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REVIEW

of the Analytical Methods

by C. Rozycki

Department ofFundamentals ofChemistry, Institute ofChemistry,

Scientific and Didactic Centre of Warsaw Technical University,

09-430 Plock, Poland

A review is given of the literature on optimization of the simplex method and its

application in various branches of analytical chemistry,

W artykule dokonano przegladu literatury dotyczacej optymallzac]! metoda simpleksowa i jcj zastosowania w roznych dziedzinach chemii an~n:t:ycznej.

Optimization of a chemical system consists in sucDa selection of the system-COlitrolling variables (parameters or factors, e.g. temperature; concentration, plf) which

enable a certain state-dependent variable y to achieve the most beneficial value within

the limitations of the attainable modifications ofthe.system.

In such a case a model of the chemical system may be represented as a function

of many variables. The rcsponse y is then a value which is a characteristic of the

system. It depends on the values of the independent variables:

%:

j{x VX2,

... ,

XII)

(1)

reaction, height of an analytical signal, or minimization of an impurity component in

an analytical signal.

A classical method for selection of the optimum conditions consists in a one-fac..

tor-at-a-time optimization procedure for finding, such a value of the given factor

which can give the most profitable result of the experiment. Such a method is better

than a random search for optimum set of the factors, but other available methods can

provide more information with less labour consumption. Such a method is the Box

682

C. Rozycki

and Wilson, steepest ascent technique [1] described among others by Nalimov and

Chemova [2]. Various optimization methods have been described by Koehler [3]. For

the sake of the smallest number of experiments needed and the simplicity of calculations the best, method, used in chemical studies, is the one involving geometric

solids referred to as simplexes. The theory of the simplex method has been developed

by Spendley et al. [4]. Literature data show that the simplex method is now the most

widely used optimization method in analytical chemistry. Deming and Morgan [5]

have discussed the bases of experimental design and quoted a bibliography of 189

papers dealing with the simplex method. Moore [6] has found that 300 papers of

chemical application of the simplex method had been abstracted in Chemical Abstracts throughout the period 1966-1985. About 25 % ofthosepapers were concerned

with analytical chemistry. Among the analytical papers 40 % were devoted to

chromatography and 15 % - to emission spectrometry. Brown-er al. [7] have noticed

that Chemical Abstracts recorded 27 papers dealing with the simplex method

throughout the.period January 1976 - October 1979, 984 papers within January 1988

- November 1989, and 1078 papers within December 1989 - November 1991. TIe

attempt of the present review is to present the simplex method and its application in

analytical chemistry.

Search for optimum

Every system reacts to changes in the value of the factors (Xi) by changing the

value of y (sometimes reffered to as the response) correspoding to the given set of

values ofthe factors. A sufficiently large set of responses forms the so-called response

surface. If the number of factors is n,the response surface is (n+1)-dimensional. Such

a surface has often an extremum, which may be a point or an area. Various kinds of

the response surface occurring in the case of 2 variables are given by, among others,

Nalimov and Chernova [2] and by Long [8]. The independent variables (factors) may

be regarded as coordinate axes thatform the so-called factor space, which is n-dimensional for n factors. Every experiment is represented by a point in the factor space.

Any optimization consists in finding the coordinates (values of the factors) that

maximize or minimize the response. The definition and the study of a function given

by the relationship (1) may proceed in three steps. The first step consists in finding

the number and the kinds of independent variables Xi' In the second step the values

of independent variables determining the position of optimum of the function are to

be found, and as the third step the relationship characterizing the response surface

near the optimum is to be found. Of course, it is not always possible to distinguish

the three steps in a particular chemical study. The second step, which is an optimization step, is often done by the simplex method.

The simplex method

Deming and Morgan [9, 10] refer to the simplex as a geometric figure defined

by a number of points higher by one compared with. the number of factors (or

dimensions of the, factor space). In the two-dimensionai factor space the simplex is

a triangle. and in the three-dimensional space it is a tetrahedron. In a similiar way it

683

is possible to define simplexes in multidimensional spaces as convex hyperpolyhedra. The simplex vertex coordinates correspond to values of the factors (or parameters) Xh X2, , X m for which an appropriate experiment may be performed.

