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近紅外光譜技術(shù)在赤芍等中藥材中定量分析應(yīng)用研究

發(fā)布時(shí)間:2019-05-25 01:35
【摘要】:中藥是一個(gè)復(fù)雜的多組分體系,中藥的質(zhì)量控制對保證臨床療效、實(shí)現(xiàn)中藥現(xiàn)代化、推動中藥產(chǎn)業(yè)的技術(shù)發(fā)展有重要的意義。因此,需要一種簡便、快捷的質(zhì)量分析方法,對中藥材進(jìn)行準(zhǔn)確、快速的含量測定。近紅外光譜技術(shù)是一種快速、無損的綠色分析方法,結(jié)合化學(xué)計(jì)量學(xué)手段,可以對中藥材進(jìn)行快速含量測定。本研究借鑒其在定量檢測方面的應(yīng)用,實(shí)現(xiàn)對赤芍、黃芪、梔子、大黃、獨(dú)活、白芷和防風(fēng)7味中藥材中指標(biāo)成分的含量進(jìn)行快速檢測的目的。主要取得了以下進(jìn)展:1.利用高效液相色譜法測定赤芍中沒食子酸、兒茶素、芍藥內(nèi)酯苷和芍藥苷的含量,選擇101批樣品,運(yùn)用偏最小二乘法建立其含量與近紅外光譜之間的校正模型。結(jié)果顯示,沒食子酸經(jīng)多元散射校正+二階導(dǎo)數(shù)處理,模型校正集r為0.9065,RMSEC值為0.10;驗(yàn)證集r為0.9163,RMSEP值為0.09;兒茶素經(jīng)多元散射校正+二階導(dǎo)數(shù)處理,模型校正集r為0.9408,RMSEC值為0.44;驗(yàn)證集r為0.9231,RMSEP值為0.40;芍藥內(nèi)酯苷經(jīng)多元散射校正+一階導(dǎo)數(shù)處理,模型校正集r為0.9406,RMSEC值為0.13;驗(yàn)證集r為0.9226,RMSEP值為0.14;芍藥苷經(jīng)Savitzky-Golay平滑+一階導(dǎo)數(shù)處理,模型校正集r為0.9674,RMSEC值為0.22;驗(yàn)證集r為0.9281,RMSEP值為0.22。4種成分的HPLC測定值與NIR模型測定值有較好的線性關(guān)系,說明模型的擬合能力較好,可用于快速測定大批量赤芍藥材中沒食子酸、兒茶素、芍藥內(nèi)酯苷和芍藥苷的含量。2.利用高效液相色譜-質(zhì)譜聯(lián)用法測定黃芪中毛蕊異黃酮葡萄糖苷和黃芪甲苷的含量,選擇91批樣品,運(yùn)用偏最小二乘法建立其含量與近紅外光譜之間的校正模型。結(jié)果顯示,毛蕊異黃酮葡萄糖苷經(jīng)多元散射校正+ 一階導(dǎo)數(shù)+Savitzky-Golay平滑處理,模型校正集r為0.8635,RMSEC值為0.019;驗(yàn)證集r為0.8266,RMSEP值為0.023;黃芪甲苷經(jīng)二階導(dǎo)數(shù)+Savitzky-Golay平滑處理,模型校正集r為0.7963,RMSEC值為0.008;驗(yàn)證集r為0.8548,RMSEP值為0.006。2種成分模型擬合關(guān)系良好,可以實(shí)現(xiàn)對黃芪中毛蕊異黃酮葡萄糖苷和黃芪甲苷的快速含量測定。3.分別使用近紅外、中紅外光譜分析技術(shù)對梔子苷進(jìn)行定量分析。首先,利用高效液相色譜法測定梔子中梔子苷含量,以藥典法為依據(jù),選擇100批樣品,運(yùn)用偏最小二乘法分別建立梔子苷含量與近紅外光譜、中紅外光譜之間的校正模型。結(jié)果顯示,近紅外光譜中,光譜經(jīng)過二階導(dǎo)數(shù)+Savitzky-Golay平滑處理,模型校正集r為0.9725,RMSEC值為0.20;驗(yàn)證集r為0.9606,RMSEP值為0.22;中紅外光譜中,光譜經(jīng)過二階導(dǎo)數(shù)+標(biāo)準(zhǔn)正態(tài)變量變換處理,模型校正集r為0.9256,RMSEC值0.24;驗(yàn)證集r為0.9174,RMSEP值為0.24。通過實(shí)驗(yàn)可以發(fā)現(xiàn),近紅外光譜、中紅外光譜均可以快速、無損、有效的對梔子中梔子苷含量進(jìn)行測定。4.采用近紅外光譜技術(shù),結(jié)合藥典含量測定方法,對106批大黃樣品中大黃酸、大黃素、大黃酚、大黃素甲醚和蘆薈大黃素的含量進(jìn)行測定,并計(jì)算總含量,通過對預(yù)處理方法的考察,建立其與近紅外光譜之間的最佳校正模型。結(jié)果顯示,光譜經(jīng)一階導(dǎo)數(shù)處理后,模型校正集r為0.9856,RMSEC值為0.13;驗(yàn)證集r為0.9445,RMSEP值為0.23。說明采用近紅外光譜技術(shù),可以對大黃中大黃酸、大黃素、大黃酚、大黃素甲醚和蘆薈大黃素的總含量進(jìn)行快速測定。5.采用近紅外光譜技術(shù),結(jié)合藥典含量測定方法,對97批獨(dú)活樣品中蛇床子素和二氫歐山芹醇當(dāng)歸酸酯的含量進(jìn)行測定,通過對預(yù)處理方法的考察,建立其與近紅外光譜之間的最佳校正模型。結(jié)果顯示,蛇床子素光譜經(jīng)一階導(dǎo)數(shù)處理后,模型校正集r為0.9233,RMSEC值為0.16;驗(yàn)證集r為0.9413,RMSEP值為0.14;二氫歐山芹醇當(dāng)歸酸酯光譜不需經(jīng)過預(yù)處理,模型校正集r為0.8315,RMSEC值為0.11;預(yù)測集r為0.8574,RMSEP值為0.10。說明采用近紅外光譜技術(shù),可以實(shí)現(xiàn)對獨(dú)活中蛇床子素和二氫歐山芹醇當(dāng)歸酸酯的快速定量分析。6.采用近紅外光譜技術(shù),結(jié)合藥典含量測定方法,對99批白芷樣品中歐前胡素的含量進(jìn)行測定,通過對預(yù)處理方法的考察,建立其與近紅外光譜之間的最佳校正模型。結(jié)果顯示,歐前胡素光譜經(jīng)二階導(dǎo)數(shù)+Savitzky-Golay平滑處理后模型最佳,校正集r為0.9755,RMSEC值為0.01;預(yù)測集r為0.9630,RMSEP值為0.01。說明通過近紅外光譜技術(shù)建立了一種快速測量白芷中歐前胡素含量的新方法。7.采用近紅外光譜技術(shù),結(jié)合藥典含量測定方法,對100批防風(fēng)樣品中升麻素苷及5-O-甲基維斯阿米醇苷的含量進(jìn)行測定,并計(jì)算總含量,通過對預(yù)處理方法的考察,建立其與近紅外光譜之間的最佳校正模型。結(jié)果顯示,光譜經(jīng)二階導(dǎo)數(shù)+多元散射校正處理后,模型最佳,模型校正集r為0.9773,RMSEC值為0.05;驗(yàn)證集r為0.9617,RMSEP值為0.05。說明采用近紅外光譜技術(shù),可以實(shí)現(xiàn)對防風(fēng)中升麻素苷及5-O-甲基維斯阿米醇苷總含量的快速測定。
