Subsurface Profiling of Ion Migration and Swelling in Conducting Polymer Actuators with Modulated Electrochemical Atomic Force Microscopy.

Understanding the dynamics of ion migration and volume change is crucial to studying the functionality and long-term stability of soft polymeric materials operating at liquid interfaces, but the subsurface characterization of swelling processes in these systems remains elusive. In this work, we address the issue using modulated electrochemical atomic force microscopy as a depth-sensitive technique to study electroswelling effects in the high-performance actuator material polypyrrole doped with dodecylbenzenesulfonate (Ppy:DBS). We perform multidimensional measurements combining local electroswelling and electrochemical impedance spectroscopies on microstructured Ppy:DBS actuators. We interpret charge accumulation in the polymeric matrix with a quantitative model, giving access to both the spatiotemporal dynamics of ion migration and the distribution of electroswelling in the electroactive polymer layer. The findings demonstrate a nonuniform distribution of the effective ionic volume in the Ppy:DBS layer depending on the film morphology and redox state. Our findings indicate that the highly efficient actuation performance of Ppy:DBS is caused by rearrangements of the polymer microstructure induced by charge accumulation in the soft polymeric matrix, increasing the effective ionic volume in the bulk of the electroactive film for up to two times the value measured in free water.

Safety injections of nuclear medicine radiotracers: towards a new modality for a real-time detection of extravasation events and 18F-FDG SUV data correction.

BACKGROUND: 18F-FDG PET/CT imaging allows to study oncological patients and their relative diagnosis through the standardised uptake value (SUV) evaluation. During radiopharmaceutical injection, an extravasation event may occur, making the SUV value less accurate and possibly leading to severe tissue damage. The study aimed to propose a new technique to monitor and manage these events, to provide an early evaluation and correction to the estimated SUV value through a SUV correction coefficient. METHODS: A cohort of 70 patients undergoing 18F- FDG PET/CT examinations was enrolled. Two portable detectors were secured on the patients' arms. The dose-rate (DR) time curves on the injected DRin and contralateral DRcon arm were acquired during the first 10 min of injection. Such data were processed to calculate the parameters ΔpinNOR = (DRinmax- DRinmean)/DRinmax and ΔRt = (DRin(t) - DRcon(t)), where DRinmax is the maximum DR value, DRinmean is the average DR value in the injected arm. OLINDA software allowed dosimetric estimation of the dose in the extravasation region. The estimated residual activity in the extravasation site allowed the evaluation of the SUV's correction value and to define an SUV correction coefficient. RESULTS: Four cases of extravasations were identified for which ΔRt [(390 ± 26) µSv/h], while ΔRt [(150 ± 22) µSv/h] for abnormal and ΔRt [(24 ± 11) µSv/h] for normal cases. The ΔpinNOR showed an average value of (0.44 ± 0.05) for extravasation cases and an average value of (0.91 ± 0.06) and (0.77 ± 0.23) in normal and abnormal classes, respectively. The percentage of SUV reduction (SUV%CR) ranges between 0.3% and 6%. The calculated self-tissue dose values range from 0.027 to 0.573 Gy, according to the segmentation modality. A similar correlation between the inverse of ΔpinNOR and the normalised ΔRt with the SUV correction coefficient was found. CONCLUSIONS: The proposed metrics allowed to characterised the extravasation events in the first few minutes after the injection, providing an early SUV correction when necessary. We also assume that the characterisation of the DR-time curve of the injection arm is sufficient for the detection of extravasation events. Further validation of these hypotheses and key metrics is recommended in larger cohorts.

Oxygen Gas Sensing Using a Hydrogel-Based Organic Electrochemical Transistor for Work Safety Applications.

