Copper oxide nanostructures are widely used for various applications due to their unique optical and electrical properties. In this work, we demonstrate an atmospheric laser-induced oxidation technique for the fabrication of highly electrochemically active copper oxide hierarchical micro/nano structures on copper surfaces to achieve highly sensitive non-enzymatic glucose sensing performance. The effect of laser processing power on the composition, crystallinity, microstructure, wettability, and color of the laser-induced oxide on copper (LIO-Cu) surface was systematically studied using scanning electron microscopy (SEM), grazing incidence X-ray diffraction (GI-XRD), Raman spectroscopy, energy dispersive X-ray spectroscopy (EDX), EDX-mapping, water contact angle measurements, and optical microscopy. Results of these investigations showed a remarkable increase in copper oxide composition by increasing the laser processing power. The pore size distribution and surface area of the pristine and LIO-Cu sample estimated by N 2 adsorption–desorption data showed a developed mesoporous LIO-Cu structure. The size of the generated nano-oxides, crystallinity, and electroactivity of the LIO-Cu were observed to be adjustable by the laser processing power. The electrocatalytic activity of LIO-Cu surfaces was studied by means of cyclic voltammetry (CV) within a potential window of −0.8 to +0.8 V and chronoamperometry in an applied optimized potential of +0.6 V, in 0.1 M NaOH solution and phosphate buffer solution (PBS), respectively. LIO-Cu surfaces with optimized laser processing powers exhibited a sensitivity of 6950 μA mM −1 cm −2 within a wide linear range from 0.01 to 5 mM, with exceptional specificity and response time (<3 seconds). The sensors also showed excellent response stability over a course of 50 days that was originated from the binder-free robust electroactive film fabricated directly onto the copper surface. The demonstrated one-step LIO processing onto commercial metal films, can potentially be applied for tuneable and scalable roll-to-roll fabrication of a wide range of high surface area metal oxide micro/nano structures for non-enzymatic biosensing and electrochemical applications.
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Non-Enzymatic Detection of Glucose in Neutral Solution Using PBS-Treated Electrodeposited Copper-Nickel Electrodes
Transition metals have been explored extensively for non-enzymatic electrochemical detection of glucose. However, to enable glucose oxidation, the majority of reports require highly alkaline electrolytes which can be damaging to the sensors and hazardous to handle. In this work, we developed a non-enzymatic sensor for detection of glucose in near-neutral solution based on copper-nickel electrodes which are electrochemically modified in phosphate-buffered saline (PBS). Nickel and copper were deposited using chronopotentiometry, followed by a two-step annealing process in air (Step 1: at room temperature and Step 2: at 150 °C) and electrochemical stabilization in PBS. Morphology and chemical composition of the electrodes were characterized using scanning electron microscopy and energy-dispersive X-ray spectroscopy. Cyclic voltammetry was used to measure oxidation reaction of glucose in sodium sulfate (100 mM, pH 6.4). The PBS-Cu-Ni working electrodes enabled detection of glucose with a limit of detection (LOD) of 4.2 nM, a dynamic response from 5 nM to 20 mM, and sensitivity of 5.47 ± 0.45 μA cm−2/log10(mole.L−1) at an applied potential of 0.2 V. In addition to the ultralow LOD, the sensors are selective toward glucose in the presence of physiologically relevant concentrations of ascorbic acid and uric acid spiked in artificial saliva. The optimized PBS-Cu-Ni electrodes demonstrate better stability after seven days storage in ambient compared to the Cu-Ni electrodes without PBS treatment.
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- Award ID(s):
- 2113864
- NSF-PAR ID:
- 10344495
- Date Published:
- Journal Name:
- Biosensors
- Volume:
- 11
- Issue:
- 11
- ISSN:
- 2079-6374
- Page Range / eLocation ID:
- 409
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract A series of non‐enzymatic electrochemical glucose sensors were prepared by template‐assisted electrodeposition of nickel to produce nickel nanowire arrays (NiNWAs) of varying lengths. These electrodes were analyzed for their performance as non‐enzymatic glucose sensors, in order to explore the relationship between nanowire structure and electrochemical sensor performance. All of the NiNWAs, regardless of length, had linear responses to glucose in the 0.05–10 mM range. However, an inverse relationship between wire length and sensitivity was observed: the shortest of the NiNWAs had a sensitivity of 160 μA mM−1 cm−2, while the longest NiNWA had a sensitivity of only 100 μA mM−1 cm−2. This indicates that, with no other change to material parameters, choosing an optimum length of nanowire provides significant improvement in performance. No change in electrochemical mechanism was observed by cyclic voltammetry, and no significant loss of selectivity was observed with varying nanowire length. This study demonstrates that the structural optimization of an electrode can provide significant performance enhancement for nickel‐based electrochemical sensors.
