干湿循环下癸酸甘油酯的非生物合成及自组装

doi:10.7503/cjcu20170857

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (5): 849.doi: 10.7503/cjcu20170857

• 研究论文: 无机化学 • 上一篇下一篇

干湿循环下癸酸甘油酯的非生物合成及自组装

高静¹, 黄科科¹, 张显龙², 孙宇¹, 冯守华¹

1. 吉林大学化学学院, 无机合成与制备化学国家重点实验室, 长春 130012
2. 中国科学院青岛生物能源与过程研究所, 中国科学院生物基材料重点实验室, 青岛 266101

收稿日期:2017-12-29 出版日期:2018-04-21 发布日期:2018-04-21
作者简介:
联系人简介: 冯守华, 男, 博士, 教授, 博士生导师, 中国科学院院士, 主要从事无机化学研究. E-mail: shfeng@jlu.edu.cn
基金资助:
国家自然科学基金(批准号: 21427802, 21671076, 21621001)资助.

Robust Self-assembly Properties of Glyceryl Decanoates Synthesized Under Wetting and Drying Cycles^†

GAO Jing¹, HUANG Keke¹, ZHANG Xianlong², SUN Yu¹, FENG Shouhua^1,^*

1.State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, China
2. CAS Key Laboratory of Biobased Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101, China

Received:2017-12-29 Online:2018-04-21 Published:2018-04-21
Contact: FENG Shouhua
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21427802, 21671076, 21621001).

摘要/Abstract

摘要：

模拟生命起源前的自然蒸干现象, 使甘油和癸酸在近中性混合溶液中发生脱水缩合, 生成了原始细胞膜前驱体癸酸甘油酯. 随着温度升高到90 ℃, 主产物一癸酸甘油酯的产率可达4.7%. 对反应后的样品直接进行再水化时, 能观测到形态良好的囊泡, 证实生成微量癸酸甘油酯的混合物体系能使两亲分子在更低浓度下自组装形成囊泡. 当蒸干体系再水化过程中存在有机物溶质时, 溶液体系中的有机化合物能在囊泡形成过程中被封装起来, 因而膜结构为生命物质的稳定存在提供了保护场所, 蒸干再水化的条件有利于增加细胞生命起源过程中两亲分子的稳定性.

关键词: 脱水缩合, 干湿循环, 癸酸甘油酯, 原始细胞膜, 生命起源

Abstract:

Nonenzymatic dehydration reactions of decanoic acid with glycerol has been reported to occur under mimicked prebiotic conditions at near neutral pH, yielding more evolved membrane precursor compound glyceryl decanoates. Two isomers of glyceryl monodecanoate were the main products after the condensation reactions, and the yield of glyceryl monodecanoates could be increased to 4.7% with temperature rising to 90 ℃. Vesicles were observed when the mixture after reactions was rehydrated. Experiments demonstrate that trace glyceryl decanoates produced in the mixture play a great role in robust self-assembly process, it is the existence of such lipid products that makes a lower critical vesicle concentration. Meanwhile, organic compounds have been encapsulated during the self-assembly of vesicles, so membranous structures provid a place for organic compounds to exist stably. The dehydration reactions at near neutral pH, followed by rehydration, are suitable for increasing protocell membrane stability to environment. It implies that the condensation reaction is plausible for yielding more complex amphiphiles and the appearance of membrane structures on the early earth.

Key words: Condensation, Wetting and drying cycle, Glyceryl decanoate, Protocell membrane, Origin of life

TrendMD:

高静, 黄科科, 张显龙, 孙宇, 冯守华. 干湿循环下癸酸甘油酯的非生物合成及自组装. 高等学校化学学报, 2018, 39(5): 849.

GAO Jing,HUANG Keke,ZHANG Xianlong,SUN Yu,FENG Shouhua. Robust Self-assembly Properties of Glyceryl Decanoates Synthesized Under Wetting and Drying Cycles^†. Chem. J. Chinese Universities, 2018, 39(5): 849.

图/表 9

Fig.1 Mass spectrum for the extracts of the dehydration/ condensation reaction at 90 ℃

Fig.2 Schematic diagram of the condensation reaction of decanoic acid with glycerol

Table 1 HRMS data of target compounds

m/z	Molecular formula	Adduct	Mass accuracy(ppm)	Assignment
269.1724	C₁₃H₂₆O₄	[M+Na]⁺	0.37	Glyceryl monodecanoate
423.3083	C₂₃H₄₄O₅	[M+Na]⁺	0.47	Glyceryl didecanoate

Fig.3 Mass spectral signals of standard GMD(A) and sample GMD(B)

Fig.4 Relationship between signal intensity and concentration of GMD ranging from 0.01—0.7 mg/L

Fig.5 Influence of temperature on the yield of GMD

Fig.6 Samples of DA under condensation reactions(A1—A6) and corresponding micrographs with DA concentrations from 40 mmol/L to 60 mmol/L(B1—B6)

