THE FTIR FINGERPRINT OF GYPSUM FIBROSUM

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1 Acta Medica Mediterranea, 2016, 32: 607 THE FTIR FINGERPRINT OF GYPSUM FIBROSUM YAN WEI 1, LIAO JUN-CHENG 1, WANG SHU-MEI 1, LIANG SHENG-WANG 1*, YU JIANG-YONG 2 1 School of Chinese MateriaMedica, Guangdong Pharmaceutical University Key Laboratory of State Administration of TCM for Digital Quality Evaluation Technology of Traditional Chinese Medicine Guangdong Academies TCM Quality Engineering Technology Research Center Guangzhou China - 2 Chinese Pharmacopoeia Commission ABSTRACT Introduction: Chinese mineral medicine plays an important part in Traditional Chinese Medicine and has a long history, such as using Gypsum Fibrosum. Aim of our study is to establish a new Gypsum Fibrosum identification method and compare Gypsum Fibrosum and CaSO 4 with the help of Fourier Transform Infrared spectroscopy (FTIR). Materials and methods: Determination and analysis of batches of Gypsum Fibrosum samples to establish the fingerprint by the OPUS acquisition system obtained from the German Bruker TENSOR 37 Fourier transform infrared spectroscopy, and then compare the Gypsum Fibrosum and CaSO 4 by initial characteristic spectrogram, first derivative spectrum and second derivative spectrum. Results: The similarity of twenty-four samples were calculated by SPSS20, which showed that the correlation coefficient of twenty-four batches of samples was more than 0.980, except for No.16. There were distinctions of the wave number, peak position, spike and peak intensity between Gypsum Fibrosum and CaSO4 in the derivative spectroscopy. In view of the difference between Gypsum Fibrosum and CaSO 4, a conclusion may be that there is a structural change. Discussion: Gypsum Fibrosum can be studied by FTIR and differences obtained between mineral medicine and the analytical reagent on the analysis of sulfate mineral. In addition, the result shows that it can provide a new, rapid and specific method for identification of Gypsum Fibrosum by FTIR. Key words: Gypsum Fibrosum, FTIR, Fingerprint, derivative spectrum. Received February 15, 2016; Accepted March 02, 2016 Introduction Chinese mineral medicine is a summary of the medical experience of Traditional Chinese Medicine (TCM), which has a very long history. It works on internal disease, surgical disease, gyneacopathia and otolaryngology. However, the study of Chinese mineral medicine started late and relatively slowly, which needed the application of modern technology for in-depth investigation. The main aspects of this study include component analysis and quality control by microscopy, X-ray diffraction, spectroscopy, inductively coupled plasmamass spectrometry and so on (1). Gypsum Fibrosum as the one of the elements of Chinese mineral medicine, is commonly used and started in ShengNong s herbal classic (2). It is described as among an-hydrite sulfate mineral medicine in the 2015 Chinese Pharmacopoeia, which is described as a long block, plate shape or irregular, and white light yellow color sometimes translucent. Besides that, the sample profile has a special luster. It has CaSO 4 2H 2 O as main ingredients and clinical applica-tions such as affect of exogenous wind-heat, high fever or dyspnea and cough due to lung-heat (3). Although it is included in the 2015 Chinese Pharmacopoeia and in strict accord-ance with the production quality requirement, there is still malpractice in the sale, which needs a new and rapid method to identity and improve specialization. Researchers like Yuan Mingyang point out that we can depend on the Raman Spectra to establish a

608 Yan Wei, Liao Jun-Cheng, et Al quantitative analysis model which re-quires collecting batches of gypsum from different origins to be used as training set and compared with the results by EN-TA

