Authors:A. Cvetkovskii, R. Bettini, Lj. Tasic, M. Stupar, I. Casini, A. Rossi, and F. Giordano
The thermal behaviour of binary mixtures between β-cyclodextrin (β-CD) and either carbamazepine polymorphic Form I (CBZ I),
Form III (CBZ III) or dihydrate was investigated in order to assess possible interactions of CBZ solid phases with β-CD. Physical
mixtures and kneaded binaries of β-CD and different CBZ crystal forms were studied by differential scanning calorimetry, thermogravimetric
analysis and hot stage microscopy. The pattern of transition of CBZ Form III into Form I is strongly influenced by β-CD. The
liquid-solid transition is practically absent when anhydrous CBZ/β-CD mixes are tested, as a consequence of an interaction
between β-CD and liquid CBZ that hinders CBZ recrystallisation as Form I occurring after CBZ Form III melting.
Water loss on heating of CBZ dihydrate in the presence of β-CD leads in all cases to the formation of CBZ Form I.
New EGA findings revealed that the small endothermal event preceding that of the main decomposition of commercial NaHCO3 involves the simultaneous evolution of water and CO2. At very high sensitivity, EGA experiments evidenced that the above (limited) evolution of gases also took place from the
recrystallized material for which thermal methods gave no indication of endotherms.
Careful reexamination of previous DSC results indicated that for one kind of recrystallized material a very small endotherm
had been neglected. Renewed experiments revealed that this endotherm can be enhanced if the samples are prepared by crushing
and sieving in a wet atmosphere. Parallel FT-IR experiments on commercial and recrystallized materials demonstrated the presence
of carbonate in samples that had previously been taken just beyond the first small endotherm; this confirmed the EGA results.
SEM experiments showed that surface texture changes take place when samples are heated to temperatures just above that of
the preliminary endotherm. On the basis of these new findings, the interpretation previously given to the small endotherm
is revised and detailed knowledge is gained on the mechanism of decomposition of NaHCO3.
The compound BR-A657 is an angiotensin II receptor antagonist. The objective of this work was to investigate the existence
of polymorphs and pseudopolymorphs of BR-A657 and the transformation of crystal forms. Three crystal forms of BR-A657 have
been isolated by recrystallization and characterized by powder X-ray diffractometry, differential scanning calorimetry, and
thermogravimetric analysis. After storage of three days at 0% RH (silica gel, 20°C), 52% RH (saturated solution of Na2Cr2O7·2H2O/20°C) and 95% RH (saturated solution of Na2HPO4/20°C), Forms 2 and 3 were transformed to Form 1.
Differential scanning calorimetry (DSC) was used to construct phase diagrams of binary mixtures of alkylcyclohexanes and to
characterize metastable phases formed in the binary mixtures. The experimentally measured liquidus curves were compared to
the liquidus curves calculated using ideal solution theory. The measured phase diagrams of pentadecylcyclohexane/nonadecylcyclohexane
and octadecylcyclohexane/nonadecylcyclohexane binary mixtures are consistent with theoretical phase diagrams constructed based
on the assumption that these mixtures form eutectic systems. It was also observed that a metastable phase formed in some binary
mixtures of pentadecylcyclohexane/nonadecylcyclohexane under fast cooling conditions. It is hypothesized that this metastable
phase recrystallizes into the eutectic phase upon heating.
Authors:P. Di Martino, P. Conflant, M. Drache, J. -P. Huvenne, and A. -M. Guyot-Hermann
The polymorphic forms II and III of paracetamol were obtained by melting the marketed form I. Under the melting and cooling conditions used, it was possible to obtain forms I, II and III. The recrystallization conditions and the physical properties of forms II and III were investigated by means of various techniques: thermomicroscopy, DSC analysis, infrared microspectrometry and X-ray powder diffraction at room temperature and as a function of temperature. Form III was found to be very unstable. However, its formation seems to be an important intermediate step in the preparation of form II.
Temperature-modulated DSC (TMDSC) was used to enhance the perfection of crystals of different poly(p-phenylene sulfide) samples formed during slow cooling from the melt. The sample preparation was made with modulated cooling using a cool-heat mode. Re-heating the samples prepared by slow conventional and modulated coolings indicated that the melting point of the samples prepared by modulated cooling is considerably higher than the melting point of the samples crystallized with conventional cooling. Thus, the perfection of crystallites can be improved if the outer layers just deposited on their surface are re-melted and re-crystallized immediately.
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.
Authors:P. Espeau, B. Nicolaï, R. Céolin, M. Perrin, L. Zaske, J. Giovannini, and F. Leveiller
Investigation into the thermal behavior of orthorhombic Forms I and II of spironolactone, by means of differential scanning
calorimetry and high-resolution X-ray powder diffraction, showed that Form I melts then recrystallizes into Form II at 373–393
K, i.e. in the temperature range within which high resolution X-ray powder diffration showed that Form I transforms into Form II.
Refinements of the lattice parameters of the two forms indicated that Form I is denser than Form II in the range from 298
K up to the temperature at which it melts.
The systematics of isotopic exchange in a heterogeneous batch system between a dilute aqueous solution and an adsorbate or the solid adsorbent are discussed. In particular, the influence of the experimental precision on the detection of an eventual non-reactive fraction of the adsorbate is considered, down to ~ 5% of which is detectable. The exchange with the solid adsorbent is illustrated by the case of45Ca2+ and calcite. The minimum layer thickness observable in surface exchange is ~ 0.05 m. The same formalism can be applied to uptake due to recrystallization of the solid. It enables distinction between this phenomenon and diffusion into the solid.
Authors:M. Matthews, I. Atkinson, Lubaina Presswala, O. Najjar, Nadine Gerhardstein, R. Wei, Elizabeth Rye, and A. Riga
Dielectric analysis (DEA), supported by thermogravimetric analysis (TG), differential scanning calorimetry (DSC), powder X-ray
diffraction analysis (PXRD) and photomicrography, reveal the chiral difference in the amino acids. The acids are classified
as dielectric materials based on their structure, relating chirality to the vector sum of the average dipole moment, composed
of the constant optical (electronic) and infra-red (atomic) polarizabilities, as well as dipole orientation. This study encompasses
14 L-and D-amino acid isomers. Physical properties recorded include AC electrical conductivity, charge transfer complexes, melting,
recrystallization, amorphous and crystalline phases, and relaxation spectra, activation energies and polarization times for
the electrical charging process.