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Application of microchip-capillary electrophoresis and pulsed electrochemical detection to the analysis of biologically relevant phenolic compounds

Authors:
  • NASA Jet Propulsion Laboratory
  • University of Chinese Academy of Sciences, China, Beijing

Abstract

In this report, the most recent results regarding the use of microchip-capillary electrophoresis and pulsed electrochemical detection are reviewed. This article is particularly focused on the analysis of three groups of compounds: phenolic contaminants, phenolic acids, and phenolic antioxidants. Background information and a brief discussion covering other related analytical strategies are also included.
Application of microchip-capillary electrophoresis
and pulsed electrochemical detection to the
analysis of biologically relevant phenolic
compounds*
Maria F. Mora, Yongsheng Ding
a
, Eric Mejia, and Carlos D. García
Department of Chemistry, The University of Texas at San Antonio, San Antonio, TX, U.S.A.
a
Permanent address: Department of Chemical Biology, Peking University Health Science Center, Beijing 100083,
China
Correspondence: Dr. Carlos D. García, Department of Chemistry, The University of Texas at San Antonio, 6900
North Loop 1604 West, San Antonio, TX 78249, U.S.A.; e-mail: carlos.garcia@utsa.edu
Abstract
This paper reviews the most recent results regarding the use of microchip-capillary electrophoresis and pulsed electrochemical detection. The arti-
cle is particularly focused on the analysis of three groups of phenolic compounds: U.S. EPA contaminants,
1
antioxidants,
2
and pharmaceuticals.
3
Background information regarding the importance of these compounds, as well as a brief discussion covering other analytical strategies for the
analysis of phenols, are also included.
I
n recent years there has been a growing concern
regarding the consequences of wildlife and human
exposure to xenobiotics. A considerable number of
these compounds have a phenol-based structure.
Depending on the type and location of substituent
groups, these phenols (phenolic compounds, pheno-
lics, or mixtures of phenols) present varying biological
activities ranging from contaminants, disinfectants, her-
bicides, pharmaceuticals, antioxidants, and hormones,
to neurotransmitters.
Phenols are also the major organic constituents
found in effluents of coal conversion processes, coke
ovens, petroleum refineries, phenolic resin manufactur-
ing, herbicide manufacturing, fiberglass manufacturing,
and petrochemicals.
4–10
In general, phenolic contami-
nants are harmful in that they can produce alteration of
cell membranes, mutation of the genetic material, and
change in the speed of photosynthesis. The effect of
human exposure to phenols depends on the com-
pound, the contact time, and the contact via. In gener-
al, they can produce a wide range of symptoms and
pathologies from headaches to different cancers.
11–14
Most phenols and their derivatives can be oxi-
dized by oxygen, allowing the use of some phenolic
compounds as antioxidants.
15–18
Indeed, the most
broadly used primary synthetic antioxidants are hin-
dered phenolics, which are used in petroleum prod-
ucts,
19
rubbers,
20
soaps, plastics,
21
as well as animal and
Indexing terms
Microchip, capillary electrophoresis, pulsed amperometric detection, phenolic compounds
Abbreviations
BHT, 3,5-di-
tert
-butyl-4-hydroxytoluene; NSAIDs, nonsteroidal anti-inflammatory drugs; AP,
N
-acetyl-
p
-amino-phenol; DFS, diflunisal
(5-2’-4’-difluorophenyl salicylic acid); DCF, diclofenac (sodium
o
-2,6-dichloroanilino-phenyl acetate); APCI, atmospheric pressure
chemical ionization; PDMS, polydimethylsiloxane; EOF, electroosmotic flow; ICP-MS, inductively coupled plasma-mass spectrome-
try; ECD, electrochemical detection; PAD, pulsed amperometric detection; PDMS, poly(dimethylsiloxane); MEKC, micellar electroki-
netic chromatography; CMC, critical micelle concentration; SDS, sodium dodecyl sulfate; PG, propyl gallate; OG, octyl gallate; LG,
lauryl gallate; NDGA, nordihydroguaiaretic acid; THF, tetrahydrofuran; PCP, pentachlorophenyl; DNOC, 4,6-dinitro-
o
-cresol
*Part of the results discussed in this minireview were presented at the LACE 2005 Meeting, December 2–6, 2005, Guaruja, Brazil.