[Abstract]:The traditional Chinese medicine is a complex multi-component system, and the quality control of the traditional Chinese medicine is of great significance for ensuring the clinical curative effect, realizing the modernization of the traditional Chinese medicine and promoting the technical development of the traditional Chinese medicine industry. Therefore, a simple and rapid quality analysis method is needed, and the accurate and rapid content determination of the traditional Chinese medicinal materials is required. The near infrared spectroscopy is a kind of fast and non-destructive green analytical method. By using the application of the method in the quantitative detection, the purpose of rapid detection of the content of the index components in the red paeony root, the yellow root, the gardenia, the rhubarb, the pubescent angelica, the dahurian angelica root and the wind-proof 7-flavor traditional Chinese medicine is realized. The following progress has been made:1. The content of gallic acid, catechin, Paeonolactone and Paeonia lactiflora in Radix Paeoniae Rubra was determined by high performance liquid chromatography, and 101 samples were selected, and the correction model between its content and near infrared spectrum was established by partial least square method. The results show that gallic acid is treated with multiple scattering correction + second order derivative, the model correction set r is 0.9065, the RMSEC value is 0.10, the verification set r is 0.9163, the RMSEP value is 0.09, the catechin is processed by the multivariate scattering correction + second order derivative, the model correction set r is 0.9408, the RMSEC value is 0.44, the verification set r is 0.9231, the RMSEP value is 0.40, the paeonolactone is processed by the multivariate scattering correction + first derivative treatment, the model correction set r is 0.9406, the RMSEC value is 0.13, the verification set r is 0.9226, the RMSEP value is 0.14, the paeonia is processed by the Savitzky-Golay smoothing + first derivative processing, the model correction set r is 0.9674, the RMSEC value is 0.22, the verification set r is 0.9281, The results showed that the value of RMSEP was 0.222.4, and the linear relationship between the measured value and the measured value of NIR model showed that the fitting ability of the model was good, and it can be used to quickly determine the content of gallic acid, catechin, Paeonolactone and Paeonia lactiflora in large batch of Radix Paeoniae Rubra. A high performance liquid chromatography-mass spectrometry (LC-MS) method was used to determine the content of the total content of the soybean isoflavone and the level of the yellow-and-green in the yellow rice, and a 91-batch sample was selected, and the correction model between the content and the near-infrared spectrum was established by using the partial least squares method. The results showed that, with the first derivative + Savitzky-Golay smoothing process, the corrected set r of the model was 0.8635, the RMSEC value was 0.019, the verification set r was 0.8266, the RMSEP value was 0.023, the second derivative of the yellow and the second derivative, the Savitzky-Golay smoothing process, the model correction set r was 0.7963, and the RMSEC value was 0.008; The results showed that the value of RMSEP was 0.8548 and the value of RMSEP was in the range of 0.006.2 species. The quantitative analysis of the gardenia was carried out by using the near-infrared and mid-infrared spectrum analysis techniques. First of all, the content of gardenia in the gardenia was determined by high performance liquid chromatography, and 100 batches of samples were selected according to the pharmacopoeia method. The correction model between the content of the gardenia and the near infrared spectrum and the mid-infrared spectrum was respectively established by the partial least square method. The results show that, in the near-infrared spectrum, the spectrum passes through the second-order derivative, the