This review aims to summarize the rapidly emerging field of real-time stress monitoring by focusing on early breakthroughs and critical developments in portable and wearable cortisol sensors. Here, brief, albeit comprehensive, information on technological advances and current state-of-the-art concepts on real-time cortisol sensing are provided. Specific examples where materials include up-to-date information related to complex sensing conditions, and methodologies, are pieced together. Examples of electrochemical cortisol sensing are categorized by sample types, focusing on sensing from body fluids in vitro and wearable sensors, which have attracted significant interest due to their integration with everyday life activity. The overall progress made to date in building such conceptualized efforts for real-time, continuous monitoring of cortisol and the future of the field is discussed.
Wound management involves repeated clinical trips and procedures of lab tests over days. To eliminate this time lag and provide real-time monitoring of a wound’s progress, we have designed an enzymatic biosensor for determining uric acid (UA) in wound fluid. Uric Acid is a biomarker, having an established correlation with wounds and their healing. This electrochemical biosensor comprises enzyme urate oxidase (uricase, UOx) entrapped in a polyvinyl alcohol based cationic polymer for enhanced stability. Results show that the use of a redox electron shuttle, ferrocene carboxylic acid (FCA), enabled electron transfer between the enzyme and the transducer. The immobilized uricase in the polymer matrix provided stable continuous measurements at body temperature for a week with minimal deviation. Detection of uric acid in wound fluid has been determined from volumes as low as 0.5–50μL.
Studies from different wound samples have shown an average recovery of 107%. The sensor has been interfaced with LMP91000 potentiostat and controlled by CC2650 microcontroller on a Kapton tape-based miniaturized flexible platform.
MP1 is a novel marinopyrrole analogue with activity in MYCN amplified neuroblastoma cell lines. A rapid, selective, and sensitive liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) method was developed and validated for quantitation of MP1 in mouse plasma. Analyte separation was achieved using a Waters Acquity UPLC®BEH C18 column (1.7 µm, 100 × 2.1 mm). Mobile phase consisted of 0.1% acetic acid in water (10%) and methanol (90%) at a total flow rate of 0.25 mL/min. The mass spectrometer was operated at unit resolution in the multiple reaction monitoring (MRM) mode, using precursor ion > product ion transitions of 324.10 > 168.30 m/z for MP1 and 411.95 > 224.15 m/z for PL-3. The MS/MS response was linear over the concentration range from 0.2-500 ng/mL for MP1, correlation coefficient (r2) of 0.988. Precision (% RSD) and accuracy (% bias) were within the acceptable limits as per FDA guidelines. MP1 was stable under storage and laboratory handling conditions. The validated method was successfully applied to assess the solubility, in-vitro metabolism, plasma protein binding, and bio-distribution studies of MP1.
The necessity of managing stress levels is becoming increasingly apparent as the world suffers from different kinds of stresses including the extent of pandemic, the corona virus disease 2019 (COVID-19). Cortisol, a clinically confirmed stress hormone related to depression and anxiety, affects individuals mentally and physically. However, current cortisol monitoring methods require expert personnel, large and complex machines, and long time for data analysis. Here, we present a flexible and wearable cortisol aptasensor for simple and rapid cortisol real-time monitoring. The sensing channel was produced by electrospinning conducting polyacrylonitrile (PAN) nanofibers (NFs) and subsequent vapor deposition of carboxylated poly(3,4-ethylenedioxythiophene) (PEDOT). The conjugation of the cortisol aptamer on the PEDOT-PAN NFs provided the critical sensing mechanism for the target molecule. The sensing test was performed with a liquid-ion gated field-effect transistor (FET) on a polyester (polyethylene terepthalate). The sensor performance showed a detection limit of 10 pM (<5 s) and high selectivity in the presence of interference materials at 100 times higher concentrations. The practical usage and real-time monitoring of the cortisol aptasensor with a liquid-ion gated FET system was demonstrated by successful transfer to the swab and the skin. In addition, the real-time monitoring of actual sweat by applying the cortisol aptasensor was also successful since the aptasensor was able to detect cortisol approximately 1 nM from actual sweat in a few minutes. This wearable biosensor platform supports the possibility of further application and on-site monitoring for changes of other numerous biomarkers.
Understanding the differences between reactions driven by elevated temperature or electric potential remains challenging, largely due to materials incompatibilities between thermal catalytic and electrocatalytic environments. We show that Ni, N-doped carbon (NiPACN), an electrocatalyst for the reduction of CO2 to CO (CO2R), can also selectively catalyze thermal CO2 to CO via the reverse water gas shift (RWGS) representing a direct analogy between catalytic phenomena across the two reaction environments. Advanced characterization techniques reveal that NiPACN likely facilitates RWGS on dispersed Ni sites in agreement with CO2R active site studies. Finally, we construct a generalized reaction driving-force that includes temperature and potential and suggest that NiPACN could facilitate faster kinetics in CO2R relative to RWGS due to lower intrinsic barriers. This report motivates further studies that quantitatively link catalytic phenomena across disparate reaction environments.
The highly unfavorable thermodynamics of direct aluminum hydrogenation can be overcome by stabilizing alane within a nanoporous bipyridine-functionalized covalent triazine framework (AlH3@CTF-bipyridine). This material and the counterpart AlH3@CTF-biphenyl rapidly desorb H2 between 95 and 154 °C, with desorption complete at 250 °C. Sieverts measurements, 27Al MAS NMR and 27Al1H REDOR experiments, and computational spectroscopy reveal that AlH3@CTF-bipyridine dehydrogenation is reversible at 60 °C under 700 bar hydrogen, >10 times lower pressure than that required to hydrogenate bulk aluminum. DFT calculations and EPR measurements support an unconventional mechanism whereby strong AlH3 binding to bipyridine results in single-electron transfer to form AlH2(AlH3)n clusters. The resulting size-dependent charge redistribution alters the dehydrogenation/rehydrogenation thermochemistry, suggesting a novel strategy to enable reversibility in high-capacity metal hydrides.