蜂蜡气相色谱指纹图谱的研究
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摘要
目的:通过对不同产地的蜂蜡进行指纹图谱研究,旨在控制蜂蜡及其相关产品的质量,并为进一步的开发利用提供实验资料。
方法:(1)依据中华人民共和国行业标准-蜂蜡SB/T 10190-93[1]的规定方法,测定全国10个产地蜂蜡的密度、熔点、折光率、酸值、碘值、皂化值等理化性质。(2)采用气相色谱法,色谱条件为:毛细管色谱柱,SE-54,30m,0.32mm×0.25m,采用程序升温法,柱初始温度50℃,以10℃.min-1的速率上升至200℃,然后以5℃.min-1的速率上升至295℃,维持26分钟,总检测时间60min。进样口温度250℃,检测器温度280℃。载气为高纯氮气,流速为40ml.min-1,氢气流速50ml.min-1,空气流速50ml.min-1,分流比50:1。测定不同产地蜂蜡的指纹图谱,找出它们的共有峰,依据《中药注射剂指纹图谱研究的技术要求(暂行)》[2]的方法,分别计算它们的共有峰相对保留时间,相对峰面积比值,还有非共有峰面积占总峰面积的百分比,共有峰的积分含量,并计算各个产地的蜂蜡之间的相似度。
结果:(1)全国10个产地蜂蜡理化性质测定结果有明显差异,但均符合中华人民共和国行业标准-蜂蜡SB/T 10190-93,表明所购买蜂蜡均系正品。可以作为蜂蜡指纹图谱测定用样品。(2)在全国10个产地蜂蜡的指纹图谱中,除参照物外,总共获得17个比较稳定的共有峰,不同产地的蜂蜡,共有峰相对保留时间变化较小,RSD均小于1%,相对峰面积的比值差别却很大,最大的为河南和河北产地的第三个共有峰,差别达到40倍以上。各产地非共有峰面积占总面积的百分比均小于10%。各产地蜂蜡相同成分的积分含量差别较大,其中第八个共有峰成分的积分含量最大,大连产地30.791%,广东产地43.489%,海南产地的更是达到52.831%,其他各产地该成分也具有较大的积分含量,这表明该成分是蜂蜡的最主要成分。在以大连产地作为参照图谱计算的相似度结果中,除上海,河北产地的相似度稍低外,分别为0.663,0.611,其它产地均有良好的相似度。广东、河南、山东产地的相似度结果最好,分别为0.953、0.967、0.919。这表明大连和这三个产地的蜂蜡在化学成分上比其它产地有更好的一致性,提示它们之间在功效上也会有较大的相似性。
结论:(1)全国10个不同产地蜂蜡的气相色谱指纹图谱,均符合《中药注射剂指纹图谱研究的技术要求(暂行)》,可以作为蜂蜡的气相色谱指纹图谱。(2)不同来源蜂蜡的化学成分相似性较大,其差异较小。作为促皮生软膏剂中主要成分的大连产的蜂蜡,只有通过它的指纹图谱来严格控制蜂蜡的来源,才能保证促皮生软膏剂具有不变的,明确的,持续的治疗功效。(3)所获得10个产地的蜂蜡指纹图谱稳定性较好,可靠性较高,可以作为不同产地蜂蜡质量严格控制的一种方法。从化学成分的分析上,我们也能对不同产地之间蜂蜡的功效差别原因提供一定的实验资料。
Objective: This study is to control beeswax and other related products quality and to provide experimental data for developing used by checking the fingerprints of beeswaxes.
Methods: (1) Select ten beeswaxes in different sources nationwide. According to the method of the People’s Republic of China professional standard- beeswax SB/T 10190-93, we determined the physico-chemical properties of these beeswaxes, i.e., density, melting point, refractive index, acid value, iodine value, and saponification number. (2) Chromatographic conditions were as following: capillary column gas chromatography, SE-54,30m,0.32mm×0.25m. Temperature programming method was applied. Temperature of the column was from 50℃to 200℃at the rate of 5℃.min-1, and then from 200℃to 295℃at the rate of 5℃.min-1, kept 26 minutes, and total time was 60 minutes. The injection port temperature was 250℃, FID temperature was 280℃. Supporting gas was highly pure nitrogen and at the rate of 40ml.min-1, hydrogen gas and air were all at the rates of 50ml.min-1, split ratio was 50:1. The beeswaxes fingerprints of ten different nationwide sources were determined by using gas chromatography and their common peaks were found. According to《Technical requirement of the fingerprint in injection of Chinese materia medica(tentative standard)》, we calculated relative retention time, relative peaks area, the percentage of non-common peaks area, relative percentage content of their common peaks ,and calculated the similar degree of beeswaxes from different sources.
