You are on page 1of 13

Trends in Analytical Chemistry 85 (2016) 3345

Contents lists available at ScienceDirect

Trends in Analytical Chemistry


j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / t r a c

Automatic ow kinetic-catalytic methods


Camelia Henrquez a, Fernando Maya b, Piyawan Phansi c,d, Fatima Z. Abouhiat b,
Kaewta Danchana c,d, Vctor Cerd b,e,*
a
Center for Nuclear Energy in Agriculture, University of Sao Paulo, 13400-970 Piracicaba, SP, Brazil
b Department of Chemistry, University of the Balearic Islands, 07122 Palma de Mallorca, Spain
c Flow Innovation-Research for Science and Technology Laboratories (FIRST labs.), Thailand
d
Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Mahidol University, Rama 6 Road, Bangkok 10400,
Thailand
e Laboratory of Environmental Analytical Chemistry, University of the Balearic Islands, 07122 Palma de Mallorca, Spain

A R T I C L E I N F O A B S T R A C T

Keywords:
Kinetic-catalytic analytical methods are simple and highly sensitive strategies for chemical analysis, that
Kinetic-catalytic methods
rely on simple instrumentation. For that reason, they have been implemented to the quantication of a
Flow injection techniques
Miniaturization
large number of chemical species such as transition metals, non-metallic anions and organic com-
Nanoparticles pounds. Flow techniques are presented as an ecient tool to overcome the main limitations of the kinetic-
Initial rate catalytic methods. Solving problems related with sample handling, the reproducible data acquisition,
Fixed time reproducible temperature control and the implementation of different kinetic determination methods
(initial rate, xed time and xed measure).
Herein we review the recent applications of novel approaches to perform fully automated kinetic-
catalytic methods based on computer controlled ow techniques. We also describe new devices and
materials such as chip-based ow injection analyzers and the use of nanoparticles to improve the per-
formance of this class of analytical methodologies.
2016 Elsevier B.V. All rights reserved.

Contents

1. Introduction ........................................................................................................................................................................................................................................................... 34
2. Kinetic-catalytic analytical methods ............................................................................................................................................................................................................ 35
2.1. Background and applications ............................................................................................................................................................................................................. 35
2.2. Analyte quantication .......................................................................................................................................................................................................................... 35
3. Automation of KC methods using ow techniques ................................................................................................................................................................................. 35
3.1. Instrumentation ...................................................................................................................................................................................................................................... 35
3.2. Procedure for kinetic-catalytic method automation ................................................................................................................................................................. 38
3.3. Features of kinetic-catalytic method automation ...................................................................................................................................................................... 38
4. Recent developments and applications ....................................................................................................................................................................................................... 38
4.1. Mathematical data process. calibration and optimization ...................................................................................................................................................... 38
4.2. Integrated thermostated devices and chips ................................................................................................................................................................................. 39
4.3. Use of nanoparticles and application using chemiluminescence detection ..................................................................................................................... 42
4.4. Sample pretreatment ............................................................................................................................................................................................................................ 42
5. Comparison of ow-based approaches for the automation of kinetic-catalytic methods ......................................................................................................... 43
6. Final remarks and future trends .................................................................................................................................................................................................................... 43
Acknowledgements ............................................................................................................................................................................................................................................. 43
References .............................................................................................................................................................................................................................................................. 44

* Corresponding author. Tel.: +34 971 173261; Fax: +34 971 173426.
E-mail address: victor.cerda@uib.es (V. Cerd).

http://dx.doi.org/10.1016/j.trac.2016.08.009
0165-9936/ 2016 Elsevier B.V. All rights reserved.
34 C. Henrquez et al. / Trends in Analytical Chemistry 85 (2016) 3345

1. Introduction tial effect on the reaction kinetics. Furthermore, temperature


oscillations affect other physical solution parameters such as vis-
Kinetic reactions have been used for analytical purposes since cosity, or gas solubility. Therefore, the control of these parameters
the late nineteenth century [1]. The kinetic-catalytic analytical during the mixing and reaction steps will be crucial for the satis-
methods were developed in parallel with instrumental methods. factory implementation of the KC method. However, the accurate
Since the 80s, they achieved a huge development and are cur- control of these parameters may be dicult to accomplish when
rently considered well established methods for chemical analysis operating in batch mode, with open systems more susceptible to
[24]. The rst catalytic method automated with ow techniques the introduction of experimental errors [6].
was presented also in this period [5]. In 1993 Chrough [6] pre- In order to overcome these limitations, initial attempts for the
sented the automation of a kinetic method as one of the trends to automation of KC methods were developed using stopped-ow ana-
be developed in the following years. For the last twenty years, im- lyzers [12]. It was followed by the implementation of KC methods
portant improvements have been introduced in parallel to the using ow techniques (FTs), offering important benets for the smart
technological developments. In year 2000, over 1000 papers were automation of this kind of analytical methods [1315]. The high au-
already published on the development of kinetic analytical methods. tomation capacity of FTs, allows highly reproducible experimental
However, less than 10% of them were dedicated to the automa- conditions due to the high precision on the control of the differ-
tion and the development of tools for this purpose [7,8]. Nowadays, ent instruments and devices. The signicant reduction of sample
kinetic methods, and particularly kinetic-catalytic methods, are still and reagent volumes, the use of closed systems, and the high anal-
an active area in constant development. Within the last 10 years, ysis throughput increased the popularity of the automation of KC
many scientic articles have been published related with automa- methods using FTs. A large number of the published papers on KC
tion and the development of new materials to kinetic-catalytic automation using FTs are based on the use of the ow injection anal-
method of analysis [4,911]. ysis (FIA) [9,10]. The sequential injection analysis (SIA) has been also
Kinetic-catalytic methods (KC) are based on the catalytic effect implemented for this purpose [16]. More recently multipumping
of a substance on a reaction capable to produce an analytical signal ow systems (MPFS) [17] and multisyringe ow injection analysis
[3]. The quantication is based on the possibility to establish a ratio (MSFIA) [1824] has been exploited as tools for the automation of
of proportionality between the analytical signal of the catalyzed re- KC methods. Additionally, novel ow devices have been devel-
action and the concentration of catalyst. Transition metals, inorganic oped for the miniaturization of KC analytical systems, such as chips
anions and some organic molecules have been determined in a wide with integrated ow conduits presented by Abouhiat et al. [19] and
variety of samples due to their catalytic effect in the oxidation of a Phansi et al. [22]. These chips are monolithic devices integrating
substance (usually an organic molecule) producing colored, uo- mixing and reaction coils, thermostatic chambers and the detec-
rescent or chemiluminescent species [3,9]. KC methods typically tion cell in a reduced space. (Fig. 1). The integration of KC methods
present very low detection limits, since the action of the catalyst is on a chip also enabled the implementation of initial rate determi-
required at a very low concentration level in order to produce a de- nation methods under controlled temperature. Table 1 shows the
tectable analytical signal. The obtained high sensitivity increased recent milestones on the automation KC methods using FTs.
the applicability of these type of reactions to the analysis at trace Apart from the advances made towards device integration and
levels because of its comparability in terms of sensitivity with other miniaturization, the use of metallic nanoparticles (NPs) has also been
techniques much more expensive such as atomic absorption spec- recently exploited as a useful strategy to advance KC methods of
trometry (AAS), or inductively coupled plasma with atomic emission analysis. NPs such as Ag-NPs, Au-NPs, and Pt-NPs, have an enhanc-
spectroscopy (ICP-AES) or mass spectrometry (ICP-MS) [9]. ing effect on the chemiluminescence (CL) of luminol-based CL
KC methods require a strict control of the experimental param- systems [29]. This effect has been explored for the KC analysis of
eters and conditions. KC methods are highly dependent of the time organic molecules with groups -OH, -NH2 and -SH, such as amino
required for the mixing, reaction and data acquisition steps. The acids, polyphenols or uric acid, among others, due to their inhib-
precise control of temperature is also required, due to an exponen- iting effect on the luminol-oxidant-NP system [29].

