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Gelation capability of cysteine-modified cyclo(L-Lys-L-Lys)s dominated by Fmoc and Trt protecting groups

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Abstract

A series of symmetrical peptidomimetics (3–8) based on cysteine-modified cyclo(L-Lys-L-Lys)s were synthesized, and their gelation capability in organic solvents was dominated by fluorenylmethyloxycarbonyl (Fmoc) and triphenylmethyl (Trt) protecting groups and the exchange of thiol-to-disulfide as well. The peptidomimetics holding Trt (3 and 4) showed no gel performance, while the Fmoc groups promoted 5 and 6 to give rise to thermo-reversible organogels in a number of organic solvents. The self-assembled fibrillar networks were distinctly evidenced in the organogels by transmission electron microscopy (TEM) and scanning electron microscopy (SEM) observations. Fourier transform infrared spectroscopy (FT-IR) and fluorescence analyses revealed that the hydrogen bonding and π-π stacking play as major driving forces for the self-assembly of these organogelators. A β-turn secondary structure was deduced for the organogel of 6 by virtue of X-ray diffraction, FT-IR and circular dichroism (CD) measurements, and an interdigitated bilayer structure was also presented.

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References

  1. Hanabusa K, Suzuki M. Development of low-molecular-weight gelators and polymer-based gelators. Polym J, 2014, 46: 776–782

    Article  CAS  Google Scholar 

  2. Buerkle LE, Rowan SJ. Supramolecular gels formed from multicomponent low molecular weight species. Chem Soc Rev, 2012, 41: 6089–6103

    Article  CAS  Google Scholar 

  3. Adams DJ. Dipeptide and tripeptide conjugates as low-molecularweight hydrogelators. Macrom Biosci, 2011, 11: 160–173

    Article  CAS  Google Scholar 

  4. **e ZG, Zhang AY, Ye L, Feng ZG. Organo- and hydrogels derived from cyclo(L-Tyr-L-Lys) and its e-amino derivatives. Soft Matter, 2009, 5: 1747–1482

    Article  CAS  Google Scholar 

  5. Kar T, Debnath S, Das D, Shome A, Das PK. Organogelation and hydrogelation of low-molecular-weight amphiphilic dipeptides: pH responsiveness in phase-selective gelation and dye removal. Langmuir, 2009, 25: 8639–8648

    Article  CAS  Google Scholar 

  6. Dasgupta A, Mondal JH, Das D. Peptide hydrogels. RSC Adv, 2013, 3: 9117–9149

    Article  CAS  Google Scholar 

  7. Zhang SG, Marini DM, Hwang W, Santoso S. Design of nano-structured biological materials through self-assembly of peptides and proteins. Curr Opin Chem Biol, 2002, 6: 865–871

    Article  Google Scholar 

  8. Koutsopoulos S, Unsworth LD, Nagai Y, Zhang SG. Controlled release of functional proteins through designer self-assembling peptide nanofiber hydrogel scaffold. Proc Natl Acad Sci USA, 2009, 106: 4623–4628

    Article  Google Scholar 

  9. Zhang YL, Yang B, Xu LX, Zhang XY, Tao L, Wei Y. Self-healing hydrogels based on dynamic chemistry and their biomedical applications. Acta Chim Sinica, 2013, 71: 485–492

    Article  CAS  Google Scholar 

  10. Chen J, Wu W, Mc Neil AJ. Detecting a peroxide-based explosive via molecular gelation. Chem Commun, 2012, 48: 7310–7312

    Article  CAS  Google Scholar 

  11. Frederix PW, Scott GG, Abul-Haija YM, Kalafatovic D, Pappas CG, Javid N, Hunt NT, Ulijn RV, Tuttle T. Exploring the sequence space for (tri-)peptide self-assembly to design and discover new hydrogels. Nat Chem, 2015, 7: 30–37

    Article  CAS  Google Scholar 

  12. Gazit E. Molecular self-assembly: searching sequence space. Nat Chem, 2015, 7: 14–15

    Article  CAS  Google Scholar 

  13. Cheng G, Castelletto V, Moulton CM, Newby GE, Hamley IW. Hydrogelation and self-assembly of Fmoc-tripeptides: unexpected influence of sequence on self-assembled fibril structure, and hydrogel modulus and anisotropy. Langmuir, 2010, 26: 4990–4998

    Article  CAS  Google Scholar 

  14. Manchineella S, Govindaraju T. Hydrogen bond directed self-assembly of cyclic dipeptide derivatives: gelation and ordered hierarchical architectures. RSC Adv, 2012, 2: 5539–5542

