Temperature-responsive star-shaped poly(2-ethyl-2-oxazoline) and poly(2-isopropyl-2-oxazoline) with central thiacalixarene fragments: structure and properties in solutions
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Temperature-responsive star-shaped poly(2-ethyl-2-oxazoline) (star-PETOX) and poly(2-isopropyl-2-oxazoline) (star-PIPOX) with arms grafted to the lower rim of thiacalixarene were studied in solutions by viscometry, sedimentation velocity, light scattering, and small-angle neutron scattering. The experiments were carried out in water and tetrahydrofuran solutions. It was revealed that in tetrahydrofuran, the studied polymers were present only as individual molecules, while in aqueous solutions, in addition to individual molecules, large polymer aggregates were found. Molecular characteristics of the star-PETOX and star-PIPOX samples were estimated; their behavior in tetrahydrofuran and water was studied over a wide temperature range. It was established that a cloud point of the aqueous solution of star-PETOX (67 °C) is higher than that of a solution of star-PIPOX (35 °C). Comparison of the data obtained by dynamic light scattering and small-angle neutron scattering turned out to be fruitful in revealing all the structural levels of the organization of star-PETOX and star-PIPOX in aqueous solutions. They include the level of the individual macromolecules and the level of supramolecular organization with a star-like architecture.
KeywordsStar-shaped polyoxazolines Thiacalixarene Molecular properties SANS DLS AUC
G.P. Kopitsa is grateful to the Department of Physics and Reactor Engineering of the St. Petersburg Institute of Nuclear Physics of the Scientific and Technical Center “Kurchatov Institute” for providing heavy water.
A.A. Lezov, A.S. Gubarev, A.N. Podsevalnikova, A.S. Senchukova, E.V. Lebedeva, N.V. Tsvetkov are grateful for the support by a grant from the Russian Science Foundation (project no. 16-13-10148) for study of molecular properties of star-PETOX and star-PIPOX in aqueous and THF solutions. Yu.E. Gorshkova is grateful for JINR-Romania grant No. 321, item 15 from 21.05.2018 for AFM study.
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Conflict of interest
The authors declare that they have no conflict of interest.
- 2.Lorson T, Lübtow MM, Wegener E, Haider MS, Borova S, Nahm D, Jordan R, Sokolski-Papkov M, Kabanov AV, Luxenhofer R (2018) Poly(2-oxazoline)s based biomaterials: a comprehensive and critical update. Biomaterials 178:204–280. https://doi.org/10.1016/j.biomaterials.2018.05.022 CrossRefGoogle Scholar
- 5.Bauer M, Lautenschlaeger C, Kempe K, Tauhardt L, Schubert US, Fischer D (2012) Poly(2-ethyl-2-oxazoline) as alternative for the stealth polymer poly(ethylene glycol): comparison of in vitro cytotoxicity and hemocompatibility. Macromol Biosci 12:986–998. https://doi.org/10.1002/mabi.201200017 CrossRefGoogle Scholar
- 8.Zhang N, Luxenhofer R, Jordan R (2012) Thermoresponsive poly(2-oxazoline) molecular brushes by living ionic polymerization: kinetic investigations of pendant chain grafting and cloud point modulation by backbone and side chain length variation. Macromol Chem Phys 213:973–981. https://doi.org/10.1002/macp.201200015 CrossRefGoogle Scholar
- 10.Morgese G, Verbraeken B, Ramakrishna SN, Gombert Y, Cavalli E, Rosenboom JG, Zenobi-Wong M, Spencer ND, Hoogenboom R, Benetti EM (2018) Chemical design of non-ionic polymer brushes as biointerfaces: poly(2-oxazine)s outperform both poly(2-oxazoline)s and PEG. Angew Chem Int Ed 57:11667–11672. https://doi.org/10.1002/anie.201805620 CrossRefGoogle Scholar
- 16.Schubert US, Heller M (2001) Metallo-supramolecular initiators for the preparation of novel functional architectures. Chem Eur J 7:5252–5259. https://doi.org/10.1002/1521-3765(20011217)7:24<5252::AID-CHEM5252>3.0.CO;2-9 CrossRefGoogle Scholar
