Abstract��Calculus Bovis is one precious traditional Chinese medicine used widely in clinical practice. Because of its high price and lack of resources, the substitutes of Calculus Bovis artificial Calculus Bovis, in vivo cultured Calculus Bovis and in vitro cultured Calculus Bovis also have been widely used in clinical practice. In order to understand the difference in chemical composition between Calculus Bovis and its substitutes, and determine whether all kinds of Calculus Bovis medicinal materials have special detection methods, the chemical constituents and quality control methods of Calculus Bovis and its substitutes were reviewed in this paper. Through the review of literature it was found that artificial Calculus Bovis mainly contain hyodeoxycholic acid and only a small amount of free bilirubin, and the chemical components of the other three kinds of Calculus Bovis medicinal materials are different. The chemical compositions of natural Calculus Bovis and in vitro cultured Calculus Bovis are similar, but the proportions of different types of bilirubin are different. At present, no characteristic ingredients of natural Calculus Bovis have been found to distinguish it from in vitro cultured Calculus Bovis and in vivo cultured Calculus Bovis.
������, ����¡, ������, ������, ��Խ, κ��, ��˫��. ţ�Ƽ�����Ʒ��ѧ�ɷ֡��������Ʒ������о���չ[J]. �й�ҩѧ��־, 2019, 54(8): 597-602.
LIUWen-xi, CHENGXian-long, GUOXiao-han, HUXiao-ru, LIUYue, WEIFeng, MAShuang-cheng. Progress in Research on Chemical Constituents and Quality Control Methods of Calculus Bovis and Its Substitutes. Chinese Pharmaceutical Journal, 2019, 54(8): 597-602.
LI S Z. Compendium of Materia Medica(���ݸ�Ŀ)[M]. Vol 50. Beijing:People��s Medical Publishing House, 1982:1754.
[3]
ZHANG N R. Types of natural bezoar and their ingredients [J]. Organ Biochem Pharma(����������ҩ), 1979,(2):33-44.
[4]
WANG C L. Overview of bezoar and its substitutes[J]. J Pract Tradit Chin Med (ʵ����ҽҩ��־), 2010, 6(213):732-733.
[5]
REN L B, ZHOU H. Identification of natural bezoar, artificial calculus bovis and artificial bezoar[J]. China Pharm(�й�ҩҵ), 2004,13(10):63.
[6]
FENG C Y, ZHANG C L, LIU D. Modern research of Calculus Bovis(second): the quality control[J]. Her Med(ҽҩ����), 2017, 36(304):117-122.
[7]
WANG F. Study on antioxidant activity of cultivated Calculus Bovis[J]. J Liaoning Univ Tradit Chin Med(������ҽ��־), 2005, 32(1):73-73.
[8]
CAI H J, QIU F Z, LIU R Z. Pharmaceutical research on in vitro cultivation of bezoar[J]. Chin J Nat Med(�й���Ȼҩ��),2004,2(6):335-338.
[9]
JIANG W H, REN J Y, LI F. Supplementary advice on quality standards for bezoar[J]. Heilongjiang Med J(������ҽҩ), 2001, 14(4):299-300.
[10]
JIANG H, WANG Z P. The authenticity of natural bezoar[J]. Cap Med(��ʳƷ��ҽҩ), 2000, 7(1):57-57.
[11]
LU C S, SHEN H Q, LUO J P. A method for the identification of fake bezoar[J]. J Shanxi Med Univ(ɽ��ҽѧԺѧ��), 1994, 25(S1):152-154.
[12]
YANG X Z.Introduction of a false bezoar[J]. J Chin Med Mater(��ҩ��), 1989,12(9):26-26.
[13]
YAO T Z. Identification of true and false bezoar[J]. Shandong J Tradit Chin Med(ɽ����ҽ��־), 1988, 7(3):38-38.
[14]
CHU L, ZHOU J, WANG Y, et al. Identification of chemical industry dyes in adulteration of Bovis Calculus artifactus[J]. Chin Tradit Pat Med(�г�ҩ),2011, 33(9):1556-1559.
[15]
KE R X. The identification of bezoar and its counterfeit goods[J]. Strait Pharm J(��Ͽҩѧ),2007, 91(8):57-58.
[16]
WANG H Z. Identification of rare medicinal herbs, natural bezoar and its fake products[J]. Qinghai Med J(�ຣҽҩ��־), 2005, 35(6):52-52.
[17]
GUAN H, LI P F, ZHAO L J, WU R G. Determination and comparison of bilirubin cholic acid in natural bezoar and cultivated bezoar[J]. J Tradit Chin Vet Med(����ҽҽҩ��־),1997,16(1):11-13.
[18]
WANG T C, WANG Z Y, SHEN H L, et al. Primary study on antagonistic effect of bilirubin and bezoar against lipid peroxidation caused by n-hexane in mice[J]. Chin J Ind Med(�й���ҵҽѧ��־), 2004, 17(6):356-358.
[19]
WEI X T, JIANG J J, SHANG L Q, et al. Protective effect of bilirubin and natural cow-bezoar on styrene-induced HepG2 cell DNA strand breaks[J]. J Chin Public Health(���������), 2004, 20(4):442-443.
