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Developing a reliable and effective quality evaluation system for traditional Chinese medicine (TCM) is both challenging and crucial for its advancement. This study employs fingerprinting techniques to establish precise and comprehensive quality control for TCM, taking Xuezhikang capsules as an example and aiming to facilitate the internationalization of TCM. The "double wavelength absorption coefficient ratio fingerprint" and "Reliability theory" are developed to determine the fingerprint peak purity and fingerprint reliability respectively. Subsequently, the dual-wavelength fusion fingerprint was obtained to avoid the limitations of a single wavelength. In addition, an electrochemical fingerprint (ECFP) was obtained to assess the similarity of electroactive components in the sample, and the Differential Scanning Calorimetry quantized fingerprint (DSC QFP) was introduced for thermal analysis. Fingerprint-efficacy correlations between PL-EC* and dual-wavelength fusion fingerprint (DWFFP) provided valuable insights that there are 76.6 % of the fingerprint compounds exhibited electroactivity. Finally, samples were classified into grades 1∼3 by combining DWFFP, ECFP and DSC QFP through the mean method, meeting the evaluation standard (SL-M > 0.9, PL-M between 80 % and 120 %). This study provides valuable information for ensuring the quality of TCM products, which represents a significant step forward in enhancing the reliability and authenticity of TCM products.

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Tianma Toutong Tablets (TMTTTs) are composed of six traditional Chinese medicines (TCMs), and there is currently no comprehensive method to evaluate the quality of TMTTT. To ensure its quality, it is necessary to propose methods for evaluation and control. To address the issue, we established an HPLC and electrochemical fingerprint of TMTTT and quantify eight components-Gastrodin, p-hydroxybenzyl alcohol, chlorogenic acid, parishin A, ferulic acid, hesperidin, imperatorin, and isoimperatorin. We used the Sub-quantified profiling method (SQPM) to calculate the actual contribution value of each individual herb and evaluated and predicted the quality of the compound medication. In addition, electrochemical fingerprinting (ECFP) was established using a Belousov-Zhabotinsky (B-Z) oscillation system in which six characteristic electrochemical parameters were recorded to compare the differences between batches. Finally, a compound synthesizing fingerprint (CSF) of TMTTT was developed by fitting the compounds of the six herbs, the contribution of individual herbs to the prescription was evaluated. Principal component analysis (PCA) was used to downscale the data of different fingerprint profiles to assist the analysis process. The rational combination of multidimensional fingerprinting and PCA provided a comprehensive and reliable method for the evaluation of TMTTT and other TCM compound preparations, SQPM could effectively link single herbs to compound preparations, avoiding the use of non-compliant TCMs at source and improving the quality of compound preparations.

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Red Yeast Rice (RYR) is an important functional food ingredient that plays a critical role in promoting dietary guidance and maintaining health. To ensure its quality, four key compounds were quantified, and both HPLC fingerprint and electrochemical fingerprint (ECFP) were applied to assess quality. Additionally, 2,2'-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) (ABTS+•) scavenging test and ECFP were applied to assay the total antioxidant activity, with ascorbic acid as the positive control. The results showed that the holistic quality of samples was divided into 4 grades based on HPLC fingerprint analysis by the comprehensive linear quantitative fingerprint method. Additionally, the area of the total peak (Atp) in ECFP was found to be linearly correlated with the antioxidant activity (R > 0.99). A further fingerprint-efficacy relationship analysis determined the significant contributions to the antioxidant activity of peaks 20-Daidzein, 21-Glycitein, and 24-Genistein. Overall, this study suggested a comprehensive and reliable approach to the quality assessment of RYR.