J. CAP. ELEC. AND MICROCHIP TECH. 009 : 5/6 2006 ###### J. CAP. ELEC. AND MICROCHIP TECH. 009 : 5/6 2006
vegetable products.
22
Synthetic phenolic antioxidants
have traditionally been based on 3,5-di-tert-butyl-4-
hydroxytoluene (BHT).
16,23
This functional moiety has
been incorporated into larger molecules, affording
products with lower volatility and color contribution.
24
Many cosmetic, pharmaceutical, and food processing
industries intensively use phenolic antioxidants in their
formulations,
25,26
either alone or in mixtures.
Although these antioxidants can increase a prod-
uct’s lifetime, some concerns have been raised about their
potential detrimental health effects.
27–30
Many products
also contain natural phenolic antioxidants.
31–40
Because of
the potential health benefits, special attention has been
directed to the content of resveratrol,
41–45
antho-
cyanins,
46,47
and catechins
36,48–53
in different matrices and
nutraceutical formulations.
54
Nonsteroidal anti-inflammatory drugs (NSAIDs)
are another group of biologically important phenolic
compounds that have very well-defined pharmaceutical
activities, and are among the most commonly used
over-the-counter pharmaceutical products. These com-
pounds are used as analgesics, antipyretics, antialler-
gics, and anti-inflammatory drugs. Aspirin (acetylsali-
cylic acid), acetaminophen (N-acetyl-p-amino-phenol,
AP), diflunisal (5-2’-4’-difluorophenyl salicylic acid,
DFS), and diclofenac (sodium o-2,6-dichloroanilino-
phenyl acetate, DCF) are commonly used with very lim-
ited age restrictions. However, if the dose exceeds the
therapeutic range, these compounds can produce a
large number of complications, including acidosis,
55
hepatic necrosis, and renal disorders.
56
A summary of
some of the biological activity and applications of phe-
nols is included in Figure 1.
Recent advances in the analysis of phenolic compounds
Various methods have been reported for the deter-
mination of environmentally important phenolic com-
pounds, such as GC
57
and HPLC
14,57–81
with different
detectors. Among others, Suliman et al.
59
reported the
analysis of chlorophenols in water by HPLC using
coumarin-6-sulfonyl chloride as a fluorogenic pre-
column label. Lee and Zhao
61
used liquid phase
microextraction with back extraction combined with
HPLC for the analysis of several chloro- and methylphe-
nols. Detection limits in the ng L
–1
range were obtained
by Rosenberg and Wissiack
82
using on-line solid-phase
extraction coupled to HPLC-atmospheric pressure
chemical ionization (APCI)-MS. Montero et al.
67
report-
ed the study of chlorophenols in lake and groundwater
samples using a polydimethylsiloxane (PDMS) stir bar
for the extraction of the derivatized phenols, and GC-
MS for the analysis. Vermeulen et al.
75
proposed a
derivatization step using acetic anhydride followed by
liquid–liquid extraction and GC-MS analysis. Recently,
Blythe et al.
68
reported a method with lower detection
limits (0.2 –3.1 ng/L) for bromophenols in water.
Chromatographic methods
83–86
are also usually cho-
sen for the determination of phenolic antioxidants in
food,
31,83,87–89
beverages,
90
plants,
31,32,50,89,91–96
cosmetics,
26
and clinical
14,97–99
samples. Nonchromatographic
40,46,100,101
electrochemical
16,18,22,23,102
flow-through,
16,23,103,104
and
electrophoretic
105–107
methods have also shown their util-
ity for this purpose. Numerous biosensors have been
designed for the analysis of phenols.
108–123
Phenol-
oxidases (laccases and tyrosinases) are the most com-
monly used enzymes for these devices.
124
Just to name a
few, Mailley et al. designed a biosensor based on the use
of electrogenerated polypyrrole surfaces.
116,117
More
recently, Pingarrón proposed the use of enzymes as
recognition elements for the analysis of propyl gallate.
118
Phenols with pharmaceutical activity can be analyzed by
means of immunoassays,
125,126
spectrophotometry,
127,128
thin-layer chromatography,
129
gas chromatography,
130,131
and high-performance liquid chromatography.
132–134
In
order to improve the selectivity and/or the sensitivity of
the above-mentioned methods, several sample pretreat-
ment steps have also been proposed.
57,63,135,136
In partic-
ular, solid phase extraction
62,137
and other sample han-
dling strategies
31,32
were recently considered.
