Faradaic Fenton Pixel: Reactive Oxygen Species Delivery Using Au/Cr Electrochemistry.

Reactive oxygen species (ROS) are an integral part of many anticancer therapies. Fenton-like processes involving reactions of peroxides with transition metal ions are a particularly potent and tunable subset of ROS approaches. Precise on-demand dosing of the Fenton reaction is an area of great interest. Herein, we present a concept of an electrochemical faradaic pixel that produces controlled amounts of ROS via a Fenton-like process. The pixel comprises a cathode and anode, where the cathode reduces dissolved oxygen to hydrogen peroxide. The anode is made of chromium, which is electrochemically corroded to yield chromium ions. Peroxide and chromium interact to form a highly oxidizing mixture of hydroxyl radicals and hexavalent Cr ions. After benchmarking the electrochemical properties of this type of device, we demonstrate how it can be used under in vitro conditions with a cancer cell line. The faradaic Fenton pixel is a general and scalable concept that can be used for on-demand delivery of redox-active products for controlling a physiological outcome.

[1,4]-sigmatropic rearrangement of chiral nitrones and their utilization in the synthesis of new iminosugars.

Reflection on the epimerization of the α-stereocenter of sugar nitrones leads to the conclusion that the process may occur through [1,4]-sigmatropic rearrangement. Participation of an ionic mechanism was excluded by a deuterium labeling experiment, and DFT calculations showed a reasonable energy barrier for the proposed [1,4]-shift. Products of the intramolecular 1,3-dipolar cycloaddition of the studied nitrones were utilized in the diversity-oriented synthesis of polyhydroxy derivatives of piperidine, indolizidine and quinolizidine. Minimal activity against the screened glucosidases and human melanoma cell lines was observed for some of the obtained compounds.

Elevating Platinum to Volumetric Capacitance: High Surface Area Electrodes through Reactive Pt Sputtering.

Platinum is the most widespread electrode material used for implantable biomedical and neuroelectronic devices, motivating exploring ways to improve its performance and understand its fundamental properties. Using reactive magnetron sputtering, PtOx is prepared, which upon partial reduction yields a porous thin-film form of platinum with favorable properties, notably record-low impedance values outcompeting other reports for platinum-based electrodes. It is established that its high electrochemical capacitance scales with thickness, in the way of volumetric capacitor materials like IrOx and poly(3,4-ethylenedioxythiophene), PEDOT. Unlike these two well-known analogs, however, it is found that PtOx capacitance is not caused by reversible pseudofaradaic reactions but rather due to high surface area. In contrast to IrOx, PtOx is not a reversible valence-change oxide, but rather a porous form of platinum. The findings show that this oxygen-containing form of Pt can place Pt electrodes on a level competitive with IrOx and PEDOT. Due to its relatively low cost and ease of preparation, PtOx can be a good choice for microfabricated bioelectronic devices.

Vertical organic electrochemical transistor platforms for efficient electropolymerization of thiophene based oligomers.

Organic electrochemical transistors (OECTs) have emerged as promising candidates for various fields, including bioelectronics, neuromorphic computing, biosensors, and wearable electronics. OECTs operate in aqueous solutions, exhibit high amplification properties, and offer ion-to-electron signal transduction. The OECT channel consists of a conducting polymer, with PEDOT:PSS receiving the most attention to date. While PEDOT:PSS is highly conductive, and benefits from optimized protocols using secondary dopants and detergents, new p-type and n-type polymers are emerging with desirable material properties. Among these, low-oxidation potential oligomers are highly enabling for bioelectronics applications, however the polymers resulting from their polymerization lag far behind in conductivity compared with the established PEDOT:PSS. In this work we show that by careful design of the OECT geometrical characteristics, we can overcome this limitation and achieve devices that are on-par with transistors employing PEDOT:PSS. We demonstrate that the vertical architecture allows for facile electropolymerization of a family of trimers that are polymerized in very low oxidation potentials, without the need for harsh chemicals or secondary dopants. Vertical and planar OECTs are compared using various characterization methods. We show that vOECTs are superior platforms in general and propose that the vertical architecture can be expanded for the realization of OECTs for various applications.

Organic thin film photofaradaic pixels for on-demand electrochemistry in physiological conditions.

