IP Library Granted Patent US 12,409,432
Granted Patent B2
US 12,409,432 · App. 17/697,148 · Granted Sep 9, 2025

Persistent micelle corona chemistry

Inventors: Morgan Stefik (Columbia, SC); Taylor Larison (Cayce, SC)
Assignee: UNIVERSITY OF SOUTH CAROLINA
B01J13/185C08F220/06
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Quick Facts
Patent No.
US 12,409,432
App. No.
17/697,148
Granted
Sep 9, 2025
Kind
B2
Abstract

A method of forming persistent micelles is described. Particularly, methods disclosed herein include dissolving a block copolymer in a first solvent to form a dispersion containing unimers or dynamic micelles. Further, a method includes contacting the dispersion with a second solvent forming the persistent micelles. The persistent micelles formed by the method of the present disclosure can be used for controlled delivery of dispersions in organic electronic coatings, paint, or drug delivery applications and can also be used to control the pore size of films that include an oxide, a nitride, a carbide, a metal, or a carbon material.

Claims (17)

1. A method of forming persistent micelles, comprising:

dissolving a block copolymer in a first solvent to form a dispersion containing unimers or dynamic micelles, wherein the block copolymer comprises poly (cyclohexyl methacrylate-b-(diethoxyphosphoryl) methyl methacrylate); and

contacting the dispersion with a second solvent forming the persistent micelles.

2. The method of claim 1 , further comprise maintaining a diameter of the persistent micelles while independently adjusting a functional group density of the persistent micelles.

3. The method of claim 1 , further comprise maintaining a diameter of the persistent micelles while independently tailoring a Coulombic interaction strength of the persistent micelles.

4. The method of claim 1 , wherein the block copolymer comprises a core block and a corona block.

5. The method of claim 1 , wherein the block copolymer has a molar mass between about 20 kg/mol and about 100 kg/mol.

6. The method of claim 4 , wherein the core block comprises a methacrylate derivative.

7. The method of claim 4 , wherein the corona block comprises a polyphosphonated ester.

8. The method of claim 1 , wherein the first solvent is a non-selective solvent.

9. The method of claim 1 , wherein the first solvent comprises tetrahydrofuran (THF), methylene chloride, chloroform, or a combination thereof.

10. The method of claim 1 , wherein the second solvent comprises acetonitrile, methanol, ethanol water, or a combination thereof.

11. The method of claim 1 , further comprising contacting the dispersion with a reagent resulting in functionalization of the persistent micelles.

12. The method of claim 11 , wherein the reagent comprises bromotrimethylsilane (TMSBr), methanol, water or a combination thereof.

13. The method of claim 11 , wherein the persistent micelles further comprise a mono acid, a diacid, or a combination thereof.

