Abstract
We present an investigation of horseradish peroxidase (HRP)/H2O2-mediated crosslinking in an inverse miniemulsion for the successful preparation of a stable colloidal nanogel from a poly(amino acid)-based polymer precursor. The precursor was obtained by the aminolysis of polysuccinimide with aminoethan-2-ol and tyramine, resulting in a poly(α,β-N-(2-hydroxyethyl)-D,L-aspartamide-co-N-(2-(4-hydroxyphenyl)ethyl)-D,L-aspartamide) polymer (PHEA-Tyr). Various concentrations of the PHEA-Tyr in aqueous solution with HRP were emulsified in the presence of cyclohexane and SPAN 80. The addition of a hydrogen peroxide solution induced crosslinking between the polymer chains via the phenol groups (Tyr) and targeted nanogel formation. The hydrodynamic radii (R h 0), mean size documented by hydrodynamic radius (R h ), and morphology of the nanoparticles were investigated by dynamic light scattering (DLS) measurements, nanoparticle tracking analysis (NTA), and cryogenic transmission electron microscopy (cryo-TEM). It was found out that nanoparticle radius, morphology, and architecture of the nanogel could be regulated by the initial concentration of the precursor.
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Vinogradov S, Batrakova E, Kabanov A (1999) Poly(ethylene glycol)−polyethyleneimine nanogel™ particles: novel drug delivery systems for antisense oligonucleotides. Colloid Surf B 16:291–304
Soni KS, Desale SS, Bronich TK (2016) Nanogels: an overview of properties, biomedical applications and obstacles to clinical translation. J Control Release 240:109–126
Zhang X, Malhotra S, Molina M, Haag R (2015) Micro- and nanogels with labile crosslinks—from synthesis to biomedical applications. Chem Soc Rev 44:1948–1973
Iwasaki Y, Kondo JI, Kuzuya A, Moriyama R (2016) Crosslinked duplex DNA nanogels that target specified proteins. Sci Technol Adv Mat 17:285–292
Pujana MA, Pérez-Álvarez L, Iturbe LCC, Katime I (2012) Water dispersible pH-responsive chitosan nanogels modified with biocompatible crosslinking-agents. Polymer 53:3107–3116
Singh S, Möller M, Pich A (2013) Biohybrid nanogels. J Polym Sci Pol Chem 51:3044–3057
Neamtu I, Rusu AG, Diaconu A, Nita LE, Chiriac AP (2017) Basic concepts and recent advances in nanogels as carriers for medical application. Drug Deliv 24:539–557
Meléndez-Ortiz HI, Peralta RD, Bucio E, Zerrweck-Maldonado L (2014) Preparation of stimuli-responsive nanogels of poly[2-(dimethylamino) ethyl methacrylate] by heterophase and microemulsion polymerization using gamma radiation. Polym Eng Sci 54:1625–1631
Oh JK, Siegwart DJ, Lee HI, Sherwood G, Peteanu L, Hollinger JO, Kataoka K, Matyjaszewski K (2007) Biodegradable nanogels prepared by atom transfer radical polymerization as potential drug delivery carriers: synthesis, biodegradation, in vitro release, and bioconjugation. J Am Chem Soc 129:5939–5945
Oh JK, Bencherif SA, Matyjaszewski K (2009a) Atom transfer radical polymerization in inverse miniemulsion: a versatile route toward preparation and functionalization of microgels/nanogels for targeted drug delivery applications. Polymer 50:4407–4423
Bhuchar N, Sunasee R, Ishihara K, Thundat T, Narain R (2012) Degradable thermoresponsive nanogels for protein encapsulation and controlled release. Bioconjug Chem 23:75–83
Averick SE, Magenau AJD, Simakova A, Woodman BF, Seong A, Mehl RA, Matyjaszewski K (2011) Covalently incorporated protein-nanogels using AGET ATRP in an inverse miniemulsion. Polym Chem 2:1476–1478
Oh JK, Lee DI, Park JM (2009b) Biopolymer-based microgels/nanogels for drug delivery applications. Prog Polym Sci 34:1261–1282
Klinger D, Landfester K (2011) Dual stimuli-responsive poly(2-hydroxyethyl methacrylate-co-methacrylic acid) microgels based on photo-cleavable cross-linkers: pH-dependent swelling and light-induced degradation. Macromolecules 44:9758–9772
McAllister K, Sazani P, Adam M, Cho MJ, Rubinstein M, Samulski RJ, DeSimone JM (2002) Polymeric nanogels produced via inversion microemulsion polymerization as potential gene and antisense delivery agents. J Am Chem Soc 124:15198–15207
Sanson N, Rieger J (2010) Synthesis of nanogels/microgels by conventional and controlled radical crosslinking copolymerization. Polym Chem 1:965–977
Yildrim T, Rinkenauer AC, Weber C, Traeger A, Schubert S, Schubert US (2015) RAFT made methacrylate copolymers for reversible pH-responsive nanoparticles. J Polym Sci Pol Chem 53:2711–2721
Gao H, Matyjaszewski K (2008) Synthesis of star polymers by a new “core-first” method: sequential polymerization of cross-linker and monomer. Macromolecules 41:1118–1125
Bencherif SA, Washburn NR, Matyjaszewski K (2009) Synthesis by AGET ATRP of degradable nanogel precursors for in situ formation of nanostructured hyaluronic acid hydrogel. Biomacromolecules 10:2499–2507