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The Keteling capsule (KC) is a traditional Chinese medicine (TCM) made from the dried extract of Ficus microphylla and an appropriate amount of chlorpheniramine maleate. It is widely used to treat cough and relieve asthma. Despite its extensive usage, a rapid and comprehensive quality evaluation strategy for KC remains a challenge. This study introduces an electrochemical fingerprint analysis technique, in addition to the commonly employed HPLC fingerprints, for efficient and convenient quality evaluation. Moreover, a cost-effective, rapid, and accurate multi-component quantification technique known as the "Multi-markers assay by the monolinear method (MAML)" and the "FT-IR quantitative model" were explored. The HPLC fingerprints were evaluated using a systematically quantified fingerprint method, while the electrochemical fingerprints, based on the Belousov-Zhabotinsky oscillation reaction principle, were effectively analyzed and characterized using oxidation induction times and oscillation lifetimes. Multi-component quantitative analysis was carried out through the MAML and FT-IR quantitative models. The HPLC fingerprint successfully classified the 22 samples into eight grades with excellent discrimination. Active ingredient content analysis was achieved using reliable parameters obtained from electrochemical fingerprinting. The no significant difference in the quantitative results proves the accuracy of the MAML method. Additionally, successful FT-IR quantitative prediction models were developed for chlorogenic acid, isovitexin, and chlorpheniramine maleate. This study offers a dependable and effective approach for enhancing the quality control of KC, and it can provide new insights for improving the quality analysis methods in the field of TCM.

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The antiviral oral liquid (AOL) was an antiviral drug currently in clinical trials against coronavirus disease 2019. This study aimed to improve its quality consistency evaluation method using fingerprint techniques from several aspects. First, the five-wavelength matched average fusion fingerprint (FMAFFP) for HPLC, electrochemical fingerprint (ECFP), and ultraviolet spectral quantum fingerprint (UVFP) was established for 22 samples, respectively. Their quality was then assessed using the average linear quantitative fingerprint method, and 22 samples were classified into eight quality grades. OPLS and PCA were then used further to explore the characteristic parameters of these three fingerprints. Five compounds were quantified simultaneously for the first time, and then the relationship between the average linear quantitative similarity (PL) and the sum of the five quantitative components (P5c) was investigated. A linear correlation (r ≥ 0.9735) between PL and P5c suggested that PL may be used to predict chemical content. Finally, to investigate the antioxidant potential of the AOL, correlation analyses were performed for FMAFFP peaks-PEC and UVFP peaks-PEC, respectively, where the PEC value was defined as the quantitative similarity of ECFP. The Pearson correlation coefficient and gray correlation analysis were consistent, allowing us to initially explore the antioxidant capacity of the unidentified components of the samples. This study researched AOL using multidimensional fingerprints to provide a comprehensive and reliable method for quality consistency control of herbal compound preparations.

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Improving the quality standard system of herbal preparations (HPs) is an arduous task for the development of traditional Chinese medicine (TCM). At present, an urgent task is to establish a comprehensive, scientific and effective evaluation method for improving the safety, effectiveness and quality consistency of HPs. In this study, Hu Gan capsules (HGCs) were used as an example. Firstly, the three quality markers (Q-markers) in 21 batches of HGCs from 4 manufacturers were determined by HPLC and great difference in content of each sample was found. Furthermore, four-wavelength fusion profiling (FWFP) was established and evaluated by systematically quantified fingerprint method (SQFM). Principal component analysis (PCA) was employed to make a preliminary analysis of the FWFP and distinguish the fluctuation of differences in chemical composition and content. Then, 9 characteristic parameters were recorded through the B-Z oscillating system, and the electrochemical fingerprint (ECFP) was constructed for jointing evaluation with the FWFP, using the equal weight of SQFM results to comprehensively evaluate the sample quality. The 21 batches of samples were divided into four groups and six grades, which indicated that there were significant differences in the content of indicator components and electrochemical active substances in samples. Finally, taking vitamin C as a positive control, 2, 2'-azino-bis (3 - ethyl -benzthiazoline - 6 - sulfonic acid) (ABTS) scavenging assay was applied to study the antioxidant activity of samples. Partial Least Squares (PLS) and bivariate correlation analysis (BCA) were used to analyze the fingerprint-efficacy relationships of FWFP-ABTS and FWFP-ECFP. Consequently, it was found that there were similar antioxidant capacities in electrochemistry and ABTS tests, and 31 of the 40 HPLC fingerprint peaks of HGCs were discovered to have antioxidant activity. The two methods supported each other, to effectively and corporately reflect the antioxidant components in HGCs. In this research, the FWFP and ECFP established could realize the quality detection of HGCs, and provide a novel direction for the improvement of the quality standard of HPs and the research of the quality standard method of TCM.