The simplex method of optimization and suitable examples of its application have

been described in a number of papers [2, 9-19]. One can find there the basic principles

of searching for an optimum by the simplex method. According to the method the

'simplex is moved in the factor space depending on the results of experiments

performed for the factor values corresponding to the simplex vertices. After having

completed experiments for all the simplex vertices the experimenter discards the

vertex corresponding to the worst experimental result. The rejected vertex is now

replaced by another one, which is its symmetrical reflection with respect to the plane

passing through the other simplex vertices. By multiple repetition of that operation

the simplex shifts gradually to the part of factor space in which the results of the

experiments improve step by step. The rules of such a movement guarantee that even

if for a new vertex the corresponding result is worse than that corresponding to the

discarded one, the movement of the simplex toward the space of optimal results

continues. The advantage of the simplex method arises from the fact, that the decision

on further step of the simplex shift is taken after each experiment, whereas in other

optimizing methods a greater number of experiments are performed before such a

decision can be taken.

There is always a possibility, that the optimum found is a local optimum. It is

impossible to establish the global optimum without knowing the functional relationship (1). An optimum is probably the global one [20] if another search beginning

from a different region of variables gives either the identical optimum position or

something very close to it. Luand Huang [21] have described a procedure that enables

to avoid the breaks in searching within a local optimum.

The simplex method for searching has, however, some disadvantages [22]. Only

in case of two factors the successive simplexes provide close packing of the space

(surface). In the case of larger number of factors it is not always possible to decide

whether a given result represents an optimum, or is only a vertex, for which the

response is better than for other vertices. In its primary version the simplex method

did not allow for acceleration of the search of optimum because of the constant size

of the simplex. It would be more reasonable to use a large simplex in the initial stage

of the search to have a possibility of quick movement in the factor space, and to

dispose a smaller simplex in the final stage for more precise localization of the

optimum. The use of a simplex of variable size might allow to avoid that inconvenience.

Modificaton of the simplex method

Modifications introduced to the simplex method have enabled to increase the

efficiency of searches for optima.

Nelder and Mead [23] have proposed a modified simplex method (the MS Modified Simplex). The modification consists in introduction of two new operations:

expansion and contraction of the simplex.

684

C. Rozycki

The contraction of the simplex involves some disadvantages: the volume of the

simplex is contracted and might give rise to premature convergence in the presence

of an error [22]. For that reason Ernest proposed, instead of contracting the simplex,

to shift it in such a manner, that the vertex corresponding to an optimum result falls

in the centre of a new simplex of identical dimensions as the former one [24]. Another

solution has been proposed by King [25]: if a vertex that was formed after the

contraction has produced a worst response, instead of it the next vertex of wrong

response should be discarded. Such a procedure was applied by Morgan and Deming

[26]. Still another solution consisting in turning the simplex has been proposed by

Burgess [27]. It has also been shown [28], that in some cases, where some factors

has no substantial effect on the optimized value, a prematural contraction of the

simplex or even the end of optimization may occur. It does not mean, however, that

such factor has an effect and that the value it has achieved is an optimum value. In

doubtful cases further experiments have to be carried out (e.g. according to experimental factor design) and the regression equation obtained should be analysed.

Izakov [29] has proposed another method for designation of a new vertex in cases

where the responses for some vertices are close to one another. In such a case two or

more vertices (instead of one) are discarded at a time thus enabling acceleration of

the simplex movement toward the optimum.

Walters and Koon [30] varied the values of coefficients determining the size of

the simplex (contraction and expansion) and applied various initial point and simplexes in the MS method in order to elucidate their effect on the optimization process.

After showing that some modifications of the simplex method are not always

confirmed in practice Routh et al. [31] proposed, a Super Modified Simplex (the SMS

method). The position of a successive simplex vertex is determined from the reponse

value of a discarded vertex, reflection of the discarded vertex, and gravity center of

the nondiscarded vertices (centroid). The values of responses in these three points

are used for calculating the equation of the polynomial of the second order (a

parabola). After having found the extremum of that polynomial for the range of

independent variable values extrapolated outside the discarded vertex and its reflection, it is possible to determine the position of the new vertex. The new simplex vertex

is either a point corresponding to an extremum (inside the range of variables under

consideration) or at a border of the range of variables. The interval of extrapolation

of the range of variables is chosen depending on the value of the first derivative of

the polynomial. In the super modification proposed, the authors have foreseen also

suitable procedures protecting from too early coming together of the simplex vertices,

that might simulate attaining the optimum. In cases where the simplex becomes

displaced outside the admissible factor space the new vertex is placed at the border

of this space.