[20]
TAI C S, ZHAO L, LI Y, et al. The antagonism of cow bezoar and bilirubin on the lipid peroxidation of mice induced by trichloroethylene[J]. China Occup Med(�й�ְҵҽѧ), 2005, 32(2):43-44.
[21]
ZHANG H Z. The role of covalently bound bilirubin in bezoar[J]. Chin J Biochem Pharm(�й�����ҩ����־), 2003, 24(4):199-199.
[22]
YUE R L, QI S P, XIN M, et al. The value of total bilirubin and albumin ratio in prediction of bilirubin neurotoxicity[J]. Chin J Pract Pediatr(�й�ʵ�ö�����־), 2003, 18(1):18-20.
[23]
XIA J, CAO S, SHA Y W, et al. Preliminary study on contents and ratios of different types of bilirubin in natural and in vitro cultured Calculus Bovis[J]. Chin Pharm J(�й�ҩѧ��־), 2017, 52(11):971-977.
[24]
ZHANG Y J, XIA J, CHOU J S, et al. Research progress in pharmacological effects and quantitative methods for biles acids in Calculus Bovis[J]. J Int Pharm(����ҩѧ�о���־), 2016, 43(2):268-274.
[25]
LIU Q, TENG W, ZHANG B C, et al. Analysis and pharmacological effects of 19 free amino acids in natural bezoar[J]. Prim J Chin Mater Med(������ҩ��־), 1996, 10(4):39-40.
[26]
WAN T C, CHENG F Y, LIU Y T, et al. Study on bioactive compounds of in vitro cultured Calculus Suis and natural Calculus Bovis[J]. Anim Sci J, 2009, 81(1):697-704.
[27]
HOU S X, LIAO G T, WU D Q, et al. Quality analysis of artificial bezoar[J]. West China J Pharm Sci(����ҩѧ��־),1990,5(3):149-151.
[28]
ZHANG Q M, YAN K D, QIAN L H. Determination of cholesterol in bezoar by gas chromatography[J]. Chin J Chin Mater Med(�й���ҩ��־), 1991,16(7):426-428.
[29]
GAO Y S, QI Y X, JIANG L M, et al. Rapid determination of cholesterol in Quail Egg Yolk by reversed-phase high performance liquid chromatography[J]. Acta Nutr Sin(Ӫ��ѧ��), 2005, 27(1):72-74.
[30]
ZHANG Q M, YAN K D, TIAN S J, et al. Comparative study on chemical constituents of cultivated bezoar and natural bezoar--determination and comparison of trace elements[J]. J Chin Med Mater(��ҩ��), 1991,14(5):15-17.
[31]
LIU P, CHENG H. Study on determination method of bilirubin content in bezoar[J]. Liaoning J Tradit Chin Med(������ҽ��־), 2003, 30(6):499-499.
[32]
HUANG H P, TAN G S. Progress in the study of bilirubin in artificial bezoar[J]. Chin Pharm Aff(�й�ҩ��), 2005, 19(2):114-116.
[33]
WANG L M, WANG B N, CHEN W H, et al. Determination of bilirubin content by water solvent method [J]. Chin Tradit Pat Med(�г�ҩ), 1991,13(6):33-34.
[34]
YU Z X, MENG L. Discussion on determination of cholic acid in artificial bezoar products[J]. China Pharm(�й�ҩҵ), 2001,10(3):27-27.
[35]
WANG W L, TANG X Z. Determination of cholic acid in pharmaceuticals by activated carbon decoloration using furfural solution[J]. Chin Tradit Pat Med(�г�ҩ), 1994,10(3):15-15.
[36]
WU C M, XIE M. Determination of bilirubin in pientzehuang ultraviolet spectrophotometry[J]. Chin Tradit Pat Med(�г�ҩ), 1995,17(6):14-14.
[37]
CHEN Q. The content of bile acid in Niuhuang Capsules Detected by ultraviolet spectrophotometry[J]. Guide China Med(�й�ҽҩָ��), 2010, 8(20):183-183.
[38]
GE L, WANG F Y, ZHANG R Z, et al. Determination of cholic acid in Artificial Bezoar by derivative spectrophotometry[J]. Chin J Chin Mater Med(�й���ҩ��־), 1991,16(3):166-167.
[39]
ZENG L F, XUE J Q. Determination of cholic acid in Artificial Bezoar and compound Preparations by second derivative spectrophotometry[J]. Chin J Pharm(�й�ҽҩ��ҵ��־), 1995,26(10):455-457.
[40]
CHEN Z Z, ZHANG Y H. Application of new chromatographic analysis technique in bilirubin analysis[J]. J Shenyang Pharm Univ(����ҩѧԺѧ��), 1989, 6(3):217-219.
[41]
YE B B, PAN L, WANG D, et al. Simultaneous TLC-scanning determination of cholic acid and ursodeoxycholic acid in Artificial Calculus Bovis[J]. Chin J Pharm Anal(ҩ�������־), 2010, 30(4):706-709.
