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Solution by FTIR/ATR Spectroscopy

Jiemei Chen1, Lingling Wu1,2, Tao Pan2,*, Jun Xie2, Huazhou Chen2,3

2

1

Department of Biological Engineering, Jinan University, Guangzhou 510632, P.R.China

Key Laboratory of Optoelectronic Information and Sensing Technologies of Guangdong Higher Educational Institutes (Jinan

University), Guangzhou 510632, P.R.China

3

Department of Mathematics, Shanghai University, Shanghai 200444, P.R.China

*tpan@jnu.edu.cn

aqueous solution was established by using the FTIR/ATR

spectroscopy, partial least squares (PLS) regression and SavitzkyGolay (SG) smoothing method. Based on the prediction effect of the

optimal single wavenumber model, calibration set and prediction set

were divided. By extending the number of smoothing points and the

degree of polynomial, 483 smooth modes were calculated. The PLS

models corresponding to all combinations of 483 SG smoothing

modes and 1-40 PLS factor were established respectively. The

optimal smoothing parameters were the first order derivative

smoothing, 5 or 6 degree polynomial, 63 smoothing points, the

optimal PLS factor, root mean squared error of predication

(RMSEP), correlation coefficient of predication (RP) and relative

root mean squared error of predication (RRMSEP) were 3, 0.3729

(mmol/L), 0.9995 and 2.48% respectively, which was obviously

superior to the direct PLS model without SG smoothing and the

optimal SG smoothing model within 25 smoothing points (the

original smoothing method). This demonstrates that the extending of

SG smoothing modes and large-scale simultaneous optimization

selection of SG smoothing parameters and PLS factor was all very

necessary, and can be effectively applied to the model optimization

of FTIR/ATR spectroscopy analysis.

Keywords-Glucose solution; FTIR/ATR spectroscopy analysis;

partial least squares; Savitzky-Golay smoothing

I.

INTRODUCTION

significant life information can be gotten by detection of

glucose concentration in the living system. Routine

measurement method of glucose concentration always needs

chemical reagents, and its not an effective method because of

possible damaging to the living system.

Fourier transform infrared spectroscopy (FTIR) and

attenuated total reflection (ATR) technology are effective

determination methods for structure and content of

components[1]. And they could be used nondestructive

quantitative analysis of online, real-time and in situ which no

chemical reagents. The FTIR/ATR spectroscopy technique

had been extensive applied to the analysis of agricultural

product and food[2], fermentation process monitoring[3],

and many other fields.

In order to establish the quantitative analysis method of

glucose in life system, in this paper, a quantification method

of glucose in aqueous solution was first development by

FTIR/ATR spectroscopy. And the glucose concentrations in

aqueous solution samples were prepared according to the

glucose concentration range in human or animal blood.

Partial least squares (PLS) was a classical effective

chemometrics method which was used widely in spectroscopy

analysis[7-11]. The PLS factor is an important parameter. If the

PLS factor is too small, the spectral information of the

samples couldnt be fully used. The model accuracy would be

decreased. If the PLS factor is too big, noises would be led

into the model and the prediction ability would be decreased

too. Therefore, it is important to select a reasonable PLS

factor.

Savitzky-Golay (SG) smoothing method was a widely

used method in spectral pretreatment which can eliminate

noise[12-15]. The SG smoothing parameters include the order of

derivative, the degree of polynomial and the number of

smoothing points. Particularly, it is important to set the

number of smoothing points. If the number is too small, it

would lead new errors to the model. If the number is too big,

the spectra data containing information would be polished and

lost. Both of the situations would decrease the model

accuracy. The SG smoothing parameters would be different

when objects are different and measurement modes are

different. It is very necessary to large-scale simultaneous

optimization of the SG smoothing parameters and the PLS

factor according to prediction effects. But as there are many

smoothing modes and different formulas, the workload would

be very large. This work was seldom accomplished in

previous study. On the other hand, more smoothing points

may be necessary in some actual measuring systems. To

widen the application scope, it is necessary to expanse the

smoothing parameters table according to the original

method[12].

