Nanotechnology for Investigating the Chronic Actions of Short-Lived Peptides in Specific Sites of the Brain. *Regul. Pept.* **2007**, *138* (2–3), 59–65. https://doi.org/10.1016/j.regpep.2006.11.021.

(57) Wang, W. Instability, Stabilization, and Formulation of Liquid Protein Pharamceuticals. *Int. J. Pharm.* **1999**, *185*, 129–188.

(58) Bilati, U.; Allémann, E.; Doelker, E. Strategic Approaches for Overcoming Peptide and Protein Instability within Biodegradable Nano- and Microparticles. *Eur. J. Pharm. Biopharm.* **2005**, *59* (3), 375–388. https://doi.org/10.1016/j.ejpb.2004.10.006.

(59) Blocher McTigue, W. C.; Perry, S. L. Protein Encapsulation Using Complex Coacervates: What Nature Has to Teach Us. *Small* **2020**, *16* (27), 1–17. https://doi.org/10.1002/smll.201907671.

(60) Israelachvili, J. N.; Mitchell, D. J.; Ninham, B. W. Theory of Self-Assembly of Hydrocarbon Amphiphiles into Micelles and Bilayers. *J. Chem. Soc. Faraday Trans. 2 Mol. Chem. Phys.* **1976**, *72*, 1525–1568. https://doi.org/10.1039/F29767201525.

(61) Feng, A.; Yuan, J. Smart Nanocontainers: Progress on Novel Stimuli-Responsive Polymer Vesicles. *Macromol. Rapid Commun.* **2014**, *35* (8), 767–779. https://doi.org/10.1002/marc.201300866.

(62) Rideau, E.; Dimova, R.; Schwille, P.; Wurm, F. R.; Landfester, K. Liposomes and Polymersomes: A Comparative Review towards Cell Mimicking. *Chem. Soc. Rev.* **2018**, *47* (23), 8572–8610. https://doi.org/10.1039/c8cs00162f.

(63) Lai, M. H.; Lee, S.; Smith, C. E.; Kim, K.; Kong, H. Tailoring Polymersome Bilayer Permeability Improves Enhanced Permeability and Retention Effect for Bioimaging. *ACS Appl. Mater. Interfaces* **2014**, *6* (13), 10821–10829. https://doi.org/10.1021/am502822n.

(64) Cheng, R.; Meng, F.; Ma, S.; Xu, H.; Liu, H.; Jing, X.; Zhong, Z. Reduction and Temperature Dual-Responsive Crosslinked Polymersomes for Targeted Intracellular Protein Delivery. *J. Mater. Chem.* **2011**, *21* (47), 19013–19020. https://doi.org/10.1039/c1jm13536h.

(65) Wang, X.; Liu, G.; Hu, J.; Zhang, G.; Liu, S. Concurrent Block Copolymer Polymersome Stabilization and Bilayer Permeabilization by Stimuli-Regulated “Traceless” Crosslinking. *Angew. Chemie - Int. Ed.* **2014**, *53* (12), 3138–3142. https://doi.org/10.1002/anie.201310589.

(66) Terreau, O.; Bartels, C.; Eisenberg, A. Effect of Poly(Acrylic Acid) Block Length Distribution on Polystyrene-b-Poly(Acrylic Acid) Block Copolymer Aggregates in Solution. *2*. A Partial Phase Diagram. *Langmuir* **2004**, *20* (3), 637–645. https://doi.org/10.1021/la035557h.

(67) Colletier, J. P.; Chaize, B.; Winterhalter, M.; Fournier, D. Protein Encapsulation in Liposomes: Efficiency Depends on Interactions between Protein and Phospholipid Bilayer. *BMC Biotechnol.* **2002**, *2*, 1–8. https://doi.org/10.1186/1472-6750-2-9.

