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Review

The Application of Electrochemical Oscillation Methods for Identification of Traditional Chinese Medicine Materials

by
Xin Shi
1,
Yuhong Zheng
2,* and
Li Fu
3,*
1
Ningxia Institute of Quality Standards and Testing Technology for Agricultural Products, Yinchuan 750002, China
2
The Jiangsu Provincial Platform for Conservation and Utilization of Agricultural Germplasm, Institute of Botany, Jiangsu Province and Chinese Academy of Sciences (Nanjing Botanical Garden, Memorial Sun Yat-Sen), Nanjing 210014, China
3
Key Laboratory of Novel Materials for Sensor of Zhejiang Province, College of Materials and Environmental Engineering, Hangzhou Dianzi University, Hangzhou 310018, China
*
Authors to whom correspondence should be addressed.
Appl. Sci. 2022, 12(2), 616; https://doi.org/10.3390/app12020616
Submission received: 29 October 2021 / Revised: 3 January 2022 / Accepted: 4 January 2022 / Published: 9 January 2022
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Abstract

:
Electrochemical oscillation reflects the overall characteristics of the system under test in terms of redox activity. It has proven to be advantageous in analyzing and processing complex components of herbal systems, such as polysaccharides and proteins. Therefore, it is widely used in the quantitative or qualitative tests of traditional Chinese medicines (TCMs) for identification and quality control. Electrochemical oscillation has several advantages such as high sensitivity, stability and micro sample requirement. Compared with other traditional methods, the interaction of multi-component in the TCMs was taken into account, which provides new ideas for the search of TCMs. Here, we presented a brief introduction on the progress on the topic, which promoted the development of electrochemical oscillation and the standardization of TCMs in the last twenty years. Electrochemical oscillation method is cheap, sensitive, fast, stable and convenient for the identification and quality control of TCMs. Reaction systems and the visualization of the fingerprints can be improved in the future.

1. Introduction

The identification is one of the important tasks in traditional Chinese medicines (TCMs). Distinct from the drugs synthesized chemically, TCMs are from tissues or organs of plants and animals as well as from minerals. In different regions in China, the homonym and synonym of herbs are quite commonly seen. In addition, many TCMs require post-treatment such as stir fry and pickle into paste, soup, pills or powder. The identification of TCMs is also the important parts in the process of quality control of TCMs [1]. After thousands of years of study and practice, the identification of TCMs can be conducted by different methods. Among them, physical property identification is the most dominant method such as the shape, color, taste, smell and texture. It is simple and quick but subjective. Its accuracy depends almost entirely on the experience of the examiner, and it is very difficult to identify processed medicinal materials. The microstructure-based method uses a microscope to observe the tissue and cell structure. It is a fast technology, but it is easily affected by harvest seasons and storage conditions [2]. Chemical identification is based on the qualitative sensing of chemical components, which is relatively simple [3,4]. For example, thin-layer chromatography is easy to operate, but it has low accuracy for TCMs from a same genus because they share many similar compositions [5]. Phytochemistry requires a large amount of samples and requires expensive equipment such as chromatographs [6,7,8]. In recent years, molecular biology technology (DNA barcode technology) has also been applied in the identification of TCMs [9,10,11]. However, it cannot be used for the identification of TCMs with post-treatment due to DNA damage. Since TCMs contain different types of samples, no single detection technique can be applied to all of them. Among various methodologies, electrochemical oscillation has been applied to the identification of TCMs since 2004. The present review aims to provide comprehensive and up-to-date information on the identification of TCMs using electrochemical oscillation. In addition, future perspectives of electrochemical oscillation have been discussed as well.

