Gabriel Feio

Self-winding of helices in plant tendrils and cellulose liquid crystal fibers

Passiflora edulis, like other climbing plants, possesses long, tender, soft, curly and flexible organs called tendrils whose circumnutation allows the plant to find support. Tendrils curl into spirals or twist into a helix, often of one handedness over half of its length and of the opposite handedness over the other half, the two halves being connected by a short straight section – a perversion, depending on whether they are supported at just one end or supported at both ends, respectively. This is a consequence of an intrinsic curvature of the tendrils. We report on liquid crystalline cellulosic fibers and jets, which mimic the shapes of helical tendril structures. Liquid crystalline and isotropic cellulosic precursor solutions of curved and straight fibers are examined using nuclear magnetic resonance imaging (MRI) and polarizing optical microscopy (POM) techniques to determine morphological and structural features contributing to fiber curvature. We study the subtle physical mechanisms responsible for self-winding behavior as a result of the intrinsic curvature due to the non-uniform deformation of filaments. In the case of liquid-crystalline cellulosic fibers, this is due to a core of disclination forming off-axis along the filament. We also highlight the critical dependence of the helical structures on temperature, which offers a potential for direct fabrication of biocompatible tunable high-surface area membranes with mechanical adaptability.

The hardening of Portland cement studied by NMR stray-field imaging

Hydration and hardening processes of Portland cement (type I) were studied by analysis of the one-dimensional projections (profiles) obtained periodically with the stray-field imaging technique over two days. The influence of additives, such as gypsum, in Portland cement (type IA) was also investigated. The decay of the signal intensity as a function of time was found to be bi-exponential for type I and mono-exponential for type IA.

Molecular mobility, composition and structure analysis in glycerol plasticised chitosan films

This study was developed with the purpose to investigate the effect of polysaccharide/plasticiser concentration on the microstructure and molecular dynamics of polymeric film systems, using transmission electron microscope imaging (TEM) and nuclear magnetic resonance (NMR) techniques. Experiments were carried out in chitosan/glycerol films prepared with solutions of different composition. The films obtained after drying and equilibration were characterised in terms of composition, thickness and water activity. Results show that glycerol quantities used in film forming solutions were responsible for films composition; while polymer/total plasticiser ratio in the solution determined the thickness (and thus structure) of the films. These results were confirmed by TEM. NMR allowed understanding the films molecular rearrangement. Two different behaviours for the two components analysed, water and glycerol were observed: the first is predominantly moving free in the matrix, while glycerol is mainly bounded to the chitosan chain.

Biaxial Nematic Mesophases from Shape-Persistent Mesogens with a Fluorenone Bending Unit

Nematic phases, applied in almost all commercial liquidcrystal (LC) displays, are LC phases with mesogens isotropically distributed and exhibiting orientational long-range order of one preferred molecular axis along a common direction defined by the so-called director. These are the phases with the lowest viscosity and besides the anisotropic properties, are most similar to isotropic liquids. Biaxial nematics should realise a long-range orientational order of all three molecular axes along three mutually perpendicular directors, but maintain the isotropic distribution of the molecular centres of gravity and their molecular mobility. Such phases are not only appealing from the viewpoint of basic research and theoretical modelling, but are also of technological interest to speed up the switching of LC displays. [1, 2, 3] After the prediction by Freiser, [4] Saupe and Yu were the first to discover such mesophases in a narrow region of the phase diagram of a lyotropic LC. [5] The much-pursued syn

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.

Nuclear magnetic resonance spectroscopic investigations of phase biaxiality in the nematic glass of a shape-persistent V-shaped mesogen

Deuterium and carbon-13 NMR spectroscopy were used to study both the high temperature uniaxial nematic and the low temperature biaxial nematic glass of a shape-persistent V-shaped mesogen. It was found that biaxial ordering determined in the domains of the latter has symmetry lower than D(2h) and is compatible with C(2h) symmetry or lower. In particular, elements of the ordering matrix including biaxial phase order parameters were determined from (2)H NMR at two temperatures, one just below the glass transition, and the other deep inside the biaxial glass, which allowed for the characterization of the dominant molecular motions at these temperatures. (13)C NMR magic angle spinning sideband patterns, collected both in the high temperature nematic phase and in the nematic glass, clearly show the difference between them in terms of the phase symmetry.

13C nuclear magnetic resonance studies of cellulose ester derivatives in solution, powder and membranes

A 13C nuclear magnetic resonance study (with cross polarization and magic angle spinning) is presented of commercially available cellulose acetate and cellulose propionate as powder samples and also in different membranes. Some physical properties of the films are interpreted in the light of data obtained for the principal components of the shielding tensor of 13C nuclei on carbonyl groups. In particular, it is shown that the shielding asymmetry factor, measured on samples with a regular shape and with a fixed orientation in the rotor, is a sensitive probe to ordered domains in the polymers.

Relaxivities of magnetoliposomes: the effect of cholesterol.

We present relaxivities measurements for both the longitudinal and transverse relaxations of two types of liposomes loaded with ultra small superparamagnetic iron oxide nanoparticles. The magnetoliposome systems presented are soybean phosphatidylcholine liposomes, with and without cholesterol, in the phospholipid bilayer with different molar ratios lipid:cholesterol. In fact, cholesterol is needed to obtain stable liposomes for intravenous administration. The longitudinal and transverse relaxivities were measured with a NMR spectrometer in a 7T magnetic field. For the studied concentrations, the liposomes show a negligible effect on the longitudinal relaxation time T1 of the medium, but they are very efficient on decreasing the transverse relaxation time T2, the behaviour one expects for a negative CA. We observed a lower transverse relaxivity for the magnetoliposome nanosystem with cholesterol, which strongly decreases with the cholesterol content in the liposome bilayer.

New long circulating magnetoliposomes as contrast agents for detection of ischemia-reperfusion injuries by MRI

UNLABELLED New long circulating magnetoliposomes coated with polyethylene glycol (PEG), and loaded with PEG-coated 10nm superparamagnetic iron oxide nanoparticles (SPION), were developed. The magnetoliposomes relaxivities r1, r2 measured in a magnetic field of 7 T showed a minor effect on T1, but a major effect on T2. These nanosystems were used as a negative contrast agent for MRI in a nonclinical study to visualize, in a rat model of liver ischemia, ischemia-reperfusion injuries. Magnetic resonance micro-images (MRM) at 7 T were obtained for rat liver with and without magnetoliposomes administration and analyzed in comparison with liver biomarkers and histological results. These new long circulating magnetoliposomes enhanced the detection of lesions indicating their potential use as efficient MRI negative contrast agent for the detection of liver ischemia-reperfusion injuries. FROM THE CLINICAL EDITOR This paper describes the generation of PEGylated magnetoliposomes and demonstrates their feasibility as negative contrast agents in a liver ischemia-reperfusion rat model.

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.