In this paper, by simulating the glucose concentration in

human or animal blood, 82 glucose aqueous solution samples

were designed. The rapid determination method and the

This work was supported by the National Natural Science Foundation of China (10771087), the Natural Science Foundation of Guangdong Province

(7005948), the Science and Technology Project of Guangdong Province (2007A020905001, 2009B030801239). *Corresponding author: Tao Pan (

tpan@jnu.edu.cn)

2159

the FTIR/ATR spectroscopy technology, PLS regression and

SG smoothing method. Especially, the simultaneous

optimization of the SG smoothing parameters and the PLS

factor was applied to FTIR/ATR spectroscopy analysis of

glucose solution.

II.

Method

82 glucose aqueous solution samples were designed, and

glucose concentration ranged from 0.416 to 39.036 (mmol/L),

the mean values and the standard deviations are 18.449 and

10.810 (mmol/L) respectively.

A VERTEX 70 FTIR spectrometer (BRUKER Company)

equipped with a KBr beamsplitter and a deuterated triglycine

sulfate KBr detector was used to collect the spectra. The MIR

spectra were obtained from 4500 to 600 cm-1 with a horizontal

ATR sampling accessory with a diamond internal reflection

element on a ZnSe crystal (SPECAC Company, 45o angle of

incidence, 3 times reflective). 32 scans of symmetrical

interferograms at 4 cm-1 resolution were added for each

spectrum. The spectra were measured at temperature 25 1

and humidity 46% RH.

0.075ml of each glucose aqueous solution sample was

taken for spectroscopy measuring. Each sample was measured

3 times, and the average spectrum was calculated.

B. Dividing Method for Calibration Set and Prediction Set

Based on the prediction effect of the optimal single

wavenumber model for all samples, calibration set and

prediction set were divided. The glucose chemical value and

spectral data of samples in calibration set were combined to

establish models for data mining. Then, the established model

was applied to the spectral data of samples in prediction set,

to calculate the theoretical value of glucose. Comparing

calculated value and actual value, model prediction effect was

evaluated.

By Beer's law, the single wavenumber linear model for the

glucose aqueous solution sample absorbance and glucose

chemical values is follows

A(v)=k(v)C+,

(1)

where A(v) is the absorbance of sample and k(v) is the unit

concentration absorption coefficient of glucose aqueous

solution, for each wavenumber v. C is the glucose chemical

value and is other unknown interference. k(v) was regression

calculated using the absorbance and chemical values of all

samples, and then the predict value C'i(v) of sample i was

calculated by using k(v) and the sample absorbance,

i=1,2,,N, N is the number of samples. Additionally, root

mean square error (RMSE) between predict values and

chemical values were calculated. Set that Ci is the chemical

value of sample i, thus

(C '

(v ) C i ) 2

.

(2)

N 1

According to the minimum value of RMSE, the optimal single

wavenumber model and the corresponding wavenumber

vOptimal were selected. Base on the optimal model, the bias

between predict value and chemical value of each sample was

calculated which named single wavenumber prediction bias

(SWPB).

SWPB(i)=|C'i(vOptimal) Ci |, i=1, 2, , N.

(3)

According to SWPB, the calibration set and the prediction set

were divided. Computer procedures were used to make a

similar distribution of SWPB for the two sets (mean value and

standard deviation are similar, relative error was less than 1%).

By this method, the chemical values and spectral data were

combined to make the calibration set and the prediction set

have consistent distribution. Consequently the dividing

method has modeling representative. To ensure the

concentration range of calibration set cover that of validation

one, the samples with maximum and minimum chemical

values were divided into the calibration set, while the samples

with second maximum and second minimum chemical values

were divided into the prediction set.

RMSE( v ) =

i =1

C. SG Smoothing Method

SG Smoothing parameters include the order of derivative

(the original spectral smoothing was recorded zero order

derivative smoothing), the degree of polynomial and the

number of smooth points. Because some actual measurement

systems (for example, the case of the spectral wavenumber

gap was small) may require more smooth points. So, in this

paper, the number of smoothing points were expanded from 5,

7 25 (odd)[12] to 5, 7 81(odd), and the degree of

polynomial were expanded to n = 2, 3, 4, 5, 6 (originally n =

2, 3, 4, 5). According to the original method[12], 14 smoothing

coefficient tables which covering the original smoothing

coefficient, and 483 smoothing modes (originally 117 modes)

were calculated by computer program. And it is a SG

smoothing preprocessing group with wider application scope.