    Article  CAS  Google Scholar 

  15. Mash EA. Crystal engineering with 1,4-piperazine-2,5-diones. Cryst Eng Comm, 2014, 16: 8620–8637

    Article  CAS  Google Scholar 

  16. Borthwick AD. 2,5-Diketopiperazines: synthesis, reactions, medicinal chemistry, and bioactive natural products. Chem Rev, 2012, 112: 3641–3716

    Article  CAS  Google Scholar 

  17. Hanabusa K, Matsumoto M, Kimura M, Kakehi A, Shirai H. Low molecular weight gelators for organic fluids: gelation using a family of cyclo(dipeptide)s. J Colloid Interf Sci, 2000, 224: 231–244

    Article  CAS  Google Scholar 

  18. Delatouche R, Durini M, Civera M, Belvisi L, Piarulli U. Foldamers of bifunctional diketopiperazines displaying a ß-bend ribbon structure. Tetrahedron Lett, 2010, 51: 4278–4280

    Article  CAS  Google Scholar 

  19. Hoshizawa H, Minemura Y, Yoshikawa K, Suzuki M, Hanabusa K. Thixotropic hydrogelators based on a cyclo(dipeptide) derivative. Langmuir, 2013, 29: 14666–14673

    Article  CAS  Google Scholar 

  20. Sasaki Y, Akustu Y, Matsui M, Suzuki K, Sakurada S, Sato T, Kisara K. Studies on analgesic olgopeptides. II. Structure-activity relationship among thirty analogs of a cyclic dipeptide, cyclo(Tyr-Arg). Chem Pharm Bull, 1982, 30: 4435–4442

    Article  CAS  Google Scholar 

  21. **e ZG, Zhang AY, Ye L, Wang X, Feng ZG. Shear-assisted hydrogels based on self-assembly of cyclic dipeptide derivatives. J Mater Chem, 2009, 19: 6100–6102

    Article  CAS  Google Scholar 

  22. a)_Majó MA, Bou JJ, Herranz C, Muñoz-Guerra S. Polycondensation of L-lysine diketopiperazine with tartaric acid—evidence on the formation of cyclic oligomers. Macromol Chem Phys, 2006, 207: 615–620

    Article  CAS  Google Scholar 

  23. Zong QY, Geng HM, Zhang AY, Ye L, Wang X, Feng ZG. A study on synthesis and gelation capability of Fmoc and Boc disubstituted cyclo(L-Lys-L-Lys)s. Acta Chim Sinica, 2015, 73: 423–430

    Article  CAS  Google Scholar 

  24. a)_Kaur N, Zhou B, Breitbeil F, Hardy K, Kraft KS, Trantcheva I, Phanstiel O IV. A delineation of diketopiperazine self-assembly processes understanding the molecular events involved in N-(Fumaroyl)- dike-topiperazine of L-lys (FDKP) Interactions. Mol Pharm, 2007, 5: 294–315

    Google Scholar 

  25. Geng HM, Zong QY, Zhang AY, Ye L, Wang X, Feng ZG. Synthesis of cyclo(L-Lys-L-Lys)-based organogelators and their applications for phase-selective gelation and dye adsorption. Chin J Appl Chem, 2015, doi: 10.11944/j.issn.1000-0518.2015.08.140423

    Google Scholar 

  26. Fleming S, Ulijn RV. Design of nanostructures based on aromatic peptide amphiphiles. Chem Soc Rev, 2014, 43: 8150–8177

    Article  CAS  Google Scholar 

  27. Yang ZM, Gu HW, Fu DG, Gao P, Lam GK, Xu B. Enzymatic formation of supramolecular hydrogels. Adv Mater, 2004, 16: 1440–1444

    Article  Google Scholar 

  28. Shao H, Parquette JR. A π-conjugated hydrogel based on an Fmocdipeptide naphthalene diimide semiconductor. Chem Commun, 2010, 46: 4285–4287

    Article  CAS  Google Scholar 

  29. Smith AM, Williams RJ, Tang C, Coppo P, Collins RF, Turner ML, Saiani A, Ulijn RV. Fmoc-diphenylalanine self aßsembles to a hydrogel via a novel architecture based π-π interlocked ß-sheets. Adv Mater, 2008, 20: 37–41

    Article  CAS  Google Scholar 

  30. Nguyen MM, Eckes KM, Suggs LJ. Charge and sequence effects on the self-assembly and subsequent hydrogelation of Fmoc-depsipeptides. Soft Matter, 2014, 10: 2693–2702

    Article  CAS  Google Scholar 

  31. **e ZG, Zhang AY, Ye L, Feng ZG. Synthesis and gelation of a series of low-molecular-weight gelators based on fmoc-dipeptide in alcoholic solvents. Acta Chim Sinica, 2008, 23: 2620–2624

