Some Polyamides,Polyesters, and Polyurethanes Containing AZO Groups

The paper discusses the synthesis of the N,N,′-azobis(formamidopropionic) acid (AFP), along with some characteristics determined from NMR spectrum, differential thermal analysis, and DSC. The behavior of AFP acid—as well as of its analogue, N,N′-azobis(formamidoacetic) acid (AFA)—has been studied in the reaction with aromatic diamine and with bis(glycol)terephthalate, leading to azopolymers of the azopolyamide, or azopolyester, type. On employing N,N′-bis(β-hydroxyethyl) azobis-formamide (HEAF) as the azo bifunctional compound in the reaction with diphenylmethane diisocyanate, a polyurethane possessing azo groups was obtained. The structure of the azopolymers has been spectroscopically confirmed.     

Polymeric Materials with Magnetic Properties

The paper deals with the study of the magnetic properties of some mechanochemically synthesized polychelates. Some spectral analysis methods such as ESR spectroscopy, atomic absorption spectroscopy, and especially Mössbauer spectroscopy are used for this purpose. The presence of metallic atoms (especially Fe) is responsible for the magnetic properties of these mechanochemically synthesized macromolecular compounds.     

Thermodynamic investigation of thermoresponsive xanthan‐poly (N‐isopropylacrylamide) hydrogels

Polysaccharide‐based hydrogels, such as xanthan maleate/poly(N‐isopropylacrylamide) (PNIPAAm) interpenetrated polymer networks, are thermostimulable materials of interest for the controlled release of biologically active components due to conformation changes at the low critical‐solution temperature (LCST) PNIPAAm phase transition. The phase transition of these interpenetrated polymer network hydrogels, where PNIPAAm is in a ‘confined’ environment, was examined by high resolution magic angle spinning nuclear magnetic resonance and differential scanning calorimetry. High resolution magic angle spinning nuclear magnetic resonance spectroscopy allows the accurate determination of LCST and an evaluation of the corresponding thermodynamic data. More particularly, the evolution of these data as a function of the composition of the hydrogel, and of the external parameters such as pH and ionic strength, was considered. LCST shows a minimal value with increasing xanthan content. Moreover, it was possible to calculate, as a function of temperature, the fraction of NIPAAm which remains uncollapsed. The data obtained for pure PNIPAAm hydrogels are in good agreement with recently published results. The phase transition of PNIPAAm in a diphasic hydrogel is broader when PNIPAAm is ‘confined’ within an interpenetrated polymer network than in a pure PNIPAAm crosslinked network. The widening of the transition with increasing xanthan content indicates a reduction of the PNIPAAm interchain aggregation in a network structure. Copyright © 2011 Society of Chemical Industry     

Texture anisotropy technique in brain degenerative diseases

Structural alterations anisotropy-based measured for different areas for the most common types of dementia diseases could be a biomarker of brain impairment. The current work aims to assess whether texture anisotropy can discriminate both healthy versus Alzheimer’s and Pick’s patients based on regional evaluation while maintaining high predictive power. The investigated area is reduced from the whole-brain surface to three major lobes (i.e., frontal, temporal and parietal). A predictive model was proposed to associate a disease with a specific area in the brain based on the anisotropy values. Simultaneous analysis of 1680 measurements from 105 brain magnetic resonance images acquired as T2w and PD sequences was performed to establish the significance of the model. The cerebral calcinosis disease has been used as artificial ground truth. The association based on textural anisotropy between targeted diseases and control patients was performed by using Pearson’s correlation coefficients. A new proposed consistency index investigated the texture anisotropy relevance for all image’s types and all analyzed classes and regions. The validation study is based on area under the receiver-operating characteristic curve that depicted the overall diagnostic performance of the texture anisotropy in each region. The proposed model demonstrated that texture anisotropy is accurate solution in diagnosis of Alzheimer’s and Pick’s diseases when the investigated area is reduced to major lobes, with sensitivity >90% and specificity >80%.

     

Polymerization of Styrene Initiated with Cumyl 4-t-Butylazo-4-Cyanoperoxypentanoate

The paper reports on the synthesis of a new bifunctional radicalic initiator and its behavior in the polymerization process. The synthesis of cumyl 4-t-butylazo-4-cyanoperoxypentanoate has been achieved by condensation of the corresponding acid chloride with cumen hydroperoxide. The structure of the azo perester is confirmed by IR, UV, and NMR spectra. The initiator has been used in styrene polymerization and the conversion of the polymer studied in connection to monomer and initiator concentration, time of reaction, and temperature. In compliance with multiple regression method, an equation correlating the PS conversion with the previously mentioned variables has been established.     

