Hubermcguire8190

erials.Although real-time monitoring of individual analytes using reversible optical chemical sensors (optodes) is well established, it remains a challenge in optical sensing to monitor multiple analyte concentrations simultaneously. Here, we present a novel sensing approach using hyperspectral imaging in combination with signal deconvolution of overlapping emission spectra of multiple luminescent indicator dyes, which facilitates multi-indicator-based chemical imaging. The deconvolution algorithm uses a linear combination model to describe the superimposed sensor signals and employs a sequential least-squares fit to determine the percent contribution of the individual indicator dyes to the total measured signal. As a proof of concept, we used the algorithm to analyze the measured response of an O2 sensor composed of red-emitting Pd(II)/Pt(II) porphyrins and NIR-emitting Pd(II)/Pt(II) benzoporphyrins with different sensitivities. selleck compound This facilitated chemical imaging of O2 over a wide dynamic range (0-950 hPa) with a hyperspectral camera system (470-900 nm). The applicability of the novel method was demonstrated by imaging the O2 distribution in the heterogeneous microenvironment around the roots of the aquatic plant Littorella uniflora. The presented approach of combining hyperspectral sensing with signal deconvolution is flexible and can easily be adapted for use of various multi-indicator- or even multianalyte-based optical sensors with different spectral characteristics, enabling high-resolution simultaneous imaging of multiple analytes.The essential role of a well-defined hydrogen-bond network in achieving chemically reversible multiproton translocations triggered by one-electron electrochemical oxidation/reduction is investigated by using pyridylbenzimidazole-phenol models. The two molecular architectures designed for these studies differ with respect to the position of the N atom on the pyridyl ring. In one of the structures, a hydrogen-bond network extends uninterrupted across the molecule from the phenol to the pyridyl group. Experimental and theoretical evidence indicates that an overall chemically reversible two-proton-coupled electron-transfer process (E2PT) takes place upon electrochemical oxidation of the phenol. This E2PT process yields the pyridinium cation and is observed regardless of the cyclic voltammogram scan rate. In contrast, when the hydrogen-bond network is disrupted, as seen in the isomer, at high scan rates (∼1000 mV s-1) a chemically reversible process is observed with an E1/2 characteristic of a one-proton-coupled electron-transfer process (E1PT). At slow cyclic voltammetric scan rates ( less then 1000 mV s-1) oxidation of the phenol results in an overall chemically irreversible two-proton-coupled electron-transfer process in which the second proton-transfer step yields the pyridinium cation detected by infrared spectroelectrochemistry. In this case, we postulate an initial intramolecular proton-coupled electron-transfer step yielding the E1PT product followed by a slow, likely intermolecular chemical step involving a second proton transfer to give the E2PT product. Insights into the electrochemical behavior of these systems are provided by theoretical calculations of the electrostatic potentials and electric fields at the site of the transferring protons for the forward and reverse processes. This work addresses a fundamental design principle for constructing molecular wires where protons are translocated over varied distances by a Grotthuss-type mechanism.A Sr2+-doping strategy is developed to engineer rich oxygen vacancies in porous titania for boosting visible-light-driven photocatalytic activity. The incorporation of strontium, with a larger atom radius than titanium, leads to the release of a lattice oxygen atom in the titania, causing the generation of an oxygen vacancy. The optimal Sr2+-doped titania sample with rich oxygen vacancies achieves a photocatalytic hydrogen production rate as high as 1092 μmol h-1 g-1, which is 4 and 16 times higher than the unmodified titania with less oxygen vacancies and the bench-marked P25, respectively.This paper describes a joint experiment-theory investigation of the formation and cyclization of 2'-alkynylacetophenone oxime radical cations using photoinduced electron transfer (PET) with DCA as the photosensitizer. Using a combination of experimental 1H and 13C nuclear magnetic resonance (NMR) spectra, high-resolution mass spectrometry, and calculated NMR chemical shifts, we identified the products to be isoindole N-oxides. The reaction was found to be stereoselective; only one of the two possible stereoisomers is formed under these conditions. A detailed computational investigation of the cyclization reaction mechanism suggests facile C-N bond formation in the radical cation leading to a 5-exo intermediate. Back-electron transfer from the DCA radical anion followed by barrierless intramolecular proton transfer leads to the final product. We argue that the final proton transfer step in the mechanism is responsible for the stereoselectivity observed in experiment. As a whole, this work provides new insights into the formation of complex heterocycles through oxime and oxime ether radical cation intermediates produced via PET. Moreover, it represents the first reported formation of isoindole N-oxides.Separator modification with metal oxide and carbon composite recently has become a potential and competitive way to confine polysulfide diffusion and mitigate the shuttling effect. However, other modification methods also have an impact on the stability of the modified layer and the enhancement of electrochemical performance. Herein, we first design a novel bifunctional separator combined with one self-assembled FeOOH layer via a chemical way and one conductive g-C3N4/KB layer by physical coating. Different from directly coating the metal oxide and carbon composite on the separator, the self-assembled FeOOH layer is firmly formed on the PP separator, which enables the chemical capture of the soluble polysulfide and prohibit the shuttling effect. Then, the coated g-C3N4/KB layer is further introduced to greatly enhance the transportation of lithium ions and physically confine the migration of intermediates. As a result, the battery with this bifunctional separator (G-SFO) achieves outstanding rate capacities (1000, 901, and 802 mA h/g at 0.