(68) Walde, P.; Cosentino, K.; Engel, H.; Stano, P. Giant Vesicles: Preparations and Applications. *ChemBioChem* **2010**, *11* (7), 848–865. https://doi.org/10.1002/cbic.201000010.
(69) Hwang, S. Y.; Kim, H. K.; Choo, J.; Seong, G. H.; Hien, T. B. D.; Lee, E. K. Effects of Operating Parameters on the Efficiency of Liposomal Encapsulation of Enzymes. *Colloids Surfaces B: Biointerfaces* **2012**, *94*, 296–303. https://doi.org/10.1016/j.colSURFB.2012.02.008.

(70) Dominak, L. M.; Keating, C. D. Macromolecular Crowding Improves Polymer Encapsulation within Giant Lipid Vesicles. *Langmuir* **2008**, *24* (23), 13565–13571. https://doi.org/10.1021/la8028403.

(71) Lasic, D. D. Les Liposomes. *Recherche* **1989**, *20* (212), 904–913.

(72) Zhu, Y.; Yang, B.; Chen, S.; Du, J. Polymer Vesicles: Mechanism, Preparation, Application, and Responsive Behavior. *Prog. Polym. Sci.* **2017**, *64*, 1–22. https://doi.org/10.1016/j.progpolymsci.2015.05.001.

(73) Carugo, D.; Bottaro, E.; Owen, J.; Stride, E.; Nastruzzi, C. Liposome Production by Microfluidics: Potential and Limiting Factors. *Sci. Rep.* **2016**, *6*, 1–15. https://doi.org/10.1038/srep25876.

(74) Kim, S. H.; Shum, H. C.; Kim, J. W.; Cho, J. C.; Weitz, D. A. Multiple Polymersomes for Programmed Release of Multiple Components. *J. Am. Chem. Soc.* **2011**, *133* (38), 15165–15171. https://doi.org/10.1021/ja205687k.

(75) Weiss, M.; Frohnmayer, J. P.; Benk, L. T.; Haller, B.; Janiesch, J. W.; Heitkamp, T.; Börsch, M.; Lira, R. B.; Dimova, R.; Lipowsky, R.; Bodenschatz, E.; Baret, J. C.; Vidakovic-Koch, T.; Sundmacher, K.; Platzman, I.; Spatz, J. P. Sequential Bottom-up Assembly of Mechanically Stabilized Synthetic Cells by Microfluidics. *Nat. Mater.* **2018**, *17* (1), 89–95. https://doi.org/10.1038/NMAT5005.

(76) Deshpande, S.; Caspi, Y.; Meijering, A. E. C.; Dekker, C. Octanol-Assisted Liposome Assembly on Chip. *Nat. Commun.* **2016**, *7*, 1–9. https://doi.org/10.1038/ncomms10447.

(77) Szoka, F.; Papahadjopoulos, D. Procedure for Preparation of Liposomes with Large Internal Aqueous Space and High Capture by Reverse-Phase Evaporation. *Proc. Natl. Acad. Sci. U. S. A.* **1978**, *75* (9), 4194–4198. https://doi.org/10.1073/pnas.75.9.4194.

(78) Sah, H. Stabilization of Proteins against Methylene Chloride/Water Interface-Induced Denaturation and Aggregation. *J. Control. Release* **1999**, *58* (2), 143–151. https://doi.org/10.1016/S0168-3659(98)00148-5.

(79) Van De Weert, M.; Hoechstetter, J.; Hennink, W. E.; Crommelin, D. J. A. The Effect of a Water/Organic Solvent Interface on the Structural Stability of Lysozyme. *J. Control. Release* **2000**, *68* (3), 351–359. https://doi.org/10.1016/S0168-3659(00)00277-7.

(80) Kwon, Y. M.; Baudys, M.; Knutson, K.; Kim, S. K. In Situ Study of Insulin Aggregation Induced by Water-Organic Solvent Interface. *Pharm. Res.* **2001**, *18* (12), 1754–1759. https://doi.org/10.1023/A:1013334916162.

(81) Yoo, H. S.; Choi, H. K.; Park, T. G. Protein-Fatty Acid Complex for Enhanced Loading and Stability
within Biodegradable Nanoparticles. **J. Pharm. Sci. 2001**, *90* (2), 194–201.
https://doi.org/10.1002/1520-6017(200102)90:2<194::AID-JPS10>3.0.CO;2-Q.

