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1002

Mojtaba Shamsipur1*, Vali Zare-Shahabadi2, Bahram Hemmateenejad2 and Morteza Akhond2

1 2

Department of Chemistry, Razi University, Kermanshah, Iran Department of Chemistry, Shiraz University, Shiraz, Iran

Ant colony optimisation (ACO) is a meta-heuristic algorithm, which is derived from the observation of real ants. Real ant colonies are distributed system that, in spite of the simplicity of their individuals, present a highly structured social organisation and can accomplish complex tasks. They always nd a short path between the nest and a food source. ACO is based on local message exchange via the deposition of pheromone trails. It is in fact a population-based approach using positive feedback as well as greedy search. Wavelength selection is a strategy used for improving the quality of calibration methods. As a rst report, this work indicated that the ACO possesses a great ability to nd best subsets of wavelengths, at a short period of time with small PRESS values, via accumulation of information in the form of pheromone trails deposited on each wavelength. Theory of ACO is described and, to carry out the wavelength selection, a tness function is dened. The ACO parameters are congured with a 3-levels full factorial design. The high ability of ACO in wavelength selection process was demonstrated by examining four different NIR and UV/Vis data sets via various ACO algorithms, including ACO-ILS, ACO-CLS and ACO-PLS. The results showed that, with the same tness function, ACO-ILS algorithm suffers from some overtting problem. This problem was overcome by constraining the algorithm to choose limited number of wavelengths, the corresponding algorithm called as ACO-ILS(limited). The results obtained by these algorithms clearly revealed the improved predictive ability of ACO in wavelength selection over the existing full-spectrum models. Copyright # 2007 John Wiley & Sons, Ltd. KEYWORDS: ant colony optimisation; wavelength selection; multivariate calibration

1. INTRODUCTION

Multivariate calibration models are used to establish a relation between independent variables (e.g. concentration) and dependent variables (e.g. UV-Vis spectra) and have been successfully applied to the IR, Raman and UV-Vis spectroscopic data for quantitative analysis [1,2]. These models provide great advantages of keeping the pre-treatment of samples to a minimum and, by the employment of high-speed computers, reducing the time spent in data collection [3]. Among common multivariate methods, including classical least squares (CLS), inverse least squares (ILS), principal component regression (PCR) and partial least-squares (PLS), the PCR and PLS are methods basing their regression models on a few orthogonal latent variables, being a linear

*Correspondence to: M. Shamsipur, Department of Chemistry, Razi University, Kermanshah, Iran. E-mail: mshamsipur@yahoo.com

combination of all original variables. The main advantage of PCR and PLS is their ability to compress the relevant spectral information into a few latent variables; however, one may prefer the ILS and CLS methods, which directly use the original variables in the modelling process. Advantages of these methods are their ease and rapidity of computation. Moreover, the statistical interpretation of the results by these models is more straightforward as the theory of ILS and, especially, CLS is better understood than that of the PCR and PLS. The detailed information about the comparison between these multivariate methods is reported in the literature [4]. It has been shown both experimentally and theoretically that the application of the above mentioned methods to multicomponent spectroscopic analysis usually requires spectral variable selection for building well-tted models and avoiding non-modelled interferences [57]. Training the multivariate calibration methods with selected spectral regions, rather than full-spectrum region, allows the informative part of the spectrum, which is related to the variation of concentration of the analyte, to be modelled and, therefore, other parts of spectrum which are related to the variation

Copyright # 2007 John Wiley & Sons, Ltd.

of concentration of other analytes and/or background variations will be discarded. Hence, the performance of multivariate calibration models will be improved. In practice, wavelength selection is composed of the decision on a subset of spectral channels with which the established calibration model gives the minimum errors in prediction. The benet gained from wavelength selection is not only the stability of the model to the colinearity in multivariate spectra but also the interpretability of the relationship between the model and the sample compositions. Meanwhile, the complexity of wavelength selection problem is discussed in many papers such as Reference [8] , where it has been shown both qualitatively and quantitatively that the wavelength selection problem is a NP-hard problem. Nevertheless, a number of procedures have already been proposed for wavelength selection in multicomponent spectral analysis. These procedures can be distinguished from each other either in the objective criterion for measuring the optimality of wavelength subsets or in the search algorithm to locate the optimal subsets. Typical objective criteria include the spectral signal-to-noise ratio, the condition number or determinant of the calibration matrix, Akaike information criterion (AIC) and Mallows Cp statistics, as well as some estimates of the mean squared error in prediction (MSEP) [2]. The routine search algorithms comprise the stepwise selection [8], simplex optimisation [9], branch and bound combinatorial search [10], simulated annealing [9], genetic algorithms (GAs) [11], successive projections algorithm [12] and moving windows selection strategy [13]. Very recently, we proposed an experimental design-neural network procedure to select the most informative spectral regions [14]. Among the wavelength selection methods used in the UV-Vis and NIR spectral regions, search algorithms, especially genetic algorithm, have found a major popularity. In spite of the success of GA to solve the feature selection problem, a study of the GA-PLS behaviour has suggested to use no more than 200 variables in the system [11]. In fact, it has been found empirically that the use of more than 200 channels, i.e. a larger search domain, would reduce the capability of obtaining a solution with good predictive ability [15 and references therein]. Some authors have proposed different procedures to overcome this limitation. For example, Goicoechea and Olivieri [16] proposed a novel initialisation strategy to lower the computation time, and Leadri et al. [15] applied an iterative approach to GA for selection of more than 200 variables. Ant colony optimisation (ACO), as a new general purpose meta-heuristic algorithm, was proposed by Dorigo et al. [17,18] in 19911992 for solving complicated optimisation processes, and rst applied in travelling salesman problem (TSP). The method inspired by the behaviour of real ant colonies, which always nd the shortest path between their nest and a food source, thanks to local message exchange via the deposition of pheromone trails. It is a population-based approach using positive feedback as well as greedy search. The applications and effectiveness of various algorithms of this technique for solving complicated optimisation problems has been clearly demonstrated [19,26]. A remarkable advantage of the ACO-based algorithm over traditional