Capillary electrophoresis, microchips, and
electrochemical detection
Although a significant amount of information can be
obtained by standard chromatographic methodologies,
they are typically time consuming, need large sample vol-
umes, generate large amounts of waste, or require bulky
and expensive instrumentation. Capillary electrophoresis
is an alternative method for the separation of phenols. In
CE, the separation takes place inside of a small capillary
(<100 µm) filled with an electrolyte solution. When a
PHENOLIC COMPOUNDS continued
J. CAP. ELEC. AND MICROCHIP TECH. 009 : 5/6 2006 ###### J. CAP. ELEC. AND MICROCHIP TECH. 009 : 5/6 2006
FIGURE 1 Some of the most common applications of phenolic
compounds.
potential difference is applied across the capillary, bulk
flow of the solution is generated inside the capillary by a
process referred to as electroosmotic flow (EOF). The
analytes, which are introduced as a sample plug at one
end of the capillary, migrate toward the detector with a
velocity that is dependent on their charge/mass ratio, the
magnitude of the applied potential, and the solution con-
ditions. CE provides high-speed, high-throughput, low
waste generation, highly efficient, and reliable separa-
tions, and offers a simple way to handle very small sam-
ples (nL) without the use of pumps or valves. Another
advantage of CE is the possibility of using a wide range
of solution conditions to control the EOF and optimize
the separation of analytes.
138–142
Additionally, CE can be
miniaturized, while offering high performance, versatility,
reagent economy, speed, and automation capabilities.
143
Many different modes of detection can be coupled to
capillary electrophoresis systems.
106,107,144–151
Phenolic com-
pounds have been analyzed by capillary electrophoresis
with UV,
136,151
chemiluminescence,
138
MS,
152–154
inductively
coupled plasma-mass spectrometry (ICP-MS),
155
and elec-
trochemical
148,156,157
detection. CE can also be coupled to
flow injection analysis systems,
158
allowing on-line precon-
centration of phenols. Combined with electrochemical
detection (ECD), CE microchips can provide inherent minia-
turization, automation, and portability.
139
A review focused
on recent advances and the key strategies in microchip-CE
with electrochemical detection for separating and detecting
a variety of environmental pollutants was recently present-
ed by Chen et al.
159
Other publications dealing with differ-
ent aspects and applications of microchips for the analysis
of phenols have also been presented.
145,160–172
Amperometry is one of the most widely reported
ECD methods used in conjunction with CE microchips.
However, the possibility of fouling the working electrode
arises when using amperometry. Generally, this problem
can be avoided through a wide variety of strategies.
16,23,173
Among other approaches to improve the electrode life-
time, pulsed amperometric detection (PAD) was proven to
be effective for a large number of analytes.
174–176
PAD uti-
lizes a simple three-potential waveform in which the elec-
trode is first cleaned at a high positive potential, which
oxidizes the electrode; reactivated at a negative potential,
which dissolves the surface oxide; and then used to detect
the analyte at a moderate positive potential. Other advan-
tages of the use of PAD include a sensitivity comparable
(or better) to dc amperometry, speed, and the possibility
of performing direct detection of analytes that are nonelec-
trochemically active by other techniques.
175
Analysis of phenols with microchip-CE-PAD
The following sections will discuss the application
of poly(dimethylsiloxane) (PDMS) microchips coupled
to pulsed amperometric detection for the determination
of three groups of phenolic compounds. The first group
includes three U.S. EPA priority contaminants phenol,
pentachlorophenol, and 4,6-dinitro-o-cresol. The second
group includes four synthetic antioxidants: propyl gal-
late, octyl gallate, lauryl gallate, and nordihydroguaiaret-
ic acid. Finally, the third group includes four NSAIDs:
salicylic acid, acetaminophen, diflunisal, and diclofenac.
In all cases, the effect of different variables such as
composition of the background electrolyte, separation
potential, injection time, and detection waveform were
optimized considering the separation efficiency, signal
magnitude (peak current), and signal stability. In addi-
tion, different real samples were also analyzed in order
to demonstrate the potential applications of the system.