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Electrochemical analysis has become a new method for plant analysis in recent years. It can not only collect signals of electrochemically active substances in plant tissues, but can also be used to identify plant species. At the same time, the signals of electrochemically active substances in plant tissues can also be used to investigate plant phylogeny. In this work, we collected electrochemical finger patterns in Malvaceae leaves based on the established methodological strategy. After the second derivative treatment, the collected electrochemical fingerprints can show more obvious differences. Three different recognition models were used to attempt electrochemical fingerprinting. The results show that linear support vector classification can be used to identify species with high accuracy by combining the electrochemical fingerprint signals collected in the phosphoric acid buffer solution and acetic acid buffer solution. In addition, the fingerprint information collected by the electrochemical sensor is further used for phylogenetic investigation. The 18 species were divided into three clusters. Species of the same genus have been clustered together. Dendrogram obtained by electrochemical fingerprinting was used to compare previously reported results deduced from morphological and complete chloroplast genomes.

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Electrochemical fingerprinting can collect the electrochemical behavior of electrochemically active molecules in plant tissues, so it is regarded as a new plant analysis technology. Because the signal of electrochemical fingerprinting is positively correlated with the amount and type of electrochemically active molecules in plant tissues, it can also be used to reflect genetic differences between different species. Previous electrochemical fingerprinting techniques have been frequently used in phylogenetic studies of herbaceous plants. In this work, 19 Quercus species (17 evergreen or semi evergreen species and 2 deciduous species) were selected for investigation. The results indicated the electrochemical fingerprint of some species share similar features but can be distinguished after changing the recording condition (extraction solvent and electrolyte). The two sets of electrochemical fingerprint data can be used to construct different pattern recognition technology, which further speeds up the recognition efficiency. These electrochemical fingerprints were further used in phylogenetic investigations. The phylogenetic results deduced from electrochemical fingerprinting were divided mainly into three clusters. These can provide evidence for some of these arguments as well as new results.

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In this paper, three-wavelength fusion fingerprint (TWFFP) combined with electrochemical fingerprint (ECFP) and antioxidant methods were used to jointly explore the quality consistency of Mingmu Dihuang Pill (MMDHP). The TWFFP fully demonstrated the maximum ultraviolet absorption characteristics at multiple wavelengths, supplemented the defects brought by the single-wavelength evaluation. ECFP was established to analyze the characteristic parameters in more depth, and all samples had inhibitory effects on the electrochemical oscillation system. Using 2,2-diaza-bis(3-ethylbenzothiazole-6-sulfonic acid) antioxidant test, combined with ECFP, the fingerprint-efficacy relationship was established with the peak areas of the TWFFP. As a result, 15 of the 36 common peaks made important contributions to both efficacy relationships at the same time. The TWFFP and ECFP were evaluated by a systematically quantified fingerprint method, and the ability of HPLC and electrochemical to distinguish samples was discussed by hierarchical clustering analysis. Content percentage was introduced to calculate the relationship between marker components and macro quantitative similarity. The method of quantitative analysis of multi-components by single marker was explored to analyze the accuracy of evaluating the marker components. This study provided a comprehensive and reliable method for the quality consistency control of complex Traditional Chinese Medicine and its compound preparations.

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Quality consistency control of traditional Chinese medicine (TCM) is often essential for providing reference and procedure to guarantee the safety and effectiveness of TCM. Taking Rong'e Yishen oral liquid (REYS) as an example, five-wavelength maximization profilings (FWMPs) of 21 samples were constructed to fully manifest the maximum UV absorption characteristics at multi-wavelength. The preliminary analysis of FWMPs by principal component analysis (PCA) suggested us focusing on evaluating the quality consistency qualitatively and quantitatively by systematically quantified fingerprint method (SQFM). Meanwhile, electrochemical fingerprints (ECFPs) were established and the related characteristic parameters were deeply analyzed. All the samples had inhibitory effect on the electrochemical oscillation system, and the oscillation life (tol) was linear with the added volume and temperature in a certain range, respectively (r > 0.94). The merging point method was first introduced to process ECFP to facilitate its evaluation with SQFM. The evaluation results of FWMPs and the merged ECFPs were integrated in an equal weight for assessing the sample quality completely, and 21 samples were classified into two grades with good quality consistency. Furthermore, 2, 2-azino-bis (3 - ethyl - benzthiazoline - 6 - sulfonic acid) (ABTS) scavenging assay was applied to study the antioxidant activity of samples using vitamin C as a positive control. Partial least squares (PLS) model and bivariate correlation analysis (BCA) was used for FWMP-ABTS efficacy relationship and FWMP-merged ECFP efficacy relationship respectively. 15 of the 48 co-possessing peaks made important contributions to the two efficacy relationships simultaneously. This study suggested a comprehensive and reliable approach for quality consistency control of complex TCM or herbal medicine.

