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Synthesis and conformational study of novel, stable, helical poly(N-propargylamides) containing dipole azobenzene chromophores in the side chains

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Abstract

A series of novel N-propargylamides carrying dipole azobenzene chromophores were synthesized and polymerized with [Rh(nbd)Cl]2 catalyst to obtain cis-transoid poly(N-propargylamides). The solubility, thermal stability and conformation of these polymers were also studied. The introduction of valeryl group increased the solubility of this kind of poly(N-propargylamides). All the polymers exhibited a good, thermal stability. CD and UV–Vis spectra showed that poly(N-propargylamide) (Poly(V2b)) took a tight helical structure with predominantly one-handed screw sense. Poly(V2b) exhibited a good stable helical structure at various temperatures (5–60 °C). It also maintained good helicity in polar solvent. The improved helix stability could be attributed to the enhanced hydrogen bonding strength and steric repulsion between the newly designed azobenzene groups. Furthermore, the electrostatic repulsion between the dipole azobenzene chromophores in the side chains improved the helix stability as well. The backbone of Poly(V2b) still kept helical sense after the isomerization of trans-azobenzene to the cis form under UV irradiation.

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References

  1. Maeda K, Mochizuki H, Osato K, Yashima E (2011) Stimuli-responsive helical poly(phenylacetylene)s bearing cyclodextrin pendants that exhibit enantioselective gelation in response to chirality of a chiral amine and hierarchical super-structured helix formation. Macromolecules 44:3217–3226

    Article  CAS  Google Scholar 

  2. Zhu ZG, Cui JX, Zhang J, Wan XH (2012) Hydrogen bonding of helical vinyl polymers containing alanine moieties: a stabilized interaction of helical conformation sensitive to solvents and pH. Polym Chem 3:668–678

    Article  CAS  Google Scholar 

  3. Maeda K, Tanaka K, Morino K, Yashima E (2007) Synthesis of optically active helical poly(phenylacetylene)s bearing oligopeptide pendants and their use as polymeric organocatalysts for asymmetric epoxidation. Macromolecules 40:6783–6785

    Article  CAS  Google Scholar 

  4. Yamamoto T, Yamada T, Nagata Y, Suginome M (2010) High-molecular-weight polyquinoxaline-based helically chiral phosphine (PQXphos) as chirality-switchable, reusable, and highly enantioselective monodentate ligand in catalytic asymmetric hydrosilylation of styrenes. J Am Chem Soc 132:7899–7901

    Article  CAS  Google Scholar 

  5. Ohsawa S, Sakurai S, Nagai K, Maeda K, Kumaki J, Yashima E (2012) Amplification of macromolecular helicity of dynamic helical poly(phenylacetylene)s bearing non-racemic alanine pendants in dilute solution, liquid crystal and two-dimensional crystal. Poylm J 44:42–50

    Article  CAS  Google Scholar 

  6. Song C, Li L, Wang FJ, Deng JP, Yang WT (2011) Novel optically active helical poly(N-propargylthiourea)s: synthesis, characterization and complexing ability toward Fe(III) ions. Polym Chem 2:2825–2829

    Article  CAS  Google Scholar 

  7. Sanda F, Teraura T, Masuda T (2004) Synthesis of chiral polyacetylenes carrying amino acids and azobenzenes and transformation of the higher order structure by photoirradiation. J Polym Sci, Part A: Polym Chem 42:4641–4647

    Article  CAS  Google Scholar 

  8. Sogawa H, Shiotsuki M, Matsuoka H, Sanda F (2011) Synthesis, chiroptical properties, and photoresponsiveness of optically active poly(m-phenyleneethynylene)s containing azobenzene moieties. Macromolecules 44:3338–3345

    Article  CAS  Google Scholar 

  9. Schwartz E, Koepf M, Kitto HJ, Nolte RJM, Rowan AE (2011) Helical poly(isocyanides): past, present and future. Polym Chem 2:33–47