Oxygen depletion in confined spaces represents one of the most serious and underestimated dangers for workers. Despite the existence of several commercially available and widely used gas oxygen sensors, injuries and deaths from reduced oxygen levels are still more common than for other hazardous gases. Here, we present hydrogel-based organic electrochemical transistors (OECTs) made with the conducting polymer poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) (PEDOT:PSS) as wearable and real-time oxygen gas sensors. After comparing OECT performances using liquid and hydrogel electrolytes, we identified the best PEDOT:PSS active layer and hydrogel coating (30 µm) combination for sensing oxygen in the concentration range of 13−21% (v/v), critical for work safety applications. The fast O2 solubilization in the hydrogel allowed for gaseous oxygen transduction in an electrical signal thanks to the electrocatalytic activity of PEDOT:PSS, while OECT architecture amplified the response (gain ~ 104). OECTs proved to have comparable sensitivities if fabricated on glass and thin plastic substrates, (−12.2 ± 0.6) and (−15.4 ± 0.4) µA/dec, respectively, with low power consumption (<40 µW). Sample bending does not influence the device response, demonstrating that our real-time conformable and lightweight sensor could be implemented as a wearable, noninvasive safety tool for operators working in potentially hazardous confined spaces.

A Wearable Electrochemical Gas Sensor for Ammonia Detection.

The next future strategies for improved occupational safety and health management could largely benefit from wearable and Internet of Things technologies, enabling the real-time monitoring of health-related and environmental information to the wearer, to emergency responders, and to inspectors. The aim of this study is the development of a wearable gas sensor for the detection of NH3 at room temperature based on the organic semiconductor poly(3,4-ethylenedioxythiophene) (PEDOT), electrochemically deposited iridium oxide particles, and a hydrogel film. The hydrogel composition was finely optimised to obtain self-healing properties, as well as the desired porosity, adhesion to the substrate, and stability in humidity variations. Its chemical structure and morphology were characterised by infrared spectroscopy and scanning electron microscopy, respectively, and were found to play a key role in the transduction process and in the achievement of a reversible and selective response. The sensing properties rely on a potentiometric-like mechanism that significantly differs from most of the state-of-the-art NH3 gas sensors and provides superior robustness to the final device. Thanks to the reliability of the analytical response, the simple two-terminal configuration and the low power consumption, the PEDOT:PSS/IrOx Ps/hydrogel sensor was realised on a flexible plastic foil and successfully tested in a wearable configuration with wireless connectivity to a smartphone. The wearable sensor showed stability to mechanical deformations and good analytical performances, with a sensitivity of 60 ± 8 µA decade-1 in a wide concentration range (17-7899 ppm), which includes the safety limits set by law for NH3 exposure.

Characterization of an organic semiconductor diode for dosimetry in radiotherapy.

PURPOSE: The development of novel detectors for dosimetry in advanced radiotherapy modalities requires materials that have a water equivalent response to ionizing radiation such that characterization of radiation beams can be performed without the need for complex calibration procedures and correction factors. Organic semiconductors are potentially an ideal technology in fabricating devices for dosimetry due to tissue equivalence, mechanical flexibility, and relatively cheap manufacturing cost. The response of a commercial organic photodetector (OPD), coupled to a plastic scintillator, to ionizing radiation from a linear accelerator and orthovoltage x-ray tube has been characterized to assess its potential as a dosimeter for radiotherapy. The radiation hardness of the OPD has also been investigated to demonstrate its longevity for such applications. METHODS: Radiation hardness measurements were achieved by observing the response of the OPD to the visible spectrum and 70 keV x rays after pre-exposure to 40 kGy of ionizing radiation. The response of a preirradiated OPD to 6-MV photons from a linear accelerator in reference conditions was compared to a nonirradiated OPD with respect to direct and indirect (RP400 plastic scintillator) detection mechanisms. Dose rate dependence of the OPD was measured by varying the surface-to-source distance between 90 and 300 cm. Energy dependence was characterized from 29.5 to 129 keV with an x-ray tube. The percentage depth dose (PDD) curves were measured from 0.5 to 20 cm and compared to an ionization chamber. RESULTS: The OPD sensitivity to visible light showed substantial degradation of the broad 450 to 600 nm peak from the donor after irradiation to 40 kGy. After irradiation, the spectral shape has a dominant absorbance peak at 370 nm, as the acceptor better withstood radiation damage. Its response to x rays stabilized to 30% after 35 kGy, with a 0.5% difference between 770 Gy increments. The OPD exhibited reproducible detection of ionizing radiation when coupled with a scintillator. Indirect detection showed a linear response from 25 to 500 cGy and constant response to dose rates from 0.31 Gy/pulse to 3.4 × 10-4  Gy/pulse. However, without the scintillator, response increased by 100% at low dose rates. Energy independence between 100 keV and 1.2 MeV advocates their use as a dosimeter without beam correction factors. A dependence on the scintillator thickness used during a comparison of the PDD to the ionizing chamber was identified. A 1-mm-thick scintillator coupled with the OPD demonstrated the best agreement of ± 3%. CONCLUSIONS: The response of OPDs to ionizing radiation has been characterized, showing promising use as a dosimeter when coupled with a plastic scintillator. The mechanisms of charge transport and trapping within organic materials varies for visible and ionizing radiation, due to differing properties for direct and indirect detection mechanisms and observing a substantial decrease in sensitivity to the visible spectrum after 40 kGy. This study proved that OPDs produce a stable response to 6-MV photons, and with a deeper understanding of the charge transport mechanisms due to exposure to ionizing radiation, they are promising candidates as the first flexible, water equivalent, real-time dosimeter.

