Instrument and Application Development in Saturation Recovery and Rapid Scan Electron Paramagnetic Resonance

Enhanced signal sensitivity by the use of Rapid Scan (RS) electron paramagnetic resonance (EPR), a technique that allows for much faster magnetic field scans than traditional field-swept techniques, has facilitated improved data acquisition for many types of samples. For example, irradiated fingernails for radiation dosimetry have been studied using RS-EPR, which resulted in substantial decreases in detection limits. Samarium-mediated reduction mechanisms in organic synthesis have been investigated by RS-EPR providing evidence for a radical intermediate. Spectra of organic radicals exhibiting both narrow lines and closely spaced hyperfine interactions have been recorded via RS-EPR. Well-resolved spectra can be recorded at a rate of 40 spectra/minute to gain insight into molecular changes on this timescale. RS-EPR performed at low temperatures using a closed cycle helium system and a cryostat containing a region with low electrical conductivity provides very wide (\u3e9000 G) spectra free of passage effects near 5 K, expanding the capabilities of RS-EPR. Recent developments in arbitrary wave form generators (AWGs) provide digital waveform synthesis at high enough frequencies to be used in EPR experiments at ca. 9 GHz (X-band). A new saturation recovery (SR) EPR spectrometer has been constructed with an AWG as the microwave source. Circuit design focuses on implementation of an X-band crossed-loop resonator with a reduced quality factor (Q) to minimize dead time due to resonator ring down processes. Increased accuracy of the AWG instrument relative to conventional sources has made nitroxide spin-lattice relaxation time measurements possible via SR-EPR with S/N high enough to permit separation of electron and nuclear spin-lattice relaxation contributions. These results enabled more accurate estimation of the saturation factor in dynamic nuclear polarization (DNP) experiments

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

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 × 109spins/√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 powerhungry 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

Long-Term Characterization of Oxidation Processes in Graphitic Carbon Nitride Photocatalyst Materials via Electron Paramagnetic Resonance Spectroscopy

Graphitic carbon nitride (gCN) materials have been shown to efficiently perform light-induced water splitting, carbon dioxide reduction, and environmental remediation in a cost-effective way. However, gCN suffers from rapid charge-carrier recombination, inefficient light absorption, and poor long-term stability which greatly hinders photocatalytic performance. To determine the underlying catalytic mechanisms and overall contributions that will improve performance, the electronic structure of gCN materials has been investigated using electron paramagnetic resonance (EPR) spectroscopy. Through lineshape analysis and relaxation behavior, evidence of two independent spin species were determined to be present in catalytically active gCN materials. These two contributions to the total lineshape respond independently to light exposure such that the previously established catalytically active spin system remains responsive while the newly observed, superimposed EPR signal is not increased during exposure to light. The time dependence of these two peaks present in gCN EPR spectra recorded sequentially in air over several months demonstrates a steady change in the electronic structure of the gCN framework over time. This light-independent, slowly evolving additional spin center is demonstrated to be the result of oxidative processes occurring as a result of exposure to the environment and is confirmed by forced oxidation experiments. This oxidized gCN exhibits lower H2 production rates and indicates quenching of the overall gCN catalytic activity over longer reaction times. A general model for the newly generated spin centers is given and strategies for the alleviation of oxidative products within the gCN framework are discussed in the context of improving photocatalytic activity over extended durations as required for future functional photocatalytic device development

Monitoring the state of charge of vanadium redox flow batteries with an EPR-on-a-Chip dipstick sensor