Van der Wiel has described [32] further modifications of the SMS method, since

the increase of difficulty of calculations involved with the modifications presents no

more problems and the economy of time due to decrease of the number of experiments

needed is of primary importance. He has proposed three procedures for improving

the SMS method. They were based on finding the new vertex by either adjusting the

Gauss curve to three response values: the worst vertex, the centroid, and the last

685

vertex, or by the use of the weighted method for calculation of coordinates of the new

vertex, or by finally calculating the response for the new vertex instead of performing

an experiment. Still another modification of the MS method has been proposed by

Ryan et al. [33]. In this method the new simplex vertex is determined from the

discarded vertex and the so-called weighted centroid. The position of the weighted

centroid depends on the interrelation of differences of response in individual simplex

vertices and in the discarded vertex. To avoid a possible occurrence of simplex

"degeneration" into an unidimensional simplex (only one variable influences substantially the responses) two versions of the procedure have been proposed.

Also Betteridge et al. [34] have proposed two modified algorithms for searching

the optimum by the simplex method and have verified them for selected mathematical

functions and for analytical methods. In. these algorithms the position of the new

simplex vertex is determined by means of the weighted centroid and the Lagrange

interpolation. A method proposed by Routh et ale [31] has been modified [35] by

giving up the experiment in the simplex centroid and replacing its result by the mean

of non-discarded simplex vertices; criteria enabling the comparison of different

versions of simplex optimization have also been proposed. Ilinko and Katsev [36]

also determined the position of the new simplex vertex from the weighted centroid

and compared this method with the common simplex method. Cave and Forshaw [37]

have adapted the simplex method for cases, where the time of setting the equilibrium

before measurement is very long; in order to reduce the time of studies they

recommend to carry out experiments for several vertices at the same time.

King and Deming [38] have described an optimization method called UNIPLEX

which is a one-factor variant of the NeIder-Mead modification.

Shao [39] has developed a modification of the simplex method which introduces,

i.a., a relation between the initial size ofthe simplex and the number ofvariables and

the size of the search space. In the case of many variables the convergency of this

modification is higher than that of the NeIder-Mead method (but not for complicated

response surfaces).

For more rapid attainment of the optimum and avoiding premature diminition of

the simplex in the Nelder-Mead method, it has been proposed that the whole simplex

is shifted parallelly [40].

Modifications of the simplex method have also been described in papers [41,42].

The described modifications have been compared [33, 34] by simulating the

results of experiments. It has been shown, that they allow to reduce considerably the

number of experiments needed to achieve the optimum. The progress of the optimization process depends, however, also on the position of the starting simplex, the

shape of the response surface, and the aim of the optimization (attainment of optimum

area or localization of the optimum position). Various modifications of the simplex

method have been compared in [35]. The conclusions from that comparison are not

univocal: the rate of attaining the optimum of the given function depends on the

algorithm applied and the response surface. Gustavsson et al. [43-45] have compared

various modifications of the simplex method for simulated experimental results, but

also in this case it is difficult to say, which of the modifications considered is the best.

It seems even, that in some cases theyhave no priority over the MS method.

686

C. Rozycki

In a number of works [46-58] the simplex optimization has been compared with

other optimizing methods. As shown in [47], optimization of the spectrophotometric

method by flow injection procedure with four variables required 88 measurements at

separate treatment of each variable, and 34 measurements with the simplex optimization. For five variables the corresponding numbers are 168 and 37. Optimum

conditions for chromatographic determination of carboxylic acids [55] were identical

in the case of the simplex method and the central composite design (in the latter case

the greater cost of labour gave also a mathematical description of the response

surface). The grid and the simplex methods have been compared in [56]. Fora number

of variables lower than 4 the grid method has been recommended, since it enables,

i.a., a graphical representation of the response surface. A comparison has also been

made [59, 60] between the simplex method and the Powell method. Although in that

case (two factors) the Powell method needed less experiments, no definite statement

in favour of one or another method has been made. Five different optimization

methods have been compared [58] for simulated data: the genetic algoritlnn was

better than other methods in the case, where the response surface comprised the global

maximum, two large local maxima, and some smaller local maxima. For such cases

Kalivas [61, 62] has proposed to effect optimization by the simulated annealing

method.

The history of the simplex optimization and relationships between various

modifications of the method have been described by Betteridge et al. [34].

