Chiral amplification of disodium cromoglycate chromonics induced by a codeine derivative.

Chromonic liquid crystals (CLC) are lyotropic phases formed by discotic mesogens in water. Simple chiral dopants such as amino acids have been reported to turn chromonic liquid crystals into their cholesteric counterparts. Here we report a chirality amplification effect in the nematic phase of a 9 wt% disodium cromoglycate (DSCG) lyotropic liquid crystal (LLC) upon doping with a water-soluble codeine derivative. The transition on cooling the isotropic to the nematic phase showed the presence of homochiral spindle-shaped droplets (tactoids). NMR DOSY experiments on a triple gradient probe revealed a small degree of diffusion anisotropy for the alkaloid embedded in the liquid crystal structure. These results in combination with XRD, CD and POM experiments agree with a supramolecular aggregation model based on simple columnar stacks.

Enhanced contrast efficiency in MRI by PEGylated magnetoliposomes loaded with PEGylated SPION: effect of SPION coating and micro-environment.

Magnetic core coatings modify the efficiency of nanoparticles used as contrast agents for MRI. In studies of these phenomena, care should be given to take into account possible effects of the specific micro-environment where coated nanoparticles are embedded. In the present work, the longitudinal and transverse relaxivities of superparamagnetic iron oxide nanoparticles stabilized with short-chain polyethylene glycol molecules (PEGylated SPIONs) were measured in a 7T magnetic field. PEGylated SPIONs with two different diameters (5 and 10nm) were studied. Two different PEGylated magnetoliposomes having liposome bilayer membranes composed of egg-phosphatidylcholine, cholesterol and 1,2-distearoyl-sn-glycerol-3-phosphoethanolamine-N-[methoxy PEG-2000] were also studied for their relaxivities, after being loaded with the PEGylated SPION of 5 or 10nm. This type of liposomes is known to have long residence time in bloodstream that leads to an attractive option for therapeutic applications. The influence of the magnetic core coating on the efficiency of the nanosystem as a negative contrast agent for MRI was then compared to the cumulative effect of the coating plus the specific micro-environment components. As a result, it was found that the PEGylated magnetoliposomes present a 4-fold higher efficiency as negative contrast agents for MRI than the PEGylated SPION.

Synthesis and characterization of magnetoliposomes for MRI contrast enhancement.

This work assesses the characteristics of magnetoliposomes of soybean phosphatidylcholine (SPC):cholesterol (Chol) loaded with superparamagnetic iron oxide nanoparticles (IONPs) stabilized with tetramethylammonium hydroxide (TMAOH) and their capacity to enhance magnetic resonance imaging (MRI) contrast. Magnetoliposomes of SPC were used for comparative studies. IONPs and magnetoliposomes were characterized using transmission electron microscopy, dynamic light scattering, SQUID magnetometry, FTIR and MRI. The saturation magnetization at 10K was ~0.06 Am(2)/kg for SPC:Chol magnetoliposomes with 7 g iron oxide/mol of lipid and ~0.05 Am(2)/kg for SPC magnetoliposomes with 21 g iron oxide/mol of lipid. As these values are associated with the number of incorporated magnetic IONPs, the saturation magnetization is 1.2 times higher for magnetoliposomes of SPC:Chol as compared with magnetoliposomes of SPC alone. The behavior of temperature dependence in both cases is typical of superparamagnetic particles. FTIR spectra evidence the increase of magnetoliposome membrane ordering with the presence of Chol. Principal component analysis (PCA) applied to FTIR spectra evidenced a clear distinction between scores for SPC:Chol, and SPC magnetoliposomes and for SPC empty liposomes. PCA applied to FTIR data differentiate magnetoliposomes from empty liposomes. MR images of aqueous phantoms obtained with and without magnetoliposomes, clearly evidence their effect on T2 image weighting.

Deuterium NMR study of mobility and fluctuations in nematic and isotropic elastomers.

Orientational ordering in polydomain nematic and isotropic elastomers with identical polysiloxane backbone and different deuterium-labeled side groups is studied by D-NMR. In the nematic elastomer the orientational order parameter grows in a critical fashion on crossing the I-N transition implying a continuous phase transition driven by critical fluctuations of local director. The orientational (nematic) ordering occurs on the background of the polymer dynamics exhibited by the backbone, which is similar in the nematic and the analogous isotropic elastomers. The temperature dependence of NMR linewidths is compatible with a Vogel-Fulcher glassy dynamics.

The influence of the preparation methods on the inclusion of model drugs in a beta-cyclodextrin cavity.

The work aims to prove the complexation of two model drugs (ibuprofen, IB and indomethacin, IN) by beta-cyclodextrin (betaCD), and the effect of water in such a process, and makes a comparison of their complexation yields. Two methods were considered: kneading of a binary mixture of the drug, betaCD, and inclusion of either IB or IN in aqueous solutions of betaCD. In the latter method water was removed by air stream, spray-drying and freeze-drying. To prove the formation of complexes in final products, optical microscopy, UV spectroscopy, IR spectroscopy, DSC, X-ray and NMR were considered. Each powder was added to an acidic solution (pH=2) to quantify the concentration of the drug inside betaCD cavity. Other media (pH=5 and 7) were used to prove the existence of drug not complexed in each powder, as the drugs solubility increases with the pH. It was observed that complexation occurred in all powders, and that the fraction of drug inside the betaCD did not depend neither on the method of complexation nor on the processes of drying considered.

Biaxial nematic order and phase behavior studies in an organosiloxane tetrapode using complementary deuterium NMR experiments.

The biaxial nematic phase was recently observed in different thermotropic liquid crystals, namely bent-core compounds, side-chain polymers, bent-core dimers, and organosiloxane tetrapodes. In this work, a series of experiments with a nematic organosiloxane tetrapode where nuclear magnetic resonance (NMR) spectra are collected while the sample is continuously rotating around an axis perpendicular to the magnetic field, are discussed in conjunction with the analysis of a deuterium NMR experiment on the same system reported earlier. The sample used is a mixture of a deuterated probe with the tetrapode. The mixture exhibits a nematic range between -40 degrees C and 37 degrees C. The results of the two independent, but complementary deuterium NMR experiments confirm the existence of a biaxial nematic phase for temperatures below 0 degrees C with high values of the asymmetry parameter at low temperatures. The presence of slow movements of the tetrapode mesogenic units in the low-temperature regime could also be detected through the analysis of the NMR spectra. Simulations indicate that these movements are mainly slow molecular reorientations of the mesogenic units associated with the presence of collective modes in the nematic phases of this compound. In the case of tetrapodes, recent investigations attribute the origin of biaxiality to the hindering of reorientations of the laterally attached mesogenic units which constitute the tetrapode. This study relates the molecular movements with the nematic biaxial ordering of the system.

Deuterium NMR investigation of the biaxial nematic phase in an organosiloxane tetrapode.

Deuterium NMR is used to examine the molecular order exhibited by an organosiloxane tetrapode giving the first experimental evidence, using a bulk sample, for the existence of a biaxial nematic phase in this type of compounds. The temperature dependence of the averaged quadrupolar coupling constant and asymmetry parameter was determined in the compound's nematic phase. Two distinct regimes could be identified, one with a vanishing asymmetry parameter corresponding to a uniaxial nematic phase and another with a significant temperature dependent asymmetry parameter, corresponding to a biaxial nematic phase. The high values obtained for the asymmetry parameter at the lower end of the nematic range are well above experimental error and constitute a definite proof of the biaxial nature of the nematic phase exhibited by the studied compound for those temperatures.