This paper presents for the first time Sb 2 S 3 -based solar cells operating on scaffold film. The scaffolds studied are Al 2 O 3 and ZrO 2 , for which no electron injection from the Sb 2 S 3 to the Al 2 O 3 or ZrO 2 is possible. As a result, one of the highest open circuit voltages (V oc ) of 0.712 V was observed for this solar cell configuration. Electron dispersive spectroscopy (EDS) was performed, revealing complete pore filling of the Sb 2 S 3 into the metal oxide pores (e.g., Al 2 O 3 or ZrO 2 ); the complete pore filling of the Sb 2 S 3 is responsible for the photovoltaic performance (PV) of this unique solar cell structure. In addition, intensity modulated photovoltage and photocurrent spectroscopy (IMVS and IMPS) were performed to extract the electron diffusion length. Electron diffusion length in the range of 900 nm to 290 nm (depending on the light intensity) was observed, which further supports the operation of metal oxide/Sb 2 S 3 solar cell configuration. Moreover, the Al 2 O 3 -based cells have longer electron diffusion length than the TiO 2 -based cells, supporting the higher open circuit voltage of the noninjected metal oxide-based cells. This work demonstrates the potential of Sb 2 S 3 to gain high voltage and to perform on a scaffold substrate without requiring electron injection.

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LinB and DhaA are well-known haloalkane dehalogenases (HLDs) capable of converting a plethora of halogenated alkanes, also those considered persistent pollutants. One way of studying the nature and efficiency of these important enzymes is to measure the kinetic isotope effect (KIE) on the metabolized reaction, in particular leaving group (either chloride or bromide) KIE. Although the general mechanism via which these two dehalogenating enzymes operate has been already studied and described, the isotope effects data providing information on the mechanistic details, especially Br KIE are scarce. In this work we aimed at gaining insights into the enzymatic dehalogenation of dibromo- and bromo-chloro- ethanes by LinB and DhaA, by combining experimental and computational methods. A model developed this way has been subsequently extended to dihalopropanes. Using the predicted free energy surface of the reaction catalyzed by HLD and kinetic isotope effects based on QM/MM calculations it has been demonstrated that with respect to the magnitudes of Br KIE conversion of 1,2-dibromoethane, 1-bromo-2-chloroethane or 1,2-dibromopropane, and therefore also other propanes should not differ. In the case of C KIE the scenario might be different as depending on the carbon position adjacent to the eliminated bromine substituent one can observe either larger or smaller isotope effect (~1.06 or 1.04 for the primary and secondary position, respectively). By predicting halogen binding isotope effects (BIEs) as well as computing interaction energy for each HLD-ligand complex the binding event preceding a chemical change in the active site has been characterized. The magnitude and direction of BIEs are discussed thoroughly by invoking the dynamics and the architecture of each active site, the strength of interactions with the first shell residues, and pointing to the dominating forces determining the binding of each of the studied ligands.