Realization of" the simplex method

Numerous papers [4, 12, 17, 34,52, 63,64] include a flow diagram showing the

logic of simplex method. Berridge [64] has discussed realization of the simplex

method by means of a microcomputer. This problem has been touched also in [44],

where various versions of the simplex method are compared. Monographs [65, 66]

and some papers [67-71] include programs for searching the extrema of mathematical

functions by the simplex method. An algorithm for rapid calculation of a new simplex

vertex in cases of large number of factors (about 60) has been described [72]. In the

market there are offers of programs assisting optimization by the simplex method,

and even special equipment adapted for simplex optimizing of chromatographic

columns [73]. A special spreadsheet [30] is useful in performing calculations by the

simplex method.

King et al. [74] have discussed the difficulties and the errors occurring in the

course of optimization by the simplex method.

Combining the simplex method with the factor design permits to reduce the

number of measurements needed (as compared with the simplex method alone) [75, 76].

Quantity to be optimized

The selection of the quantity to be optimized (the response) depends directly on

the problem formulation. This can be, for example, the yield of reaction, absorbance,

stability of solution. Sometimes the experiments provide joint information on several

Quantities. In such cases the most important Quantity should be optimized. All the

687

other quantities may serve, if this is needed, for correcting the position of the optimum

with respect to the position determined only for the main quantity optimized. A

method for simultaneous optimization of several quantities has recently been proposed [77, 78]. The criteria applied in simultaneous optimization of several features

of chromatograms have been discussed in a number of papers [21,52, 79-85].

In fitting theoretical curves to experimental data [86] the optimized value was a

criterion evaluating the quality of the fitting (the criterion of the nonlinear least

squares method).

The course of the simplex optimization depends [78] on the choice of the

optimized value.

Selecting the factors

To avoid excessive complication of experiments only the most important factors

should be tested. The importance of a factor is determined by comparing the changes

in the response caused by a change in level of each of the factors prior to the

knowledge of the system or upon preliminary experiments. The selection depends on

experience of the experimenter or on the results of preliminary experiments. But

Deming and Morgan [9, 10] did not find any disadvantageous effect of including

factors of smaller importance on the movement of the simplex, although they can

possibly lead to premature diminishing of the simplex in modification of the simplex

method [28].

The selection of the factors can be. done by using the factorial design method,

especially the fractional factor design method [87, 88], and the methods of planning

screening experiments [2, 11]. Examples of such use of factorial planning are given

in [89-91]. The estimation of the effect of a given factor on the results depends also

on the range of its values taken for the tests. Sometimes, if the range has been

improperly selected, it may lead to omitting some important factors, as the results

are close to each other. For that reason it is usually more disadventageous to include

in the study some less important factors than to neglect an important one [92]. There

is a possibility of increasing the number of factors at any stage of the optimization

process [2, 11].

The amount of the component determined and the volume of the analysed solution

cannot serve as the factors. It was shown [22, 93] that that condition had not been

satisfied in some works.

Selecting the range of the factors

It is important to select for each factor an appropriate difference of values (step

size) to be accepted in individual vertices of the initial simplex. The selection is made

arbitrarily but it is better to do it in such a way that the effect of each factor on the

response value is similar to each other. Otherwise an apparent decrease of the number

of important factors may occur. It has been proposed [92] to select a step size that is

inversely proportional to the expected value of its influence on the response.

It is advisable tobegin the search for an optimum with a large simplex (large step

size of individual factors), as the effect of the factor should then exceed the value of

688

c. Rozycki

the experimental error [92]. A small effect of one of the factors, as compared with

that of the other factors, may arise from selection of its value near to the optimum

searched, independence of the system of that factor, or too small difference of values

of that factor in simplex vertices.

In the literature on the simplex method there are two ways of determining the

value of the factors. The most frequently applied method consists in using variables

determined in physical units, such as C, Pa, or units of concentration. In another

method the values of the factors are expressed as normalized values. This system is

easier for the purpose of presentation of the theory of the simplex method [2, 8, 11, 13].

These papers include also formulas and tables of normalized variable values for any

number of the factors. The normalized values can easily be scaled for values

expressed in natural units.

