Authors:Marta Fernandez-Tarrio, Carmen Alvarez-Lorenzo, and A. Concheiro
comprises X-shaped copolymers formed by four poly(propylene oxide) (PPO) and
poly(ethylene oxide) (PEO) block chains bonded to an ethylene diamine central
group. Micellization behaviour of three representative Tetronics (T304, T904
and T1307) was characterized to gain an insight into the interactions between
the copolymer unimers and the state of water in their solutions. The enthalpy
of demicellization, recorded at 37°C in an isoperibol microcalorimeter,
indicated that the process was in all cases exothermic and the enthalpy ranked
in the order T1307≥T904>>T304. Micellization is entropy-driven owing to
hydrophobic interactions between the PPO chains.
showed that the crystallization and melting peaks of the free water remaining
in T304 and T904 solutions were progressively shifted toward lower temperatures
as the surfactant proportion increased, owing to a colligative effect. Bound
water corresponded to 3 water molecules per EO repeating unit. In the case
of T1307, which has longer PEO chains, a splitting of the melting peak was
observed, one peak appearing around 0°C due to free water and another
at –15°C due to interfacial water. As T1307 proportion raised, the
enthalpy of the former decreased, whilst the enthalpy of the latter increased.
In 40% T1307 solutions, interfacial water overcame the proportion of free
water; there being 1 interfacial and 3 bound water molecules per EO repeating
unit. Gaussian deconvolution of FTIR spectra also enabled to characterize
the evolution of free water as a function of Tetronic proportion. The dependence
of micellization and water interaction behaviour on Tetronics structure should
be taken into account to use these copolymers as drug solubilizers and micellar
Authors:A. Marini, V. Berbenni, G. Bruni, R. Riccardi, and M. Villa
The thermodynamics of β-cyclodextrin dehydration is investigated, by parallel DSC/TG experiments, on both fully and partially
hydrated samples. The apparent dehydration enthalpies per mole of water are impossibly high and this fact suggests that another
phenomenon, in addition to the rupture of the β-cyclodextrin/H2O hydrogen bonds, contributes to the peak area. All the experimental evidence agrees with an ‘interaction model’ which assumes
that deydration is accompanied by a slow and reversible rearrangement of the β-cyclodextrin structure.
Modern thermal analysis, microcalorimetry and new emerging combined techniques which deliver calorimetric, microscopic and
spectroscopic data offer a powerful analytical battery for the study of pharmaceuticals. These techniques are very useful
in all steps of development of new drug products as well as methods for quality control in production. The characterization
of raw materials enables to understand the relationships between polymorphs, solvates and hydrates and to choose the proper
development of new drug products with very small amount of material in a very short time. Information on stability, purity
is valuable for new entities as well as for marketed drug substances from different suppliers. Excipients which vary from
single organic or inorganic entity to complexes matrixes or polymers need to be characterized and properly controlled. The
thermodynamic phase-diagrams are the basis of the studies of drug-excipients interactions. They are very useful for the development
of new delivery systems. A great number of new formulations need proper knowledge of the behaviour of the glass transition
temperature of the components. Semi-liquid systems, interactions in aqueous media are also successfully studied by these techniques.
Authors:A. Abdel-Rassoul, H. Aly, A. Borhan, and M. Abdel-Hamid
The kinetics of the exchange of sulphate and chloride ions on the strongly basic anion exchanger Dowex 1X8, of different particle
diameters is investigated. The diffusion coefficient values are calculated by two diferent methods, discussed in the light
of the processes governing the exchange reactions encountered, and found to be mainly controlled by particle diffusion. The
distribution behaviour of sulphate, sulphite, thiosulphate and sulphide between aqueous KCl solutions of different concentrations
and a number of selected anion exchange resins is studied. The data are explained on the premises of the different interactions
involved in both aqueous and resineous phases. The effect of the alkali metal chloride molarities in the aqueous phase (LiCl,
NaCl and KCl) on the exchange behaviour of the different S-anions is also investigated. The results are interpreted in the
light of the water—water interaction and the competition for hydration between the alkali metal cations and the exchanged
The research was carried out at the Department of Hydraulic Engineering, Faculty of Civil Engineering, Slovak University of Technology in Bratislava with close cooperation with Institute of Water Structures, Faculty of Civil Engineering, Brno University of Technology. One of the important goals was the determination of the most accurate approach related to the computational fluid dynamics modeling of the air-water interaction. Research consists of two main research methods to ensure the accuracy, set up the possibilities of cooperation and the results control. The first method was the physical model of broad-crested weir installed in collapsible canal in hydraulic laboratory and the second was numerical computational fluid dynamics model of broad-crested weir created in same scale. In free surface flows the air entrainment phenomena plays an important role. Air entrainment is affecting the volume fraction, velocity field, energy dissipation and many other parameters related to dynamic behavior of water near the crests. Different approaches were carried out to identify most accurate computational fluid dynamics setup compared to physical model measurements. Compared results and the accuracy assessment are summarized and the best computational fluid dynamics parameterization is recommended.