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Uniform and porous CoNi 2 Se 4 was successfully synthesized by electrodeposition onto a composite electrode comprising reduced graphene oxide (rGO) anchored on a Ni foam substrate (prepared hydrothermally). This CoNi 2 Se 4 –rGO@NF composite electrode has been employed as an electrocatalyst for the direct oxidation of glucose, thereby acting as a high-performance non-enzymatic glucose sensor. Direct electrochemical measurement with the as-prepared electrode in 0.1 M NaOH revealed that the CoNi 2 Se 4 –rGO nanocomposite has excellent electrocatalytic activity towards glucose oxidation in an alkaline medium with a sensitivity of 18.89 mA mM −1 cm −2 and a wide linear response from 1 μM to 4.0 mM at a low applied potential of +0.35 V vs. Ag|AgCl. This study also highlights the effect of decreasing the anion electronegativity on enhancing the electrocatalytic efficiency by lowering the potential needed for glucose oxidation. The catalyst composite also exhibits high selectivity towards glucose oxidation in the presence of several interferents normally found in physiological blood samples. A low glucose detection limit of 0.65 μM and long-term stability along with a short response time of approximately 4 seconds highlights the promising performance of the CoNi 2 Se 4 –rGO@NF electrode for non-enzymatic glucose sensing with high precision and reliability.more » « less
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Neurotransmitters are small molecules involved in neuronal signaling and can also serve as stress biomarkers.1Their abnormal levels have been also proposed to be indicative of several neurological diseases such as Alzheimer’s disease, Parkinson’s disease, Huntington disease, among others. Hence, measuring their levels is highly important for early diagnosis, therapy, and disease prognosis. In this work, we investigate facile functionalization methods to tune and enhance sensitivity of printed graphene sensors to neurotransmitters. Sensors based on direct laser scribing and screen-printed graphene ink are studied. These printing methods offer ease of prototyping and scalable fabrication at low cost.
The effect of functionalization of laser induced graphene (LIG) by electrodeposition and solution-based deposition of TMDs (molybdenum disulfide2and tungsten disulfide) and metal nanoparticles is studied. For different processing methods, electrochemical characteristics (such as electrochemically active surface area: ECSA and heterogenous electron transfer rate: k0) are extracted and correlated to surface chemistry and defect density obtained respectively using X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. These functionalization methods are observed to directly impact the sensitivity and limit of detection (LOD) of the graphene sensors for the studied neurotransmitters. For example, as compared to bare LIG, it is observed that electrodeposition of MoS2on LIG improves ECSA by 3 times and k0by 1.5 times.3Electrodeposition of MoS2also significantly reduces LOD of serotonin and dopamine in saliva, enabling detection of their physiologically relevant concentrations (in pM-nM range). In addition, chemical treatment of LIG sensors is carried out in the form of acetic acid treatment. Acetic acid treatment has been shown previously to improve C-C bonds improving the conductivity of LIG sensors.4In our work, in particular, acetic acid treatment leads to larger improvement of LOD of norepinephrine compared to MoS2electrodeposition.
In addition, we investigate the effect of plasma treatment to tune the sensor response by modifying the defect density and chemistry. For example, we find that oxygen plasma treatment of screen-printed graphene ink greatly improves LOD of norepinephrine up to three orders of magnitude, which may be attributed to the increased defects and oxygen functional groups on the surface as evident by XPS measurements. Defects are known to play a key role in enhancing the sensitivity of 2D materials to surface interactions, and have been explored in tuning/enhancing the sensor sensitivity.5Building on our previous work,3we apply a custom machine learning-based data processing method to further improve that sensitivity and LOD, and also to automatically benchmark different molecule-material pairs.
Future work includes expanding the plasma chemistry and conditions, studying the effect of precursor mixture in laser-induced solution-based functionalization, and understanding the interplay between molecule-material system. Work is also underway to improve the machine learning model by using nonlinear learning models such as neural networks to improve the sensor sensitivity, selectivity, and robustness.
References A. J. Steckl, P. Ray, (2018), doi:10.1021/acssensors.8b00726.
Y. Lei, D. Butler, M. C. Lucking, F. Zhang, T. Xia, K. Fujisawa, T. Granzier-Nakajima, R. Cruz-Silva, M. Endo, H. Terrones, M. Terrones, A. Ebrahimi,
Sci. Adv. 6 , 4250–4257 (2020).V. Kammarchedu, D. Butler, A. Ebrahimi,
Anal. Chim. Acta .1232 , 340447 (2022).H. Yoon, J. Nah, H. Kim, S. Ko, M. Sharifuzzaman, S. C. Barman, X. Xuan, J. Kim, J. Y. Park,
Sensors Actuators B Chem. 311 , 127866 (2020).T. Wu, A. Alharbi, R. Kiani, D. Shahrjerdi,
Adv. Mater. 31 , 1–12 (2019). -
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Rationale Purification of recombinant proteins is a necessary step for functional or structural studies and other applications. Immobilized metal affinity chromatography is a common recombinant protein purification method. Mass spectrometry (MS) allows for confirmation of identity of expressed proteins and unambiguous detection of enzymatic substrates and reaction products. We demonstrate the detection of enzymes purified on immobilized metal affinity surfaces by direct or ambient ionization MS, and follow their enzymatic reactions by direct electrospray ionization (ESI) or desorption electrospray ionization (DESI).
Methods A protein standard, His‐Ubq, and two recombinant proteins, His‐SHAN and His‐CS, expressed in
Escherichia coli Results Small proteins (His‐Ubq) and medium proteins (His‐SAHN) could readily be detected from 96‐well plates by direct infusion ESI, or from microscope slides by DESI‐MS after purification on surface from clarified
E. coli cell lysate. Protein oxidation was observed for immobilized proteins on both Cu‐NTA and Ni‐NTA; however, this did not hamper the enzymatic reactions of these proteins. Both the nucleosidase reaction products for His‐SAHN and the methylation product of His‐CS (theobromine to caffeine) were detected.Conclusions The immobilization, purification, release and detection of His‐tagged recombinant proteins using immobilized metal affinity surfaces for direct infusion ESI‐MS or ambient DESI‐MS analyses were successfully demonstrated. Recombinant proteins were purified to allow identification directly out of clarified cell lysate. Biological activities of the recombinant proteins were preserved allowing the investigation of enzymatic activity via MS.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3390/bios11110409