[42]
LIU S S,WU Z S,XING L, et al. Identification of bezoar and artificial bezoar powder using near infrared microspectroscopy[J]. Chin J Tradit Chin Med Pharm(�л���ҽҩ��־), 2014, 29(1):84-87.
[43]
MA Q, HAO G Q, QIAO Y J, et al. Determination of the artificial bezoar powder in bezoar powder by near-infrared spectrometry and support vector machine[J]. Spectrosc Spect Anal(����ѧ�������), 2006, 26(10):1842-1845.
[44]
LIN J M, ZHAO C W, ZHANG H M. Differential thermal analysis of natural bezoar and artificial bezoar[J]. Pharm Inf Bull(ҩѧ�鱨ͨѶ), 1990, 8(4):37-38.
[45]
ZHENG X W, LV Y, ZHANG J, et al. Powder X-ray diffraction analysis with fourier pattern on four Artificial Bezoars[J]. Chin Tradit Pat Med(�г�ҩ), 2000, 22(5):371-373.
[46]
LV Y, ZHENG X W, GONG N B, et al. X-ray diffraction fourier pattern analysis of natural Caculus Bovis[J]. Chin J Chin Mater Med(�й���ҩ��־), 2000, 25(4):202-205.
[47]
ZHANG Q M,YAN K D,TIAN S J, et al. Comparative study on chemical constituents of cultivated bezoar and natural bezoarv. determination and comparison of free and total amino acids[J]. J Chin Med Mater(��ҩ��), 1991, 14(9):15-17.
[48]
LI C M. Objective to improve the RP-HPLC method for the determination of free bilirubin in bezoar and Niuhuang Niuhuang pills to ensure the quality and safety of Niuhuang pills and Niuhuang Niuhuang pills[J]. Chin Pract Med(�й�ʵ��ҽҩ), 2015, 10(5):282-282.
[49]
FANG G P, ZHU J J, WANG Z H. Determination of multicomponent contets in bile acids of 25 Calculus Bovis samples[J]. Chin Tradit Pat Med(�г�ҩ), 1996, 18(5):39-41.
[50]
YANG H, QIU R J, DING Y Z, et al. Quantification of main bile acids in in vitro cultivated Calculus Bovis by high-performance liquid chromatography with pre-column derivatization[J]. J Beijing Univ Tradit Chin Med(������ҽҩ��ѧѧ��),2017,40(6):503-508.
[51]
SHI Y, SUN D M, WEI F, et al. Quantification of main bile acids in vitro cultivated Calculus Bovis by high-performance liquid chromatography with pre-column derivatization[J]. Chin J Pharm Anal(ҩ�������־), 2016, 36(11):2046-2050.
[52]
HUANG J. Determination of Taurine Particles by HPLC-ELSD[J]. Chin Pharm J(�й�ҩѧ��־), 2006, 41(17):1353-1354.
[53]
LIU W, JIN C, KONG W J, et al. Simultaneous determination of multi-active components in Calculus Bovis for quality control by high performance liquid chromatography-evaporative light scattering detection[J]. Chin J Anal Chem(������ѧ), 2010, 38(4):522-526.
[54]
LI K, GAO Y S, LI B L, et al. Content determination of cholesterol in natural Calculus Bovis and cultivated Calculus Bovis by glucuronidase with HPLC-ELSD[J]. China Med Her(ҽҩ����),2011,30(242):1633-1636.
[55]
PENG C, TIAN J X, LV M Y, et al. Development and validation of a sensitive LC-MS/MS method for the simultaneous determination of multicomponent contents in artificial Calculus Bovis[J]. J Chromatogr Sci, 2014, 52(2):128-136.
[56]
QIAO X, YE M, PAN D L, et al. Differentiation of various traditional Chinese medicines derived from animal bile and gallstone: simultaneous determination of bile acids by liquid chromatography coupled with triple quadrupole mass spectrometry[J]. J Chromatogr A, 2011, 1218(1):107-117.
[57]
FENG C Y,LI X P, ZHANG C L, et al. Development of a rapid and simple LC-MS /MS method for identification and quality control of natural Calculus Bovis and Calculus Bovis sativus[J]. Anal Methods, 2015, 7(18):7606-7617.
[58]
LEI K, LIU Y N, ZHANG C L, et al. Simultaneous quantification of 26 bile acids in Calculus Bovis Sativus and Calculus Bovis by HPLC-MS/MS[J]. Chin Tradit Herb Drugs(�в�ҩ),2018,621(10):2447-2453.
[59]
LIU Y G, TAN P,LIU S S, et al. A new method for identification of natural,artificial and in vitro cultured Calculus Bovis using high-performance liquid chromatography-mass spectrometry[J]. Pharmacogn Mag, 2015, 11(42):304-310.
[60]
ZHANG Q M, YAN K D, TIAN S J, et al. Comparative study on chemical constituents of cultivated bezoar and natural bezoar--determination and comparison of trace elements[J]. J Chin Med Mater(��ҩ��), 1991, 14(5):15-17.