Inulin mixed esters crosslinked with 2-ethyl-hexyl-acrylate and their promotion as bio-based materials

New inulin-based materials were obtained by graft-copolymerization of inulin (poly-β(1 → 2)-fructoside) with 2-ethyl-hexyl acrylate. Inulin mixed esters were first synthesized by acylation using methacryloyl and palmitoyl chlorides. Further, these esters were copolymerized with 2-ethyl-hexyl acrylate in order to obtain bio-based crosslinked materials that could be used as commodity plastics and that would have biodegradable properties. The obtained products were characterized using FT-IR and ¹H NMR spectroscopies, thermogravimetry; differential scanning calorimetry, and activation energy for the degradation processes (using Kissinger method) was calculated. These biomaterials were also subjected to density measurement, tensile and torsion tests to evaluate their mechanical properties.     

Upper eyelid orbicularis oculi flap with tarsoconjunctival island for reconstruction of full-thickness lower lid defects

BACKGROUND: Various cryopreservation techniques have been investigated to elongate preservation time, however, most have failed to be clinically induced because of damage due to ice crystal formation. Subzero nonfreezing conditions could theoretically reduce organ metabolism without damage due to ice crystal formation. We evaluated the superiority of subzero nonfreezing storage compared with conventional hypothermic storage using isolated rat hepatocytes stored in University of Wisconsin (UW) solution without cryoprotectants. METHODS: Hepatocytes of Wistar rats isolated by collagenase digestion were suspended in UW solution and divided into the following three groups: subzero nonfreezing group (-4 degrees C), zero nonfreezing group (0 degrees C), and control group (4 degrees C). They were stored for 48 hr at the temperatures indicated. After 24 and 48 hr of storage, we carried out a trypan blue exclusion test and a 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide (MTT) assay, and measured lactate dehydrogenase release, lactic acid, ATP content, and the ability of hepatocytes to synthesize urea. After 48 hr of storage, morphological differences between the control group and the subzero nonfreezing group were investigated by scanning and transmission electron microscopy. RESULTS: Significant improvements of the trypan blue exclusion test and ATP contents in the subzero nonfreezing group were observed. Lactic acid production was also significantly suppressed in the subzero nonfreezing group compared with that in the control group. The MTT assay value was significantly better at -4 degrees C than at 4 degrees C. The rate of urea synthesis at -4 degrees C was higher than that at 4 degrees C. Electron microscopy revealed that subzero nonfreezing delayed the lethal bleb-forming process of stored hepatocytes, which was followed by mitochondrial swelling, compared with the control group. CONCLUSIONS: Subzero nonfreezing storage (-4 degrees C) in UW solution could provide better preservability for isolated rat hepatocytes with protection against hypoxic cell injury compared with conventional hypothermic storage (4 degrees C).     

Lanthanum cobaltite nanoparticles using the polymeric precursor method

The present study reports the evolution of reactive lanthanum cobaltite nanoparticles obtained by a polymeric precursor route, using citric acid as chelating agent. The crystallization from amorphous precursor, particle growth and the formation of nanoparticle agglomerates at different calcination temperatures was carried out by conventional and high-resolution electron microscopy, electron diffraction and energy-dispersive X-ray analysis and Raman spectroscopy. Microstructure measurements were compared with X-ray diffraction and chemical analysis results. Electron diffraction, combined with TEM, was used to determine the proportion of amorphous phase. The presence of amorphous carbon during the decomposition of the amorphous precursor was analyzed by Raman spectroscopy. The coherent crystalline domain size and the particle size have been monitored by XRD and electron microscopy in order to determine the evolution of both crystal size and the temperature onset for the formation of polycrystalline aggregates.The results demonstrate that at 550 °C we obtain pure single-phase equiaxed nanopowders of LaCoO₃ with crystal size of 20 nm, free of amorphous carbon and without the presence of polycrystalline aggregates.     

Synthesis and optical properties of water-soluble poly(vinylpyrrolidone) - modified fullerene C<Subscript>60</Subscript>

Summary  The effect of fullerene on the radical polymerization of N-vinylpyrrolidone with lauroyl peroxide in toluene was investigated kinetically. C₆₀ was found to act both as inhibitor and as retarder because the polymerization rate and the molecular weight of resulting poly(vinylpyrrolidone) is decreasing with the increase of the fullerene concentration (0-6.94 x 10^-4 mol l^-1). The water-soluble poly(vinylpyrrolidone)-modified fullerene C₆₀ compound was characterized by differential scanning calorimetric, Infrared and Raman spectroscopy, UV absorption and photoluminescence. Based on the results obtained by optical measurements, it is argued that by the covalent attachment of the polymeric radicals to fullerene cage the extended electronic conjugation system of the C₆₀ is broken leading to the appearance of a polyene structure.