Electrocatalytic on-site oxygenation for transplanted cell-based-therapies.

Implantable cell therapies and tissue transplants require sufficient oxygen supply to function and are limited by a delay or lack of vascularization from the transplant host. Previous exogenous oxygenation strategies have been bulky and had limited oxygen production or regulation. Here, we show an electrocatalytic approach that enables bioelectronic control of oxygen generation in complex cellular environments to sustain engineered cell viability and therapy under hypoxic stress and at high cell densities. We find that nanostructured sputtered iridium oxide serves as an ideal catalyst for oxygen evolution reaction at neutral pH. We demonstrate that this approach exhibits a lower oxygenation onset and selective oxygen production without evolution of toxic byproducts. We show that this electrocatalytic on site oxygenator can sustain high cell loadings (>60k cells/mm3) in hypoxic conditions in vitro and in vivo. Our results showcase that exogenous oxygen production devices can be readily integrated into bioelectronic platforms, enabling high cell loadings in smaller devices with broad applicability.

Non-Flammable Sodium Asymmetric Imide Salt-Based Deep Eutectic Solvent for Supercapacitor Applications.

This study reports two deep eutectic solvents (DESs) based on alkaline imide salts with asymmetric anions as functional electrolytes for supercapacitor (SC) application. The eutectic mixture of sodium (fluorosulfonyl) (trifluoromethanesulfonyl) imide (NaFTFSI) or sodium cyano-trifluoromethanesulfonyl imide (NaTFSICN) with ethylene carbonate (EC) delivers a non-flammable and stable liquid. The eutectic diagrams of the electrolytes directed to an optimal composition (wsalt =0.25), hinging to that of conventional carbonate-based electrolytes, i. e., 1 mol L-1 . The volumetric properties of the DESs revealed a "stacking" effect, reflecting a strong coordination bond between the imide and EC anions without solvating the Na+ cations. The DES transport properties (i. e., viscosity, conductivity, and ionicity) and temperature variations designate a high organization, similar to ionic liquids. The DESs, when coupled with activated carbon electrodes in a two-electrode symmetric configuration, yield specific capacities of 150 F g-1 at a normalized current density of 0.5 A g-1 (and 120 F g-1 at 2 A g-1 ). The SC maintained 80 % of its initial capacity beyond 100 h of floating at an operating voltage of 2.4 V and showed a 150 mV per hour potential loss under self-discharge. The devised eutectic mixtures offer a promising new pathway for simple, safe, and effective electrolytes for SC applications.

Performance of PEDOTOH/PEO-based Supercapacitors in Agarose Gel Electrolyte.

Poly(3,4-ethylenedioxythiophene) (PEDOT) is a prime example of conducting polymer materials for supercapacitor electrodes that offer ease of processability and sophisticated chemical stability during operation and storage in aqueous environments. Yet, continuous improvement of its electrochemical capacitance and stability upon long cycles remains a major interest in the field, such as developing PEDOT-based composites. This work evaluates the electrochemical performances of hydroxymethyl PEDOT (PEDOTOH) coupled with hydrogel additives, namely poly(ethylene oxide) (PEO), poly(acrylic acid) (PAA), and polyethyleneimine (PEI), fabricated via a single-step electrochemical polymerization method in an aqueous solution. The PEDOTOH/PEO composite exhibits the highest capacitance (195.2 F g-1 ) compared to pristine PEDOTOH (153.9 F g-1 ), PEDOTOH/PAA (129.9 F g-1 ), and PEDOTOH/PEI (142.3 F g-1 ) at a scan rate of 10 mV s-1 . The PEDOTOH/PEO electrodes were then assembled into a symmetrical supercapacitor in an agarose gel. The type of supporting electrolytes and salt concentrations were further examined to identify the optimal agarose-based gel electrolyte. The supercapacitors comprising 2 M agarose-LiClO4 achieved a specific capacitance of 27.6 F g-1 at a current density of 2 A g-1 , a capacitance retention of ∼94% after 10,000 charge/discharge cycles at 10.6 A g-1 , delivering a maximum energy and power densities of 11.2 Wh kg-1 and 17.28 kW kg-1 , respectively. The performance of the proposed supercapacitor outperformed several reported PEDOT-based supercapacitors, including PEDOT/carbon fiber, PEDOT/CNT, and PEDOT/graphene composites. This study provides insights into the effect of incorporated hydrogel in the PEDOTOH network and the optimal conditions of agarose-based gel electrolytes for high-performance PEDOT-based supercapacitor devices.

