X-Ray Diffraction, Calorimetric and Dielectric Relaxation Study of the Amorphous and Smectic States of a Main Chain Liquid Crystalline Polymer

Los polímeros cristales líquidos (LCP) son sistemas complejos que forman mesofases que presentan orden orientacional y polímeros amorfos. Con frecuencia, el estado amorfo isotrópico no puede ser estudiado debido a la rápida formación de mesofases. En este trabajo se ha sintetizado y estudiado un nuevo LCP: poli(trietilenglicol metil p, p '-bibenzoato), PTEMeB. Este polímero presenta una formación de mesofase bastante lenta haciendo posible estudiar de forma independiente tanto los estados amorfo y de cristal líquidos. La estructura y las transiciones de fase del PTEMeB han sido investigados por calorimetría (DSC), con MAXS / WAXS con temperatura variable que emplean radiación de sincrotrón y con difracción de rayos X. Estos estudios han mostrado la existencia de dos transiciones vítreas, relacionadas con las fases amorfa y cristal líquido. Se ha realizado un estudio de relajación dieléctrica en amplios intervalos de temperatura y presión. Se ha encontrado que la transición vítrea dinámica de la fase amorfa es más lenta que la del cristal líquido. El estudio de la relajación ? nos ha permitido seguir la formación isoterma de la mesofase a presión atmosférica. Además, con el estudio el comportamiento dinámico a alta presión se ha encontrado que se produce la formación rápida de la mesofase inducida por cambios bruscos de presión. Liquid crystalline polymers (LCPs) are complex systems that include features of both orientationally ordered mesophases and amorphous polymers. Frequently, the isotropic amorphous state cannot be studied due to the rapid mesophase formation. Here, a new main chain LCP, poly(triethyleneglycol methyl p,p'-bibenzoate), PTEMeB, has been synthesized. It shows a rather slow mesophase formation making possible to study independently both the amorphous and the liquid crystalline states. The structure and phase transitions of PTEMeB have been investigated by calorimetry, variable-temperature MAXS/WAXS employing synchrotron radiation, and X-ray diffraction in oriented fibers. These experiments have pointed out the presence of two glass transitions, related to the amorphous or to the liquid crystal phases. Additionally, the mesophase seems to be a coexistence of orthogonal and tilted smectic phases. A dielectric relaxation study of PTEMeB over broad ranges of temperature and pressure has been performed. The dynamic glass transition turns out to be slower for the amorphous state than for the liquid crystal. Monitoring of the α relaxation has allowed us to follow the isothermal mesophase formation at atmospheric pressure. Additionally, the dynamical behavior at high pressures has pointed out the fast formation of the mesophase induced by sudden pressure changes.

Glassy State and Cryopreservation of Mint Shoot Tips

Vitrification refers to the physical process by which a liquid supercools to very low tem- peratures and finally solidifies into a metastable glass, without undergoing crystallization at a practical cooling rate. Thus, vitrification is an effective freeze-avoidance mechanism and living tissue cryopreservation is, in most cases, relying on it. As a glass is exceedingly vis- cous and stops all chemical reactions that require molecular diffusion, its formation leads to metabolic inactivity and stability over time. To investigate glassy state in cryopreserved plant material, mint shoot tips were submitted to the different stages of a frequently used cryopreservation protocol (droplet-vitrification) and evaluated for water content reduction and sucrose content, as determined by ion chromatography, frozen water fraction and glass transitions occurrence by differential scanning calorimetry, and investigated by low-tempera- ture scanning electron microscopy, as a way to ascertain if their cellular content was vitri- fied. Results show how tissues at intermediate treatment steps develop ice crystals during liquid nitrogen cooling, while specimens whose treatment was completed become vitrified, with no evidence of ice formation. The agreement between calorimetric and microscopic observations was perfect. Besides finding a higher sucrose concentration in tissues at the more advanced protocol steps, this level was also higher in plants precultured at 25/21?C than in plants cultivated at 25?C.

Thermomechanical relaxation and different water states in cottonseed protein derived bioplastics

Thermomechanical relaxation events and different water states in cottonseed protein bioplastics are presented whilst investigating the effects of aldehyde cross-linking agents. Thermomechanical relaxation of cottonseed protein bioplastics associated with protein denaturation, moisture absorption and broad glass transitions (Tg) were observed from DSC and DMA measurements. It was shown that variation of the aldehyde influences the storage modulus at very low temperature (below Tg). From measurements of the water fusion point, enthalpy, vaporisation, and weight loss, three water states in the water-absorbed bioplastics are suggested; namely strongly-bound-to-polymer, weakly-bound-to-polymer and bulk-like water. The water content and unreacted cross-linking agents are influential factors in controlling formation of the different water states, whilst the selection of different aldehydes was found to be negligible. These results could be valuable for adjusting the thermomechanical relaxations of protein based bioplastics, and tailoring their properties in wet environments.