Thermal Characterization of Warifteine by Means of TG and a DSC Photovisual System

This work proposes thermal characterization as analytical methodology for the identification and purity assay of warifteine, an alkaloid in Cissampelos sympodialis Eichl. Thermal and kinetic parameters were determined by means of TG and DSC photovisual studies. The TG results showed that the decomposition of warifteine in air and nitrogen atmospheres proceeds in three and four steps, respectively. The TG data allowed calculation of the kinetic parameters of warifteine. The activation energy values obtained by different methods displayed a good correlation. With the DSC photovisual system applied it is possible to detect the impurity level in warifteine after its purification. This revised version was published online in July 2006 with corrections to the Cover Date.     

TG and DSC studies on plaster residues as recycled material

The aim of the present work is to study plaster residues produced in industries in Goiás State (Brazil). The study analyzes the trituration and dehydrating processes of the plaster and compares its chemical, mechanical and physical characteristics to the natural plaster samples aiming its possible recycling. Plaster samples were submitted to X-ray diffraction, infrared spectroscopy, thermogravimetric (TG) and differential scanning calorimetry (DSC) analyses. By the comparison of the results obtained for both samples it was observed that they have similar chemical characteristics. No reason was found against the use of recycled plaster.     

Thermal Decomposition of Hydrated Lanthanide Picrates by TG/DTG and DSC Analyses

Hydrated lanthanide picrates with a composition of: Ln(pic)₃⋅xH₂O (Ln=La–Lu, Y) were synthesized and characterized. Thermal decomposition of the picrates by TG/DTG and DSC techniques are reported. This revised version was published online in July 2006 with corrections to the Cover Date.     

TG and DSC as tools for confirming hybrid vermiculites derived from intercalation

Vermiculite was prepared to react with aliphatic diamines (ethylene-, trimethylene-, tetramethylene- and hexamethylene-) diamine. The products were characterized by elemental analysis, infrared spectroscopy and X-ray diffraction. The amounts of diamines adsorbed were 0.89, 0.86, 0.79 and 0.68 mmol g^–1, respectively for NH₂(CH₂)⋅nNH₂ where n=2, 3, 4, 6. The basal spacings of the intercalated vermiculites varied between 1300 and 1470 pm. Thermogravimetry and DSC data confirmed intercalation of diamines in gallery space of vermiculite.     

Fractional analysis of technical polyoxaalkyl borates by TG

Results of preliminary thermoanalytical investigations (DSC/TG) of polyoxaalkyl esters of boric acid are presented. One aim of these investigations was the development of a method of characterization of the technical esterificate. The optimum parameters of quantitative thermogravimetric analysis of boric acid esters and the excess of polyoxaalkanols were assumed. The precision and accuracy of the developed method are discussed.     

Kinetics of the oxidation of magnetite using simultaneous TG/DSC

Kinetics of the oxidation of magnetite (Fe₃O₄) to hematite (a-Fe₂O₃) are studied in air using simultaneous TG/DSC. The mechanism is complex and the differences between the kinetic conclusions and Arrhenius parameters based on either TG or DSC are discussed. As in our previous work on CaCO₃ [1], the determination of a satisfactory baseline for the DSC results adds considerable uncertainty to those kinetic results. Consequently the calculations based on the TG data are considered superior. Solid state reactivity varies from one source of material to another and the results are compared for two different commercial samples of magnetite, both presumably prepared by wet chemical methods. These materials are much more reactive than the material studied previously [2], which had been coarsened and refined at high temperatures. In that earlier study, the metastable spinel, g-Fe₂O₃, was formed as an intermediate in the oxidation to the final stable form, a-Fe₂O₃. The exothermic reaction of the gamma to alpha form of the product during the oxidation process destroys the direct comparison between the TG and DSC results, since the former only detects the change in mass of the sample and not the crystallographic transformation. The TG results, however, represent the true oxidation process without superposition of the structural aspects. This revised version was published online in July 2006 with corrections to the Cover Date.     