Environmental isotope (
18O) techniques supported by hydrochemical surveying, water balance and conventional hydrogeological mapping were used to study the hydrogeological system of four major lakes located in a closed central Ethiopian rift basin. The focus of attention is the groundwater and surface water interaction and the subsurface hydraulic connection of the lakes. The result shows that despite their geographic proximity, the lakes have highly variable isotopic and hydrochemical signature owing to geological and geomorphological factors. Two of the lakes are alkaline and found to be terminal from both surface water and groundwater point of view. They are in the state of high evaporation with respect to present day precipitation. The groundwater flow converges from all sides of the basin and plays very important role in the water balance of all the lakes. Major flow system in the rift and the hydraulic connection of the lakes is strongly controlled by the direction and extent of the extensional normal faults.
Authors:Enikő Kádár, J. Salánki, J. Powell, and et al
Significant amounts of aluminium (Al) are commonly present in rivers and lakes, largely in particulate form in neutral waters. Freshwater bivalves, as filter feeders are therefore exposed to both particulate and dissolved metal and are potentially vulnerable to Al. The effect of Al on filtering behaviour of the freshwater mussel Anodonta cygnea L. was investigated during short (1 hour) and long-term (15 days) exposure to environmentally relevant concentrations (250 and 500 mg l-1) at neutral pH. Water flow through the outflow siphon was monitored as an indicator of pumping capacity. Short-term (1 hour) exposure to 500 mg l-1 added Al produced an irreversible decrease in the duration of filtering periods, presumably as an avoidance response to the toxicant. One-hour exposure 250 mg l-1 Al had no detectable effect. When mussels were exposed to 250 or 500 mg l-1 added Al for 15 days, siphon activity measured in days 11-15 of exposure was inhibited by 50% and 65%, respectively, compared to pre-exposure levels. Recovery occurred following transfer of mussels to uncontaminated water. Interaction between Al and freshwater bivalves at neutral pH may affect both the performance of the mussels and the chemical speciation of the metal in the natural environment.
A DSC study has been carried out on isomalt, a commercial sugar alcohol derived from sucrose and widely used as a sweetener
in the food industry. Isomalt is a mixture of two isomers:α-D-glucopyranosyl–1-6-mannitol (GPM) and α-D-glucopyranosyl–1-6-sorbitol (GPS). Release of the water of crystallisation (around 100C)and melting (around 150C) have
been phenomenologically characterised using different scanning rates and heat treatments. The effect of dehydration/re-hydration
on the melting has been investigated. The isomalt glass transition, at about 60C, was studied on samples cooled after melting.
The dynamic aspect of structural relaxation of isomalt has been quantified by its fragility parameter. Glassy state stability
has been evaluated by performing ageing experiments at sub-Tg temperatures. During ageing, apart from the expected enthalpy relaxation effects, isomalt showed a peculiar behaviour, due
to its isomeric composition. These preliminary and phenomenological results have been interpreted in terms of isomer structure
and of carbohydrate-water interactions in the mixture.
Authors:J. Silverio, E. Svensson, Ann-Charlotte Eliasson, and G. Olofsson
In the present study, isothermal microcalorimetry was introduced as a tool to investigate properties of starch retrogradation during the first 24 h. The study was made on purified amylose and amylopectin from corn, as well as on native starches, such as wheat, potato, maize, waxy maize and amylomaize, differing in their amylose content. The results were obtained in the form ofP-t traces (thermal powervs. time), and integration of these traces gave a net exothermic enthalpy of reaction, caused by the crystallization of amylose and amylopectin. TheP-t traces reflected the quantities of amylose and amylopectin in the starch studied. Depending on the amylose content and the botanical source of the starch, the rate of crystallization of amylose was high and predominated over that of amylopectin during the first 5–10 h. The contribution from amylose crystallization to the measured exothermic enthalpy was very substantial during this period. After ∼10 h, amylose crystallized at a lower constant rate. During the first 24 h, amylopectin crystallized at a low steady rate. The exothermic enthalpies obtained by the isothermal microcalorimetric investigations during the first 24 h of retrogradation were generally low in relation to the endothermic melting enthalpies observed by differential scanning calorimetry (DSC) measurements after 24 h of storage. The discrepancies in enthalpy values between the two methods are discussed in relation to phase separation and the endothermic effects owing to the decrease in polymer-water interactions when polymer-rich regions in the starch gel separate. Besides the exothermic enthalpies obtained, theP-t traces also made it possible to study the initial gelation properties of amylose from different botanical sources. The present study further demonstrated that isothermal microcalorimetry can provide a possible way to investigate the antistaling effect of certain polar lipids, such as sodium dodecylsulphate (SDS) and 1-monolauroyl-rac-glycerol (GML), when added to starches of different botanical origin. The net exothermic heat of reaction for starch retrogradation during the first 24 h was decreased when GML or SDS was added to the starch gels. The recordedP-t traces also showed how the effect of the added lipid influenced different periods during the first 24 h of starch retrogradation, and that the effect depended mainly on the amylose content, the botanical source of the starch, and the type of lipid used. When GML or SDS was added to waxy maize, the isothermal microcalorimetric studies clearly indicated some interaction between amylopectin and the polar lipids. These results concerning the action of anti-staling agents are further discussed in relation to the helical inclusion complexes formed between amylose-polar lipid and amylopectin-polar lipid.