Design of cross-linked semicrystalline poly(ε-caprolactone)-based networks with one-way and two-way shape-memory properties through Diels-Alder reactions

Cross‐linked poly(ε‐caprolactone) (PCL)‐based polyesterurethane (PUR) systems have been synthesized through Diels–Alder reactions by reactive extrusion. The Diels–Alder and retro‐Diels–Alder reactions proved to be useful for enhancing the molecular motion of PCL‐based systems, and therefore their crystallization ability, in the design of cross‐linked semicrystalline polymers with one‐way and two‐way shape‐memory properties. Successive reactions between α,ω‐diol PCL (PCL₂), furfuryl alcohol, and methylene diphenyl 4,4′‐diisocyanate straightforwardly afforded the α,ω‐furfuryl PCL‐based PUR systems, and subsequent Diels–Alder reactions with N,N‐phenylenedimaleimide afforded the thermoreversible cycloadducts. The cross‐linking density could be modulated by partially replacing PCL‐diol with PCL‐tetraol. Interestingly, the resulting PUR systems proved to be semicrystalline cross‐linked polymers, the melting temperature of which (close to 45 °C) represented the switching temperature for their shape‐memory properties. Qualitative and quantitative measurements demonstrated that these PUR systems exhibited one‐way and two‐way shape‐memory properties depending on their cross‐linking density.     

Cryogenic Chemistry and Quantitative Non-Thermal Desorption from Pure Methanol Ices: High-Energy Electron versus X-Ray Induced Processes

X-Ray irradiation of interstellar ice analogues has recently been proven to induce desorption of molecules, thus being a potential source for the still-unexplained presence of gaseous organics in the coldest regions of the interstellar medium, especially in protoplanetary disks. The proposed desorption mechanism involves the Auger decay of excited molecules following soft X-ray absorption, known as X-ray induced electron-stimulated desorption (XESD). Aiming to quantify electron induced desorption in XESD, we irradiated pure methanol (CH₃OH) ices at 23 K with 505 eV electrons, to simulate the Auger electrons originating from the O 1s core absorption. Desorption yields of neutral fragments and the effective methanol depletion cross-section were quantitatively determined by mass spectrometry. We derived desorption yields in molecules per incident electron for CO, CO₂, CH₃OH, CH₄/O, H₂O, H₂CO, C₂H₆ and other less abundant but more complex organic products. We obtained desorption yields remarkably similar to XESD values.     

UV photodesorption of interstellar CO ice analogues: from subsurface excitation to surface desorption

Carbon monoxide is after H(2) the most abundant molecule identified in the interstellar medium (ISM), and is used as a major tracer for the gas phase physical conditions. Accreted at the surface of water-rich icy grains, CO is considered to be the starting point of a complex organic--presumably prebiotic--chemistry. Non-thermal desorption processes, and especially photodesorption by UV photons, are seen as the main cause that drives the gas-to-ice CO balance in the colder parts of the ISM. The process is known to be efficient and wavelength-dependent, but, the underlying mechanism and the physical-chemical parameters governing the photodesorption are still largely unknown. Using monochromatized photons from a synchrotron beamline, we reveal that the molecular mechanism responsible for CO photoejection is an indirect, (sub)surface-located process. The local environment of the molecules plays a key role in the photodesorption efficiency, and is quenched by at least an order of magnitude for CO interacting with a water ice surface.