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Acer Linn. is a highly divergent species morphology in the maple family (Aceraceae). It is one of the genera facing a very difficult taxonomic situation. The phylogeny of the genus and the taxonomic system under the genus remain unclear. The use of electrochemical fingerprints for plant phylogenetic study is an emerging application in biosensors. In this work, leaves of 18 species of Acer Linn. with an exo-taxa were selected for electrochemical fingerprint recording. Two different conditions were used for improving the data abundance. The fingerprint of all species showed a series of oxidation peaks. These peaks can be ascribed to the oxidation of flavonols, phenolic acids, procyanidins, alkaloids, and pigments in plant tissue. These electrochemical fingerprints can be used for the identification of plant species. We also performed a phylogenetic study with data from electrochemical fingerprinting. The phylogenetic tree of Acer is divided into three main clades. The result is in full agreement with A. shangszeense var. anfuense, A. pictum subsp. mono, A. amplum, A. truncatum, and A. miaotaiense, belonging to the subsection Platanoidea. A. nikoense and A. griseum were clustered together in the dendrogram. Another group that fits the traditional classification results is in the subsection Integrifolia.

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The illicit consumption of heroin is an increasing concern in our society. For this reason, rapid analytical methods to seize heroin samples in the field are of paramount importance to hinder drug trafficking, and thus prevent the availability of heroin in the drug market. The present work reports on the enriched electrochemical fingerprint of heroin, allowing its selective detection in street samples, based on the use of electrochemical pretreated screen printed electrodes (p-SPE). The voltammetric identification is built on two oxidation peaks of both heroin and its degradation product 6-monoacetylmorphine (6-MAM), generated in alkaline conditions. Interestingly, an anodic pretreatment of the screen printed electrodes (SPE) shifts the peak potential of paracetamol (the most encountered cutting agent in heroin seizures), allowing the detection of 6-MAM peak, overlapping with the paracetamol signal in the case of untreated SPE. Subsequently, the characterization of the p-SPE with scanning electron microscopy, cyclic voltammetry, electrochemical impedance spectroscopy, Raman and Fourier transform infrared (FTIR) spectroscopy is provided to demonstrate local changes on the surface of the electrode. From an analytical perspective, p-SPE provide higher sensitivity (0.019 µA µM-1), excellent reproducibility (6-MAM, RSD = 2.85%, and heroin RSD = 0.91%, n = 5) and lower limits of detection (LOD) (5.2 µM) in comparison to untreated SPE. The proposed protocol which integrates a tailor-made script is interrogated against common cutting agents, and finally, validated with the screening of 14 street samples, also analyzed by standard methods. Besides, a comparison with portable spectroscopic techniques on the confiscated samples shows the better performance of the electrochemical strategy. Overall, this sensing approach offers promising results for the rapid on-site profiling of suspicious heroin samples, also in the presence of paracetamol.