Fig.7 Images of DA alone in a solution of 300 mmol/L NaCl at pH=7.0(A) and DA+glyceryl decanoates in a solution of 400 mmol/L NaCl at pH=7.0(B)

Fig.8 Light micrographs of the structures of amphiphiles (A) Vesicles produced from micelles at pH=7.0 were disturbed once dehydrated; (B) no vesicle was formed when rehydrated the sample of 30 mmol/L DA with equivalent glycerol; (C) vesicles were formed again after a second condensation reaction of DA with glycerol; (D) vesicles were not formed after a second dehylration cycle with only DA; (E) Rhodamine 6G molecules were encapsulated within decanoate vesicles. Concentration of DA for (A) and (C)—(E): 60 mmol/L.

参考文献 21

[1]	Hanczyc M.M., Fujikawa S. M., Szostak J. W., Science, 2003, 302(5645), 618—622
[2]	Zhu T.F., Szostak J. W., [J]. Am. Chem. Soc., 2009, 131(15), 5705—5713
[3]	Mansy S.S., Szostak J. W., P. Natl. Acad. Sci., 2008, 105(36), 13351—13355
[4]	Apel C.L., Deamer D. W., Mautner M. N., Biochim. Biophys. Ac., 2002, 1559(1), 1—9
[5]	Adamala K., Szostak J.W., Nat. Chem., 2013, 5(6), 495—501
[6]	Monnard P.A., Apel C. L., Kanavarioti A., Deamer D. W., Astrobiology, 2002, 2(2), 139—152
[7]	Nooner D.W., Gibert J. M., Gelpi E., Oró [J]., Geochim. Cosmochim. Ac., 1976, 40(8), 915—924
[8]	McCollom T. M., Ritter G., Simoneit B. R. T., Origins Life Evol. B., 1999, 29(2), 153—166
[9]	Huang Y.D., Wu R. F., Chu Y. Q., Ding C. F., Chem. [J]. Chinese Universities, 2017, 38(5), 743—751
	(黄彦东, 吴若菲, 储艳秋, 丁传凡. 高等学校化学学报, 2017, 38(5), 743—751)
[10]	Wang Z.Y., Luo W., Fu J. Y., Li Z. B., Wang Z. M., Lü P. M., Chem. Res. Chinese Universities, 2017, 33(1), 1—5
[11]	Simoneit B.R. T., Rushdi A. I., Deamer D. W., Adv. Space Res., 2007, 40(11), 1649—1656
[12]	Apel C.L., Deamer D. W., Origins Life Evol. B., 2005, 35(4), 323—332
[13]	de Ronde C. E. J., deR Channer D. M., Faure K., Bray C. J., Spooner E. T., Geochim. Cosmochim. Ac., 1997, 61(19), 4025—4042
[14]	Zaia D.A. M., Int. [J]. Astrobiol., 2012, 11(4), 229—234
[15]	Eichberg J., Sherwood E., Epps D.E., Oró J., [J]. Mol. Evol., 1977, 10(3), 221—230
[16]	Schwartz A.W., Biochim. Biophys. Ac., 1972, 281(4), 477—480
[17]	Namani T., Walde P., Langmuir, 2005, 21, 6210—6219
[18]	Deamer D., Chem. Soc. Rev., 2012, 41, 5375—5379
[19]	Pohorille A., Deamer D., Res. Microbiol., 2009, 160(7), 449—456
[20]	Schrum J.P., Zhu T. F., Szostak J. W., CSH Perspect. Biol., 2010, 2(9), a002212
[21]	Maurer S.E., Deamer D. W., Boncella J. M., Monnard P. A., Astrobiology, 2009, 9(10), 979—987

干湿循环下癸酸甘油酯的非生物合成及自组装

Robust Self-assembly Properties of Glyceryl Decanoates Synthesized Under Wetting and Drying Cycles^†

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 9

参考文献 21

相关文章 3

编辑推荐

Metrics

本文评价

[1]	王羽, 冯守华. 条件下C—O—P键的形成[J]. 高等学校化学学报, 2014, 35(4): 707.
[2]	胡建军, 巨勇, 赵玉芬. N-磷酰化氨基酸与核糖核苷反应的研究[J]. 高等学校化学学报, 2000, 21(11): 1667.
[3]	戚生初, 王文清, 汪永刚, 吴季兰. HCN、H₂S、PH₃、N₂-NH₃与CH₄-H₂O气体混合物的前生物分子合成[J]. 高等学校化学学报, 1991, 12(1): 114.

干湿循环下癸酸甘油酯的非生物合成及自组装

Robust Self-assembly Properties of Glyceryl Decanoates Synthesized Under Wetting and Drying Cycles†

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 9

参考文献 21

相关文章 3

编辑推荐

Metrics

本文评价

Robust Self-assembly Properties of Glyceryl Decanoates Synthesized Under Wetting and Drying Cycles^†