TG and DSC studies of filled porous copolymers

A complex approach including thermogravimetry, differential thermal analysis and differential scanning calorimetry was applied to study characteristics of non-filled and filled porous copolymers of divinylbenzene with styrene or some acrylic monomers: di(methacryloyloxymethyl)naphthalene, methacrylic ester of p,p’-dihydroxydiphenylpropane diglycidyl ether, and dimethacrylglycolethylene. High disperse silicas with the grafted methyl and silicon hydride groups in the surface layer were used as fillers. The kinetic parameters of thermal degradation for composites obtained were determined by different methods.     

The Influence of Silica to Alumina Ratio on Y Zeolite Activity by Simultaneous TG and DSC Analysis

Simultaneous TG and DSC analyses of n-butylamine adsorption/desorption were carried out over several zeolites with different degrees of dealumination. The samples used consisted of high crystalline zeolites, preparedvia steam/leaching sequential treatments, and characterized by various techniques. Catalyticactivity measured as the initial rate of cracking of 1,3,5-triisopropylbenzene did not correlate with total acidity, however, the energy required to the complete desorption of the probe molecule, determined by integration of DSC curves, correlates with the catalytic activity of zeolites with any or little extra-framework alumina content. High amounts of extra-framework alumina give significant constraint effect to acessibility to acid sites as shown by applying the Crank's method to the TG curves. This method allowed to determine the intra-crystalline diffusivity of the probe molecule, which seems to be the controlling step to the cracking reaction. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal analysis of Moroccan phosphates 'Youssoufia' in an oxidative atmosphere by TG and DSC

A non-isothermal experimental study using thermogravimetry (TG) and differential scanning calorimetry (DSC) was conducted for investigation the oxidation reactivity of natural phosphate and its demineralised products. The analyses were carried out in oxygen atmosphere and at different heating rate (5, 10, 20, 30, 50, 60°C min-1) up to 1000°C. The results indicated that the material washed with HCl from the original phosphate, mainly apatite and carbonates of calcium and magnesium, as well as with HCl/HF, silicates minreals, had an inhibition effect during oxidation reactions of organic material. The increase of the heating rate shifted the reactions to higher temperatures. In addition, kinetic parameters were determined by assuming a single first-order kinetic model, using the Coats-Redfern method. The influences of demineralization process of natural phosphate and the heating rate were examined and discussed. This revised version was published online in August 2006 with corrections to the Cover Date.     

TG and DSC study of the properties of coked molecular sieve catalyst

A cracking catalyst designatedSRNY was manufactured from a commercialSRNY molecular sieve (M.S.). The support consisted of kaolin, clay and SiO₂. The coking behaviour of theSRNY M.S., the support and the catalyst were examined with light diesel oil (LDO) as feedstock in a microreactor. The physico-chemical properties of both fresh and aged samples, subjected to or not subjected to the cracking reaction ofLDO, were sequentially characterized by means of pore structure determination and thermal analysis. The pore structure included the specific surface area and the pore volume or porosity. Thermal analysis methods used included TG and DSC. The results indicated that all coked samples exhibited obvious changes in surface pore structure and acidity in comparison with non-coked samples. Their specific surface area and acid amount decreased with increase in the coke content of the samples. The apparent activation energy data obtained from decoking samples in an air flow, using the temperature-programmed oxidation (TPO) method, showed that the kinetic parameters of theSRNY M.S. differed from those of theSRNY catalyst and its support.     

Use of DSC and TG for identification and quantification of the dosage form

Thermal analysis techniques, DSC and TG can advantageously be used in quality control of drug products.The methods are commonly used in preformulation for the study of polymorphism and for the study of the interactions drug substance-excipients, since these physical interactions can be the basis of the dosage form performance.For routine control of the drug products, DSC and TG methods which are quick, which require only few mg of the samples and which are automated, are very attractive for routine analysis of drug products. A single scan can give several qualitative and quantitative informations.DSC offer analytical possibilities only if the drug substance and the excipients do not have physical interactions or limited interactions (e.g. eutectic behaviour). About twenty marketed products have been analyzed by DSC and TG. In most of them identification of drug substance is easy. Several excipients could be identified in a tablet. Quantitations are demonstrated for some drug substances and excipients. DSC purity calculations have been applied to acetyl salicylic acid, paracetamol, cimetidine, pindolol, ibuprofen.     

