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Purpose: The formation of photoresponsive hydrogels were reported by irradiation of star-shaped poly(ethylene glycol)s with terminal cinnamylidene acetic acid (CAA) groups, which are capable of a photoinduced [2+2] cycloaddition. In this study we explored whether oligo(ethylene glycol) s and oligo(propylene glycol)s of varying molecular architecture (linear or star-shaped) or molecular weights could be functionalized with CAA as terminal groups by esterification or by amide formation.
Methods: Oligo(ethylene glycol) (OEG) and oligo(propylene glycol) (OPG) with varying molecular architecture (linear, star-shaped) and weight average molecular weights between 1000 and 5000 g.mol(-1) were functionalized by means of esterification of hydroxyl or amine endgroups with cinnamylidene acetic acid (CAA) or cinnamylidene acetyl chloride (CAC) as telechelic endgroups. The chemical structure, thermal properties, and molecular weights of the oligoethers obtained were determined by NMR spectroscopy, UV spectroscopy, DSC, and MALDI-TOF.
Results: CAA-functionalized linear and star-shaped OEGs or OPGs could be obtained with a degree of functionalization higher than 90%. In MALDI-TOF measurements an increase in Mw of about 150 g.mol(-1) (for each terminal end) after the functionalization reaction was observed. OEGCAA and OPGCAA showed an increase in glass transition temperature (T-g) from about -70 degrees C to -50 degrees C, compared to the unfunctionalized oligoethers. In addition, the melting temperature (T-m) of OEGCAA decreased from about 55 C to 30 degrees C, which can be accounted for by the hampered crystallization of the precursors because of the bulky CAA end groups as well as by the loss of the hydroxyl telechelic end groups.
Conclusion: The synthesis of photoresponsive oligoethers containing cinnamylidene acetic acid as telechelic endgroup was reported and high degrees of functionalization could be achieved. Such photosensitive oligomers are promising candidates as reactive precursors, for the preparation of biocompatible high molecular weight polymers and polymer networks.
Although the shape-changing capabilities of LCEs hold great potential for applications ranging from micropumps to artificial muscles, customization of the LCE functionality to the applications' requirements is still a challenge. It is studied whether the orientation of NMC-LCPs and NMC-LCEs based on 2-tert-butyl-1,4-bis[4-(4-pentenyloxy)benzoyl]hydroquinone can be enhanced by copolymerization with 2-methyl-1,4-bis[4-(4-pentenyloxy)benzoyl]hydroquinone or 2,6-bis[4-(4-pentenyl-oxy)-benzoyl]anthracene. An increasing content of the comonomers stabilizes the nematic phase, which enables a tailoring of T-NI for the NMC-LCP between 45 and 68 degrees C, while for the NMC-LCE T-NI ranges between 69 and 76 degrees C. In addition, NMC-LCE show an increased actuation performance.
The release of greenhouse gases from the large organic carbon stock in permafrost deposits in the circumarctic regions may accelerate global warming upon thaw. The extent of this positive climate feedback is thought to be largely controlled by the microbial degradability of the organic matter preserved in these sediments. In addition, weathering and oxidation processes may release inorganic carbon preserved in permafrost sediments as CO2, which is generally not accounted for. We used C-13 and C-14 analysis and isotopic mass balances to differentiate and quantify organic and inorganic carbon released as CO2 in the field from an active retrogressive thaw slump of Pleistocene-age Yedoma and during a 1.5-years incubation experiment. The results reveal that the dominant source of the CO2 released from freshly thawed Yedoma exposed as thaw mound is Pleistocene-age organic matter (48-80%) and to a lesser extent modern organic substrate (3-34%). A significant portion of the CO2 originated from inorganic carbon in the Yedoma (17-26%). The mixing of young, active layer material with Yedoma at a site on the slump floor led to the preferential mineralization of this young organic carbon source. Admixtures of younger organic substrates in the Yedoma thaw mound were small and thus rapidly consumed as shown by lower contributions to the CO2 produced during few weeks of aerobic incubation at 4 degrees C corresponding to approximately one thaw season. Future CO2 fluxes from the freshly thawed Yedoma will contain higher proportions of ancient inorganic (22%) and organic carbon (61-78%) as suggested by the results at the end, after 1.5 years of incubation. The increasing contribution of inorganic carbon during the incubation is favored by the accumulation of organic acids from microbial organic matter degradation resulting in lower pH values and, in consequence, in inorganic carbon dissolution. Because part of the inorganic carbon pool is assumed to be of pedogenic origin, these emissions would ultimately not alter carbon budgets. The results of this study highlight the preferential degradation of younger organic substrates in freshly thawed Yedoma, if available, and a substantial release of CO2 from inorganic sources.