J. Cent. South Univ. (2018) 25: 1895-1903

DOI: https://doi.org/10.1007/s11771-018-3879-4

A new reaction system to determine nonlinear chemical fingerprint and its use in Panax ginseng identification method based on double reaction system

TAN Xue-ying(谭雪莹), DENG Fei-yue(邓飞跃), ZHANG Tai-ming(张泰铭),HUANG Jian(黄坚), CHEN Chun-nan(陈春楠)

School of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China

Central South University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2018

Abstract: A new reaction system to determine nonlinear chemical fingerprint (NCF) and its use in identification method based on double reaction system was researched. Panax ginsengs, such as ginseng, American ginseng and notoginseng were identified by the method. The NCFs of the three samples of Panax ginsengs were determined through two nonlinear chemical systems, namely system 1 consisting of sample components, H₂SO₄, MnSO₄, NaBrO₃, acetone and the new system, system 2 consisting of sample components, H₂SO₄, (NH₄)₄Ce(SO₄)₂, NaBrO₃ and citric acid. The comparison between the results determined through systems 1 and 2 shows that the speed to determine NCF through system 2 is much faster than that through system 1; for systems 1 and 2, the system similarities of the same kind of samples are ≥ 98.09% and 99.78%, respectively, while those of different kinds of samples are ≤ 63.04% and 86.34%, respectively. The results to identify the kinds of some samples by system similarity pattern show that both the accuracies of identification methods based on single system 1 and 2 are ≥ 95.6%, and the average values are 97.1% and 96.3%, respectively; the accuracy of the method based on double system is ≥ 97.8%, and the average accuracy is 99.3%. The accuracy of the method based on double system is higher than that based on any single system.

Key words: nonlinear chemical fingerprint; double reaction system; single reaction system; authenticity identification; Panax ginsengs

Cite this article as: TAN Xue-ying, DENG Fei-yue, ZHANG Tai-ming, HUANG Jian, CHEN Chun-nan. A new reaction system to determine nonlinear chemical fingerprint and its use in Panax ginseng identification method based on double reaction system [J]. Journal of Central South University, 2018, 25(8): 1895–1903. DOI: https://doi.org/ 10.1007/s11771-018-3879-4.

1 Introduction

Ginseng, notoginseng and American ginseng are the roots of Panax ginseng, Panax notoginseng and Panax quinquefolium, respectively, and they are invoked as popular traditional Chinese medicine (TCM) [1]. All of the medicinal materials belong to the genus Panax plants, and both their plant morphology and chemical compositions are very similar. For example, they contain some biologically active compounds such as ginseng, notoginsenosides and quinquenosides [2]. Therefore, western pharmaceutical researchers often classify the three as ginseng drugs with nourishing function according to the correlation between chemical composition and pharmacological action. However, ginseng, American ginseng and notoginseng are considered to possess different properties according to the traditional theory of TCM. Modern clinical study has also shown that they are of different therapeutic functions, especially notoginseng is a drug for promoting blood circulation and hemostasis, instead of tonic drugs. The functional variety shows that there are differences between the bioactive components of the three medicinal materials, and their chemical or active components are not entirely clear so far. So, the three medicinal materials must not be confused in the use. In addition, the market prices of the three medicinal materials differ remarkably so that the phenomenon of their substitution of the fake for the genuine often occurs. Therefore, in order to ensure the applied safety and efficacy of the medicinal materials, it is very important to establish a method for accurately identify the three medicinal materials of Panax ginsengs.

Many analytical methods have been used to identify the species of genus Panax plants, including HPLC [3, 4], Fourier transform infrared spectroscopy and IR spectroscopy [5, 6], DNA barcoding [7–9], HPLC-ESI-MS [10], LC-MS [11], IRMS [12], and NMR spectroscopy [13]. Although most among the methods are of high sensitivity and may be used to district the species of genus Panax plants, they only focused on some chemical compounds in the medicinal materials, which could not efficiently describe the whole characteristics of TCMs. NCF technique is of higher accuracy of identification, and its methods based on single reaction system have been systematically researched [14–16]. In order to further improve the accuracy of the identification, a new NCF method based on double reaction system has been established in this paper. The method used two reaction systems consisting of sample components, H₂SO₄, MnSO₄, NaBrO₃, acetone and sample components, H₂SO₄, (NH₄)₄Ce(SO₄)₂, NaBrO₃, citric acid, respectively, and it has been successfully used in the identification of samples of panax ginsengs.