Constraints of the simplex method

The response surface is confined to such boundaries of variables, which result

from physico-chemical conditions, e.g. aggregation state, concentrations (within the

range of solubility), etc. The admissible range of the factors may be defined as the

experimental region. If the vertex of a simplex moves outside this region the

realization of the experiment becomes impossible. The simplest solution to this

problem is to assign a very bad result to the unrealizable experiment and to continue

the search for the optimum. An alternative procedure to be used in cases where

simplex shifts outside the admissible region was described by Van der Wiel et al.

[94]. Cave has proposed [95] a procedure in which an experiment is done for a vertex

shifted to the border of the region of variables. The usability of such a procedure has

been checked using simulated results.

Initial simplex

The position of the initial simplex is determined from preliminary experiments.

The coordinates of the vertices may be calculated from the step size of individual

factors and from the initial point selected in the factor space.

Yarboro and Deming [92] have discussed, i.a., the problems connected with

determination of the size of the initial simplex. It depends on the expected results of

the experiments corresponding to particular vertices of the selected simplex.

End of search

The search for optimum by the simplex method ends after a certain value of an

accepted criterion has been reached (e.g. the range of values of individual variables

differs less than 1 % of the range in the initial simplex; the yield of the reaction

reaches a value considered to be optimim by the experimenter; the variance of the

measurements for simplex vertices becomes equal to the variance of the measurements [10]). In the work [40] the search for a minimum was completed when the

value of the response in three successive simplexes was lower than a predetermined

value. In the work [90] the search for optimum was ended when the differences in

689

response in vertices of the final simplex were small and one of the vertices occurred

in five successive simplexes.

An algorithm has been proposed [94] for controlling the shape of the simplex (in

fact its symmetry) to avoid its premature contraction and thus ending the search for

the optimum. Other solutions of the problem has been given in [33].

Surface response

After having ended the optimization process by means of the simplex method,

some authors [26, 96-98] applied the factorial experiment design and canonical

analysis of the regression equation for description of the surface response in the

optimum area and for more precise localization of the. optimum of the analysed

system [2, 11]. The reader can also find a description of the transition from a set of

simplex vertices to factorial experiment design enabling the determination of the

second order regression equation [4]. In this way it is possible to acquire the

description of the surface response in the form of a regression equation and a

statistical analysis of this equation.

Applications

The following review of applications of the simplex method concerns not only

the determining of optimum conditions for performninganalyses and measunnents,

but also the selection of parameters that describe the functional relationships, solving

systems of equations, and other problems.

Turoff and Deming [96] have described the optimization of the extraction method

of isolation of iron (III) by means of hexafluoroacetyloacetone and tri-a-butyl phosphate for four variables. After having defined the optimum, they have achieved the

description of the optimum area with a polynomial of the second order by means of

. a composite design. The simplex method was used by McDevitt and Barker to

determine the optimum conditions of copper extraction with acetylacetone and

8-hydroxyquinoline (3 factors were optimized) [99].

Harper et al. have determined optimum conditions for an ultrasonic method of

separation of 13 metals from atmospheric dust deposited on a filter [100].

Michalowskiet al. have used the simplex method for optimization of gravimetric

determination of zinc in the form of 8-hydroxyquinoline complex [101].

Meuss et al. applied the simplex method for optimization of the conditions of

zinc titration with potassium ferrocyanide [102]; the conditions thus established

enabled for more precise determination of zinc than other variants of the titration

method. The simplex method was used by Aggeryd and Olin to determine the end

point of titration [103]. Using the relationship between the titrant volume and the

concentration of H+ cations they have determined the experimental parameter 11-, the

dissociation constantKw and the titrant volume in the endpoint Ve . This method was

also used for determining the number of carboxymethyl groups per glucose unit in

carboxymethylcellulose.

The simplex method was applied for determining the equivalence point of

sigmoidal and segment titration curves [86].

690

c. Rozycki

Booksh et al. have described the use of the Monte Carlo method and simplex

optimization for forecasting the precision of results and selection of points of

potentiometric curve for determining the equivalent mass with minimum error [104].

Hanatey et al. [105] have proposed that the simplex method is applied for

determining the mechanism of the electrochemical process. Wade described the

optimization of polarographic methods [106]. The work [107] has been devoted to

optimization of the amperometric determination of glucose by the flow injection

method. The working conditions of enzymatic electrodes were optimized [108, 109],

and the use of the simplex method for evaluation of voltammetric curve parameters

have been described [54]. The simplex method of optimization has been applied to

nonlinear calibration of ion selective electrode array applied for determination of

Na(I), K(I), and Ca(ll) [110, 111]. The method was also applied [112] for determination of the standard rate constant and the charge transfer coefficient in the case 'of

quasi-reversible electron transfer in an electrode process.

