XRD and Rietveld refinement data showed that the solids are constituted at least by 97 wt% of perovskite phase and by agglomerates smaller than 100 nm constituted by crystallites of about 6 nm. TGA/DTG results demonstrated carbon oxidation during the perovskite formation, thus eliminating the template effect and facilitating the occurrence of sintering, which limited the SSA increase. The nanocast perovskites were more active in the reduction of NO than the uncast ones, behavior that was attributed to the increase in their SSA that allows the exposure of a higher number of accessible active sites. However, the perovskite composition and the presence of impurities can reduce the effect of the improvement of the textural properties. The nanocast perovskites also showed high thermal and catalytic stability, corroborating their potential as catalysts for the studied reaction. (C) 2009 Elsevier B.V. All rights reserved.

Thermal analysis of prednicarbate and characterization of thermal decomposition product

In the present work, the thermal behavior of prednicarbate was studied using DSC and TG/DTG. The solid product remaining at the first decomposition step of the drug was isolated by TG, in air and N(2) atmospheres and was characterized using LC-MS/MS, NMR, and IR spectroscopy. It was found that the product at the first thermal decomposition step of prednicarbate corresponds to the elimination of the carbonate group bonding to C(17), and a consequent formation of double bond between C(17) and C(16). Structure elucidation of this degradation product by spectral data has been discussed in detail.

V(2)O(5) nanoparticles obtained from a synthetic bariandite-like vanadium oxide: Synthesis, characterization and electrochemical behavior in an ionic liquid

Highly stable and crystalline V(2)O(5) nanoparticles with an average diameter of 15 nm have been easily prepared by thermal treatment of a bariandite-like vanadium oxide, V(10)O(24)center dot 9H(2)O. Their characterization was carried out by powder X-ray diffractometry (XRD). Fourier transform infrared (FT-IR) and Raman spectroscopies, and transmission electron microscopy (TEM). The fibrous and nanostructured film obtained by electrophoretic deposition of the V(2)O(5) nanoparticles showed good electroactivity when submitted to cyclic voltammetry in an ionic liquid-based electrolyte. The use of this film for the preparation of a nanostructured electrode led to an improvement of about 50% in discharge capacity values when compared with similar electrodes obtained by casting of a V(2)O(5) xerogel. (C) 2009 Elsevier Inc. All rights reserved.