(82) Panganiban, B.; Qiao, B.; Jiang, T.; Delre, C.; Obadia, M. M.; Nguyen, T. D.; Smith, A. A. A.; Hall, A.; Sit, I.; Crosby, M. G.; Dennis, P. B.; Drockenmuller, E.; Olvera, M.; Cruz, D.; Xu, T. Random Heteropolymers Preserve Protein Function in Foreign Environments. *Science* (80-). **2018**, *1243*, 1239–1243. https://doi.org/10.1126/science.aao0335.

(83) Penfold, N. J. W.; Yeow, J.; Boyer, C.; Armes, S. P. Emerging Trends in Polymerization-Induced Self-Assembly. *ACS Macro Lett.* **2019**, *8* (8), 1029–1054.
https://doi.org/10.1021/acsmacrolett.9b00464.

(84) Zhang, W. J.; Hong, C. Y.; Pan, C. Y. Efficient Fabrication of Photosensitive Polymeric Nano-Objects via an Ingenious Formulation of RAFT Dispersion Polymerization and Their Application for Drug Delivery. *Biomacromolecules* **2017**, *18* (4), 1210–1217.
https://doi.org/10.1021/acs.biomac.6b01887.

(85) Charleux, B.; Delaittre, G.; Rieger, J.; D'Agosto, F. Polymerization-Induced Self-Assembly: From Soluble Macromolecules to Block Copolymer Nano-Objects in One Step. *Macromolecules* **2012**, *45* (17), 6753–6765. https://doi.org/10.1021/ma300713f.

(86) D'Agosto, F.; Rieger, J.; Lansalot, M. RAFT-Mediated Polymerization-Induced Self-Assembly. *Angew. Chemie - Int. Ed.* **2020**, *59* (22), 8368–8392. https://doi.org/10.1002/anie.201911758.

(87) Warren, N. J.; Armes, S. P. Polymerization-Induced Self-Assembly of Block Copolymer Nano-Objects via RAFT Aqueous Dispersion Polymerization. *J. Am. Chem. Soc.* **2014**, *136* (29), 10174–10185. https://doi.org/10.1021/ja502843f.

(88) Albertsen, A. N.; Szymaski, J. K.; Pérez-Mercader, J. Emergent Properties of Giant Vesicles Formed by a Polymerization-Induced Self-Assembly (PISA) Reaction. *Sci. Rep.* **2017**, *7*, 41534.
https://doi.org/10.1038/srep41534.

(89) Blackman, L. D.; Varlas, S.; Arno, M. C.; Fayter, A.; Gibson, M. I.; O'Reilly, R. K. Permeable Protein-Loaded Polymersome Cascade Nanoreactors by Polymerization-Induced Self-Assembly. *ACS Macro Lett.* **2017**, *6* (11), 1263–1267. https://doi.org/10.1021/acsmacrolett.7b00725.

(90) Varlas, S.; Blackman, L. D.; Findlay, H. E.; Reading, E.; Booth, P. J.; Gibson, M. I.; O'Reilly, R. K. Photoinitiated Polymerization-Induced Self-Assembly in the Presence of Surfactants Enables Membrane Protein Incorporation into Vesicles. *Macromolecules* **2018**, *51* (16), 6190–6201.
https://doi.org/10.1021/acs.macromol.8b00994.

(91) Kabanov, A. V.; Vinogradov, S. V. Nanogels as Pharmaceutical Carriers: Finite Networks of Infinite Capabilities. *Angew. Chemie - Int. Ed.* **2009**, *48* (30), 5418–5429.
https://doi.org/10.1002/anie.200900441.
(92) Mauri, E.; Giannitelli, S. M.; Trombetta, M.; Rainer, A. Synthesis of Nanogels: Current Trends and Future Outlook. *Gels* **2021**, 7 (2), 1–23. https://doi.org/10.3390/gels7020036.