Graff RW, Shi Y, Wang X, Gao H (2009) Comparison of loading efficiency between hyperbranched polymers and cross-linked nanogels at various branching densities. Macromol Rapid Commun 36:2076–2082
Landfester K, Willert M, Antonietti M (2000) Preparation of polymer particles in nonaqueous direct and inverse miniemulsions. Macromolecules 33:2370–2376
Capek I (2010) On inverse miniemulsion polymerization of conventional water-soluble monomers. Adv Colloid Interf Sci 156:35–61
Dou XQ, Feng CL (2017) Amino acids and peptide-based supramolecular hydrogels for three-dimensional cell culture. Adv Mater 29:1604062
Svobodová J, Proks V, Karabiyik Ö, Koyuncu ACÇ, Köse GT, Rypáček F, Studenovská H (2017) Poly(amino acid)-based fibrous scaffolds modified with surface-pendant peptides for cartilage tissue engineering. J Tissue Eng Regen Med 11:831–842
Park CW, Yang HM, Woo MA, Lee KS, Kim JD (2017) Completely disintegrable redox-responsive poly(amino acid) nanogels for intracellular drug delivery. J Ind Eng Chem 45:182–188
Wu DQ, Cui HC, Zhu J, Qin XH, Tie T (2016) Novel amino acid based nanogel conjugated suture for antibacterial application. J Mater Chem B 4:2606–2613
Pitarresi G, Tomarchio V, Cavallaro G, Giammona G (1996) α,β-poly(N-hydroxy)-DL-aspartamide hydrogels as drug delivery devices. J Bioact Compat Polym 11:328–340
Giammona G, Pitarresi G, Tomarchio V, Cacciaguerra S, Govoni P (1997) A hydrogel based on a polyaspartamide: characterization and evaluation of in-vivo biocompatibility and drug release in the rat. J Pharm Pharmacol 49:1051–1056
Mandracchia D, Pitarresi G, Palumbo FS, Carlisi B, Giammona G (2004) pH-sensitive hydrogel based on a novel photocross-linkable copolymer. Biomacromolecules 5:1973–1982
Rypáček F, Drobnik J, Chmelař V, Kálal J (1982) The renal excretion and retention of macromolecules. The chemical structure effect. Pflügers Arch 392:211–217
Bae JW, Choi JH, Lee Y, Park D (2015) Horseradish peroxidase-catalysed in situ-forming hydrogels for tissue-engineering applications. J Tissue Eng Regen Med 9:1225–1232
Neri P, Antoni G, Benvenuti F, Cocola F, Gazzei G (1973) Synthesis of α,β-poly [(2-hydroxyethyl)-DL-aspartamide], a new plasma expander. J Med Chem 16:893–897
Jakeš J (1995) Regularized positive exponential sum (REPES) program—a way of inverting Laplace transform data obtained by dynamic light scattering. Collect Czechoslov Chem Commun 60:1781–1797
Cavallaro G, Pitarresi G, Giammona G (2004) Advanced biomaterials for medical applications. Kluwer Academic Publishers, Dordrecht
Coviello T, Yuguchi Y, Kajiwara K, Giammona G, Cavallaro G, Alhaique F, Palleschi A (1998) Conformational analysis of α,β-poly(N-hydroxyethyl)-DL-aspartamide (PHEA) and α,β-polyasparthydrazide (PAHy) polymers in aqueous solution. Polymer 39:4159–4164
Jansen TGT, Meuldijk J, Lovell PA, van Herk AM (2016) On the miniemulsion polymerization of very hydrophobic monomers initiated by a completely water-insoluble initiators: thermodynamics, kinetics, and mechanism. J Polym Sci Polym Chem 54:2731–2745
Filipe V, Hawe A, Jiskoot W (2010) Critical evaluation of nanoparticle tracking analysis (NTA) by NanoSight for the measurement of nanoparticles and protein aggregates. Pharm Res 27:796–810
Gonzáles de Torre I, Quintanilla L, Pinedo-Martín G, Alonso M, Rodríguez-Cabello JC (2014) Nanogel formation from dilute solutions of clickable elastine-like recombinamers and its dependence on temperature: two fractal gelation modes. ACS Appl Mater Interfaces 6:14509–14515
Wang R, Xu DI, Liang L, Xu TT, Liu W, Ouyang PK, Chi B, Xu H (2016) Enzymatically crosslinked epsilon-poly-L-lysine hydrogels with inherent antibacterial properties for wound infection prevention. RSC Adv 6:8620–8627
Koul V, Mohamed R, Kuckling D, Adler HJP, Choudhary V (2011) Interpenetrating polymer network (IPN) nanogels based on gelatin and poly(acrylic acid) by inverse miniemulsion technique: synthesis and characterization. Colloid Surf B 83:204–213
Wu C, Böttcher C, Haag R (2015) Enzymatically crosslinked dendritic polyglycerol nanogels for encapsulation of catalytically active proteins. Soft Matter 11:972–980
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Financial support from the Czech Science Foundation (No. 16-02702S) is gratefully acknowledged.
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Petr, Š., Jana, D., Peter, Č. et al. Poly(amino acid)-based nanogel by horseradish peroxidase catalyzed crosslinking in an inverse miniemulsion. Colloid Polym Sci 296, 995–1003 (2018). https://doi.org/10.1007/s00396-018-4318-7
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DOI: https://doi.org/10.1007/s00396-018-4318-7