14. The method of claim 11 , wherein the persistent micelles comprise a zeta potential from about 0 mV to 15 mV.

15. The method of claim 1 , wherein average core diameter of the persistent micelles ranges from about 10 nm to about 200 nm.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 2, 2023
From: STEFIK, MORGAN; LARISON, TAYLOR
To: UNIVERSITY OF SOUTH CAROLINA
Reel/Frame 063509/0943 →
Continuity (2)
Provisional Application 63189381 · May 17, 2021
Related Publication 20220362733A1 · Nov 17, 2022
References Cited (67)
US 10954393B2 · Stefik et al. · 2021 [cited by applicant]
US 20200146987A1 · Stefik · 2020 [cited by examiner]
Alexandridis et al., Amphiphilic Block Copolymers, Elsevier, 2000, Book. (No Abstract Available) Retrieved Mar. 10, 2023 from weblink: https://books.google.com/books?hl=en&lr=&id=HsUuCbPeiUUC&oi=fnd&pg=PP1&ots=Z48U2KL_0… [cited by applicant]
Anikin et al., Polyelectrolyte-Mediated Protein Adsorption: Fluorescent Protein Binding to Individual Polyelectrolyte Nanospheres, The Journal of Physical Chemistry B Letters, vol. 109, 2005, 5418-5420. https://doi.org/… [cited by applicant]
Anraku et al., Size-Controlled Long-Circulating PICsome as a Ruler to Measure Critical Cut-off Disposition Size into Normal and Tumor Tissues, Chemical Communications, vol. 47, No. 21, 2011, 6054-6056. (Abstract Only) h… [cited by applicant]
Asri et al., An Efficient Process for Synthesizing and Hydrolyzing a Phosphonated Methacrylate: Investigation of the Adhesive and Anticorrosive Properties, Journal of Polymer Science: Part A: Polymer Chemistry, vol. 46,… [cited by applicant]
Bolto et al., Organic Polyelectrolytes in Water Treatment, Water Research, vol. 41, Issue 11, 2007, 2301-2324. (Abstract Only) https://doi.org/10.1016/j.watres.2007.03.012. [cited by applicant]
Borkovec et al., Ion Binding to Polyelectrolytes, Current Opinion in Colloid & Interface Science, vol. 11, Issue 5, 2006, 280-289. (Abstract Only) https://doi.org/10.1016/j.cocis.2006.08.004. [cited by applicant]
Brondino et al., Adhesive Properties onto Galvanized Steel Plates of Grafted Poly(Vinylidene Fluoride) Powders with Phosphonated Acrylates, Journal of Applied Polymer Science, vol. 72, Issue 5, 2999, 611-620. (Abstract … [cited by applicant]
Canniccioni et al., RAFT Polymerization of Dimethyl(Methacryloyloxy)Methyl Phosphonate and its Phosphonic Acid Derivative: A New Opportunity for Phosphorus-Based Materials, Polymer Chemistry, vol. 4, No. 13, 2013, 3676-… [cited by applicant]
Cho et al., Nanoporous Block Copolymer Micelle/Micelle Multilayer Films with Dual Optical Properties, Journal of the American Chemical Society, vol. 128, No. 30, 2006, 9935-9942. (Abstract Only) https://doi.org/10.1021/… [cited by applicant]
Choi et al., Molecular Exchange in Ordered Diblock Copolymer Micelles, Macromolecules, vol. 44, No. 9, 2011, 3594-3604. (Abstract Only) https://doi.org/10.1021/ma102788v. [cited by applicant]
Chopra et al., Sustained Release Micellar Carrier Systems for Iontophoretic Transport of Dexamethasone Across Human Sclera, Journal of Controlled Release: Official Journal of the Controlled Release Society, vol. 160, No… [cited by applicant]
Dai et al., Reinforcement of Polymer Interfaces with Random Copolymers, Physical Review Letters, vol. 73, Issue 18-31, 1994, 2472-2475. (Abstract Only) https://doi.org/10.1103/PhysRevLett73.2472. [cited by applicant]
Dormidontova, Micellization Kinetics in Block Copolymer Solutions: Scaling Model, Macromolecules, vol. 32, No. 22, 1999, 7630-7644. (Abstract Only) https://doi.org/10.1021/ma9809029. [cited by applicant]
Falireas et al., Synthesis and Aqueous Solution Properties of an Amino Bisphosphonate Methacrylate Homopolymer via RAFT Polymerization, Polymers, vol. 10, No. 7, 2018, 711, 22-26. https://doi.org/10.3390/polym10070711. [cited by applicant]
