| The fluoritum has used in gynecology for more than two thousand years.It was first recorded in the Han dynasty ShenNong’s Herbal.The processing method of Fluoritum was first seen in the Tang dynasty Qian Jin Yi Fang.The taste of Fluoritum is sweet and property is warm.It belongs to kidney,heart and lung.The fluoritum can warm kidney,soothe nerves and relieve asthmatic symptoms.It has been used to kidney yang deficiency,Gong cold sterility,palpitation due to fright,insomnia and dreaminess and cold cough.The fluoritum originates from fluorite which belong to fluoride minerals.Its main content is CaF2.It also contain impurities such as calcium carbonate and calcium oxide.The determination method of CaF2 in Fluoritum in Chinese Pharmacopoeia and many current researches is EDTA titrimetric method which is not accurate.In the market,there are large difference in quality and it has various colors.Besides of the ruled color of purple and green,white and yellow are also common colors.The Modern pharmacological studies have shown that Fluoritum can promote ovarian secretion,but it contains the arsenic,cadmium,copper,lead and mercury whose content were not stipulated in 2015 edition Chinese Pharmacopoeia.Besides,processing temperature,heating time and acidity of vinegar were also not stipulated in Chinese Pharmacopoeia when quenching Fluoritum.The topic is a part of National Chinese herbal medicine processing standard.Objective:1.To establish revise with F-ion-EDTA titrimetric method for determining the content of calcium fluoride in Fluoritum.2.To comprehend coloration mechanism and fluorescence characteristics.To explore the reasonable color range of Fluoritum.To further improve the Chinese Pharmacopoeia on the characteristics of Fluoritum.3.To establish the determination method of harmful elements in Fluoritum.4.To establish the best processing method of Fluoritum combined with actual industrial production.Methods and results:1.The samples were dissolved in dilute acetic acid and filtered.Quantification of the CaF2 in filtrate was done using ultraviolet-visible spectrophotometry(UV-Vis).In addition,atomic absorption spectrophotometry(AAS)was used to determinate the total calcium in filtrate.The results of UV-Vis and AAS were used to calculate the content of total soluble calcium in Fluoritum.Moreover,total calcium in Fluoritum was determined by EDTA method.Therefore,the content of CaF2 was calculated by subtracting the total soluble calcium from the total calcium in Fluoritum.The results showed that the UV-Vis average recoveries(n=6)ranged from 98.01%to 102.22%with an RSD below 2%.The AAS average recoveries(n=6)ranged from 95.43%to 104.27%with an RSD below 2%.This method was proved to be accurate,reliable and can be used for a wide range.It can be used to determine the CaF2 content in Fluoritum accurately.2.In our study,38 samples of commercial Fluoritum were determined by Deduction method established in this paper,the EDTA titrimetric method in Chinese Pharmacopoeia,Acid digestion method and X-ray power diffraction method,respectively.The results of the four methods were compared.The results of XRD phase analysis showed that 23 samples were Fluoritum,the XRD patterns were simple and sharp.Fluorite was the main phase of Fluoritum,and often accompanied by a small amount of impurities such as quartz and iron.The results also indicated that 13 samples non-conformed with Fluoritum,the content of calcite,gypsum and mica group in which were high.These XRD patterns were complicated and sharp.According to the phase analysis,2 samples were counterfeiter whose main content was carbonate minerals,the XRD patterns were complicated and sharp.On the other hand,the results of determination analysis showed that calcium fluoride content analyzed by X-ray power diffraction method were higher and even content to hundred,non-conformed Fluoritum were lower when compared with Pharmacopoeia method.From determination results,it can be found that X-ray power diffraction method was semi-quantitative analysis so this method is indeterminate.It was found that the results analyzed by Pharmacopoeia method have great errors(RSD>2%)because titration outcome of Pharmacopoeia method is total calcium content contains calcium carbonate content.Acid digestion method is complicated and involve secondary titration.When analyzing the CaF2 content in samples containing high fluorite content and low impurity content,Deduction method data close to the Pharmacopoeia method.When analyzing the CaF2 content in samples containing low fluorite content and high impurity content,Deduction method data close to the Acid digestion method,and Deduction method data were between Pharmacopoeia method data and Acid digestion method data.Deduction method is accurate and specific.3.By digging into and analysis the relevant research literature of fluorite which belong to fluoride minerals,colors,coloration mechanism and fluorescence characteristics of fluorite are summarized in this article.To analyze the fluorescence characteristics and chemical composition of Fluoritum with different colors,the reasonable color range of Fluoritum was explored in this article.The results showed that the white Fluoritum has simple chemical composition,calcium fluoride content is high and impurities content is very low.In the UV lamp,white Fluoritum is generally bright purple fluorescence.Purple transparent Fluoritum has simple chemical composition,calcium fluoride content is high and impurities content is very low.In the UV lamp,Purple transparent Fluoritum is generally purple fluorescence.Purple opaque Fluoritum has simple chemical composition,calcium fluoride content is high and impurities content is very low.In the UV lamp,purple opaque Fluoritum has no fluorescence.The minerals has no fluorescence when the mineral does not contain impurity elements or impurities too much.It is presumed that white Fluoritum has bright purple fluorescence because of low impurity content and lattice defects,purple opaque Fluoritum has no fluorescence because of high impurity content.4.In this study,we used microwave digestion to deal with Fluoritum samples,content of As,Cd,Cu and Pb in 11 samples were determined by inductively coupled plasma optical emission spectrometry.The results showed that the liner correlation was 0.998392～0.999999,the value of detection limit(3σ)was 0.0014445～0.0242061 μg·L-1,the relative standard deviation of precision was 0.81%～1.71%,the relative standard deviation of repeatability was 3.19%～6.90%,the rate of recovery of standard sample addition was 83.01%～91.02%and the relative standard deviation was 3.65%～6.33%.5.The test was carried out by using orthogonal table L9(33).The factors were heating temperature,heating time and acidity of vinegar and there were three levels of each factor.An aggregative weighted method was used with crispness,calcium content in water decoction and harmful elements content as the evaluative criteria.The best processing method of Fluoritum was analyzed by Comprehensive Weighted Scoring.Combined with the result of variance analysis,the optimal processing of Fluoritum was identified as calcining for 30 minutes under the temperature of 700℃,quenching with the total acid content of vinegar up to 6.72 g·100mL-1.6.To analyze changes in chemical composition in the process,the phase of Fluoritum processed by different conditions were prepared by X-ray diffraction method.The results showed that the main components of Fluoritum products and processed products are calcium fluoride.Conclusions:1.In order to obtain the accurate content of calcium fluoride in Fluoritum,it is necessary to remove soluble calcium impurities such as CaCO3 and CaSO4 in the sample.As a method for the determination of calcium fluoride in Fluoritum,deduction method is specific,accurate reliable and can be used for a wide range.2.The color and fluorescence properties of fluorite are related to impurity elements and lattice defects.It is speculated that white Fluoritum is bright purple with low impurity content.Purple opaque Fluoritum has high impurity content without fluorescence.3.Microwave digestion-inductively coupled plasma atomic emission spectrometry was used to determine the content of harmful elements in Fluoritum,and the reproducibility was good and the accuracy was high.The determination process was simple and the content of harmful elements in Fluoritum samples could be determined quickly.4.Mineral fluorite is quite stable.After processed by high temperature,the main chemical composition of Fluoritum did not significantly change.5.This study provides a scientific basis for quantifying the Process Parameters of Fluoritum and the Development of Quality Standard for Fluoritum. |
PDF Full Text Request