Amide-based deep eutectic solvents containing LiFSI and NaFSI salts as superionic electrolytes for supercapacitor applications.

This work proposes two deep eutectic solvents (DESs) based on lithium bis(fluorosulfonyl)imide and sodium bis(fluorosulfonyl)imide together with N-methylacetamide and formamide as electrolytes for activated carbon (AC) electrochemical double-layer capacitors (EDLCs) at 25 °C. The formulated DESs exhibit a large electrochemical window (ΔE > 2.5 V), good thermal stability (∼150 °C) and ionic conductivity (3-4 mS cm-1), and moderate viscosity (11.3 mPa s). Through the Vogel-Tamman-Vulcher fitting equation, the evolution of pseudo-energy activation was delineated with respect to the nature of the H-bond donor or alkali salt. These electrolytes present a superionic character gleaned from the Walden classification, and their ionicity exceeds that of standard organic electrolytes based on similar alkali salts. The performance of the AC-based EDLC was assessed by cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge/discharge, yielding 140 F g-1 with an 8% capacity retention during 200 h of floating. Based on the physicochemical properties and electrochemical performance of these DESs, they represent a promising green-alternative electrolyte for supercapacitor applications.

Low-Concentrated Lithium Hexafluorophosphate Ternary-based Electrolyte for a Reliable and Safe NMC/Graphite Lithium-Ion Battery.

Current commercial lithium-ion battery (LIB) electrolytes are heavily influenced by the cost, chemical instability, and thermal decomposition of the lithium hexafluorophosphate salt (LiPF6). This work studies the use of an unprecedently low Li salt concentration in a novel electrolyte, which shows equivalent capabilities to their commercial counterparts. Herein, the use of 0.1 M LiPF6 in a ternary solvent mixture of ethylene carbonate (EC), ethyl methyl carbonate (EMC), and 1,1,2,2-tetrafluoroethyl 2,2,2-trifluoroethyl ether (TFE) (3EC/7EMC/20TFE, by weight) is investigated for the first time in LiNi1/3Mn1/3Co1/3O2 (NMC111)/graphite pouch cells. In solution, the Li+ transport number and diffusion are governed by the Grotthuss mechanism, with transport properties being independent of salt concentration. The proposed electrolyte operates in a wide temperature window (0-40 °C), is nonflammable (self-extinguishing under 2 s), and shows adequately fast wetting (4 s). When incorporated into the NMC/graphite pouch cell, it initially forms a solid electrolyte interphase (SEI) with minimal gas formation followed by a comparable battery performance to standard LiPF6 electrolytes, validated by a high specific capacity of 165 mAh g-1, Coulombic efficiencies of 99.3%, and capacity retention of 85% over 700 cycles.

Benchmarking the Performance of Electropolymerized Poly(3,4-ethylenedioxythiophene) Electrodes for Neural Interfacing.

The development of electronics adept at interfacing with the nervous system is an ever-growing effort, leading to discoveries in fundamental neuroscience applied in clinical setting. Highly capacitive and electrochemically stable electronic materials are paramount for these advances. A systematic study is presented where copolymers based on 3,4-ethylenedioxythiophene (EDOT) and its hydroxyl-terminated counterpart (EDOTOH) are electropolymerized in an aqueous solution in the presence of various counter anions and additives. Amongst the conducting materials developed, the copolymer p(EDOT-ran-EDOTOH) doped with perchlorate in the presence of ethylene glycol shows high specific capacitance (105 F g-1 ), and capacitance retention (85%) over 1000 galvanostatic charge-discharge cycles. A microelectrode array-based on this material is fabricated and primary cortical neurons are cultured therein for several days. The microelectrodes electrically stimulate targeted neuronal networks and record their activity with high signal-to-noise ratio. The stability of charge injection capacity of the material is validated via long-term pulsing experiments. While providing insights on the effect of additives and dopants on the electrochemical performance and operational stability of electropolymerized conducting polymers, this study highlights the importance of high capacitance accompanied with stability to achieve high performance electrodes for biological interfacing.

Water stable molecular n-doping produces organic electrochemical transistors with high transconductance and record stability.

