Comparison of the differential isosteric adsorption enthalpies and entropies calculated from chromatographic data

The differential isosteric enthalpies, -deltaH(ads), and entropies, -deltaS(ads), of adsorption were calculated taking the retention times of the peak maxima and the centres of gravity of peaks into account and compared with the results obtained from the adsorption second virial coefficients. A mathematical link between the -deltaH(ads) and -deltaS(ads) magnitudes and experimental data was derived through the Antoine-type equation which enables the -deltaH(ads) and -deltaS(ads) magnitudes to be found from adsorption second virial coefficients, B2S, calculated on the basis of chromatographically determined adsorption isotherm data. The virial coefficients were calculated employing the values of the Tóth and Unilan equation parameters. There are no significant differences to be found between the isosteric enthalpies obtained, whereas the values of the adsorption entropies were the highest for the centre of peak gravity data.     

Influence of diffusion on nonradiative energy transfer between FMN molecules in aqueous solutions

Concentration dependence of photoluminescence quantum yield of FMN aqueous solutions (66mM potassium phosphate buffer, pH 7.0) is investigated over the concentration range from 6.31x10(-5) M to 1.8x10(-2) M at temperatures 298.2 and 323.9K. Experimental data are compared with those obtained theoretically based on two different models of excitation energy transfer and migration in the system of FMN monomers and dimers. The first model does not take the material diffusion into account [Acta Phys. Acad. Sci. Hung. 30 (1971) 145] and the second model is based on the second-order transfer rates which are diffusion dependent [Chem. Phys. Lett. 41 (1976) 139; J. Lumin. 27 (1982) 441]. The comparison shows that the process of material diffusion cannot be neglected in the solutions studied as the relative contribution of the diffusion accelerated nonradiative energy transfer to the total drop of the quantum yield can be even higher then 70%. It is also shown, that in order to obtain a good agreement of the experimental and theoretical data it is necessary to introduce into the theory an additional channel of deactivation for the excitation energy. It is proposed that this additional channel can be partial degradation of excitation energy during its migration between the monomers.     

Chromatographic determination of the differential isosteric adsorption enthalpies and differential entropies on ordered silica materials

The adsorption properties of the ordered mesoporous siliceous materials: MCM-41C16 (denoted as C16), MCM-41C16-SH and MCM-41C16-NH(2) (known as MCMs) having different surface functionalities were studied by inverse gas chromatography to assess their suitability for adsorption of analytes from gas and liquid phases. Polar and non-polar adsorbates were employed. The differential isosteric enthalpies, -DeltaH(ads), and differential entropies, -DeltaS(ads), of adsorption of different 'molecular probes' were determined chromatographically. A mathematical link between the -DeltaH(ads), and -DeltaS(ads) magnitudes and experimental data was derived through an Antoine-type equation. The present studies have been entirely restricted to the region of low adsorbate concentration. The problem of the interrelationship between the -DeltaH(ads), and -DeltaS(ads) values, known as the 'thermodynamic compensation effect', and interpretation of chromatographic data for the adsorption of different adsorbates on the MCMs have been considered in the light of both experimental data obtained in the present studies and the data available in the literature for siliceous adsorbents with randomly ordered structures. It was shown chromatographically that there is substantial parallelism between the magnitudes of the differential isosteric enthalpy and differential entropy for some 'molecular probes' chromatographed on C16 and its derivatives. Complementary information was obtained by atomic-force microscopy (AFM), X-ray photoelectron spectroscopy and X-ray diffraction (XRD) spectroscopy.     

Rediscovering the problem of interpretation of chromatographically determined enthalpy and entropy of adsorption of different adsorbates on carbon materials. Critical appraisal of literature data

Adsorbate-adsorbent and adsorbate-adsorbate interactions having decisive influence on the distribution of adsorbate between gas-solid phases in inverse gas chromatography (IGC) have been thermodynamically explained. Specific retention volumes, second adsorption virial coefficients and Kováts retention indices, likewise their dependencies on column temperature, T, number of carbon atoms, n(C) (or methylene groups CH(2)) and mutual ones have been briefly presented. The results of the molar differential enthalpy and entropy of adsorption obtained for different carbon materials employing inverse gas chromatography have been collected and interpreted. An attempt has been made to elucidate abnormal behaviour of the specific and net retention volumes, the second adsorption virial coefficients and the Kováts retention indices, e.g., the magnitudes on which the values of the afore-mentioned thermodynamic values have been determined and compared. The detailed analysis of the errors associated with the experimental parameters necessary for calculating retention volumes, second adsorption virial coefficients and Kováts retention indices has been presented.     