The vanadium redox flow battery (VRFB) is considered a promising candidate for large-scale energy storage in the transition from fossil fuels to renewable energy sources. VRFBs store energy by electrochemical reactions of different electroactive species dissolved in electrolyte solutions. The redox couples of VRFBs are VO2+/VO2+ and V2+/V3+, the ratio of which to the total vanadium content determines the state of charge (SOC). V(iv) and V(ii) are paramagnetic half-integer spin species detectable and quantifiable with electron paramagnetic resonance spectroscopy (EPR). Common commercial EPR spectrometers, however, employ microwave cavity resonators which necessitate the use of large electromagnets, limiting their application to dedicated laboratories. For an SOC monitoring device for VRFBs, a small, cost-effective submersible EPR spectrometer, preferably with a permanent magnet, is desirable. The EPR-on-a-Chip (EPRoC) spectrometer miniaturises the complete EPR spectrometer onto a single microchip by utilising the coil of a voltage-controlled oscillator as both microwave source and detector. It is capable of sweeping the frequency while the magnetic field is held constant enabling the use of small permanent magnets. This drastically reduces the experimental complexity of EPR. Hence, the EPRoC fulfils the requirements for an SOC sensor. We, therefore, evaluate the potential for utilisation of an EPRoC dipstick spectrometer as an operando and continuously online monitor for the SOC of VRFBs. Herein, we present quantitative proof-of-principle submersible EPRoC experiments on variably charged vanadium electrolyte solutions. EPR data obtained with a commercial EPR spectrometer are in good agreement with the EPRoC data

Microwave field mapping for EPR-on-a-chip experiments

Electron paramagnetic resonance–on-a-chip (EPRoC) devices use small voltage-controlled oscillators (VCOs) for both the excitation and detection of the EPR signal, allowing access to unique sample environments by lifting the restrictions imposed by resonator-based EPR techniques. EPRoC devices have been successfully used at multiple frequencies (7 to 360 gigahertz) and have demonstrated their utility in producing high-resolution spectra in a variety of spin centers. To enable quantitative measurements using EPRoC devices, the spatial distribution of the B1 field produced by the VCOs must be known. As an example, the field distribution of a 12-coil VCO array EPRoC operating at 14 gigahertz is described in this study. The frequency modulation–recorded EPR spectra of a “point”-like and a thin-film sample were investigated while varying the position of both samples in three directions. The results were compared to COMSOL simulations of the B1-field intensity. The EPRoC array sensitive volume was determined to be ~19 nanoliters. Implications for possible EPR applications are discussed

The Vehicle, November 1960, Vol. 3 no. 1

CONTENTS To the ReaderStaffpage 2 N’ = N : 1Donald C. Blairpage 3 ConsistencyDonald C. Blairpage 3 Unto MeLinda Kay Campbellpage 4 The Meek Shall InheritE. J. B. page 5 The Infinite QuestLarry W. Dudleypage 6 Dreamer’s DawnMike Hindmanpage 7 BirthNancy Coepage 7 The Lost DutchmanDonald C. Blairpage 8 W. E. Noonan IRobert S. Hodgepage 8 A Soldier’s OrdealDonald E. Shephardsonpage 9 Personal PossessionMary Beilpage 11 Thine The GloryDonald C. Blairpage 12 The ThornJan Holstlawpage 13 A Lord’s Day MorningLinda Campbellpage 14 Observations of a 6-Year-OldTom McPeakpage 15 Jewels of TimeJudith Jerintspage 16 LavenderE. J. B. page 16https://thekeep.eiu.edu/vehicle/1008/thumbnail.jp

Electrically Detected Magnetic Resonance on a Chip (EDMRoC) for Analysis of Thin-Film Silicon Photovoltaics

Electrically detected magnetic resonance (EDMR) is a spectroscopic technique that provides information about the physical properties of materials through the detection of variations in conductivity induced by spin-dependent processes. EDMR has been widely applied to investigate thin-film semiconductor materials in which the presence of defects can induce the current limiting processes. Conventional EDMR measurements are performed on samples with a special geometry that allows the use of a typical electron paramagnetic resonance (EPR) resonator. For such measurements, it is of utmost importance that the geometry of the sample under assessment does not influence the results of the experiment. Here, we present a single-board EPR spectrometer using a chip-integrated, voltage-controlled oscillator (VCO) array as a planar microwave source, whose geometry optimally matches that of a standard EDMR sample, and which greatly facilitates electrical interfacing to the device under assessment. The probehead combined an ultrasensitive transimpedance amplifier (TIA) with a twelve-coil array, VCO-based, single-board EPR spectrometer to permit EDMR-on-a-Chip (EDMRoC) investigations. EDMRoC measurements were performed at room temperature on a thin-film hydrogenated amorphous silicon (a-Si:H) pin solar cell under dark and forward bias conditions, and the recombination current driven by the a-Si:H dangling bonds (db) was detected. These experiments serve as a proof of concept for a new generation of small and versatile spectrometers that allow in situ and operando EDMR experiments