Results:(1) The results of determination of the physico-chemical property of beeswaxes from 10 nationwide sources were significant different; however, they were all consistent with the requirement of People’s Republic of China professional standard-beeswax SB/T 10190-93. We have showed that the beeswaxes we purchased were qualified products. They can be used as samples for determining beeswax fingerprint. (2) Among the beeswaxes fingerprints of ten nationwide sources, we obtained seventeen comparatively steady common peaks except the control. The relative retention times were of little variable, their RSD were small than 1%. Relative peaks area were large different, the largest difference was between Henan and Hebei sources, the third common peak area was of 40 times difference. The percentage of non-common peaks area was lower than 10%. Different content were determined in different sources beeswaxes. The content of the eighth common peak composition were the largest different, the composition content of Dalian source was 30.791%, Guangdong source was 43.489% and Hainan source was 52.831%. This composition content of other sources was also large. The result showed that this composition was the essential component of beeswax. We calculated the similar degree according to the Dalian source, which was used for reference. The similar degrees of Shanghai and Hebei sources were low but other sources were high. The sources of Guangdong, Henan, Shandong had the best similar degree, separately for 0.953, 0.967, and 0.919. It showed that the compositions and therapeutic effect between Dalian and the three sources had a good concordance.
Conclusions:(1) In the determination of beeswaxes fingerprints of ten different nationwide sources. We found that they were all consistent with《Technical requirement of the fingerprint in injection of Chinese materia medica(tentative standard)》. And they can be used for beeswax fingerprint. (2) The chemical ingredients of beeswaxes from different source were much similar and little different. As the basic ingredient of Skin Growth Promoting Ointment, beeswax was selected from Dalian source. We control beeswax source strictly from fingerprint. By this way, we suggest that Skin Growth Promoting Ointment has invariable,definite and persistent therapeutic effect.(3) The fingerprint we got from ten different sources have good stability and validity, they can be used as a method for strict quality control of beeswax source. From identification of their chemical ingredient, we have provided information those different sources beeswaxes were of different therapeutic effect.
方法:(1)依据中华人民共和国行业标准-蜂蜡SB/T 10190-93[1]的规定方法,测定全国10个产地蜂蜡的密度、熔点、折光率、酸值、碘值、皂化值等理化性质。(2)采用气相色谱法,色谱条件为:毛细管色谱柱,SE-54,30m,0.32mm×0.25m,采用程序升温法,柱初始温度50℃,以10℃.min-1的速率上升至200℃,然后以5℃.min-1的速率上升至295℃,维持26分钟,总检测时间60min。进样口温度250℃,检测器温度280℃。载气为高纯氮气,流速为40ml.min-1,氢气流速50ml.min-1,空气流速50ml.min-1,分流比50:1。测定不同产地蜂蜡的指纹图谱,找出它们的共有峰,依据《中药注射剂指纹图谱研究的技术要求(暂行)》[2]的方法,分别计算它们的共有峰相对保留时间,相对峰面积比值,还有非共有峰面积占总峰面积的百分比,共有峰的积分含量,并计算各个产地的蜂蜡之间的相似度。
结果:(1)全国10个产地蜂蜡理化性质测定结果有明显差异,但均符合中华人民共和国行业标准-蜂蜡SB/T 10190-93,表明所购买蜂蜡均系正品。可以作为蜂蜡指纹图谱测定用样品。(2)在全国10个产地蜂蜡的指纹图谱中,除参照物外,总共获得17个比较稳定的共有峰,不同产地的蜂蜡,共有峰相对保留时间变化较小,RSD均小于1%,相对峰面积的比值差别却很大,最大的为河南和河北产地的第三个共有峰,差别达到40倍以上。各产地非共有峰面积占总面积的百分比均小于10%。各产地蜂蜡相同成分的积分含量差别较大,其中第八个共有峰成分的积分含量最大,大连产地30.791%,广东产地43.489%,海南产地的更是达到52.831%,其他各产地该成分也具有较大的积分含量,这表明该成分是蜂蜡的最主要成分。在以大连产地作为参照图谱计算的相似度结果中,除上海,河北产地的相似度稍低外,分别为0.663,0.611,其它产地均有良好的相似度。广东、河南、山东产地的相似度结果最好,分别为0.953、0.967、0.919。这表明大连和这三个产地的蜂蜡在化学成分上比其它产地有更好的一致性,提示它们之间在功效上也会有较大的相似性。
结论:(1)全国10个不同产地蜂蜡的气相色谱指纹图谱,均符合《中药注射剂指纹图谱研究的技术要求(暂行)》,可以作为蜂蜡的气相色谱指纹图谱。(2)不同来源蜂蜡的化学成分相似性较大,其差异较小。作为促皮生软膏剂中主要成分的大连产的蜂蜡,只有通过它的指纹图谱来严格控制蜂蜡的来源,才能保证促皮生软膏剂具有不变的,明确的,持续的治疗功效。(3)所获得10个产地的蜂蜡指纹图谱稳定性较好,可靠性较高,可以作为不同产地蜂蜡质量严格控制的一种方法。从化学成分的分析上,我们也能对不同产地之间蜂蜡的功效差别原因提供一定的实验资料。
Objective: This study is to control beeswax and other related products quality and to provide experimental data for developing used by checking the fingerprints of beeswaxes.