From established to emergent technologies, doping plays a crucial role in all semiconducting devices. Doping could, theoretically, be an excellent technique for improving repressively low transconductances in n-type organic electrochemical transistors - critical for advancing logic circuits for bioelectronic and neuromorphic technologies. However, the technical challenge is extreme: n-doped polymers are unstable in electrochemical transistor operating environments, air and water (electrolyte). Here, the first demonstration of doping in electron transporting organic electrochemical transistors is reported. The ammonium salt tetra-n-butylammonium fluoride is simply admixed with the conjugated polymer poly(N,N'-bis(7-glycol)-naphthalene-1,4,5,8-bis(dicarboximide)-co-2,2'-bithiophene-co-N,N'-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide), and found to act as a simultaneous molecular dopant and morphology-additive. The combined effects enhance the n-type transconductance with improved channel capacitance and mobility. Furthermore, operational and shelf-life stability measurements showcase the first example of water-stable n-doping in a polymer. Overall, the results set a precedent for doping/additives to impact organic electrochemical transistors as powerfully as they have in other semiconducting devices.

Biofuel powered glucose detection in bodily fluids with an n-type conjugated polymer.

A promising class of materials for applications that rely on electron transfer for signal generation are the n-type semiconducting polymers. Here we demonstrate the integration of an n-type conjugated polymer with a redox enzyme for the autonomous detection of glucose and power generation from bodily fluids. The reversible, mediator-free, miniaturized glucose sensor is an enzyme-coupled organic electrochemical transistor with a detection range of six orders of magnitude. This n-type polymer is also used as an anode and paired with a polymeric cathode in an enzymatic fuel cell to convert the chemical energy of glucose and oxygen into electrical power. The all-polymer biofuel cell shows a performance that scales with the glucose content in the solution and a stability that exceeds 30 days. Moreover, at physiologically relevant glucose concentrations and from fluids such as human saliva, it generates enough power to operate an organic electrochemical transistor, thus contributes to the technological advancement of self-powered micrometre-scale sensors and actuators that run on metabolites produced in the body.

On the Role of Contact Resistance and Electrode Modification in Organic Electrochemical Transistors.

Contact resistance is renowned for its unfavorable impact on transistor performance. Despite its notoriety, the nature of contact resistance in organic electrochemical transistors (OECTs) remains unclear. Here, by investigating the role of contact resistance in n-type OECTs, the first demonstration of source/drain-electrode surface modification for achieving state-of-the-art n-type OECTs is reported. Specifically, thiol-based self-assembled monolayers (SAMs), 4-methylbenzenethiol (MBT) and pentafluorobenzenethiol (PFBT), are used to investigate contact resistance in n-type accumulation-mode OECTs made from the hydrophilic copolymer P-90, where the deliberate functionalization of the gold source/drain electrodes decreases and increases the energetic mismatch at the electrode/semiconductor interface, respectively. Although MBT treatment is found to increase the transconductance three-fold, contact resistance is not found to be the dominant factor governing OECT performance. Additional morphology and surface energy investigations show that increased performance comes from SAM-enhanced source/drain electrode surface energy, which improves wetting, semiconductor/metal interface quality, and semiconductor morphology at the electrode and channel. Overall, contact resistance in n-type OECTs is investigated, whilst identifying source/drain electrode treatment as a useful device engineering strategy for achieving state of the art n-type OECTs.

High and intermediate temperature sodium-sulfur batteries for energy storage: development, challenges and perspectives.

In view of the burgeoning demand for energy storage stemming largely from the growing renewable energy sector, the prospects of high (>300 °C), intermediate (100-200 °C) and room temperature (25-60 °C) battery systems are encouraging. Metal sulfur batteries are an attractive choice since the sulfur cathode is abundant and offers an extremely high theoretical capacity of 1672 mA h g-1 upon complete discharge. Sodium also has high natural abundance and a respectable electrochemical reduction potential (-2.71 V vs. standard hydrogen electrode). Combining these two abundant elements as raw materials in an energy storage context leads to the sodium-sulfur battery (NaS). This review focuses solely on the progress, prospects and challenges of the high and intermediate temperature NaS secondary batteries (HT and IT NaS) as a whole. The already established HT NaS can be further improved in terms of energy density and safety record. The IT NaS takes advantage of the lower operating temperature to lower manufacturing and potentially operating costs whilst creating a safer environment. A thorough technical discussion on the building blocks of these two battery systems is discussed here, including electrolyte, separators, cell configuration, electrochemical reactions that take place under the different operating conditions and ways to monitor and comprehend the physicochemical and electrochemical processes under these temperatures. Furthermore, a brief summary of the work conducted on the room temperature (RT) NaS system is given seeking to couple the knowledge in this field with the one at elevated temperatures. Finally, future perspectives are discussed along with ways to effectively handle the technical challenges presented for this electrochemical energy storage system.