We report ultrathin organic photovoltaic elements optimized to run photofaradaic reactions in biological conditions. We demonstrate concurrent oxygen reduction to hydrogen peroxide and glucose oxidation. The devices are powered by deep-red irradiation in the tissue transparency window. We utilize bilayers of phthalocyanine, acting as the light absorber, and perylene diimide, functioning as both electron-acceptor and the hydrogen peroxide evolution electrocatalyst. These heterojunction bilayers are stable when irradiated in simulated physiological conditions, producing photovoltages sufficient to simultaneously drive cathodic oxygen reduction to H2O2 and anodic oxidation of glucose. We find that optimization of the anode metal is critical for sustained photofaradaic reactivity. Our results demonstrate a robust "wet" thin film photovoltaic with potential for physiological applications where localized electrochemical manipulation is desired, in particular the delivery of reactive oxygen species.

Optoelectronic control of single cells using organic photocapacitors.

Optical control of the electrophysiology of single cells can be a powerful tool for biomedical research and technology. Here, we report organic electrolytic photocapacitors (OEPCs), devices that function as extracellular capacitive electrodes for stimulating cells. OEPCs consist of transparent conductor layers covered with a donor-acceptor bilayer of organic photoconductors. This device produces an open-circuit voltage in a physiological solution of 330 mV upon illumination using light in a tissue transparency window of 630 to 660 nm. We have performed electrophysiological recordings on Xenopus laevis oocytes, finding rapid (time constants, 50 µs to 5 ms) photoinduced transient changes in the range of 20 to 110 mV. We measure photoinduced opening of potassium channels, conclusively proving that the OEPC effectively depolarizes the cell membrane. Our results demonstrate that the OEPC can be a versatile nongenetic technique for optical manipulation of electrophysiology and currently represents one of the simplest and most stable and efficient optical stimulation solutions.

Correction: Organic semiconductor perylenetetracarboxylic diimide (PTCDI) electrodes for electrocatalytic reduction of oxygen to hydrogen peroxide.

Correction for 'Organic semiconductor perylenetetracarboxylic diimide (PTCDI) electrodes for electrocatalytic reduction of oxygen to hydrogen peroxide' by Magdalena Warczak et al., Chem. Commun., 2018, 54, 1960-1963.

Correction: Organic semiconductor perylenetetracarboxylic diimide (PTCDI) electrodes for electrocatalytic reduction of oxygen to hydrogen peroxide.

Correction for 'Organic semiconductor perylenetetracarboxylic diimide (PTCDI) electrodes for electrocatalytic reduction of oxygen to hydrogen peroxide' by Magdalena Warczak et al., Chem. Commun., 2018, DOI: .

Organic semiconductor perylenetetracarboxylic diimide (PTCDI) electrodes for electrocatalytic reduction of oxygen to hydrogen peroxide.

Hydrogen peroxide is one of the most important industrial chemicals and there is great demand for the production of H2O2 using more sustainable and environmentally benign methods. We show electrochemical production of H2O2 by the reduction of O2, enabled by an organic semiconductor catalyst, N,N'-dimethyl perylenetetracarboxylic diimide (PTCDI). We make PTCDI cathodes that are capable of stable and reusable operation in aqueous electrolytes in a pH range of 1-13 with a catalytic figure of merit as high as 26 g H(2)O(2) per g catalyst per h. [corrected] These performance and stability open new avenues for organic small molecule semiconductors as electrocatalysts.

General Observation of Photocatalytic Oxygen Reduction to Hydrogen Peroxide by Organic Semiconductor Thin Films and Colloidal Crystals.

Low-cost semiconductor photocatalysts offer unique possibilities for industrial chemical transformations and energy conversion applications. We report that a range of organic semiconductors are capable of efficient photocatalytic oxygen reduction to H2O2 in aqueous conditions. These semiconductors, in the form of thin films, support a 2-electron/2-proton redox cycle involving photoreduction of dissolved O2 to H2O2, with the concurrent photooxidation of organic substrates: formate, oxalate, and phenol. Photochemical oxygen reduction is observed in a pH range from 2 to 12. In cases where valence band energy of the semiconductor is energetically high, autoxidation competes with oxidation of the donors, and thus turnover numbers are low. Materials with deeper valence band energies afford higher stability and also oxidation of H2O to O2. We found increased H2O2 evolution rate for surfactant-stabilized nanoparticles versus planar thin films. These results evidence that photochemical O2 reduction may be a widespread feature of organic semiconductors, and open potential avenues for organic semiconductors for catalytic applications.

Synthesis and surface chemistry of high quality wurtzite and kesterite Cu2ZnSnS4 nanocrystals using tin(II) 2-ethylhexanoate as a new tin source.

A novel synthesis method for the preparation of Cu2ZnSnS4 nanocrystals is presented using a liquid precursor of tin, namely tin(II) 2-ethylhexanoate, which yields small and nearly monodisperse NCs either in the kesterite or in the wurtzite phase depending on the sulfur source (elemental sulfur in oleylamine vs. dodecanethiol).