Fig. 1. Schematic diagram of a kinetic-catalytic system fully automated using ow techniques. PS, propulsion system; MC, mixing and reaction coils; D, integrated detec-
tion cell with light source and detector.
C. Henrquez et al. / Trends in Analytical Chemistry 85 (2016) 3345 35

Table 1 2.2. Analyte quantication


Milestones in KC-FT automation

Year Development Reference The analyte quantication using KC methods requires the con-
1978 Computer controlled stop-ow evaluation of kinetic [12] tinuous acquisition of the analytical signal versus time. The signal
studies acquisition methods are classied as differential or integral, ac-
1983 KC method automation using the FIA technique [5] cording with the mathematical form of the kinetic equation. In both
1985 FIA incorporating temperature control devices, and [25] cases, it is possible to apply the tangent method, xed time and vari-
implementation of stop-ow mode for increasing the
sensitivity of KC methods
able time methods [3].
1994 FIA incorporating a thermostated detection ow cell [26] The variable time method has been rarely used in the develop-
2001 SIA automation of KC methods [16] ment of analytical applications. The xed time method has been
2002 FIA with two thermostated mixing coils. The rst one [27] more extensively implemented, due to their mathematical simplic-
for sample zone heating, and the second one to stop
ity. Additionally, the xed time method can be easily automated with
the kinetic reaction by cooling
2004 Initial rate implementation in a FIA system [28] FTs, which are generally considered xed time kinetic methods
2005 Application of metal nanoparticles to enhance the [29] [13,14]. In Fig. 2 is shown an example of calibration obtaining using
sensitivity of chemiluminescence KC determinations this method. The simplicity of application, automation, and math-
automated using FIA ematical data process make the xed time method the most used
2006 FIA with two loops for sample injection and two [30]
mini-columns for the separation of potential
approach in the implementation of KC methods of analysis using
interfering species FTs [9].
2006 MPFS-PLS multicomponent analysis [17] The automation with FTs allows two modes of implementation
2013 Chip-MSFIA applied to kinetic catalytic determinations [19] of KC methods: continuous ow and stop-ow. For the tempera-
2014 Chip-MSFIA including detection cell. Implementation [22]
ture control of the ow manifold, the mixing coil is usually
of initial rate method with controlled temperature
2014 FIA-trapping zones, with thermostated ow cell [31] introduced into a thermostatic chamber [31]. Working at higher tem-
peratures could require the additional heating of the reagents
and the sample containers and other parts of the ow manifold
[23].
Other development facilitating the implementation of KC methods In the stop-ow mode after mixing sample and reagents, the sub-
using FTs is the use of software for data acquisition and data process. sequent mixture is stopped in a holding coil for a determined reaction
Online data process enabled the development of smart methods time. After that, the mixing plug is propelled towards the detector
capable to modify the analytical procedure automatically in order recording the analytical signal. A thermostatic chamber around the
to obtain the desired analytical response [32]. holding coil enables the control of the reaction temperature
In this review, we briey describe new trends on the automa- [19,27,31,37,38]. The stop-ow mode can be implemented in situ
tion of kinetic-catalytic methods using ow techniques, and focusing within the detection cell rather than in the mixing coil, making
on homogeneous and non-enzymatic methods. Advantageous fea- feasible to apply the Initial Rate determination method. In this
tures of the implemented ow technique with representative case, kinetic curves are obtained as the recorded analytical signals
examples of the developed applications are also discussed. We crit- (Fig. 3a).
ically compare the different approaches to automate the kinetic- The initial rate determination method consists on the
catalytic analytical methods and outline future directions for the establishment of a proportional relationship between the slope
development of new methods using ow techniques. of the kinetic curve obtained in the rst seconds of the reaction
and the concentration of the analyte (Fig. 3b and Fig. 3c)
2. Kinetic-catalytic analytical methods [18,2022,39]. In some cases, a dedicated thermostated ow
cell is implemented to obtain the kinetics curves at different
2.1. Background and applications temperatures [31].
The initial rate method is signicantly advantageous in terms of
KC methods have been applied to the determination of sub- sensitivity and sample frequency. However, the xed time method
stances that can catalyze redox or complexing reactions. For example, may need up to 10 min to carry out the reaction and the subse-
ionic species that change easily their oxidation state (such as tran- quent signal measurement [20,21]. Furthermore, the difference on
sition metals) to a higher oxidation state, as well as some anions, the reaction rate caused by different analytes on the same cata-
like halides, nitrite, or cyanides [3,4,9]. KC methods are also useful lytic reaction has also been exploited for the development of
in the analysis of some organic molecules, such as organic acids, multicomponent KC methods [10,39].
aldehydes, amino acids and other molecules with -NH2, -OH, or SH
groups [24,29,3335]. In these catalyzed reactions an oxidant reagent,
such as H2O2, O2, BrO3-, ClO3-, IO3-, IO4-, S2O82-, Fe(III), Ce(IV), or Ag(I), 3. Automation of KC methods using ow techniques
is involved. Additionally, an inorganic reducing reagent, such as Sn(II),
Fe(II), As(III), I-, or S2O32-, or an organic compound, such as amines, 3.1. Instrumentation
phenols, azoic colorants, or luminol participate in the KC reaction
[3,4]. The combination of the appropriate oxidant and reducing The automation of KC methods using FT relies on simple instru-
reagent will dene the selectivity towards a specic analyte. mentation. Fig. 1 represents a general conguration for KC methods
In KC methods, the acquisition of the analytical signal just re- automated with FTs, including its principal components. Fig. 4 shows
quires of simple and economic detectors, which are easy to various approaches developed for KC method automation using dif-
couple to FTs. Additionally, a considerable number of KC methods ferent FTs. The basic set-up comprises:
with thermometric detection have been also reported, some of them
semiautomatic [36]. Thermometric detection offers some interest- i A propulsion system (PS), which propels the uids from their
ing advantages, such as a very high sensitivity and lack of optical respective reservoirs towards the detection system. Most
interferences. However, it is affected by environmental tempera- systems based on KC-FTs described in the literature use peri-
ture changes and often requires long waiting periods to reach the staltic pumps (Fig. 4a and Fig. 4c). However double plunger
initial thermal equilibrium of the catalytic reaction. micropumps as FIA liquid drivers have been also reported
36 C. Henrquez et al. / Trends in Analytical Chemistry 85 (2016) 3345

Fig. 2. Example of analytical signals (a) and calibration curve (b) obtained with using the Fixed Time Method (reproduced from [21] with permission from Royal Society of
Chemistry).

Fig. 3. Example of analytical signal acquisition (a), kinetic curves for different concentration of catalyst (b), and calibration curve obtained with initial rate determination
method (c) (reproduced from [21] with permission from Royal Society of Chemistry).
C. Henrquez et al. / Trends in Analytical Chemistry 85 (2016) 3345 37

Fig. 4. FIA system for the determination of organic molecules using the Luminol-H2O2-PtNP system (a). MPFS system for the determination of Fe and V (b). FIA system with
a thermostated ow cell exploiting zone trapping for the determination of V (c). Chip-MSFIA system for the determination of Mo applying the initial rate method (d). (Re-
produced from [40] [17], [31], and [21], with permission from Elsevier, Wiley, and the Royal Society of Chemistry).