Thermal decomposition of silver cyano complex and characterization its decomposition products by ETA,DSC, DTA and TG

It was found by DTA and TG that [Phenyl₂I][Ag(CN)₂] in the solid state is chemically stable on heating in argon up to 160°C. During heating to higher temperatures it decomposes, forming volatile products such as [Phenyl]I, [Phenyl]NC and (CN)₂ [1]. After heating the sample to 500°C metallic silver resulted. The volatile and intermediate solid products were analysed by IR-spectroscopy.It was found by means of DTA and ETA that an isophase reversible transition takes place when the sample is heated and cooled, not higher than 100°C. At heating higher than 100°C the sample melts (melting pointT _m=135°C). The enthalpy melting was determined by means of DSC (H=–28 kJ·mol^–1).By means of ETA the disorder degree of the final decomposition product was estimated. The value of the activation energy of radon diffusion in the temperature range 720°–500°C equals 32.6 kJ·mol^–1.Dedicated to Prof. I. N. Bekman Moscow State University at the occasion of his 50th birthday     

Kinetics of crystallization of metallic glasses studied by non-isothermal and isothermal DSC

A method for describing the lengths of induction periods at linear-heating measurements, is employed for the study of induction periods in the crystallisation of metallic glasses. For Fe₇₅Si₁₅B₁₀ glass, close values of the related kinetic parameters were obtained from isothermal and nonisothermal measurements. On the basis of the results obtained, the absence of induction period in the first crystallisation step of Al₉₀Fe₇Nb₃ glass in the isothermal DSC measurement has been elucidated.     

Characterization of silk fibroin/hyaluronic acid polyelectrolyte complex (PEC) films

This study aimed the characterization of the films casted from the aqueous mixtures of the pH induced complexes between silk fibroin (SF) and hyaluronic acid (HA). The insoluble and transparent films were subjected to scanning electron microscopy (SEM) analyses to show the morphological changes. Thermal analysis of complex films was determined by a differential scanning calorimeter (DSC). The changes in the crystalline state were monitored by X-ray diffractometer (XRD) and Fourier transform infrared spectroscopy (FTIR). It was shown that the complexation between HA and SF was dominantly induced by pH. It was shown that the complex films comprised mixtures of crystalline and non-crystalline regions.     

Determination of kerogen type by using DSC and TG analysis

The rate of pyrolysis and oxidation of 8 different samples of oil shale kerogen concentrate (KC) were investigated using DSC analysis. Recently performed thermogravimetric studies (TG and DTG) with the same samples of KC indicated that the activation energy of the pyrolysis of specific KCs increases with increasing paraffinic structure in the KC. An opposite effect, i.e. a decrease of the activation energy with an increase of paraffinic structure was determined in the case of KC oxidation. In this study, using the standard ASTM E-698 method based on the determined temperature at which the maximum heat effect could be observed (exo in the case of oxidation and endo in the case of pyrolysis), an activation energy for the pyrolysis, as well as for the oxidation process was determined and also successfully correlated with the content of paraffinic structure of KC. Thus, the higher content of paraffinic structure in KCs indicates that higher values of the activation energy could be determined either in the case of pyrolysis or oxidation followed by DSC analysis.     

