Joanna Kowalczuk

Novel supramolecular organogels based on a hydrazide derivative: non-polar solvent-assisted self-assembly, selective gelation properties, nanostructure, solvent dynamics

In this work, we report the complementary studies of supramolecular organogels composed of a newly synthesized low molecular mass gelator 4-(4-morpholinyl)-3-nitro-benzoylhydrazide (1) with benzene, toluene, and p-xylene. Intermolecular hydrogen bonding and π–π stacking interactions are the main driving forces promoting gelation of the system and the self-assembly of the new gelator molecules. The former interactions were revealed by the FT-IR and Raman studies, whereas the latter ones were postulated on the basis of the molecular structure of the gelator, UV-Vis spectra and comparison with the previously published data for other hydrazide derivatives. The strengths of the hydrogen bonding interactions are comparable as indicated by the FT-IR spectra analysis. Therefore, we correlated the differences in the calculated enthalpies of the gelator aggregates of 1 in the gels studied with the differences in the strengths of the π–π stacking interactions. The gel of 1 with benzene is characterized by the highest value of enthalpy. The images taken by the SEM and POM methods reveal differences in the architecture of gelator 1 aggregates, which are lamellar-like in toluene and fibrillar in benzene and p-xylene. The dispersion of spin–lattice relaxation times of solvents in the gel phase, observed by the NMR relaxometry method at low frequencies, is an indicator of the solvent–gelator interactions. As a result of this interaction, a significant slowing down of the motion (5 orders of magnitude as compared to bulk solvents) of the fraction of solvent molecules at the pore surface in the gel phase takes place. The diffusion of solvents in gels is restricted as shown by PGSE NMR. The apparent diffusion coefficient measured as a function of diffusion time can be used to estimate the pore size of the gel matrix, which for the gel of 1 with toluene is about 22 μm.

In situ, real time observation of the disintegration of paracetamol tablets in aqueous solution by magnetic resonance imaging

The disintegration behavior of paracetamol tablets was studied by magnetic resonance imaging (MRI) using the Snapshot FLASH method. The total time of the single experiment is 425 ms and allows the study of the disintegration process in real time. The study was carried out in vitro under acidic gastric pH conditions and may help to predict the behavior of paracetamol tablets in the stomach after oral administration. It was shown that in spite of identical conditions, the disintegration of the tablets under study was different. The distribution of protons of 4-(N-acetyl)aminophenol within the paracetamol tablet was shown to be homogeneous. The study was carried out in a non-destructive way by the SPI MRI method.

MRI study of Fickian, case II and anomalous diffusion of solvents into hydroxypropylmethylcellulose

Magnetic resonance imaging was used to investigate the diffusion and swelling processes of a hydroxypropylmethylcellulose (HPMC) matrix. Polymer in the form of a cylinder was hydrated in a water solvent with pH 2, 7, and 12 at 37 °C and monitored at equal intervals on a Bruker Avance 300 MHz spectrometer. The spatially resolved spin-spin relaxation times and spin densities together with the change in the dimension of the glass core of the polymer were determined for the HPMC tablets as a function of hydration times. FromT2 parameters, the solvent molecule mobility within the gel layer of the HPMC was estimated. All studied parameters allow the determination of the diffusion of the solvent into the HPMC matrix as Fickian diffusion for alkaline solvents, case II for acidic solvent, and anomalous diffusion for neutral solvent.

A possible application of magnetic resonance imaging for pharmaceutical research

Magnetic resonance imaging (MRI) is a non-destructive and non-invasive method, the experiment can be conducted in situ and allows the studying of the sample and the different processes in vitro or in vivo. 1D, 2D or 3D imaging can be undertaken. MRI is nowadays most widely used in medicine as a clinical diagnostic tool, but has still seen limited application in the food and pharmaceutical sciences. The different imaging pulse sequences of MRI allow to image the processes that take place in a wide scale range from ms (dissolution of compact tablets) to hours (hydration of drug delivery systems) for mobile as well as for rigid spins, usually protons. The paper gives examples of MRI application of in vitro imaging of pharmaceutical dosage based on hydroxypropyl methylcellulose which have focused on water-penetration, diffusion, polymer swelling, and drug release, characterized with respect to other physical parameters such as pH and the molecular weight of polymer. Tetracycline hydrochloride was used as a model drug. NMR imaging of density distributions and fast kinetics of the dissolution behavior of compact tablets is presented for paracetamol tablets.

Magnetic resonance imaging study of the transport phenomena of solvent into the gel layer of hypromellose matrices containing tetracycline hydrochloride

Magnetic resonance imaging was used to study the diffusion of a water solution of hydrochloric acid into hypromellose (hydroxypropylmethylcellulose) matrices. Spatially resolved information was obtained about the self‐diffusion coefficient and spin–spin relaxation time of solvent protons in the gel layer of hypromellose matrices loaded with different amounts of tetracycline hydrochloride. The data showed the influence of the drug concentration on the diffusion and spin–spin relaxation. Higher drug concentrations in the hypromellose matrix led to greater swelling of the matrix and faster diffusion of the water molecules inside the gel layer of the polymer. The observed differences between the radial and axial diffusion were interpreted in terms of the stresses imposed in the axial direction during the compression of the samples. The spin–spin and diffusion profiles indicated that the diffusion of a water solution of hydrochloric acid into hypromellose, pure and loaded with different amounts of tetracycline hydrochloride, was characterized as a Case II mechanism.

Effect of gel matrix confinement on the solvent dynamics in supramolecular gels.

