CN102453058B - 13C稳定性同位素标记1,6-缩水-β-D-吡喃葡萄糖的制备方法 - Google Patents
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Abstract
本发明提供一种13C稳定性同位素标记的1,6-缩水-β-D-吡喃葡萄糖(简称:13C内醚糖)的制备方法,属于生物化工技术领域。该制备方法主要是采用13C稳定性同位素标记的葡萄糖(简称13C葡萄糖)为原料,在真空或惰性气体保护条件下,于280-550℃热解,使13C葡萄糖失去1分子水,得到13C内醚糖含量50%以上的热解产物,再将热解产物纯化,获得含量大于95%的13C内醚糖产品,进一步纯化得到含量大于99%的13C内醚糖产品。
Description
技术领域
本发明属于生物化工技术领域。
技术背景
1,6-缩水-β-D-吡喃葡萄糖(简称:内醚糖,Levoglucosan),分子式为C6H10O5,它是D型葡萄糖的脱水形式。内醚糖分子结构中C-1和C-6间含有一个内缩醛环,还存在三个仲羟基基团。这些结构的特征使得它成为合成立体化合物的一个重要单体。脱水内醚糖特有的结构决定了其可以发生如下的反应:内缩醛环在反应中被打断可生成高分子化合物,羟基基团的选择性酯化反应及其配位反应。以内醚糖为手性合成子可以合成寡糖,高聚物,树脂,药物,炸药,表面活性剂,塑料,增塑剂等的大规模合成及相关产品。
内醚糖的生产方法研究最早是Pictet在1920年申请的专利(Pictet,A.Levoglucosanmanufacture,Canadian Patent 195897,1920),报道了淀粉热解获得脱水内醚糖的方法,并确定了脱水内醚糖结构是葡萄糖1位和6位键间的脱水形式。美国专利(专利号:3309356)描述了以木材为热解原料制备内醚糖的方法。中国专利(专利号:001079565)公开了一种从淀粉或纤维素类生物质的热解油中制备内醚糖的方法。近期的研究表明,内醚糖可以作为微生物的碳源和能源发酵生产多种人类生活所需的产品,如:乙醇、柠檬酸、乳酸、衣康酸等;内醚糖还是合成寡糖的常用中间体(Hongmei Liu,et al.Synthesis of pentasaccharide andheptasaccharide derivatives and their effects on plant growth.Journal of Agricultural and FoodChemistry,2008,56(14),5634-5638)。由于纤维素类生物质是地球上最丰富的可再生资源,使得内醚糖的制备与应用研究更具重要意义。
但是,微生物利用内醚糖作为碳源的代谢方式别具特色,而且并不是所有常见的发酵菌株都能利用内醚糖,因此,为了深入认识微生物对内醚糖的代谢方式,以及内醚糖利用微生物的多样性,利用13C稳定性同位素标记的内醚糖(简称13C内醚糖)是一种有效的手段。另外,研究以内醚糖为原料合成的药物(如:肝素戊糖、葡聚寡糖等)的药理和代谢过程,也可以采用13C稳定性同位素标记的内醚糖来合成这些药物。
发明内容
本发明的目的是提供一中13C稳定性同位素标记的1,6-脱水-β-D-吡喃葡萄糖(简称13C内醚糖)的制备方法。内容如下:
(1)原料:采用13C稳定性同位素标记的葡萄糖(简称13C葡萄糖);
(2)真空或惰性气体保护热解:将13C葡萄糖放入真空固定床热解反应器或有惰性气体 保护的流化床热解反应器中,加热到280℃-550℃,使13C葡萄糖失去1分子水,并将高温气态产物迅速冷却至室温,得到粘稠状液态产物,其中13C内醚糖含量50%以上;
(3)13C内醚糖的纯化:向第(2)步得到的粘稠状液态产物中加入3-10倍蒸馏水溶解,使其全部溶解,静置30分钟以上,双层定量滤纸抽滤,收集滤液,减压浓缩至加蒸馏水溶解前的体积,连续搅拌,缓慢加入无水乙醇或丙酮,直至有晶体析出,再将容器放入冰浴中,连续搅拌30分钟以上,再静置30分钟以上,双层定量滤纸抽滤,收集结晶,自然晾干,即获得13C内醚糖,含量大于95%;如需要进一步纯化,重复第(3)步前面的操作,可得到含量大于99%的13C内醚糖。
具体实施方式