Passive radiofrequency x-ray dosimeter tag based on flexible radiation-sensitive oxide field-effect transistor.

Distributed x-ray radiation dosimetry is crucial in diverse security areas with significant environmental and human impacts such as nuclear waste management, radiotherapy, or radioprotection devices. We present a fast, real-time dosimetry detection system based on flexible oxide thin-film transistors that show a quantitative shift in threshold voltage of up to 3.4 V/gray upon exposure to ionizing radiation. The transistors use indium-gallium-zinc-oxide as a semiconductor and a multilayer dielectric based on silicon oxide and tantalum oxide. Our measurements demonstrate that the threshold voltage shift is caused by the accumulation of positive ionization charge in the dielectric layer due to high-energy photon absorption in the high-Z dielectric. The high mobility combined with a steep subthreshold slope of the transistor allows for fast, reliable, and ultralow-power readout of the deposited radiation dose. The order-of-magnitude variation in transistor channel impedance upon exposure to radiation makes it possible to use a low-cost, passive radiofrequency identification sensor tag for its readout. In this way, we demonstrate a passive, programmable, wireless sensor that reports in real time the excess of critical radiation doses.

Physical and Electrochemical Properties of PEDOT:PSS as a Tool for Controlling Cell Growth.

Conducting polymers are promising materials for tissue engineering applications, since they can both provide a biocompatible scaffold for physical support of living cells, and transmit electrical and mechanical stimuli thanks to their electrical conductivity and reversible doping. In this work, thin films of one of the most promising materials for bioelectronics applications, poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) ( PEDOT: PSS), are prepared using two different techniques, spin coating and electrochemical polymerization, and their oxidation state is subsequently changed electrochemically with the application of an external bias. The electrochemical properties of these different types of PEDOT: PSS are studied through cyclic voltammetry and spectrophotometry to assess the effectiveness of the oxidation process and its stability over time. Their surface physical properties and their dependence on the redox state of PEDOT: PSS are investigated using atomic force microscopy (AFM), water contact angle goniometry and sheet resistance measurements. Finally, human glioblastoma multiforme cells (T98G) and primary human dermal fibroblasts (hDF) are cultured on PEDOT: PSS films with different oxidation states, finding that the effect of the substrate on the cell growth rate is strongly cell-dependent: T98G growth is enhanced by the reduced samples, while hDF growth is more effective only on the oxidized substrates that show a strong chemical interaction with the cell culture medium.

Organic semiconducting single crystals as solid-state sensors for ionizing radiation.

So far, organic semiconductors have been mainly proposed as detectors for ionizing radiation in the indirect conversion approach, i.e. as scintillators, which convert ionizing radiation into visible photons, or as photodiodes, which detect visible photons coming from a scintillator and convert them into an electrical signal. The direct conversion of ionizing radiation into an electrical signal within the same device is a more effective process than indirect conversion, since it improves the signal-to-noise ratio and it reduces the device response time. We report here the use of Organic Semiconducting Single Crystals (OSSCs) as intrinsic direct ionizing radiation detectors, thanks to their stability, good transport properties and large interaction volume. Ionizing radiation X-ray detectors, based on low-cost solution-grown OSSCs, are here shown to operate at room temperature, providing a stable linear response with increasing dose rate in the ambient atmosphere and in high radiation environments.