2. Oscillatory Reaction and Electrochemical Oscillation

Ordinary chemical reactions gradually reach equilibrium by decreasing the concentration of reactants and increasing the concentration of products as the reaction proceeds. However, in some complex chemical systems, the concentration of certain components or intermediates will show certain periodic changes with time, and this phenomenon is called chemical oscillation reaction. Oscillatory reactions have a wide range of applications in many fields and have, therefore, attracted the interest of physicists and chemists.
In 1958, chemist B. P. Belousov discovered the oscillation reaction system [12]. He observed concentration oscillations in a closed system of dilute sulfuric acid solutions of potassium bromate, citric acid and cerium sulfate, which was the most ordered oscillation phenomenon found at that time. In 1964, A. M. Zhabotinsky optimized the reaction system, which is now called the Belousov–Zhabotinsky system (B-Z system) [13,14]. Later, Field et al. [15,16] established the FKN model, which further improved the basic theory of chemical kinetics of oscillating systems. So far, many other oscillation reaction systems were found, such as Bray–Liebhafsky (B-L) oscillation system [17], Peroxidase–Monoxidase biochemical oscillation system [18] and Briggs–Rauscher oscillation system [19]. Oscillation reactions are reactions far from an equilibrium state and are extremely sensitive to reaction conditions. Factors include reactant concentration, catalyst concentration, reaction temperature, stirring speed, light conditions and the effect of oxygen, etc. Therefore, electrochemical methods such as potentiometry, ion selective electrode and conductometry are often used to study oscillatory systems [20,21].
In recent years, the chemical oscillation system was applied to determine the content or concentration of a variety of organic, inorganic and gaseous substances. The mechanism of chemical oscillation reactions for analytical assays lies mainly in the fact that the substance to be measured can interfere with the oscillation reaction. In the last three decades, techniques such as regular oscillation combined with flow injection [22], analyte pulse perturbation technique [23] and continuous-flow stirred tank reactor [24] have been applied to chemical oscillation reactions, making them widely used for the determination of inorganic and organic compounds, such as CO, Vitamin B1, Vitamin C, Vitamin B6, phenol and formaldehyde [25,26,27,28,29,30]. Among them, electrochemical oscillation, as an important branch of chemical oscillation, is the phenomenon of order in time and space in an electric field, which is apart from equilibrium. For electrochemical systems, it is generally always a non-equilibrium state where the reaction occurs by using the polarization property to deviate the potential from the equilibrium potential of that electrode [31]. The electrode reaction itself is a complex multiphase reaction process. Each factor is correlated with each other, which is a nonlinear reaction process, and this makes the oscillation phenomenon easily generated in the electrochemical system [32]. It developed quite rapidly after the chemical oscillation theory was established and has the same advantages as chemical oscillation systems. Moreover, electrochemical oscillation fingerprints contain several characteristic indicators such as induction time, highest and lowest potential, oscillation period and maximum amplitude, and it can be applied to analyze the chemical composition of the TCMs with no requirement of separation and purification and other pre-treatments [33,34]. Electrochemical oscillation also has certain limitations, such as the need to match the sample and the oscillation system and the need to enhance the oscillation signal. Figure 1 shows a schematic diagram of electrochemical oscillation fingerprints.

3. Identification of Chinese Medicinal Materials

TCMs come from plants, but when used as medicinal materials, they have been processed, and they lose their phytological characteristics. Although each TCM has its own active pharmacological components, the low levels of these components make it difficult to use them directly for identification. However, if the technology is available to display a part of the components of the plant to form a fingerprint profile, this fingerprinting process can then be used for the identification of different TCMs. Electrochemical oscillation techniques can present different fingerprint profiles due to the differences in electrochemical oxidizing, and it can reduce substances in plant systems. Therefore, this technique can be used for TCMs identification. In this review, we will focus on three aspects of species identification: genuine and counterfeit identification and genuineness identification.

