{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,23]],"date-time":"2026-08-23T18:08:54Z","timestamp":1787508534910,"version":"build-2736575974"},"reference-count":48,"publisher":"MDPI AG","issue":"15","license":[{"start":{"date-parts":[[2021,7,30]],"date-time":"2021-07-30T00:00:00Z","timestamp":1627603200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100004156","name":"Mahidol University","doi-asserted-by":"publisher","award":["BRF2-NDFR17\/2564"],"award-info":[{"award-number":["BRF2-NDFR17\/2564"]}],"id":[{"id":"10.13039\/501100004156","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Polymers"],"abstract":"<jats:p>Zinc oxide polymeric nanoparticles (ZPPs) of poly (styrene-co-acrylic acid) P(St\/AA), containing oleic acid modified zinc oxide nanoparticles (OA-ZnO NPs), were synthesized via miniemulsion polymerization. By simply adjusting the quantity of reactants, i.e., sodium dodecyl sulfate (SDS) surfactant, potassium persulfate (KPS) initiator, and divinyl benzene (DVB) crosslinking agent, the location of ZnO NPs were altered from the inner (core) to the outer (shell), leading to core-shell and Pickering-like morphologies, respectively. The Pickering-like ZPPs were obtained when using SDS at below or equal to the critical micelle concentration (CMC). At above the CMC, the complete encapsulation of OA-ZnO NPs within the ZPPs depicted a kinetically controlled morphology. The transition to Pickering-like ZPPs also occurred when reducing the KPS from 2 to 0.5\u20131%. Whereas the DVB accelerated the polymerization rate and viscosity in the growing monomer-swollen nanodroplets and, hence, contributed to kinetic parameters on particle morphology, i.e., an increase in the DVB content increased the rate of polymerization. A hollow structure was obtained by replacing styrene with the more hydrophilic monomer, i.e., methyl methacrylate. All ZPPs-incorporated poly (vinyl alcohol) (PVA) films greatly improved shielding performance over the UV region and were relatively transparent on a white paper background. Due to the large number of ZnO NPs in the central region and, hence, the ease of electron transfer, composite films containing core-shell ZPPs possessed the highest UV blocking ability. ZnO NPs in the outer part of the hollow and Pickering-like ZPPs, on the other hand, facilitated the multiple light scattering according to the difference of refractive indices between the inorganic shell and organic\/air core. These results confirm the advantage of structured ZPPs and their potential use as transparent UV shielding fillers.<\/jats:p>","DOI":"10.3390\/polym13152526","type":"journal-article","created":{"date-parts":[[2021,8,1]],"date-time":"2021-08-01T21:44:32Z","timestamp":1627854272000},"page":"2526","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":15,"title":["Facile Control of Structured ZnO Polymeric Nanoparticles through Miniemulsion Polymerization: Kinetic and UV Shielding Effects"],"prefix":"10.3390","volume":"13","author":[{"given":"Narissara","family":"Sudjaipraparat","sequence":"first","affiliation":[{"name":"Department of Chemistry, Faculty of Science, Mahidol University, Rama 6 Road, Phyathai, Bangkok 10400, Thailand"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Teeraporn","family":"Suteewong","sequence":"additional","affiliation":[{"name":"Department of Chemical Engineering, School of Engineering, King Mongkut\u2019s Institute of Technology Ladkrabang, Ladkrabang, Bangkok 10520, Thailand"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3486-7433","authenticated-orcid":false,"given":"Pramuan","family":"Tangboriboonrat","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Faculty of Science, Mahidol University, Rama 6 Road, Phyathai, Bangkok 10400, Thailand"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2021,7,30]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"396","DOI":"10.1016\/j.jpcs.2011.11.004","article-title":"Excellent UV absorption in spin-coated thin films of oleic acid modified zinc oxide nanorods embedded in Polyvinyl alcohol","volume":"73","author":"Augustine","year":"2012","journal-title":"J. Phys. Chem. Solids"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"2127","DOI":"10.1016\/j.polymer.2006.01.071","article-title":"Preparation and characterization of transparent ZnO\/epoxy nanocomposites with high-UV shielding efficiency","volume":"47","author":"Li","year":"2006","journal-title":"Polymer"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"136","DOI":"10.1063\/1.4895185","article-title":"Polymer-ZnO nanocomposites foils and thin films for UV protection","volume":"1614","author":"Shanshool","year":"2014","journal-title":"AIP Conf. Proc."