以下通过具体实施例详细说明本发明的实施,目的在于帮助读者更好地理解本发明的精神实质,但不作为对本发明实施范围的限定。
实施例1:6个碳原子全部为13C稳定性同位素的内醚糖(简称:六-13C内醚糖)的制备。包括如下步骤:
(1)原料:6个碳原子全部为13C稳定性同位素的葡萄糖(简称:六-13C葡萄糖);
(2)真空热解:将六-13C葡萄糖放入真空固定床热解反应器中,加热到390℃,使六-13C葡萄糖失去1分子水,并将高温气态产物迅速冷却至室温,得到粘稠状液态产物,其中六-13C内醚糖含量60%以上;
(3)六-13C内醚糖的纯化:向第(2)步得到的粘稠状液态产物中加入3-10倍蒸馏水溶解,使其全部溶解,静置30分钟以上,双层定量滤纸抽滤,收集滤液,减压浓缩至加蒸馏水溶解前的体积,连续搅拌,缓慢加入无水乙醇或丙酮,直至有晶体析出,再将容器放入冰浴中,连续搅拌30分钟以上,再静置30分钟以上,双层定量滤纸抽滤,收集结晶,自然晾干,即获得六-13C内醚糖,含量大于95%;如需要进一步纯化,重复第(3)步前面的操作,可得到含量大于99%的六-13C内醚糖。
实施例2:第1位和第3位的碳原子为13C稳定性同位素标记的内醚糖(简称:1,3-二-13C内醚糖)的制备。包括如下步骤:
(1)原料:第1位和第3位的碳原子为13C稳定性同位素标记的葡萄糖(简称:1,3-二-13C葡萄糖);
(2)真空热解:将1,3-二-13C葡萄糖放入真空固定床热解反应器中,加热到370℃,使其失去1分子水,并将高温气态产物迅速冷却至室温,得到粘稠状液态产物,其中1,3-二-13C内醚糖含量60%以上;
(3)1,3-二-13C内醚糖的纯化:向第(2)步得到的粘稠状液态产物中加入3-10倍蒸馏 水溶解,使其全部溶解,静置30分钟以上,双层定量滤纸抽滤,收集滤液,减压浓缩至加蒸馏水溶解前的体积,连续搅拌,缓慢加入无水乙醇或丙酮,直至有晶体析出,再将容器放入冰浴中,连续搅拌30分钟以上,再静置30分钟以上,双层定量滤纸抽滤,收集结晶,自然晾干,即获得1,3-二-13C内醚糖,含量大于95%;如需要进一步纯化,重复第(3)步前面的操作,可得到含量大于99%的1,3-二-13C内醚糖。
实施例3:只有第6位的碳原子为13C稳定性同位素标记的内醚糖(简称:6-13C内醚糖)的制备。包括如下步骤:
(1)原料:只有第6位的碳原子为13C稳定性同位素标记的葡萄糖(简称:6-13C葡萄糖);
(2)真空热解:将6-13C葡萄糖放入真空固定床热解反应器中,加热到400℃,使其失去1分子水,并将高温气态产物迅速冷却至室温,得到粘稠状液态产物,其中6-13C内醚糖含量60%以上;
(3)6-13C内醚糖的纯化:向第(2)步得到的粘稠状液态产物中加入3-10倍蒸馏水溶解,使其全部溶解,静置30分钟以上,双层定量滤纸抽滤,收集滤液,减压浓缩至加蒸馏水溶解前的体积,连续搅拌,缓慢加入无水乙醇或丙酮,直至有晶体析出,再将容器放入冰浴中,连续搅拌30分钟以上,再静置30分钟以上,双层定量滤纸抽滤,收集结晶,自然晾干,即获得6-13C内醚糖,含量大于95%;如需要进一步纯化,重复第(3)步前面的操作,可得到含量大于99%的6-13C内醚糖。
Claims (1)
1.一种13C稳定性同位素标记的1,6-脱水-β-D-吡喃葡萄糖的制备方法,其特征在于,将13C稳定性同位素标记的葡萄糖在真空条件下或有惰性气体保护的条件下加热到280℃—550℃进行热解,使其失去1分子水,并将高温气态产物迅速冷却至室温,得到粘稠状液态产物;
向所述粘稠状液态产物中加入3-10倍蒸馏水溶解,使其全部溶解,静置30分钟以上,双层定量滤纸抽滤,收集滤液,减压浓缩至加蒸馏水溶解前的体积,连续搅拌,缓慢加入无水乙醇或丙酮,直至有晶体析出,再将容器放入冰浴中,连续搅拌30分钟以上,再静置30分钟以上,双层定量滤纸抽滤,收集结晶,自然晾干,得到含量大于95%的13C稳定性同位素标记的1,6-脱水-β-D-吡喃葡萄糖;重复前面的操作,得到含量大于99%的13C稳定性同位素标记的1,6-脱水-β-D-吡喃葡萄糖。
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