scholarly journals Rapid-scan electron paramagnetic resonance using an EPR-on-a-Chip sensor

2021 ◽  
Vol 2 (2) ◽  
pp. 673-687
Author(s):  
Silvio Künstner ◽  
Anh Chu ◽  
Klaus-Peter Dinse ◽  
Alexander Schnegg ◽  
Joseph E. McPeak ◽  
...  

Abstract. Electron paramagnetic resonance (EPR) spectroscopy is the method of choice to investigate and quantify paramagnetic species in many scientific fields, including materials science and the life sciences. Common EPR spectrometers use electromagnets and microwave (MW) resonators, limiting their application to dedicated lab environments. Here, novel aspects of voltage-controlled oscillator (VCO)-based EPR-on-a-Chip (EPRoC) detectors are discussed, which have recently gained interest in the EPR community. More specifically, it is demonstrated that with a VCO-based EPRoC detector, the amplitude-sensitive mode of detection can be used to perform very fast rapid-scan EPR experiments with a comparatively simple experimental setup to improve sensitivity compared to the continuous-wave regime. In place of a MW resonator, VCO-based EPRoC detectors use an array of injection-locked VCOs, each incorporating a miniaturized planar coil as a combined microwave source and detector. A striking advantage of the VCO-based approach is the possibility of replacing the conventionally used magnetic field sweeps with frequency sweeps with very high agility and near-constant sensitivity. Here, proof-of-concept rapid-scan EPR (RS-EPRoC) experiments are performed by sweeping the frequency of the EPRoC VCO array with up to 400 THz s−1, corresponding to a field sweep rate of 14 kT s−1. The resulting time-domain RS-EPRoC signals of a micrometer-scale BDPA sample can be transformed into the corresponding absorption EPR signals with high precision. Considering currently available technology, the frequency sweep range may be extended to 320 MHz, indicating that RS-EPRoC shows great promise for future sensitivity enhancements in the rapid-scan regime.

2021 ◽  
Author(s):  
Silvio Künstner ◽  
Anh Chu ◽  
Klaus-Peter Dinse ◽  
Alexander Schnegg ◽  
Joseph E. McPeak ◽  
...  

Abstract. Electron paramagnetic resonance (EPR) spectroscopy is the method of choice to investigate and quantify paramagnetic species in many scientific fields, including materials science and the life sciences. Common EPR spectrometers use electromagnets and microwave (MW) resonators, limiting their application to dedicated lab environments. Here, we present an improved design of a miniaturized EPR spectrometer implemented on a silicon microchip (EPR-on-a-chip, EPRoC). In place of a microwave resonator, EPRoC uses an array of injection-locked voltage-controlled oscillators (VCOs), each incorporating a 200 µm diameter coil, as a combined microwave source and detector. The individual miniaturized VCO elements provide an excellent spin sensitivity reported to be about 4 × 109 spins/√Hz, which is extended by the array over a larger area for improved concentration sensitivity. A striking advantage of this design is the possibility to sweep the MW frequency instead of the magnetic field, which allows the use of smaller, permanent magnets instead of the bulky and power-hungry electromagnets required for field-swept EPR. Here, we report rapid scan EPR (RS-EPRoC) experiments performed by sweeping the frequency of the EPRoC VCO array. RS-EPRoC spectra demonstrate an improved SNR by approximately two orders of magnitude for similar signal acquisition times compared to continuous wave (CW-EPRoC) methods, which may improve the absolute spin and concentration sensitivity of EPR-on-a-Chip at 14 GHz to about 6 × 107 spins/√Hz and 3.6 nM/√Hz, respectively.


2016 ◽  
Vol 172 (1-3) ◽  
pp. 133-138 ◽  
Author(s):  
Hanan Elajaili ◽  
Joseph McPeak ◽  
Alexander Romanyukha ◽  
Priyanka Aggarwal ◽  
Sandra S. Eaton ◽  
...  