Copyright # 2007 John Wiley & Sons, Ltd.

optimisation algorithms is the ability to produce a good suboptimal solution in a very short time [20]. It is interesting to note that in spite of high abilities of the ACO, this procedure was entered to the eld of chemistry with some delay, and only a few publications based on ACO have been reported in the chemical literature, e.g. feature selection in QSAR analysis [21,22] and analysis of the rst derivative uorescence spectra [23]. To the best of our knowledge, the application of ant colony algorithm to the wavelength selection problem in analytical chemistry is an unexplored eld of research. Thus, in this paper, we wish to report the rst application of ACO to wavelength selection in different UV-vis and NIR experimental data sets and the results are compared with those obtained by some stochastic methods such as forward selection and backward elimination. It was found that the use of ACO considerably improves the results of various multivariate methods including ILS, CLS and PLS.

Articial ants are characterised as agents that imitate the behaviour of real ants. An ACO algorithm involves simple articial ants that cooperate with one another to achieve a exible, emergent and unied behaviour for the system as a whole, producing a robust system capable of nding high-quality solutions for problems with a large search space. In many ant species, individual ants may deposit a pheromone (a particular chemical that ants can smell) on the ground while walking. By depositing pheromone, they create a trial that is used, for example, to mark the path from the nest to food sources and back. Also they are capable of exploiting pheromone trails to choose shortest among the available paths taking to food. Articial ants used in ACO are stochastic solution construction procedures that probabilistically build a solution by picking out component(s) and adding to partial solution by taking into account articial pheromone trials, which change dynamically at run time to reect the agents acquired search experience. It should be noted that an articial ant colony has some differences in comparison with a real ant colony, as follows [24]: (a) articial ants have memory, (b) they are not completely blind and (c) they live in an environment where time is discrete. On the other hand, an articial ant colony has several characteristics adopted from real ant colony: (a) articial ants have a probabilistic preference for paths with a larger amount of pheromone, (b) shorter paths tend to have larger rates of growth in their amount of pheromone and (c) the ants use an indirect communication system based on the amount of pheromone deposited in each path. In essence, an ACO iteratively performs a loop containing two basic procedures: a procedure specifying how the ants construct/modify solutions of the problem being solved and a procedure to update the pheromone trails. At the beginning of the search process, in ACO, a constant amount of pheromone (e.g. Pk 1) is assigned to all variables, e.g. wavelengths. From this probability vector (pheromone vector), a colony of ants are built, so that each ant is a row vector containing as many as elements as the variables, each element being coded as 1, if the

J. Chemometrics 2006; 20: 146157 DOI: 10.1002/cem

corresponding variable was selected and 0, if it was not. The number of elements in an ant coded as 1 (i.e. the selected variable by the ant) can be varied from 1 to c, where c is overall number of variables. The length of the ant (l) is dened as the number of selected variables by the ant. Each ant builds a solution to the problem and its tness is equal to the evaluation of response, which is to be optimised by the algorithm. In the next step, ants use this evaluation to modulate the amount of pheromone deposit on each variable. It should be making the pheromone update a function of the generated solution quality that can help in directing future ants more strongly toward a better selection. The best ants deposit an amount of pheromone on the variables included in their candidate solution, so that the best variables (the ones used by the best ants) get a higher amount of pheromone. In fact, existing higher amount of pheromone on the best variable, the ants variable searching is more quickly biased toward the best variables. In the last step, pheromone evaporation is occurred. Pheromone evaporation reduces the inuence of pheromones deposited on the variables where articial ants can build a poor-quality solution. A pheromone vector (t) is built and a probability vector, which shows the probability of occurrence of each wavelength in the ant, is calculated from the entries of pheromone vector (tk). At the beginning, the pheromone vector sets to 1 for all wavelengths. This pheromone value is then varied through an iterative procedure to assign wavelengths, which are informative and possess larger probability to use by the ants. Form pheromone vector, a probability (P) vector and from that a cumulative probability (CP) vector are calculated (Equation 1) and a colony with size f (number of ants in the colony) is built based on the CP vector. Pk tk c P tk

k1 k P i1

(1)

CPk

It should be noted that the elements of P are the probability for the occurrence of each variable. For each ant in a colony, the number of selected variables by the ant (i.e. length of ant, l), which can be varied from 1 to c, is randomly chosen. As an example to show how an ant is build, one can consider a spectrophotometric measurement in four wavelengths. For this situation, a pheromone vector (t) with unity entries is initially generated and, consequently, the CP vector is calculated by Equation (1). Assume that the length of ant is randomly chosen to 3 (i.e. l 3). Here, three random numbers, between 0 and 1, are generated from a uniform distribution. In a typical loop of ACO, each of the random numbers is compared with each entries of the CP vector, i.e. [0.25 0.50 0.75 1.00], to assign one variable. Now, if the generated random number lies between 0 and 0.25, the rst variable is chosen, if it is between 0.25 and 0.50, the second variable is selected, if it is between 0.50 and 0.75, the hird variable is selected and if it is greater than 0.75, the fourth variables is selected. It is clear that this loop is done for at least three times. A constrain, in which ant is not allowed to select a variable more than one times, is applied to this