For the described experiments, a PDMS microchip
with a previously described design
177
was used (Figure
2). Briefly, a mold was fabricated using a silicon wafer
and SU-8 2035 negative photoresist (Microchem,
Newton, MA, U.S.A.). The height of the positive pattern
on the molding master, which represents the channel
depth created on the PDMS layer, was measured with a
profilometer. PDMS layers were fabricated by pouring a
degassed mixture of Sylgard 184 silicone elastomer and
curing agent (10:1) (Dow Corning, Midland, MI, U.S.A.)
onto either a molding master or a blank wafer, followed
by curing for at least 2 hr at 65 °C. The cured PDMS was
separated from the mold and reservoirs were made at
the end of each channel using a 6-mm circular punch.
A 25-µm gold wire was aligned at the end of the sepa-
ration channel in a perpendicular electrode channel to
serve as the working electrode. After that, the two
PDMS layers were placed in an air plasma cleaner, oxi-
dized for 20 sec, and immediately brought into confor-
mal contact to form an irreversible seal. Finally, the
extremities of the electrode channel were sealed with a
high-performance adhesive and the electrical connec-
tion to the working electrode was made using silver
paint and a copper wire.
PHENOLIC COMPOUNDS continued
J. CAP. ELEC. AND MICROCHIP TECH. 009 : 5/6 2006 ###### J. CAP. ELEC. AND MICROCHIP TECH. 009 : 5/6 2006
FIGURE 2 Schematic drawing of the microchip-CE with PAD.
Channel width: 50 µm, channel depth: 50 µm, double-T
arms: 4 mm long, double-T volume: 1.25 nL, separation
channel length: 70 mm, solution reservoirs: 6 mm diam,
detection electrode: 25 µm diam.
1. Pulsed amperometric detection. As stated above,
phenols can be electrochemically oxidized under a
wide range of conditions.
145,164,166,167,178,179
However, a
decrease in current is frequently observed if the elec-
trode is not protected or frequently polished.
16,18,23,180
PAD can minimize the electrode fouling and increase
the signal stability. In order to maximize the signal mag-
nitude of the different studied phenols, the potential
waveform must be optimized. Figure 3 shows the
hydrodynamic voltammograms corresponding to phe-
nol, propyl gallate, and acetaminophen. Although these
voltammograms were obtained under different condi-
tions, the general behavior does not change significant-
ly,
177,181,182
thus allowing the comparison of the three
data sets.
As can be observed in the three cases, the peak
current (Ip) increases as the detection potential increas-
es until a maximum is obtained. This maximum was
observed to be around +0.7 V for most of the studied
phenols except the antioxidants, for which the maxi-
mum current was obtained at +0.5 V. This finding is not
surprising because these compounds are designed to
protect goods from oxidation damage and therefore
must be easily oxidized. The current decrease observed
at higher potentials is the result of the formation of a
passivating oxide layer on the electrode surface.
182,183
The effect of other parameters, such as the cleaning
(oxidization) and reconstruction (reduction) potentials,
and the time length for each step must also be studied
considering the signal-to-noise ratio, signal stability, and
sampling frequency. It was observed that a +1.6-V/50-
msec oxidation step, followed by a –0.9-V/25-msec
reduction step effectively cleans the electrode, thus
increasing the signal stability and allowing a sampling
rate of 4.4 Hz (approximately 30 points/peak).
Pulsed electrochemical detection also requires
alkaline conditions in order to favor the formation of
gold (or platinum) oxide, which is fundamental for
cleaning the electrode.
183
Although phenols can be
oxidized at a wide range of pH values,
166,184,185
lower
limits of detection are typically obtained under alka-
line conditions.
18,23,173,180,181,186–188
If lower pH values
are required for the separation of a particular set of
phenols, the detection pH can be easily adjusted after
the separation.
181
Using microchip-CE-PAD, most of
the phenols can be detected with clear anodic peaks.
Moreover, no passivation problems were observed
when using the microchip-CE-PAD for a series of more
than 100 repetitive injections of a 90 µM phenol solu-
tion over 8 hr (Figure 4). The relative standard devia-
tions of migration time and electrochemical response
(Ip) were 1.6% and 6.1%, respectively. Such high sta-
bility is attributed to the successful use of PAD for
electrochemical cleaning of the working electrode.
Similar values were also obtained during the analysis
of antioxidants and NSAIDs. It was also observed that
if no preconcentration step is performed and sample
volumes in the nL range are used, limits of detection
in the low µM range can be obtained.
1–3
With only a
few exceptions,
189,190
these values are of the same
magnitude than previously reported for similar devices
and analytes.