3.1. Species Identification

In 2004, Li et al. [35] reported the first study of using electrochemical oscillation for TCMs identification. KBrO3-MnSO4-H2SO4 and acetone have been used for construction of an oscillating system. The fingerprints of 30 species of TCMs were reported. The fingerprints of every species have significant differences, which indicated that they can be used for identification. During the following years, the fingerprints of hundreds of TCMs have been reported [36,37,38,39,40]. At the same time, the optimization of the technology system and improvement of data statistics were carried on. Factors such as temperatures, sample dosage, reaction systems and stirring speed were taken into consideration [41]. The method of similarity calculation was applied for data analysis [42].
Yuan et al. [43] recorded the fingerprints of nine species of TCMs, among which some of them have similar functions. By comparing fingerprints, they found that even if the same types of herbal medicines contain the same chemical components, their fingerprints are quite different, which can be used for their identification. A similar study was reported by Du et al. [44]. They obtained the fingerprints of seven species (five families) on the basis of an oscillation behavior mechanism. Traditionally, TCMs are often taken from a certain organ of plants. Zhang et al. [45] investigated fingerprints of different organs of the same TCMs using H+-Mn2+CH3COOCH-BrO3− as the reaction system. The results indicated that the fingerprints of different organs had significant differences. This study demonstrates that the electrochemical oscillation technique is not only applicable to species identification but, in some cases, can also be used for the identification of different plant organs. In 2018, Du et al. [46] reported fingerprints of 30 species using KBrO3-CeSO4-H2SO4-malonic acid-tartaric acid as the reaction system. The results showed that not only fingerprint shapes but also induction time, maximum amplitude and oscillation period were also significantly different [47,48,49]. These indicators can be also used for discrimination. A similar study was reported by Wang et al. [50]. They distinguished four TCMs in Zingiberaceae using KBrO3-MnSO4-H2SO4-malonic acid as the mixed oscillation system. In addition, Astragali Radix (Astragalus membranaceus var. mongholicus or A. membranaceus); Cassiae Semen (Cassia obtusifolia or Cassia tora); Puerariae Lobatae Radix (Pueraria lobata); Radix Sophorae Flavescentis (Sophora flavescens); Glycyrrhizae Radix (Glycyrrhiza uralensis, Glycyrrhiza inflata or Glycyrrhiza glabra); Coptidis Rhizoma (Coptis chinensis, Coptis deltoidea or Coptis teeta), Pulsatillae Radix (Pulsatilla chinensis) [51]; Polygoni Cuspidati Rhizoma Et Radix (Reynoutria japonica) and Polygoni Multiflori Radix (Polygonum multiflorum) [52]; Rhei Radix et Rhizoma (Rheum officinale) [51]; and four species in Fritillaria L. [53] were identified by different studies.

3.2. Genuine and Counterfeit Identification

Identification of genuine and counterfeit refers to the substitution of some similar plants for the target TCMs. Another scenario is that the TCMs are mixed with a portion of other substances to increase profitability.
Wang et al. [54] distinguished Notoginseng Radix et Rhizoma (Panax notogitiseng) and its adulterants Atractylodis Rhizoma (Atractylodes lancea or Atractylodes chinensis) and Curcumae Longae Rhizoma (Curcuma longa), Curcumae Rhizoma (Curcuma phaeocaulis, Curcuma kwangsiensis, Curcuma wenyujin) and Curcumae Radix (Curcuma wenyujin, Curcuma longa, Curcuma kwangsiensis or Curcuma phaeocaulis) using the KBrO3-MnSO4-H2SO4–acetone system. The system also worked on Codonopsis Radix (Codonopsis pilosula, Codonopsis pilosula var. modesta or Codonopsis tangshen) and its adulterant Gentianae Radix et Rhizoma (Gentiana manshurica, Gentiana scabra, Gentiana triflora or Gentiana rigescens) [55], Panacis Quinquefolii Radix (Panax quinquefolium) and Ginseng Radix et Rhizoma (Panax ginseng). Another report described a similar method for distinguishing Gastrodiae Rhizoma (Gastrodia elata) with its counterfeits Mirabilis jalapa, Dahlia pinnata, Canna edulis and Solanum tuberosum [56]. In addition, Zanthoxyli Radix (Zanthoxylum nitidum) and its counterfeit Toddalia asiatica can be identified as well [57]. In addition to identifying similar samples from different plants, electrochemical oscillations can be used to identify mixed samples. Tan et al. [58] applied recorded electrochemical fingerprints of Acori Tatarinowii Rhizoma (Acorus tatarinowii), Anemones Raddeanae Rhizoma (Anemone raddeana) and their mixture. The similarity was calculated for identification. In addition, fingerprinting differences between different samples, the induction time and oscillation period can be used as index for determining the percentage of each component in the mixture. Table 1 summarizes the application of KBrO3-MnSO4-H2SO4-CH3COCH3 system in electrochemical oscillation for genuine and counterfeit identification for TCMs.

