A Study on Synthesis and Gelation Capability of Fmoc and Boc Disubstituted Cyclo(L-Lys-L-Lys)s

doi:10.6023/A15020111

Acta Chim. Sinica ›› 2015, Vol. 73 ›› Issue (5): 423-430.DOI: 10.6023/A15020111 Previous Articles Next Articles

Article

Fmoc和Boc双取代赖氨酸环二肽的合成及其凝胶化性能研究

宗倩颖, 耿慧敏, 王璐, 叶霖, 张爱英, 邵自强, 冯增国

北京理工大学材料学院北京 100081

投稿日期:2015-02-09 发布日期:2015-03-20
通讯作者: 冯增国 E-mail:sainfeng@bit.edu.cn
基金资助:
项目受国家自然科学基金(No. 21174018)资助.

A Study on Synthesis and Gelation Capability of Fmoc and Boc Disubstituted Cyclo(L-Lys-L-Lys)s

Zong Qianying, Geng Huimin, Wang Lu, Ye Lin, Zhang Aiying, Shao Ziqiang, Feng Zengguo

School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081

Received:2015-02-09 Published:2015-03-20
Supported by:
Project supported by the National Natural Science Foundation of China (No. 21174018).

Fmoc and Boc disubstituted cyclo(L-Lys-L-Lys)s were synthesized using Boc-Lys(Cbz)-OH as starting material to prepare lysine cyclic dipeptide followed by the reaction with Fmoc-OSu and (Boc)₂O, respectively. Using test tube inversion method, two derivatives were found to form stable organogels in common alcoholic, methylbenzene and chlorinated solvents holding a minimum gelation concentration (MGC) in a range of 1%～5% (w). All the formed organogels exhibited thermal reversibility, which can change into transparent solutions under heating. The TEM and SEM observations of their xerogels showed that these organogelators were self-assembled into 3D network structures, such as nanofibres, nanoribbons or nanosheets. The thinner the fiber diameter was, the more transparent the organogel became. The rheological measurements revealed that the storage modulus of two kinds of gels was higher than the loss modulus, and the complex viscosity was reduced linearly with the increase of scanning frequency. Fluorescence spectroscopy of Fmoc disubstituted cyclo(L-Lys-L-Lys) (6) in methanol and 1,2-dichloroethane showed that the main emission peak of Fmoc red-shifted to 342 and 328 nm respectively, and more multiple emission peaks appeared between 350 nm and 600 nm. FT-IR results of Boc disubstituted cyclo(L-Lys-L-Lys) (7) organogels and its solid sample indicated that not only lysine cyclic dipeptide skeleton itself participated in the self-assembly, but also the hydrogen bondings between the urethane on the side-chain contributed to the organogel formation. The hydrogen bondings played mainly a role in driving the self-assembly process of gelators in methylbenzene and chlorinated solvents, whereas π-π stacking generally acted as a driving force for the self-assembly process in alcoholic solvents. A X-Ray diffraction pattern was obtained from the sample prepared with 7 in methylbenzene, showing reflections at 4.6 and 24.4 Å, attributed to the molecular simulation size and the interstrand distances between β-sheet structures, respectively.

Key words: lysine cyclic dipeptide, low molecular weight gelator, self-assembly, hydrogen bond, π-&pi, stacking

Cite this article

Zong Qianying, Geng Huimin, Wang Lu, Ye Lin, Zhang Aiying, Shao Ziqiang, Feng Zengguo. A Study on Synthesis and Gelation Capability of Fmoc and Boc Disubstituted Cyclo(L-Lys-L-Lys)s[J]. Acta Chim. Sinica, 2015, 73(5): 423-430.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