Copyright # 2007 John Wiley & Sons, Ltd.

loop. Another constrain is that if the predened length of ant is equal to three, the number of selected variables after terminating the loop must be also equal to three. If two out of three random numbers are mapped to the same entry of CP vector, the same variables are selected by these numbers. Therefore, the later is replaced with a new generated random number. This process is continued until the length of ant become equal to the number of selected variables. Of course, in all of the above processes, the higher value of tk for a variable will result in a higher probability by which it will be present in the ant. It should be noted here that the main difference between the present algorithm and that described in Reference [22] is in the variable selection step. In the later case [22], an ant should move in a c-dimensional space of c variables and its motion is restricted to 0 or 1 on each variable. In this procedure, which is also employed by many genetic algorithm systems, the probability of variable selection is 50%. This means that an ant or a chromosome contains almost 50% of total variables. For this reason, to improve variable selection, it is popular to predene the probability of presence of variables, e.g. 10%, which also causes a reduction in convergence velocity. However, as mentioned above in our algorithm, a generated random number is compared with each entries of CP vector to select a variable. In this procedure, the length of ant can vary from 1 to c, and so, with comparing to the later results, there is no need to predene the probability of variable selection by the ant. This allows ACO to converge to the nearly optimum number of variables with higher speed, and to decrease the probability of information loose. In the case of later advantage, assuming a colony with the size 10 and 10% probability of variable selection from a 100-dimensional variable space by the ant; the number of wavelengths that used by all of the ants in the rst built colony is 100 and it is rarely that all of the 100 wavelengths are present in the rst colony. However, by our algorithm with the same condition, 50% of all of ants (ve ants) probably have a length of greater than 50. Thus, at least 250 wavelengths are used by these ve ants, and it can be concluded that, in the rst colony, all of the wavelengths have a chance to present in at least one ant. Consequently, the probability of losing information is decreased. Size of a colony (number of ants included in colony, i.e.f) is a parameter that usually must be set experimentally [25]. The larger number of ants decreases the probability of convergence of ACO to the local optimum [26]. On the other hand, in complex problems, this large colony of ants consumes a long time for computation. From initial experiments, it is concluded that for many complex models (large number of wavelength), there is no need to assign f more that 150 (the data not shown). Therefore, according to the model complexity (i.e. number of variables), f is selected in an order that it is not exceeded 150. For fth ant, the interested multivariate model is build just with the wavelengths selected by this ant and a PRESS value based on cross-validation is calculated as:

N X i1

PRESSf

^i xi 2 x

f 1; 2; . . . ; f

(2)

^i is the predicted concentration of interested where x component in ith mixture by the model imposed by fth ant, xi is real concentration, and N is the number of mixtures in calibration set. A tness function (Gf) is then dened for the fth ant in the colony as follows: fitness function : Gf 1 PRESSf lf f 1; 2; . . . ; f (3)

where lf is the length of the fth ant (number of wavelengths coded as 1). The G value is normalised and multiplied by a, usually 0.8, to keep the tness value (Gn) between 0 and 0.8: 3 2 6 G 7 6 f 7 Gnf a 6 f 7 4P 5 Gf

f 1

(4)

Gn shows the quality of job done by the ant; the larger the value of Gn, the larger the quality of job. Note that after normalisation of G values, Gn varies in the range: 0 < Gn < 1; but it is convenient, in this problem, to keep Gn lower than 1. The reason of this, and later normalisation process, is intuitively clear because large tness value tend to amplify the inuence of initial random uctuations. Therefore, the Gn vector is multiplied by coefcient lower than 1 (a). It was found, by trial and error, that the value of this coefcient equal to 0.8 gives better results. As it will be seen in the next sections, the same result was obtained by factorial design optimisation of the parameter. From a statistical point of view, in feature selection problems, ideally the number of records (data points) should be considerably larger than the number of original variables, otherwise the data set is very sparse and the feature selection algorithms tends to be prone to over-tting. Now, in the case of multivariate calibration data, the datasets in general contain many more variables than records. Therefore, denition of the tness function is critical in this case. There are many criteria of error estimate for model evaluation, where some of them lead to more over-tted models. Cross-validation is a standard procedure for estimating the error of a model [27]. In the current feature selection problem, different scoring function criteria were examined and it was obtained that calculating of tness by Equation (3) leads to nal models with optimum performances (i.e. low prediction error and as low as possible number of selected variables). The ants are ranked based on their quality at the end of each of the iteration. Just 50% of ants (fbest) with higher quality allow updating the pheromone vector. This causes faster convergence to best subset of wavelengths. The number of ants used for pheromone updating, at any iteration, was chosen by trail and error. If the overall set of wavelengths and the subset of selected wavelengths by fth ant are called as l and bf, respectively, then the entries of pheromone vector corresponding to the selected wavelengths (tk, k 2 bf) by each updating ant ( f 1,2,. . ., fbest) is changed as: t k t 1 t k t t k t Gnf f 1; 2; . . . ; fbest k 2 bf (5) where tk (t) is the amount pheromone deposit on kth wavelength at time t. It should be noted that the

Copyright # 2007 John Wiley & Sons, Ltd.