The simplex method was applied [40] for identification and determination of

components of mixtures on the basis of UV-VIS spectra by comparing the obtained

spectrum with spectra from data base containing La. spectra of the components

(dyestuffs and drugs) likely to occur in the mixture.

Vanroelen et al. [90] have optimized the determination of phosphates via molybdenum blue. Basing on an experimental design of the type 33, (three factors and

three levels; 27 experiments repeated three times) they have identified the important

factors, and determined their interaction and approximate range of the optimum

conditions. Then they applied the simplex method (3 factors, 19 experiments) and

obtained an about five-fold increase of absorbance.

Spectrophotometric determination 0 f phosphate by the flow injection method was

optimized by Janse et al. [89], and Vacha and Strouhal applied the method for

optimizing the determination of samarium with chlorophosphonazo III [113]. Betteridge et al. applied the simplex method for optimization of the absorbance measured

for the reaction of PAR with the Mn04 anion, for 4 factors [34], for spectrophotometric determination of isoprenaline [47], and for extraction and spectrophotometric

determination of U(VI) with PAN by the flow injection method, for 12 factors [34].

The method was used for optimizing the determination of aluminium with Chromazurol S [37], cholesterol in blood plasma [10], dibenzyl sulfoxide [88], and formaldehyde (with chromotropic acid) [93]. Kleeman and Bailey have determined, by the

simplex method, the conditions for maximum absorption by hydrocortizone solutions (5 factors) [114].

The simplex method was applied for simultaneous determination of organic

complexes of: La, Pr, Nd, Ce, and Sm (VIS spectrum) [115], and of organic compounds (UV-VIS spectrum) [40].

Leggett [48] has described the use of simplex method and the least squares

method for determining the composition of a mixture of indicators by solving a

system of equations based on spectrophotometric measurements.

Wilx and Brown applied the simplex optimization of the Kalman filter for

determination of a known component in presence on unknown ones (or with a matrix

effect) from an UV or VIS spectra [116].

691

of aluminium [117].

The simplex method was utilized [56, 60, 106,109, 118, 119] for establishing the

determination conditions in flow injection analysis, i.a., of ammonium ion [59],

Fe(III) and Fe(II) in solutions [120], glucose [107, 108, 121], isoprenaline [34,47,

122], hydroxylamine [123], chlorohexadine (by turbidimetric method) [124], ni-.

trogencompounds after enzymatic reduction to ammonium ion [91], uranium(VI)

[34], and tetracyclin group antibiotics [125].

The possibility of using the simplex method for optimization of the kinetic

method of determination of Mo(VI) [126] and Cu(II) [127] has been discussed. The

parameters of kinetic curves used in photometric determination of Mn(II) and Pb(II)

were also determined [128] with the use of the simplex method.

Stieg and Nieman have described the simplex optimization of the determination

of Co(II) and Ag(I) by chemiluminescence in presence of gallic acid and HZ02 [129];

3 variables were optimized. Guo described the use of the. simplex method for

determining the optimum conditions of chemiluminescence method [77].

Mauro and Delaney [130] have described a method for identification of the

components of an IR spectrum using it. simplex optimizationIfor an unresolved

chromatographic peak).'

In an extensive work, Morgan and Deming have shown the possibility of the

simplex method in optimization of the peak resolution in gas chromatography [26].

They have analysed the effect of two factors: temperature and gas flow rate (without

and with a 30 min limit for the separation time for two-; three-, and five-component

mixtures of octane isomers. In the latter case the optimum area has been attained in

the 21st experiment. The optimum area has been described with the use of the second

order regression equations determined on the basis of the fractional design of factorial

experiments of the type 32 (two factors and 3 levels). In the work [83], a description

has 'been given of the use of a joint criterion for evaluation of chromatograms (basing

on the extent of separation, number of peaks, and duration of the analysis) in simplex

optimization. Another criterion for evaluation of gas chromatograms has been discussed in [84]. An additional reduction of the number of experiments has been

achieved [75, 76] by simultaneous use of the factorial design and the. simplex

optimization for separation of a mixture of ten components. The application of the

simplex method togas chromatography has been described in papers [84, 131-134].

