Organic electrolytic photocapacitors for stimulation of the mouse somatosensory cortex

Objective. For decades electrical stimulation has been used in neuroscience to investigate brain networks and been deployed clinically as a mode of therapy. Classically, all methods of electrical stimulation require implanted electrodes to be connected in some manner to an apparatus which provides power for the stimulation itself. Approach. We show the use of novel organic electronic devices, specifically organic electrolytic photocapacitors (OEPCs), which can be activated when illuminated with deep-red wavelengths of light and correspondingly do not require connections with external wires or power supplies when implanted at various depths in vivo. Main results. We stimulated cortical brain tissue of mice with devices implanted subcutaneously, as well as beneath both the skin and skull to demonstrate a wireless stimulation of the whisker motor cortex. Devices induced both a behavior response (whisker movement) and a sensory response in the corresponding sensory cortex. Additionally, we showed that coating OEPCs with a thin layer of a conducting polymer formulation (PEDOT:PSS) significantly increases their charge storage capacity, and can be used to further optimize the applied photoelectrical stimulation. Significance. Overall, this new technology can provide an on-demand electrical stimulation by simply using an OEPC and a deep-red wavelength illumination. Wires and interconnects to provide power to implanted neurostimulation electrodes are often problematic in freely-moving animal research and with implanted electrodes for long-term therapy in patients. Our wireless brain stimulation opens new perspectives for wireless electrical stimulation for applications in fundamental neurostimulation and in chronic therapy

Downsizing the Channel Length of Vertical Organic Electrochemical Transistors

Organic electrochemical transistors (OECTs) are promising building blocks for bioelectronic devices such as While the majority of OECTs use simple planar geometry, there is interest in exploring how these devices operate with much shorter channels on the submicron scale. Here, we show a practical route toward the minimization of the channel length of the transistor using traditional photolithography, enabling large-scale utilization. We describe the fabrication of such transistors using two types of conducting polymers. First, commercial solution-processed poly(dioxyethylenethiophene):poly(styrene sulfonate), PEDOT:PSS. Next, we also exploit the short channel length to support easy in situ electropolymerization of poly(dioxyethylenethiophene):tetrabutyl ammonium hexafluorophosphate, PEDOT:PF6. Both variants show different promising features, leading the way in terms of transconductance (gm), with the measured peak gm up to 68 mS for relatively thin (280 nm) channel layers on devices with the channel length of 350 nm and with widths of 50, 100, and 200 m. This result suggests that the use of electropolymerized semiconductors, which can be easily customized, is viable with vertical geometry, as uniform and thin layers can be created. Spin-coated PEDOT:PSS lags behind with the lower values of gm; however, it excels in terms of the speed of the device and also has a comparably lower off current (300 nA), leading to unusually high on/off ratio, with values up to 8.6 × 104. Our approach to vertical gap devices is simple, scalable, and can be extended to other applications where small electrochemical channels are desired

How to Achieve High Spatial Resolution in Organic Optobioelectronic Devices?

Light activated local stimulation and sensing of biological cells offers enormous potential for minimally invasive bioelectronic interfaces. Organic semiconductors are a promising material class to achieve this kind of transduction due to their optoelectronic properties and biocompatibility. Here we investigate which material properties are necessary to keep the optical excitation localized. This is critical to single cell transduction with high spatial resolution. As a model system we use organic photocapacitors for cell stimulation made of the small molecule semiconductors H2Pc and PTCDI. We investigate the spatial broadening of the localized optical excitation with photovoltage microscopy measurements. Our experimental data combined with modelling show that resolution losses due to the broadening of the excitation are directly related to the effective diffusion length of charge carriers generated at the heterojunction. With additional transient photovoltage measurements we find that the H2Pc/PTCDI heterojunction offers a small diffusion length of lambda = 1.5 +/- 0.1 um due to the small mobility of charge carriers along the heterojunction. Instead covering the heterojunction with a layer of PEDOT:PSS improves the photocapacitor performance but increases the carrier diffusion length to lambda = 7.0 +/- 0.3 um due to longer lifetime and higher carrier mobility. Furthermore, we introduce electrochemical photocurrent microscopy experiments to demonstrate micrometric resolution with the pn-junction under realistic aqueous operation conditions. This work offers valuable insights into the physical mechanisms governing the excitation and transduction profile and provide design principles for future organic semiconductor junctions, aiming to achieve high efficiency and high spatial resolution