},{"key":"ref_4","doi-asserted-by":"crossref","unstructured":"Razavi-Khosroshahi, H., Shao, W., and Fuji, M. (2020). Synthesis of TiO2 hollow nanoparticles with different shell thickness and effect of structure on photocatalytic activity. Solid State Sci., 103.","DOI":"10.1016\/j.solidstatesciences.2020.106179"},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"36281","DOI":"10.1021\/acsami.7b08763","article-title":"A Novel UV-Shielding and Transparent Polymer Film: When Bioinspired Dopamine\u2013Melanin Hollow Nanoparticles Join Polymers","volume":"9","author":"Wang","year":"2017","journal-title":"ACS Appl. Mater. Interfaces"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"298","DOI":"10.1016\/S0925-8388(03)00371-2","article-title":"Surface modification of zinc oxide nanoparticles by Aminopropyltriethoxysilane","volume":"360","author":"Grasset","year":"2003","journal-title":"J. Alloys Compd."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"5227","DOI":"10.1016\/j.apsusc.2005.08.004","article-title":"Surface modification of zinc oxide nanoparticle by PMAA and its dispersion in aqueous system","volume":"252","author":"Tang","year":"2006","journal-title":"Appl. Surf. Sci."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"52","DOI":"10.1016\/j.jcis.2011.12.001","article-title":"Synthesis of zinc oxide-encapsulated poly(methyl methacrylate)\u2013chitosan core\u2013shell hybrid particles and their electrochemical property","volume":"369","author":"Petchthanasombat","year":"2012","journal-title":"J. Colloid Interface Sci."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"1025","DOI":"10.1007\/s00396-009-2057-5","article-title":"Preparation of styrene polymer\/ZnO nanocomposite latex via miniemulsion polymerization and its anti-bacterial property","volume":"287","author":"Tang","year":"2009","journal-title":"Colloid Polym. Sci."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"87","DOI":"10.1016\/j.msec.2016.03.058","article-title":"Design and development of anisotropic inorganic\/polystyrene nanocomposites by sur-face modification of zinc oxide nanoparticles","volume":"64","author":"Han","year":"2016","journal-title":"Mater. Sci. Eng. C"},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"3271","DOI":"10.1016\/j.eurpolymj.2008.07.023","article-title":"Synthesis of ZnO\/polystyrene composites particles by Pickering emulsion polymerization","volume":"44","author":"Chen","year":"2008","journal-title":"Eur. Polym. J."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"2","DOI":"10.1002\/ese3.50","article-title":"Conducting polymer-based flexible supercapacitor","volume":"3","author":"Shown","year":"2014","journal-title":"Energy Sci. Eng."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"78","DOI":"10.1016\/j.jcis.2006.05.005","article-title":"ZnO\/PS core\u2013shell hybrid microspheres pre-pared with miniemulsion polymerization","volume":"301","author":"Zhang","year":"2006","journal-title":"J. Colloid Interface Sci."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"39","DOI":"10.1016\/j.colsurfa.2018.10.062","article-title":"Simultaneous encapsulation of zinc oxide and octocrylene in poly(methyl methacrylate-co-styrene) nanoparticles obtained by miniemulsion polymerization for use in sunscreen formulations","volume":"561","author":"Frizzo","year":"2019","journal-title":"Colloids Surf. A Physicochem. Eng. Asp."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"757","DOI":"10.1080\/02652040701610472","article-title":"Preparation of nanocapsules containing the two-phase core materials","volume":"24","author":"Wang","year":"2007","journal-title":"J. Microencapsul."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"300","DOI":"10.1016\/j.cej.2015.02.025","article-title":"Film forming hybrid acrylic\/ZnO latexes with excellent UV absorption capacity","volume":"270","author":"Aguirre","year":"2015","journal-title":"Chem. Eng. J."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"590","DOI":"10.1007\/s13233-012-0081-7","article-title":"Preparation of superparamagnetic polystyrene-based nanoparticles functionalized by acrylic acid","volume":"20","author":"Charoenmark","year":"2012","journal-title":"Macromol. Res."},{"key":"ref_18","doi-asserted-by":"crossref","unstructured":"Wichaita, W., Polpanich, D., Kaewsaneha, C., Jangpatarapongsa, K., and Tangboriboonrat, P. (2019). Fabrication of functional hollow magnetic polymeric nanoparticles with controllable magnetic location. Colloids Surf. B Biointerfaces, 184.","DOI":"10.1016\/j.colsurfb.2019.110557"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"50","DOI":"10.1016\/j.msec.2017.02.160","article-title":"Construction of N-halamine labeled silica\/zinc oxide hybrid nanoparticles for enhancing antibacterial ability of Ti implants","volume":"76","author":"Li","year":"2017","journal-title":"Mater. Sci. Eng. C"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"155","DOI":"10.1016\/j.colsurfa.2006.05.007","article-title":"Facile preparation of monodispersed core\/shell zinc oxide@polystyrene (ZnO@PS) nanoparticles via soapless seeded microemulsion polymerization","volume":"291","author":"Liu","year":"2006","journal-title":"Colloids Surf. A Physicochem. Eng. Asp."