scanning calorimetry (DSC) is a thermal analytical tool for preformulation
studies. Extrapolated melting temperature (TP)
and heat of fusion (ΔHf)
can be used as parameters for optimizing the DSC performance. Two model pharmaceuticals
acetaminophen and nicotinamide are used in this study. Using a factorial design
for the experimental model and matrix analysis the results, the effect of
sample mass, heating rate and the nitrogen flow rate were evaluated on the
and TP values. Two
levels for each of the procedural variables were used as a balanced experimental
design with two sample sizes, two heating rates and two nitrogen flow rates.
It was found that the change in the heating rate caused significant changes
in the ΔHf
values but not the Tp
values for acetaminophen. However, no significant effect was found for the Tp value but ΔHf value was affected to a
certain extent for nicotinamide.
This project investigated the interaction between poly-L-lactic acid (PLLA) and several therapeutic agents. Low percentage crystallinity PLLA (melt-pressed, molded and drawn) was
studied. X-ray diffraction (XRD) and differential scanning calorimetry (DSC) were used to characterize the crystallinity and
thermal properties in a thermal cycling process. Repeatable melting and crystallization events were observed. The thermal
properties of a drug-polymer combination using PLLA and an acidic, basic, neutral and zwitterionic material were investigated.
A sufficient quantity of the drug must be present in the polymer to be observed thermally. Release of atropine sulfate from
a PLLA tablet showed a two-phase process.
Snake skin is a viable and readily available material as a model for human skin. Pharmaceutical applications use shed snake skin to study the effects of sunscreens on exposure to UV radiation (e.g. benzophenone on Boa integument). In order to understand the effects of radiation or drug transport through this model skin, one must determine its basic physical properties. This preliminary study evaluated two types of snake skin, namely Cuban Boa a 'dark' skin (Epicrates angulifer) and Green tree python a 'light' skin (Morelia viridis). Previous studies by other investigators have used pig, rabbit and snake skin as a human skin substitute. The structure of both snake skins was comparable based on IR spectroscopy and were functionally amino acids and moisture. Photomicrography by light and scanning electron microscopy revealed strong anatomic similarities. Morphologically there were two structures visible, namely a cellular and hinge-fibrous area. The thermal techniques indicated a phase transition at 35-75°C, which is associated with lipid melting. There was an 8 and 12% mass loss for the light skin and dark skin, respectively, which is interpreted, in part, as moisture loss at <100°C. The physical and analytical properties establish a base line that will be used in the future to differentiate various sunscreen types, such as benzophenone and octyl salicylate. Study was also done to determine the effect of an application of a commercially available sunscreen using SEM.
Five poorly soluble drugs namely hydrochlorothiazide, menadione, propylthiouracil, quinine sulfate and sulfamerazine were
used to evaluate the ability of an index (Ic) based on the van't Hoff equation to predict the eutectic composition at a higher heating rate than previously published.
The term Ic is a dimensionless index which has been defined in the literature and is used to predict eutectic composition. This current
work uses this study to determine if the correlation holds true at the higher heating rate of 10C min-1. The maximum deviation was observed for quinine sulfate, for which the predicted eutectic composition was 10% lower than
what was observed with the DSC. It can be concluded that the Index developed here has a good correlation with the experimentally
determined eutectic composition.
Poly-L-lactic acid (PLLA) is a semi-crystalline, optically active, biodegradable, and biocompatible polymer that has been utilized
extensively in biomedical applications as an implantable artificial cell scaffold material. In its crystalline form, PLLA
is piezoelectric and it has been implicated in the enhancement of electromechanically induced osteogenesis in vivo. In its
amorphous state, however, PLLA does not exhibit piezoelectricity. By uniaxially cold-drawing the polymer, PLLA can be endowed
with varying degrees of piezoelectricity. It is important to understand the crystalline architecture of drawn PLLA so that
the osteogenic potential imparted by piezoelectricity, if any, can be differentiated from the effects of sample crystallinity.
In our work we investigate the induced crystallinity for samples of drawn PLLA at draw ratios between 1.0 and 5.5 by differential
scanning calorimetry (DSC). As long-range molecular ordering occurs along the draw axis, we observe an increase in the average
percent crystallinity up to a draw ratio of 5.0 and a slight decrease at a draw ratio of 5.5. More importantly, we observe
significant heterogeneity in the crystalline content along the draw axis of standard dumbbells cut from PLLA and cold-drawn
to representative draw ratios of 2.5 and 4.0. On average, the highest percent crystallinity occurs nearest the dumbbell center,
but the maximum crystallinity is independent of draw ratio. Therefore, the draw ratio should not be considered a semi-quantitative
estimate of localized PLLA crystallinity and point-to-point analysis of crystallinity in PLLA samples is required for constructing
scaffolds with enhanced cell growth properties.
