Materials that efficiently transport and couple ionic and electronic charge are key to advancing a host of technological developments for next-generation bioelectronic, optoelectronic and energy ...storage devices. Here we highlight key progress in the design and study of organic mixed ionic-electronic conductors (OMIECs), a diverse family of soft synthetically tunable mixed conductors. Across applications, the same interrelated fundamental physical processes dictate OMIEC properties and determine device performance. Owing to ionic and electronic interactions and coupled transport properties, OMIECs demand special understanding beyond knowledge derived from the study of organic thin films and membranes meant to support either electronic or ionic processes only. We address seemingly conflicting views and terminology regarding charging processes in these materials, and highlight recent approaches that extend fundamental understanding and contribute to the advancement of materials. Further progress is predicated on multimodal and multi-scale approaches to overcome lingering barriers to OMIEC design and implementation.
R-loops, consisting of an RNA-DNA hybrid and displaced single-stranded DNA, are physiological structures that regulate various cellular processes occurring on chromatin. Intriguingly, changes in ...R-loop dynamics have also been associated with DNA damage accumulation and genome instability; however, the mechanisms underlying R-loop-induced DNA damage remain unknown. Here we demonstrate in human cells that R-loops induced by the absence of diverse RNA processing factors, including the RNA/DNA helicases Aquarius (AQR) and Senataxin (SETX), or by the inhibition of topoisomerase I, are actively processed into DNA double-strand breaks (DSBs) by the nucleotide excision repair endonucleases XPF and XPG. Surprisingly, DSB formation requires the transcription-coupled nucleotide excision repair (TC-NER) factor Cockayne syndrome group B (CSB), but not the global genome repair protein XPC. These findings reveal an unexpected and potentially deleterious role for TC-NER factors in driving R-loop-induced DNA damage and genome instability.
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•The RNA-DNA helicase AQR prevents R loop-induced DSB formation•R loop-dependent DSBs are formed by the endonucleases XPF and XPG•The processing of R loops is a TC-NER-like event•The processing of R loops by XPG drives genome instability in yeast
R loops can form during transcription when an emerging RNA molecule hybridizes with DNA. Sollier et al. investigate how unscheduled R loops cause DNA breaks and genome instability, finding that R loops which form in the absence of RNA processing factors or with camptothecin are processed into double-strand breaks by transcription-coupled nucleotide excision repair factors.
Microwave breast imaging (using electromagnetic waves of frequencies around 1 GHz) has mostly remained at the research level for the past decade, gaining little clinical acceptance. The major hurdles ...limiting patient use are both at the hardware level (challenges in collecting accurate and noncorrupted data) and software level (often plagued by unrealistic reconstruction times in the tens of hours). In this paper we report improvements that address both issues. First, the hardware is able to measure signals down to levels compatible with sub-centimeter image resolution while keeping an exam time under 2 min. Second, the software overcomes the enormous time burden and produces similarly accurate images in less than 20 min. The combination of the new hardware and software allows us to produce and report here the first clinical 3-D microwave tomographic images of the breast. Two clinical examples are selected out of 400+ exams conducted at the Dartmouth Hitchcock Medical Center (Lebanon, NH). The first example demonstrates the potential usefulness of our system for breast cancer screening while the second example focuses on therapy monitoring.
We examine the broadband behavior of complex electrical properties of glycerin and water mixtures over the frequency range of 0.1-25.0 GHz, especially as they relate to using these liquids as ...coupling media for microwave tomographic imaging. Their combination is unique in that they are mutually miscible over the full range of concentrations, which allows them to be tailored to dielectric property matching for biological tissues. While the resultant mixture properties are partially driven by differences in the inherent low-frequency permittivity of each constituent, relaxation frequency shifts play a disproportionately larger role in increasing the permittivity dispersion while also dramatically increasing the effective conductivity over the frequency range of 1-3 GHz. For the full range of mixture ratios, the relaxation frequency shifts from 17.5 GHz for 0% glycerin to less than 0.1 GHz for 100% glycerin. Of particular interest is the fact that the conductivity stays above 1.0 S/m over the 1-3-GHz range for glycerin mixture ratios (70%-90% glycerin) we use for microwave breast tomography. The high level of attenuation is critical for suppressing unwanted multipath signals. This paper presents a full characterization of these liquids along with a discussion of their benefits and limitations in the context of microwave tomography.
N‐type conjugated polymers as the semiconducting component of organic electrochemical transistors (OECTs) are still undeveloped with respect to their p‐type counterparts. Herein, we report two rigid ...n‐type conjugated polymers bearing oligo(ethylene glycol) (OEG) side chains, PgNaN and PgNgN, which demonstrated an essentially torsion‐free π‐conjugated backbone. The planarity and electron‐deficient rigid structures enable the resulting polymers to achieve high electron mobility in an OECT device of up to the 10−3 cm2 V−1 s−1 range, with a deep‐lying LUMO energy level lower than −4.0 eV. Prominently, the polymers exhibited a high device performance with a maximum dimensionally normalized transconductance of 0.212 S cm−1 and the product of charge‐carrier mobility μ and volumetric capacitance C* of 0.662±0.113 F cm−1 V−1 s−1, which are among the highest in n‐type conjugated polymers reported to date. Moreover, the polymers are synthesized via a metal‐free aldol‐condensation polymerization, which is beneficial to their application in bioelectronics.
Two new n‐type semiconducting polymers, PgNaN and PgNgN, bearing oligo(ethylene glycol) (OEG) side chain are developed with a fully conformationally locked backbone and deep‐lying LUMO energy level. As a result, the polymer of PgNaN exhibits a good performance on OECT devices with a maximum dimensionally normalized transconductance of 0.212 S cm−1 and a product μC* of 0.662±0.113 F cm−1 V−1 s−1.