D. Model Evaluation Indicators

The model evaluation indicators main includes root mean

squared error of predication (RMSEP) and correlation

coefficient of predication (RP) and the relative root mean

squared error of predication (RRMSEP) as follows:

M

RMSEP =

M

(C

ip

RP =

(C '

ip

C ip ) 2

i =1

M 1

Cmp )(C 'ip C 'mp )

i =1

(C

ip

i =1

(5)

i =1

RMSEP

RRMSEP =

100 (%)

C mp

2160

(4)

(6)

the sample i in the prediction set, C'mp, Cmp were the mean

predicted value and mean chemical value of all samples in the

prediction set, M is the sample number in the prediction set.

RMSEP used as the goal of model optimization and parameter

design.

III.

Figure 1. According to the method of section IIB, all single

wavenumber models were established, and the optimal

wavenumber vOptimal was 1034 cm-1 according to the minimum

RMSE. Based on 1034 cm-1 model, the SWPB of each sample

samples.

distribution of all the samples were shown in the Figure 2. All

82 samples were used for modeling. The calibration set

consists of 55 samples and the prediction set of 27 samples. By

the method mentioned in section IIB, the samples were split

into the calibration set and prediction set. TABLE I show the

mean value and standard deviation of SWPB and chemical

value. TABLE I and Figure 2 indicate that SWPBs distribution

in the calibration set and the prediction set was very consistent.

The optimal RMSEPs based on whole spectral region and

fingerprint region were 1.109 and 0.6604 (mmol/L)

respectively. The prediction accuracy of the later was

obviously better than the former. So the fingerprint region

(1600-900 cm-1) was selected as the spectral band for modeling

by PLS method, and the corresponding optimal PLS factor was

6, the optimal RMSEP was 0.6604 (mmol/L), RP was 0.9981,

RRMSEP was 4.40%.

TABLE I.

THE MEANS AND THE STANDARD DEVIATIONS OF

SWPBS AND CHAMICAL VALUES IN CALIBRATION SET AND

PREDICTION SET

Chemical value

(mmol/L)

Standard

Mean

deviation

SWPB

(mmol/L)

Standard

Mean

deviation

Calibration set

20.131

10.851

8.615

5.829

Prediction set

15.021

10.064

8.664

5.810

built. Based on computer algorithms platform which was

developed by authors, PLS models corresponding to all

combinations of 483 smoothing modes and PLS factor

changing from 1 to 40 were established. According to the

prediction effect, the SG smoothing parameters and the PLS

factor were simultaneously optimized. The RMSEP values of

the optimal models with different derivative modes and

different smoothing points were shown in Figure 3. The degree

of polynomial, smooth points, PLS factor and RMSEP of the

optimal model with different derivation order were shown in

TABLE II. The result of the direct PLS model without SG

smoothing points for each order derivative mode

(0) Original spectra smoothing; (1) 1st order derivative; (2)2nd

order derivative; (3) 3rd order derivative; (4) 4th order

Derivative; (5) 5th order derivative

Figure 2 The distributions of SWPBs and chemical values.

cm-1) and the fingerprint range (1600-900 cm-1) were also

first order derivative smoothing, 5 or 6 degree of polynomial,

63 smoothing points. And the corresponding optimal PLS

factor, the optimal RMSEP, RP, RRMSEP were 3, 0.3729

2161

was obvious better than the result obtained without SG

smoothing. TABLE II and Figure 3 showed that the optimal

smoothing points and the optimal PLS factor corresponding to

different derivative order were different. If using the

designated smoothing parameters which used by previous

researches, without a large-scale selection, it is difficult to

find the optimal SG smoothing parameters and the PLS factor.