3.3. Genuineness Identification

Genuineness refers to some TCMs that have been preferentially selected in a specific geographical area by using long-term clinical results. They have better quality and efficacy compared with the same kind of TCMs produced in other regions. Genuineness identification has always been a difficult point in the identification of TCMs because it only related to the interaction of genetic and ecological factors. Since there are little differences at the genetic level between genuine and non-genuine herbs, they do not differ particularly much in their phytochemical compositions. The fingerprints reported by Li et al. [43] contain Atractylodis Rhizoma, Angelicae Sinensis Radix and Codonopsis Radix from different locations. The results showed that the fingerprints of the same TCMs from different areas are quite similar. However, they have differences with respect to induction time and oscillation period, which can be used to identify the same species cultivated at different locations [66]. Chen et al. [67] reported fingerprints of Acori Rhizoma using B-Z oscillating system in several areas in the Anhui province. The fingerprints from different areas have great differences with respect to induction time, maximum potential, oscillation period and oscillation life, which proved that electrochemical oscillation can be used to identify the genuineness of TCMs. The same system was then applied for identifying Polygonati Rhizoma growing at different locations as well [68]. Xue [51] recorded the fingerprints of Glycyrrhizae Radix using the NaBrO3-(NH4)4Ce(SO4)4-H2SO4-malonic acid oscillatory system from different provinces including Anhui, Gansu, Inner Mongolia and Ningxia. All results prove that the fingerprints of the same herbs in different geographical areas can have some differences. However, subsequent studies are needed to quantify these differences in fingerprints. It is necessary to establish a system that can be quantitatively analyzed.

3.4. Quality Control and Evaluation

Since reactions happening in oscillation systems involve kinetics, it can be used to study the mechanism of action, which can provide a new idea for the determination of active ingredients in TCMs. For example, Zhang et al. [69] used an electrochemical oscillation system to determine glucose and fructose in honey and proposed a new method for honey quality evaluation. The results show that this method can be used very effectively for the classification of honey grades. In addition, this method does not require pre-treatment, purification and separation of the honey. The same method was used to measure Chinese medical extract content. The active ingredients content in Notoginseng Radix et Rhizoma drop pills and gastrodin content in Gastrodiae Rhizoma from different areas were evaluated for their quality [56]. Yuan and Li [70] recorded fingerprints of Chinese herbal compound prescription Liuweidihuang pills from five companies. The results showed, with the exception of the products from Baoji Chenji Company, the other four products had very similar fingerprints, indicating that they have the same quality.

4. Conclusions and Perspectives

This review summarizes the development of electrochemical oscillation and the prospective application of this analytical technique in analysis and process control of TCMs. The reactions in electrochemical oscillations are highly correlated with kinetics. Therefore, this technique is expected to be used for TCMs for mechanisms of action in addition to identification and quality control. The oscillatory chemical fingerprinting of TCMs is studied by using the sample as a whole as a reaction substrate, and fingerprinting reflects activity changes of the overall composition. The existing reports have only analyzed the characteristic samples of TCMs, while the study of complex and mixed herbal samples is still lacking. At the same time, fingerprinting data analysis only rested on preliminary numerical comparisons and lacked in-depth data analysis. Similarity calculation can reveal differences of some samples in terms of data homology, but this method is not applicable in the analysis of samples with weak similarity differences. Thus, it is still necessary for deep analysis and mining of the fingerprint. The analysis of fingerprints has mostly focused on the induction time, while the oscillation period, which is relatively rich in information, is not studied in depth. Current information collection on the oscillation process only stops at recording potential values at different times. This interpretation renders it difficult to obtain real information of each time point and is not conducive to the in-depth analysis of the data. Therefore, the application of electrochemical oscillation technique in the analysis of TCMs needs to improve the richness of detected information. Electrode surface modification can be used for assistance of signal enhancement in electrochemical oscillation. It is also important to develop fingerprint analysis algorithms and software. Scientific and systematic connotation of fingerprint information can be improved to better guide and serve quality evaluation and control of TCMs.

Author Contributions

Conceptualization, X.S. and Y.Z.; writing—original draft preparation, X.S. (with the help of Y.Z.); writing—review and editing, L.F.; supervision, L.F. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by Ningxia Agricultural High-quality Development and Ecological Protection Technological Innovation Demonstration Project (NGSB-2021-5-01); Natural Science Foundation of Ningxia (2021AAC03280) and Ningxia Excellent Talent Support Program.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Not applicable.

Conflicts of Interest

The authors declare no conflict of interest.