Avoiding faradaic side reactions during the operation of electrochemical devices is important to enhance the device stability, to achieve low power consumption, and to prevent the formation of ...reactive side‐products. This is particularly important for bioelectronic devices, which are designed to operate in biological systems. While redox‐active materials based on conducting and semiconducting polymers represent an exciting class of materials for bioelectronic devices, they are susceptible to electrochemical side‐reactions with molecular oxygen during device operation. Here, electrochemical side reactions with molecular oxygen are shown to occur during organic electrochemical transistor (OECT) operation using high‐performance, state‐of‐the‐art OECT materials. Depending on the choice of the active material, such reactions yield hydrogen peroxide (H2O2), a reactive side‐product, which may be harmful to the local biological environment and may also accelerate device degradation. A design strategy is reported for the development of redox‐active organic semiconductors based on donor–acceptor copolymers that prevents the formation of H2O2 during device operation. This study elucidates the previously overlooked side‐reactions between redox‐active conjugated polymers and molecular oxygen in electrochemical devices for bioelectronics, which is critical for the operation of electrolyte‐gated devices in application‐relevant environments.
Faradaic side‐reactions of redox‐active materials, that can produce harmful side‐products, should be minimized when employed in bioelectronic devices for studying biological systems. This work sheds light on side‐reactions with oxygen in state‑of‑the‑art materials for electrochemical transistors, forming hydrogen peroxide (H2O2), and provides design rules toward high‐performance materials that prevent adverse reactions by tailoring the energy levels of the redox‐active material.
Associative learning, a critical learning principle to improve an individual's adaptability, has been emulated by few organic electrochemical devices. However, complicated bias schemes, high write ...voltages, as well as process irreversibility hinder the further development of associative learning circuits. Here, by adopting a poly(3,4-ethylenedioxythiophene):tosylate/Polytetrahydrofuran composite as the active channel, we present a non-volatile organic electrochemical transistor that shows a write bias less than 0.8 V and retention time longer than 200 min without decoupling the write and read operations. By incorporating a pressure sensor and a photoresistor, a neuromorphic circuit is demonstrated with the ability to associate two physical inputs (light and pressure) instead of normally demonstrated electrical inputs in other associative learning circuits. To unravel the non-volatility of this material, ultraviolet-visible-near-infrared spectroscopy, X-ray photoelectron spectroscopy and grazing-incidence wide-angle X-ray scattering are used to characterize the oxidation level variation, compositional change, and the structural modulation of the poly(3,4-ethylenedioxythiophene):tosylate/Polytetrahydrofuran films in various conductance states. The implementation of the associative learning circuit as well as the understanding of the non-volatile material represent critical advances for organic electrochemical devices in neuromorphic applications.
n-Type (electron transporting) polymers can make suitable interfaces to transduce biological events that involve the generation of electrons. However, n-type polymers that are stable when ...electrochemically doped in aqueous media are relatively scarce, and the performance of the existing ones lags behind their p-type (hole conducting) counterparts. Here, we report a new family of donor–acceptor-type polymers based on a naphthalene-1,4,5,8-tetracarboxylic-diimide-bi-thiophene (NDI-T2) backbone where the NDI unit always bears an ethylene glycol (EG) side chain. We study how small variations in the side chains tethered to the acceptor as well as the donor unit affect the performance of the polymer films in the state-of-the-art bioelectronic device, the organic electrochemical transistor (OECT). First, we find that substitution of the T2 core with an electron-withdrawing group (i.e., methoxy) or an EG side chain leads to ambipolar charge transport properties and causes significant changes in film microstructure, which overall impairs the n-type OECT performance. We thus show that the best n-type OECT performer is the polymer that has no substitution on the T2 unit. Next, we evaluate the distance of the oxygen from the NDI unit as a design parameter by varying the length of the carbon spacer placed between the EG unit and the backbone. We find that the distance of the EG from the backbone affects the film order and crystallinity, and thus, the electron mobility. Consequently, our work reports the best-performing NDI-T2-based n-type OECT material to date, i.e., the polymer without the T2 substitution and bearing a six-carbon spacer between the EG and the NDI units. Our work provides new guidelines for the side-chain engineering of n-type polymers for OECTs and insights on the structure–performance relationships for mixed ionic–electronic conductors, crucial for devices where the film operates at the aqueous electrolyte interface.
Organic electrochemical transistors are a promising technology for bioelectronic devices, with applications in neuromorphic computing and healthcare. The active component enabling an organic ...electrochemical transistor is the organic mixed ionic-electronic conductor whose optimization is critical for realizing high-performing devices. In this study, the influence of purity and molecular weight is examined for a p-type polythiophene and an n-type naphthalene diimide-based polymer in improving the performance and safety of organic electrochemical transistors. Our preparative GPC purification reduced the Pd content in the polymers and improved their organic electrochemical transistor mobility by ~60% and 80% for the p- and n-type materials, respectively. These findings demonstrate the paramount importance of removing residual Pd, which was concluded to be more critical than optimization of a polymer's molecular weight, to improve organic electrochemical transistor performance and that there is readily available improvement in performance and stability of many of the reported organic mixed ionic-electronic conductors.
Using an electrical method and high-speed imaging, we probe drop coalescence down to 10 ns after the drops touch. By varying the liquid viscosity over two decades, we conclude that, at a sufficiently ...low approach velocity where deformation is not present, the drops coalesce with an unexpectedly late crossover time between a regime dominated by viscous and one dominated by inertial effects. We argue that the late crossover, not accounted for in the theory, can be explained by an appropriate choice of length scales present in the flow geometry.
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