[27,37,38,41]. Syringe pumps have been used for the devel- vi A control system, composed by a PC with an appropriate soft-
opment of SIA [16] and MSFIA KC systems [1824] (Fig. 4d), ware for automation, capable to control the PS, the different
and micropumps (Fig. 4b) have been also introduced for the valves, and the detection system.
automation of KC methods [17,18].
ii A system for the transportation of uids to all units. This is A recent trend, is based on the integration of KC methods in
the ow network or manifold, which is generally composed monolithic uidic devices or Chips developed by Sciware Systems
of tubes with an internal diameter ranging from 0.2 to 2.0 mm. (http://www.sciware-sl.com/), integrating conuence points, mixing
Typical tubing materials are silicone tubing (used in the peri- coils, the detection cell and a thermostatic chamber, reducing sig-
staltic pumps of FIA systems), and polytetrauoroethylene nicantly the size of the ow manifold [1822]. Other devices can
(PTFE) tubes used in SIA, MSFIA and MPFS systems. be added to the system for sample pretreatment (UV-oxidation or
iii A multi-commutation system (valves) to direct the uids to reduction lamps) and separation devices (columns, membranes, gas-
the different components of the manifold. Three-way sole- diffusion chambers, etc.), but few examples have been reported using
noid valves are the most frequently used devices, but also this kind of devices to improve the performance of a FT-KC methods
injection and selection valves are used in some congura- [30,38,44].
tions. Autosamplers are also used to increase the autonomic To achieve a full automation is required the use of an appropri-
functionality of the system for larger sets of samples. ate software including the acquisition and data processing steps,
iv Mixing and reaction coils (MC), where reagents, samples and as well as the precise control of the devices and instruments.
standards converge to mix and react. Several mixing loops can However, the use of two different software packages is often re-
be used in the same conguration depending on the com- quired, needing different software to control pumps/valves and the
plexity of the selected reaction in each case. detection/data acquisition system. This has been one the main bottle-
v A detection system (D), composed by a ow cell and a de- necks to develop fully automated methods of analysis, hindering
tector: an adequate radiation source combined with a the online data process and feedback. In order to overcome this draw-
spectrophotometer [18], a luminescence detector for uo- back, Cerd et al. [45] developed the software AutoAnalysis, enabling
rescence detection [42], or just a photomultiplier in the the simultaneous control of the ow instrumentation and the
absence of radiation source for chemiluminescence mea- detection/data acquisition system. This software is based on user-
surements [24]. Additionally, optical bers have been used friendly tools for method development and automated optimization
to facilitate the integration of different types of ow cells with of experiments. Due to its versatility, the AutoAnalysis software
the required detectors. Liquid Waveguide Capillary Cells enabled the fully automation of both initial rate and xed time de-
(LWCC) can also be implemented in order to increase the sen- termination methods and their application in real samples analysis
sitivity when the blank signal is negligible [43]. [16,1823].
38 C. Henrquez et al. / Trends in Analytical Chemistry 85 (2016) 3345

3.2. Procedure for kinetic-catalytic method automation Versatility: the exibility of FTs to implement multiple possi-
bilities for sample treatment, and analyte separation and
The general procedure for KC-FT automation consists in the derivatization previous or post-catalytic reaction, together with
mixing of the sample with oxidizing and reducing reagents through the potential for the use of different types of detectors en-
conuence points and a mixing coil followed by the injection of the hances the applicability of FTs for the development of KC
resulting mixture to the detection ow cell. The number of con- methods.
uent points and mixing coils, as well as the order of reagent addition
depend on the characteristics of the catalytic reactions and the an-
alytical signal production. SIA congurations do not usually present 4. Recent developments and applications
conuent points. In the SIA technique, samples and reagents are se-
quentially loaded and mixed due to controlled dispersion in a holding 4.1. Mathematical data process. calibration and optimization
coil [16].
For the implementation of the xed time determination method, Different chemometric techniques have been used to shorten the
continuous ow and stop-ow mode can be used. In the continu- number of factors to be optimized and the large amount of infor-
ous ow mode, the reaction time will be dened by the volume of mation resulting from KC analysis. Factor analysis, full or fractionated,
the holding coil and the ow rate. However, in the stop-ow mode, has been used for the optimization of the experimental condi-
the reaction mixture will be stopped in the mixing coil during the tions minimizing the number of experiments. Modern experimental
reaction time, before the injection of the mixture into the detec- designs such as Doehlert matrix, Box-Behnken, or Central Compos-
tion ow cell. The optimum reaction time will be a compromise ite Design, provide a surface response capable to predict the optimum
between sensitivity and analysis throughput. conditions eciently [18,2022,39]. Simplex optimization has been
For the implementation of the initial rate method, the stop- also used to establish the optimum conditions in KC-FT analysis [42].
ow mode is mandatory. In this case, sample and reagents are mixed The Desirability Function extracted from these factors of the anal-
quickly and the reaction mixture is stopped into the detection ow ysis allows a graphical view, and the simple understanding of the
cell. The analytical signal is recorded in order to register the kinetic system behavior in the studied experimental domain [18,21,22]. The
curve at the early stages of the reaction. To implement differential advantage of automation based on FTs together with online data
reaction rate methods [10], FTs based on the generation of two or processing facilitated the implementation of these chemometric
multiple sampling zones, such as: ow stream splitting, with one methods, decreasing the time and effort required for method op-
or two detectors delaying one of the sampling zones; replacing the timization in comparison with manual methods.
reactor by injecting the sample in different places of the manifold, The selection of an appropriate response variable is one of the
or changing the reactor with an injector-commuter; installing most important items to consider during the optimization step. Gen-
multisite detection, with one or two detectors separated or relo- erally, in catalytic methods the non-catalyzed reaction is strongly
cated; or recycling the sampling zone inside a close loop including affected by the chemical and physicochemical factors such as reagent
the detector. concentration, pH, temperature, reaction time, or the reagent ad-
dition order. For that reason, the appropriate response variable should
include the analytical signal related to the non-catalyzed (NC) and
3.3. Features of kinetic-catalytic method automation the catalyzed (C) reaction. In earlier work by Fang and Xu [5], the
ratio between the absorbance of the catalyzed and non-catalyzed
The different advantages of the automation of KC methods using reactions (C/NC) was used as response variable, considering C the
FTs are: peak height of an standard injection of the analyte and NC the ab-
sorbance of the baseline, similar to signal/noise ratio. This
Robustness: computer-controlled ow manipulation and data ac- consideration of NC (as baseline absorbance) is only valid when the
quisition enabling the development of highly reproducible sample matrix does not affect the catalytic reaction. Otherwise,
methods, using a strict time control, thus avoiding experimen- similar solution without analyte should be injected and measured
tal errors due to manual manipulation. to obtain a real non-catalyzed signal. For initial rate, C and NC should
Economic: Low detection limits and high sensitivity are ob- be the slope of the rst instant of the C and NC reaction [18,21,22].
tained, comparable with those obtained using more expensive Although, C/NC ratio evaluation takes into account the non-
instrumentation (ICP-OES, ICP-MS, ion chromatography), but using catalytic effects, very high or very low values of NC could distort
simple instrumentation, with low cost of both acquisition and the real objective of the optimization. The sensitivity includes the
maintenance. In addition, steps for sample pretreatment, sep- difference between C and NC (C-NC divided or not by standard con-
aration or derivatization are easily integrated in the manifold centration). Phansi et al. [18] performed a comparison of the use
enabling speciation and multicomponent quantication. of these two response variables (ratio and sensitivity) during op-
Eciency: the combined use of a ow network with integrated timization, showing that possible difference can be obtained.
control and data acquisition by using a single software package Nevertheless, the appropriate selection of the response variable is
for automation. It facilitates the application of different deter- directly related with the chemical system and the expertise of the
mination methods and increase the analysis throughput for slow analyst.
kinetic applications. Multicomponent kinetic determinations enabled the simulta-
Compact size: The small size of the instrumentation used in FTs neous determination of two or more analytes without prior physical
allows the development of compact and portable systems with separation of components. When multicomponent discrimination
potential applicability for in-situ KC analysis and real time relies on chemical reaction rates, they are called Differential Reaction-
monitoring. Rate Methods. This discrimination can be based on the different rates
Environmentally friendly: The minimization of the amount of of physical processes, such as diffusion, vaporization, or radioac-
reagent consumption and waste generation due to the small size tive decay.
of the conduits of the system, makes KC-FTs environmentally In the multicomponent determination of n analytes, which is cata-
friendly analysis techniques. Moreover, the use of a closed and lyzed by a common reaction giving the same product P, the analytical
fully automated system prevents the analyst to the exposure to response contains the contribution of each analyte. In the pres-
toxic reagents. ence of excess of reagents, the reaction is considered of pseudo
C. Henrquez et al. / Trends in Analytical Chemistry 85 (2016) 3345 39

rst-order reaction, i.e. the analytical signal (AS) is proportional to ation in the ow system timing, hence the analytical procedure
the catalyst concentration [C] (1), became more robust.