DSC Study of Oxidation Induction Periods

A theory of the evaluation of kinetic parameters of induction periods for non-isothermal processes is outlined and a method to obtain the parameters from non-isothermal differential scanning calorimetry measurements, based on the dependence of onset temperature of oxidation peak on heating rate, is presented. The applicability of the method is demonstrated on the study of oxidation induction periods of edible oils and polyolefines. In all cases, the parameters of an Arrhenius-like equation describing the temperature dependence of induction period have been obtained. It is shown that the method gives the parameters not affected by oxygen diffusion which are transferable to be used in modelling the non-isothermal induction periods where the effects of diffusion, heat transfer and evolution of reaction heat are explicitly involved. A method of estimating the residual stability after a thermooxidative stress of the material is suggested. This revised version was published online in July 2006 with corrections to the Cover Date.     

Highly efficient syntheses of hyaluronic acid oligosaccharides

Highly efficient syntheses of hyaluronic acid oligosaccharides have been accomplished through the pre-activation based iterative one-pot strategy. A series of oligosaccharides ranging from di- to hexasaccharides were rapidly assembled using only near stoichiometric amounts of the building blocks without aglycon adjustment or purifications of intermediate oligosaccharides. Deprotection and oxidation protocols were developed for protective group removal and oxidation-state adjustment. The availability of such structurally well defined synthetic hyaluronic acid oligosaccharides will greatly facilitate the establishment of detailed structure-function relationships.     

Thermal Characterization of Lapachol by Means of TG and DSC Coupled to a Photovisual System

Thermal characterization is proposed as analytical methodology for the purity assay of lapachol, and for determination of the quality parameters of capsules containing this molecule. The TG data revealed that lapachol is more stable in the presence of adjuvants, showing the good quality of the formulation. The kinetic parameters obtained were lower for lapachol drug than for the formulated lapachol. The DSC data demonstrated good compatibility between lapachol drug and the adjuvant in the formulated lapachol, and did not reveal impurities such as secondary products of the isolation and recrystallization processes. The data were confirmed by the DSC-photovisual findings. This revised version was published online in July 2006 with corrections to the Cover Date.     

Crosslinking of hyaluronic acid with glutaraldehyde

Hyaluronic acid (HA) was chemically crosslinked with glutaraldehyde (GA) to produce water-insoluble films having low water contents when brought into contact with water. The crosslinking reaction was performed using uncrosslinked HA films in acetone–water mixtures. This method could produce water-insoluble HA films with water contents as low as 60 wt % when subjected to swelling with phosphate-buffered saline of pH 7.4 at 37°C. This 60 wt % water content was lower than any values for HA ever reported. There was an optimal HCl concentration around 0.01N for the HA crosslinking with GA in acetone—water mixtures. To get information on the crosslinking mechanism, alginic acid, which possesses hydroxyl and carboxyl groups in one molecule, similar to HA, and poly(vinyl alcohol) (PVA) and amylopectin, which possess only hydroxyl groups, were subjected to crosslinking with GA. PVA and amylopectin were also found to become water-insoluble after reaction with GA. On the basis of the infrared spectra of these crosslinked films, it was concluded that intermolecular formation of hemiacetal bonds with GA between the hydroxyl groups belonging to different HA molecules led to crosslinking. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 3553–3559, 1997     

Tunable biohybrid hydrogels from coacervation of hyaluronic acid and PEO-based block copolymers

Accurately tuning the macroscopic properties of biopolymer-based hydrogels remains challenging due to the ill-defined molecular architecture of the natural building blocks. Here, we report a biohybrid coacervate hydrogel, combining the biocompatibility and biodegradability of naturally occurring hyaluronic acid (HA) with the tunability of a synthetic polyethylene oxide (PEO) -based ABA-triblock copolymer. Coacervation of the cationic ammonium or guanidinium-functionalized copolymer A-blocks with the anionic HA leads to hydrogel formation. Both mechanical properties and water content of the self-healing hydrogels can be controlled independently by altering the copolymer structure. By controlling the strength of the interaction between the polymer network and small-molecule cargo, both release rate and maximum release are controlled. Finally, we show that coacervation of HA and the triblock copolymer leads to increased biostability upon exposure to hyaluronidase. We envision that noncovalent crosslinking of HA hydrogels through coacervation is an attractive strategy for the facile synthesis of tunable hydrogels for biomedical applications.