Farhat et al., Ion Transport and Equilibria in Polyelectrolyte Multilayers, Langmuir, vol. 17, No. 4, 2001, 1184-1192. https://doi.org/10.1021/la001298+. [cited by applicant]
Ge et al., Polyelectrolyte-Promoted Forward Osmosis-Membrane Distillation (FO—MD) Hybrid Process for Dye Wastewater Treatment, Environmental Science & Technology, vol. 46, No. 11, 2012, 6236-6243. (Abstract Only) https:… [cited by applicant]
Graillot et al., Synthesis by RAFT of Innovative Well-Defined (co)polymers From a Novel Phosphorus-Based Acrylamide Monomer, Polymer Chemistry, vol. 4, Issue 3, 2013, 795-803. https://dx.doi.org/10.1039/c2py20720f. [cited by applicant]
Guo et al., Parallel Control over Surface Charge and Wettability Using Polyelectrolyte Architecture: Effect on Protein Adsorption and Cell Adhesion, ACS Applied Materials & Interfaces, vol. 8, No. 44, 2016, 30552-30563.… [cited by applicant]
Halperin et al., Polymeric Micelles: Their Relaxation Kinetics, Macromolecules, vol. 22, No. 5, 1989, 2403-2412. (Abstract Only) https://doi.org/10.1021/ma00195a069. [cited by applicant]
Han et al., Effect of pH on the Structure and Drug Release Profiles of Layer-by-Layer Assembled Films Containing Polyelectrolyte, Micelles, and Graphene Oxide, Scientific Reports, vol. 6, Article No. 24158, 2016, 10 Pag… [cited by applicant]
Harris et al., Ion Transport and Interfacial Dynamics in Disordered Block Copolymers of Ammonium-Based Polymerized Ionic Liquids, Macromolecules, vol. 51, No. 9, 2018, 3477-3486. (Abstract Only) https://doi.org/10.1021/… [cited by applicant]
Hu et al., Controlled Rupture of Magnetic Polyelectrolyte Microcapsules for Drug Delivery, Langmuir, vol. 24, No. 20, 2008, 11811-11818. (Abstract Only) https://doi.org/10.1021/la801138e. [cited by applicant]
Jain et al., Consequences of Nonergodicity in Aqueous Binary PEO-PB Micellar Dispersions, Materials Science, Macromolecules, vol. 37, No. 4, 2004, 1511-1523. (Abstract Only) http://dx.doi.org/10.1021/ma035467j. [cited by applicant]
Jang et al., Phosphonated Polymers with Fine-Tuned Ion Clustering Behavior: Toward Efficient Proton Conductors, Macromolecules, vol. 51, No. 3, 2018, 1120-1128. (Abstract Only) https://doi.org/10.1021/acs.macromol.7b024… [cited by applicant]
Justyna et al., The McKenna Reaction—Avoiding Side Reactions in Phosphonate Deprotection, Beilstein Journal of Organic Chemistry, vol. 16, 2020, 1436-1446. https://doi.org/10.3762%2Fbjoc.16.119. [cited by applicant]
Kataoka et al., Block Copolymer Micelles for Drug Delivery: Design, Characterization and Biological Significance, Advanced Drug Delivery Reviews, vol. 64, Supp, 2012, 34-48. (Abstract Only) https://doi.org/10.1016/j.add… [cited by applicant]
Keddie et al., RAFT Agent Design and Synthesis, Macromolecules, vol. 45, Issue 13, 2012, 5321-5620. https://doi.org/10.1021/ma300410v. [cited by applicant]
Kelley et al., Size Evolution of Highly Amphiphilic Macromolecular Solution Assemblies Via a Distinct Bimodal Pathway, Nature Communications, vol. 5, Article No. 3599, 2014, 10 Pages. https://doi.org/10.1038/ncomms4599. [cited by applicant]
Kelly et al., Intrinsic Properties of Polyelectrolyte Multilayer Membranes: Erasing the Memory of the Interface, Langmuir, vol. 34, No. 13, 2018, 3874-3883. (Abstract Only) https://doi.org/10.1021/acs.langmuir.8b00336. [cited by applicant]
Kembaren et al., Balancing Enzyme Encapsulation Efficiency and Stability in Complex Coacervate Core Micelles, Langmuir, vol. 36, No. 29, 2020, 8494-8502. https:/doi.org/10.1021/acs.langmuir.0c01073. [cited by applicant]
Krasemann et al., Selective Ion Transport across Self-Assembled Alternating Multilayers of Cationic and Anionic Polyelectrolytes, Langmuir, vol. 16, No. 2, 2000, 287-290. (Abstract Only) https://doi.org/10.1021/a991240z. [cited by applicant]