pheromone value for all wavelength at the beginning was set as 1. At the end of each of iteration, pheromone evaporation is done. This step is performed to simulate the phenomenon of pheromone evaporation in real ant colony systems, and applies to the model in the direct and indirect ways. More precisely (in the indirect method), the effect of pheromone evaporation for unused wavelengths is achieved by normalising the value of each trial pheromone tk to obtain P vector. The probability value of an unused term will be computed from dividing its current pheromone value (with no modication) by the total summation of pheromones for all terms (which was increased as a result of applying Equation (4) to the used terms). The nal effect will be the reduction of the probability of occurrence of unused term. The other way for pheromone evaporation, direct way, is done at the end of each of iterations as follows: t k t k r for all k 2 l (6)

where r is a scalar set between 0.3 and 1. It should be noted here that the convergence (i.e. all ants select the same wavelengths) is highly dependent on the amounts of both r and Gn. Large amount of Gn and lower amount of r cause faster convergence, which in turn increases the chance of locating at local minima. This means that if the pheromone evaporation or pheromone deposition is done energetically, ACO enters very fast in the exploitation phase and, consequently, converge to poor results. Thus, our goal in the pheromone updating step is to remove some pheromone amounts from wavelengths that their entrance into the model causes poorer tting and, simultaneously, to deposit some pheromone amounts on those wavelengths that their entrance into the model cause a better tting so that ACO will remain in the exploration phase (at least up to 50 iterations). The main advantage of the above mentioned procedure is to nd quickly very high-quality solution, instead of reaching to the convergence [25]. In the other hand, because of the colinearity between the neighbourhood wavelengths in NIR and, more especially, in UV-vis spectroscopy, one can nd several sets of wavelengths (i.e. solutions or models) near to the optimum solution. It means that, at the end of an ACO algorithm, high values of pheromone are deposited on several wavelengths that are not in the same set. In conclusion, an ACO procedure for wavelength selection should not reach essentially to a real convergence. a and r values are both set to 0.8 by trail and error (the results are not shown), however the same results are drawn from Section Data set 1". To return information lost and also to introduce information that was never present in the ant population, a mutation process is also added to the algorithm. In a more generic way, mutation increases the diversity of the candidate solutions represented in the current population of ants. This step is the same as local search step that recently used in ACO algorithms [26 and references therein]. If an informative variable is not selected in the initial colonies, the probability of choosing this variable, because of the pheromone evaporation, becomes lower and lower as the algorithm proceeded. The mutation gives a chance for such variable to be included in the colony. A question, which is

J. Chemometrics 2006; 20: 146157 DOI: 10.1002/cem

concerned with mutation, is that to how may candidate solutions, this step should be applied. In fact, in most local search procedures, the better the solution quality returned, the higher the computational time required [26] and therefore there is a challenge between solution quality and computational time in applying the mutation step. So, we set the probability of mutation to 20%. Mutation randomly changes the state of a variable in an ant from 0 to 1 or vice versa. If PRESS is decreased by deselecting of a wavelength, the mutation is accepted. Instead, if PRESS decreases by selection of new wavelength, a statistical F-ratio is calculated to accept or reject the mutation: F PRESSBM =PRESSAM (7)

is quite different from ordering problems. There is no concept of a path (or graphical representation) here, so it is difcult to apply the conventional ACO directly to variable selection [22]. In our ACO algorithm, which designed for wavelength selection, there is no heuristic information and ant is constructed in a different way. These are the main differences between our ACO and conventional ACO. High-level view of ACO algorithm for wavelength selection is shown in Figure 1.

To test wavelengths selection ability of ant colony algorithm in multivariate calibration, different UV-Vis and NIR spectroscopic experimental data sets were used. Summary of these data sets are given in Table I and description of them are in following sections. Three multivariate models including classical least squares (CLS), inverse least squares (ILS) and partial least squares (PLS) were applied on each data set. The integration of ACO with these multivariate models was in such a way that after construction of a colony, evaluation of each ant in the colony was accomplished with each of the multivariate models. Therefore, each ACO-multivariate model was run separately and the ants were scored (or evaluated) with interested multivariate models such as ILS, CLS and PLS. To do so, for a typical ACO-multivariate model (i.e. ACO-ILS, ACO-CLS and ACO-PLS), the interested multivariate model between the absorbance data, just at the wavelengths selected by the ant, and concentration of the analyte of interest were made. In the case of ACO-ILS and ACO-CLS algorithms, leave-one-out cross validation (LOO-CV) was used for calculating the PRESS value. LOO-CV consists of deleting a row from the training set (this row contains information about one sample in the data matrix), construction the model based on interested multi-

where PRESSBM and PRESSAM are PRESS before and after applying mutation, respectively. The calculated value of F is compared with tabulated F-value with the respective degree of freedom of the numerator and denominator equal to the number of selected variables in candidate solution minus one after and before mutation. The F-test was accepted if its corresponding p-value (signicant level) was lower than 0.3. It is concluded from the above discussion that the ACO parameters, including number of ants in a colony (i.e. size of colony, f), a value, pheromone evaporation (r), number of ants used for pheromone updating at every iteration, and number of iteration need to run the algorithm, must be optimised. In the present work, a full factorial design was employed to adjust f, a and r values. Other parameters were adjusted by a trail and error procedure. At the end, it should be noticed that the conventional ACO was designed for solving ordering problems such as the TSP. In the conventional ACO, depending on the problem representation chosen, pheromone trails can be associated to all or some of the arcs in a given problem. Arcs can also have an associated heuristic value representing prior information about the problem instance denition [28]. However, variable selection is a subset selection problem and

Copyright # 2007 John Wiley & Sons, Ltd. J. Chemometrics 2006; 20: 146157 DOI: 10.1002/cem

Table I. Data set: number of samples in training and test sets, and no. of variables included in each data set

No. of samples (spectra) Data set Antasoline and naphazoline Phenol and nitrophenols Gasoline samples Wheat samples Training set 36 16 40 70 Test set 15 12 20 30 Original number of wavelengths 101 321 401 701

variate model and prediction the deleted row using the model. It should be noted that, in the case of ACO-CLS, although all of the components were predicted by the model, the PRESS was calculated just based on the interested component. In the case of ACO-PLS, to increase the run speed, n-fold CV was performed. n-fold CV is the same as LOO-CV except that n samples (or rows) is deleted from the training set. To do this, the training set was separated into n (usually set to 10) deletion groups of samples, the model was performed with n-1 groups, and the concentration of the samples in the left out group was predicted. This procedure was repeated n times so that each deletion group has been left out once, as in usual cross-validation method. In all cases, the number of PLS factors was xed to that obtained from PLS analysis of full spectral data. It should be noted that, during the running all the ACO algorithms, PRESS was calculated based on Equation (1), whereas, for better showing the results in all following Tables, mean of sum of square errors of CV (MSSE-CV) and mean of sum of square errors of prediction (MSSEP) were used (Equation 7).

