Scutellaria baicalensis charcoal processing technology optimization method

Abstract

The invention relates to the field of traditional Chinese medicines, in particular to an optimization method for a charcoal processing process of scutellaria baicalensis, which adopts a TG-DSC coupling technology to dynamically monitor thermodynamic change in the processing process, establishes a'temperature-time 'quadratic regression model in combination with Box-Behnken response surface design, and determines a multi-index comprehensive score weight through an AHP-entropy weight method to realize systematic optimization of process parameters. Experimental verification shows that the relative error between a model predicted value and a measured value is controlled within 3%, and the model reliability is proved. By means of an electronic nose and electronic tongue sensor array, an objective evaluation system of shape distinguishing theory based on an intelligent sensory technology is established. According to the process optimization-process monitoring-quality evaluation three-in-one method provided by the research, the limitation of subjective judgment of a traditional processing terminal point is broken through, and an innovative technical scheme with process monitoring and terminal evaluation functions is provided for the quality control of the traditional Chinese medicine charcoal.

Description

Technical Field

[0001] The present invention relates to the field of traditional Chinese medicine, and in particular to a method for optimizing the processing technology of scutellaria baicalensis charcoal. Background Art

[0002] Modern research shows that Scutellaria baicalensis mainly contains flavonoids (baicalin, baicalein, wogonin, baicalin), volatile oils (phthalic acid compounds, β-patchoulene isoprene, acetophenone, etc.), polysaccharides (polysaccharides, etc.), and trace elements such as iron, zinc, copper, manganese, lead, and cadmium. These active ingredients give Scutellaria baicalensis significant biological activities, including anti-inflammatory, antibacterial, antiviral, and anti-tumor effects. Among them, baicalein can maintain the function of cardiac myocardial cells, and baicalin can achieve anti-organ fibrosis by increasing cellular antioxidant capacity and inhibiting inflammatory responses, showing broad development and application prospects. The 2020 edition of the Chinese Pharmacopoeia includes two kinds of Scutellaria baicalensis slices: Scutellaria baicalensis slices and Scutellaria baicalensis wine slices. Many local pharmacopoeias include processed products such as stir-fried Scutellaria baicalensis and Scutellaria baicalensis charcoal.

[0003] With the advancement of technology and the continuous deepening of research, common processing methods for Scutellaria baicalensis include stir-frying, stir-frying to charcoal, and wine processing. Among these, the cutting process is relatively simple, while wine processing has been the subject of extensive research on quality evaluation and process optimization. However, research on charcoal processing of Scutellaria baicalensis is relatively limited, and the processing endpoint of charcoal processing remains unclear. Some researchers have optimized the processing of charcoal processing of Scutellaria baicalensis using orthogonal experiments using rutin, baicalin, baicalein, wogonin, and baicalein as indicators. However, the optimized results are inaccurate and do not accurately reflect the processing endpoint of charcoal processing of Scutellaria baicalensis. Summary of the Invention

[0004] In view of the deficiencies of the above-mentioned prior art, the purpose of the present invention is to provide a processing technology for preparing Scutellaria baicalensis charcoal. The present invention intends to analyze the pyrolysis rules of the main components of Scutellaria baicalensis through thermal analysis technology, take multiple effective components of Scutellaria baicalensis charcoal as evaluation indicators, empower them through AHP-entropy weight method, utilize Box-Behnken design-response surface method to optimize the processing technology for Scutellaria baicalensis charcoal, and introduce electronic sensory technology to construct a trait-component association model, study the high correlation between appearance color and odor and its chemical composition, screen the processing technology parameters of Scutellaria baicalensis charcoal from multiple dimensions, and realize the scientific judgment of the processing end point of Scutellaria baicalensis charcoal.

[0005] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0006] A method for optimizing the processing technology of scutellaria baicalensis charcoal comprises the following steps:

[0007] The total flavonoids, total tannins, total polysaccharides and effective components of the scutellaria baicalensis charcoal are extracted to obtain the total flavonoids extract, the total tannins extract, the total polysaccharide extract and the effective components.

[0008] The TG-DSC combined technology was used to dynamically monitor the pyrolysis characteristics of total flavonoid extract, total tannin extract, total polysaccharide extract and the active ingredients during the processing process. The processing temperature of Scutellaria baicalensis charcoal was preliminarily obtained based on the pyrolysis characteristics results.

[0009] The effective ingredients and appearance properties of Scutellaria baicalensis charcoal were used as evaluation indicators. The weight coefficient and entropy weight coefficient were determined by AHP and entropy weight method respectively. The composite weight coefficient was determined based on the weight coefficient and entropy weight coefficient.

[0010] Taking processing temperature and processing time as single factor variables, within the preliminarily determined processing temperature range, the comprehensive score M of each single factor variable was determined according to the composite weight coefficient and the evaluation index content corresponding to the single factor variable. Based on the comprehensive score, the optimal range of processing time of Scutellaria baicalensis charcoal was determined.

[0011] Combined with the processing temperature range of Scutellaria baicalensis charcoal preliminarily determined by the pyrolysis characteristics results and the optimal processing time range of Scutellaria baicalensis charcoal determined by the single factor experiment results, the Box-Behnken response surface methodology was used to further optimize the processing technology of Scutellaria baicalensis charcoal to determine the optimal processing temperature and processing time.

