The electrochemical detection of chemical warfare agent (CWA) mimics was explored using multiwalled carbon nanotubes (MWCNTs) on indium tin oxide (ITO) surfaces in connection with ferrocene-amino acid conjugates. Various ferrocene-amino acid conjugates were synthesized and utilized as the recognition layer for the detection of CWA mimics. The ferrocene-amino acid conjugates were noncovalently attached to the pretreated MWCNTs on the ITO surface and reacted with CWA mimics, upon which the electrical properties of the MWCNTs and the Fc group were affected significantly. Alternating current voltammetry and capacitance-based detection offered large dynamic ranges for the detection of methylphosphonic acid, diethyl cyanophosphonate, ethylmethylphosphonate, and pinacolyl methylphosphonate in water. Electrochemical measurements showed dramatic changes upon the electrostatic interaction between the CWA mimics and the ferrocene-amino acid conjugates immobilized on MWCNTs on ITO surfaces. Electrochemical sensing in connection with MWCNTs is shown to be a promising analytical tool for the trace-level detection of CWA mimics in aqueous solutions.
A recognition layer formed by multiwalled carbon nanotubes (MWCNTs) covalently modified with a ferrocene-lysine conjugate deposited on the indium tin oxide (ITO) was investigated as a sensor for chemical warfare agent (CWA) mimics. Electrochemical impedance spectroscopy measurements showed that upon addition of CWA mimic dramatic changes occurred in the electrical properties of the recognition layer. These changes allowed the detection of nerve agent analogues at the micromolar level, and a limited sensitivity was observed toward a sulfur mustard mimic. Experimental parameters were optimized so as to allow the detection of CWAs at single frequency, thereby significantly reducing acquisition time and simplifying data treatment. A proposed method of detection represents a significant step toward the design of an affordable and "fieldable" electrochemical CWA sensor.
A comparison of the CH vibrational overtone spectra of vapor phase neopentane-d
0 (C(CH3)4), -d
6 (C(CH3)2(CD3)2), and -d
9 (C(CH3)(CD3)3) and tetramethylsilane (TMS) in the frequency range Δv
CH = 4−8 (10 800−18 200 cm-1) has revealed pronounced differences between the spectra of TMS and the neopentanes, and
subtle differences among the spectra of the neopentanes. These spectral differences are interpreted as a
manifestation of geometry and vibrational frequency dependent differences in coupling efficiencies that facilitate
the de-excitation of local modes of vibration via IVR. Fermi resonance plays a key role in this coupling.
Some of the states are perturbed by through space coupling (a collision-like van der Waals interaction) that
can facilitate IVR. The normal modes of vibration, which are implicated in Fermi resonance of the neopentanes
and TMS, have been calculated ab initio using density functional theory and are shown to be affected by
through space interactions.
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