22,118,145,162,169,191
PHENOLIC COMPOUNDS continued
J. CAP. ELEC. AND MICROCHIP TECH. 009 : 5/6 2006 ###### J. CAP. ELEC. AND MICROCHIP TECH. 009 : 5/6 2006
FIGURE 3 Hydrodynamic voltammograms corresponding to
phenol (––), propyl gallate (––), and acetaminophen
(––). (Adapted from Refs. 1–3.)
FIGURE 4 Electrochemical response and migration time
obtained with repetitive injections of 90 µM phenol.
Conditions: 5 mM phosphate buffer pH = 12.4, injection
time: 10 sec, detection potential: +0.7 V, separation potential:
+1200 V. (Reproduced with permission from Ref. 1.)
2. Electrophoretic separation using microchips.
One of the most challenging aspects of microchip-CE is
to achieve the separation of analytes in a relatively short
channel. Simpler phenols (single substituted phenolic
ring) can be separated by CE using uncoated fused-sil-
ica capillaries.
158
Under alkaline conditions, the majori-
ty of the phenolic compounds become anions and
migrate according to their charge-to-mass ratio,
192
reflecting a clear dependence of electrophoretic mobil-
ity with respect to molecular weight. Using alkaline
conditions (5.0 mM phosphate buffer, pH 12.4), phenol,
4,6-dinitro-o-cresol, and pentachlorophenol were base-
line separated in less than 2 min using a microchip.
193
Salicylic acid, acetaminophen, diflunisal, and diclofenac
were also separated in less than 2 min using a 5 mM
borate buffer (pH 11.5) with no other additives.
3
Alkaline aqueous electrolytes are not suitable for
the separation of every phenolic compound due to
problems associated with solubility and stability.
16,18,23
In some of those cases, micellar electrokinetic chro-
matography (MEKC) has proven to be a very attractive
separation method.
191,194–196
MEKC is based on including
surfactants in the background electrolyte at concentra-
tions above the critical micelle concentration (CMC).
Under these conditions, a pseudostationary phase is
created, and micelles with a charged surface and a non-
polar core provide the means for the separation.
Generally, the partition coefficient of the analyte and
the micelle is the main factor determining selectivity.
More hydrophobic analytes have higher affinities for the
micelles and therefore are delayed with respect to the
migration time of more hydrophilic analytes. Sodium
dodecyl sulfate (SDS) was used for the separation of a
group of alkyl gallates and nordihydroguaiaretic acid.
2
In Figure 5, the dependence of the migration time of
these phenolic antioxidants as a function of SDS con-
centration is shown. As can be observed, a clear
decrease in the migration time (tM) was obtained for all
the selected compounds upon the first addition of SDS
(10 mM). This decrease in tM is the result of an increase
in electroosmotic flow produced by the adsorption of
SDS onto the PDMS surface.
142
As the SDS concentration
and the concentration of micelles was progressively
increased, the migration times of the antioxidants
increased while preserving the migration order. At 30
mM SDS, all of the peaks were baseline separated. It is
also worth mentioning that SDS not only improves the
separation, but also the electrochemical detection of
many compounds.
18,142,181,182,197,198
This is particularly
significant in the case of propyl gallate, for which the
peak current increased.
3. Effect of organic additives. The use of organic sol-
vents has been reported to improve separations by stan-
dard CE.
199
The resolution enhancement results from a
combination of a change in the viscosity of the electrolyte
and a change in the electroosmotic flow. However, most
of the organic solvents are either electrochemically active
under PAD or can adsorb to fresh electrode surfaces,
177
and decrease the signal-to-noise ratio. Although some
additives such as tetrahydrofuran (THF), alcohols, or ace-
tonitrile have improved the separations by CE,
200–203
their
use in combination with PAD is discouraged.
PHENOLIC COMPOUNDS continued
J. CAP. ELEC. AND MICROCHIP TECH. 009 : 5/6 2006 ###### J. CAP. ELEC. AND MICROCHIP TECH. 009 : 5/6 2006
a b
FIGURE 5 Effect of SDS concentration on the migration time (a) and peak current (b) for 28 µM propyl gallate (PG, ––), 25 µM
octyl gallate (OG, ––), 81 µM lauryl gallate (LG, ––), and 20 µM nordihydroguaiaretic acid (NDGA, ––). Other conditions:
10 mM borate (pH 9.6), separation potential: +1200 V (B–D), 5-sec injection, detection potential: +0.5 V. (Reproduced with per-
mission from Ref. 2.)