N P

The UV absorbance spectra of mixtures of phenol and its three mononitro isomers were obtained from our previous experiment [30]. The UV-Vis spectra of the mixtures of four phenol derivatives have been recorded between 200 and 520 nm and digitised in 1 nm intervals (321 wavelengths). The data set was composed of 16 training mixtures and 12 mixtures in the test set. The spectra of pure components and those of training set are shown in Figure 3.

NIR spectra of gasoline samples with specied octane numbers, recorded from 900 to 1700 nm with a 2 nm-step (401 wavelengths), have been reported by Kalivas in 1997 [31]. This data set made available on the Internet by J. H. Kalivas [32]. They consisted of 60 spectra of the gasoline samples. These data were partitioned to training and test sets with size of 40 and 20, respectively, by a method termed as SPXY (sample set partitioning based on joint x-y distances) which is described in Reference [33]. The corresponding spectra are shown in Figure 4.

^i xi 2 x N (8)

MSSE

i1

^i is the predicted concentration of interested where x component in ith mixture, xi is real concentration, and N is the number of samples. It should be noted that in the case of crossvalidation (MSSE-CV), in Equation (7), the real concentrations are those of training set and the predicted concentrations are those calculated by cross-validation procedure. While, MSSEP is calculated from Equation (7) by using the real and predicted concentrations for the test set. Home-made programs for ACO-ILS, ACO-CLS and ACO-PLS, written in MATLAB (version 7, Math Work, Inc.) environment, were used. The PLS program was adopted from that reported by Brereton [29]. A Pentium IV PC computer with Windows XP operating system was used throughout.

Experimental NIR data set of real samples of wheat made available on the Internet by J. H. Kalivas [32]. The data set contained 100 spectra of wheat grain samples with specied moisture and protein content measured by diffuse reectance from 1100 to 2500 nm in 2 nm intervals (701 wavelengths). Of these spectra, 70 were utilised for a training set and 40 for a test set, the choice of which were done by the SPXY method [33]. The spectra of calibration set are shown in Figure 5.

3.2. Data set 1 (UV data of antasoline and naphazoline mixtures) [14]

In the process of net analyte signal-based simultaneous determination of antazoline and naphazoline, we have recently reported the UV spectra of mixtures of their binary mixtures, recorded from 225 to 325 nm with a step of 1 nm (101 wavelengths) [14]. The test and training sets used in the present study contained 15 and 36 spectra of the abovementioned binary mixtures, respectively. The spectra of pure

Copyright # 2007 John Wiley & Sons, Ltd.

The rst data set contains the UV spectra of mixtures of antazoline and naphazoline drugs as shown in Figure 1, consisting of 101 absorbance readings between 225 and 325 nm in 1.0 nm internals. Thus, each ant in each ACO had 101 elements. As it is discussed in the theory section, to set optimised values to a, r and f parameters, a 3-levels full factorial

J. Chemometrics 2006; 20: 146157 DOI: 10.1002/cem

Figure 2. UV spectra of pure antazoline (1) and naphazoline (2) and selected wavelengths from various ACO algorithms. Inset: UV spectra of calibration set. The two boxes show about 90% of wavelengths selected by ACO-PLS in 16 run.

Figure 4. NIR spectra of gasoline samples, and selected wavelengths from various ACO algorithms.

Figure 3. UV/Vis spectra of pure phenol (1), o-nitrophenol (2), m-nitrophenol (3) and p-nitrophenol (4). Only the selected wavelengths for o-nitrophenol with various ACO algorithms are included. Inset: spectra of calibration set.

Copyright # 2007 John Wiley & Sons, Ltd.

experimental design involving these parameters was chosen and for each conguration, the ACO-CLS was run ve times for selection of the best subset of wavelengths for determination of naphazoline (component 2). It should be emphasised that the experimental design was employed just for obtaining the most likely conguration in nding the

J. Chemometrics 2006; 20: 146157 DOI: 10.1002/cem

Table II. Results of ACO in 27 experiments according to a three-level full factorial design (data set 1)

No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 a 0.3 0.5 0.8 0.3 0.5 0.8 0.3 0.5 0.8 0.3 0.5 0.8 0.3 0.5 0.8 0.3 0.5 0.8 0.3 0.5 0.8 0.3 0.5 0.8 0.3 0.5 0.8 r 0.3 0.3 0.3 0.5 0.5 0.5 0.8 0.8 0.8 0.3 0.3 0.3 0.5 0.5 0.5 0.8 0.8 0.8 0.3 0.3 0.3 0.5 0.5 0.5 0.8 0.8 0.8 f 25 25 25 25 25 25 25 25 25 50 50 50 50 50 50 50 50 50 101 101 101 101 101 101 101 101 101 SD of PRESS 69.15 2.37 859.02 16.68 1.81 2.99 686.85 1.07 8.67 2.08 1.23 1.68 3.17 1.25 4.22 4.20 2.33 1.33 2.63 1.53 2.18 1.23 1.76 2.18 1.56 1.44 0.73 Mean of PRESS 45.62 13.98 403.72 20.85 13.45 12.98 333.36 13.01 17.02 13.50 12.55 12.67 13.25 11.85 16.57 15.62 15.29 11.82 14.34 12.04 13.11 11.88 11.43 12.13 12.65 12.09 11.75