Authors:A. Vora, A. Riga, D Dollimore, and K. Alexander
This study attempts to identify the degradative process which folic acid undergoes in the solid-state under thermal stress.
In order to facilitate the process, the various pieces of the chemical structure, namely, p-amino benzoic acid, pterin and glutamic acid as both its d- and l-isomers were investigated as separate entities. These structured solid-state pieces were then compared to the composite solid
state folic acid degradative curves in order to identify the peaks seen and provide direction for the interpolation of the
degradative mechanism. It was observed that none of the structural pieces could be superimposed as assumed earlier and hence
an attempt was made to identify the decomposition products using various analytical techniques such as infrared spectroscopy,
mass spectroscopy and X-ray diffraction which suggested that the glutamic acid fragment is lost first as evidenced by acid
loss and amide enhancement in the IR spectra. The vitamin was ultimately degrading to carbon fragments and that further identification
was not necessary.
Authors:A. Hazra, K. Alexander, D. Dollimore, and A. Riga
The present study was aimed at determining the kinetics of evaporation and establishing vapor pressure curves for both single and multi-component systems by thermogravimetry (TG) and differential scanning calorimetry (DSC). Essential oils (e.g. lavender oil, orange oil, clove oil and eucalyptus oil, etc.) are typically multi-component systems consisting of various volatile pure components (e.g. linalyl acetate, limonene, cinnamaldehyde, etc.) which resemble single component systems. In this study linalyl acetate was taken as the calibration compound for TG. The vapor pressure curves for the pure substances were plotted using TG and vapor pressure plots for clove oil and eucalyptus oil were constructed using DSC. The thermodynamic and kinetic parameters of the pure compounds were compared to that of the multi-component systems to quantitatively and qualitatively measure the influence of different compounds on each other. The k-value from the vapor pressure data for linalyl acetate was calculated as 112006 Pa kg0.5mol0.5s-1 m-2 K-0.5. The vapor pressure values were used to determine the Antoine constants using the SPSS 10.0 software.
Authors:A. Riga, D. Young, G. Mlachak, and P. Kovach
A commercial set of polymers has been characterized by TG-DTA, DSC, TMA, FTIR spectroscopy and X-ray diffraction analysis
(XRD). Thermal and mechanical stability, as well as the polymer glass transition temperature,Tg, and melt temperature,Tm, have been documented. There is a good correlation between measuredTg andTm values and published data. The degree of polymer crystallinity for polyethylene has been verified by XRD. The credibility
and stability of these reference polymers is based on a comparison of their thermal properties, over a wide range of temperatures
from two versions of a reference set, published in 1979 (A) and 1994 (B). The thermal properties and crystallinity of these
polymers have stood the test of time and are reliable, readily available and consistent.
Authors:H. Sobhi, M. Matthews, B. Grandy, J. Masnovi, and A. Riga
This biomaterials overview for selecting polymers for medical devices focuses on polymer materials, properties and performance.
An improved understanding of thermoplastics and thermoset properties is accomplished by thermal analysis for device applications.
The medical applications and requirements as well as the oxidative and mechanical stability of currently used polymers in
devices are discussed. The tools used to aid the ranking of the thermoplastics and thermosets are differential scanning calorimetry
(DSC), thermogravimetry (TG), thermal mechanical analysis (TMA) and dynamic mechanical analysis (DMA) as well as a number
of key ASTM polymer tests. This paper will spotlight the thermal and mechanical characterization of the bio-compatible polymers
e.g., olefins, nylon, polyacetals, polyvinyl chloride and polyesters.
Authors:C. Mothé, D. Correia, F. de França, and A. Riga
Enhanced oil recovery
process is based on the injection of chemical products (e.g. polymers, surfactants,
gases) or thermal energy (originating from the injection of e.g. steam, hot
water, in situ combustion) to recover crude oil. One of these processes use
polymer solution to mobilize the oil in the reservoir. In this work the thermal
decomposition kinetic of xanthan gum, guar gum and a blend (50/50 mass/mass%)
was studied according to Ozawa–Flynn–Wall method. According to
the kinetic analysis, the studied systems were copmpatible. The rheological
behavior of the samples was studied in distilled water and seawater at different
temperatures. Only the blend was studied in distilled water presented synergism
(enhancement in material properties like stability and viscosity) which was
confirmed through rheology.