4. Effect of separation voltage. The separation
potential can be used to control EOF, resolution, and
the residence time of the analytes in the detection zone.
In order to evaluate the effect of separation potential, a
series of injections of standards were performed and the
migration times and signal magnitudes were evaluated.
As expected, when lower separation potentials were
applied, lower baseline noise and higher signal magni-
tudes were achieved, with a consequent increase in
analysis time. As a compromise between the analysis
time and the signal-to-noise ratio, +1200 V (171 V/cm)
was selected as the optimum separation voltage, at
which a baseline separation was typically achieved for
the selected analytes within 2 min.
5. Separation and real sample analysis. The suit-
ability of the CE microchip for separating low levels of
PHENOLIC COMPOUNDS continued
J. CAP. ELEC. AND MICROCHIP TECH. 009 : 5/6 2006 ###### J. CAP. ELEC. AND MICROCHIP TECH. 009 : 5/6 2006
a b
c
FIGURE 6 a) Separation and PAD of 67.7 µM phenol, 39.4 µM pentachlorophenol (PCP), and 25.0 µM 4,6-dinitro-o-cresol
(DNOC). Conditions: 5 mM phosphate buffer pH = 12.4, injection time: 10 sec, detection potential: +0.7 V, separation potential:
+1200 V. (Adapted from Ref. 1.) b) Electropherograms corresponding to a standard mixture (A), a food sample (B), and the food
sample spiked with propyl gallate (PG), nordihydroguaiaretic acid (NDGA), octyl gallate (OG), and lauryl gallate (LG) (C).
Conditions: 30 mM borate, 30 mm SDS pH = 9.6, detection potential: 0.5 V, 5-sec injection. (Reproduced with permission from
Ref. 2.) c) Electropherograms corresponding to a standard mixture and a bovine serum sample spiked with four NSAIDs.
Conditions: 5 mM borate (pH 11.5), separation potential: +1200 V (B–W), injection time: 5 sec, oxidation potential: 1.6 V,
reduction potential: –0.9 V, detection potential: + 0.7 V. (Adapted from Ref. 3.)
phenolic compounds was demonstrated. Figure 6a
shows an electropherogram obtained with a standard
mixture of phenols (pentachlorophenol, 4,6-dinitro-o-
cresol, and phenol). Clear peaks were also observed for
all of the studied compounds, showing recovery assays
of about 95% when spiked city water or sore throat
medicine samples were analyzed.
193
Figure 6b shows
the electropherograms corresponding to a standard
mixture of antioxidants and the analysis of a commer-
cial food sample containing propyl gallate.
2
As can be
observed, the baseline separation of the four selected
antioxidants was achieved in less than 2 min. Using the
optimized conditions, a gravy mix sample was also ana-
lyzed (b), and the corresponding amount of propyl gal-
late was calculated to be 45 mg of PG/kg of sample.
Figure 6c shows the electropherograms corresponding
to four NSAIDs and a bovine serum sample spiked with
the selected compounds. Although lower yields were
obtained for salicylic acid (72 ± 5%), good recoveries
were obtained for the case of acetaminophen (90 ± 5%),
diclofenac (99 ± 6%), and diflunisal (81 ± 6%).
3
Conclusion
This minireview describes recent applications of
microchip-CE with pulsed amperometric detection for
the analysis of different phenolic compounds.
Specifically, the discussed methodologies illustrate prac-
tical, simple, rapid, and inexpensive methods for the
simultaneous analysis of contaminants, antioxidants, and
pharmaceutical compounds. Under the optimum condi-
tions, the selected compounds were baseline separated
within 2 min and detected above the low-µM range.
Although the presented system offers a low-cost,
portable, and custom-made device for the analysis of
very small (nL) samples, the detection limits must be
improved in order to allow effective applicability to real-
world problems. Without a doubt, microchip-CE-PAD has
the potential to become a well-established methodology
for the analysis of phenolics in a wide variety of samples.
Acknowledgment
We thank The University of Texas at San Antonio
and the San Antonio Area Foundation for financial sup-
port. E. Mejia also thanks the MBRS-RISE program for the
research fellowship (NIH/NIGMS MBRS-RISE GM60655).
©Copyright 2006. ISC Technical Publications, Inc.