AS j = (bij [Ci ]) ( j = 1, 2, 3, , s)
4.2. Integrated thermostated devices and chips
where bjj is the proportional coecient for components i at point
of time j, and excluding the background signal: With the aim of enabling the use of slow kinetic reactions, heating
devices for the temperature control of the mixing and reaction coils
AS = b0 j + (bij [Ci ]) ( j = 1, 2, 3, , s) have been developed. Many of them consisted in the immersion of
the reaction coil in a thermostated water bath [38. 39], or alterna-
If m standard samples are prepared, Eq (1) can be extended and
tively oil or glycerin have been used as heat exchangers [31]. In some
expressed in matrix form:
cases a heated reactor followed by a cooled reactor is required in
AS mxs = Cmx(n+1)B(n+1) xs order to stabilize the base line, stopping the kinetic reaction due
to a temperature drop [27]. Other heat exchange mechanisms have
As can be seen, the resolution of a mixture of n analytes by the been used to increase the temperature of the catalytic reaction, for
differential reaction rate method assumes three criteria: example Chaparro et al. [23] used a sand bath to heat reagents up
to 67 C for Co(II) catalytic determination. But in these cases just
a the common reaction involved conform to rst or pseudo rst the xed time determination method could be implemented due
kinetic order, for this the presence of an excess reagents is to the lack of temperature control in the detection cell. Moreover,
required; these heating systems generally present large dimensions making
b the product formation rate are additive, i.e. no interaction dicult the assembly the analytical system.
between analyte occur; and The proper reaction temperature and heating transfer is achieved
c the rate constant should be invariable under the experimental by using a very long thermostated holding coil (10 or 15 m) and
condition. the simultaneous use of a very low ow rate (0.5 mL min1) in con-
tinuous ow mode; or stopping the sampling zone inside the holding
Chemometric solutions have been used to solve the obtained coil for the convenient time (from 1 min to 15 min) in stopped ow
matrix such as: proportional equation methods [26], or Kalman lters mode. In continuous ow, high sample dilution and dispersion occur
[46]. However, the strong dependency of the reaction rate with due to the death volume of the holding coil. Consequently, long
several factors (temperature, pH, ionic strength,. . .) and synergic cleaning times are required reducing analysis throughput and in-
effects between the analytes catalytic effects conduce to a non- creasing waste generation and reagent consumption. In the stopped
linear behavior of the system during multi-component kinetic ow mode a high mixture eciency before the stop-ow period of
determinations. To solve this problem, non-linear chemometric pro- time is required, which is achieved propelling solutions with high
cedures are required. ow rates creating turbulent ows and favoring mass transfer.
According to this, multicomponent catalytic analysis of real In order to overcome this limitation special heating devices for
samples requires several measurements with different analyte com- holding coils and for detection cells have been developed. Smiderle
position and complex matrix calculation [47]. For this, the et al. [63] developed a micro-heater device, which may be inte-
combination of automated FTs and chemometric tools, such as partial grated on a ow system. This device consists of a wire of Ni-Cr coated
least squares (PLS) [17,35,48,49], principal component regression by a heat-shrinkable tube, which is inserted into a Teon tube and
(PCR) and articial neural networks (ANN), have been explored [39]. xed at the ends between two blocks of poly(methyl methacry-
The most recently reported multicomponent catalytic methods are late) (PMMA). The heating of the solution owing into the Teon
summarized in Table 2. PLS is the multivariate calibration more used tube is achieved by applying a potential difference (5-10V) between
in differential reaction rate methods because it is well established the extremes of Ni-Cr coated wire. The temperature inside the micro-
and known calibration technique [10]. Although ANN calibration is heater device is computer controlled using a relay system for
more dicult to implement and requires a larger number of ex- switching the current through the wire. However, this device did
periments and mathematical data treatment, reported papers not integrate the detection cell inside the thermostated area.
conrm that the system prediction obtained by this method is much One of the main bottlenecks presented in ow systems with
more effective and exact than using PLC or PCR [39]. heated zones is the presence of gas bubbles. Their formation within
PLS is a multivariate calibration in which the calibration data are the ow conduits is generally related with the degasication, or
decomposed by an iterative algorithm, for correlating the data with water evaporation due to the high temperature. Also the release of
the calibration concentration, providing a set of regression coe- gases as reaction products, such as CO2, or O2, can also dicult the
cient to be applied to a new sample. During the calibration, all model detection step. In this case, carrying out the reaction in an isocratic
parameters are optimized. This optimized models are further used loop with an increased pressure inside the loop avoided the pro-
to estimate the analyte concentration in unknown samples [48]. ductions of bubbles during the reaction. This approach was applied
Fortes et al. [49] proposed an interesting design of a ow system, by Vida and Zagatto [31] for the determination of V(V) in mineral
which is able to provide the kinetic-spectrophotometric informa- waters. In this work, the authors inserted the heater reactor inside
tion needed for differential kinetic analysis of sequential the zone trapping of an injector commuter. The authors compared
determination of two components with different effect on the re- two different manifold designs. In the rst one, the thermostated
action rate. In this work, the authors used the ow system depicted reactor consisted of a polyethylene loop inserted in a glycerin bath.
in Fig. 4c, with an acrylic Z-shape ow cell. Three different sample In the second one, a thermostated ow cell was placed in the zone
plugs were inserted sequentially into the reagent carrier stream (R1) trapping (Fig. 4c). This heated ow cell consisted of a typical de-
leading to the formation of a complex overlapped sample zone. tection ow cell inserted in a cuboidal aluminum block connected
During the sample pass through the detector, ve different absor- to an electronic temperature controller. Two optical bers con-
bance values were considered; two minima of the non-catalyzed duced the light from the radiation source to the thermostated ow
reaction considered the baseline, and three maxima of the cata- cell and then to the detector. A good reproducibility working at high
lyzed reaction. These ve variables were used build up the PLS model. temperature (97C) was obtained, due to the zone trapping effec-
With this strategy, measurements became less affected by a vari- tiveness in preventing the formation of bubbles. The proles obtained
Table 2

40
Kinetic-catalytic methods automated with ow techniques

Analyte Kinetic FT Reaction Detection Samples LOD T C Sample Remarks Ref.


method throughtput

Co(II) FT MSFIA Oxidation catalyzed by alizarine UV-Vis Waters and 0.3 g L1 67C 30 h1 Sand bath to control reagent [23]
pharmaceutical temperature. Use of a LWCC to increase
products sensitivity
Co(II) FT MSFIA Catalytic effect of Co in the oxidation of UV-Vis Waters and 0.02 g L1 RT 68 h1 Automation based on a multisyringe ow [50]
hydroxybenzoic acid by pharmaceutical injection system coupled to a monolithic
H2O2 in basic medium. formulations ow conduit chip (chip-MSFIA)
Co(II)/Cu(II) CF FIA Analyte catalyzed luminol-O2 reaction CL Spring water 0.2400 g L1 and RT - PLS data treatment [48]
FT 0.0220 mg L1
Cu(II) IR vs FT Chip-MSFIA Analyte catalyzed 2,6- UV-Vis Waters and 0.12 g L1 25C 31 h1 Multivariate optimization Doehlert. Chip [18]
dichlorophenolindophenol oxidation pharmaceutical with thermostated chamber integrating
with H2O2 products reaction coil and detection cell
Cu(II)/Ni(II) SF FIA Reduction resazurin by sulde UV-vis Electroplating bath 0.56.0 and 34C 8 and 6 h1 ANN data treatment [39]
FT 115.0 mg L1
Cr(III) FT FIA Oxidative coupling of 3-methyl-2- UV-Vis Vehicle exhaust 2 g L1 70C and 25h1 Use of double plunger micropumps [27]
CF benzothiazolinone hydrazone with particulates and 25C instead of peristaltic pumps. Use a