2 Materials and method

2.1 Chemicals and materials

Sulfuric acid (1.00 mol/L), citric acid (1.00 mol/L, taking sulfuric acid (1.00 mol/L) as solvent), acetone (0.800 mol/L), ceric ammonium sulfate (0.0100 mol/L, taking sulfuric acid (1.00 mol/L) as solvent), manganic sulfates (0.0800 mol/L) and sodium bromate (0.800 mol/L) were used. All chemical reagents used were of analytical grade. Deionized water was used. Both ginseng from Jilin and American ginseng from Canada were provided by Beijing Medical Research Institute, and notoginseng was bought from Tianjian drugstore in Changsha, Hunan, China.

2.2 Instrumentation

A NCF analyzer (Model MZ-1B-2) was used, which was manufactured by Hunan Shangtai Ltd., for Science & Technology of Measurement & Control), Xiangtan, Hunan, China. The platinum electrode was soaked in chromic acid solution for 10 min before use.

2.3 Sample pretreatment

The sample was pulverized and passed through a 100-mesh sieve, placed in a vacuum dryer (model DZ-1BC) at 60 °C for 6 h, and then placed in a sealed bag and placed in a desiccator.

2.4 Method for determining NCF

For system 1, 25.00 mL of the H₂SO₄ solution, 10.00 mL of the acetone solution, 12.00 mL of the MnSO₄ solution, 10.00 mL of double distilled water and appropriate amount of the sample powder were accurately added into the reactor. While for system 2, 15.00 mL of the H₂SO₄ solution, 15.00 mL of the citric acid solution, 6.00 mL of the ceric ammonium sulfate solution and appropriate amount of the sample powder were accurately added into the reactor. Then cover the reactor lid with the injection hole, two electrodes and a thermometer, and turn on the instrument. The temperature in the reactor was adjusted to 37.0 °C, the stirring rate was adjusted to 900 r/min, and the stirring time was immediately monitored. When constant stirring was continued for 10 min, 3.00 mL of NaBrO₃ solution was immediately injected into the reactor, and the potential–time curve (E–t curve) was recorded until the potential was constant.

2.5 Test of reproducibility of method

NCF of Jilin ginseng was obtained by 3 parallel assays. Using the average of the specified feature parameters as a comparison and calculating the system similarity of the fingerprints, they are 0.9990, 0.9987 and 0.9989, respectively. The results indicate that the method is reproducible.

3 NCF principle

3.1 Substances to influence NCF characteristic

NCF characteristic depends on the components in the sample and their contents. It is quite complex to describe the effects of all the components on the NCF characteristic because the components are very many and the influence degree of each component would vary [14, 15]. However, the multitudinous components and their influences can be classified and outlined as follows.

3.1.1 Substrates to induce nonlinear chemical reaction

Substrates are the substances which decide whether a nonlinear chemical reaction can occur. Any one substrate in the system is indispensable for a nonlinear chemical reaction; otherwise, it is impossible for the nonlinear chemical reaction to take place, that is, it is impossible to obtain a NCF fingerprint. Most of substrates can participate in the consumption–regeneration cycle in the nonlinear chemical reaction process [14, 15].

3.1.2 Dissipative substances to induce nonlinear chemical reaction and control reaction time

A dissipative substance is actually the substrate which cannot participate in the consumption–regeneration cycle. Because of its continuous consumption in reaction process, when the activity of the dissipative substance is less than its critical value, the nonlinear chemical reaction will stop immediately. Therefore, the substance not only decides whether the nonlinear chemical reaction can occur, but also makes the reaction complete in a certain period of time, namely it can make the determination of NCF complete as soon as possible.

3.1.3 Coexisting components with chemical activity

Coexisting components with chemical activity are the substances which are not the reaction substrates, but are from the sample, and can influence the reaction course of nonlinear chemical reaction, thus influencing the characteristic of NCF. In addition, the physical activity of the substances can also influence the characteristic of NCF; however, this influence is much less than that of the chemical activity.