Synthesis of OMS Materials and Investigation of Their Acceptor–Donor Characteristics

Three ordered mesoporous siliceous (OMS) materials known as MCM41s—unmodified MCM-41C16 (“C16”), and two MCM41s with different surface functionalities: MCM-41C16-SH (“C16-SH”) and MCM-41C16-NH₂ (“C16-NH₂”)—were synthesized and studied by inverse gas chromatography in order to determine their acceptor–donor properties. The specific retention volumes of nonpolar and polar probes that were chromatographed on these ordered mesoporous silica adsorbents were evaluated under infinite dilution conditions. Two methods were employed to calculate the standard free energy of adsorption, ΔG _ads, of each chromatographed probe on the basis its specific retention volume. These ΔG _ads values were then employed to estimate the van der Waals contribution and the specific contribution of the free surface energy for each MCM41. DN values (donor numbers, based on the Gutmann scale) and AN* values (acceptor numbers, based on the Riddle–Fowkes scale) were employed to determine the values of parameters that characterize the ability of the MCM41s to act as electron acceptors (parameter: K _A) and donors (parameter: K _D). Considering the different compositions of the probes, each of which has different acceptor–donor properties, a new chromatographic test to supplement the Grob test is suggested.

     

Liquid Crystals as Stationary Phases in Chromatography

The most correct analysis of the compositions of diverse analytes mixtures is significant for analytical studies in different fields; however, many prevalent analytes cannot be identified employing traditional partition gas chromatographic methods. Thus, the increasing requirements on analytes of isomeric compounds and the problems encountered in their separation demand a study of more diverse analytical systems which are characterised by higher selectivity. Therefore, the selectivity and polarities of various liquid crystals (rod-like, banana-shape, biforked, oxygen, sulphur, nitrogen, and metal containing molecules, Schiff-base, and polymeric dendrimers) employed as liquid crystalline stationary phases (LCSPs) have been discussed from both points of views, namely, their analytical applications and thermodynamic characteristics of infinitely diluted probes with different acceptor–donor properties. Extreme particular effort has been paid to the different interdependencies between the bound up chemical structures of liquid crystal molecules with their different acceptor–donor properties and the connected resolution capabilities in the interpretation of the probe—LCSP systems, on the basis of the \( { \ln }V_{g\left( T \right)} = f\left( {\frac{1}{T}} \right) \) and \( { \ln }\left( {\frac{{a_{1} }}{{w_{1} }}} \right)^{\infty } = f\left( {\frac{1}{T}} \right) \) dependencies, with regard to the LCSP compositions, which have been controlled by the counterbalancing of the enthalpy and entropy factors. The properties of binary systems composed of liquid crystalline poly(propyleneimine) dendrimers—rod-like molecules of liquid crystals and effects of the dendrimer structure, the chemical nature, and molecular size of the non-mesogens on the ability to dissolve in the liquid crystalline phases, have been interpreted. Practical applications of metallomesogenes and chiral stationary phases for analytical separation of different organic substances have also been taken into consideration.

     

Resolution of the excitation-emission spectra of FMN in rigid poly(vinyl alcohol) matrices

The excitation-emission spectra of flavin mononucleotide (FMN) were measured in rigid PVA films for concentrations ranging from 6.92 x 10(-4)M to 1.03 M. The theoretical three-linear decomposition of the excitation-emission spectra indicated the presence of two absorption and emission centers corresponding to FMN monomer and dimer, respectively. The component of the fluorescence profile corresponding to the FMN monomer has a large negative part which is the mirror image of the emission band profile of the dimer. The elimination of this part by taking a linear combination of the emission components of the monomer and of the dimer resulted in emission spectrum, which is in a very good agreement with the monomer spectrum measured directly. The appearance of a negative part of the monomer emission profile obtained by trilinear decomposition of the emission-absorption spectra of FMN can be explained in terms of the non-radiative reverse energy transfer from the FMN dimers to the FMN monomers. The presented results confirm that the FMN molecules in rigid PVA form dimers but not higher order aggregates. Moreover, they enable to obtain fluorescence spectra of dimers and suggest that FMN dimers may take part in the process of non-radiative energy transfer occurring in photoreception phenomena.     

Synthesis of OMS Materials and Investigation of Their Acceptor–Donor Characteristics

Three ordered mesoporous siliceous (OMS) materials known as MCM41s—unmodified MCM-41C16 (“C16”), and two MCM41s with different surface functionalities: MCM-41C16-SH (“C16-SH”) and MCM-41C16-NH₂ (“C16-NH₂”)—were synthesized and studied by inverse gas chromatography in order to determine their acceptor–donor properties. The specific retention volumes of nonpolar and polar probes that were chromatographed on these ordered mesoporous silica adsorbents were evaluated under infinite dilution conditions. Two methods were employed to calculate the standard free energy of adsorption, ΔG _ads, of each chromatographed probe on the basis its specific retention volume. These ΔG _ads values were then employed to estimate the van der Waals contribution and the specific contribution of the free surface energy for each MCM41. DN values (donor numbers, based on the Gutmann scale) and AN* values (acceptor numbers, based on the Riddle–Fowkes scale) were employed to determine the values of parameters that characterize the ability of the MCM41s to act as electron acceptors (parameter: K _A) and donors (parameter: K _D). Considering the different compositions of the probes, each of which has different acceptor–donor properties, a new chromatographic test to supplement the Grob test is suggested.