Liquid crystalline polymers, 9. Synthesis and thermal behavior of some oligomers containing a diethyletheric spacer

Polyethers based on bis(2-chloroethyl) ether and various bisphenols were obtained using a phase transfer catalysis technique in a liquid/liquid system. 4,4′-Dihydroxyazobenzene, 4,4′-dihydroxybiphenyl, bisphenol A, 2,7-dihydroxynaphthalene and 4,4′-dihydroxydiphenyl) sulfide were used. Only the polymers with azobenzene and biphenyl units exhibited mesophases, since the others have semi-crystalline or amorphous structures. The polymers were characterized by ¹H NMR, DSC and optical microscopy in polarized light. The molecular weights of the samples were low, situated in the oligomeric domain. The various transfer rates of the bisphenols from the aqueous to the organic phase, in some cases, led to very different copolymerization ratios as compared to the feed ratios. The LC polymers exhibited monotropic mesophases, probably for conformational reasons. A comparison between similar polyether structures containing the diethyletheric spacer and an oxetanic one was effectuated.     

Photosensitive micelles based on polysiloxanes containing azobenzene moieties

Photosensitive micelles based on amphiphilic azo-polysiloxanes were obtained and characterized. The amphiphilic polymers were synthesized in a two-step reaction, starting from a polysiloxane containing chlorobenzyl groups in the side chain. In the first step, the polysiloxane was modified with azo-aromatic groups (35–45% substitution degree) and in the second step the unreacted chlorobenzyl groups were quaternized, using different tertiary amines. The structure of the polysiloxanes and their aggregation/disaggregation capacity were evaluated by 1H-NMR, DSC, fluorescence and UV–VIS spectroscopy, dynamic light scattering and transmission electron microscopy. All the amphiphilic polysiloxanes are capable of generating micelles, the critical concentration of the aggregation values being situated in the range 10⁻³–10⁻² g/L. As a function of the ternary amine structure used in the quarterisation reaction, the micellar aggregation process is different, individual micelles or micellar clusters being obtained. The clusters' dimension cannot be controlled, the polydispersity index having high values. The disaggregation processes of the micelles under UV irradiation reveal that the polymer chemical structure influences the aggregates stability. A total micelles disaggregation was obtained for the polysiloxane modified with azophenol and amine containing a long hydrocarbon segment. In the other cases, only a partially disaggregation process takes place.     

New quality and quantity indices in science (NewQIS): results of the first decade—project progress review

Scientometrics - Strategies employing information science and scientometric approaches were introduced to science policy and management over the past decades. As a rapidly evolving field, new...     

p53 protein expression in peripheral lymphocytes from atrazine chronically intoxicated rats

The p53 expression in peripheral lymphocytes of rats chronically exposed to atrazine was investigated. The experiment was performed in female Wistar rats. Atrazine was administrated in different doses (2.7 and 5.4 mg/kg body weight), each dose once a day, 5 days per week, for 6 and 12 months. The percentage of rats peripheral lymphocytes expressing p53 protein was evaluated by immunocytochemical technique, using a monoclonal antibody (clone PAb 122) against a common epitope, both for the wild type and the mutant p53 protein. The results indicate that in the atrazine long-term administration, the serum level of atrazine is associated with: (i) Significantly increased percentage of lymphocytes expressing p53 protein for all treated animals; (ii) different p53 intracellular compartmentalization (nucleus and cytoplasm), depending on dose and time of atrazine administration. The present study suggests that atrazine modifies the p53 expression, which could confirm the clastogenicity of this herbicide, and that the detection of the p53 protein may serve as a biomarker for the long-term exposure to atrazine.     

Influence of microfibrillated cellulose and soft biocomponent on the morphology and thermal properties of thermoplastic polyurethanes

Composite materials from thermoplastic polyurethanes (TPUs) with biodegradable segments and microfibrillated cellulose (MFC) were developed as alternatives to traditional materials used in packaging or biomedical applications. Two TPUs were synthesized by the prepolymer method starting from different soft segments, poly(ε-caprolactone)/poly(butylene adipate) (PUBA) or poly(ε-caprolactone)/poly(ethylene oxide) (PUEO), and isophorone diisocyanate/aliphatic chain extender. Proton nuclear magnetic resonance (¹H NMR) confirmed the structure and Fourier transform infrared spectroscopy (FTIR) along with scanning electron microscopy showed that the soft segments with different hydrophobicity led to a higher phase mixing in PUBA and improved microphase separation in PUEO. MFC was added in the TPUs with different soft segments to increase biocompatibility, strength, and degradation rate. A better thermal stability, a gradual increase of crystallinity and a better dispersion of MFC were noticed in PUEO composites compared to PUBA ones. The crystallinity increased with 78% and 50% in PUBA and PUEO composites with 5 wt% MFC compared to the neat polyurethanes showing the nucleating ability of MFC. In addition, the enhanced storage modulus, with 75% and 25% in PUEO and PUBA composites, highlighted the reinforcing efficiency of MFC. Therefore, the addition of MFC to the already synthesized TPUs allows tailoring the morphology and thermal properties of TPUs for industrial application.