Savitzky-Golay smoothing process, the model correction set r is 0.9725, the RMSEC value is 0.20, the verification set r is 0.9606, the RMSEP value is 0.22, the mid-infrared spectrum, the spectrum passes through the second-order derivative + standard positive-state variable conversion processing, the model correction set r is 0.9256, The RMSEC value is 0.24; the validation set r is 0.9174 and the RMSEP value is 0.24. It can be found that in the near infrared spectrum, the infrared spectrum can be fast, non-destructive and effective in the determination of the content of the gardenia in the gardenia. The content of rhein, emodin, chrysophanol, emodin and aloe emodin in 106 rhubarb samples was determined by near-infrared spectroscopy, and the total content was calculated. The best correction model between the near-infrared spectrum and the near-infrared spectrum is established. The results show that, after the first derivative treatment, the model correction set r is 0.9856, the RMSEC value is 0.13, the verification set r is 0.9445, and the RMSEP value is 0.23. The total content of rhein, emodin, chrysophanol, emodin and aloe emodin in Radix et Rhizoma Rhei can be quickly determined by near-infrared spectroscopy. In this paper, the content of cnidium and dihydro-ocarvanol in 97 batches of pubescent angelica is determined by near-infrared spectroscopy, and the best correction model between them and near-infrared spectrum is established by the investigation of the pre-treatment method. The results showed that, after the first derivative treatment, the model correction set r is 0.9233, the RMSEC value is 0.16, the verification set r is 0.9413, the RMSEP value is 0.14, the dihydro-parsley alcohol angelica ester spectrum does not need to be pre-processed, the model correction set r is 0.8315, the RMSEC value is 0.11, the prediction set r is 0.8574, The RMSEP value is 0.10. In this paper, the rapid quantitative analysis of cnidium and dihydro-ocarvanol in the radix angelicae pubescentis can be realized by using the near-infrared spectroscopy. By means of near-infrared spectroscopy and the method of the method of compendial content determination, the content of the pre-determination of the content of the former in the 99 batches of Radix Angelicae Dahuricae is determined, and the optimal calibration model between the two-infrared spectrum and the near-infrared spectrum is established by the investigation of the pretreatment method. The results show that the model is best after the second derivative + Savitzky-Golay smoothing process, the correction set r is 0.9755, the RMSEC value is 0.01, the prediction set r is 0.9630, and the RMSEP value is 0.01. A new method for rapid measurement of the content of imperatorin of Radix Angelicae Dahuricae by near-infrared spectroscopy is presented. In this paper, the content of L-O-methyl and 5-O-methyl-vibriol in 100 batches of wind-proof samples was determined by near-infrared spectroscopy, and the total content was calculated. The results show that the model is the best after the second-order derivative + multi-element scattering correction process, and the model correction set r is 0.9773, the RMSEC value is 0.05, the verification set r is 0.9617, and the RMSEP value is 0.05. The method of near-infrared spectroscopy can be used to measure the total content of L-and 5-O-methyl-vibriol in the wind-proof.
【學(xué)位授予單位】:中國中醫(yī)科學(xué)院
【學(xué)位級別】:碩士
【學(xué)位授予年份】:2017
【分類號】:R284.1;O657.33

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