    Article  CAS  Google Scholar 

  10. Nakano T, Okamoto Y (2001) Synthetic helical polymers: conformation and function. Chem Rev 101:4013–4038

    Article  CAS  Google Scholar 

  11. Okamoto Y, Suzuki K, Ohta K, Hatada K, Yuki H (1979) Optically active poly(triphenylmethyl methacrylate) with one-handed helical conformation. J Am Chem Soc 101:4763–4765

    Article  CAS  Google Scholar 

  12. Lu H, Wang J, Bai YG, Lang JW, Liu SY, Lin Y, Chen JJ (2011) Ionic polypeptides with unusual helical stability. Nat Commun 2:206

    Article  Google Scholar 

  13. Gabrielson NP, Lu H, Yin LC, Li D, Wang F, Cheng JJ (2012) Reactive and bioactive cationic α-helical polypeptide template for nonviral gene delivery. Angew Chem Int Ed 124:1169–1173

    Article  Google Scholar 

  14. Shiotsuki M, Sanda F, Masuda T (2011) Polymerization of substituted acetylenes and features of the formed polymers. Polym Chem 2:1044–1058

    Article  CAS  Google Scholar 

  15. Liu JZ, Lam JWY, Tang BZ (2009) Acetylenic polymers: syntheses, structures, and functions. Chem Rev 109:5799–5867

    Article  CAS  Google Scholar 

  16. Yashima E, Maeda K, Sato O (2001) Switching of a macromolecular helicity for visual distinction of molecular recognition events. J Am Chem Soc 123:8159–8160

    Article  CAS  Google Scholar 

  17. Cheuk KKL, Lam JWY, Chen J, Lai LM, Tang BZ (2003) Amino acid-containing polyacetylenes: synthesis, hydrogen bonding, chirality transcription, and chain helicity of amphiphilic poly(phenylacetylene)s carrying l-leucine pendants. Macromolecules 36:5947–5959

    Article  CAS  Google Scholar 

  18. Cheuk KKL, Lam JWY, Lai LM, Dong YP, Tang BZ (2003) Syntheses, hydrogen-bonding interactions, tunable chain helicities, and cooperative supramolecular associations and dissociations of poly(phenylacetylene)s bearing l-valine pendants: toward the development of proteomimetic polyenes. Macromolecules 36:9752–9762

    Article  CAS  Google Scholar 

  19. Li BS, Cheuk KKL, Salhi F, Lam JWY, Cha JAK, Xiao XD, Bai CL, Tang BZ (2001) Tuning the chain helicity and organizational morphology of an l-valine-containing polyacetylene by pH change. Nano Lett 1:323–328

    Article  CAS  Google Scholar 

  20. Nomura R, Tabei J, Nishiura S, Masuda T (2003) A helix in helices: a helical conjugated polymer that has helically arranged hydrogen-bond strands. Macromolecules 36:561–564

    Article  CAS  Google Scholar 

  21. Nomura R, Tabei J, Masuda T (2001) Biomimetic stabilization of helical structure in a synthetic polymer by means of intramolecular hydrogen bonds. J Am Chem Soc 123:8430–8431

    Article  CAS  Google Scholar 

  22. Nomura R, Tabei J, Masuda T (2002) Effect of side chain structure on the conformation of poly(N-propargylalkylamide). Macromolecules 35:2955–2961

    Article  CAS  Google Scholar 

  23. Tabei J, Nomura R, Masuda T (2002) Conformational study of poly(N-propargylamides) having bulky pendant groups. Macromolecules 35:5405–5409

    Article  CAS  Google Scholar 

  24. Bandara HMD, Burdette SC (2012) Photoisomerization in different classes of azobenzene. Chem Soc Rev 41:1809–1825

    Article  CAS  Google Scholar 

  25. Wu WB, Huang LJ, Song CF, Yu G, Ye C, Liu YQ, Qin JG, Li QQ, Li Z (2012) Novel global-like second-order nonlinear optical dendrimers: convenient synthesis through powerful click chemistry and large NLO effects achieved by using simple azo chromophore. Chem Sci 3:1256–1261

