Effect of duration of potential cycle
Typical results for the duration of pretreatment are shown in Fig. lb for a
potential cycle of 0 to 2 V at a frequency of 10 Hz. After 1 min there was no
improvement in sensitivity, and in fact after 5 min a steady decline in sensitivity
occurred. An increase in noise was also observed when the pretreatment was
continued for periods longer than 5 min.
Effect of frequency
The influence of the frequency of the potential program was explored from 1 to
30 Hz for a potential cycle of 0 to 2 V for 1 min. The test voltammograms obtained
at the lower frequencies, i.e. 1 to 10 Hz, yielded higher sensitivities than those
observed at higher frequencies. The optimum frequency was chosen as 10 Hz as it
yielded high sensitivity and was fast enough to avoid damage to the fibre.
Effect of supporting electrolyte
The effectiveness of pretreatment appeared to be influenced by the supporting
electrolyte composition. Hydrochloric acid (0.1 M), perchloric acid (0.1 M) and BR
buffers of pH 2-12 were all tested, with the highest degree of activation being
obtained using pH 2 BR buffer. Such observations have been made previously with
macro-carbon electrodes, where anodisation of the electrode in citrate-acetate media
resulted in activation, but anodisation in acetate buffer alone was not effective [21].
Reproducibility of pretreatment
The pretreament selected as optimal was a potential cycle from 0 to 2 V at a
frequency of 10 Hz for a period of 1 min in pH 2 BR buffer. When 10 consecutive
voltammograms were obtained for folic acid without intermediate electrochemical
pretreatment, the current response decreased with each successive scan. Using the
optimal pretreatment between each DPV scan, the response was constant, with the
precision calculated as the relative standard deviation (n = 10) being better than
2.5%.
Functional characteristics of the pretreated microelectrode
A voltammetric study was then carried out to examine the effects of pretreatment
on the functional characteristics of the microelectrode. The effect of pretreatment
on both the faradaic and charging currents are shown in Figs. 2 and 3 respectively.
The increase in charging current obtained after pretreatment could be interpreted as
being due to an increase in the surface area of the microelectrode. Bjelica et al. [22]
have reported that glassy carbon electrodes subjected to prolonged electrolysis at
extreme positive potentials caused roughening of the surface. However, the enhanced
faradaic current obtained after pretreatment for folic acid would not, alone,
be explained by the relatively small increase in surface area indicated by the
charging current.
Effect of duration of potential cycleTypical results for the duration of pretreatment are shown in Fig. lb for apotential cycle of 0 to 2 V at a frequency of 10 Hz. After 1 min there was noimprovement in sensitivity, and in fact after 5 min a steady decline in sensitivityoccurred. An increase in noise was also observed when the pretreatment wascontinued for periods longer than 5 min. Effect of frequencyThe influence of the frequency of the potential program was explored from 1 to30 Hz for a potential cycle of 0 to 2 V for 1 min. The test voltammograms obtainedat the lower frequencies, i.e. 1 to 10 Hz, yielded higher sensitivities than thoseobserved at higher frequencies. The optimum frequency was chosen as 10 Hz as ityielded high sensitivity and was fast enough to avoid damage to the fibre. Effect of supporting electrolyteThe effectiveness of pretreatment appeared to be influenced by the supportingelectrolyte composition. Hydrochloric acid (0.1 M), perchloric acid (0.1 M) and BRbuffers of pH 2-12 were all tested, with the highest degree of activation beingobtained using pH 2 BR buffer. Such observations have been made previously withmacro-carbon electrodes, where anodisation of the electrode in citrate-acetate mediaresulted in activation, but anodisation in acetate buffer alone was not effective [21]. Reproducibility of pretreatmentThe pretreament selected as optimal was a potential cycle from 0 to 2 V at afrequency of 10 Hz for a period of 1 min in pH 2 BR buffer. When 10 consecutivevoltammograms were obtained for folic acid without intermediate electrochemicalpretreatment, the current response decreased with each successive scan. Using theoptimal pretreatment between each DPV scan, the response was constant, with theprecision calculated as the relative standard deviation (n = 10) being better than2.5%. Functional characteristics of the pretreated microelectrodeA voltammetric study was then carried out to examine the effects of pretreatmenton the functional characteristics of the microelectrode. The effect of pretreatmenton both the faradaic and charging currents are shown in Figs. 2 and 3 respectively.The increase in charging current obtained after pretreatment could be interpreted as being due to an increase in the surface area of the microelectrode. Bjelica et al. [22]have reported that glassy carbon electrodes subjected to prolonged electrolysis atextreme positive potentials caused roughening of the surface. However, the enhancedfaradaic current obtained after pretreatment for folic acid would not, alone,be explained by the relatively small increase in surface area indicated by thecharging current.
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