The Vehicle, 1961, Vol. 3 no. 2

Vol. 3, No. 2 Table of Contents The Voting CattleLinda Kay Campbellpage 5 But For the Passage of TimeDon Shepardsonpage 14 LoveJon Woodspage 16 Infinite JourneyJames E. Martinpage 19 The Clover ChainRichard W. Blairpage 20 SnowballSusan Daughertypage 24 Sureness Is NeverDon Shepardsonpage 26 ConceptionChristine McCollpage 34 Comedy: Relief and GriefTom McPeakpage 35 The Unspoken WordChristine McCollpage 35 CharmBenjamin Polkpage 36 Screaming SpiderTom McPeakpage 39 Just Once in an Early SpringE.J.B.page 39 HummingbirdPauline B. Smithpage 40 Willow TreesPauline B. Smithpage 40 MaturityChristine McCollpage 41 The New YearLinda Campbellpage 41 The StormMary-Jean Pitratpage 42 Ebony IvoryJean Danenbargerpage 42 The Fireball MailAllen Engelbrightpage 43 ExpectationChristine McCollpage 44 CatastropheChristine McCollpage 44 SophisticationBenjamin Polkpage 45 On Playing BridgeMyrna Jo Handleypage 46 SonnetMignon Stricklandpage 48https://thekeep.eiu.edu/vehicle/1009/thumbnail.jp

The Vehicle, 1961, Vol. 3 no. 2

Vol. 3, No. 2 Table of Contents The Voting CattleLinda Kay Campbellpage 5 But For the Passage of TimeDon Shepardsonpage 14 LoveJon Woodspage 16 Infinite JourneyJames E. Martinpage 19 The Clover ChainRichard W. Blairpage 20 SnowballSusan Daughertypage 24 Sureness Is NeverDon Shepardsonpage 26 ConceptionChristine McCollpage 34 Comedy: Relief and GriefTom McPeakpage 35 The Unspoken WordChristine McCollpage 35 CharmBenjamin Polkpage 36 Screaming SpiderTom McPeakpage 39 Just Once in an Early SpringE.J.B.page 39 HummingbirdPauline B. Smithpage 40 Willow TreesPauline B. Smithpage 40 MaturityChristine McCollpage 41 The New YearLinda Campbellpage 41 The StormMary-Jean Pitratpage 42 Ebony IvoryJean Danenbargerpage 42 The Fireball MailAllen Engelbrightpage 43 ExpectationChristine McCollpage 44 CatastropheChristine McCollpage 44 SophisticationBenjamin Polkpage 45 On Playing BridgeMyrna Jo Handleypage 46 SonnetMignon Stricklandpage 48https://thekeep.eiu.edu/vehicle/1009/thumbnail.jp

An X-band Continuous Wave Saturation Recovery Electron Paramagnetic Resonance Spectrometer Based on an Arbitrary Waveform Generator

An X-band (ca. 9-10 GHz) continuous wave saturation recovery spectrometer to measure electron spin-lattice relaxation (T1) was designed around an arbitrary waveform generator (AWG). The AWG is the microwave source and is used for timing of microwave pulses, generation of control signals, and digitizer triggering. Use of the AWG substantially simplifies the hardware in the bridge relative to that in conventional spectrometers and decreases the footprint. The bridge includes selectable paths with different power amplifications to permit experiments requiring hundreds of milliwatts to fractions of nanowatts for the pump and observe periods. The signal is detected with either a single or quadrature-output double balanced mixer. The system can operate with reflection or crossed-loop resonators. The source noise from the AWG was decreased by addition of a Wenzel high-stability clock. The source is sufficiently stable that automatic frequency control is not needed. The spectrometer was tested with samples that contained 1 × 1015 to 8 × 1017 spins and have T1 between a few hundred ns and hundreds of μs. Excellent signal-to-noise ratio was obtained with acquisition times of 2–90 s. Signal-to-noise performance is similar to that of a conventional saturation recovery spectrometer with a solid-state source. The stability and data reproducibility are better than with conventional sources. With replacement of frequency-sensitive components, this spectrometer can be used to perform saturation recovery measurements at any frequency within the range of the AWG