Structural Gating Enhances Long-Distance Light-Driven Interfacial Electron Transfer.

Structural gating provides a molecular means to transfer electrons preferentially in one desired vectorial direction, a behavior needed for applications in artificial photosynthesis. At the interfaces utilized herein, visible-light absorption by a transition metal complex a "structural gate" by planarization of otherwise rotating phenyl rings in phenylene ethynylene (PE) bridge units. Planarization provides a conjugated pathway for electron flow toward a conductive oxide surface.

Ligand field exciton annihilation in bulk CrCl3.

The layered van der Waals material CrCl3 exhibits very strongly bound ligand field excitons that control optoelectronic applications and are connected with magnetic ordering by virtue of their d-orbital origin. Time-resolved photoluminescence of these exciton populations at room temperature shows that their relaxation is dominated by exciton-exciton annihilation and that the spontaneous decay lifetime is very long. These observations allow the rough quantification of the exciton annihilation rate constant and contextualization in light of a recent theory of universal scaling behavior of the annihilation process.

Matrix stiffness regulates the protein profile of extracellular vesicles of pancreatic cancer cell lines.

The fibrotic stroma characterizing pancreatic ductal adenocarcinoma (PDAC) derives from a progressive tissue rigidification, which induces epithelial mesenchymal transition and metastatic dissemination. The aim of this study was to investigate the influence of matrix stiffness on PDAC progression by analyzing the proteome of PDAC-derived extracellular vesicles (EVs). PDAC cell lines (mPDAC and KPC) were grown on synthetic supports with a stiffness close to non-tumor (NT) or tumor tissue (T), and the protein expression levels in cell-derived EVs were analyzed by a quantitative MS label-free mass spectrometry approach.

Steric and Electronic Influence of Excited-State Decay in Cu(I) MLCT Chromophores.

ConspectusFor the past 11 years, a dedicated effort in our research group focused on fundamentally advancing the photophysical properties of cuprous -phenanthroline-based metal-to-ligand charge transfer (MLCT) excited states. We rationalized that, by gaining control over the numerous factors limiting the more widespread use of Cu MLCT photosensitizers, they would be readily adopted in numerous light-activated applications given the earth-abundance of copper and the extensive library of 1,10-phenanthrolines developed over the last century. Significant progress has been achieved by recognizing valuable structure-property concepts developed by other researchers in tandem with detailed ultrafast and conventional time-scale investigations, -inspired molecular designs to predict spectroscopic properties, and applying novel synthetic methodologies.