[0012] The present invention analyzes the pyrolysis rules of the main components of Scutellaria baicalensis through thermal analysis technology, takes multiple effective components of Scutellaria baicalensis charcoal as evaluation indicators, assigns weights through AHP-entropy weight method, utilizes Box-Behnken design-response surface method to optimize the processing technology of Scutellaria baicalensis charcoal, introduces electronic sensory technology to construct a trait-component association model, studies the high correlation between appearance color and odor and its chemical composition, screens the processing technology parameters of Scutellaria baicalensis charcoal from multiple dimensions, and experimental verification shows that the relative error between the model prediction value and the measured value is controlled within 3%, confirming the reliability of the model. The processing technology optimization method of the present invention can ensure the uniformity and stability of product quality.

[0013] In a preferred embodiment of the present invention, the plurality of active ingredients include baicalein, baicalin and wogonin.

[0014] In a preferred embodiment of the present invention, when the processing temperature range of Scutellaria baicalensis charcoal is preliminarily determined based on the pyrolysis characteristics results, the highest value of the peak temperature range of the maximum thermal weight loss rate in the first pyrolysis stage is used as the starting temperature of the processing temperature range of Scutellaria baicalensis charcoal, and the starting temperature of the pyrolysis of baicalein is used as the upper limit of the processing temperature range of Scutellaria baicalensis charcoal.

[0015] In a preferred embodiment of the present invention, the method for determining the weight coefficient by AHP is as follows: according to the increase or decrease of the effective ingredients of Scutellaria baicalensis charcoal before and after processing and the degree of influence on the appearance and shape of Scutellaria baicalensis charcoal, the various indicators for evaluating the quality of Scutellaria baicalensis charcoal are quantified, and the priority order is baicalein>baicalin>wogonin>appearance traits. A relative score is assigned to each indicator according to the priority order, and the sum-product method is used to calculate the weight coefficient of each evaluation indicator.

[0016] In a preferred embodiment of the present invention, the weight coefficient is baicalein>wogonin>baicalin>appearance properties.

[0017] In a preferred embodiment of the present invention, the method for determining the entropy weight coefficient by the entropy weight method is: the evaluation index data is processed using a deviation standardization method to obtain standardized data, a probability matrix is ​​calculated using the standardized data, and the entropy weight coefficient is calculated using the probability matrix.

[0018] In a preferred embodiment of the present invention, the entropy weight coefficient is baicalin>baicalein>appearance properties>wogonin.

[0019] In a preferred embodiment of the present invention, the calculation formula for the comprehensive score M is: M = 0.2391×(baicalin content / maximum baicalin content) + 0.5006×(baicalein content / maximum baicalein content) + 0.1802×(wogonin content / maximum wogonin content) + 0.0801×(appearance trait content / maximum appearance trait content).

[0020] In a preferred embodiment of the present invention, a three-factor three-level experiment was designed using the Box-Behnken response surface method, with processing temperature and processing time as independent variables and the comprehensive score as the response value, and a quadratic polynomial model was fitted using Design-Expert 8.0 software.

[0021] Another object of the present invention is to provide a quality evaluation system for Scutellaria baicalensis charcoal to evaluate the quality of the processing process described in any of the above items. With the help of electronic nose and electronic tongue sensor arrays, an objective evaluation system of "identifying appearance and judging quality" based on intelligent sensory technology is established to evaluate the processing quality of Scutellaria baicalensis charcoal.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] 1. The present invention adopts TG-DSC combined technology to dynamically monitor the thermodynamic changes of total flavonoids, total tannins and total polysaccharides and effective ingredients in the processing process of Scutellaria baicalensis charcoal, obtains the processing temperature of Scutellaria baicalensis charcoal according to the thermodynamic change results, takes the effective ingredients and appearance properties of Scutellaria baicalensis charcoal as evaluation indicators, determines the weight of multi-index comprehensive score by AHP-entropy weight method, calculates the composite score calculation formula according to the multi-index comprehensive score weight, takes the processing temperature and processing time as single factor variables, calculates the comprehensive score according to the composite score calculation formula, determines the optimal range of processing time, combines the processing temperature range of Scutellaria baicalensis charcoal preliminarily determined by the pyrolysis characteristics results and the optimal range of processing time of Scutellaria baicalensis charcoal determined by the single factor experimental results, and further optimizes the processing process of Scutellaria baicalensis charcoal by using Box-Behnken response surface method to determine the optimal processing temperature and processing time. Experimental verification shows that the relative error between the model prediction value and the measured value is controlled within 3%, which confirms the reliability of the model and the more accurate the optimization result. The processing process optimization method of the present invention can ensure the uniformity and stability of product quality.

[0024] 2. The present invention analyzes the pyrolysis rules of the main components of Scutellaria baicalensis through thermal analysis technology, takes multiple effective ingredients of Scutellaria baicalensis charcoal as evaluation indicators, assigns weights through AHP-entropy weight method, utilizes Box-Behnken design-response surface method to optimize the processing technology of Scutellaria baicalensis charcoal, and introduces electronic sensory technology to construct a trait-component association model, studies the high correlation between appearance color and odor and its chemical composition, screens the processing technology parameters of Scutellaria baicalensis charcoal from multiple dimensions, and realizes the scientific judgment of the processing end point of Scutellaria baicalensis charcoal. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 These are the pyrolysis characteristic curves of raw scutellaria powder and its ethanol extract, where A is the TG-DTG curve of raw scutellaria powder; B is the TG-DTG curve of its ethanol extract; C is the TG curve of the raw scutellaria powder and its ethanol extract; and D is the DTG curve of the raw scutellaria powder and its ethanol extract.

[0026] Figure 2 These are the thermal decomposition characteristic curves of total flavonoid extract, baicalin and baicalein, among which A is the TG-DTG curve of total flavonoid extract; B is the TG-DTG curve of baicalin standard; C is the TG-DTG curve of baicalein standard; D is the comparative TG curve of total flavonoid extract, baicalin and baicalein; E is the comparative DTG curve of total flavonoid extract, baicalin and baicalein.