Methods: (1) Select ten beeswaxes in different sources nationwide. According to the method of the People’s Republic of China professional standard- beeswax SB/T 10190-93, we determined the physico-chemical properties of these beeswaxes, i.e., density, melting point, refractive index, acid value, iodine value, and saponification number. (2) Chromatographic conditions were as following: capillary column gas chromatography, SE-54,30m,0.32mm×0.25m. Temperature programming method was applied. Temperature of the column was from 50℃to 200℃at the rate of 5℃.min-1, and then from 200℃to 295℃at the rate of 5℃.min-1, kept 26 minutes, and total time was 60 minutes. The injection port temperature was 250℃, FID temperature was 280℃. Supporting gas was highly pure nitrogen and at the rate of 40ml.min-1, hydrogen gas and air were all at the rates of 50ml.min-1, split ratio was 50:1. The beeswaxes fingerprints of ten different nationwide sources were determined by using gas chromatography and their common peaks were found. According to《Technical requirement of the fingerprint in injection of Chinese materia medica(tentative standard)》, we calculated relative retention time, relative peaks area, the percentage of non-common peaks area, relative percentage content of their common peaks ,and calculated the similar degree of beeswaxes from different sources.
Results:(1) The results of determination of the physico-chemical property of beeswaxes from 10 nationwide sources were significant different; however, they were all consistent with the requirement of People’s Republic of China professional standard-beeswax SB/T 10190-93. We have showed that the beeswaxes we purchased were qualified products. They can be used as samples for determining beeswax fingerprint. (2) Among the beeswaxes fingerprints of ten nationwide sources, we obtained seventeen comparatively steady common peaks except the control. The relative retention times were of little variable, their RSD were small than 1%. Relative peaks area were large different, the largest difference was between Henan and Hebei sources, the third common peak area was of 40 times difference. The percentage of non-common peaks area was lower than 10%. Different content were determined in different sources beeswaxes. The content of the eighth common peak composition were the largest different, the composition content of Dalian source was 30.791%, Guangdong source was 43.489% and Hainan source was 52.831%. This composition content of other sources was also large. The result showed that this composition was the essential component of beeswax. We calculated the similar degree according to the Dalian source, which was used for reference. The similar degrees of Shanghai and Hebei sources were low but other sources were high. The sources of Guangdong, Henan, Shandong had the best similar degree, separately for 0.953, 0.967, and 0.919. It showed that the compositions and therapeutic effect between Dalian and the three sources had a good concordance.
Conclusions:(1) In the determination of beeswaxes fingerprints of ten different nationwide sources. We found that they were all consistent with《Technical requirement of the fingerprint in injection of Chinese materia medica(tentative standard)》. And they can be used for beeswax fingerprint. (2) The chemical ingredients of beeswaxes from different source were much similar and little different. As the basic ingredient of Skin Growth Promoting Ointment, beeswax was selected from Dalian source. We control beeswax source strictly from fingerprint. By this way, we suggest that Skin Growth Promoting Ointment has invariable,definite and persistent therapeutic effect.(3) The fingerprint we got from ten different sources have good stability and validity, they can be used as a method for strict quality control of beeswax source. From identification of their chemical ingredient, we have provided information those different sources beeswaxes were of different therapeutic effect.
引文
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