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The high bond dissociation energy of C–C σ-bonds presents a challenge to chemical conversions in organic synthesis, polymer degradation, and biomass conversion that require chemoselective C–C bond cleavage at room temperature. Dye-sensitized photoelectrochemical cells (DSPECs) incorporating molecular organic dyes could offer a means of using renewable solar energy to drive these types of energetically demanding chemoselective C–C bond cleavage reactions. This study reports the solar light-driven activation of a bicyclic aminoxyl mediator to achieve C–C bond cleavage in the aryl-ether linkage of a lignin model compound (LMC) at room temperature using a donor–π-conjugated bridge–acceptor (D–π–A) organic dye-based DSPEC system. Mesoporous TiO 2 photoanode surfaces modified with 5-[4-(diphenylamino)phenyl]thiophene-2-cyanoacrylic acid (DPTC) D–π–A organic dye were investigated along with a bicyclic aminoxyl radical mediator (9-azabicyclo[3,3,1]nonan-3-one-9-oxyl, KABNO) in solution with and without the presence of LMC. Photophysical studies of DPTC with KABNO showed intermolecular energy/electron transfer under 1 sun illumination (100 mW cm −2 ). Under illumination, the D–π–A type DPTC sensitized TiO 2 photoanodes facilitate the generation of the reactive oxoammonium species KABNO+ as a strong oxidizing agent, which is required to drive the oxidative C–C bond cleavage of LMC. The photoelectrochemical oxidative reaction in a complete DSPEC with KABNO afforded C–C bond cleavage products 2-(2-methoxyphenoxy)acrylaldehyde (94%) and 2,6-dimethoxy-1,4-benzoquinone (66%). This process provides a first report utilizing a D–π–A type organic dye in combination with a bicyclic nitroxyl radical mediator for heterogeneous photoelectrolytic oxidative cleavage of C–C σ-bonds, modeled on those found in lignin, at room temperature. 

We present initial results from a James Webb Space Telescope (JWST) survey of the youngest Galactic core-collapse supernova remnant, Cassiopeia A (Cas A), made up of NIRCam and MIRI imaging mosaics that map emission from the main shell, interior, and surrounding circumstellar/interstellar material (CSM/ISM). We also present four exploratory positions of MIRI Medium Resolution Spectrograph integral field unit spectroscopy that sample ejecta, CSM, and associated dust from representative shocked and unshocked regions. Surprising discoveries include (1) a weblike network of unshocked ejecta filaments resolved to ∼0.01 pc scales exhibiting an overall morphology consistent with turbulent mixing of cool, low-entropy matter from the progenitor’s oxygen layer with hot, high-entropy matter heated by neutrino interactions and radioactivity; (2) a thick sheet of dust-dominated emission from shocked CSM seen in projection toward the remnant’s interior pockmarked with small (∼1″) round holes formed by ≲0.″1 knots of high-velocity ejecta that have pierced through the CSM and driven expanding tangential shocks; and (3) dozens of light echoes with angular sizes between ∼0.″1 and 1′ reflecting previously unseen fine-scale structure in the ISM. NIRCam observations place new upper limits on infrared emission (≲20 nJy at 3μm) from the neutron star in Cas A’s center and tightly constrain scenarios involving a possible fallback disk. These JWST survey data and initial findings help address unresolved questions about massive star explosions that have broad implications for the formation and evolution of stellar populations, the metal and dust enrichment of galaxies, and the origin of compact remnant objects.

 

We used the Immersion GRating Infrared Spectrometer (IGRINS) to determine fundamental parameters for 61 K- and M-type young stellar objects (YSOs) located in the Ophiuchus and Upper Scorpius star-forming regions. We employed synthetic spectra and a Markov chain Monte Carlo approach to fit specificK-band spectral regions and determine the photospheric temperature (T), surface gravity ($\log g$), magnetic field strength (B), projected rotational velocity ($v\sin i$), andK-band veiling (r_K). We determinedBfor ∼46% of our sample. Stellar parameters were compared to the results from Taurus-Auriga and the TW Hydrae association presented in Paper I of this series. We classified all the YSOs in the IGRINS survey with infrared spectral indices from Two Micron All Sky Survey and Wide-field Infrared Survey Explorer photometry between 2 and 24μm. We found that Class II YSOs typically have lower$\log g$and$v\sin i$, similarB, and higherK-band veiling than their Class III counterparts. Additionally, we determined the stellar parameters for a sample of K and M field stars also observed with IGRINS. We have identified intrinsic similarities and differences at different evolutionary stages with our homogeneous determination of stellar parameters in the IGRINS YSO survey. Considering$\log g$as a proxy for age, we found that the Ophiuchus and Taurus samples have a similar age. We also find that Upper Scorpius and TWA YSOs have similar ages, and are more evolved than Ophiuchus/Taurus YSOs.