3.1.4 Coexisting components with only physical activity

Coexisting components with only physical activity are the substances which do not participate in any chemical reaction in the determination of NCF, and influence the characteristic parameters only through their physical properties. This influence is much smaller than that of chemical activity.

3.1.5 Substrates and dissipative substances only causing a basal nonlinear chemical reaction

The nonlinear chemical reaction caused by the substrates and dissipative substance is only a fundamental nonlinear chemical reaction. The relationship curve between the potential of fundamental reaction system and the reaction time, namely E–t curve is not the NCF of a sample.

3.1.6 Characteristic of NCF depend on common effect of all substances from a sample

Only when all chemical active substances in a sample participate in the nonlinear chemical reaction and all the physical active substances have also corresponding effects on the reaction through their physical properties, such as ionic strength, surface tension, osmotic pressure, viscosity,polarity, the determined E–t curve is the NCF which is of the function to identify the authenticity of the sample and determine the contents of the sample components. Therefore, characteristic of NCF depends on the common effect of all substances in the sample.

3.2 Principle to determine NCF

The principle to determine a NCF is actually the dynamic Nernst principle, namely, the determined fingerprint information may be described by a dynamic Nernst equation. Although in different processes of a nonlinear chemical reaction, such as induction and oscillation processes, the kinds of resultant i and reactant j and their activities (a_i and a_j) may be different, but the general formula of these dynamic Nernst equations may be expressed as follows:

                            (1)

All the a_i(t) and a_j(t) in the formula denote the activities of resultant i and reactant j in the reaction process and are the function of reaction time. The activities of many substances in nonlinear chemical reaction systems undulate with time [14, 15], eventually resulting in the fact that the potential in the determined fingerprint also undulate with the reaction time. The NCF of ginseng is shown in Figure 1.

Figure 1 NCF of ginseng and its part of characteristic information (a–b: Inductive curve; b–c: Undulatory curve; a and c are the start and end points of the nonlinear chemical reaction, respectively; dosage: 0.6000 g; system 1)

4 Results and discussions

4.1 Basic information of NCF

NCF contains a wealth of information, including visual and quantifiable, where quantifiable information is also called characteristic parameters. The visual information can be divided into inductive curve, oscillation curve, periodic wave shape and potential drift curve, etc. The quantifiable information primarily includes canyon potential E_can, canyon time t_can, peak top potential E_pet, peak top time t_pet, inductive time t_ind, undulatory start potential E_uns, undulatory end potential E_une, undulatory end time t_une, undulatory amplitude △E_und, the maximum undulatory amplitude △E_max, undulatory life t_und, undulatory period τ_und (or average undulatory periodwave number n_wav and so on. A detailed explanation of the meaning of each characteristic parameter was given in Refs. [14, 15]. The NCF of ginseng and its part of characteristic information are shown in Figure 1. The characteristic parameters can be used to calculate the system similarity between NCFs, and the similarity can be used to identify and evaluate the sample. The NCFs of three samples of Panax ginsengs were determined by reaction systems 1 and 2, respectively, and the relevant average values of main characteristic parameters of the NCFs are listed in Tables 1 and 2.

4.2 Selection of method for similarity calculation and pattern recognition

Pattern recognition is divided into two categories, coefficient recognition and cluster pattern recognition. The former is widely used because its evaluation method is quantifiable. Researchers have compared several common coefficient pattern recognition methods in Refs. [14, 15] and came to some conclusion. For instance, correlation coefficient and included angle cosine could not reflect the difference between the NCFs; therefore, it is not appropriate to adopt them to evaluate the similarity between NCFs. Euclidean distance could correctly reflect the feature differences of fingerprints when it was used to calculate the non-parametric similarity of fingerprints; but, when it was used to calculate the parametric similarity, the relative degree of characteristic difference of the sample’s NCFs may not be correctly reflected. However, system similarity can correctly reflect differences between the fingerprint characteristics, which is highly consistent with the intuitive difference in nonlinear chemical fingerprints and it can discriminate samples faster, easier and more accurate by combining with the visual information. Therefore, this article selected the system similarity as a coefficient recognition pattern, and its computational model is as follows:

         (2)