[0027] Figure 3 Figure 3 is the thermal decomposition characteristic curve of total polysaccharide and anhydrous glucose, where A is the TG-DTG curve of polysaccharide extract; B is the TG-DTG curve of anhydrous glucose standard; C is the TG curve of total polysaccharide extract and anhydrous glucose; D is the DTG curve of total polysaccharide extract and anhydrous glucose.

[0028] Figure 4 These are the thermal decomposition characteristic curves of total tannins and gallic acid, where A is the TG-DTG curve of total tannin extract; B is the TG-DTG curve of gallic acid standard; C is the comparative TG curve of total tannins and gallic acid; D is the DTG curve of total polysaccharide extract and anhydrous glucose.

[0029] Figure 5 is the overall pyrolysis characteristic curve, where A is the TG curve diagram of all samples compared; B is the DTG curve diagram of all samples compared.

[0030] Figure 6 a and b are the HPLC spectra of baicalin, baicalein and wogonin reference solutions and scutellaria baicalensis charcoal sample solution.

[0031] Figure 7 Figures a and b are response surface experiment results.

[0032] Figure 8 These are the electronic nose results of Scutellaria baicalensis charcoal samples with different degrees of processing, where a is a three-dimensional graph, b is a two-dimensional graph, and c is the electronic nose radar graph.

[0033] Figure 9 These are the electronic tongue results of Scutellaria baicalensis charcoal samples with different degrees of processing, where a is a three-dimensional graph, b is a two-dimensional graph, and c is an electronic tongue radar graph.

[0034] Figure 10 The heat map of odor-component correlation.

[0035] Figure 11 This is a heat map of flavor-ingredient correlation. DETAILED DESCRIPTION

[0036] The following is a detailed description of the technical solutions in the embodiments of the present invention, using preferred embodiments and accompanying drawings in conjunction with the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0037] It should be noted that all professional terms used in the present invention are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention. Unless otherwise specified, the various raw materials, reagents, instruments and equipment used in the following embodiments of the present invention can be purchased from the market or prepared by existing methods.

[0038] Drugs and reagents

[0039] The original medicinal material was purchased from Shanxi Guotai Traditional Chinese Medicine Co., Ltd. and identified as the dried root of Scutellaria baicalensis Georgi (Lamiaceae) by Professor Zhang Shuosheng of the College of Traditional Chinese Medicine and Food Engineering at Shanxi University of Traditional Chinese Medicine. Gallic acid standard (batch number 18032703, mass fraction 98%) was purchased from Shanghai Shidande Co., Ltd.; anhydrous glucose (batch number 131208, mass fraction 98%); baicalin (batch number 21121404, mass fraction 98.03%); baicalein (batch number 23022804, mass fraction 98.57%); and wogonin (batch number 22053002, mass fraction 99.25%) were purchased from Chengdu Pufeide Co., Ltd.; and anhydrous ethanol (analytical grade, 20 14-01-8, Tianjin Jinfeng Chemical Co., Ltd.); gelatin (batch number: 20220702, Tianjin Tianli Chemical Reagent Co., Ltd.); acetone (batch number: 20051009, Tianjin Yaohua Chemical Reagent Co., Ltd.); phosphomolybdic tungstic acid (batch number: 20230516, Beijing Huakesheng Fine Chemical Products Trading); anhydrous sodium carbonate (batch number: 20221108A, Tianjin Komiou Chemical Reagent Co., Ltd.); casein (batch number: 20210901, Tianjin Damao Chemical Reagent Factory).

[0040] instrument

[0041] Thermogravimetric-differential thermal analyzer (STA449-F5, NETZSCH, Germany), analytical balance (AR223CN, OHAUS, USA), UV-visible spectrophotometer (Spectrophotometer, Shanghai Mepta Instrument Co., Ltd.), multifunctional herbal medicine stir-frying machine (ABL series, 25L, feeding range >100g, Lanzhou Apollo Electronic Equipment Co., Ltd.), rotary evaporator (RE-52AA, Shanghai Yarong Biochemical Instrument Factory), constant temperature water bath (HH-2 digital display, Jintan Jierui Electric Co., Ltd.), electric blast drying oven (GZX-9076, Shanghai Boxun Industrial Co., Ltd. Medical Equipment Factory), cNose electronic nose, Easytongue electronic tongue, Shanghai Baosheng Industrial Development Co., Ltd., multifunctional crusher (DE-500g, Zhejiang Hongjingtian Industry and Trade Co., Ltd.), electronic analytical balance (AR223CN, OHAUS Instrument Shanghai Co., Ltd.).

[0042] Example 1

[0043] A method for optimizing the processing technology of scutellaria baicalensis charcoal comprises the following steps:

[0044] (1) The total flavonoids, total tannins, total polysaccharides and effective components of Scutellaria baicalensis charcoal are extracted to obtain total flavonoid extracts, total tannin extracts, total polysaccharide extracts and effective components.

[0045] Extraction of total flavonoids from Scutellaria baicalensis: 2g of Scutellaria baicalensis powder (dried Scutellaria baicalensis powder crushed in a multifunctional grinder and passed through a No. 4 sieve, the same below) was added to 100mL of 60% ethanol (volume fraction) (solid-liquid ratio 1:50g / mL), stirred evenly, and soaked for 45min. Heat the mixture in a water bath at 60°C for 1.5h. After cooling, filter to remove solid waste, combine the filtrates, and dry. The dried extract was transferred to a mortar and ground into a powder, then stored in a sealed container at 4°C.

