Saturn's moon Enceladus harbours a global water ocean , which lies under an ice crust and above a rocky core . Through warm cracks in the crust a cryo-volcanic plume ejects ice grains and vapour into space that contain materials originating from the ocean. Hydrothermal activity is suspected to occur deep inside the porous core, powered by tidal dissipation . So far, only simple organic compounds with molecular masses mostly below 50 atomic mass units have been observed in plume material. Here we report observations of emitted ice grains containing concentrated and complex macromolecular organic material with molecular masses above 200 atomic mass units. The data constrain the macromolecular structure of organics detected in the ice grains and suggest the presence of a thin organic-rich film on top of the oceanic water table, where organic nucleation cores generated by the bursting of bubbles allow the probing of Enceladus' organic inventory in enhanced concentrations.

UV-Light induced electron-hole (e−/h+) pair generation and free radical production in TiO2 based nanoparticles is a major conceptual paradigm for biological injury. However, to date, this hypothesis has been difficult to experimentally verify due to the high energy of UV light that is intrinsically highly toxic to biological systems. Here, a versatile flame spray pyrolysis (FSP) synthetic process has been exploited to synthesize a library of iron doped (0–10 at wt%) TiO2 nanoparticles. These particles have been tested for photoactivation-mediated cytotoxicity using near-visible light exposure. The reduction in TiO2 band gap energy with incremental levels of Fe loading maintained the nanoparticle crystalline structure in spite of homogeneous Fe distribution (demonstrated by XRD, HRTEM, SAED, EFTEM, and EELS). Photochemical studies showed that band gap energy was reciprocally tuned proportional to the Fe content. The photo-oxidation capability of Fe-doped TiO2 was found to increase during near-visible light exposure. Use of a macrophage cell line to evaluate cytotoxic and ROS production showed increased oxidant injury and cell death in parallel with a decrease in band gap energy. These findings demonstrate the importance of band gap energy in the phototoxic response of the cell to TiO2 nanoparticles and reflect the potential of this material to generate adverse effects in humans and the environment during high intensity light exposure.

The synthesis and structure of an azobenzene functionalized isoreticular metal-organic framework (azo-IRMOF-74-III) [Mg 2 (C 26 H 16 O 6 N 2 )] are described and the ability to controllably release a guest from its pores in response to an external stimulus has been demonstrated. Azo-IRMOF-74-III is an isoreticular expansion of MOF-74 with an etb topology and a 1-D hexagonal pore structure. The structure of azo-IRMOF-74-III is analogous to that of MOF-74, as demonstrated by powder X-ray diffraction, with a surface area of 2410 m 2 g À1 BET. Each organic unit within azo-IRMOF-74-III is decorated with a photoswitchable azobenzene unit, which can be toggled between its cis and trans conformation by excitation at 408 nm. When propidium iodide dye was loaded into the MOF, spectroscopic studies showed that no release of the luminescent dye was observed under ambient conditions. Upon irradiation of the MOF at 408 nm, however, the rapid wagging motion inherent to the repetitive isomerization of the azobenzene functionality triggered the release of the dye from the pores. This light-induced release of cargo can be modulated between an on and an off state by controlling the conformation of the azobenzene with the appropriate wavelength of light. This report highlights the ability to capture and release small molecules and demonstrates the utility of self-contained photoactive switches located inside highly porous MOFs.

Photochemistry has the potential to substantially impact the atmospheric composition of exoplanets with consequences on the radiative transfer, thermal structure and dynamics of the atmospheres, particularly in UV-rich stellar environments. Here, we present the results of a first laboratory experimental simulation of photochemistry in carbon-rich exoplanet atmospheres at elevated temperatures. Evolution of gas-phase molecular composition was quantitatively monitored with infrared spectroscopy and mass spectrometry. We found that H2/CO gas compositions can change significantly from thermal equilibria compositions when irradiated with Ly-α photons at temperatures ranging from 600 K to 1500 K. Carbon dioxide and water were found to be the main products caused by photolysis, while formation of methane was also observed to a lesser extent. We find that photochemistry efficiency is strongly correlated with increasing temperature. Our finding that water is efficiently produced by photochemistry in a super Solar C/O=1 environment, representing C enhancement relative to solar values C/O ratio = 0.54, has significant implications for the interpretation of many exoplanet transmission spectra. We also find the formation of an organic solid condensate at 1500 K and under Ly-α UV-radiation, confirming the possibility of forming photochemical hazes in hot-Jupiter exoplanet atmospheres with an enhanced C/O ratio compared to Solar.

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