The application of the simplex optimization to HPLC separations has been

described in many papers [57, 64, 73,76,80,135-140]. Berridge [141] and Burton

[142] have published reviews on the use of the simplex method in high pressure liquid

chromatography.

The simplex optimization has been applied for chromatographir studies of fruit

juices [143], scent compounds [144], phospholipids [142], plan' extracts [145],

amino acids [80], 12 polychlorinated biphenyls congeners [146, 147], and other

compounds (antipyretis) [82]. The paper [52] presents the elaboration on the separation of nucleotides by adsorption chromatography or by reversed-phase partition

chromatography. Carboxylic acids were determined in wine [55] on the basis of the

sum of the peak surfaces under optimum conditions found by the simplex method or

692

C. Rozycki

by the factorial design. Use of the factorial design followed by the simplex method

can reduce (76] the number of experiments needed to achieve the optimum (as

compared with the simplex method alone). Thus, in the paper [148], the factorial

design.was used for selecting the variables, for which the conditions of determination

of polycyclic aromatic hydrocarbons by gas chromatography were then determined

by the-simplex method.

The-optimization in thin-layer chromatography has been described also [85, 149].

Blanco applied that method jointly with the factorial design [149], and Howard and

Boenicke have described the optimization criterion applied [85].

The separation of ion mixtures on ion exchange resins has been optimized by

Smits et al, {ISO]. To avoid the effect of the ammonium ion on the determination of

trace amounts of chlorides or sulfates, Balconi and Sigon [151] applied the NelderMeadmethod (MS) for optimization of the working conditions of the ion exchange

column.which depended on two variables (concentrations of NaOH and NaHC0 3 ) .

The simplex method was applied for optimizing the separation of Cl-, F", N03',

SO~~.Olfthe ion exchange resins [152].

The PREOPT program, which is described in [153], permits to obtain preliminary determination of the optimum conditions for chromatographic separation on the

basis of a theoretical model, the simplex method, and the data on the retention time.

The program was applied to the literature data, and the results of the calculations

have to be checked experimentally.

Berridge has discussed the problems of automatic optimization of liquid chromatOg1:J[>:hy with particular consideration of the simplex method [73]. It has been shown

that.the rcarc available at least two automatic devices that enable the optimization by

thc;.simpJex method (TAMED, Laboratory Data Control, and SUMMIT, Brucker

Spcetrospin),

1l.lre use of the simplex optimization to atomic absorption spectroscopy has been

diseussed [154].

Parker et al, have described the simplex optimization of atomic absorption

det'qnninations for five variables [28]. The determination of arsenic and selenium in

theform of hydrides by atomic emission spectroscopy was optimized by Parker et al.

[911;Pycn et al. [155], and Sneddon [156]. Cullaj (Albania) optimized the working

pararuetcrs of the burner in a method of calcium determination [157]. The simplex

method was used in the optimization of determination of Co, Fe, Mn, and Ni in glasses

by atomic absorption [53]. In the work [158], the Iactorial design followed by the

simplex method was used for optimization of mercury determination by the cold

vapour method.

Also the conditions of determination with use of an inductively coupled plasma

emission spectrometer [35, 50, 51, 159-168] or capacitively coupled microwave

plasma [87] were optimized by the simplex method. Pb, AI, Na or Ca were determined

[5l).ln these works the measured signal was maximized or the signal to background

ratio or other essential signal-influencing factors were optimized (for 2-5 factors).

Thesimplex method was utilized [169] for optimization of the working conditions

of plasma source applied in atomic emission spectrometry.

693

spectrometry have been published by Moore [6J, Burton [142J and Golightly and Lear

(the ICP-AES method) [170J.

Jablonsky et at. applied the simplex method of optimization for selection of the

excitation conditions in determinations by X-ray fluorescence [46]. The obtained

results were compared with the excitation conditions proposed by a group of experts.

Fiori et at. applied the simplex method for selecting the parameters of the overlapping

Gauss bands and determination of the area of the bands obtained in X-ray fluorescence spectra [63]. Shew and Olsen combined the simulated annealing and the

simplex method for determining the parameters of the bi-cxpoucutial function describing the fluorescence process [171].

Basing on a model of predicted spectrum in activation analysis, Burgess and

Hayumbu determined the optimum analytical conditions for four parameters: sample

size, duration of exposure, cooling time, and decay time, which determine the

spectrum [1721. Davydov and Naumov optimized the activation determination of

many elements [173].