The physical meanings of all symbols in Eq. (2) have been described in detail in Refs. [11, 12], and here, they are repeatedly explained no longer. The computation of system similarity was carried out by the software programmed according to Eq.(1)

Table 1 Average values of main characteristic parameters in NCFs of three samples of Panax ginsengs for reaction system 1

Table 2 Average values of main characteristic parameters in NCFs of three samples of Panax ginsengs for reaction system 2

4.3 Influence of determining dosage on NCF

Sample components can affect the feature of NCFs, namely, the changes of components will transform the visual shape of the fingerprint and the parameter information [14, 15]. Moreover, NCF parameter information is also affected by changes in the content of the same component; sometimes this change may even lead to the difference in the visual shape of fingerprint. Therefore, an appropriate sample dosage can help to obtain a NCF with rich parameter information and good characteristic. If not only the fingerprint contains rich information but also the time expended in its determination is the shortest, the related measuring dosage is optimal. The experimental results have shown that 0.6000 g is the optimal measuring dosage.

4.4 Reproducibility and characteristic of NCFs of Panax ginsengs

The NCFs of Panax ginsengs were determined by reaction systems 1 and 2, and the reproducibilities of the NCFs are shown in Figures 2 and 3, respectively. It is obvious from the figures that all of the NCFs determined by the two systems have good reproducibility, that is, on determining under the same conditions, the characteristics of NCFs of the same kind of the sample are almost alike completely due to the same components and contents.

Figure 2 Reproducibility of NCFs of ginseng (a), American ginseng (b) and notoginseng (c) and their characteristic difference (d) for reaction system 1

Figure 3 Reproducibility of NCFs of ginseng (a), American ginseng (b) and notoginseng (c) and their characteristic difference (d) for reaction system 2

4.5 Comparison of NCFs determined by single reaction system

The characteristic differences of NCFs determined by system 1 and system 2 are shown in Figures 2(d) and 3(d), respectively. Obviously, on determining by any one in the two systems, all of the NCFs obtained can well reflect the differences of the sample components and their contents. The main components of ginseng and American ginseng are highly similar; therefore, the visual shapes of the fingerprints are highly similar, too (see fingerprints 1 and 2 in Figures 2(d) and 3(d)). However, the fingerprint characteristic parameters, such as the undulatory amplitude, undulatory life, undulatory period and wave number, are obvious different because the contents of the main components and the species of the secondary components in the samples are somewhat different. In contrast, the main components in notoginseng have larger differences from those in ginseng and American ginseng; therefore, the characteristic of notoginseng fingerprint has also larger differences from those of ginseng and American ginseng (see Figures 2(d) and 3(d)). For example, the tail shape of undulatory curve profile of notoginseng fingerprint is obvious different from that of ginseng and American ginseng. In addition, it is obvious from the comparison between Figures 2(d) and 3(d) that the characteristic difference between three sample fingerprints determined by system 1 is more obvious than that determined by system 2. For example, the shapes of the inductive curves or the values of the inductive times shown in Figure 2(d) determined by system 1 are significantly different from each other, but the differences between the shapes or the values shown in Figure 3(d) determined by system 2 are less significant. However, it is obvious from the comparison between the determination times of NCFs in Figures 2(d) and 3(d) that the speeds to determine the NCFs by reaction system 2 are much faster than by reaction system 1 which has been currently widely used [14–22]. Therefore, the method established by system 2 not only is a new method for determining the NCFs but also can be used as a method for rapidly determining the NCFs of samples of Panax ginsengs, which is one of advantages of this method for determining the NCFs.

4.6 Applications of calculation and pattern recognition of system similarity

As mentioned before, the characteristic parameters of NCFs can be used to calculate the system similarity. For example, taking the average values of characteristic parameters in NCFs obtained by 3 parallel determinations as the parameters in the common pattern used in the comparison [11], the calculated system similarities between NCFs of the three samples of Panax ginsengs are shown in Table 3. The similarities may be used for identifying the species of Panax ginsengs. On determining through reaction systems 1 and 2, respectively, the system similarities between the NCFs of the same kind of sample≥ 0.9809 and 0.9978, respectively. The maximum system similarities between the NCFs of different kinds of samples are 0.6304 and 0.8634,respectively, and the average values of the system similarities 0.9809 and 0.6304 or 0.9978 and 0.8634 are 0.8057 and 0.9306, respectively. In the method for determining NCFs through system 1 or system 2, the average value 0.8057 or 0.9306 may be used as the criterion to identify the kind of each sample of Panax ginsengs. In other words, for the method based on system 1 or system 2, when the system similarity ≥0.8057 or 0.9036, the kind of the compared sample is the same as the standard sample; when <0.8057 or 0.9306, that of the compared sample is different from the standard sample.

