Abstract
Luminescent core–shell polymer particles carrying amino groups for covalent immobilization of enzymes were synthesized for practical applications in immunoassays. The polystyrene core particles were synthesized by miniemulsion polymerization of oil-in-water emulsion styrene droplets dissolving 2-(2-chloropropionyl)ethyl methacrylate and the europium complex emulsified with 2-methacryloyloxyethyl-N,N-dimethyl-N–n-dodecylammonium bromide. The red luminescence attributed to europium complexes embedded in the core particles was observed upon UV irradiation. The PSt-g-POEGMAx-NH2 aminated core–shell particles were prepared by surface-initiated atom transfer radical polymerization of oligo(ethylene glycol) methyl ether methacrylate (OEGMAx), followed by Gabriel synthesis. The densities of grafted chains were determined by the composition, the hydrodynamic diameters, and the fluorescence labeling method. POEGMAx-grafted chains were found to affect the dispersion stability of the particles. The nonspecific adsorption of bovine serum albumin was suppressed by the POEGMAx-grafted chains. The enzymatic activity of horseradish peroxidase covalently bound to the terminal amino groups of POEGMAx-grafted chains was evaluated by colorimetric immunosorbent assay.
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Peer D, Karp JM, Hong S, Farokhzad OC, Margalit R, Langer R (2007) Nanocarriers as an emerging platform for cancer therapy. Nat Nanotechnol 2:761–770. https://doi.org/10.1038/nnano.2007.387
Al-Muntasheri GA, Hussein IA, Nasr-El-Din HA, Amin MB (2007) Viscoelastic properties of a high temperature cross-linked water shut-off polymeric gel. J Petrol Sci Eng 55:56–66. https://doi.org/10.1016/j.petrol.2006.04.004
Cao J, Pan X, Huang W, Wang Y, Hua D, Zhu X, Liang H (2012) Synthesis of cationic poly(4-vinylpyridine)-functionalized colloidal particles by emulsion polymerization with reactive block copolymer for protein adsorption. J Colloid Interface Sci 381:137–142. https://doi.org/10.1016/j.jcis.2012.05.010
Gao D, Feng J, Ma J, Lü B, Lin J, Zhang J (2014) Synthesis of cationic binder through surfactant-free emulsion polymerization for textile pigment applications. Prog Org Coat 77:1834–1840. https://doi.org/10.1016/j.porgcoat.2014.06.007
Gehan TS, Bag M, Renna LA, Shen X, Algaier DD, Lahti PM, Russell TP, Venkataraman D (2014) Multi-scale active layer morphologies for organic photovoltaics through self-assembly of nanospheres. Nano Lett 14:5238–5243. https://doi.org/10.1021/nl502209s
Gärtner S, Christmann M, Sankaran S, Röhm H, Prinz EM, Penth F, Pütz A, Türeli AE, Penth B, Baumstümmler B, Colsmann A (2014) Eco-friendly fabrication of 4% efficient organic solar cells from surfactant-free P3HT:ICBA nanoparticle dispersions. Adv Mater 26:6653–6657. https://doi.org/10.1002/adma.201402360
Nuasaen S, Tangboriboonrat P (2015) Optical properties of hollow latex particles as white pigment in paint film. Prog Org Coat 79:83–89. https://doi.org/10.1016/j.porgcoat.2014.11.012
Wang F, Guo L, Qiu T, Ye J, He L, Li X (2019) A direct polymerization approach toward hindered phenol/polymer composite latex and its application for waterborne damping coating. Prog Org Coat 130:1–7. https://doi.org/10.1016/j.porgcoat.2019.01.032
Fitch RM (1997) Polymer colloids: a comprehensive introduction. Academic Press, California
Norde W (2003) Colloids and interfaces in life science. Marcel Dekker, New York
Elaïssari A (2008) Colloidal nanoparticles in biotechnology. Wiley-Interscience, New Jersey
Ohtsu Y, Ohba R, Imamura Y, Kobayashi M, Zenkoh H, Hatakeyama M, Manabe T, Hino M, Yamaguchi Y, Kataoka K, Kawaguchi H (2005) Selective ligand purification using high-performance affinity beads. Anal Biochem 338:245–252. https://doi.org/10.1016/j.ab.2004.10.006
