花蕊石的本草考证、品质评价及物相分析

Herbal Textual Research,Quality Evaluation and Phase Analysis of Ophicalcitum

通过查阅历代本草、医书及现代文献,笔者对花蕊石的名称、基原、产地、品质、功效主治、炮制加工进行系统整理与本草考证。考证结果表明,清代前的本草多以“花乳石”之名记载,现以“花蕊石”为正名,另有混异品名“白云石”;本草所述“淡白点”与大理岩具闪星状光泽特征一致,结合“色如硫黄”“色皆青绿”“黑点”等蛇纹石特征,推断其为蛇纹大理岩,与今用花蕊石一致,且宋代花蕊石的蛇纹石含量较高;产地以河南、陕西、山西、四川为主,江苏,浙江,河北等地亦有;历代本草对花蕊石品质评价较少,现代以整齐质坚、夹有黄绿色斑纹者为佳。花蕊石味酸、涩,性平,归肝经,具“治金疮血流,内漏目翳,下死胎,落胞衣”等功效,现以“化瘀止血”描述其功效。古代炮制方法最早为“火烧”,随后有“硫黄煅”“煅”“童便制”“醋淬”“水飞”“研”等方法,现代将其简化为明煅、醋制并新增水淬等方法。通过重量法与乙二胺四乙酸滴定法分别检测花蕊石中CO_(3)^(2-)和CaCO_(3)的含量,结果发现市售花蕊石中CaCO_(3)含量差异较大,且样品S13与样品S18的CaCO_(3)含量相同,但其组成不同,根据CO_(3)^(2-)与CaCO_(3)含量可计算其中白云石[CaMg(CO_(3))2]与方解石(CaCO_(3))含量,其中方解石含量越高其外观闪星状光泽越明显。采用拉曼光谱与X射线衍射(XRD)检测花蕊石样品粉末的物相组成,并对条纹部分进行拉曼光谱快速无损检测,结果表明花蕊石主要由白云石、方解石、蛇纹石、橄榄石、辉石等组成,条纹部分以蛇纹石为主。综上分析,2020年版《中华人民共和国药典》规定花蕊石CaCO_(3)质量分数不小于40%,较难控制其质量,建议增加CO_(3)^(2-)含量检测。该研究可为花蕊石的溯本清源提供科学依据,并更好地指导临床用药和资源合理利用。

By reviewing the historical materia medica,medical books and modern literature,this paper has systematically sorted out and verified the name,origin,quality and other aspects of Ophicalcitum.After herbal textual research,it is shown that before the Qing dynasty,the mineral medicine was mostly recorded in the name of Huarushi,but now it is called Huaruishi,and there is another mixed name Baiyunshi.The light white spots described in the historical materia medica are consistent with the characteristics of marble with sparkling star-like luster,combined with the color like sulfur,color are green,black spots and other serpentine features,it is deduced that it is serpentine marble,consistent with the present-day Ophicalcitum,and Ophicalcitum in the Song dynasty has a high content of serpentine.The main producing areas are Henan,Shaanxi,Shanxi and Sichuan,Jiangsu,Zhejiang,Hebei and other places are also available.Successive generations of materia medica on the quality evaluation of Ophicalcitum is less,the modern to neat and firm in the texture,sandwiched with yellow-green mottled for the best.Ophicalcitum is acidic,astringent and neutral in nature,belonging to the liver meridian,with the efficacy of treatment of gold sores and blood flow,internal leakage of cataracts,dropping afterbirth,now describing its efficacy as removing blood stasis and stopping bleeding.In ancient times,the earliest processing method was burning,followed by calcination by sulphur,calcination,quenching with vinegar and other methods.In modern times,it has been simplified to open calcination,processing with vinegar and the addition of water quenching.The gravimetric method and ethylenediaminetetraacetic acid titration were used to detect the contents of CO_(3)^(2-)and CaCO_(3)in Ophicalcitum,respectively,and it was found that the gap in CaCO_(3)content among commercially available products was wide,and the content of CaCO_(3)in sample S13 and sample S18 was the same,but their compositions were different,and according to the contents of CO_(3)^(2-)and CaCO_(3),the dolomite and calcite contents could be calculated,of which the higher the calcite content the more obvious the sparkling star-like luster.Raman spectroscopy and X-ray diffraction(XRD)were used to detect the physical phase composition of the powder of the samples,and Raman spectroscopy was used for the rapid non-destructive testing of the striped part,which showed that Ophicalcitum was mainly composed of dolomite,calcite,serpentine,olivine and pyroxene,with serpentine dominanting the striped part.In summary,the 2020 edition of Chinese Pharmacopoeia stipulates that the content of CaCO_(3)in Ophicalcitum is not less than 40%,which is difficult to control its quality,and it is suggested to increase the detection of CO_(3)^(2-)content.This study can provide a scientific basis for the traceability of Ophicalcitum and better guide the clinical medication and rational utilization of resources.