[0046] Extraction of total tannins from Scutellaria baicalensis: Soak in 200 mL of 70% ethanol twice, each time for 1 hour, concentrate the extract to 1 / 4 of the original volume, add gelatin to a concentration of 4%, separate the precipitate, dissolve it with 50% acetone, and dry it under reduced pressure to obtain total tannins. Store in a sealed, dry place away from light.

[0047] Extraction of Scutellaria baicalensis total polysaccharide sample: Extract in 240 mL of distilled water at 90°C for 120 minutes, twice. Centrifuge the extract at 4000 rpm for 15 minutes. Concentrate the supernatant to approximately 100 mL (at room temperature). Add ethanol to a concentration of 60% ethanol and allow to stand overnight. Filter, remove the precipitate, dry in a vacuum oven, and store sealed in a cool, dry place.

[0048] Extraction of baicalinol extract: Reflux extraction with 200 mL of 60% ethanol twice, 2 hours each time. After filtration, the filtrate and concentrate were combined and freeze-dried to obtain baicalinol extract powder, which was then stored in a sealed container at 4°C.

[0049] (2) TG-DSC combined technology was used to dynamically monitor the pyrolysis characteristics of total flavonoid extracts, total tannin extracts, total polysaccharide extracts and the processing of active ingredients. Based on the pyrolysis characteristics results, the processing temperature range of Scutellaria baicalensis charcoal was preliminarily obtained.

[0050] Thermal analysis sample content determination

[0051] Chromatographic conditions: chromatographic column: Diamonsilcls chromatographic column (250mm×4.6mm, 5μm); acetonitrile (A)-0.1% phosphoric acid aqueous solution (B) as mobile phase; gradient elution: 15%→50%A (0-30min), 50%-60%A (30-40min), 60%→20%A (40-50min), flow rate: 1mL / min; injection volume: 10μL; column temperature: 30℃; detection wavelength: 276nm; injection volume: 10μL. According to the chromatographic conditions, the injection volume was changed, and the peak area was measured with the injection volume (μL) as the horizontal axis. The standard curve was drawn on the vertical axis, and the mother solution of total flavonoid extract was prepared. The peak area of ​​the test sample was measured. The result of total flavonoid content determination was as follows: regression equation Y = 39.135X - 37.815, R2 = 0.9992; the total tannin content was determined by UV standard curve method. The total tannin content was 2.68% by UV spectrophotometry. The regression equation was Y = 84.503X + 0.0126, R2 = 0.9984; the total polysaccharide content was determined by phenol-concentrated sulfuric acid method. The total polysaccharide compound content was 12.8% by phenol-concentrated sulfuric acid method. The regression equation was Y = 0.5461X + 0.0898, R 2 =0.9975.

[0052] Sample amounts (15 mg) of raw Scutellaria baicalensis powder, total flavonoids extract of Scutellaria baicalensis, total tannin extract of Scutellaria baicalensis, total polysaccharide extract of Scutellaria baicalensis, baicalin standard, baicalein standard, gallic acid standard, anhydrous glucose standard, and Scutellaria baicalensis extract powder were taken and evenly dispersed horizontally in a crucible. The pyrolysis characteristics were studied by STA449-F5 thermogravimetric-differential thermal simultaneous thermal analyzer using simulated air (N2:O2=4:1) as the carrier gas, a heating rate of 10℃ / min, and a volume flow rate of 60mL / min. The temperature was raised from room temperature to 600℃, and each sample was tested in parallel 3 times.

[0053] Thermal analysis experimental results and analysis

[0054] The thermal decomposition characteristic curves of raw Scutellaria powder, alcohol extract, total flavonoid extract, baicalin, baicalein, total polysaccharides, anhydrous glucose, total tannins and gallic acid are shown in Figures 1 to 5 , related parameters are shown in Table 1.

[0055] Table 1 Parameters related to the pyrolysis characteristics of raw Scutellaria baicalensis and its active ingredients

[0056]

[0057]

[0058] By comparing the combustion pyrolysis characteristics of raw Scutellaria powder, it can be seen that the main pyrolysis stage is 154.2℃~393.4℃, and the peak value of thermal weight loss rate of the pyrolysis combustion stage with an intensity of 6.50% / min appears at 305.8℃; by comparing the combustion pyrolysis characteristics of ethanol extract, it can be seen that the main pyrolysis stage is 164.5℃~245.4℃, and the peak value of thermal weight loss rate of the pyrolysis combustion stage with an intensity of 7.08% / min appears at 195.9℃; by comparing the pyrolysis characteristics of total flavonoids extract, baicalin and baicalein, it can be seen that the main pyrolysis stage of total flavonoids is 180℃~380℃, among which 180℃~270.4℃ is the main pyrolysis stage of baicalin, and 270.4℃~380℃ is the main pyrolysis stage of baicalein; by comparing the combustion pyrolysis characteristics of total polysaccharide extract and pollutant, it can be seen that the main pyrolysis stage of total flavonoids is 180℃~270.4℃, and the main pyrolysis stage of baicalein is 270.4℃~380℃. From the thermal decomposition characteristics of glucose, it can be seen that the thermal decomposition of anhydrous glucose occurs at 153.3℃~430.9℃, and the thermal decomposition of anhydrous glucose is mainly divided into two stages, with 252.9~430.9℃ as its main thermal decomposition stage; comparing the thermal decomposition characteristic curves of total tannin extract and gallic acid, it can be seen that the thermal decomposition of gallic acid occurs mainly at 190℃~260℃; following the principle of charcoal preservation, the starting temperature of baicalein thermal decomposition of 260℃ was selected as the upper limit of the temperature for charcoal preparation of Scutellaria baicalensis. The peak temperature of the maximum thermal weight loss rate in the first thermal decomposition stage of raw product, total polysaccharide extract and total tannin is in the range of 210℃~220℃, so 220℃ was selected as the starting temperature for charcoal preparation of Scutellaria baicalensis. It can be inferred that the optimal temperature range for charcoal preparation of Scutellaria baicalensis is 220℃~260℃.