Oba S, Hatakeyama M, Handa H, Kawaguchi H (2005) Development of polymer latex particles for selective cleavage of mismatched DNA and their application for DNA diagnosis. Bioconjug Chem 16:551–558. https://doi.org/10.1021/bc049728l
Yordanov G, Simeonova M, Alexandrova R, Yoshimura H, Dushkin C (2009) Quantum dots tagged poly(alkylcyanoacrylate) nanoparticles intended for bioimaging applications. Colloids Surf A 339:199–205. https://doi.org/10.1016/j.colsurfa.2009.02.027
Goto Y, Matsuno R, Konno T, Takai M, Ishihara K (2009) Artificial cell membrane-covered nanoparticles embedding quantum dots as stable and highly sensitive fluorescence bioimaging probes. Biomacromol 9:3252–3257. https://doi.org/10.1021/bm800819r
Pan J, eng S.-S, (2009) Targeting and imaging cancer cells by Folate-decorated, quantum dots (QDs)- loaded nanoparticles of biodegradable polymers. Biomaterials 30:1176–1183. https://doi.org/10.1016/j.biomaterials.2008.10.039
Mittal V (2010) Advanced polymer nanoparticles: synthesis and surface modifications. CRC Press, Florida
Sarı MM, Armutcu C, Bereli N, Uzun L, Denizli A (2011) Monosize microbeads for pseudo-affinity adsorption of human insulin. Colloids Surf B 84:140–147. https://doi.org/10.1016/j.colsurfb.2010.12.025
Kohri M, Abo F, Miki S, Fujii T, Kasuya M, Taniguchi T (2013) Effects of graft shell thickness and compositions on lectin recognition of glycoparticles. J Colloid Sci Biotechnol 2:42–52. https://doi.org/10.1166/jcsb.2013.1028
Antonietti M, Landfester K (2002) Polyreactions in miniemulsion. Prog Polym Sci 27:689–757. https://doi.org/10.1016/S0079-6700(01)00051-X
Asua JM (2002) Miniemulsion polymerization. Prog Polym Sci 27:1283–1346. https://doi.org/10.1016/S0079-6700(02)00010-2
Chern C-S (2008) Principles and applications of emulsion polymerization. Wiley, New Jersey
Chern C-S, Y.-C. Liou Y.-C, (1999) Styrene miniemulsion polymerization initiated by 2,2’-azobisisobutyronitrile. J Polym Sci Part A: Polym Chem 37:2537–2550. https://doi.org/10.1002/(SICI)1099-0518(19990715)37:14%3c2537::AID-POLA27%3e3.0.CO;2-C
Chern C-S, Sheu J-C (2000) Effects of 2-hydroxyalkyl methacrylates on the styrene miniemulsion polymerizations stabilized by SDS and alkyl methacrylates. J Polym Sci Part A: Polym Chem 38:3188–3199. https://doi.org/10.1002/1099-0518(20000901)38:17%3c3188::AID-POLA180%3e3.0.CO;2-Y
Chern C-S, Sheu J-C (2001) Effects of carboxylic monomers on the styrene miniemulsion polymerizations stabilized by SDS/alkyl methacrylates. Polymer 42:2349–2357. https://doi.org/10.1016/S0032-3861(00)00608-X
Mittal V (2011) Polymer nanocomposites by emulsion and suspension polymerization. RSC Publishing, Cambridge
Pichot C, Taniguchi T, Delair Th, Elaïssari A (2003) Functionalized thermosensitive latex particles: Useful tools for diagnostics. J Dispersion Sci Tech 24:423–437. https://doi.org/10.1081/DIS-120021799
Pichot C (2004) Surface-functionalized latexes for biotechnological applications. Curr Opin Colloid Interface Sci 9:213–221. https://doi.org/10.1016/j.cocis.2004.07.001
Tsarevsky NV, Sumerlin BS (2013) Fundamentals of controlled/living radical polymerization. RSC Publishing, Cambridge
Kamigaito M, Sawamoto M (2020) Synergistic advances in living cationic and radical polymerizations. Macromolecules 53:6749–6753. https://doi.org/10.1021/acs.macromol.0c01392
Matyjaszewski K, Xia J (2001) Atom transfer radical polymerization. Chem Rev 101:2921–2990. https://doi.org/10.1021/cr940534g
Kamigaito M, Ando T, Sawamoto M (2001) Metal-catalyzed living radical polymerization. Chem Rev 101:3689–3746. https://doi.org/10.1021/cr9901182