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Applsci 12 00616 g001 550
Figure 1. Schematic diagram of typical electrochemical oscillation fingerprints.
Figure 1. Schematic diagram of typical electrochemical oscillation fingerprints.
Applsci 12 00616 g001
Table
Table 1. The application of KBrO3-MnSO4-H2SO4-CH3COCH3 system in electrochemical oscillation for TCMs analysis.
Table 1. The application of KBrO3-MnSO4-H2SO4-CH3COCH3 system in electrochemical oscillation for TCMs analysis.
Name of TCMsReferences
Rhei Radix et Rhizoma (Rheum palmatum, Rheum tanguticum or Rheum officinale) and Rheum franzenbachii[51]
Coptidis Rhizoma (Coptis chinensis, Coptis deltoidea or Coptis teeta) and its counterfeit[59]
Carthami Flos (Carthamus tinctorius) and its counterfeit[60]
Rhodiolae Crenulatae Radix et Rhizoma (Rhodiola crenulat) and its counterfeit[61]
Notoginseng Radix et Rhizoma (Panax notoginseng) and its counterfeit[54]
Codonopsis Radix (Codonopsis pilosula, Codonopsis pilosula var. modesta or Codonopsis tangshen) and Gentianae Macrophyllae Radix (Gentiana macrophylla, Gentiana straminea or Gentiana crassicaulis)[55]
Persicae Semen (Prunus persica or Prunus davidiana), Semen armeniacae, Armeniacae Semen Amarum (Prunus armeniaca var. ansu, Prunus sibirica, Prunus mandshurica, Prunus armeniaca)[62]
Polygoni Cuspidati Rhizoma Et Radix (Reynoutria japonica) and Gentianae Macrophyllae Radix (Gentiana macrophylla, Gentiana straminea or Gentiana crassicaulis)
Pulsatillae Radix (Pulsatilla chinensis) and Rhapontici Radix (Rhaponticum uniflorum)
Polygoni Multiflori Radix (Polygonum multiflorum) and Rhei Radix et Rhizoma (Rheum officinale)[52]
Fritillariae Cirrhosae Bulbus (Fritillaria cirrhosa, F. unibracteata, F. przewalskii, F. delavayi, F. taipaiensis or F. unibracteata var. wabuensis ), Fritillariae Ussuriensis Bulbus (F. ussuriensis), Fritillariae Thunbergii Bulbus (F. thunbergii)[53]
Coptidis Rhizoma (Coptis chinensis, Coptis deltoidea or Coptis teeta), Pulsatillae Radix (Pulsatilla chinensis) and Clematidis Radix et Rhizoma (Clematis chinensis, Clematis hexa petala or Clematis manshurica)[51]
Astragali Radix (Astragalus membranaceus var. mongholicus or Astragalus membranaceus), Citri Reticulatae Pericarpium (Citrus reticulata), Puerariae Lobatae Radix (Pueraria lobata), Glycyrrhizae Radix et Rhizoma (Glycyrrhiza uralensis, Glycyrrhiza inflata or Glycyrrhiza glabra), Paeoniae Radix Alba (Paeonia ladiflora), Salviae Miltiorrhizae Radix et Rhizoma (Salvia miltiorrhiza) and Acanthopanacis Cortex (Acanthopanax gracilistylus)[44]
Astragali Radix (Astragalus membranaceus), Cassia Semen (Cassia obtusifolia or Cassia tora), Sophorae Flavescentis Radix (Sophora flavescens)[63]
Paeoniae Radix Rubra (Paeonia lactiflora or Paeonia veitchii), Paridis Rhizoma (Paris polyphylla var. yunnanensis or Paris polyphylla var. chinensis), Citri Reticulatae Pericarpium (Citrus reticulata), Pinalliae Rhizoma (Pineilia ternata), Ophiopogonis Radix (Ophiopogon japonicus), Stephaniae Tetrandrae Radix (Stephania tetrandra)[64]
Chuanxiong Rhizoma (Ligusticum chuanxiong), Paridis Rhizoma (Paris polyphylla var. yunnanensis or Paris polyphylla var. chinensis), Citri Reticulatae Pericarpium (Citrus reticulata), Pinalliae Rhizoma (Pineilia ternata), Ophiopogonis Radix (Ophiopogon japonicus), Stephaniae Tetrandrae Radix (Stephania tetrandra)[65]
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Shi, X.; Zheng, Y.; Fu, L. The Application of Electrochemical Oscillation Methods for Identification of Traditional Chinese Medicine Materials. Appl. Sci. 2022, 12, 616. https://doi.org/10.3390/app12020616

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Shi X, Zheng Y, Fu L. The Application of Electrochemical Oscillation Methods for Identification of Traditional Chinese Medicine Materials. Applied Sciences. 2022; 12(2):616. https://doi.org/10.3390/app12020616

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Shi, Xin, Yuhong Zheng, and Li Fu. 2022. "The Application of Electrochemical Oscillation Methods for Identification of Traditional Chinese Medicine Materials" Applied Sciences 12, no. 2: 616. https://doi.org/10.3390/app12020616

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