[0059] (3) Taking the effective ingredients and appearance characteristics of Scutellaria baicalensis charcoal as evaluation indicators, the weight coefficient and entropy weight coefficient were determined by AHP and entropy weight method respectively. The composite weight coefficient was determined based on the weight coefficient and entropy weight coefficient, and the calculation formula of the comprehensive score M was obtained based on the composite weight coefficient.

[0060] Based on the changes in the chemical components of Scutellaria baicalensis before and after processing and their impact on the efficacy of Scutellaria baicalensis charcoal, the various indicators for evaluating Scutellaria baicalensis quality were quantified. The priority order was baicalein > baicalin > wogonin > appearance traits. Relative scores were assigned to each indicator based on the priority order. The weight coefficients of each evaluation indicator were calculated using the sum-product method. The results showed that the weight coefficients (Wj) of baicalein, baicalin, wogonin, and appearance traits after hierarchical analysis were 0.46582, 0.16107, 0.27714, and 0.09597, respectively. The consistency index C1 was 0.01. The random consistency index (RI) table was 0.882 based on n = 4. The calculated consistency ratio factor (CI / RI) of the model was 0.012, which was less than 0.1. This indicates that the pairwise comparison priority judgment matrix has good consistency and the determined weight coefficients are valid.

[0061] The j evaluation index data of the i-th experiment (X ij ) The data were processed by using the deviation standardization method to obtain the standardized data (Yij ), calculate the probability matrix (P ij ) Calculate the information entropy of the indicator (H) according to the following formula t ) and entropy weight coefficient (W t ), where X min and X max The results show that baicalein, baicalin, wogonin, appearance traits H t They are 0.8869, 0.8437, 0.9316, 0.9121, respectively. t They are 0.2657, 0.3671, 0.1608 and 0.2064 respectively.

[0062]

[0063] The composite weight coefficient of the indicator (Z j ), the results showed that baicalein, baicalin, wogonin, appearance characteristics Z j They are 0.5006, 0.2391, 0.1802, and 0.0801 respectively. j , and obtain the comprehensive score (M).

[0064]

[0065] M = 0.2391 × (baicalin content / maximum baicalin content) + 0.5006 × (baicalein content / maximum baicalein content) + 0.1802 × (wogonin content / maximum wogonin content) + 0.0801 × (appearance property content / maximum appearance property content).

[0066] (4) The processing temperature and processing time were used as single-factor variables, and the comprehensive score M was calculated according to the comprehensive score calculation formula to determine the optimal range of the processing time of Scutellaria baicalensis charcoal.

[0067] Preparation of reference solution

[0068] Place baicalin, baicalein, and wogonin reference substances in 10 mL volumetric flasks and adjust to volume. This results in single reference substance solutions with concentrations of 0.26 mg / mL for baicalin, 0.12 mg / mL for baicalein, and 0.18 mg / mL for wogonin, respectively.

[0069] Test sample preparation

[0070] Take the sample and crush it through a No. 4 sieve. Weigh 0.3 g of the sample and add 40 mL of 60% ethanol. Soak for 2 h. Soak twice. Combine the filtrates in a 100 mL volumetric flask and make up to volume.

[0071] System suitability

[0072] The chromatograms of the three reference solutions (baicalin, baicalein, wogonin) and the scutellaria baicalensis carbon sample solution were compared. The results showed that the three reference solutions had chromatographic peaks at 12 min, 22 min, and 27 min, respectively, and the peak shapes were good. Figure 6 .

[0073] Establishment of linear regression equation

[0074] The standard curve of baicalein was established with the contents of baicalein, baicalin, and wogonin as the horizontal axis (X) and the peak area as the vertical axis (Y). The results showed that the standard curve of baicalein was Y=32.777X-33.169, and the correlation coefficient R 2 The correlation coefficient R 2 The content of baicalin showed a good linear relationship in the range of 0-5.2 μg. The standard curve of wogonin was Y=53.147x-54.897, R 2 The content of wogonin showed a good linear relationship in the range of 0 to 3.6 μg.

[0075] Single factor investigation-processing temperature

[0076] Five portions of Scutellaria baicalensis slices, 50g each, were placed in a stir-fryer and stir-fried at 220°C, 230°C, 240°C, 250°C, and 260°C for 13 minutes. The slices were then removed and allowed to cool, yielding samples of Scutellaria baicalensis charcoal slices processed at different temperatures. Based on the chromatographic conditions, the total flavonoid content was measured and a comprehensive score was calculated. The results showed that the charcoal had the highest comprehensive score when processed at 230°C, thus establishing the optimal processing temperature range for Scutellaria baicalensis charcoal to be 220°C to 240°C. The results are shown in Table 2.

[0077] Single factor investigation-preparation time

[0078] Five portions of Scutellaria baicalensis slices, 50g each, were placed in a stir-fryer and stir-fried at 230°C for 7, 10, 13, 16, and 19 minutes, respectively. After removal and cooling, the charcoaled Scutellaria baicalensis slices were obtained. Total flavonoid content was measured according to chromatographic conditions, and a comprehensive score was calculated. The results showed that the charcoaled Scutellaria baicalensis slices had the highest comprehensive score when processed for 13 minutes, thus establishing the optimal processing time range for charcoaled Scutellaria baicalensis to be 10 to 16 minutes. Specific results are shown in Table 2.

