Jadwiga Tritt-Goc

Solvent Effect on 1,2-O-(1-Ethylpropylidene)-α-D-glucofuranose Organogel Properties

The solvent effect on organogel formation in nitrobenzene and chlorobenzene using 1,2-O-(1-ethylpropylidene)-alpha-d-glucofuranose (1) as the gelator is presented. Fourier transform infrared (FTIR) spectroscopy revealed that hydrogen bonding between the molecules of gelator 1 is the main driving force for gelator self-aggregation. The gels are characterized by different hydrogen-bonding patterns, which are reflected in a different microstructure of the networks. The morphology of fibers of nitrobenzene organogel consists of straight, rod-like, and thinner fibers, in comparison to the elongated but generally not straight and thicker fibers in chlorobenzene organogel. The thermal stability of gels also differs, and the DeltaH is equal to 50.1 and 65.0 kJ/mol for nitrobenzene and chlorobenzene gels, respectively. The properties of the gels reported here were compared to benzene and toluene gels of 1 presented in previous work and correlated with different solvent parameters: epsilon, delta, and E(T)(30). We have shown that the polarity of the solvent influences the thermal stability of the gel, the hydrogen-bonding network, and finally the structure of gel network. Therefore, in the studied sugar-based gelator, the hydrogen bonding alone is insufficient to fully describe the gelation process.

Magnetic resonance imaging study of the swelling kinetics of hydroxypropylmethylcellulose (HPMC) in water.

Magnetic resonance imaging has been used to monitor the hydration of hydroxypropylmethylcellulose samples by two-dimensional mapping of properties such as spin density and relaxation times. The measurements were performed at two pH values of water: 2 and 6 and two temperatures 25 and 37 degrees C. It is shown that transport behavior of water into HPMC changes from being almost completely relaxation controlled (case II) at pH=2 to Fickian behavior for pH=6. It was also observed that radial swelling is larger for the system composed of HPMC and water at pH=6 than at pH=2.

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.

Evidence of Solvent-Gelator Interaction in Sugar-Based Organogel Studied by Field-Cycling NMR Relaxometry

The dynamics of bulk toluene and toluene confined in the 1,2-O-(1-ethylpropylidene)-α-D-glucofuranose gel was studied using (1)H field-cycling nuclear magnetic resonance relaxometry. The proton spin-lattice relaxation time T(1) was measured as a function of the magnetic field strength and temperature. The observed dispersion in the frequency range 10(4)-10(6) Hz for the relaxation rate of toluene in the gel system give evidence of the interaction between the toluene and the gelator aggregates. The data were interpreted in terms of the two-fraction fast-exchange model. Additionally it was also shown that a cooling rate during gel preparation process influences the gel microstructure and leads to different gelator-solvent interactions as reflected in a different behavior of the proton spin-lattice relaxation rate of toluene within the gel observed at the low frequency range.

The influence of the superplasticizer on the hydration and freezing processes in white cement studied by 1H spin-lattice relaxation time and single point imaging

The influence of the superplasticizer Sikament 92 on the hydration process of white cement paste and freezing behavior of hardened white cement was investigated by 1H spin-lattice relaxation and Single Point Imaging (SPI) methods. The study shows that this superplasticizer extends the workability of the cement paste by about 5 h and significantly increases the hydration rate when compared with pure sample. The pore structures in hardened cement were studied by MRI and demonstrate that Sikament 92 lowers the porosity and increases resistance to freezing.

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.

Spin-lattice relaxation study of the methyl proton dynamics in solid 9,10-dimethyltriptycene (DMT)

Proton spin-lattice relaxation studies are performed for powder samples of 9,10-dimethyltriptycene (DMT) and its isotopomer DMT-d(12) in which all the non-methyl protons in the molecule are replaced by deuterons. The relaxation data are interpreted in terms of the conventional relaxation theory based on the random jump model in which the Pauli correlations between the relevant spin and torsional states are discarded. The Arrhenius activation energies, obtained from the relaxation data, 25.3 and 24.8 kJ mol(-1) for DMT and DMT-d(12), respectively, are very high as for the methyl groups. The validity of the jump model in the present case is considered from the perspective of Haupt theory in which the Pauli principle is explicitly invoked. To this purpose, the dynamic quantities entering the Haupt model are reinterpreted in the spirit of the damped quantum rotation (DQR) approach introduced recently for the purpose of NMR lineshape studies of hindered molecular rotators. Theoretical modelling of the relevant methyl group dynamics, based on the DQR theory, was performed. From these calculations it is inferred that direct assessments of the torsional barrier heights, based on the Arrhenius activation energies extracted from relaxation data, should be treated with caution.

The structural dynamics in the proton-conducting imidazolium oxalate

The 1H spin–lattice relaxation times and high-resolution solid-state nuclear magnetic resonance (NMR) under fast magic spinning were used to study the structural dynamics in the proton-conducting material imidazolium oxalate. The measurements provide evidence for the ordered and disordered domains within the studied material. The two components drastically differ in their 1H spin–lattice relaxation times and 1H–13C cross-polarization magic-angle-spinning (CP/MAS) spectra. The coalescence phenomenon of the resonances of the basal carbons of the imidazole ring undergoing a reorientation is observed only for mobile molecules in the disordered domains. Therefore, only these molecules can be responsible for proton conductivity allowing for the Grotthus mechanism.