References

[1] Steed, J. W. Chem. Commun. 2011, 47, 1379.
[2] Suzaki, Y.; Taira, T.; Osakada, K. J. Mater. Chem. 2011, 21, 930.
[3] Hanabusa, K.; Suzuki, M. Polym. J. 2014, 46, 776.
[4] Plekan, O.; Feyer, V.; Ptasinska, S.; Tsud, N.; Prince, K. C. Phys. Chem. Chem. Phys. 2014, 16, 6657.
[5] Xie, Z. G.; Zhang, A. Y.; Ye, L.; Wang, X.; Feng, Z. G. J. Mater. Chem. 2009, 19, 6100.
[6] Adams, D. J.; Butler, M. F.; Frith, W. J.; Kirkland, M.; Mullen, L.; Sanderson, P. Soft Matter. 2009, 5, 1856.
[7] Sadownik, J. W.; Ulijn, R. V. Chem. Commun. 2010, 46, 3481.
[8] Shen, L. Y.; Chen, X. Z.; Yu, H. T. Chin. J. Org. Chem.2009, 29, 321. (沈丽英, 陈肖卓, 于海涛, 有机化学, 2009, 29, 321.)
[9] Fleming, S.; Ulijn, R. V. Chem. Soc. Rev. 2014, 43, 8150.
[10] Fichman, G.; Adler, A. L.; Manohar, S. ACS Nano 2014, 8, 7220.
[11] Yan, X.; Zhu, P.; Li, J. Chem. Soc. Rev. 2010, 39, 1877.
[12] Aggeli, A.; Bell, M.; Boden, N. J. Mater. Chem. 1997, 7, 1135.
[13] Hanabusa, K.; Fukui, H.; Suzuki, M.; Shirai, H. Langmuir 2005, 21, 10383.
[14] Hoshizawa, H.; Minemura, Y.; Yoshikawa, K.; Suzuki, M.; Hanabusa, K. Langmuir 2013, 29, 14666.
[15] Xie, Z. G.; Zhang, A. Y.; Ye, L.; Feng, Z. G. Soft Matter 2009, 5, 1474.
[16] Manchineella, S.; Govindaraju, T. RSC Adv. 2012, 2, 5539.
[17] Xie, Z. G.; Zhang, A. Y.; Ye, L.; Feng, Z. G. Acta Chim. Sinica 2008, 66, 2620. (谢志国, 张爱英, 叶霖, 冯增国, 化学学报, 2008, 66, 2620. )
[18] Ma, L. X. Ph.D. Dissertation, Shandong University, Jinan, 2008. (马丽霞, 博士论文, 山东大学, 济南, 2008.)
[19] Geng, H.; Zong Q.; You J.; Ye L.; Zhang, A. Y.; Feng, Z. G. Chin. J. Appl. Chem. 2015 (in revision) (耿慧敏, 宗倩颖, 尤劼, 叶霖, 张爱英, 冯增国, 应用化学, 2015(修稿中))
[20] Maria, A. M.; Jordi, J. B. Macromol. Chem. Phys. 2006, 207, 615.
[21] Kaur, N.; Zhou, B.; Breitbeil, F.; Hardy, K.; Kraft, K. S.; Trantcheva, I.; Phanstiel, O. Mol. Pharm. 2008, 5, 294.
[22] Skilling, K. J.; Citossi, F.; Bradshaw, T. D.; Ashford, M.; Kellam, B.; Marlow, M. Soft. Matter. 2014, 10, 237.
[23] Yang, Z. M.; Xu, B. J. Mater. Chem. 2007, 17, 2385.
[24] Solsona, M. T.; Miravet, J. F. Chem. Eur. J. 2014, 20, 1023.
[25] Yang, Z. M.; Liang, G. L.; Ma, M. L.; Gao, Y.; Xu, B. Small 2007, 3, 558.
[26] Sadownik, J. W.; Ulijn, R. V. Chem. Commun. 2010, 46, 3481.
[27] Shao, H.; Parquette, J. R. Chem. Commun. 2010, 46, 4285.
[28] Cui, H. G.; Muraoka, T.; Cheetham, A. G.; Stupp, S. I. Nano Lett. 2009, 9, 945.
[29] Cheng, P. N.; Pham, J. D.; Nowick, J. S. J. Am. Chem. Soc.2013, 135, 5477.

Fmoc和Boc双取代赖氨酸环二肽的合成及其凝胶化性能研究

A Study on Synthesis and Gelation Capability of Fmoc and Boc Disubstituted Cyclo(L-Lys-L-Lys)s