[0079] Table 2 Single factor experimental plan and results

[0080]

[0081]

[0082] Methodological investigation

[0083] Precision experiment: Accurately aspirate 10 μL of the reference solution, and continuously inject 10 μL of baicalein, baicalin, and wogonin reference solutions 6 times according to the chromatographic conditions, record the peak area value of each component, and calculate the RSD value of the baicalein peak area to be 0.54%, the RSD value of the baicalin peak area to be 0.33%, and the RSD value of the wogonin peak area to be 0.71%, indicating good precision.

[0084] Stability test: Accurately pipette the same test solution at 0, 2, 4, 6, 8, 10, 12, and 24 hours after preparation. Record the peak areas according to the above chromatographic conditions and calculate the relative standard deviations (RSDs). The RSDs for the peak areas of baicalin, baicalein, and wogonin were 0.70%, 0.89%, and 1.16%, respectively, indicating that the solution was essentially stable within 24 hours at room temperature.

[0085] Repeatability test: Take 6 samples of the same batch of Scutellaria baicalensis charcoal, 1 g each, accurately weighed, and prepare 6 test solutions. The samples were injected for detection and RSD was calculated. The results showed that the average mass fractions of baicalin, baicalein, and wogonin were 12.07%, 4.76%, 2.31%, and 0.23%, respectively, and the RSD values ​​were 1.66%, 1.37%, 0.78%, and 1.17%, respectively.

[0086] Sample recovery experiment: Accurately weigh 6 portions of Scutellaria baicalensis powder with known content, 1 g each, and add appropriate amounts of baicalein, baicalin, and wogonin reference substances to prepare test solutions. Enter the solution into the high performance liquid chromatography according to the chromatographic conditions, record the peak area and calculate the sample recovery. The results showed that the average recoveries of baicalin, baicalin, and wogonin were 102.22%, 100.83%, and 98.48%, respectively, and the RSD values ​​were 1.20%, 2.10%, and 1.41%, respectively.

[0087] (5) Combining the processing temperature range of Scutellaria baicalensis charcoal preliminarily determined by the pyrolysis characteristics results and the optimal processing time range of Scutellaria baicalensis charcoal determined by the single-factor experimental results, the Box-Behnken response surface methodology was used to further optimize the processing technology of Scutellaria baicalensis to determine the optimal processing temperature and processing time.

[0088] Combined with the above single-factor investigation results, the response surface methodology was used to further optimize the processing technology of Scutellaria baicalensis charcoal. A three-factor three-level experiment was designed using Box-Behnken, with processing temperature (X1: 220–260°C) and time (X2: 10–20 min) as independent variables, and the comprehensive score (Y) as the response value. A quadratic polynomial model was fitted using Design-Expert 8.0 software.

[0089] The corresponding quadratic equation model obtained from the three-dimensional model diagram and experimental results is: total flavonoid content = 0.8433 + 0.0211A + 0.0320B - 0.0437AB - 0.0439A2 - 0.0144B2, r 2 =0.9410, indicating that the model can explain 94.1% of the response value variation. Therefore, the model has a good degree of fit and a small experimental error, and can be used for analysis and prediction. The variance analysis of the response surface results is shown in Table 3. Combining the thermogravimetric analysis experiment and the response surface design experiment, the optimal processing technology of Scutellaria baicalensis charcoal was 227.425℃, 16min. Based on this model, a 3D response surface diagram of the frying time and frying temperature was drawn, see Figure 7 .

[0090] Table 3 Analysis of variance of regression equation

[0091]

[0092] Analysis of the processing degree of Scutellaria baicalensis charcoal based on electronic bionic sensory technology

[0093] Odor identification of charcoal of Scutellaria baicalensis with different processing degrees using electronic nose

[0094] 10 g of Scutellaria baicalensis slices from each group were weighed and sealed in a 50 mL headspace bottle. After heating in an oven, the gas in the bottle was measured using an electronic nose probe with a cleaning time of 90 s, an analysis time of 60 s, and a gas flow rate of 1 L / min.

[0095] Depend on Figure 4 From Figures 4a and 4b, the contribution rate of PC1 is 84.7523%, the contribution rate of PC2 is 12.1038%, and the cumulative contribution rate of the first two principal components is 96.8561%. The contribution rate of principal component PC1 is significantly greater than that of principal component PC2, indicating that the scutellaria baicalensis charcoal samples with different processing degrees can be clearly distinguished on the principal component PC1.

[0096] The electronic nose radar images of the samples of Scutellaria baicalensis charcoal with different processing degrees are shown in the figure. Figure 8 c. By Figure 4 As shown in Figure 3, the response value of sensor 9 for the moderately processed charcoaled Scutellaria baicalensis sample was the highest, followed by sensor 1. The response values ​​of sensors 2, 15, 4, 5, 6, 16, 17, and 18 showed minimal differences. The response values ​​of sensors 9 and 18 for raw Scutellaria baicalensis were the highest, with minimal differences in the response values ​​of the remaining sensors. Both the under-processed and over-processed charcoaled Scutellaria baicalensis samples showed higher response values ​​for sensors 2, 9, and 15. In summary, sensor 9 for the moderately processed charcoaled Scutellaria baicalensis sample was the most sensitive, and the electronic nose primarily distinguished charcoaled Scutellaria baicalensis samples at different degrees of processing using sensors 2, 9, 15, and 18.

[0097] Taste identification of charcoal Scutellariae with different processing degrees using electronic tongue

[0098] Take 2.00 g of raw Scutellaria baicalensis and different processed powders (passed through No. 4 sieve) and place them in a 100 mL stoppered conical flask. Add 100 mL of deionized water, stir, ultrasonicate for 30 min, centrifuge at 3000 rpm for 10 min, filter, take 30 mL of the filtrate, immerse it in the electronic tongue analysis probe, collect data for 120 s, wash for 30 s, and record the response signals of each sensor.