Manuscript received ???.
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J. CAP. ELEC. AND MICROCHIP TECH. 009 : 5/6 2006 ###### J. CAP. ELEC. AND MICROCHIP TECH. 009 : 5/6 2006
... In this regard, electrochemical detection (ECD) can provide competitive advantages [4,[22][23][24] with respect to other detection methods such as portability, low cost, and low power requirements. Additionally, ECD can analyze turbid samples, is not impaired by miniaturizing the system [25,26], requires electrodes that can be fabricated using minimal instrumentation, and offers different techniques to balance selectivity and sensitivity [25][26][27][28]. In particular, pulsed amperometric detection (PAD) has demonstrated to be one of the most efficient techniques to analyze environmental samples [18,19,29]. ...
... The electrochemical detector is capable of performing DC amperometry and PAD. The advantages of PAD over conventional ECD techniques have been described previously [26][27][28]. All test stages cover the indicated auxiliary voltage range. ...
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A review with 46 refs. covering solid-phase extn. of phenols (for detn, of PhOH in water) into graphitized C, octadecyl-coated silica, or modified resins, e.g., polystyrene-divinylbenzene, and their structure, derivatization of PhOH prior to extn., matrix effects, and microextn. involving preconcn. of phenols on adsorption layers, yields of 19 chloro-derivatives extracted by polyacrylate, polydivinyloxane-polydivinylbenzene, or Carbowax-divinylbenzene, new fiber coatings, operating conditions, addn. salts, solvents and desorption of analytes.
Article
A dynamic approach has been proposed for the ultrasound-assisted extraction of twenty phenolic compounds from alperujo, a semisolid waste from the olive oil industry, that is a representative example of samples with a complex matrix. Multivariate methodology was used to carry out a detailed optimisation study of both the separation–determination and extraction steps in terms of resolution-analysis time and extraction efficiency, respectively. Consequently, the proposed method was able to extract the target analytes in 13 min; then, after dilution and centrifugation, the extract was injected into the capillary electrophoresis–diode array detection system for individual separation determination in 11 min. No cleanup of the extract was required. This method is less time-consuming, more selective and provides a larger information level than the Folin–Ciocalteau spectrophotometric method. Alperujo was demonstrated to be a powerful source of phenolic compounds, particularly as compared with olive oil—8680 versus 50–1200 μg/g.
Article
In order to detect and quantify with a biosensor the phenol contents in animal tissue (salmon flesh) by simple contact, we have undertaken experimental study on nonwoven cellulose fibers soaked with phenolic compounds. An electrochemical biosensor made of carbon paste and tyrosinase mixed together with electropolymerized pyrrole was elaborated. Phenol detection was realized by electrochemical reduction of quinones produced by the tyrosinase activity. The biosensor was first optimized based on enzyme loading and nature of the carbon paste. A semipermeable membrane containing cyclodextrin moieties was deposited on the biosensor in order to test its sensitivity for phenol detection. Finally, the biosensor was put in contact with phenol absorbing cellulose fibers. Results showed that the relaxation time response of the sensor was relevant of phenol concentration.
Article
Electrosynthesis of benzoquinone from phenol was investigated in acetonitrile–water mixtures on α-PbO2 and β-PbO2 electrodes. The influence of water concentration, electrolysis potential, initial phenol concentration and temperature on benzoquinone production was also studied. Different electrocatalytic activities of α and β structures of PbO2 were determined.
Article
The development of electrochemiluminescence (ECL) detection for capillary electrophoresis (CE) is critically reviewed. After a simple discussion of the mechanism of ECL concerning in CE–ECL system and CE mode, special attention is focused on the instrumental design, mainly including addition of reagent, field decoupler, and ECL efficiency. Application of the CE–ECL technique was also given.
Article
This paper reports on a study by reflectometry of the adsorption process of phenolic compounds electrochemically oxidized on glassy carbon electrodes. This technique provides information about the adsorption rate and the maximum adsorbed amount. The adsorption process depends on several variables like adsorbent concentration, solution pH and working potential, while ionic strength has no significant influence. The best adsorption conditions were obtained at high phenolic concentrations (0.1 M), high pH values (>10) and working potential values higher than 0.600 V. The adsorption process on glassy carbon electrodes showed irreversible behavior, reaching the maximum adsorbed amount at relatively short times (less than 100 s).