Abstract
We developed a W/O miniemulsion reactor system enabling the preparation of biopolymer nanoparticles and control of their morphologies and inner microstructures. First, the W/O miniemulsion was prepared by suspending water nanodroplets containing agarose in oil. Then, we produced agarose hydrogel nanoparticles (AgarH) by the gelation of agarose in nanodroplets. Next, we prepared agarose xerogel nanoparticles (AgarX) by precisely tuning the water evaporation from AgarH. We controlled the morphologies (solid and hollow) and crystal structure of AgarX by changing the pressure and temperature during water evaporation. In fact, AgarX with a hollow structure was generated through rapid evaporation at a low pressure. AgarH was dissolved in Milli-Q water when the temperature was raised to 90 °C. On the other hand, AgarX remained a solid particle under the same conditions, likely because of its high crystallinity. We expect that this technique can be applied to prepare xerogels of diverse biomass-based polymers for the replacement of synthetic polymers.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Rent or buy this article
Get just this article for as long as you need it
$39.95
Prices may be subject to local taxes which are calculated during checkout









References
Nitta SK, Numata K. Biopolymer-based nanoparticles for drug/gene delivery and tissue engineering. Int J Mol Sci. 2013;14:1629–54.
Stanisz M, Klapiszewski L, Jesionowski T. Recent advances in the fabrication and application of biopolymer-based micro- and nnanostructures: a comprehensive review. Chem Eng J. 2020;397:125409.
van Dongen SFM, de Hoog HPM, Peters R, Nallani M, Nolte RJM, van Hest JCM. Biohybrid polymer capsules. Chem Rev. 2009;109:6212–74.
Matalanis A, Jones OG, McClements DJ. Structured biopolymer-based delivery systems for encapsulation, protection, and release of lipophilic compounds. Food Hydrocoll. 2011;25:1865–80.
Akiyoshi K, Kobayashi S, Shichibe S, Mix D, Baudys M, Kim SW, et al. Self-assembled hydrogel nanoparticle of cholesterol-bearing pullulan as a carrier of protein drugs: complexation and stabilization of insulin. J Controlled Release. 1998;54:313–20.
Fukui Y, Fukuda M, Fujimoto K. Generation of mucin gel particles with self-degradable and -releasable properties. J Mater Chem B. 2018;6:781–8.
Fukui Y, Sakai D, Fujimoto K. Preparation of protein nano-objects by assembly of polymer-grafted proteins. Colloids Surf B-Biointerfaces. 2016;148:503–10.
Fukui Y, Kabayama N, Fujimoto K. Fine-tuning in mineral cross-linking of biopolymer nanoparticle for incorporation and release of cargo. Colloids Surf B-Biointerfaces. 2015;136:168–74.
Kaihara S, Suzuki Y, Fujimoto K. In situ synthesis of polysaccharide nanoparticles via polyion complex of carboxymethyl cellulose and chitosan. Colloids Surf B-Biointerfaces. 2011;85:343–8.
Fujimoto K, Iwasaki C, Arai C, Kuwako M, Yasugi E. Control of cell death by the smart polymeric vehicle. Biomacromolecules. 2000;1:515–8.
Gref R, Minamitake Y, Peracchia MT, Trubetskoy V, Torchilin V, Langer R. Biodegradable long-circulating polymeric nanospheres. Science. 1994;263:1600–3.
Reis CP, Neufeld RJ, Vilela S, Ribeiro AJ, Veiga F. Review and current status of emulsion/dispersion technology using an internal gelation process for the design of alginate particles. J Microencapsul. 2006;23:245–57.
Hecht LL, Winkelmann M, Wagner C, Landfester K, Gerlinger W, Sachweh B, et al. Miniemulsions for the production of nanostructured particles. Chem. Eng. Technol. 2012;35:1670–6.
Rao JP, Geckeler KE. Polymer nanoparticles: preparation techniques and size-control parameters. Prog Polym Sci. 2011;36:887–913.
Morikawa M, Yoshihara M, Endo T, Kimizuka N. Alpha-helical polypeptide microcapsules formed by emulsion-templated self-assembly. Chemistry. 2005;11:1574–8.