[0099] Depend on Figure 9 From a and b, we can see that the contribution rate of PC1 is 60.0398%, the contribution rate of PC2 is 22.7319%, and the cumulative contribution rate of the first two principal components is 92.7717%. The contribution rate of principal component PC1 is significantly greater than that of principal component PC2, indicating that the scutellaria baicalensis charcoal samples with different processing degrees can be clearly distinguished on the principal component PC1.

[0100] The electronic tongue radar images of the samples of Scutellaria baicalensis charcoal with different processing degrees are shown in the figure. Figure 9 In c. By Figure 9 As shown in Figure c, the samples of Scutellaria baicalensis charcoal with different processing degrees are all sensitive to sensors 1, 2, 4, 5, 7, 8, 10, 11, and 13, but the corresponding signal values ​​are different. In summary, the above sensors can be used to distinguish Scutellaria baicalensis charcoal pieces with different processing degrees.

[0101] Correlation analysis between odor value and components of Scutellaria baicalensis charcoal

[0102] The 18 electronic nose sensor response values ​​of the four samples and the relative contents of the three active ingredients were input into OriginPro software for Pearson correlation analysis and a visual heat map was drawn. An absolute value of the correlation coefficient r greater than 0.8 was considered a strong correlation, 0.5-0.8 was considered a moderate correlation, 0.3-0.5 was considered a low correlation, and <0.3 was considered to be basically uncorrelated.

[0103] The correlation between the odor of Scutellaria baicalensis charcoal and the content of active ingredients is shown in Figure 10 As shown in the figure, S7, S10, and S13 were strongly positively correlated with baicalin, S10 and S13 were strongly negatively correlated with baicalein, and S10 was strongly negatively correlated with wogonin. S8, S11, and S12 were moderately positively correlated with baicalin, S7 and S11 were moderately negatively correlated with baicalein, and S7 and S13 were moderately negatively correlated with wogonin. In summary, S7, S11, and S13 are extremely sensitive to flavonoids.

[0104] Correlation analysis between the taste value and components of Scutellaria baicalensis charcoal

[0105] The 18 electronic tongue sensor response values ​​of the four samples and the relative contents of the three active ingredients were input into OriginPro software for Pearson correlation analysis and a visual heat map was drawn. An absolute value of the correlation coefficient r greater than 0.8 was considered a strong correlation, 0.5-0.8 was considered a moderate correlation, 0.3-0.5 was considered a low correlation, and <0.3 was considered to be basically uncorrelated.

[0106] The correlation between the taste of Scutellaria baicalensis charcoal and the content of active ingredients is shown in Figure 11 As shown in the figure, S3, S13, S15, S16, S17, and S18 were strongly positively correlated with baicalin, S3, S16, S17, and S18 were strongly negatively correlated with baicalein, and S16, S17, and S18 were strongly negatively correlated with wogonin. S2 and S14 were moderately positively correlated with baicalin, S13 and S15 were moderately negatively correlated with baicalein, and S3 was moderately negatively correlated with wogonin. In summary, S3, S16, S17, and S18 were extremely sensitive to flavonoids.

[0107] Optimization of the processing technology of charcoal Scutellaria baicalensis

[0108] The preparation of charcoalized medicinal materials emphasizes "preserving the medicinal properties during charcoaling," meaning that the inherent properties of the medicinal material are maintained during the preparation process, which is crucial for its efficacy. Excessive or insufficient preparation can affect its efficacy. To further standardize the preparation of charcoalized Scutellaria baicalensis and improve the quality of traditional Chinese medicine, this study employed the AHP-entropy weight method combined with the response surface methodology. Using baicalein, baicalin, wogonin, and baicalin as indicators, and temperature and time as influencing factors, the process was optimized. The optimal preparation temperature for charcoalized Scutellaria baicalensis was 227.425°C for 16 minutes. After optimization, the processing parameters for charcoalized Scutellaria baicalensis were clearly defined, which can preserve the content of the active ingredients to a certain extent, thereby ensuring the quality of the charcoalized Scutellaria baicalensis.

[0109] The main active ingredients of Scutellaria baicalensis are baicalein, baicalin, wogonin, and baicalin. Studies have shown that changes in the active ingredients of Scutellaria baicalensis after charcoaling are due to the cleavage of glycoside bonds in the glycosides, which are converted into aglycones. Response surface experiments revealed that the content of the main active ingredients in charcoaled Scutellaria baicalensis increased after processing, likely due to the increase in temperature and cleavage of glycoside bonds during the charcoaling process. In the experiment, the processing process corresponding to the sample with the lowest overall score did not significantly increase the active ingredient content, possibly due to insufficient charcoaling time, resulting in an incomplete reaction. This result is consistent with relevant literature reports.

[0110] Correlation analysis between internal components, appearance, color and odor of Scutellaria baicalensis charcoal

[0111] The determination of the properties and flavors of traditional Chinese medicine is an important method of traditional quality evaluation, but the traditional property evaluation is subjective and it is difficult to accurately control the quality of the medicinal pieces. In modern times, Mr. Xie Zongwan proposed the "distinguishing appearance from quality" theory based on the traditional empirical evaluation theory, where "appearance" refers to the appearance properties of the medicinal materials, such as shape, size, color, smell, etc.; "quality" refers to the intrinsic quality of the medicinal materials. By observing the appearance properties of the medicinal materials, analyzing and summarizing them based on experience, the intrinsic quality of the medicinal materials can be judged. Studies have shown that after the Chinese medicinal materials are processed, the chemical composition changes, and the color, taste and smell will also change. In order to clarify the optimal process parameters for the processing of Scutellaria baicalensis charcoal, the present invention associates the content of the effective ingredients of the Scutellaria baicalensis charcoal samples with the taste and smell, and explores the correlation between the internal components of Scutellaria baicalensis charcoal with different processing degrees. The electronic nose sensor S9 has the highest response value for moderately processed samples ( Figure 4 c), which was correlated with the volatile characteristics of baicalin pyrolysis products (r=0.87), confirming the scientific connotation of "distinguishing appearance from quality". This study compensates for the subjectivity and ambiguity of traditional visual identification of the degree of processing, and provides new ideas for the quality control research of scutellaria baicalensis charcoal.