Direct measurement of oxygen reduction reactions at neurostimulation electrodes

Objective. Electric stimulation delivered by implantable electrodes is a key component of neural engineering. While factors affecting long-term stability, safety, and biocompatibility are a topic of continuous investigation, a widely-accepted principle is that charge injection should be reversible, with no net electrochemical products forming. We want to evaluate oxygen reduction reactions (ORR) occurring at different electrode materials when using established materials and stimulation protocols. Approach. As stimulation electrodes, we have tested platinum, gold, tungsten, nichrome, iridium oxide, titanium, titanium nitride, and poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate). We use cyclic voltammetry and voltage-step amperometry in oxygenated versus inert conditions to establish at which potentials ORR occurs, and the magnitudes of diffusion-limited ORR currents. We also benchmark the areal capacitance of each electrode material. We use amperometric probes (Clark-type electrodes) to quantify the O-2 and H2O2 concentrations in the vicinity of the electrode surface. O-2 and H2O2 concentrations are measured while applying DC current, or various biphasic charge-balanced pulses of amplitude in the range 10-30 mu C cm(-2)/phase. To corroborate experimental measurements, we employ finite element modelling to recreate 3D gradients of O-2 and H2O2. Main results. All electrode materials support ORR and can create hypoxic conditions near the electrode surface. We find that electrode materials differ significantly in their onset potentials for ORR, and in the extent to which they produce H2O2 as a by-product. A key result is that typical charge-balanced biphasic pulse protocols do lead to irreversible ORR. Some electrodes induce severely hypoxic conditions, others additionally produce an accumulation of hydrogen peroxide into the mM range. Significance. Our findings highlight faradaic ORR as a critical consideration for neural interface devices and show that the established biphasic/charge-balanced approach does not prevent irreversible changes in O-2 concentrations. Hypoxia and H2O2 can result in different (electro)physiological consequences

Prominent members of the human gut microbiota express endo-acting O-glycanases to initiate mucin breakdown

Epithelial cells that line the gut secrete complex glycoproteins that form a mucus layer to protect the gut wall from enteric pathogens. Here, the authors provide a comprehensive characterisation of endo-acting glycoside hydrolases expressed by mucin-degrading members of the microbiome that are able to cleave the O-glycan chains of a range of different animal and human mucins

CHARMM at 45: Enhancements in Accessibility, Functionality, and Speed.

Since its inception nearly a half century ago, CHARMM has been playing a central role in computational biochemistry and biophysics. Commensurate with the developments in experimental research and advances in computer hardware, the range of methods and applicability of CHARMM have also grown. This review summarizes major developments that occurred after 2009 when the last review of CHARMM was published. They include the following: new faster simulation engines, accessible user interfaces for convenient workflows, and a vast array of simulation and analysis methods that encompass quantum mechanical, atomistic, and coarse-grained levels, as well as extensive coverage of force fields. In addition to providing the current snapshot of the CHARMM development, this review may serve as a starting point for exploring relevant theories and computational methods for tackling contemporary and emerging problems in biomolecular systems. CHARMM is freely available for academic and nonprofit research at https://academiccharmm.org/program

State-of-the-Art Electronic Materials for Thin Films in Bioelectronics

This review is dedicated to electronics materials enabling thin-film-based neural interface and bioelectronics devices. First-generation bioelectronic medicine devices feature hand-crafted bulk interface electrodes, wires and interconnects, and insulators. This review discusses how modern materials science, especially know-how repurposed from semiconductor and microdevice technologies, enables next-generation bioelectronics. Those are divided into two subgroups: second and third generation. The former refers to rigid microscaled devices, while the latter is defined as soft, ultrathin, and flexible microdevices. A critical assessment of different biointerface electrodes, conductors for interconnects, and insulators for substrates, passivation, and encapsulation layers is made. The goal is not to give an exhaustive account of every use-example of given materials, but to point out specific aspects that are relevant to making the right choices for materials for a given device or application. Unique advantages of specific materials are highlighted, while also focusing on weaker points and caveats that those materials may have. The goal is to have an up-to-date handbook for persons entering the field which also points out tips and tricks as well as challenging problems that researchers can be inspired to confront and overcome

Questions about the role of P3HT nanoparticles in retinal stimulation

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High-Capacitance Nanoporous Noble Metal Thin Films via Reduction of Sputtered Metal Oxides

Increasing the electrochemical surface area of noble metal electrodes is vital for many applications, including catalysis and bioelectronics. Herein, a method is presented for obtaining porous noble metal thin films via reactive magnetron sputtering of noble metal oxides, MOx, followed by their reduction using chemical reducers or electrochemical current. Variation of reduction conditions yields a range of different electrochemical and morphological properties. This method for obtaining porous noble metals is rapid, facile, and compatible with microfabrication processes. The resulting metallic films are porous and have competitively high capacitance and low impedance