Electrochemiluminescence
(ECL) has increased in popularity as a
result of its inherent advantages, including but not limited to portability,
simplicity of use, and low reagent consumption. However, its significant
advantages are often over shadowed as a result of its limited specificity.
ECL emissions are intrinsically broad and lack the definition of other
available analytical techniques. Furthermore, species with similar
functional groups have almost identical electrochemical behavior and
thus typically emit within approximately the same potential region.
Within this contribution we have demonstrate the use of pH controlled
ECL to prove the presence of two individual species within a mixed
sample. Analysis at a single pH would not provide this information.
We have illustrated the potential of this methodology to quantify
scopolamine alongside sister tropane alkaloid atropine, a known ECL
interferent. Previously the two alkaloids could not be distinguished
from one another using a single technique which did not involve a
separation strategy. pH controlled ECL is a simple approach to improve
the specificity of a basic [Ru(bpy)3]2+ film
based sensor. By exploiting molecular characteristics, such as pK
a, we have been able to fine-tune our methodology
to facilitate identification of analytes previously exhibiting indistinguishable
ECL emission. Thus, by improving specificity, while maintaining operational
simplicity and inexpensive design, we have been able to highlight
the potential power of ECL for identification of structurally similar
compounds. Further improvements of specificity, such as demonstrated
within this contribution, will only further future applications of
ECL sensors across a range of different fields.
Electrochemiluminescent sensors for point-of-care devices; a screening strategy for the direct detection of hallucinogens within a variety of biological matrices.
Herein, the efficient serotonin (5-HT) sensing studies have been conducted using the (ZnO NRs)1−x(CNs)x nanocomposites (NCs) having appropriate structural and electrochemical properties. Initially, the different compositions of ZnO nanorods (NRs), with varying content of carbon nanostructures (CNs=MWCNTs and RGO), are prepared using simple in-situ wet chemical method and thereafter these NCs have been characterized for physico-chemical properties in correlation to the 5-HT sensing activity. XRD Rietveld refinement studies reveal the hexagonal Wurtzite ZnO NRs oriented in (101) direction with space group ‘P63mc’ and both orientation as well as phase of ZnO NRs are also retained in the NCs due to the small content of CNs. The interconnectivity between the ZnO NRs with CNs through different functional moieties is also studied using FTIR analysis; while phases of the constituents are confirmed through Raman analysis. FESEM images of the bare/NCs show hexagonal shaped rods with higher aspect ratio (4.87) to that of others. BET analysis and EIS measurements reveal the higher surface area (97.895 m2/g), lower charge transfer resistance (16.2 kΩ) for the ZCNT 0.1 NCs to that of other NCs or bare material. Thereafter, the prepared NCs are deposited on the screen printed carbon electrode (SPCE) using chitosan as cross-linked agent for 5-HT sensing studies; conducted through cyclic voltammetry (CV) and square wave voltammetry (SWV) measurements. Among the various composites, ZCNT0.1 NCs based electrodes exhibit higher sensing activity towards 5-HT in accordance to its higher surface area, lower particle size and lower charge transfer resistance. SWV measurements provide a wide linear response range (7.5–300 μM); lower limit of detection (0.66 μM), excellent limit of quantification (2.19 μM) and good reproducibility to ZCNT 0.1 NCs as compared to others for 5-HT sensing studies.
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