Radiobiologic comparison of helical tomotherapy, intensity modulated radiotherapy, and conformal radiotherapy in treating lung cancer accounting for secondary malignancy risks.

The aim of the present study is to examine the importance of using measures to predict the risk of inducing secondary malignancies in association with the clinical effectiveness of treatment plans in terms of tumor control and normal tissue complication probabilities. This is achieved by using radiobiologic parameters and measures, which may provide a closer association between clinical outcome and treatment delivery. Overall, 4 patients having been treated for lung cancer were examined. For each of them, 3 treatment plans were developed based on the helical tomotherapy (HT), multileaf collimator-based intensity modulated radiation therapy (IMRT), and 3-dimensional conformal radiation therapy (CRT) modalities. The different plans were evaluated using the complication-free tumor control probability (p+), the overall probability of injury (pI), the overall probability of control/benefit (pB), and the biologically effective uniform dose (D¯¯). These radiobiologic measures were used to develop dose-response curves (p-D¯¯ diagram), which can help to evaluate different treatment plans when used in conjunction with standard dosimetric criteria. The risks for secondary malignancies in the heart and the contralateral lung were calculated for the 3 radiation modalities based on the corresponding dose-volume histograms (DVHs) of each patient. Regarding the overall evaluation of the different radiation modalities based on the p+ index, the average values of the HT, IMRT, and CRT are 67.3%, 61.2%, and 68.2%, respectively. The corresponding average values of pB are 75.6%, 70.5%, and 71.0%, respectively, whereas the average values of pI are 8.3%, 9.3%, and 2.8%, respectively. Among the organs at risk (OARs), lungs show the highest probabilities for complications, which are 7.1%, 8.0%, and 1.3% for the HT, IMRT, and CRT modalities, respectively. Similarly, the biologically effective prescription doses (DB¯¯) for the HT, IMRT, and CRT modalities are 64.0, 60.9, and 60.8Gy, respectively. Regarding the risk for secondary cancer, for the heart, the lowest average risk is produced by IMRT (0.10%) compared with the HT (0.17%) and CRT (0.12%) modalities, whereas the 3 radiation modalities show almost equivalent results regarding the contralateral lung (0.8% for HT, 0.9% for IMRT, and 0.9% for CRT). The use of radiobiologic parameters in the evaluation of different treatment plans and estimation of their expected clinical outcome is shown to provide very useful clinical information. The radiobiologic analysis of the response probabilities showed that different radiation modalities appear to be more effective in different patient geometries and target sizes and locations. Furthermore, there is not a clear pattern between the plans that appear to be more effective for the treatment and the risk of secondary malignancy. It seems that radiobiologically based treatment planning taking into account the risk of secondary cancer can be established as an effective clinical tool for a more clinically relevant treatment optimization.

Cell-nuclear data reduction and prognostic model selection in bladder tumor recurrence.

OBJECTIVE: The paper aims at improving the prediction of superficial bladder recurrence. To this end, feedforward neural networks (FNNs) and a feature selection method based on unsupervised clustering, were employed. MATERIAL AND METHODS: A retrospective prognostic study of 127 patients diagnosed with superficial urinary bladder cancer was performed. Images from biopsies were digitized and cell nuclei features were extracted. To design FNN classifiers, different training methods and architectures were investigated. The unsupervised k-windows (UKW) and the fuzzy c-means clustering algorithms were applied on the feature set to identify the most informative feature subsets. RESULTS: UKW managed to reduce the dimensionality of the feature space significantly, and yielded prediction rates 87.95% and 91.41%, for non-recurrent and recurrent cases, respectively. The prediction rates achieved with the reduced feature set were marginally lower compared to the ones attained with the complete feature set. The training algorithm that exhibited the best performance in all cases was the adaptive on-line backpropagation algorithm. CONCLUSIONS: FNNs can contribute to the accurate prognosis of bladder cancer recurrence. The proposed feature selection method can remove redundant information without a significant loss in predictive accuracy, and thereby render the prognostic model less complex, more robust, and hence suitable for clinical use.