C. Henrquez et al. / Trends in Analytical Chemistry 85 (2016) 3345


N-ethyl-N-(2-hydroxy-3-sulfopropyl)-3- river water heating bath followed by a cooling bath
methoxyaniline as a modied Trinders
reagent in presence of H2O2 and EDTA
Cr(VI) FT FIA Alizarine oxidation with BrO3 UV-Vis Surface waters 0.05 g L1 90C 10 h1 Analyte column preconcentration [30]
Fe(II)/V(IV) CF MPFS Analyte catalyzed the oxidation of I- by UV-vis Alloys 7.015.0 mg L1 RT 50 h1 PLS data treatment [17]
FT Cr(VI) forming I3-
Fe(II)/Fe(III) FT FIA N,N-dimethyl-p-phenylenediamine UV-Vis Tap water and river 0.02 g L1 50C 20 h1 Thermostatic bath [51]
oxidation by H2O2 water 0.06 g L1
Fe(II)/Fe(III) CF FIA Leucomalaquite green + S2O82- + 1,10 UV-vis Synthetic mixtures 0.3 mg L1 Fe(II) RT 25 h 1 FT double peak formation [52]
FT fenantroline 0.6 mg L1 Fe(III)
Fe(II)/Fe(III) CF FIA KI oxidation by BrO3- UV-Vis Pharmaceutical 0.03 and 0.04 mg L1 30C 17 h1 Use a Cd-Hg column for Fe(III) reduction [53]
FT products to Fe(II)
- 1
Fe(II)/V(IV) CF FIA Analyte catalyzed the oxidation of I by UV-vis Alloys 8.010.0 and 6.0 RT 25 h PLS data treatment [49]
FT Cr(VI) forming I3- 8.0 mg L1
Fe(III)/ FT MPFS Catalytic effect of Cu(II) and Fe(III) on UV-Vis Wastewaters and 0.95 g L1 for Cu(II) 40C 1
32 h Fe(III) Analyte discrimination by changing the [54]
Cu(II) hydroxylamine oxidation in a basic pharmaceuticals 21 g L1 for Fe(III). 39 h1 buffer composition and adding a
medium Cu(II). complexing agent using a very simple
manifold conguration
Hg(II)/Ag(I) SF FIA Fe(CN)64- and ,-bipyridil using UV-Vis Tap water. 0.5 g L1Hg and 90C 18 h1 Use a long holding coil after ow cell to [26]
thiourea as activator Wastewater 1 g L1Ag avoid bubble generation due to high
temperature (Syntone FIA-TO1)
I- SF SIA Sandell Kolthoff reaction between As(III) UV-Vis Pharmaceutical 3 g L1 45C 15 h1 SIA technique applied to KC analysis [16]
FT and Ce(IV) catalyzed by I- preparation
I-
FT Chip-MSFIA Sandell-Kolthoff reaction As(III) + Ce(IV) UV-Vis Seawater and 4.7 g L1 40C 23 h 1
Chip with thermostated reaction coil. [19]
SF pharmaceutical Standard addition calibration with
formulation negative slope
Mn(II) IR vs FT Chip-MSFIA Analyte catalyzed auto-oxidation of UV-Vis Natural waters 0.33 g L1 35C 22 h1 Chip with thermostatic chamber for [21]
succinimidoxime reaction coil and detection cell.
Comparison of initial rate and FT
determination methods, high automation
degree. High precision 0.6 % RSD
Mn(II) SFF FIA 4,4-bis(dimethylamino)- UV-vis Mineral and river 0.073 g L1 RT 60 h1 Stopped-ow [28]
FT diphenylmethane oxidated by periodate water
using nitriloacetic acid at pH 5.4 as
activator
Mn(II) FT, SF vs. CF MCFIA Analyte catalytic effect on N,N -bis(2- UV-Vis Lake and river 0.01 g L1 15C 20 h1 Use double plunger micropumps instead [37]
hydroxy-3-sulfopropyl)tolidine (HSPT) waters of peristaltic pumps, a thermostatic bath,
oxidation by periodate, using and an immersion cooler to stop catalytic
2,2-Bipyridine as activator. reaction
Mn(II) FT MSFIA Based on the catalytic effect of Mn2+ on UV-Vis Seawater and 0.010 g L1 RT 30 h1 Lab-on-valve (LOV) device exploiting [43]
the oxidation of tiron by hydrogen drinking water online spectrophotometric detection by a
peroxide in presence of Pb2+ as an LWCC
activator
(continued on next page)
Table 2
(continued)

Analyte Kinetic FT Reaction Detection Samples LOD T C Sample Remarks Ref.


method throughtput

Mo(VI) IR Chip-MSFIA Analyte catalyzed 4-amino-3-hydroxy- UV-Vis Water and 1.2 g L1 55C 20 h1 Chip with thermostatic chamber for [22]
naphthalenesulphonicacid oxidation by pharmaceutical reaction coil and detection cell. Initial
H2O2 products rate determination methods, high
automation degree
Mo(VI) FT FIA Analyte catalyzed bromate oxidative UV-Vis Plants 0.5 g L1 60C 15 h1 Thermostatic bath [38]
coupling of p-hydrazinobenzenesulfonic
acid with N-(1-
naphthyl)ethylenediamine
Mo(VI)/ FT FIA KI oxidation by H2O2 UV-vis Steel 08 mg L1 RT 70 h1 Use two loops for sampling and two [44]
W(VI) cation-exchange mini-columns to
eliminate potential interferences. Use
citric acid for W(VI) effect masking

C. Henrquez et al. / Trends in Analytical Chemistry 85 (2016) 3345


NO3- /NO2- CF FIA Galocianine + BrO3- UV-vis Beef, cheese 1 g L1 (NO2-) 2 g 20 h1 NO3- speciation by reduction with Cd-Cu [55]
FT L1 (NO3-) minicolumn
NO3- /NO2- CF FIA Pyrogallolsulfonephthalein + BrO3- UV-vis River and tap water, 1.6 g L1 (NO2-) 30C - NO3- speciation by reduction with Cd-Cu [56]
FT sausage 3 g L1 (NO3-) minicolumn inserted in the injection
valve
NO2- FT FIA Catalytic effect on the redox reaction UV-Vis Waters 0.6 ng mL1 32.5C 15 h1 Absorption spectra obtained in [57]
between thionine and bromate continuous mode by using a double ow
analysis system.
V(V) IR vs FT Chip-MSFIA Analyte catalyzed gallic acid oxidation by UV-Vis Natural waters 0.24 and 0.33 g L1 40C 30 h1/6 h1 Chip with thermostatic chamber for [20]
BrO3- reaction coil and detection cell.
Comparison of initial rate and xed time
determination methods, high automation
degree
V(V) FT with FIA Analyte catalyzed p-anisidine oxidation UV-Vis Mineral waters 0.1 g L1 95C 25 h1 Thermostated spectrophotometric ow [31]
kinetic by bromate, activated by Tiron. cell
curve peak
prole
V(V) FT FIA Bromate oxidation of N,N-bis(2- UV-Vis River , tap and 8 g L1 60C 30 h1 Use double plunger micropumps instead [41]
CF hydroxyl-3-sulfopropyl)-tolidine. mineral water of peristaltic pumps
V(V) SF FIA p-anisidine oxidation by bromate UV-Vis Drinking waters 0.05 g L1 65C 20 h1 Thermostatic bath [58]
FT activated by Tiron
Ascorbic CF FIA Fe reduction by the analytes: luminol- CL Pharmaceutical 0.066.0 and 0.4 RT - PLS data treatment [35]
acid/ FT Fe2+- O2 reaction products and human 40.0 mg L1
cysteine urine
Cysteine CF FIA Luminol- H2O2-AgNP CL Synthetic samples - RT - [59]
FT
1
Fluoroquinolones CF FIA Luminol- H2O2-AuNP CL Urine 3.29.0 g L RT - Analyte CL inhibition [60]
FT
Multiple CF FIA Luminol- H2O2-AuNP CL Synthetic samples 0,001-5 mol L1 RT - Analyte CL inhibition [29]
organic FT
analytes
Multiple CF FIA Luminol- H2O2-PtNP CL Synthetic samples 25 nmol L1 RT - Analyte CL inhibition [40]
organic FT
analytes
Polyphenols CF MSFIA Luminol- H2O2-peroxidase CL Wine and water 0,01-5 mg L1 RT 12 h1 Analyte inhibition or enhancement of CL. [24]
FT samples Low reagent consumption
Polyphenols CF FIA Luminol-NaIO4-AgNPs CL Tap water and 0.12.1 g L1 RT - Analyte CL inhibition [61]
FT synthetic samples
Isoniazid CF FIA Luminol-O2 or H2O2- AgNP CL Synthetic samples 2.7 g L1 RT - Analyte CL inhibition [62]
FT

RT: Room temperature; FT: xed time; CL: Chemiluminescence; CF: continuous ow; SF: stop ow; IR: initial rate; MPFS: multipumping ow system.

