玉米芯木聚糖硫酸酯的合成、表征及其抗凝血活性

doi:10.3969/j.issn.1673-5854.2019.04.001

生物质化学工程 ›› 2019, Vol. 53 ›› Issue (4): 1-8.doi: 10.3969/j.issn.1673-5854.2019.04.001

• 研究报告 • 下一篇

玉米芯木聚糖硫酸酯的合成、表征及其抗凝血活性

樊洪玉¹(),卫民^1,^2,*(),赵剑¹,蒋剑春¹

1. 中国林业科学研究院林产化学工业研究所; 生物质化学利用国家工程实验室; 国家林业和草原局林产化学工程重点实验室; 江苏省生物质能源与材料重点实验室, 江苏南京 210042
2. 中国林业科学研究院林业新技术研究所, 北京 100091

收稿日期:2018-03-18 出版日期:2019-07-30 发布日期:2019-08-05
通讯作者: 卫民 E-mail:fanhongyulc@163.com;nanjingwm@163.com
作者简介:樊洪玉(1993-),女,山东聊城人,硕士生,主要从事生物质利用等方面的研究; E-mail:fanhongyulc@163.com
基金资助:
国家自然科学基金资助项目(31530010);中国林科院林产化学工业研究所研究团队建设创新工程项目(LHSXKQ14)

Synthesis, Characterization and Anticoagulant Activity of Corncob Xylan Sulfate

Hongyu FAN¹(),Min WEI^1,^2,*(),Jian ZHAO¹,Jianchun JIANG¹

1. Institute of Chemical Industry of Forest Products, CAF; National Engineering Lab. for Biomass Chemical Utilization; Key Lab. of Chemical Engineering of Forest Products, National Forestry and Grassland Administration; Key Lab. of Biomass Energy and Material, Jiangsu Province, Nanjing 210042, China
2. Research Institute of Forestry New Technology, CAF, Beijing 100091, China

Received:2018-03-18 Online:2019-07-30 Published:2019-08-05
Contact: Min WEI E-mail:fanhongyulc@163.com;nanjingwm@163.com
Supported by:
国家自然科学基金资助项目(31530010);中国林科院林产化学工业研究所研究团队建设创新工程项目(LHSXKQ14)

摘要/Abstract

摘要：

以碱法提取的玉米芯木聚糖为原料，LiCl为催化剂，在非质子溶剂中，采用三氧化硫-吡啶法合成了玉米芯木聚糖硫酸酯（XS），通过正交试验对合成工艺进行了优化，并采用凝胶渗透色谱（GPC）、红外光谱（FT-IR）、元素分析和¹³C NMR对其结构与性能进行了表征，进一步考察了其体外抗凝血活性。结果表明：在DMF溶剂中，当三氧化硫-吡啶络合物与木糖羟基单元的物质的量之比为1.5：1时，于55℃反应3 h，木聚糖的酯化效果最好，所制备的XS的取代度（D_S）为1.53，得率为78.2%，重均相对分子质量为36 754，分散系数为1.191。结构表征发现，硫酸酯基已经成功引入木聚糖中。体外抗凝血活性结果表明：XS可以延长APTT和TT，具有一定的抗凝血活性；当取代度为1.53、质量浓度为20 mg/L时，XS的APTT、PT和TT分别为36.37、14.22和14.70 s，与阳性对照肝素钠基本相当。

关键词: 玉米芯, 非质子溶剂, 木聚糖, 硫酸酯, 抗凝血剂

Abstract:

A new corncob xylan sulfate(XS) was synthesized by sulfur trioxide-pyridine(SO₃·Py) method with corncob xylan extracted by alkali method as raw material and LiCl as catalyst in aprotic solvent. The influences of solvent, temperature, reaction time and material ratio on the degree of substitution(D_S) of XS were investigated and the optimal conditions were determined by orthogonal test. The structures and properties of sulfated polysaccharides were investigated by GPC, FT-IR, elemental analysis and ¹³C NMR spectroscopy. And the in vitro anticoagulant activity of XS was studied.The results indicated that the optimal conditions for sulfation were DMF as solvent, molar ratio of SO₃·Py complex and hydroxyl unit of xylose 1.5:1, 55℃ and 3 h, and the degree of substitution of XS was 1.53 and the yield of XS was 78.2%. And the weight average molecular mass of the xylan sulfate product was 36 754 and the dispersion coefficient was 1.191. Structural characterization revealed that sulfate groups were successfully introduced into xylan. A preliminary study of vitro anticoagulant activity was conducted and the results showed that the xylan sulfate had anticoagulant activity, which could significantly prolong the APTT and TT. When the degree of substitution was 1.53 and the mass concentration was 20 mg/L, the APTT, PT and TT of XS were 36.37, 14.22 and 14.70 s, respectively, which were basically equivalent to the positive control heparin sodium.

Key words: corncob, aprotic solvents, xylan, sulfate, anticoagulant

中图分类号:

TQ35

樊洪玉,卫民,赵剑,蒋剑春. 玉米芯木聚糖硫酸酯的合成、表征及其抗凝血活性[J]. 生物质化学工程, 2019, 53(4): 1-8.

Hongyu FAN,Min WEI,Jian ZHAO,Jianchun JIANG. Synthesis, Characterization and Anticoagulant Activity of Corncob Xylan Sulfate[J]. Biomass Chemical Engineering, 2019, 53(4): 1-8.

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参考文献 24

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试验号 No.	A 温度/℃ temperature	B 时间/h time	C n(SO₃·Py) : n(—OH)	D 溶剂 solvent	取代度 D_S
1	45	2	1:1	DMF	0.70
2	45	3	1.5:1	DMSO	1.29
3	45	4	2:1	FA	1.03
4	55	2	1.5:1	FA	1.32
5	55	3	2:1	DMF	1.53
6	55	4	1:1	DMSO	0.80
7	65	2	2:1	DMSO	1.04
8	65	3	1:1	FA	0.71
9	65	4	1.5:1	DMF	1.50
k₁	1.007	1.020	0.737	1.243
k₂	1.217	1.177	1.370	1.043
k₃	1.083	1.110	1.200	1.020
R	0.210	0.157	0.633	0.223

%
样品 sample	C	H	O	S
玉米芯木聚糖 corncob xylan	42.45	7.56	49.98	0.00
木聚糖硫酸酯 xylan sulfate	20.97	2.26	47.77	16.89

样品sample	反应时间/h reaction time	M_W/ku	D_S	质量浓度/(mg·L^-1) mass concentration	APTT/s	PT/s	TT/s
空白对照blank					30.93	13.70	12.48
肝素钠heparin				1	37.50	14.84	15.23
木聚糖硫酸酯XS-1 xylan sulfate XS-1	1	41.231	0.79	1	31.01	13.72	12.50
				10	31.74	13.74	13.52
				20	32.23	13.86	13.63
木聚糖硫酸酯XS-2 xylan sulfate XS-2	2	40.311	1.22	1	31.67	13.90	13.69
				10	33.42	13.92	13.85
				20	33.98	14.03	13.93
木聚糖硫酸酯XS-3 xylan sulfate XS-3	3	36.754	1.53	1	32.63	14.05	13.88
				10	35.77	14.08	14.33
				20	36.37	14.22	14.70

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玉米芯木聚糖硫酸酯的合成、表征及其抗凝血活性

Synthesis, Characterization and Anticoagulant Activity of Corncob Xylan Sulfate

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