Table 3 System similarities obtained by taking characteristic parameters of each mutual mode of NCFs of Panax ginsengs as comparison criteria

If there is an inconsistent result, a new criterion suitable for the two methods must be reset in order to accurately identify the relevant sample. The average value 0.8682 (=(0.8057+0.9306)/2) may be used as a new criterion to accurately identify the relevant sample. Analogously, when the system similarity ≥0.8682, the kind of the sample is the same as the standard sample; when <0.8682, the kind is different. Obviously, the accuracy of the result identified by the method based on double system is higher than that identified by any one based on single system. According to the theory of statistical probability, if the sample is identified by the two methods based on single system, respectively, and the error probabilities of their identification results are P₁ and P₂, respectively, then that of the identification by the method based on double system will be less than P₁ or P₂. In other words, the error probability of identification results obtained by the method based on double systems will be lower than P₁ or P₂, that is, the identification accuracy will be higher.

Both the system similarities and visual characteristics of NCFs of Panax ginsengs can be used to identify the kinds of Panax ginsengs. The accuracies to identify the kinds of some samples of Panax ginsengs by system similarity pattern are shown in Table 4. Both the accuracies of identification methods based on single systems 1 and 2 are greater than 95.6%, and their average accuracies are 97.1% and 96.3%, respectively. The accuracy of the method based on double system is greater than 97.8%, and the average accuracy is 99.3%. Distinctly, the accuracy of the method based on double system is higher than that based on any single system, namely, the method based on double reaction system can be used to more accurately identify the samples.

Table 4 Accuracy to identify sample authenticity by system similarity pattern

5 Conclusions

In order to accurately identify Panax ginsengs such as ginseng, American ginseng and notoginseng, a NCF method based on double system was researched, a new reaction system to determine NCF was also proposed, and successfully used in the identification of some samples of Panax ginsengs. The method based on double reaction system has higher identification accuracy than one based on single system. The compared results of two methods based on single system have indicated that although both the two methods have good characteristic and reproducibility, the method based on system 2 can save more determination time than one based on system 1. Therefore, the new reaction system can be used to rapidly determine the NCFs of Panax ginsengs and other samples.

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(Edited by YANG Hua)

中文导读

一种测定非线性化学指纹图谱新反应体系以及它在双反应体系中人参鉴别的应用

摘要：本文研究了一种测定非线性化学指纹图谱新反应体系及其在双体系鉴别方法中的应用。采用该方法对人参、西洋参、三七进行了鉴别。运用2种体系测定了3种样品的非线性化学指纹图谱，体系1由样品成分、硫酸、硫酸锰、溴酸钠、丙酮构成，体系2为新体系，由样品成分、硫酸、硫酸铈铵、溴酸钠、柠檬酸构成。比较2种体系的测定结果，发现体系2的测定速度比体系1快很多；同种样品在2种体系中的系统相似度分别≥ 98.09% 和99.78%，不同样品的系统相似度分别≤ 63.04% 和86.34%。采用系统相似度模型对样品进行鉴定，任一单体系鉴别方法准确度均≥95.6%，双体系的准确度≥ 97.8%，这表明，双体系的鉴别方法比任何单一体系的准确度都要高。

关键词：非线性化学指纹图谱；双体系；单体系；真伪鉴别；人参

Foundation item: Project(61533021)supported by the National Natural Science Foundation of China; Project (R201706) supported by Hunan Food Pharmaceutical, China

Received date: 2017-07-07; Accepted date: 2018-03-09

Corresponding author: DENG Fei-yue, Associate Professor; Tel: +86–13874886995; E-mail: 520175284@qq.com; ORCID: 0000-0002- 2387-9535