Machado AHE, Lundberg D, Ribeiro AJ, Veiga FJ, Lindman B, Miguel MG, et al. Preparation of calcium alginate nanoparticles using water-in-oil (W/O) nanoemulsions. Langmuir. 2012;28:4131–41.
Ethirajan A, Schoeller K, Musyanovych A, Ziener U, Landfester K. Synthesis and optimization of gelatin nanoparticles using the miniemulsion process. Biomacromolecules. 2008;9:2383–9.
Ku KH, Shin JM, Yun H, Yi GR, Jang SG, Kim BJ. Multidimensional design of anisotropic polymer particles from solvent-evaporative emulsion. Adv. Funct. Mater. 2018;28:1802961.
Li H, Mao X, Wang HY, Geng Z, Xiong BJ, Zhang LB, et al. Kinetically dependent self-assembly of chiral block copolymers under 3D confinement. Macromolecules. 2020;53:4214–23.
Yiamsawas D, Beckers SJ, Lu H, Landfester K, Wurm FR. Morphology-controlled synthesis of lignin nanocarriers for drug delivery and carbon materials. Acs Biomater Sci Eng. 2017;3:2375–83.
Meldrum FC, O’Shaughnessy C. Crystallization in confinement. Adv Mater. 2020;32:2001068.
Staff RH, Landfester K, Crespy D. Recent advances in the emulsion solvent evaporation technique for the preparation of nanoparticles and nanocapsules. In: Percec V, editor. Hierarchical macromolecular structures: 60 years after the Staudinger Nobel Prize II. Advances in Polymer Science. Springer International Publishing AG, Gewerbestrasse 11, Cham, CH-6330, Swizerland. 2622013. pp. 329–44.
Taden A, Landfester K. Crystallization of poly(ethylene oxide) confined in miniemulsion droplets. Macromolecules. 2003;36:4037–41.
Argudo PG, Guzman E, Lucia A, Rubio RG, Ortega F. Preparation and application in drug storage and delivery of agarose nanoparticles. Int J Polym Sci. 2018;2018:7823587.
Fukui Y, Fujimoto K. Bio-inspired nanoreactor based on a miniemulsion system to create organic-inorganic hybrid nanoparticles and nanofilms. J Mater Chem. 2012;22:3493–9.
Antonietti M, Landfester K. Polyreactions in miniemulsions. Prog Polym Sci. 2002;27:689–757.
Bulone D, Giacomazza D, Martorana V, Newman J, San Biagio PL. Ordering of agarose near the macroscopic gelation point. Phys Rev E. 2004;69:041401.
Freile-Pelegrin Y, Madera-Santana T, Robledo D, Veleva L, Quintana P, Azamar JA. Degradation of agar films in a humid tropical climate: thermal, mechanical morphological and structural changes. Polym Degrad Stab. 2007;92:244–52.
Foord SA, Atkins EDT. New X-ray-diffraction results from agarose - extended single helix structures and implications for gelation mechanism. Biopolymers 1989;28:1345–65.
Valentin E, Nam HG, Kim PH, Joo HW, Shim HJ, Chang YK, et al. Application of a Dowex-50WX8 chromatographic process to the preparative-scale separation of galactose, levulinic acid, and 5-hydroxymethylfurfural in acid hydrolysate of agarose. Sep Purif Technol. 2014;133:297–302.
Prado HJ, Matulewicz MC, Bonelli PR, Cukierman AL. Studies on the cationization of agarose. Carbohydr Res. 2011;346:311–21.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare no competing interests.
Additional information
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary information
Rights and permissions
About this article
Cite this article
Fukui, Y., Inamura, R. & Fujimoto, K. Preparation of agarose xerogel nanoparticles by solvent evaporation from water nanodroplets. Polym J 53, 815–821 (2021). https://doi.org/10.1038/s41428-021-00471-5
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41428-021-00471-5
This article is cited by
-
PJ ZEON Award for outstanding papers in Polymer Journal 2021
Polymer Journal (2022)