41
42 C. Henrquez et al. / Trends in Analytical Chemistry 85 (2016) 3345

Fig. 5. Picture of a chip with an integrated thermostated cell (a), and a chip for the KC determination of Mn(II) using the MSFIA technique [21] (b). Scheme of a MSFIA (c)
and a MPFS (d) system with integrated chips for the automation of KC methods [54].

with the thermostated ow cell included the kinetic curve similar amples, a ow injection analysis system (FIA) was used for
to the obtained by Phansi et al. (Fig. 3a). automation. Reagents and samples were pumped using a peristal-
In order to increase the compactness and portability of KC an- tic pump and NP colloidal solutions were injected via an injection
alytical systems, a monolithic ow conduit, named chip, was valve, to minimize the consumption of NP colloidal dispersion
coupled to a multisyringe pump (Chip-MSFIA). Monolithic ow con- [35,61,62]. Xu et al [40] coupled an additional injection valve, merging
duits have been formerly reported for the integration of different the sample and NP colloidal solution. With this, a reduction of sample
functions in one single and purpose made ow device [64,65]. In consumption and system cleaning time were achieved. In order to
this case, a chip made of PMMA, can be customized to different overcome FIA limitations related with reagent and samples con-
designs on depending of the requirements for a specic KC analyt- sumption, other FTs could be used for automation of this kind of
ical method leading to a robust and simple device. Chips can integrate KC methods. The use of special devices such as Chips, and the pos-
the different steps of the analytical procedure such as: mixers, re- sibility to immobilize NPs on solid supports [66], are other
actors, detection cells, as well as integrated thermostatic chambers automation options not exploited yet, which can increase the ap-
to control the temperature during the measurement step. Fig. 5 de- plicability of KC methods in the future.
picted example of a Chip-MSFIA system presented by Phansi et al. The CL enhancing effect of metal nanoparticles, can be also used
[21], and Abouhiat et al. [54]. These new devices allow the appli- for NP determination. Based in this effect Tsogas et al. [67] pro-
cation of both, initial rate and xed time determination methods, posed a FIA system for silver, gold and iron oxide nanoparticles
in function of the part of the chip where the reaction plug is stopped, determination in environmental samples. The authors used a manual
in the mixing coil before arriving the detection cell (xed time) pretreatment step consisting in cloud point extraction-back-
or in the detection cell (initial rate) [18,2022]. The exibility of their extraction for the separation and preconcentration of three different
conguration allows to incorporated additional loops, chambers and metallic NPs. The new trends in liquid-liquid extraction automa-
heating devices in order to improve the analytical characteristics tion with FT [68] could be proposed for the full automation of KC
of the KC method, expanding its applicability without sacricing methods in order to enhance the KC method selectivity and sen-
compactness and reduced system size. sitivity. Table 2 summarizes the applications of different approaches
based on FT automation of KC methods improved by metallic NPs.
4.3. Use of nanoparticles and application using chemiluminescence On the other hand, Araujo et al. [24] proposed a MSFIA system
detection for the automation of a KC method based on the catalytic effects
of phenolic compounds in the CL emission of luminol-H 2 O 2 -
In recent years, many attention have been paid to the use of metal peroxidase system. Inhibition or enhancement effects of different
nanoparticles (NPs) as nano catalysts in chemiluminescence reac- phenols were screened in order to discriminate them with a very
tions, which are very useful for the improvement of KC method simple and fast system. The automated method was applied to the
applications. Au, Ag, and Pt nanoparticles enhance the chemilumi- determination of total polyphenol index and phenol contents in wine
nescence by their catalytic effects on the luminol-oxidant-NP systems and waters [24].
[29,35,48,59,66]. The analytical applications of these systems are
based on the inhibition effect of some organic compounds on the 4.4. Sample pretreatment
chemiluminescence produced in the former system. In this way some
FT approaches have been developed for the automatic determina- The combination of a preconcentration step, such as solid-
tion of polyphenols, based on the luminol-NaIO4-AuNP system [61], phase extraction (SPE), is crucial to further increase the sensitivity
or isoniazid with luminol-H2O2-AgNP systems [62]. In these ex- of the method, and concomitantly remove potentially interfering
C. Henrquez et al. / Trends in Analytical Chemistry 85 (2016) 3345 43

Fig. 6. (a) FIA automated determination of Mo(VI) and W(VI) using a two sample loop and two cation-exchange mini-column to remove potential interferences. (B) FIA
automated determination of Cr(VI) with online analyte preconcentration using a anion-exchange mini-column. (Reproduced from [44] and [30], with permission from Elsevier).

species present in the matrix of the sample [69,70]. Furthermore, quisition and online data processing [21]. Different temperature
novel materials with interesting features as sorbents for SPE are con- control systems and other devices have been developed as is de-
stantly developed, opening additional possibilities for automated tailed in Table 3, where the advantages and disadvantages of different
SPE using FTs [7174]. Gervasio et al [44] designed a ow system FTs for the automation of KC methods are listed.
for the simultaneous catalytic determination of Mo(VI) and W(VI).
The system consisted in two loops for sample injection and two 6. Final remarks and future trends
cation-exchange mini-columns for the separation of potential in-
terfering species, inserted in a manual operated injector-commuter The automation using different types of ow techniques shows
(Fig. 6a). The alternative addition of W(VI) masking reagent (citric a great potential for the development of novel methodologies of anal-
acid, R3 in the gure) allowed to obtain a peak corresponding to ysis based on kinetic-catalytic methodologies, or the improvement
Mo(VI) + W(VI) catalyzed reaction signal, followed by a peak cor- of already stablished ones. In comparison with manual KC methods,
responding just to the Mo(VI) catalyzed reaction signal. automated KC-FT methods enabled the implementation of initial
Cui et al. [30] on-line coupled a mini-column packed with poly- rate and xed time methods at controlled temperature, increase the
styrene anion exchange resin to preconcentrate chromium (VI), analysis throughputs. FTs also enabled the safe handling of toxic re-
increasing the sensitivity of KC-FIA method (Fig. 6b). This method pre- agents, including metal nanoparticles, and the minimization of
sented a 26.5 enrichment factor achieving a 50 ng L1 detection limit, sample loss and sample contamination.
which is more superior than those obtained using FAAS (and com- Future possibilities for the development of KC methods using FTs
parable to ICP-MS and ETAAS), using a very simple and economic FIA can be their use as post-column detection systems coupled with sep-
manifold. Later, Nakano et al. [38] inserted a cation-exchange column aration techniques. The implementation of quality-assurance/quality-
in a loop of a six-way valve to remove foreign ions such as Fe(III), control systems to evaluate the potential of KC methods for routine,
which interfere on the catalytic determination of Mo(VI). or the development of fast-screening approaches for the detection
of minute amounts of metallic nanoparticles on the environment.
5. Comparison of ow-based approaches for the automation
of kinetic-catalytic methods Acknowledgements

Different automation degrees can be obtained on depending of The Spanish Ministerio de Economa y Competitividad (MINECO)
the selected FT, from FIA systems with manual sample injection [31], and the European Funds for Regional Development (FEDER) are grate-
to fully automated of FTs including sample introduction, data ac- fully acknowledged for nancial support through Project No.

Table 3
Advantages and limitations of different approaches of ow techniques applied to the automation of kinetic-catalytic methods

FT Ref. Advantages Disadvantages

FIA [27,44] High sample throughput High reagent consumption. Possible incompatibilities
with some organic solvents.
SIA [16] Full automation, computer controlled, low reagent consumption Sequential aspiration of sample and reagent, low
and waste generation mixture eciency, lower analysis throughput than FIA
FIA-NP [29,35,48,66] High sensitivity, high applicability to the determination of organic High reagent consumption
molecules
MPFS [17] High mixture eciency. Low reagent consumption Need frequent recalibration. Limitations for the
implementation of some sample pretreatments.
MSFIA [23,24] High versatility and mixture eciency. Low reagent consumption Lower analysis throughput than FIA
and waste generation
Chip-MSFIA [1822] Full automation, computer controlled ow instrument, detector May require changes on the Chip design on depending
and data acquisition. Compact ow manifold, integrated on the selected KC method
thermostated detection ow cell, initial rate method
implementation at controlled temperature.
FIA-traping zones [31] Ecient system for preventing bubble generation. Possibility of Low automation degree
initial rate implementation at controlled temperature
44 C. Henrquez et al. / Trends in Analytical Chemistry 85 (2016) 3345