Figure 5. NIR spectra for wheat samples, and selected wavelengths from various ACO algorithms.

global optimum, and not for tting of the responses according to an assumed model. The criteria for optimisation included the average and standard deviation of PRESS of 50% of the best ants in each ACO-CLS run. The results obtained from the factorial design process for naphazoline (component 2) are summarised in Table II. As can be seen, the global solution was obtained at experiment number 27, where a, r and f values are 0.8, 0.8 and 101, respectively. Similar results were found for the other data sets. Therefore, these optimum values were used for the entire feature ACO running. It should be noted that, in all cases, setting a and r was also checked with the aid of bar diagram of pheromone

concentration; the results conrmed the remaining of ACO in the exploration phase (at least during the rst 50 iterations). As it is obvious from Table II, the worst results were associated with the lowest f values (i.e. 25), especially for the cases where the a/r (or r/a) ratio was high (e.g. Nos. 3 and 7). In Figure 6A is shown the variation of the PRESS of the best ant, as obtained by ACO-CLS, as a function of number of iterations. As is obvious, the graph emphasises the fast evolution of the ACO to nd the best solution for the system. To show the comparative evolution of other ants, the averaged PRESS for 50% of the best ants, fbest, in each loop (Figure 6B) as well as the standard deviation of the corresponding PRESS values (Figure 6C) are also plotted against the number of iterations. The results show that the performances of the ants are getting closer, as the number of iterations increased. Indeed, at the end of ACO, a population of ants with relatively similar performances is obtained (Figure 6C). The terminating criterion was to obtain ants with relatively equal PRESS. However, because of the colinearity between the neighbouring wavelengths, the ants in nal colony should not necessarily have similar wavelengths.

Figure 6. (A) PRESS of the best ant in each loop, (B) mean of PRESS values for fbest in each loop, and (C) standard deviation of PRESS values for fbest in each loop.

Copyright # 2007 John Wiley & Sons, Ltd. J. Chemometrics 2006; 20: 146157 DOI: 10.1002/cem

Table III. Data set 1. Results obtained from data set 1 in various models

Component Antazoline Naphazoline Error MSSE-CV MSSEP MSSE-CV MSSEP ACO-ILS 0.0078 (30) 0.6005 0.0794(17) 1.3510 ACO-ILS(limited) 0.1025 (4) 0.2066 0.2923(3) 0.9047 ACO-CLS 0.3191(4) 0.6352 0.3534(5) 0.8007 CLStot 28.0179 31.9511 1.1961 1.8743 ACO-PLS 0.1845(20) 0.2857 0.2650(3) 0.7455 PLStot 0.5064 0.3965 0.4189 0.8231

Thus the ACO was terminated when 50% of the best ants reached to relatively the same PRESS. It was found, by preliminary experiments, that 70 iterations are enough to reach convergence. The optimisation of ACO parameters were also performed for the ILS and PLS modelling procedures, and similar results were obtained in both cases. The selected wavelengths by ACO and the corresponding MSSE-CV and MSSEP values obtained by different multivariate calibration methods (i.e. ILS, CLS and PLS) are included in Figure 2 and Table III. The proper numbers of latent variables in PLS modelling found to be 4 and 3 for antazoline and naphazoline, respectively. Inspection of the results revealed that very often the number of wavelengths selected by the algorithm is larger than the corresponding number of factors. As it is seen from the results, this event does not affect the prediction ability of the CLS and PLS modelling. This is due to the native characteristics of these models as full spectrum methods. Meanwhile, this event affected the results of ACO-ILS algorithm and caused overtting in the results. In fact, the MSSE-CV values obtained, by this algorithm, are 0.0078 and 0.0794, and the MSSEP values are 0.6005 and 1.3510 for antazoline and naphazoline, respectively. An approach for solving the overtting problem in ACO-ILS is to force the algorithm to conne the numbers of selected wavelengths to the number of PLS factors. As it is seen from Table III, the application of this approach, referred as ACO-ILS(limited), resulted in a distinct improvement in the prediction ability of the algorithm. It can be seen that, although the selected wavelengths in ACO-ILS(limited) and ACO-CLS models correspond to well-dened and characteristic spectral region, the selected wavelengths in ACO-PLS model are scattered throughout the spectrum especially in the case of antazoline response. To show the reproducibility of the algorithms, the ACO-PLS was run for 16 times for measuring naphazoline.

The selected wavelengths are shown in Figure 2 and from that it is obviously found that almost 90% of the selected wavelengths correspond to two well-dened spectral regions, one is greater than 300 nm in which antazoline has almost no absorbance and the other is between 236 and 258 nm where antazoline has little absorbance while naphazoline has maximum absorbance. RSD for MSSE-CV and MSSEP values are 8.8% and 7.8%, respectively. These results clearly indicate the reproducibility of the system via close MSSE-CV and MSSEP values and selected wavelengths for different runs. From the previous reports [11], one may be expect to achieve an improvement in the results of ACO algorithms by some pretreatments as elimination of the regions of spectra that contain no information and/or reducing the number of wavelengths by averaging two or more wavelengths. These two pretreatments were applied to this data set and ACO-PLS algorithm was run for ve times to obtain the best subset for determination of antazoline in this data set. However, the results of these pretreatments revealed no improvement in the results.