- 18.Tenkovtsev AV, Amirova AI, Filippov AP (2018) Star-shaped poly(2-alkyl-2-oxazolines): synthesis and properties. Temperature-responsive polymers. Wiley, pp 67–92Google Scholar
- 21.Kumagai H, Hasegawa M, Miyanari S, Sugawa Y, Sato Y, Hori T, Ueda S, Kamiyama H, Miyano S (1997) Facile synthesis of p-tert-butylthiacalixarene by the reaction of p-tert-butylphenol with elemental sulfur in the presence of a base. Tetrahedron Lett 38:3971–3972. https://doi.org/10.1016/S0040-4039(97)00792-2 CrossRefGoogle Scholar
- 24.Tsvetkov VN, Eskin VE (1971) Structure of macromolecules in solution. National Lending Library for Science and technologyGoogle Scholar
- 26.Pamies R, Hernández Cifre JG, del Carmen López Martínez M, García de la Torre J (2008) Determination of intrinsic viscosities of macromolecules and nanoparticles. Comparison of single-point and dilution procedures. Colloid Polym Sci 286:1223–1231. https://doi.org/10.1007/s00396-008-1902-2 CrossRefGoogle Scholar
- 32.Pike ER (1974) Photon correlation and light beating spectroscopy, 1st ed. Springer USGoogle Scholar
- 33.Schärtl W (2007) Light scattering from polymer solutions and nanoparticle dispersions, 1st ed. Springer-Verlag, BerlinGoogle Scholar
- 34.Berne BJ, Pecora R (1976) Dynamic light scattering, with application to chemistry, biology and physics. WileyGoogle Scholar
- 35.Tsvetkov VN (1989) Rigid-chain polymers: hydrodynamic and optical properties in solution. Consultants BureauGoogle Scholar
- 39.SasView. http://www.sasview.org/
- 41.Radulescu A, Kentzinger E, Stellbrink J, Dohmen L, Alefeld B, Rücker U, Heiderich M, Schwahn D, Brückel T, Richter D (2005) KWS-3: the new (very) small-angle neutron scattering instrument based on focusing-mirror optics. Neutron News 16:18–21. https://doi.org/10.1080/10448630500454270 CrossRefGoogle Scholar
- 46.Arnaud-Neu F, Collins EM, Deasy M, Ferguson G, Harris SJ, Kaitner B, Lough AJ, McKervey MA, Marques E (1989) Synthesis, x-ray crystal structures, and cation-binding properties of alkyl calixaryl esters and ketones, a new family of macrocyclic molecular receptors. J Am Chem Soc 111:8681–8691. https://doi.org/10.1021/ja00205a018 CrossRefGoogle Scholar
- 50.Bugrov AN, Zavialova AY, Smyslov RY, Anan’eva TD, Vlasova EN, Mokeev MV, Kryukov AE, Kopitsa GP, Pipich V (2018) Luminescence of Eu3+ ions in hybrid polymer-inorganic composites based on poly(methyl methacrylate) and zirconia nanoparticles. Luminescence 33:837–849. https://doi.org/10.1002/bio.3476 CrossRefGoogle Scholar
- 51.Velichko EV, Buyanov AL, Saprykina NN, Chetverikov YO, Duif CP, Bouwman WG, Smyslov RY (2017) High-strength bacterial cellulose–polyacrylamide hydrogels: mesostructure anisotropy as studied by spin-echo small-angle neutron scattering and cryo-SEM. Eur Polym J 88:269–279. https://doi.org/10.1016/j.eurpolymj.2017.01.034 CrossRefGoogle Scholar
- 57.Setchell KDR, Kritchevsky D, Nair PP (1988) The bile acids: chemistry, physiology, and metabolism: volume 4: methods and applications. Springer USGoogle Scholar
- 59.Burchard W (1983) Static and dynamic light scattering from branched polymers and biopolymers. In: Light scattering from polymers. Advances in Polymer Science, vol 48. Springer, Berlin, Heidelberg, pp 1–124Google Scholar
- 60.Gelardi G, Sanson N, Nagy G, Flatt RJ (2017) Characterization of comb-shaped copolymers by multidetection SEC, DLS and SANS. Polymers 9(2). https://doi.org/10.3390/polym9020061
- 62.Luef KP, Hoogenboom R, Schubert US, Wiesbrock F (2015) Microwave-assisted cationic ring-opening polymerization of 2-oxazolines. Microwave-assisted Polymer Synthesis:183–208. https://doi.org/10.1007/12_2015_340
- 63.Amirova A, Tobolina A, Kirila T, Blokhin A, Razina A, Tenkovtsev A, Filippov A (2018) Influence of core configuration and arm structure on solution properties of new thermosensitive star-shaped poly(2-alkyl-2-oxazolines). Int J Polym Anal Charact 23:278–285. https://doi.org/10.1080/1023666X.2018.1441483 CrossRefGoogle Scholar