CTQ2013-47461-R. The scholarships from Royal Golden Jubilee TRF- [29] Z.F. Zhang, H. Cui, C.Z. Lai, L.J. Liu, Gold nanoparticle-catalyzed luminol
chemiluminescence and its analytical applications, Anal. Chem. 77 (2005)
Ph.D., the Thailand Research Fund for P. Phansi is gratefully
33243329.
acknowledged. [30] H. Cui, R. He, J. Wang, A simple and sensitive chromium speciation procedure
by hyphenating ow injection on-line preconcentration with catalytic
spectrophotometry, Talanta 70 (2006) 139145.
References [31] A.C.E. Vida, E.A.G. Zagatto, Exploiting zone trapping to avoid liberation of air
bubbles in ow-based analytical procedures requiring heating, Anal. Sci. 30
(2014) 833838.
[1] H.T. Guyard, Ueber die erzeungung von anilinsghwarz mittels der vanadinsalze [32] V. Cerd, L. Ferrer, J. Avivar, A. Cerd, Software, in: Flow Analysis: A Practical
und ber die theorie der bildung dieses farbstoffes, Chemis. Zentralblatt 10 Guide, Elsevier, Amsterdam, 2014, pp. 163174.
(1875) 420423. [33] S. Abbasi, M. Esfandyarpour, M.A. Taher, A. Daneshfar, Catalytickinetic
[2] C. Camara, C. Prez-Conde, Anlisis Qumico de Trazas, Editorial Sintes, Madrid, determination of trace amount of formaldehyde by the spectrophotometric
2011. method with a bromateJanus green system, Spectrochim. Acta Mol. Biomol.
[3] D. Prez-Bendito, M. Silva, Kinetic Methods in Analytical Chemistry, Ellis Spectrosc. 67 (2007) 578581.
Horwood Ltd, 1988. [34] A.A. Ensa, S. Abbasi, B. Rezaei, Kinetic spectrophotometric method for the
[4] M. Trojanowicz, Advances in Flow Analysis, Wiley-VCH Verlag, 2008. determination of oxalic acid by its catalytic effect on the oxidation of safranine
[5] F. Zhao-Lun, X. Shu-Kun, Determination of molybdenum at l1 levels by by dichromate, Spectrochim. Acta Mol. Biomol. Spectrosc. 57 (2001) 18331838.
catalytic spectrophotometric ow injection analysis, Anal. Chim. Acta 145 (1983) [35] B. Li, D. Wang, C. Xu, Z. Zhang, Flow-injection simultaneous chemiluminescence
143150. determination of ascorbic acid and L-cysteine with partial least squares
[6] S.R. Crouch, Trends in kinetic methods of analysis, Anal. Chim. Acta 283 (1993) calibration, Microchim. Acta 149 (2005) 205212.
453470. [36] M.T. Oms, R. Forteza, V. Cerd, Automatic kinetic thermometric method for
[7] S.R. Crouch, A. Scheeline, E.S. Kirkor, Kinetic determinations and some kinetic the determination of ultratraces of cobalt, Anal. Chim. Acta 258 (1992) 177
aspects of analytical chemistry, Anal. Chem. 72 (2000) 5370. 182.
[8] H.A. Mottola, D. Perez-Bendito, Kinetic determinations and some kinetic aspects [37] S. Nakano, Y. Matumoto, M. Yoshii, Flow-injection photometric determination
of analytical chemistry, Anal. Chem. 66 (1994) 131R162R. of manganese(II) based on its catalysis of the periodate oxidation of N,N-bis(2-
[9] Z. Chen, N. Zhang, L. Zhuo, B. Tang, Catalytic kinetic methods for photometric hydroxy-3-sulfopropyl)tolidine, Talanta 68 (2005) 312317.
or uorometric determination of heavy metal ions, Microchim. Acta 164 (2009) [38] S. Nakano, C. Kamaguchi, N. Hirakawa, Flow-injection catalytic
311336. spectrophotometic determination of molybdenum(VI) in plants using
[10] M.K. Sasaki, S. Vicente, V. Grassi, E. Zagatto, Differential reaction-rate methods bromate oxidative coupling of p-hydrazinobensenesulfonic acid with N-(1-
in ow analysis, Open Anal. Chem. J. 6 (2012) 2838. naphthyl)ethylenediamine, Talanta 81 (2010) 786791.
[11] V. Cerd, L. Ferrer, J. Avivar, A. Cerd, Flow Analysis: A Practical Guide, Elsevier, [39] D.M. Magni, A.C. Olivieri, A.L. Bonivardi, Articial neural networks study
Amsterdam, 2014. of the catalytic reduction of resazurin: stopped-ow injection kinetic-
[12] G.E. Mieling, H.L. Pardue, Evaluation of a computer-controlled stopped-ow spectrophotometric determination of Cu(II) and Ni(II), Anal. Chim. Acta 528
system for fundamental kinetic studies, Anal. Chem. 50 (1978) 13331337. (2005) 275284.
[13] E.H. Hansen, Exploiting kinetic-based ow-injection methods for quantitative [40] S.L. Xu, H. Cui, Luminol chemiluminescence catalysed by colloidal platinum
chemical assays, Anal. Chim. Acta 261 (1992) 125136. nanoparticles, Luminescence 22 (2007) 7787.
[14] J. Ruzicka, E.H. Hansen, Stopped ow and merging zones a new approach to [41] S. Nakano, E. Tanaka, Y. Mizutani, Flow-injection spectrophotometry of
enzymatic assay by ow injection analysis, Anal. Chim. Acta 106 (1979) vanadium by catalysis of the bromate oxidation of N,N-bis(2-hydroxyl-3-
207224. sulfopropyl)-tolidine, Talanta 61 (2003) 203210.
[15] T. Kawashima, S. Nakano, Flow-injection analysis of trace-elements by use of [42] F. Lazaro, M.D.L. De Castro, M. Valcarcel, Sequential and differential catalytic-
catalytic reactions, Anal. Chim. Acta 261 (1992) 167182. uorimetric determination of manganese and iron by ow injection analysis,
[16] J.A. Erustes, R. Forteza, V. Cerd, Sequential-injection procedure for Anal. Chim. Acta 169 (1985) 141148.
determination of iodide in pharmaceutical and drinking water samples by [43] L. Chaparro, L. Ferrer, L.O. Leal, V. Cerd, Automated and rapid method to
catalytic reaction with spectrophotometric detection, J. AOAC Int. 84 (2001) determine traces of Mn2+ in sea and drinking waters by a kinetic catalytic
337341. process using LWCC-spectrophotometric detection, Talanta 148 (2016) 583
[17] P.R. Fortes, S.R. Meneses, E.A. Zagatto, A novel ow-based strategy for 588.
implementing differential kinetic analysis, Anal. Chim. Acta 572 (2006) 316320. [44] A.P.G. Gervasio, P.R. Fortes, S.R. Meneses, C.E. Miranda, E.A.G. Zagatto, An
[18] P. Phansi, C. Henriquez, E. Palacio, D. Nacapricha, V. Cerd, An automated improved ow-injection system for spectrophotometric determination of
in-chip-catalytic-spectrophotometric method for determination of copper(ii) molybdenum and tungsten in tool steels, Talanta 69 (2006) 927931.
using a multisyringe ow injection analysis-multipumping ow system, Anal. [45] E. Becerra, A. Cladera, V. Cerd, Design of a very versatile software program
Methods 6 (2014) 84948504. for automating analytical methods, Lab. Rob. Autom. 11 (1999) 131140.
[19] F.Z. Abouhiat, C. Henriquez, B. Horstkotte, F. El Yous, V. Cerd, A miniaturized [46] Y.Z. Ye, H.Y. Mao, Y.H. Chen, Catalytic kinetic simultaneous determination of
analyzer for the catalytic determination of iodide in seawater and iron, silver and manganese with the Kalman lter by using ow injection
pharmaceutical samples, Talanta 108 (2013) 92102. analysis stopped-ow spectrophotometry, Talanta 45 (1998) 11231129.
[20] F.Z. Abouhiat, C. Henriquez, E. Palacio, F. El Yous, V. Cerd, Automatic integrated [47] M. Blanco, J. Coello, H. Iturriaga, S. Maspoch, M. Redon, Articial neural networks
system for catalytic spectrophotometric determination of vanadium in water for multicomponent kinetic determinations, Anal. Chem. 67 (1995) 4477
samples, Anal. Methods 6 (2014) 91429151. 4483.
[21] P. Phansi, C. Henriquez, E. Palacio, P. Wilairat, D. Nacapricha, V. Cerd, An [48] B. Li, D. Wang, J. Lv, Z. Zhang, Flow-injection chemiluminescence simultaneous
automated catalytic spectrophotometric method for manganese analysis using determination of cobalt(II) and copper(II) using partial least squares calibration,
a chip-multisyringe ow injection system (Chip-MSFIA), Anal. Methods 6 (2014) Talanta 69 (2006) 160165.
50885096. [49] P.R. Fortes, M.A. Feres, E.A.G. Zagatto, J.L.F.C. Lima, Sequential injections as an
[22] P. Phansi, C. Henriquez, E. Palacio, D. Nacapricha, V. Cerd, Automated in-chip alternative to gradient exploitation for implementing differential kinetic analysis
kinetic-catalytic method for molybdenum determination, Talanta 119 (2014) in a ow injection system, Talanta 81 (2010) 14091412.
6874. [50] F.Z. Abouhiat, C. Henrquez, F. El Yous, V. Cerd, Sensitive kinetic-catalytic
[23] L. Chaparro, L. Ferrer, L.O. Leal, V. Cerd, Multicommutated ow-based spectrophotometric method for cobalt determination using a chip coupled to
automated kinetic-catalytic method for determination of cobalt(II) exploiting a multisyringe ow injection analysis system, Talanta (2015) doi:10.1016/
the catalytic effect of Co on the oxidative coupling of alizarin, Talanta 133 (2015) j.talanta.2015.12.005.
9499. [51] S. Lunvongsa, M. Oshima, S. Motomizu, Determination of total and dissolved
[24] A.R.T.S. Araujo, F. Maya, M.L.M.F.S. Saraiva, J.L.F.C. Lima, J.M. Estela, V. Cerd, amount of iron in water samples using catalytic spectrophotometric ow
Flow system for the automatic screening of the effect of phenolic compounds injection analysis, Talanta 68 (2006) 969973.
on the luminol-hydrogen peroxide-peroxidase chemiluminescence system, [52] H. Muller, V. Mulller, E.H. Hansen, Simultaneous differential rate determination
Luminescence 26 (2011) 571578. of iron(II) and iron(III) by ow-injection analysis, Anal. Chim. Acta 230 (1990)
[25] T. Kawashima, T. Minami, M. Ata, M. Kamada, S. Nakano, Catalytic determination 113123.
of ultratrace amount of cobalt by ow injection analysis, J. Flow Injection Anal. [53] A.A. Ensa, M.A. Chamjangali, H.R. Mansour, Sequential determination of
2 (1985) 4049. iron(II) and iron(III) in pharmaceutical by ow-injection analysis with
[26] J. Wang, R. He, Stopped-ow injection kinetic determination of multicomponent spectrophotometric detection, Anal. Sci. 20 (2004) 645650.
samples: simultaneous determination of mercury(II) and silver(I), Anal. Chim. [54] F.Z. Abouhiat, C. Henrquez, F. El Yous, V. Cerd, Kinetic-catalytic method for
Acta 294 (1994) 195199. sequential determination of iron and copper using a monolithic ow conduit
[27] M. Kaneko, M. Kurihara, S. Nakano, T. Kawashima, Flow-injection determination coupled to a multipumping ow system, Anal. Methods 7 (2015) 78587865.
of chromium(III) by its catalysis on the oxidative coupling of 3-methyl-2- [55] A.A. Ensa, A. Kazemzadeh, Simultaneous determination of nitrite and nitrate
benzothiazolinone hydrazone with N-ethyl-N-(2-hydroxy-3-sulfopropyl)-3- in various samples using ow injection with spectrophotometric detection, Anal.
methoxyaniline, Anal. Chim. Acta 474 (2002) 167176. Chim. Acta 382 (1999) 1521.
[28] L. Su, J. Li, H. Ma, G. Tao, Determination of trace amounts of manganese [56] A.A. Ensa, B. Rezaei, S. Nouroozi, Simultaneous spectrophotometric
in natural waters by ow injection stopped-ow catalytic kinetic determination of nitrite and nitrate by ow injection analysis, Anal. Sci. 20
spectrophotometry, Anal. Chim. Acta 522 (2004) 281288. (2004) 17491753.
C. Henrquez et al. / Trends in Analytical Chemistry 85 (2016) 3345 45