Supramolecular gels formed by the sugar gelator of methyl-4,6-O-(p-nitrobenzylidene)-α-d-glucopyranoside (1) with 1,3-propanediol (PG) and 1-butanol (BU) were prepared with different gelator concentrations. The solvent dynamics within gels, characterized by the diffusion coefficient (D) and the spin-lattice relaxation time (T1), was the subject of NMR diffusometry and relaxometry studies. The diffusion was studied as a function of diffusion time and gelator concentrations. The relaxation time was measured as a function of Larmor frequency. The decrease of the diffusion coefficient was observed as a function of diffusion time for both gels and for all studied gelator concentrations. It is indicative of the confinement effect due to the geometrical restrictions of the gel matrix. The relaxation data for PG solvent confined in 1/PG gel revealed the low frequency dispersion (in kHz region) which is a fingerprint of a specific interaction experienced by PG solvents in the presence of the rigid structure of gelator 1 aggregates. The relaxation model, well known from the interpretation of liquid confined in nanopores as reorientations mediated by translational displacements (RMTD), was successfully applied to analyze the data of studied solvents confined in matrices of supramolecular gels. The microstructures of gel matrices were imaged by Polarized Microscopy.

Diffusive diffraction phenomenon observed by PGSE NMR technique in a sugar-based low-molecular-mass gel.

The paper presents the diffusive diffraction phenomenon observed by the single-pulse-gradient spin-echo (s-PGSE) NMR technique in a real porous material: a gel composed of low-molecular-mass gelator methyl-4,6-O-(p-nitrobenzylidene)-α-D-glucopyranoside and toluene. Thanks to this phenomenon, we can probe the true microstructure (not xerogel) in which the toluene diffuses. To analyze the measured diffusion-diffraction pattern, we employed a composite bicompartmental model that superimposes restricted diffusion in small cavities of the gel matrix within the bundles of crossing fibers, with free diffusion in large and unconfined compartments between the bundles of crossing fibers. For restricted diffusion a pore-hopping formalism was applied. The observation of the diffraction pattern and its analysis leads to the conclusion that the pores, in the slow diffusing compartment of studied gel are ordered, at least locally, and relatively monodisperse with a size of 64 μm. Moreover, the restricting walls formed by the crossing fibers are perpendicular to the direction of the diffusion gradient.

Moisture content (MC) and multinuclear magnetic resonance imaging (MRI) study of water absorption effect on wood treated with aminofunctional silane

The aim of this study was to determine susceptibility of aminoethyl aminopropyl trimethoxysilane (AEAPTMOS)-treated wood to absorption of liquid water. Absorbability was analysed by measuring absolute moisture content of wood and by MRI. These analyses were based on the results of previous studies on resistance against decay fungi in case of wood treated with the same chemical compound. In their previous studies the authors found that AEAPTMOS exhibits enhanced hydrophobic properties and thus increased resistance to the action of specific abiotic and biotic factors. The advantageous fungicidal properties of wood treatment systems indicate that AEAPTMOS may be considered as an environmentally friendly solution, being an alternative to conventional biocidal agents. Results indicate that this method may be used in laboratory analyses assessing the relative amount of water uptake through the wood surface.ZusammenfassungZiel dieser Studie war es, den Einfluss einer Behandlung von Holz mit Aminoethylaminopropyltrimethoxysilan (AEAPTMOS) auf die Aufnahme von flüssigem Wasser zu bestimmen. Die Absorptionsfähigkeit wurde durch Untersuchung des absoluten Feuchtegehalts von Holz und mittels Magnetresonanztomographie (MRI) ermittelt. Als Grundlage dieser Studie dienten Ergebnisse früherer Untersuchungen über die Fäuleresistenz von mit der gleichen chemischen Verbindung behandeltem Holz. Die Autoren kamen darin zu dem Schluss, dass AEAPTMOS verbesserte hydrophobische Eigenschaften bewirkt und somit die Resistenz gegenüber bestimmten abiotischen und biotischen Faktoren erhöht. Die guten fungiziden Eigenschaften dieser Holzbehandlungsmethode deuten darauf hin, dass AEAPTMOS als umweltfreundliche Lösung angesehen werden kann und eine Alternative zu herkömmlichen Biozidmitteln darstellt. Die Ergebnisse zeigen, dass diese Methode in Laboruntersuchungen zur Bestimmung der relativen Menge an durch das Holz aufgenommenem Wasser verwendet werden kann.

The structural parameters of rigid matrix of saccharide-based gel described by short and long diffusion regime analysis

The tortuosity–porosity relation and internal structure diameters in a selected organogel are studied. The diffusion coefficient measured by pulsed field gradient NMR at short and long observation times can be used to estimate the tortuosity and the pore surface-to-volume (S/Vpore) ratio of a porous material (Latour et al. in J Magn Res A 112:83–91, 1995; Mair et al. in Magn Res Imaging 19:345–351, 2001; Mitra et al. in Phys Rev B 47(14):8565–8574, 1993; Valiullin and Skirda in J Chem Phys 114:452–458, 2001). The value of S/Vpore allows to calculate the average pore and barrier diameters. In the experiment, the time-dependent diffusion coefficient of toluene in a low molecular weight gelator methyl-4,6-O-(p-nitrobenzylidene)-α-d-glucopyranoside (Gluco-NO2) matrix was measured. The results revealed the relation between the diffusion coefficient of toluene and the concentration of gelator Gluco-NO2 in the system. With increasing Gluco-NO2 compound in the sample, the diffusion coefficient of toluene decreases. On the basis of the diffusion coefficient behaviour as a function of time and gelator concentration, the fibrous structure of the gel matrix was identified and the structural parameters of the system were investigated.