(93) Chan, M.; Almutairi, A. Nanogels as Imaging Agents for Modalities Spanning the Electromagnetic Spectrum. *Mater. Horizons* **2016**, 3 (1), 21–40. https://doi.org/10.1039/c5mh00161g.

(94) Sanson, N.; Rieger, J. Synthesis of Nanogels/Microgels by Conventional and Controlled Radical Crosslinking Copolymerization. *Polym. Chem.* **2010**, 1 (7), 965–977. https://doi.org/10.1039/c0py00010h.

(95) Taton, D.; Baussard, J. F.; Dupayage, L.; Poly, J.; Gnanou, Y.; Ponsinet, V.; Destarac, M.; Mignaud, C.; Pitois, C. Water Soluble Polymeric Nanogels by Xanthate-Mediated Radical Crosslinking Copolymerisation. *Chem. Commun.* **2006**, No. 18, 1953–1955. https://doi.org/10.1039/b601456a.

(96) Es Sayed, J.; Lorthioir, C.; Perrin, P.; Sanson, N. PEGylated NiPAM Microgels: Synthesis, Characterization and Colloidal Stability. *Soft Matter* **2019**, 15 (5), 963–972. https://doi.org/10.1039/c8sm02156b.

(97) Ryu, J.-H.; Chacko, R. T.; Jiwpanich, S.; Bickerton, S.; Babu, R. P.; Thayumanavan, S. Self-Cross-Linked Polymer Nanogels: A Versatile Nanoscopic Drug Delivery Platform. *J. Am. Chem. Soc.* **2010**, 132 (48), 17227–17235. https://doi.org/10.1021/ja1069932.

(98) Mueller, E.; Alsop, R. J.; Scotti, A.; Bleuel, M.; Rheinstädter, M. C.; Richtering, W.; Hoare, T. Dynamically Cross-Linked Self-Assembled Thermoresponsive Microgels with Homogeneous Internal Structures. *Langmuir* **2018**, 34 (4), 1601–1612. https://doi.org/10.1021/acs.langmuir.7b03664.

(99) Chen, X.; Chen, L.; Yao, X.; Zhang, Z.; He, C.; Zhang, J.; Chen, X. Dual Responsive Supramolecular Nanogels for Intracellular Drug Delivery. *Chem. Commun.* **2014**, 50 (29), 3789–3791. https://doi.org/10.1039/c4cc00016a.

(100) Gao, L.; Zabihi, F.; Ehrmann, S.; Hedtrich, S.; Haag, R. Supramolecular Nanogels Fabricated via Host–Guest Molecular Recognition as Penetration Enhancer for Dermal Drug Delivery. *J. Control. Release* **2019**, 300 (February), 64–72. https://doi.org/10.1016/j.jconrel.2019.02.011.

(101) Es Sayed, J.; Lorthioir, C.; Banet, P.; Perrin, P.; Sanson, N. Reversible Assembly of Microgels by Metallo-Supramolecular Chemistry. *Angew. Chemie - Int. Ed.* **2020**, 59 (18), 7042–7048. https://doi.org/10.1002/anie.201915737.

(102) Chattopadhyay, S.; Heine, E.; Mourran, A.; Richtering, W.; Keul, H.; Möller, M. Waterborne Physically Crosslinked Antimicrobial Nanogels. *Polym. Chem.* **2016**, 7 (2), 364–369. https://doi.org/10.1039/c5py01566a.

(103) Black, K. A.; Priftis, D.; Perry, S. L.; Yip, J.; Byun, W. Y.; Tirrell, M. Protein Encapsulation via Polypeptide Complex Coacervation. *ACS Macro Lett.* **2014**, 3 (10), 1088–1091.
https://doi.org/10.1021/mz500529v.

(104) Perro, A.; Giraud, L.; Coudon, N.; Shanmugathasan, S.; Lapeyre, V.; Goudeau, B.; Douliez, J. P.; Ravaine, V. Self-Coacervation of Ampholyte Polymer Chains as an Efficient Encapsulation Strategy. *J. Colloid Interface Sci.* **2019**, *548*, 275–283. https://doi.org/10.1016/j.jcis.2019.04.033.