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"282","DOI":"10.1016\/j.dyepig.2015.05.037","article-title":"Synthesis of ZnO nanoparticles and studying its influence on the antimicrobial, anticorrosion and mechanical behavior of polyurethane composite for surface coating","volume":"121","author":"Azzam","year":"2015","journal-title":"Dyes Pigments"},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"69836","DOI":"10.1039\/C6RA10042B","article-title":"Tribological properties of oleic acid-modified zinc oxide nanoparticles as the lubricant additive in poly-alpha olefin and diisooctyl sebacate base oils","volume":"6","author":"Wu","year":"2016","journal-title":"RSC Adv."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"8081","DOI":"10.1002\/pola.23105","article-title":"Synthesis of P(AA-SA)\/ZnO composite latex particles via inverse miniemulsion polymerization and its application in pH regulation and UV shielding","volume":"46","author":"Luo","year":"2008","journal-title":"J. Polym. Sci. A Polym. Chem."},{"key":"ref_24","unstructured":"Tong, Z. (2007). Water-Based Suspension of Polymer Nanoclay Composite Prepared via Miniemulsion Polymerization, Georgia Institute of Technology."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"458","DOI":"10.1002\/macp.201300696","article-title":"Mapping the Morphology of Polymer-Inorganic Nanocomposites Synthesized by Miniemulsion Polymerization","volume":"215","author":"Asua","year":"2014","journal-title":"Macromol. Chem. Phys."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"5222","DOI":"10.1021\/ma990299+","article-title":"Formulation and stability mechanisms of polymerizable miniemulsions","volume":"32","author":"Landfester","year":"1999","journal-title":"Macromolecules"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"2731","DOI":"10.1002\/pola.28155","article-title":"On the miniemulsion polymerization of very hydrophobic monomers initiated by a completely water-insoluble initiator: Thermodynamics, kinetics, and mechanism","volume":"54","author":"Jansen","year":"2016","journal-title":"J. Polym. Sci. Part A Polym. Chem."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"173","DOI":"10.1016\/j.jcis.2008.09.056","article-title":"Effect of adding anionic surfactant on the stability of Pickering emulsions","volume":"329","author":"Whitby","year":"2009","journal-title":"J. Colloid Interface Sci."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"1393","DOI":"10.1007\/s00396-010-2277-8","article-title":"Synthesis of microcapsules with polystyrene\/ZnO hybrid shell by Pickering emulsion polymerization","volume":"288","author":"Chen","year":"2010","journal-title":"Colloid Polym. Sci."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"203","DOI":"10.1039\/C6EN00339G","article-title":"Effect of surfactants, pH and water hardness on the surface properties and agglomeration behavior of engineered TiO nanoparticles","volume":"4","author":"Loosli","year":"2017","journal-title":"Environ. Sci. Nano."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"83","DOI":"10.1002\/(SICI)1097-4628(19960103)59:1<83::AID-APP13>3.0.CO;2-9","article-title":"Dynamic modeling of limited particle coagulation in emulsion polymerization","volume":"59","author":"Mayer","year":"1996","journal-title":"J. Appl. Polym. Sci."},{"key":"ref_32","doi-asserted-by":"crossref","unstructured":"Liu, B., Wang, Y., Zhang, M., and Zhang, H. (2016). Initiator Systems Effect on Particle Coagulation and Particle Size Distribution in One-Step Emulsion Polymerization of Styrene. Polymers, 8.","DOI":"10.3390\/polym8020055"},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"50176","DOI":"10.1039\/C7RA10111B","article-title":"One-Pot preparation of poly(styrene-codivinylbenzene)\/silver nanoparticles composite microspheres with tunable porosity and their catalytic degradation of methylene blue in aqueous solution","volume":"7","author":"Ji","year":"2017","journal-title":"RSC Adv."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"293","DOI":"10.1007\/BF03218520","article-title":"Preparation of highly cross-linked, monodisperse poly(methyl methacrylate) microspheres by dispersion polymerization; Part II. Semi-continuous processes","volume":"16","author":"Lee","year":"2008","journal-title":"Macromol. Res."