    Article  CAS  Google Scholar 

  26. Lee MJ, Jung DH, Han YK (2006) Photo-responsive polymers and their applications to optical memory. Mol Cryst Liq Cryst 444:41–50

    Article  CAS  Google Scholar 

  27. Camorani P, Fontana MP (2006) Optical control of structural morphology in azobenzene containing polymeric liquid crystals. Phy Rev E 73:011703

    Article  Google Scholar 

  28. Fujii T, Shiotsuki M, Inai Y, Sanda F, Masuda T (2007) Synthesis of helical poly(N-propargylamides) carrying azobenzene moieties in side chains. Reversible arrangement-disarrangement of helical side chain arrays upon photoirradiation keeping helical main chain intact. Macromolecules 40:7079–7088

    Article  CAS  Google Scholar 

  29. Zhou JL, Chen XF, Fan XH, Lu CX, Zhou QF (2006) Synthesis and chiroptical properties of optically active poly(N-propargylamide) bearing photoisomerizable azobenzene moieties. J Polym Sci, Part A: Polym Chem 44:6047–6054

    Article  CAS  Google Scholar 

  30. Zhao HC, Sanda F, Masuda T (2006) Stimuli-responsive conjugated polymers. synthesis and chiroptical properties of polyacetylene carrying l-glutamic acid and azobenzene in the side chain. Polymer 47:2596–2602

    Article  CAS  Google Scholar 

  31. Robinson BH, Dalton LR (2000) Monte Carlo statistical mechanical simulations of the competition of intermolecular electrostatic and poling-field interactions in defining macroscopic electro-optic activity for organic chromophore/polymer materials. J Phys Chem A 104:4785–4795

    Article  CAS  Google Scholar 

  32. Ma H, Chen BQ, Sassa T, Dalton LR, Jen AK-Y (2001) Highly efficient and thermally stable nonlinear optical dendrimer for electrooptics. J Am Chem Soc 123:986–987

    Article  CAS  Google Scholar 

  33. Kishimoto Y, Itou M, Miyatake T, Ikariya T, Noyori R (1995) Polymerization of monosubstituted acetylenes with a zwitterionic Rhodium(I) complex, Rh+(2,5-norbornadiene)[η6-C6H5)B-(C6H5)3. Macromolecules 28:6662–6666

    Article  CAS  Google Scholar 

  34. Sanda F, Tabei J, Shiotsuki M, Masuda T (2006) Chiroptical study and conformation analysis of helical polymers surrounded by helical hydrogen-bonding strands. Sci Tech Adv Mater 7:572–577

    Article  CAS  Google Scholar 

  35. Gao G, Sanda F, Masuda T (2003) Synthesis and properties of amino acid-based polyacetylenes. Macromolecules 36:3932–3937

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The work described in this article was supported by grants from the Shanghai Natural Science Foundation of China (11ZR1410600), the National Natural Science Foundation of China (21204021), and Fundamental Research Funds for the Central Universities of China.

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Authors and Affiliations

  1. Department of Chemistry, East China Normal University, 500 Dongchuan Road, Shanghai, 200241, People’s Republic of China

    Junmei Zhang, Xiao Ren, Shujing Li & Wei Huang

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  1. Junmei Zhang
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  2. Xiao Ren
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Correspondence to Wei Huang.

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Zhang, J., Ren, X., Li, S. et al. Synthesis and conformational study of novel, stable, helical poly(N-propargylamides) containing dipole azobenzene chromophores in the side chains. Polym. Bull. 71, 2803–2818 (2014). https://doi.org/10.1007/s00289-014-1223-1

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  • DOI: https://doi.org/10.1007/s00289-014-1223-1

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