    Google Scholar 

  32. Dou X, Li P, Zhang D, Feng CL. C2-symmetric benzene-based hydrogels with unique layered structures for controllable organic dye adsorption. Soft Matter, 2012, 8: 3231–3238

    Article  CAS  Google Scholar 

  33. Tang C, Ulijn RV, Saiani A. Effect of glycine substitution on Fmoc–diphenylalanine self-assembly and gelation properties. Langmuir, 2011, 27: 14438–14449

    Article  CAS  Google Scholar 

  34. a)_Xu XD, Chen CS, Lu B, Cheng SX, Zhang XZ, Zhuo RX. Coassembly of oppositely charged short peptides into well-defined supramolecular hydrogels. J Phys Chem B, 2010, 114: 2365–2372

    Google Scholar 

  35. Schweitzer D, Hausser KH, Haenel MW. Transanular interaction in [2.2] phanes; [2.2] (4,4′) diphenylophane and [2.2] (2,7) fluorenophane. Chem Phys, 1978, 29: 181–185

    Article  CAS  Google Scholar 

  36. a)_Wang HM, Yang CH, Tan M, Wang L, Kong DL, Yang ZM. A structure-gelation ability study in a short peptide-based “Super Hydrogelator” system. Soft Matter, 2011, 7: 3897–3905

    Article  CAS  Google Scholar 

  37. Gosal WS, Clark AH, Pudney PDA, Ross-Murphy SB. Novel amyloid fibrillar networks derived from a globular protein: beta-lactoglobulin. Langmuir, 2002, 18: 7174–7781

    Article  CAS  Google Scholar 

  38. Gosal WS, Clark AH, Pudney PDA, Ross-Murphy SB. Fibrillar beta-lactoglobulin gels: Part 1. Fibril formation and structure. Biomacromolecules, 2004, 5: 2408–2419

    Article  CAS  Google Scholar 

  39. Zhu P, Yan X, Su Y, Yang Y, Li J. Solvent-induced structural transition of self-assembled dipeptide: from organogels to microcrystals. Chem Eur J, 2010, 16: 3176–3183

    Article  CAS  Google Scholar 

  40. a)_Nalluri SK, Shivarova N, Kanibolotsky AL, Zelzer M, Gupta S, Frederix PW, Skabara PJ, Gleskova H, Ulijn RV. Conducting nanofibers and organogels derived from the self-assembly of tetrathiafulvalene- appended dipeptides. Langmuir, 2014, 30: 12429–12437

    Article  CAS  Google Scholar 

  41. Tang C, Smith AM, Collins RF. Fmoc-diphenylalanine self-assembly mechanism induces apparent pKa shifts. Langmuir, 2009, 25: 9447–9453

    Article  CAS  Google Scholar 

  42. Dave N, Troullier A, Mus-Veteau I, Dunach M, Leblanc G, Padros E. Secondary structure components and properties of the melibiose permease from escherichia coli: a fourier transform infrared spectroscopy analysis. Biophys J, 2008, 78: 747–755

    Google Scholar 

  43. Koch O. Advances in the prediction of turn structures in peptides and proteins. Mol Inf, 2012, 31: 624–630

    Article  CAS  Google Scholar 

  44. Gunasekaran K, Gomathi L, Ramakrishnan C, Chandrasekhar J, Balaram P. Conformational interconversions in peptide ß-turns: analysis of turns in proteins and computationnal estimates of barriers. J Mol Biol, 1998, 284: 1505–1516

    Article  CAS  Google Scholar 

  45. Tena-Solsona M, Miravet JF, Escuder B. Tetrapeptidic molecular hydrogels: self-aßsembly and co-aggregation with amyloid fragment Aß1-40. Chem Eur J, 2014, 20: 1023–1031

    Article  CAS  Google Scholar 

  46. John G, Masuda M, Yoshida K, Shinkai S, Shimizu T. Self-assembly of a sugar-based gelator in water: its remarkable diversity in gelation ability and aggregate structure. Langmuir, 2001, 17: 7229–7232

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. School of Materials Science and Engineering, Bei**g Institute of Technology, Bei**g, 100081, China

    Huimin Geng, Qianying Zong, Jie You, Lin Ye, Aiying Zhang, Ziqiang Shao & Zengguo Feng

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  1. Huimin Geng
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  2. Qianying Zong
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  3. Jie You
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  4. Lin Ye
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  7. Zengguo Feng
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Correspondence to Zengguo Feng.

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Geng, H., Zong, Q., You, J. et al. Gelation capability of cysteine-modified cyclo(L-Lys-L-Lys)s dominated by Fmoc and Trt protecting groups. Sci. China Chem. 59, 293–302 (2016). https://doi.org/10.1007/s11426-015-5477-8

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  • DOI: https://doi.org/10.1007/s11426-015-5477-8

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