Review—Electrochemistry's Potential to Reach the Ultimate Sensitivity in Measurement Science
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A holy grail in analytical chemistry is the specific quantification of a single entity, be that entity an atom, a molecule, a nanoparticle, a virus, or a circulating tumor cell. Analytical chemistry is entering an era where this sensitivity can be achieved. In these experiments, the limit of detection is 1, and the limit of quantitation is not only measured in units of concentration but units of time: the waiting time before positively identifying a single entity. Electrochemistry is front and center in single entity experiments with hundreds of publications per year detailing observations of various entities colliding with micro- and nano-electrodes. These types of experiments are referred to as 'stochastic electrochemistry' due to the stochastic nature of the collision of an entity with an electrode surface. If methods of detection can be made specific, simple, inexpensive, and robust, the techniques hold the promise of transforming diagnostics (i.e., the specific detection of a single cancerous cell in blood). This review will critically analyze the stochastic electrochemistry literature and focus on reports detailing methods to ensure the response at the electrode surface is specific to the colliding entity. The topic of specificity, and strategies to achieve it, are highlighted.
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Lee et al. demonstrated a linear relationship between collision frequency f_exp and E. coli concentration C_bac, as expected by Equation 1.
“The authors have demonstrated a linear relationship between the collision frequency f exp (number of step-shaped transients) and the E. coli concentration C bac , as expected by Equation 1 below (in conditions where the mass transport is controlled by diffusion) [10,16,32].”
From Trends in single-impact electrochemistry for bacteria analysis (2023) · cites this paper as [10]
In “Methods to Decrease Limit of Quantitation” (page unavailable), the review gives a diffusion-controlled equation in which collision frequency is proportional to the concentration of colliding entities. Its discussion of bacterial blocking experiments (page unavailable) reports detection of single E. coli collisions, but does not report that Lee et al. experimentally demonstrated a linear relationship between step-shaped transient frequency and E. coli concentration. (LLM, conf=0.85)
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- Authors
- Goines, S., & Dick, J. E.
- Affiliations
- University of North Carolina at Chapel Hill (US)
- Venue
- Journal of The Electrochemical Society
- Publisher
- The Electrochemical Society
- Published
- 2019-11-20
- Volume
- 167
- Issue
- 3
- Pages
- 037505
- ISSN
- 0013-4651 (ISSN-L)
- 1945-7111
- OpenAlex
- W2990758229
- Cited by
- 81
- References
- 128
- Citations by year
- 2026: 5 · 2025: 5 · 2024: 14 · 2023: 16 · 2022: 12 · 2021: 10 · 2020: 19
- FWCI
- 4.61
- Type
- journal article
- Language
- en
- Open access
- hybrid
- doi.org
- Locations
- Journal of The Electrochemical Society (publishedVersion, cc-by)
- Funders
- The University of North Carolina at Chapel Hill (Start-Up)
- Topics
- Physical Sciences › Chemistry › Electrochemistry › Electrochemical Analysis and Applications
- Physical Sciences › Engineering › Electrical and Electronic Engineering › Electrochemical sensors and biosensors
- Life Sciences › Biochemistry, Genetics and Molecular Biology › Molecular Biology › Advanced biosensing and bioanalysis techniques
- Keywords
- single-molecule detection, single-cell detection, detection limit, detection specificity, nanoelectrodes, microelectrodes, cancer cell detection, point-of-care testing, single-atom detection
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