The second data set examine was the UV-Vis absorbance spectra of the quaternary mixtures of phenol and its mononitro derivatives reported in a basic medium (Figure 3) [30]. The data matrix consisted of 321 absorbance readings between 200 and 520 nm in 1.0 nm internals. The MSSE-CV and MSSEP for the best ant at the end of the ACO algorithms for simultaneous determination of phenol and its mono-nitro isomers using ACO-ILS, ACO-ILS(limited), ACO-CLS and ACO-PLS algorithms are listed in Table IV and the spectra of pure components and the selected wavelengths for component 2 (o-nitrophenol) are shown in Figure 3. The proper numbers of factors for the determination of the components 14 were found to be 5, 6, 6

Table IV. Data set 2. Results obtained from data set 2 in various models

Component Phenol o-Nitrophenol m-Nitrophenol p-Nitrophenol Mean of PRESS MSSE-CV MSSEP MSSE-CV MSSEP MSSE-CV MSSEP MSSE-CV MSSEP ACO-ILS 0.0013(13) 0.2359 0.0003(15) 5.8914 0.0065(9) 0.5706 0.0000(15) 0.1320 ACO-ILS(limited) 0.0070 (4) 0.0963 0.0058(5) 4.6162 0.0006(6) 0.0142 0.0004(8) 0.1085 ACO-CLS 0.0072(16) 0.1361 0.0064(14) 4.1338 0.0052(5) 0.0741 0.0037(7) 0.0931 CLStot 16.6213 6.4838 9.4201 3.9538 7.2914 2.2509 0.0903 0.1076 ACO-PLS 0.0060(20) 0.1436 0.0121(8) 4.3850 0.0026(19) 0.0328 0.0006(19) 0.1376 PLStot 0.0194 0.1938 1.0144 4.0523 0.0938 0.0437 0.0222 0.0914

Values in parentheses show the number of selected wavelengths. Copyright # 2007 John Wiley & Sons, Ltd. J. Chemometrics 2006; 20: 146157 DOI: 10.1002/cem

Table V. Data set 3. Results obtained from data set 3 in various models

Component Octane number Error MSSE-CV MSSEP ACO-ILS 0.0271(38) 0.6747 ACO-ILS(limited) 0.0545(4) 0.0426 ACO-CLS 2.0450(15) 1.5778 CLStot 3.5830 2.2669 ACO-PLS 0.0345(37) 0.0392 PLStot 0.0981 0.0545

and 7, respectively. As it is seen from Figure 3, the number of selected wavelengths, out of 321, is 5 for ACO-ILS(limited), 8 for ACO-CLS and 13 for ACO-PLS. It is interesting to note that, due to a strong overlapping with other components, o-nitrophenol (component 2) shows the highest MSSEP, although its MSSE-CV is quite low. A comparison between the results obtained from the use of entire set of wavelengths (i.e. CLStot and PLStot) and those after ACO wavelength selection indicated that ILS(limited) and CLS (as simple modelling procedures) give results comparable with those obtained by PLS method.

In order to check the validity of the proposed ACO for selecting the best subset of wavelengths to other spectral region, the NIR spectra recorded over 9001700 nm (401 wavelengths) for gasoline samples of different octane numbers [31] were examined. A numbers of 100 ants were chosen for this data set. Figure 4 shows the selected wavelengths in various algorithms and the corresponding MSSE-CV and MSSEP values for the best ant after ACO process are shown in Table V. It should be noted that this data set was already used by Leardi [11] for wavelength selection using GA modelling in which he eliminated the rst hundred variables because of their low level signals. While, in our case, we applied ACO to the entire data points, and as it is seen from Figure 4, the ACO selected several wavelengths from the rst hundred variables. Meanwhile, in a separate procedure, we eliminated the rst hundred variables from the data set and applied the ACO-PLS algorithm to that. The average values of MSSE-CV and MSSEP for ve replications were equal to 0.026 and 0.147, respectively. However, the corresponding results obtained from the application of ACO-PLS to the entire data set were found to be 0.027 and 0.068, respectively. Moreover, in another experiment, PLS was applied on the only rst hundred of variables and the results revealed R-square and MSSEP values equal to 0.907 and 4.916, respectively. These observations clearly demonstrate the high ability of ACO for choosing the wavelengths that have high correlation with the independent variable (i.e. concentration). Also, by looking at the regions from which ACO-ILS(limited) and ACO-CLS

were selected wavelengths (Figure 4), one can get valuable help in understanding which parts of the spectra are the relevant to the independent variable. The regions that are selected by ACO-ILS(limited) and ACO-CLS correspond to the rst hundred variables (as discussed above), the peaks at 1150, 1200 and 1390 nm, the plateau from 1260 to 1340 nm and the shoulders at 1420 and 1650 nm. These results can be compared with reported results in Reference [11]. It should be mentioned again that ACO algorithms were not in constrain to select dened number of wavelengths. In the case of ACO-PLS, the selected wavelengths are sparse in all spectra. This is probably due to the intrinsic characteristic of PLS modelling which has a little dependency to collinearity of wavelengths and also due to the complexity of the data set. As it is seen from Table V, the prediction ability of the calibration methods used decrease in the order ACO-PLS > ACO-ILS > ACO-CLS. Interestingly, ACO-ILS showed more or less similar results to ACO-PLS, by using only four selected wavelengths. To show the reproducibility of the algorithms, the ACO-PLS was run for ve times and RSD of MSSE-CV and MSSEP values are 8.44% and 32.3%. As it is seen from this table, although the MSSE-CV values are quite close together, there are some differences between MSSEP values. It should be noted again that the main task of the algorithm dened is to reduce the MSSE-CV. Thus, if the design of samples of calibration set is not right, i.e. it does not span the entire space of calibration, the reduction of MSSE-CV will not result in a reduction in MSSEP. Table V also shown the analysis of entire data set without wavelength selection. It is clearly seen that the use of a subset of wavelengths instead of entire set of spectral range will enhance the quality of the multivariate calibration methods signicantly.

