Study on the influence of advanced treatment processes on the surface properties of polylactic acid for a bio-based circular economy for plastics.

New biotechnological processes using microorganisms and/or enzymes to convert carbonaceous resources, either biomass or depolymerized plastics into a broad range of different bioproducts are recognized for their high potential for reduced energy consumption and reduced GHG emissions. However, the hydrophobicity, high molecular weight, chemical and structural composition of most of them hinders their biodegradation. A solution to reduce the impact of non-biodegradable polymers spread in the environment would be to make them biodegradable. Different approaches are evaluated for enhancing their biodegradation. The aim of this work is to develop and optimize the ultrasonication (US) and UV photodegradation and their combination as well as dielectric barrier discharge (DBD) plasma as pre-treatment technologies, which change surface properties and enhance the biodegradation of plastic by surface oxidation and thus helping bacteria to dock on them. Polylactic acid (PLA) has been chosen as a model polymer to investigate its surface degradation by US, UV, and DBD plasma using surface characterization methods like X-ray Photoelectron Spectroscopy (XPS) and Confocal Laser Microscopy (CLSM), Atomic Force Microscopy (AFM) as well as FT-IR and drop contour analysis. Both US and UV affect the surface properties substantially by eliminating the oxygen content of the polymer but in a different way, while plasma oxidizes the surface.

Photoexcited Aromatic Reactants Give Multicolor Carbon Nanotube Fluorescence from Quantum Defects.

Covalent functionalization of single-wall carbon nanotubes (SWCNTs) can be valuable for modifying their electronic properties and creating fluorescent quantum defects. We report here a previously unreported category of such reactions involving interactions of photoexcited aromatic compounds with SWCNT sidewalls. When aqueous suspensions of SWCNTs are exposed to organic aromatic compounds and then irradiated by UV light, fluorescent defects are formed in the nanotubes at rates that depend on the aromatic ring substituents. In reactions with aniline or iodoaniline, strong spectral sidebands appear within 1 min. Total SWCNT photoluminescence can be enhanced by a factor as large as ∼5. Notably, emission spectra of reacted SWCNTs depend on the presence or absence of dissolved oxygen during the reaction. For (6,5) SWCNTs, treatment when oxygen is present gives an additional emission band red-shifted by 160 meV from the pristine position, whereas treatment without oxygen leads to two additional emission bands red-shifted by 140 and 270 meV. Variance spectroscopy shows the presence of individual "multicolor" nanotubes with three distinct emission bands (pristine plus two shifted). The facile generation of dual fluorescent quantum defects in SWCNTs provides emission closer to standard telecom wavelengths, advancing the prospects for applications as single-photon sources in quantum information processing.

Towards a Scalable Synthesis of 2-Oxabicyclo[2.2.0]hex-5-en-3-one Using Flow Photochemistry.

Cyclobutene lactones hold great potential as synthetic building blocks, yet their preparation by photochemical rearrangement in batch can often be a bottleneck in synthetic studies. We report the use of flow photochemistry as a tool to enable a higher-throughput approach to the synthesis of 2-oxabicyclo[2.2.0]hex-5-en-3-one, which reduces reaction times from 24 h to 10 min. Accordingly, a significantly improved throughput of 144 mg/h (vs 14-21 mg/h in batch) was achieved. Scale-out experiments showed problematic reactor fouling and steps were taken to explore and minimize this effect.

Exploring Autoionization and Photoinduced Proton-Coupled Electron Transfer Pathways of Phenol in Aqueous Solution.

The excited state dynamics of phenol in water have been investigated using transient absorption spectroscopy. Solvated electrons and vibrationally cold phenoxyl radicals are observed upon 200 and 267 nm excitation, but with formation time scales that differ by more than 4 orders of magnitude. The impact of these findings is assessed in terms of the relative importance of autoionization versus proton-coupled electron transfer mechanisms in this computationally tractable model system.

Mitotic spindle assembly on chromatin patterns made with deep UV photochemistry.

We provide a detailed method to generate arrays of mitotic spindles in vitro. Spindles are formed in extract prepared from unfertilized Xenopus laevis eggs, which contain all the molecular ingredients of mitotic spindles. The method is based on using deep UV photochemistry to attach chromatin-coated beads on a glass surface according to a pattern of interest. The immobilized beads act as artificial chromosomes, and induce the formation of mitotic spindles in their immediate vicinity. To perform the experiment, a chamber is assembled over the chromatin pattern, Xenopus egg extract is flowed in and after incubation the spindles are imaged with a confocal microscope.

Synergistic Formation of Radicals by Irradiation with Both Vacuum Ultraviolet and Atomic Hydrogen: A Real-Time In Situ Electron Spin Resonance Study.

We report on the surface modification of poly(tetrafluoroethylene) (PTFE) as an example of soft materials and biomaterials that occur under plasma discharge by kinetics analysis of radical formation using in situ real-time electron spin resonance (ESR) measurements. During irradiation with hydrogen plasma, simultaneous measurements of the gas-phase ESR signals of atomic hydrogen and the carbon dangling bond (C-DB) on PTFE were performed. Dynamic changes of the C-DB density were observed in real time, where the rate of density change was accelerated during initial irradiation and then became constant over time. It is noteworthy that C-DBs were formed synergistically by irradiation with both vacuum ultraviolet (VUV) and atomic hydrogen. The in situ real-time ESR technique is useful to elucidate synergistic roles during plasma surface modification.