Lai et al., Hypromellose-Graft-Chitosan and Its Polyelectrolyte Complex as Novel Systems for Sustained Drug Delivery, ACS Applied Materials & Interfaces, vol. 7, No. 19, 2015, 10501-10510. https://doi.org/10.1021/acsami… [cited by applicant]
Lantz et al., Full Gamut Wall Tunability from Persistent Micelle Templates via Ex Situ Hydrolysis, Nano-Micro Small, vol. 15, Issue 18, 1900393, 2019. (Abstract Only) https://doi.org/10.1002/smll.201900393. [cited by applicant]
Larison et al., Persistent Micelle Corona Chemistry Enables Constant Micelle Core Size with Independent Control of Functionality and Polyelectrolyte Response, Langmuir, vol. 37, No. 32, 2021, 9817-9825. https:/doi.org/1… [cited by applicant]
Lee et al., Structure of pH-Dependent Block Copolymer Micelles: Charge and Ionic Strength Dependence, Macromolecules, vol. 35, No. 22, 2002, 8540-8551. https://doi.org/10.1021/ma0114842. [cited by applicant]
Lee et al., Super pH-Sensitive Multifunctional Polymeric Micelle for Tumor pHe Specific TAT Exposure and Multidrug Resistance, Journal of Controlled Release, vol. 129, Issue 3, 2008, 228-236. https://doi.org/10.1016/j.i… [cited by applicant]
Li et al., Self-Assembly of Random Copolymers, Chemical Communications, vol. 50, Issue 88, 2014, 13417-13432. https://doi.org/10.1039/C4CC03688C. [cited by applicant]
Lu et al., Addition of Corona Block Homopolymer Retards Chain Exchange in Solutions of Block Copolymer Micelles, Macromolecules, vol. 49, No. 4, 2016, 1405-1413. https://doi.org/10.1021/acs.macromol.5b02395. [cited by applicant]
Lu et al., Chain Exchange in Binary Copolymer Micelles at Equilibrium: Confirmation of the Independent Chain Hypothesis, ACS Macro Letters, vol. 2, No. 5, 2013, 451-455. (Abstract Only) https://doi.org/10.1021/mz400167x. [cited by applicant]
Lu et al., Molecular Exchange in Diblock Copolymer Micelles: Bimodal Distribution in Core-Block Molecular Weights, ACS Macro Letters, vol. 1, No. 8, 2012, 982-985. (Abstract Only) https://doi.org/10.1021/mz300285x. [cited by applicant]
Lu et al., Remarkable Effect of Molecular Architecture on Chain Exchange in Triblock Copolymer Micelles, Macromolecules, vol. 48, No. 8, 2015, 2667-2676. (Abstract Only) https://doi.org/10.1021/acs.macromol.5b00294. [cited by applicant]
Lund et al. Equilibrium Chain Exchange Kinetics of Diblock Copolymer Micelles: Tuning and Logarithmic Relaxation, Macromolecules, vol. 39, No. 13, 2006, 4566-4575. https://doi.org/10.1021/ma060328y. [cited by applicant]
Luo et al., Thermodynamic Size Control of Block Copolymer Vesicles in Solution, Langmuir, vol. 17, No. 22, 2001, 6804-6811. (Abstract Only) https://doi.org/10.1021/la0104370. [cited by applicant]
Mark, Polymer Data Handbook, Oxford University Press, Inc., 1999, 390-393. [cited by applicant]
Meli et al., Path-Dependent Morphology and Relaxation Kinetics of Highly Amphiphilic Diblock Copolymer Micelles in Ionic Liquids, Macromolecules, vol. 43, No. 4, 2010, 2018-2027. (Abstract Only) https://doi.org/10.1021/… [cited by applicant]
Milsom et al., Layer-by-Layer Deposition of Open-Pore Mesoporous TiO2—Nafion® Film Electrodes, Journal of Solid State Electrochemistry, vol. 11, 2007, 1109-1117. https://hdl.handle.net/2134/3035 ; https://doi.org/10.100… [cited by applicant]
Monge et al., Chapter 1: Polymerization of Phosphorus-Containing (Meth)acrylate Monomers, Phosphorus-Based Polymers: from Synthesis to Applications, 2014, 1-18. https://doi.org/10.1039/9781782624523-00001. [cited by applicant]
Mura et al., Stimuli-Responsive Nanocarriers for Drug Delivery, Nature Materials, vol. 12, No. 11, 2013, 991-1003. (Abstract Only) https://www.nature.com/articles/nmat3776. [cited by applicant]