Ejaz M, Yamamoto S, Ohno K, Tsujii Y, Fukuda T (1998) Controlled graft polymerization of methyl methacrylate on silicon substrate by the combined use of the Langmuir-Blodgett and atom transfer radical polymerization techniques. Macromolecules 31:5934–5936. https://doi.org/10.1021/ma980240n
Kim J-B, Bruening M, L, Baker G. L, (2000) Surface-initiated atom transfer radical polymerization on gold at ambient temperature. J Am Chem Soc 122:7616–7617. https://doi.org/10.1021/ja001652q
Xu FJ, Zhao JP, Kang ET, Neoh KG, Li J (2007) Functionalization of nylon membranes via surface-initiated atom-transfer radical polymerization. Langmuir 23:8585–8592. https://doi.org/10.1021/la7011342
Matrab T, Save M, Charleux B, Pinson J, Cabet-Deliry E, Adenier A, Chemi M, Delamar M (2007) Grafting densely-packed poly(n-butyl methacrylate) chains from an iron substrate by aryl diazonium surface-initiated ATRP: XPS monitoring. Surf Sci 601:2357–2366. https://doi.org/10.1016/j.susc.2007.03.046
Kim S, Sikes HD (2020) Radical polymerization reactions for amplified biodetection signals. Polym Chem 1:1424–1444. https://doi.org/10.1039/C9PY01801H
Chiefari J, Chong YK, Ercole F, Krstina J, Jeffery J, Le TPT, Mayadunne RTA, Meijs GF, Moad CL, Moad G, Rizzardo E, Thang SH (1998) Living free-radical polymerization by reversible addition-fragmentation chain transfer: The RAFT process. Macromolecules 31:5559–5562. https://doi.org/10.1021/ma9804951
Moad G, Rizzardo E, Thang SH (2005) Living radical polymerization by the RAFT process. Aust J Chem 58:379–410. https://doi.org/10.1071/CH05072
Barner-Kowollik C (2008) Handbook of RAFT polymerization. Wiley-VCH, Weinheim
Motokawa R, Taniguchi T, Sasaki Y, Enomoto Y, Murakami F, Kasuya M, Kohri M, Nakahira T (2012) Small-angle neutron scattering study on specific polymerization loci induced by copolymerization of polymerizable surfactant and styrene during miniemulsion polymerization. Macromolecules 45:9435–9444. https://doi.org/10.1021/ma301776b
Perrier S (2017) 50th anniversary perspective: RAFT polymerization: A user guide. Macromolecules 50:7433–7447. https://doi.org/10.1021/acs.macromol.7b00767
Hawker CJ, Bosman AW, Harth E (2001) New polymer synthesis by nitroxide mediated living radical polymerizations. Chem Rev 101:3661–3688. https://doi.org/10.1021/cr990119u
Colombani D, Steenbock M, Klapper M, Müllen K (1997) 1,3,5,5-tetraphenyl-Δ3-1,2,4-triazolin-2-yl radical-properties in the controlled radical polymerization of poly(methyl methacrylate) and polystyrene. Macromol Rapid Commun 18:243–251. https://doi.org/10.1002/marc.1997.030180305
Georges MK, Veregin RPN, Kazmaier PM, Hamer GK. Narrow molecular weight resins by a free-radical polymerization process. Macromolecules 26:2987–2988. https://doi.org/10.1021/ma00063a054
Matyjaszewski K, Gaynor SG, Kulfan A, Podwika M (1997) Preparation of hyperbranched polyacrylates by atom transfer radical polymerization. 1. Acrylic AB* monomers in “living” radical polymerizations. Macromolecules 30:5192–5194. https://doi.org/10.1021/ma970359g
Guerrini MM, Charleux B, Vairon J-P (2000) Functionalized polystyrene latex particles as substrates for ATRP: Surface and colloidal characterization. Macromol Rapid Commun 21:669–674
Taniguchi T, Kasuya M, Kunisada Y, Miyai T, Nagasawa H, Nakahira T (2009) Surface modification of polymer latex particles by AGET ATRP of a styrene derivative bearing a lactose residue. Colloids Surfaces B: Biointerfaces 71:194–199. https://doi.org/10.1016/j.colsurfb.2009.02.010
Taniguchi T, Kashiwakura T, Inada T, Kunisada Y, Kasuya M, Kohri M, Nakahira T (2010) Preparation of organic/inorganic composites by deposition of silica onto shell layers of polystyrene (core)/poly[2-(N,N-dimethylamino)ethyl methacrylate] (shell) particles. J Colloid Interface Sci 347:62–68. https://doi.org/10.1016/j.jcis.2010.03.019
