Biomedical subjects

M Pompe

Publications and source records attributed to M Pompe.

4 recordsLinked to original sources

PubMed2000

Justification of statistical overlap theory in programmed temperature gas chromatography: thermodynamic origin of random distribution of retention times.

A specific distribution of compounds' standard-state changes of enthalpy and entropy between mobile and stationary phases in programmed temperature gas chromatography (PTGC) is shown to produce the Poisson distribution of retention times often postulated in statistical-overlap theory (SOT). A three-part model is proposed, in which the enthalpy change is Poisson distributed, the average entropy change depends on the enthalpy change, and the actual entropy change varies in a uniformly random manner about the average entropy change. To test the model, the entropy and enthalpy changes of 350 aliphatic and aromatic hydrocarbons in petroleum were calculated with commercial GC software. These changes are shown to follow the three-part model. The model then was used with Monte Carlo methods to mimic the enthalpy and entropy changes. The substitution of the mimicked enthalpy and entropy changes into an equation for the retention temperature in PTGC is shown to produce a Poisson distribution of retention times that is statistically significant. This finding establishes a scientific link between the thermodynamics governing retention in PTGC and the superficially ad hoc assumption of the Poisson retention time distribution in SOT. Similar thermodynamic distributions are found for flavors and fragrances and for tetrachlorodibenzo-p-dioxins and furans, which follow SOT based on the Poisson distribution, but not for polychloronaphthalenes, which do not follow that SOT.

Journal Article↗

PubMed2000

Development of a calibration system to evaluate VOC losses in a branch enclosure.

Considerable uncertainties are associated with the experimental estimates of emission rates of different volatile organic compound (VOC) species from the biosphere to the atmosphere. Some of this uncertainty derives from the sampling and analytical procedures used in emission rate measurements. A calibration system was developed in order to evaluate possible errors in the measurements of biogenic emission rates using a branch enclosure system. Two types of calibration procedures were tested, a standard additions technique and an internal standard procedure. Both techniques were used to evaluate possible losses while sampling isoprene and monoterpenes, which are the most abundant VOCs of biogenic origin. The losses to Teflon lines and the empty sampling system were tested and losses to the branch enclosure system installed on two VOC emitting plant species were evaluated. A considerable loss of isoprene (approximately 18% of inflow concentration 65 ng l(-1)) to the empty enclosure system and to the system installed on the plant was measured, but no losses of monoterpenes were observed.

Calibration↗

PubMedDate not supplied

The variable molecular descriptors based on distance related matrices.

Recently variable molecular connectivity index and variable paths have been tested as molecular descriptors in several structure-property regressions. Here we outline the construction of several variable molecular descriptors, derived from the distance matrix and the "reversed" distance matrix. This includes the variable Balaban J index and the "reversed" Balaban index 1/J as well as a novel index 1/JJ derived from J and 1/J. All the variable descriptors mentioned were constructed by augmenting the distance matrix by replacing the diagonal zeroes with the variables x, y, z,.

Journal Article↗

PubMedDate not supplied

The variable connectivity index 1chi(f) versus the traditional molecular descriptors: a comparative study of 1chi(f) against descriptors of CODESSA.

In this study we compared the prediction abilities of the variable connectivity index 1chi(f) (not included in CODESSA) with topological indices available from CODESSA. We selected the boiling points of n = 100 alcohols as the property and examined the pool of 56 topological indices. Prediction capabilities of the developed models were evaluated by classical training/test set approach. RMS errors calculated from the prediction set for the MLR models obtained from CODESSA software with 1, 2, 3, 4, and 5 parameters were 9.06, 5.69, 5.40, 4.9, and 3.37 degrees C, respectively. Using the variable connectivity index with weights x = 0.10 and y = -0.92 for carbon and oxygen atom respectively, we obtain regression BP = 38.12 1chi(f) - 37.56 with the correlation coefficient r = 0.9915, RMS error 4.21 degrees C calculated from the test set, and Fisher ratio F = 5691. Prediction capability of the variable connectivity index was better than for MLR regression model with up to four parameters.

Journal Article↗