2021 ◽  
Author(s):  
◽  
Rebecca Jane Sutton

<p>Organic light emitting diodes (OLEDs) are an emerging technology based on electrically conducting polymer films, with great promise for large area lighting and flexible ultra-thin displays. However, despite the rapid technological development, there is still a poor understanding of the degradation and spindependent recombination processes that take place inside an OLED. In this thesis, Electron Paramagnetic Resonance (EPR) was used to investigate these processes in blue-emitting OLEDs.  A successful procedure was developed and refined for fabricating OLEDs with the structure ITO/PEDOT:PSS/emissive layer/Al/Ag, with and without the PEDOT:PSS hole-transporting layer. The organic emissive layer was either F8BT, PFO, or PVK:OXD-7:FIrpic (PB). These OLEDs were fabricated in air and with a geometry optimised for EPR experiments. Critical features for satisfactory devices were found to be a sufficiently thick organic layer and minimal exposure to the air.  A compact apparatus was developed for simultaneous light output, current, and voltage measurements on the OLEDs while in an inert glove box environment. Electroluminescence and current-voltage parameters measured for these devices showed predominantly trap-controlled space-charge-limited conduction.   OLEDs with PFO as the emissive layer and with a PEDOT:PSS layer were investigated with conventional, electrically-detected (ED) and optically-detected (OD) EPR techniques. EDEPR and ODEPR signals were observed at ~9.2 GHz and in the low (<50 mT) and high (~330 mT) magnetic field regimes and were found to change markedly with time during operation as the device degraded. The low field signals initially showed a composite broad quenching and superimposed narrow enhancing response centred around zero field strength. These signals were attributed to magneto-resistance (MR) and magneto-electroluminescence (MEL). Following operational ageing, a third, narrow quenching line was observed in the MR and the ratio of the initial two MR responses changed substantially. These effects are tentatively attributed to a hyperfine interaction.  For both EDEPR and ODEPR, quenching high field resonances with a g-value (gyromagnetic ratio) of 2.003±0.001 were observed. The current-quenching resonance gradually diminished during operation and after 4–5 hours was replaced by a current-enhancing resonance. The appearance of this latter resonance could be explained by chemical changes in the OLED due to the diffusion of oxygen through the device from the oxygen-plasma-treated ITO. A working model is proposed which can explain this observed change as spindependent trapping and recombination at free radicals, although the model requires further experimentation to test its validity.</p>


Author(s):  
Alfonso Zoleo ◽  
Laura Speri ◽  
Maddalena Bronzato

AbstractElectron Paramagnetic Resonance (EPR) is a technique devoted to the identification and characterization of paramagnetic species, i.e. chemical species with unpaired electrons. Very common paramagnetic species which can be detected through EPR in historic paper are Fe(III), Mn(II), Cu(II) ions and radicals, where Fe(III), Cu(II) and radicals play a relevant role in paper degradation. Specifically, Fe(III) is almost ubiquitous in historic paper. Here we propose an overview of the EPR signals in historic and artificially aged paper, and in particular, we would like to show how a deep analysis of EPR signals from paper could provide useful information about the paper’s origin and unique indications of the degradation and oxidation level of the paper.


2014 ◽  
Vol 242 ◽  
pp. 162-168 ◽  
Author(s):  
Joshua R. Biller ◽  
Mark Tseitlin ◽  
Richard W. Quine ◽  
George A. Rinard ◽  
Hilary A. Weismiller ◽  
...  

1991 ◽  
Vol 261 (4) ◽  
pp. L81-L86 ◽  
Author(s):  
Enno K. Ruuge ◽  
Alexander N. Ledenev ◽  
Vladimir L. Lakomkin ◽  
Alexander A. Konstantinov ◽  
Marina Yu. Ksenzenko

Low-temperature electron paramagnetic resonance (EPR) spectroscopy and spin traps were used to measure paramagnetic species generation in rat hearts and isolated mitochondria. The hearts were freeze-clamped at 77 K during control perfusion by the Langendorff procedure, after 20–30 min of normothermic ischemia or 10–30 s of reperfusion with oxygenated perfusate. All EPR spectra measured at 4.5–50 K exhibited signals of both mitochondrial free radical centers and FeS proteins. The analysis of spectral parameters measured at 243 K showed that free radicals in heart tissue were semiquinones of coenzyme Q10 and flavins. The appearance of a typical “doublet” signal at g = 1.99 in low-temperature spectra indicated that a part of ubisemiquinones formed a complex with a high potential FeS protein of succinate dehydrogenase. Ischemia decreased the free radical species in myocardium ≈50%; the initiation of reflow of perfusate resulted in quick increase of the EPR signal. Mitochondria isolated from hearts during control perfusion and after 20–30 min of ischemia were able to produce superoxide radicals in both the NADH-coenzyme Q10 reductase and the bc1 segments of the respiratory chain. The rate of oxyradical generation was significantly higher in mitochondria isolated from ischemic heart. electron paramagnetic resonance; oxygen paradox; oxyradicals; rat heart; semiquinones


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