Taniguchi T, Murakmi F, Kasuya M, Kojima T, Kohri M, Saito K, Nakahira T (2013) Preparation of titania hollow particles with independently controlled void size and shell thickness by catalytic templating core–shell polymer particles. Colloid Polym Sci 291:215–222. https://doi.org/10.1007/s00396-012-2658-2
Kasuya M, Taniguchi T, Motokawa R, Kohri M, Kishikawa K, Nakahira T (2013) Quantification of ATRP initiator density on polymer latex particles by fluorescence labeling technique using copper-catalyzed azide-alkyne cycloaddition. J Polym Sci A: Polym Chem 51:4042–4051. https://doi.org/10.1002/pola.26800
Kasuya M, Taniguchi T, Kohri M, Kishikawa K, Nakahira T (2014) Preparation of polymer latex particles carrying salt-responsive fluorescent graft chains. Polymer 55:5080–5087. https://doi.org/10.1016/j.polymer.2014.08.030
Yamagami T, Kitayama Y, Okubo M (2014) Preparation of stimuli-responsive “mushroom-like” Janus polymer particles as particulate surfactant by site-selective surface-initiated AGET ATRP in aqueous dispersed systems. Langmuir 30:7823–7832. https://doi.org/10.1021/la501266t
Taniguchi T, Kunisada Y, Shinohara M, Kasuya M, Ogawa T, Kohri M, Nakahira T (2010) Preparation of glycopolymer hollow particles by sacrificial dissolution of colloidal templates. Colloids Surfaces A: Physicochem Eng Aspects 369:240–245. https://doi.org/10.1016/j.colsurfa.2010.08.030
Kohri M, Sato M, Abo F, Inada T, Kasuya M, Taniguchi T, Nakahira T (2011) Preparation and lectin binding specificity of polystyrene particles grafted with glycopolymers bearing S-linked carbohydrates. Eur Polym J 47:2351–2360. https://doi.org/10.1016/j.eurpolymj.2011.09.016
Taniguchi T, Obi S, Kamata Y, Kashiwakura T, Kasuya M, Ogawa T, Kohri M, Nakahira T (2012) Preparation of organic/inorganic hybrid and hollow particles by catalytic deposition of silica onto core/shell heterocoagulates modified with poly[2-(N, N-dimethylamino)ethyl methacrylate]. J Colloid Interface Sci 368:107–114. https://doi.org/10.1016/j.jcis.2011.11.077
Coessens V, Nakagawa Y, Matyjaszewski K (1998) Synthesis of azido end-functionalized polyacrylates via atom transfer radical polymerization. Polym Bull 40:135–142. https://doi.org/10.1007/s002890050234
Coessens V, Pyun J, Miller PJ, Gaynor SG, Matyjaszewski K (2000) Functionalization of polymers prepared by ATRP using radical addition reactions. Macromol Rapid Commun 21:103–109. https://doi.org/10.1002/(SICI)1521-3927(20000201)21:2%3c103::AID-MARC103%3e3.0.CO;2-H
Snijder A, Klumperman B, Linde RVD (2002) End-group modification of poly(butyl acrylate) prepared by atom transfer radical polymerization: mechanistic study using gradient polymer elution chromatograph. J Polym Sci A: Polym Chem 40:2350–2359. https://doi.org/10.1002/pola.10321
Postma A, Davis TP, Moad G, O’Shea MS. Approaches to phthalimido and amino end-functional polystyrene by atom transfer radical polymerisation (ATRP). React Funct Polym 66:137–147. https://doi.org/10.1016/j.reactfunctpolym.2005.07.012
Gutekunst WR, Anastasaki A, Lunn DJ, Truong NP, Whitfield R, Jones GR, Treat NJ, Abdilla A, Barton BE, Clark PG, Haddleton DM, Davis TP, Hawker CJ (2017) Practical chain-end reduction of polymers obtained with ATRP. Macromol Chem Phys 218:1700107. https://doi.org/10.1002/macp.201700107
Lunn DJ, Discekici EH, Alaniz JR, Gutekunst WR, Hawker CJ (2017) Established and emerging strategies for polymer chain-end modification. J Polym Sci A: Polym Chem 55:2903–2914. https://doi.org/10.1002/pola.28575
Taniguchi T, Takeuchi N, Kobaru S, Nakahira T (2008) Preparation of highly monodisperse fluorescent polymer particles by miniemulsion polymerization of styrene with a polymerizable surfactant. J Colloid Interface Sci 327:58–62. https://doi.org/10.1016/j.jcis.2008.08.003