This data set is composed of the diffuse reectance NIR spectra (from 1100 to 2500 nm in 2 nm intervals) of 100 wheat grains for analysis of their moisture and protein contents (Figure 5). Number of ants for this set was chosen as 140. Figure 5 shows the selected wavelengths using various algorithms. The corresponding of MSSE-CV and MSSEP values, for entire data set and the data after ACO process, are

Table VI. Data set 4. Results obtained from data set 4 in various models

Component Protein Moisture Error MSSE-CV MSSEP MSSE-CV MSSEP ACO-ILS 0.0206(69) 6.3776 0.0001(69) 12.4480 ACO-ILS(limited) 0.2831(5) 0.3711 0.0848(6) 0.1325 ACO-CLS 1.0169(3) 0.5875 2.7372(3) 1.5198 CLStot 1.7094 1.2821 6.7170 3.6538 ACO-PLS 0.3890(4) 0.2422 0.0399(5) 0.0627 PLStot 0.6019 0.4614 0.0494 0.0707

Values in parentheses show the number of selected wavelengths. Copyright # 2007 John Wiley & Sons, Ltd. J. Chemometrics 2006; 20: 146157 DOI: 10.1002/cem

Table VII. Results obtained from data set 3, 4 by forward selection and backward elimination algorithms together with ACO-PLS

Forward selection Data Set 1 Set 4 Analyte Antazoline Naphazoline Protein Moisture MSSECV 0.2619 0.3132 0.5142 0.0431 MSSEP 0.3218 0.8146 0.8027 0.0715 WL 28 19 9 5 Backward elimination MSSECV 0.4857 0.3806 0.5957 0.0415 MSSEP 0.4134 0.8465 0.4830 0.0631 WL 27 23 423 170 MSSECV 0.1845 0.2650 0.3890 0.0399 ACO-PLS MSSEP 0.2857 0.7455 0.2422 0.0627 WL 20 3 4 5

shown in Table VI. It is surprising that ILS modelling by using only four wavelengths revealed better results for the determination of component 1 (moisture) than PLS with overall wavelengths. The number of selected wavelengths, out of 701, is very small (i.e. in the case of component 1, 5 for ACO-ILS(limited), 3 for ACO-CLS and 4 for ACO-PLS). The statistical data in Table VI indicate the superiority of ACO-ILS(limited) and ACO-PLS over the ACO-CLS method. A reduction in MSSE-CV and MSSEP values for different multivariate models can be easily found by comparing the results of analysis by the entire data and the results of ACO algorithms (Table VI). In order to get further insight into observing the ability of ACO to solve wavelength selection problem, the results of ACO-PLS were compared with those obtained from forward selection and backward elimination, as stochastic methods. In these methods, PLS modelling was performed repeatedly on the selected wavelengths by forward or backward methods. The results are listed in Table VII for data sets 1 and 4. The resulted statistical quantities reveal that improved PLS models have been obtained by wavelength selection with the stochastic methods in comparison with the case when entire set of data are employed. However, comparison with the results of ACO-PLS conrms the superiority of this method over the stochastic methods. For example, in the case of naphazoline (data set 1), the number of selected wavelengths by forward selection, backward elimination and ACO-PLS is 19, 23 and 3 whereas resulted MSSECV is 0.3132, 0.3806 and 0.2650, respectively. It is surprising that ACO-PLS with only three wavelengths produces lower MSSECV and higher prediction ability in comparison with stochastic methods. For the wheat data set, it is observed that the number of selected wavelengths by backward elimination method is very large. In the other hand, the number of selected wavelengths by forward selection method is comparable with that of ACO-PLS, however, the latter produces lower prediction errors. For example, in the case of protein, the number of selected wavelengths by forward selection and ACO-PLS is 9 and 4 whereas resulted MSSEP is 0.803 and 0.242, respectively. It should be noted that similar results were obtained for the other data sets.

by using different multivariate calibration models. The proposed algorithm was tested with four different experimental data sets involving UV, UV-Vis and NIR spectral information. Conguring of the parameters of ACO can be easily done in conjunction with an experimental design or via a trial and error process. The results of the present study clearly demonstrated the high ability of ACO for wavelength selection in various data sets. After wavelength selection, the predictive ability of the proposed model, with only a small number of wavelengths, is very often better than that obtained from full spectrum analysis. Furthermore, the ACO algorithms can be helpful in understanding which part of spectra are the relevant to the independent variable. The advantages of the proposed algorithm are as follows: i The number of iterations needed for obtaining a proper subset of wavelengths and, consequently, the time needed for this purpose, is very low. ii There is no need for reducing the original variables. The MATLAB source code of the program is available from the authors upon request.

Acknowledgements

The authors would like to thank Mr. J. Afchangi for helpful discussions and Dr. J. H. Kalivas for sharing his data sets.

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J. Chemometrics 2006; 20: 146157 DOI: 10.1002/cem

5. CONCLUSIONS

ACO, which is constructed based on the behaviour of real ants, is described as a powerful optimisation algorithm for the selection of useful wavelengths in spectroscopic analyses

Copyright # 2007 John Wiley & Sons, Ltd.

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