2 608 Yan Wei, Liao Jun-Cheng, et Al quantitative analysis model which re-quires collecting batches of gypsum from different origins to be used as training set and compared with the results by EN-TA The content was between 97.93% and 99.81% pure (4). In recent years, infrared spectroscopy (IR) has attracted attention due to its advantages of being convenient and pol-lution-free for simultaneous determination of multi-components, such as in authentic identification, quantitative analysis and quality control (5). Compared with the chromatographic fingerprint, the infrared fingerprint has many more advantages, for example, in being systematic, reproducible, and non-destructive. The test adopted FTIR to characterize the similarity of Gypsum Fibrosum, and explore experimental contrast with analytical reagent (AR), with the purpose of getting a new and rapid method. Experiment A series of pertinent experiments were carried out to know the fingerprint of Gypsum Fibrosum, and provide the-oretical references for quality evaluation and improvement scheme selection. KBr and CaSO 4 were supplied by Guangzhou Chemical Reagent Factory. An OPUS acquisition system was obtained from the German Bruker TENSOR 37 Fourier transform infrared spectroscopy, a FW-5 pelletizer, WS70-1 infrared dryer (Tianjin, China), a AY120 SHIMADZU electronic balance, a BP211D Sartorius electronic balance and an agate mortar were used to prepare samples. The twenty-five different samples were collected from medical markets and the content was determined according to the 2015 Chinese Pharmacopoeia. The instrumental conditions were as follows: the test humidity was kept at 40. After grinding and mixing the dry simples and KBr, whose weigh was the 10mg and150mg respectively, then tablet scanning. The scanning determina-tion was within the scope of cm -1 and scanned 16 times. The interpretation of results was analyzed by OPUS with the baseline correction, smoothness and background correction. Twenty-five samples were prepared and the FTIR spectra of samples were used, with the help of the SPSS20 to obtain similarity analysis. Precise, repeatable experimental method, stability test and average models were utilized in this work. A method of FTIR was developed for the establishment of TCM fingerprints of Gypsum Fibrosum from different places, according to the wave number, peak position and spike. Results Twenty-five samples from different places located in China were prepared and analyzed. Testing showed that the content of the rest of the samples were not less than %, except No.16 (Table 1) (3). Table 1: The production area and content of twenty-five batches of samples. The results also showed the precision and repeatability of the method and stability test, which randomly chose one of the samples. In this part, the Relative Standard Deviations (%) of the common peaks were less than 0.1%, 0.31%, and 0.52% respectively, and the Relative Standard Deviations (%) of the transmittance were not more than 0.1%, 3.00% and 2.98% respectively. The results for twenty-five samples analyzed were evalu-ated by OPUS and SPSS.20. Twentyfour samples were used for analysis and development of the average model in OPUS to set up the greatest one (Figure 1) which depicted FTIR spectra of samples, and the FTIR spectra of the com- Fig. 1: The FTIR fingerprint of Gypsum Fibrosum. Fig. 2: The FTIR of Gypsum Fibrosum (except No.16).

The FTIR fingerprint of gypsum fibrosum 609 mon clearly appears in wave number and transmittance of Gypsum Fibrosum (Figure 2) except for No.16.

16) were (3549±1)cm -1, (3404±2)cm - 1, (2240±2)cm -1, (2118±2)cm -1, (1687±1)cm-1, (1622±2) cm -1, (1116±2)cm -1, (670±1) cm -1, (602±1) cm -1, (461±3) cm -1, (423±5) cm -1, shown in Table 2 (6,7,8).

997 0.980 0.993 0.999 0.999 Table 4: Results of correlation coefficient of thirteen Gypsum Fibrosum samples. Table 2: Eleven common peak wave numbers of Gypsum Fibrosum.