Fukushima H, Kohri M, Kojima T, Taniguchi T, Saito K, Nakahira T (2012) Surface-initiated enzymatic vinyl polymerization: synthesis of polymer-grafted silica particles using horseradish peroxidase as catalyst. Polym Chem 3:1123–1125. https://doi.org/10.1039/C2PY20036H
Kohri M, Kobayashi A, Fukushima H, Taniguchi T, Nakahira T (2012) Effect of surfactant type on enzymatic miniemulsion polymerization using horseradish peroxidase as a catalyst. Chem Lett 41:1131–1133. https://doi.org/10.1246/cl.2012.1131
Kohri M, Uzawa S, Kobayashi A, Fukushima H, Taniguchi T, Nakahira T (2013) Enzymatic emulsifier-free emulsion polymerization to prepare polystyrene particles using horseradish peroxidase as a catalyst. Polym J 45:354–358. https://doi.org/10.1038/pj.2012.129
Aikawa T, Mizuno A, Kohri M, Taniguchi T, Kishikawa K, Nakahira T (2016) Polystyrene latex particles containing europium complexes prepared by miniemulsion polymerization using bovine serum albumin as a surfactant for biochemical diagnosis. Colloids Surfaces B: Biointerfaces 145:152–159. https://doi.org/10.1016/j.colsurfb.2016.04.055
Postma A, Davis TP, Moad G, O’Shea MS (2006) Approaches to phthalimido and amino end-functional polystyrene by atom transfer radical polymerisation (ATRP). React Funct Polym 66:137–147. https://doi.org/10.1016/j.reactfunctpolym.2005.07.012
Long J, Osmond D, Vincent B (1973) The equilibrium aspects of weak flocculation. J Colloid Interface Sci 42(1973):545–553. https://doi.org/10.1016/0021-9797(73)90040-4
Mason WT (1999) Fluorescent and luminescent probes for biological activity: a practical guide to technology for quantitative real-time analysis, 2nd edn. Elesevier, Oxford
Worsfold P, Townshend A, Poole C (2005) Encyclopedia of analytical science, 2nd edn. Elesevier, Oxford
Tsujii Y, Ohno K, Yamamoto S, Goto A (2006) Fukuda T (2006) Structure and properties of high-density polymer brushes prepared by surface-initiated living radical polymerization. Adv Polym Sci 197:1–45. https://doi.org/10.1007/12_063
Kizhakkedathu JN, Janzen J, Le Y, Kainthan RK, Brooks DE (2009) Poly(oligo(ethylene glycol)acrylamide) brushes by surface initiated polymerization: effect of macromonomer chain length on brush growth and protein adsorption from blood plasma. Langmuir 25:3794–3801. https://doi.org/10.1021/la803690q
Taniguchi T, Duracher D, Delair Th, Elaïssari A, Pichot C (2003) Adsorption/desorption behavior and covalent grafting of an antibody onto cationic amino-functionalized poly(styrene-N-isopropylacrylamide) core-shell latex particles. Colloids Surfaces B: Biointerfaces 29:53–65. https://doi.org/10.1016/S0927-7765(02)00176-5
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The authors would like to thank Shin-Nakamura Chemicals and LSI Medience for providing the reagents.
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This work was partially supported by a Grant-in-Aid for Scientific Research (JSPS KAKENHI Grant Numbers JP21K05164).
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Yusuke Sasaki: Investigation, formal analysis, writing — original draft, Naho Konishi: Investigation, formal analysis, Michinari Kohri: Supervision, Tatsuo Taniguchi: Conceptualization, methodology, writing — original draft, editing, supervision, project administration, funding acquisition, Keiki Kishikawa: Supervision, Takashi Karatsu: Supervision.
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Sasaki, Y., Konishi, N., Kohri, M. et al. Synthesis of luminescent core–shell polymer particles carrying amino groups for covalent immobilization of enzymes. Colloid Polym Sci 300, 319–331 (2022). https://doi.org/10.1007/s00396-021-04913-7
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DOI: https://doi.org/10.1007/s00396-021-04913-7