In addition, TABLE II and Figure 3 also showed that the

optimal smoothing points were not less than 25, if using any

smoothing point within 25, the optimal prediction effect

would not be obtained (within 25 smoothing points, the best

RMSEP was 0.6604 (mmol/L), RP was 0.9981). Figure 4

showed the comparison of the predictive value and the

chemical value for the optimal SG smoothing model of each

sample. It was seen that the correlation between the predictive

value and the chemical value of all samples was very good.

These indicated the expansion of SG smoothing mode was

very necessary.

TABLE II. PREDICTION EFFECT OF THE OPTIMAL MODEL

CORRESPODING TO EACH ORDER DERIVATION

Number of

Polynomi

PLS RMSEP RRMS

smoothing

al degree

factor (mmol/L) EP

points

RP

No SG

smoothing

Original

spectra

smoothing

1st order

derivative

0.6604

4.40%

0.9981

45

41

0.6418

4.27%

0.9983

56

63

0.3729

2.48% 0.9995

2nd order

derivative

45

67

0.4762

3.17%

0.9989

3rd order

derivative

34

57

0.5279

3.51%

0.9988

4th order

derivative

45

65

0.5483

3.65%

0.9987

5th order

derivative

56

75

0.5459

3.63%

0.9985

formula was the follows:

~ =

a

0

31

a

i

(7)

i = 31

~ were the

Where a i were the original spectral data, a

0

spectral data after SG smoothing,

i were

the smoothing

3.353, 3.364, 3.045, 2.472, 1.713, 0.830, -0.125, -1.104,

-2.067, -2.978, -3.808, -4.536, -5.141, -5.611, -5.937, -6.113,

-6.138, -6.016, -5.752, -5.354, -4.833, -4.204, -3.480, -2.679,

-1.820, -0.920, 0, 0.920, 1.820, 2.6789, 3.480, 4.204, 4.834,

5.354, 5.752, 6.016, 6.139, 6.113, 5.937, 5.611, 5.141, 4.536,

3.808, 2.978, 2.067, 1.104, 0.125, -0.830, -1.713, -2.472,

-3.045, -3.364, -3.353, -2.928, -1.997, -0.459, 1.796, 4.887

( 103 ).

IV.

CONCLUSION

parameters and the PLS factor was applied to FTIR/ATR

analysis of glucose solution. Based on the optimal single

wavenumber model, the calibration set and the prediction set

were divided. For direct PLS model without SG smoothing,

the optimal PLS factor, RMSEP, RP and RRMSEP were 6,

0.6604 (mmol/L), 0.9981 and 4.40% respectively. By

extending the number of smoothing points and the degree of

polynomial, 483 smooth modes were calculated. The PLS

models corresponding to all combinations of 483 SG

smoothing modes and 1-40 PLS factor were established

respectively. The optimal smoothing parameters were the first

order derivative smoothing, 5 or 6 degree polynomial, 63

smoothing points, the optimal PLS factor, RMSEP, RP and

RRMSEP were 3, 0.3729 (mmol/L), 0.9995 and 2.48%

respectively, which was obviously superior to the direct PLS

model without SG smoothing and the optimal SG smoothing

model within 25 smoothing points (the original smoothing

method). This demonstrates that the extending of SG

smoothing modes and large-scale simultaneous optimization

selection of SG smoothing parameters and PLS factor was all

very necessary, and can be effectively applied to the model

optimization of FTIR/ATR analysis.

REFERENCES

[1]

[2]

[3]

[4]

Figure 4 Comparison of predictive value and chemical value of

each sample for the optimal SG smoothing model

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P. H. Axelsen, W. D. Braddock, H. L. Brockman, et al., Use of internal

reflectance infrared spectroscopy for in situ study of supported lipid

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[7] D. A. Burns, E. W. Ciurczak, Handbook of near-infrared analysis, 2nd

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8, pp. 16271637, 1964.

[13] J. M. Chen, T. Pan, X. D. Chen, Application of second derivative

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[14] H. Yin, T. Pan, D. F. Liu, et al., A simultaneous quantification method

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[15] H. Yin, T. Pan, P. L. Tian, et al., Rapid Quantitative Analysis for the

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2163

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