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"3271","DOI":"10.1021\/la2043137","article-title":"Toward Designer Magnetite\/Polystyrene Colloidal Composite Microspheres with Controllable Nanostructures and Desirable Surface Functionalities","volume":"28","author":"Xu","year":"2012","journal-title":"Langmuir"},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"1559","DOI":"10.1007\/s10934-019-00753-7","article-title":"Effect of various synthesis parameters on styrene\u2013divinylbenzene copolymer properties","volume":"26","author":"Chaudhary","year":"2019","journal-title":"J. Porous Mater."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"23","DOI":"10.1049\/iet-nbt.2008.0009","article-title":"Preparation of carboxyl-coated polystyrene nanoparticles using oleic acid","volume":"3","author":"Liu","year":"2009","journal-title":"IET Nanobiotechnol."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"1097","DOI":"10.1080\/10601326808051881","article-title":"Monomer Reactivity Ratios for the Copolymerization of Methyl Methacrylate with Pure Meta- and Pure Para-Divinylbenzene","volume":"2","author":"Wiley","year":"1968","journal-title":"J. Macromol. Sci. Part A Chem."},{"key":"ref_39","first-page":"S132","article-title":"Monomer reactivity ratios for styrene-methyl-14C methacrylate copolymerization","volume":"62","author":"Wiley","year":"1962","journal-title":"J. Polym. Sci."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"53","DOI":"10.1007\/s11998-004-0025-z","article-title":"Particle morphology development in hybrid miniemulsion polymerization","volume":"1","author":"Tsavalas","year":"2004","journal-title":"J. Coatings Technol. Res."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"250","DOI":"10.1007\/BF03218688","article-title":"Effect of crosslinking agents on the morphology of polymer particles produced by one-step seeded polymerization","volume":"17","author":"Kim","year":"2009","journal-title":"Macromol. Res."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"75","DOI":"10.1016\/j.jcis.2013.01.012","article-title":"Highly charged hollow latex particles prepared via seeded emulsion polymerization","volume":"396","author":"Nuasaen","year":"2013","journal-title":"J. Colloid Interface Sci."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"287","DOI":"10.1016\/j.molliq.2016.07.025","article-title":"Does poly(vinyl alcohol) act as an amphiphilic polymer? An interaction study with simvastatin","volume":"222","author":"Baptista","year":"2016","journal-title":"J. Mol. Liq."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"95","DOI":"10.2147\/NSA.S19419","article-title":"Titanium dioxide and zinc oxide nanoparticles in sunscreens: Focus on their safety and effectiveness","volume":"4","author":"Smijs","year":"2011","journal-title":"Nanotechnol. Sci. Appl."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"422","DOI":"10.1007\/s00396-005-1389-z","article-title":"Synthesis of nano-ZnO\/poly(methyl methacrylate) composite microsphere through emulsion polymerization and its UV-shielding property","volume":"284","author":"Tang","year":"2006","journal-title":"Colloid Polym. Sci."},{"key":"ref_46","doi-asserted-by":"crossref","unstructured":"Urbina, J.E., Alonso, A.C., Gonz\u00e1lez, M.S., Albores, A.M., and Dur\u00e1n, A.V. (2018). Nanoscale zinc oxide particles for improving the physiological and sanitary quality of a Mexican landrace of red maize. Nanomaterials, 8.","DOI":"10.3390\/nano8040247"},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"117","DOI":"10.1111\/j.1468-2494.2011.00689.x","article-title":"UV absorption and scattering properties of inorganic-based sunscreens","volume":"34","author":"Egerton","year":"2011","journal-title":"Int. J. Cosmet. Sci."},{"key":"ref_48","doi-asserted-by":"crossref","unstructured":"Yoon, J., Lee, J.H., Lee, J.B., and Lee, J.H. (2020). Highly Scattering Hierarchical Porous Polymer Microspheres with a High-Refractive Index Inorganic Surface for a Soft-Focus Effect. Polymers, 12.","DOI":"10.3390\/polym12102418"}],"container-title":["Polymers"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2073-4360\/13\/15\/2526\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T06:37:51Z","timestamp":1760164671000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2073-4360\/13\/15\/2526"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2021,7,30]]},"references-count":48,"journal-issue":{"issue":"15","published-online":{"date-parts":[[2021,8]]}},"alternative-id":["polym13152526"],"URL":"https:\/\/doi.org\/10.3390\/polym13152526","relation":{},"ISSN":["2073-4360"],"issn-type":[{"value":"2073-4360","type":"electronic"}],"subject":[],"published":{"date-parts":[[2021,7,30]]}}}