Nel et al., Understanding Biophysicochemical Interactions at the Nano-Bio Interface, Nature Materials, vol. 8, No. 7, 2009, 543-557. (Abstract Only) https://doi.org/10.1038/nmat2442. [cited by applicant]
Nishiyama et al., Current State, Achievements, and Future Prospects of Polymeric Micelles as Nanocarriers for Drug and Gene Delivery, Pharmacology & Therapeutics, vol. 112, Issue 3, 2006, 630-648. (Abstract Only) https:… [cited by applicant]
Nylander et al., Formation of Polyelectrolyte-Surfactant Complexes on Surfaces, Advances in Colloid and Interface Sciences, vols. 123-126, 2006, 105-123. (Abstract Only) https://doi.org/10.1016/i.cis.2006.07.005. [cited by applicant]
Paren et al., Percolated Ionic Aggregate Morphologies and Decoupled Ion Transport in Precise Sulfonated Polymers Synthesized by Ring-Opening Metathesis Polymerization, Macromolecules, vol. 53, No. 20, 2020, 8960-8973. h… [cited by applicant]
Park et al., Effects of Protein Charge Heterogeneity in Protein-Polyelectrolyte Complexation, Macromolecules, vol. 25, No. 1, 1992, 290-295. (Abstract Only) https://doi.org/10.1021/ma00027a047. [cited by applicant]
Peters et al., Nanostructured Antimony-Doped Tin Oxide Layers with Tunable Pore Architectures as Versatile Transparent Current Collectors for Biophotovoltaics, Advanced Functional Materials, vol. 26, Issue 37, 2016, 668… [cited by applicant]
Sanchez et al., Thermodynamics and Crystallization of Random Copolymers, Macromolecules, vol. 8, No. 5, 1975, 638-641. (Abstract Only) https://doi.org/10.1021/ma60047a012. [cited by applicant]
Sharma et al., Multilayer Capsules Made of Weak Polyelectrolytes: A Review on the Preparation, Functionalization an Applications in Drug Delivery, Beilstein Journal of Nanotechnology, vol. 11, 2020, 508-532. https://doi… [cited by applicant]
Templin et al., Organically Modified Aluminosilicate Mesostructures from Block Copolymer Phases, Science, vol. 278, No. 5344, 1997, 1795-1798. (Abstract Only) https://doi.org/10.1126/science.278.5344.1795. [cited by applicant]
Urade et al., Synthesis of Thermally Stable Highly Ordered Nanoporous Tin Oxide Thin Films with a 3D Face-Centered Orthorhombic Nanostructure, The Journal of Physical Chemistry B, vol. 109, Issue 21, 2005, 10538-10541. … [cited by applicant]
Van Den Bergh et al., Nanostructure Dependence of T-Nb205 Intercalation Pseudocapacitance Probed Using Tunable Isomorphic Architectures, Advanced Functional Materials, vol. 31, Issue 1, 2021, 12 Pages. https://doi.org/1… [cited by applicant]
Wang et al., Polyelectrolyte Multilayer Nanoreactors for Preparing Silver Nanoparticle Composites: Controlling Metal Concentration and Nanoparticle Size, Langmuir, vol. 18, Issue 8, 2002, 3370-3375. (Abstract Only) http… [cited by applicant]
Warren et al., Ordered Mesoporous Materials from Metal Nanoparticle-Block Copolymer Self-Assembly, Science, vol. 320, Issue 5884, 2008, 1748-1752. (Abstract Only) https://doi.org/10.1126/science.1159950. [cited by applicant]
Xu et al., Interaction of Proteins with Polyelectrolytes: Comparison of Theory to Experiment, Langmuir, vol. 35, Issue 16, 2019, 5373-5391. https://doi.org/10.1021/acs.langmuir.8b01802. [cited by applicant]
Yang et al., pH-Responsive Carrier System Based on Carboxylic Acid Modified Mesoporous Silica and Polyelectrolyte for Drug Delivery, Chemistry of Materials, vol. 17, Issue 24, 2005, 5999-6003. (Abstract Only) https://do… [cited by applicant]
Zhao et al., Triblock Copolymer Syntheses of Mesoporous Silica with Periodic 50 to 300 Angstrom Pores, Science, vol. 279, Issue 5350, 1998, 548-552. (Abstract Only) https://doi.org/10.1126/science.279.5350.548. [cited by applicant]
Zhu et al., Metallo-Polyelectrolytes as a Class of Ionic Macromolecules for Functional Materials, Nature Communications, vol. 9, Article No. 4329, 2018, 15 Pages. https://www.nature.com/articles/s41467-018-06475-9. [cited by applicant]