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The mechanisms of extracellular electron transfer and the microbial taxa associated with the observed electroactivity are fundamental to oxygen-reducing microbial cathodes. Here we confirmed the apparent 'electroautotrophic' behavior of electroactive biofilms (EABs) grown on carbon electrodes at + 0.20V vs. Ag/AgCl under air. The EABs catalyzed O2 electroreduction into water ─ as demonstrated by a rotating ring disc experiment ─ and performed quasi-reversible heterogeneous electron transfer (HET). By using electrodes of low surface capacitance, we report for the first time nonturnover redox peaks that are very likely intrinsic to the redox protein(s) performing the HET. Because the formal potential of redox proteins is pH-dependent, we investigated the evolution of characteristic potentials of the EABs with the solution pH: (i) open circuit potential, (ii) half-wave potential, and (iii) averaged peak potential of nonturnover cyclic voltammograms, which is presumably the formal potential of the primary electron acceptor(s) for the community. In addition to describing the redox thermodynamics behind HET, we suggest that the corresponding data provides an electrochemical fingerprint that could help in comparing the electroactivity of diverse microbial communities. The taxon with the highest relative abundance in our EABs was an unclassified member of the Gammaproteobacteria that was phylogenetically closely related to most other abundant unclassified Gammaproteobacteria commonly reported in EABs reducing O2 at high potentials, further suggesting that those taxa are responsible for the bioelectroactivity. Phylogenetic and electrochemical similarities between reported EABs jointly support the hypothesis that similar biomolecular mechanisms may be responsible for this highly probable electroautotrophic metabolism.

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The identification of plant species not only is a hobby but also has important application value in plant resources science. Traditional plant identification often relies on the experience of botanists. The infrageneric identification of plants is easily mistaken due to similarities in organ features. In this work, we propose an electrochemical method to obtain fingerprints of plant petal tissue. Fourteen species of Lycoris were used as a model for validating this methodology. Pattern and color recognition were established for visualization of electrochemical fingerprints recorded after various solvent extractions. In addition, the infrageneric relationships of these Lycoris species were deduced from the electrochemical fingerprints since the type and content of electroactive compounds in plants are controlled by genes. The results indicate that the electrochemical fingerprints of Lycoris petals are correlated with the infrageneric relationships of native Lycoris species.

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As is known to all, it is difficult for the quality control of herbs and products of Chinese materia medica (CMM) because of its complex composition and unstable source. Fingerprint technology is an effective process analysis tool, which can be used in the quality control of CMM. Among them, the electrochemical fingerprint method based on oscillatory chemistry is convenient, sensitive, and accurate, which has been used in qualitative and quantitative analysis and process quality control of CMM. In this paper, we reviewed the development history of oscillatory chemistry, the types of oscillatory systems, and the application of oscillatory chemical fingerprint in the quality control of herbs and products of CMM. Besides, the existing problems in data testing and analysis and the possible improvement direction have been introduced. The paper aimed to provide a new method or new idea for the scientific and systematical quality control of CMM.

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A new composite organic oscillating reaction system based on BrO3-Ce(SO4)2-H2SO4-malonic acid/tartaric acid was proposed in this paper. On the basis of the influence of the concentration of each component on the stability and characteristic parameters of the blank system, the electrochemical fingerprints of 30 kinds of traditional Chinese medicines (TCM) were obtained. The results showed that the electrochemical fingerprint can be used for the identification of TCMs, the distinguishment of different parts and the appraisal of genuineness, which is fast, sensitive and accurate. At the same time, we explored and verified the mechanism of oscillation and the formation mechanism of TCM fingerprint.

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The detection and identification of multiple components in a complex sample such as food in a cost-effective way is an ongoing challenge. The development of on-site and rapid detection methods to ensure food quality and composition is of significant interest to the food industry. Here we report that an electrochemical method can be used with an unmodified glassy carbon electrode for the identification of the key ingredients found within Thai green curries. It was found that green curry presents a fingerprint electrochemical response that contains four distinct peaks when differential pulse voltammetry is performed. The reproducibility of the sensor is excellent as no surface modification is required and therefore storage is not an issue. By employing particle swarm optimization algorithms the identification of ingredients within a green curry could be obtained. In addition, the quality and freshness of the sample could be monitored by detecting a change in the intensity of the peaks in the fingerprint response.

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A new composite organic oscillating reaction system based on BrO₃-Ce(SO₄)₂-H₂SO₄-malonic acid/tartaric acid was proposed in this paper. On the basis of the influence of the concentration of each component on the stability and characteristic parameters of the blank system, the electrochemical fingerprints of 30 kinds of traditional Chinese medicines (TCM) were obtained. The results showed that the electrochemical fingerprint can be used for the identification of TCMs, the distinguishment of different parts and the appraisal of genuineness, which is fast, sensitive and accurate. At the same time, we explored and verified the mechanism of oscillation and the formation mechanism of TCM fingerprint.

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