3 The FTIR fingerprint of gypsum fibrosum 609 mon clearly appears in wave number and transmittance of Gypsum Fibrosum (Figure 2) except for No.16. Through analysis and comparison, the eleven common waves of twenty-four samples (except No.16) were (3549±1)cm -1, (3404±2)cm - 1, (2240±2)cm -1, (2118±2)cm -1, (1687±1)cm-1, (1622±2) cm -1, (1116±2)cm -1, (670±1) cm -1, (602±1) cm -1, (461±3) cm -1, (423±5) cm -1, shown in Table 2 (6,7,8). shown in Table 4 and Table 5 (12). Table 3: The transmittance (%) of FTIR fingerprint from Gypsum Fibrosum. Samples S1 S2 S3 S4 S5 S6 S7 S8 S9 S10 S11 S12 S13 CC Table 4: Results of correlation coefficient of thirteen Gypsum Fibrosum samples. Table 2: Eleven common peak wave numbers of Gypsum Fibrosum. The H-O H peak around 3549 cm -1 ± 1622cm-1± covers a significant area in the fingerprint region in the FTIR spectrum, such as 3549 cm -1 ±(S) and 3404 cm -1 ±(S). The broad band in the range of 2240 cm -1 ± and 2118 cm -1 ± is attributed to the O-H stretching the deformation vibration and rock vibration, where exhibited. It displayed some sharp peaks in a small area between 1687 cm -1 ± and 1622 cm -1 ±. Gypsum Fibrosum S-O which including the asymmet-rical stretching vibration (1116 cm -1 ±) and the asymmetrical deformation vibration (670 cm -1 ± and 602 cm -1 ±), gave the main contribution to the strong band. The band centered around 461cm -1 ± and 423cm -1 ± is mainly from the S-O symmetrical stretching vibration, for it seems like tetrahedron (9,10,11). Transmittance (%) performed for each mineral to develop for the excellent model are shown in Table 3, and the correlation coefficient is Samples S14 S15 S16 S17 S18 S19 S20 S21 S22 S23 S24 S25 Average CC Table 4: Results of correlation coefficient of the rest of Gypsum Fibrosum samples. Gypsum Fibrosum and CaSO 4 were performed using the routine prescribed test method by initial characteristic spec-trogram, first derivative spectrum and second derivative spectrum. Fig. 3 shows the dissimilarity between Gypsum Fibrosum and CaSO 4 in the initial characteristic spectrogram. Fig. 3: The IR of Gypsum Fibrosum and CaSO 4. However, it was almost identical around the cm -1 in the FTIR. With the action of the OPUS, first derivative spectrum and second derivate analyses was performed for testing. The difference, which concentrated on the spike, transmittance and wave num-

4 610 Yan Wei, Liao Jun-Cheng, et Al ber, noticeable at cm -1 was found in the first derivative spectrum (Fig.4). In the second derivative spectrum, the transmittance spectra of Gypsum Fibrosum and CaSO4 was obviously different, such as near cm -1 and cm -1 (Fig. 5). The difference in FTIR between Gypsum Fibrosum and CaSO4 in the experiment described above shows the FTIR has enormous advantages in the identification of the mineral and reagent. Fig. 4: The Derivate IR of Gypsum Fibrosum and CaSO 4 Fig. 5: The Second Derivate IR of Gypsum Fibrosum and CaSO 4 Discussion Chinese mineral medicine, as a valuable aspect of the Chinese nation, is an essence of Traditional Chinese Medicine. Preparation of the fingerprint of Gypsum Fibrosum is a key factor in generating a good calibration model. FTIR spectroscopy is a simple and powerful tool for quantitative analysis of mineral samples with the help of OPUS and SPSS.20 analysis. The excellent models constructed using average analysis show good calibration and prediction abilities, which can set up the fingerprint to identify the genuine and fake. The similarity of twenty-four samples is above 0.980, besides the No.16 whose similarity and content is and 52.98%. The considerable characteristic bands above 3549 cm -1, part of the O-H were 3549 cm -1 ±, 3404 cm -1 ±, 2240 cm -1 ±, 2118 cm -1, 1687 cm -1 ± and 1622 cm -1 ± and S-O were 1116 cm -1 ±, 670 cm -1 ±, 602 cm -1 ±,461cm -1 ±and 423cm -1 ±. All the above results demonstrated that the fingerprint of the FTIR has huge advantages in the application of the mineral, moreover, in the TCM (13). It is no significant difference between the derivative spectroscopy from the excellent model and the derivative spectroscopy from the twentyfour samples. By comparison the derivative spectroscopy to identity CaSO4 and Gypsum Fibrosum in FTIR, which the difference focus on the cm -1 and cm-1, what s more obvious is the spike, peak number and transmittance. There is supporting theory of the difference between mineral medicine and AR on the analysis of sulfate mineral. Researchers like You Yu pointed out the differences between the weathered sodium sulfate and anhydrous sodium sulfate in the experiment by using the AX-IOS X-ray Fluorescence Spectrometer, and further find that there are two crystal forms: orthogonality and cube in weathered sodium sulfate, while only orthogonality in anhydrous sodium sulfate (14). It is also reported that Gypsum fibrosum was investigated by infrared spectrum coupled with inductively coupled plasmamass spectrom-etry (ICP-MS), which is related to the content of ele-ments, such as Ca, Mg, Zn and Na (15). Crystal form and the content of the element may account for the difference. It s said that the derivative spectroscopy is of more value to distinguish than initial spectroscopy, for reflecting small changes happening in the baseline and the crossover point of each peak and improving resolution. It was found that the sensitivity of derivate transmittance spectrum is much higher than the absorption spectrum (16). References 1) Liu. Shengjin, Wang Rui, Wu Dekang, Lin Ruichao, Wu luting, et al. Application of Modern Technology in Study of Mineral Chinese Medicine. Modern Chinese Medicine, 2015; 17: ) Sun. Jingyan, Sun. Fengyi, ShengNong s herbal classic. Science and Technology Press: Shanxi, ) The Pharmacopoeia Commission of the People s Republic of China, Chian Medical Science Press: Beijing 2015: ) Yuan Mingyang, Sun Xiaojing, Chen Long, Zhang Yisheng, Fan Yanbo, et al. Rapid Determination of CaSO4 2H2O in Gypsum by Raman Spectra. Chinese Pharmacist, 2015; 18:

5 The FTIR fingerprint of gypsum fibrosum 611 5) Shen Yunxia, Zhao Yanli, Zhang Ji, Shen Tao, Wang Yuanzhong, et al. Application of Infrared Spectroscopy in Traditional Chinese Medicine. World Science and Technology/Modernization of Traditional Chinese Medicine and Materia Medica 2015; 17: ) You Shuxia, Liu Shengjin. Wu Dekang, Liu Xunhong, Lin Rui-chao. The comparative study on FTIR fingerprint for alum and calcined alum.china J Pharm Anal 2011; 31: ) Liu Shengjin, Wu Dekang, Lin Ruichao, Liu Xunhong, Fu Xingsheng, et al. Fingerprints of Chloriti Lapis by FTIR. Chinese Traditional Patent Medicine 2012; 34: ) Lin Ruichao, The DetectingTechnology and Quality Control of Mineral Medicine. Science Press: Beijing ) Wang Dong, Wang Yonglu, Guo Xiao,Wang Yiqun,Wang Bota. Similarity Analysis of FTIR of Lapis Micae Aureum. Spectroscopy and Spectral Analysis 2011; 31: ) Sujeewa S, Palayangoda, Quoc P, Nguyen. An ATR- FTIR procedure for quantitative analysis of mineral constituents and kerogen in oil shale. Estonian Academy Publishers 2012; 29: ) Weng S F. The analysis of FTIR. Chemical Industry press: Beijing, ) Xue Wei. The statiscal analysis and application of SPSS. Renmin university of China press: Beijing, ) Zhang Nanping, Xiao Xinyue, Zhang Ping, Fu Hong, Lin Ruichao. Study on the Establishing of Reference Fingerprint for the Tradi-tional Chinese Medicine. Chinese Pharmaceuital Affairs 2003; 17: ) You Yu, Fu Chaomei, Chen Qiuwei, Nie Yingjun, Hu Huiling, Comparison on structure-efficacy between mineral drugs weath-ered sodium sulfate and anhydrous sodium sulfate. Chinese Traditional and Herbal Drug 2013; 44: ) Bao Yongrui, Yang Xinxin, Wang Shuai, Bian Jing, Yu Ying, et al. Difference of Material Base of Gypsum Before snd After Pro-cessing Drugs by IR Spectroscopy and ICP-MS. Chinese Journal of Spectroscopy Laboratory 2012; 29: ) Song Yuanzhi. Comparison between the derivative transmittancy spectrum and derivative absorption spectrum. PTCA(PART B:CHENMICAL ANALYSIS) 2003; 39: Acknowledgements This work was financially supported by project of Chinese Pharmacopoeia Commission s research project of State of TCM for Standardization ( ). Corresponding author LIANG SHENG-WANG School of Chinese MateriaMedica, Guangdong Pharmaceutical University Key Laboratory of State Administration of TCM for Digital Quality Evaluation Technology of Traditional Chinese Medicine Guangdong Academies TCM Quality Engineering Technology Research Center Guangzhou (China)

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