[0112] It should be noted that when numerical ranges are mentioned in the present invention, it should be understood that both endpoints of each numerical range and any value between the two endpoints may be selected. Since the steps and methods used are the same as those in the embodiments, in order to avoid redundancy, the present invention describes preferred embodiments. Although preferred embodiments of the present invention have been described, those skilled in the art may make additional changes and modifications to these embodiments once they understand the basic inventive concepts. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications that fall within the scope of the present invention.

[0113] Obviously, those skilled in the art may make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if such changes and modifications fall within the scope of the claims and their equivalents, the present invention is intended to include such changes and modifications.

Claims

1. A method for optimizing the processing technology of Scutellaria baicalensis charcoal, characterized in that: The following steps are involved: Extracting total flavonoids, total tannins, total polysaccharides and effective components from the scutellaria baicalensis charcoal to obtain total flavonoids extract, total tannins extract, total polysaccharide extract and effective components; The pyrolysis characteristics of total flavonoid extracts, total tannin extracts, total polysaccharide extracts, and active ingredients during the processing were dynamically monitored using TG-DSC technology. Based on the pyrolysis characteristics, the processing temperature range of Scutellaria baicalensis charcoal was preliminarily determined. Taking the active ingredients and appearance characteristics of Scutellaria baicalensis charcoal as evaluation indicators, the weight coefficient and entropy weight coefficient were determined by AHP and entropy weight method respectively, and the composite weight coefficient was determined based on the weight coefficient and entropy weight coefficient. The processing temperature and processing time were taken as single factor variables, and the comprehensive score M of each single factor variable was determined according to the composite weight coefficient and the evaluation index content corresponding to the single factor variable. The optimal range of the processing time of Scutellaria baicalensis charcoal was determined based on the comprehensive score M. Combined with the processing temperature range of Scutellaria baicalensis charcoal preliminarily determined by the pyrolysis characteristics results and the optimal processing time range of Scutellaria baicalensis charcoal determined by the single factor experiment results, the Box-Behnken response surface methodology was used to further optimize the processing technology of Scutellaria baicalensis charcoal to determine the optimal processing temperature and processing time.

2. The method for optimizing the processing technology of Scutellaria baicalensis charcoal according to claim 1, characterized in that: The active ingredients include baicalein, baicalin and wogonin.

3. The method for optimizing the processing technology of Scutellaria baicalensis charcoal according to claim 2, characterized in that: When the processing temperature range of Scutellaria baicalensis charcoal was preliminarily determined based on the pyrolysis characteristics results, the highest value of the peak temperature range of the maximum thermal weight loss rate in the first pyrolysis stage was used as the starting temperature of the processing temperature range of Scutellaria baicalensis charcoal, and the starting temperature of baicalein pyrolysis was used as the upper limit of the processing temperature range of Scutellaria baicalensis charcoal.

4. The method for optimizing the processing technology of Scutellaria baicalensis charcoal according to claim 1, characterized in that: The method for determining the weight coefficient by AHP is as follows: according to the increase or decrease of the effective ingredients of Scutellaria baicalensis charcoal before and after processing and the degree of influence on the appearance of Scutellaria baicalensis charcoal, the various indicators for evaluating the quality of Scutellaria baicalensis charcoal are quantified, and the priority order is baicalein>baicalin>wogonin>appearance. A relative score is assigned to each indicator according to the priority order, and the weight coefficient of each evaluation indicator is calculated using the sum-product method.

5. The method for optimizing the processing technology of Scutellaria baicalensis charcoal according to claim 4, characterized in that: The weight coefficient is baicalein>wogonin>baicalin>appearance properties.

6. The method for optimizing the processing technology of Scutellaria baicalensis charcoal according to claim 1, characterized in that: The method for determining the entropy weight coefficient by the entropy weight method is as follows: the evaluation index data is processed using the deviation standardization method to obtain standardized data, the probability matrix is ​​calculated through the standardized data, and the entropy weight coefficient is obtained through the probability matrix calculation.

7. The method for optimizing the processing technology of Scutellaria baicalensis charcoal according to claim 6, characterized in that: The entropy weight coefficient was determined by the entropy weight method, and the entropy weight coefficient was baicalin > baicalein > appearance characteristics > wogonin.

8. The method for optimizing the processing technology of Scutellaria baicalensis charcoal according to claim 1, characterized in that: The calculation formula for the comprehensive score M is: M = 0.2391×(baicalin content / maximum baicalin content) + 0.5006×(baicalein content / maximum baicalein content) + 0.1802×(wogonin content / maximum wogonin content) + 0.0801×(appearance trait content / maximum appearance trait content).

9. The method for optimizing the processing technology of Scutellaria baicalensis charcoal according to claim 1, characterized in that: A three-factor three-level experiment was designed using the Box-Behnken response surface methodology. Processing temperature and processing time were used as independent variables, and the comprehensive score was used as the response value. A quadratic polynomial model was fitted using Design-Expert 8.0 software.

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