PDF

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Liwei Hu, Xianhu Liu, Chuntai Liu, Yanlin Song, Mingzhu Li. Self-assembly Fabrication and Applications of Photonic Crystal Structure Color Materials^★ [J]. Acta Chimica Sinica, 2023, 81(7): 809-819.
[2]	Lanying Li, Qing Tao, Yanli Wen, Lele Wang, Ruiyan Guo, Gang Liu, Xiaolei Zuo. Poly-adenine-based DNA Probes and Their Applications in Biosensors^★ [J]. Acta Chimica Sinica, 2023, 81(6): 681-690.
[3]	Xu Pu, Zejuan Li, Junqiu Shi, Yunqing Zhu, Jianzhong Du. Recent Advances in Organ-Targeting Polymeric Delivery Vectors for Nucleic Acids^★ [J]. Acta Chimica Sinica, 2023, 81(10): 1438-1446.
[4]	Xiaomao Tian, Yuequn Lin, Han Zhu, Chao Huang, Bixue Zhu. Enantiomers Identification of Penicillamine by Chiral Mono-Schiff Base Macrocycles [J]. Acta Chimica Sinica, 2023, 81(1): 20-28.
[5]	Jamshid Kadirkhanov, Feng Zhong, Wenjian Zhang, Chunyan Hong. Preparation of Multi-chambered Vesicles by Polymerization-induced Self-assembly and the Influence of Solvophilic Fragments in the Core-forming Blocks [J]. Acta Chimica Sinica, 2022, 80(7): 913-920.
[6]	Zhiqin Wang, Bo Xiang, Xiaoyu Huang, Guolin Lu. Effect of Phosphotungstic Acid on Self-seeding of Oligo(p-phenylenevinylene)-b-poly(2-vinylpyridine)^※ [J]. Acta Chimica Sinica, 2022, 80(3): 297-302.
[7]	Chuanzhi Liu, Fen Li, Jingjing Wang, Xiaolu Zhao, Tingmei Zhang, Xin Huang, Mengli Wu, Zhiyuan Hu, Xinming Liu, Zhanting Li. Self-assembly of Supramolecular Planar Macrocycle Driven by Intermolecular Halogen Bonding [J]. Acta Chimica Sinica, 2022, 80(10): 1365-1368.
[8]	Dong Yin, Hongyi Shang, Wenhao Yu, Shikai Xiang, Ping Hu, Keqing Zhao, Chun Feng, Biqin Wang. Synthesis, Mesomorphism and Gelation Properties of Triazole-Modified Triphenylene 2,3-Dicarboxylic Esters and 2,3-Dicarboxyimides [J]. Acta Chimica Sinica, 2022, 80(10): 1376-1384.
[9]	Yanmei Jin, Ye Meng, Yuan Li, Jianhua Shi, Lei Deng. Supramolecular Self-assembly of Symmetric Dicyclohexanocucurbit[6]uril and Nicotinic Hydrazide [J]. Acta Chimica Sinica, 2022, 80(1): 44-48.
[10]	Xusheng Wang, Xu Yang, Chunhui Chen, Hongfang Li, Yuanbiao Huang, Rong Cao. Graphene Quantum Dots Supported on Fe-based Metal-Organic Frameworks for Efficient Photocatalytic CO₂ Reduction^※ [J]. Acta Chimica Sinica, 2022, 80(1): 22-28.
[11]	Weihua Li. “Bridge” Makes Differences to the Self-assembly of Block Copolymers [J]. Acta Chimica Sinica, 2021, 79(2): 133-138.
[12]	Zhao Jingjing, Zhang Zhengzhong, Chen Xiaolang, Wang Bei, Deng Jinyuan, Zhang Dieqing, Li Hexing. Microwave-induced Assembly of CuS@MoS₂ Core-shell Nanotubes and Study on Their Photocatalytic Fenton-like Reactions [J]. Acta Chimica Sinica, 2020, 78(9): 961-967.
[13]	Jiang Jinhui, Zhu Yunqing, Du Jianzhong. Challenges and Perspective on Ring-Opening Polymerization-Induced Self-Assembly [J]. Acta Chimica Sinica, 2020, 78(8): 719-724.
[14]	Yin Cen, Wang Zikuan, Liu Dan, Peng Zhantao, Song Huanjun, Zhu Hao, Chen Qiwei, Wu Kai. Adsorption and Self-assembly of meso-tetra(p-methoxyphenyl)-porphyrinatocobalt(II) on Coinage Metal Surfaces [J]. Acta Chimica Sinica, 2020, 78(7): 695-702.
[15]	Liu Mingqian, Wan Xizi, Wang Shutao. Super Adhesive of Nanoparticle Solutions [J]. Acta Chimica Sinica, 2020, 78(6): 463-465.