Krause and Lou applied the simplex method for optimization of the conditions

of clinic analyses [174].

The simplex optimization was also applied in mass spectrometry [115, 176].

Evans and Caruso applied the simplex optimization for elimination of nonspectroscopic interferences in the mass spectrometry involving inductively coupled plasma

[177]. The simplex method was also used for determining the conditions enabling to

eliminate the effect of chlorides on the results obtained in mass spectrometry [178].

Shavers et at. 1179], Leggett [12J, and Stieg (180] have proposed to include a

special training of the simplex optimization of analytical methods (spectrophotometry, gas chromatography, and atomic absorption spectrometry) to the programme

of the university studies in chemistry.

Taule and Cassas [181 J have proposed to use the simplex method for determining

the maximum or the minimum equilibrium concentration of a given chemical form

basing on the equilibrium constants, the analytical concentration, and pH of the

solution.

Rutledge and Ducause, basing on the simplex conception have developed a

method for determining the linear range of detectors [182].

An interesting and different group of papers are those devoted to the usc of the

simplex method for the other purposes. Some papers [183-185] deal with a possibility

of using the simplex method for selecting parameters of non-linear equations. The

method presented in [184] has been discussed in papers [186, 187]. The work [188]

compares the results obtained in selecting the parameters of the Arrhenius equation

by different methods including the simplex method. This method can also be used

for finding a non-linear equation which fits best to experimental results [189). Akitt

[190] has described a method for selecting the parameters of the overlapped lines in

NMR spectrum; the criterion of quality of the spectrum was optimized by the simplex

method. A solution of a similar problem with chromatographic peaks has been

described by Tomas and Sabate (191). Danielson and Malmquist basing on a local

linear model, have described the use ofsimplcxes to interpolation and calculation of

694

C. Rozycki

of the simplex method was also applied for determination of absolute rate constans

of racemization of amino acids [193].

The problems arising from the use of the simplex method for determination of

the extremums of various functions have been discussed in several papers [67-71].

Optimization by the simplex method has also been proposed for determination

of the discrimination function in the pattern recognition (mass spectra were used for

distinguishing 11 functional groups in organic compounds) [194]. Wilkins et al.

[195-197] have utilized the simplex optimization for determining the parametrs of

the discriminant functions in classification of mass and NMR spectra by pattern

recognition.

Lochmueller et al. have discussed the use of the simplex method in automatic

analytical devices [198].

The simplex method enables the automatic fOCUSSIng of an ion beam [199].

Examples of the use of the simplex method for increasing the yield of a chemical

reaction are given in [200, 201].

The simplex method may also be used for optimization of the Kalman filter

[116, 202].

.

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9

201. Bicking M. K L. and Adinolfe N. A,J. 'Chromatogn Sci., 23, 348 (1985); Chem. Abstr., 1".:3,16578 J{

(1985).

202. Rutan S. C. and Brown S. D.,Anal. Chim. Acta, 167,39 (1985).

AcceptedJune 1993

ADDITIONAL REFERENCES

General:

Bezegh A, Magy. Kem. Foly, 96, 522 (1990); Chem. Abstr., 118, 115679a (1993).

Plonvier J. Ch., Corkan L. A and Lindsey J. S., Chemom. Intell. Lab, Syst., 17, 75 (1992).

Titrimetric methods:

Lim Ho Jin, Lae Mang Ho and Kim In Whan,PunsokKwahak, 1, 179 (198,8);Chem.Abstr., 118, la;z3:1 8V

(1993).

PIA - spectrophotometry:

Sultan S. M. and Suliman E E. a., Anal. Sci., 8, 841 (1992).

Electrochemical methods:

Oduza C. E, Chemom. Intell. Lab. Syst., 17, 243 (1992).

Chromatographic methods:

.

Rakotomanga S., Baillet A, and Pellerin E,J. Pharm. Biomed.Anal.,lO, 587 (1992).

Palasota J. A, Leonodou 1, Palasota J. M., Chang H. and Deming'S, N.,Anal. Chim.Acta, 270, 101 (1~2)

Haernaelaeinen M. D., Liang Y., Kvalheim a. M. and Andersson R.,Ana/. Chlm. Acta, 271, 101 (19~2)' .

)

Curve fitting:

Glab S., {(oncki R. and Holona I.,Analyst, 117, 1671 (1992).

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