[57] M. Valero, M. Gallignani, V. Cerd, R. Brunetto, Development of a kinetic ow [66] L. Luo, Z. Zhang, L. Hou, Development of a gold nanoparticles based
analysis spectrophotometric method for determination of nitrite traces, based chemiluminescence imaging assay and its application, Anal. Chim. Acta 584
on its catalytic effect on the redox reaction between thionine and bromate, (2007) 106111.
Ciencia 12 (2004) 189204. [67] G.Z. Tsogas, D.L. Giokas, A.G. Vlessidis, Ultratrace determination of silver, gold,
[58] N. Teshima, M. Kuno, M. Ueda, H. Ueda, S. Ohno, T. Sakai, Automated stopped- and iron oxide nanoparticles by micelle mediated preconcentration/selective
in-dual-loop ow analysis system for catalytic determination of vanadium in back-extraction coupled with ow injection chemiluminescence detection, Anal.
drinking water, Talanta 79 (2009) 517522. Chem. 86 (2014) 34843492.
[59] J.Z. Guo, H. Cui, W. Zhou, W. Wang, Ag nanoparticle-catalyzed chemiluminescent [68] F. Maya, B. Horstkotte, J.M. Estela, V. Cerd, Automated in-syringe dispersive
reaction between luminol and hydrogen peroxide, J. Photochem. Photobiol. A liquid-liquid microextraction, Trends Anal. Chem. 59 (2014) 18.
193 (2008) 8996. [69] A. Andrade-Eiroa, M. Canle, V. Leroy-Cancellieri, V. Cerd, Solid-phase extraction
[60] L. Wang, P. Yang, Y. Li, H. Chen, M. Li, F. Luo, A ow injection chemiluminescence of organic compounds: a critical review (Part I), Trends Anal. Chem. 80 (2016)
method for the determination of uoroquinolone derivative using the reaction 641654.
of luminol and hydrogen peroxide catalyzed by gold nanoparticles, Talanta 72 [70] A. Andrade-Eiroa, M. Canle, V. Leroy-Cancellieri, V. Cerd, Solid-phase extraction
(2007) 10661072. of organic compounds: a critical review (Part II), Trends Anal. Chem. 80 (2016)
[61] S. Li, X. Li, J. Xu, X. Wei, Flow-injection chemiluminescence determination of 655667.
polyphenols using luminolNaIO4gold nanoparticles system, Talanta 75 (2008) [71] F. Maya, C.P. Cabello, J.M. Estela, V. Cerd, G.T. Palomino, Automatic in-syringe
3237. dispersive microsolid phase extraction using magnetic metalorganic
[62] B. Haghighi, S. Bozorgzadeh, Flow injection chemiluminescence determination frameworks, Anal. Chem. 87 (2015) 75457549.
of isoniazid using luminol and silver nanoparticles, Microchem. J. 95 (2010) [72] M. Ghani, F. Maya, V. Cerd, Automated solid-phase extraction of organic
192197. pollutants using melamineformaldehyde polymer-derived carbon foams, RSC
[63] M. Smiderle, M.C. Tomazzini, B.F. Reis, Development of a micro-heater for ow Adv. 6 (2016) 4855848565.
analysis systems. Spectrophotometric determination of manganese in plant [73] M. Ghani, M. Saraji, F. Maya, V. Cerd, Automated multisyringe stir bar sorptive
digest, Quim. Nova 27 (2004) 5054. extraction using robust montmorillonite/epoxy-coated stir bars, J. Chromatogr.
[64] J. Ruzicka, E.H. Hansen, Integrated microconduits for ow-injection analysis, A 1445 (2016) 1018.
Anal. Chim. Acta 161 (1984) 125. [74] R.M. Frizzarin, C.P. Cabello, M.D.M. Bauz, L.A. Portugal, F. Maya, V. Cerd, et al.,
[65] E.R.G.O. Rodrigues, R.A.S. Lapa, Development of ow systems by direct-milling Submicrometric magnetic nanoporous carbons derived from metalorganic
on poly(methyl methacrylate) substrates using UV-photopolymerization as frameworks enabling automated electromagnet-assisted online solid-phase
sealing process, Anal. Sci. 25 (2009) 443448. extraction, Anal. Chem. 88 (2016) 69906995.