(105) Bewersdorff, T.; Gruber, A.; Eravci, M.; Dumbani, M.; Klinger, D.; Haase, A. Amphiphilic Nanogels: Influence of Surface Hydrophobicity on Protein Corona, Biocompatibility and Cellular Uptake. *Int. J. Nanomedicine* **2019**, *14*, 7861–7878. https://doi.org/10.2147/IJN.S215935.

(106) Gruber, A.; Işik, D.; Fontanezi, B. B.; Böttcher, C.; Schäfer-Korting, M.; Klinger, D. A Versatile Synthetic Platform for Amphiphilic Nanogels with Tunable Hydrophobicity. *Polym. Chem.* **2018**, *9* (47), 5572–5584. https://doi.org/10.1039/c8py01123k.

(107) Akagi, T.; Shima, F.; Akashi, M. Intracellular Degradation and Distribution of Protein-Encapsulated Amphiphilic Poly(Amino Acid) Nanoparticles. *Biomaterials* **2011**, *32* (21), 4959–4967. https://doi.org/10.1016/j.biomaterials.2011.03.049.

(108) Krisch, E.; Messager, L.; Gyarmati, B.; Ravaine, V.; Szilágyi, A. Redox- and PH-Responsive Nanogels Based on Thiolated Poly(Aspartic Acid). *Macromol. Mater. Eng.* **2016**, *301* (3), 260–266. https://doi.org/10.1002/mame.201500119.

(109) Simonson, A. W.; Lawanprasert, A.; Goralski, T. D. P.; Keiler, K. C.; Medina, S. H. Bioresponsive Peptide-Polysaccharide Nanogels — A Versatile Delivery System to Augment the Utility of Bioactive Cargo. *Nanomedicine Nanotechnology, Biol. Med.* **2019**, *17*, 391–400. https://doi.org/10.1016/j.nano.2018.10.008.

(110) Plucinski, A.; Lyu, Z.; Schmidt, B. V. K. J. Polysaccharide Nanoparticles: From Fabrication to Applications. *J. Mater. Chem. B* **2021**, *9* (35), 7030–7062. https://doi.org/10.1039/d1tb00628b.

(111) Labie, H.; Perro, A.; Lapeyre, V.; Goudeau, B.; Catargi, B.; Auzély, R.; Ravaine, V. Sealing Hyaluronic Acid Microgels with Oppositely-Charged Polypeptides: A Simple Strategy for Packaging Hydrophilic Drugs with on-Demand Release. *J. Colloid Interface Sci.* **2019**, *535*, 16–27. https://doi.org/10.1016/j.jcis.2018.09.048.

(112) Azagarsamy, M. A.; Alge, D. L.; Radhakrishnan, S. J.; Tibbitt, M. W.; Anseth, K. S. Photocontrolled Nanoparticles for On-Demand Release of Proteins. *Biomacromolecules* **2012**, *13* (8), 2219–2224. https://doi.org/10.1021/bm300646q.

(113) Koppolu, B. prasanth; Smith, S. G.; Ravindranathan, S.; Jayanthi, S.; Suresh Kumar, T. K.; Zaharoff, D. A. Controlling Chitosan-Based Encapsulation for Protein and Vaccine Delivery. *Biomaterials* **2014**, *35* (14), 4382–4389. https://doi.org/10.1016/j.biomaterials.2014.01.078.

(114) Zhang, Y.; Zhu, W.; Wang, B.; Ding, J. A Novel Microgel and Associated Post-Fabrication Encapsulation Technique of Proteins. *J. Control. Release* **2005**, *105* (3), 260–268.
https://doi.org/10.1016/j.jconrel.2005.04.001.

(115) Johansson, C.; Hansson, P.; Malmsten, M. Interaction between Lysozyme and Poly(Acrylic Acid) Microgels. *J. Colloid Interface Sci.* **2007**, *316* (2), 350–359.
https://doi.org/10.1016/j.jcis.2007.07.052.

(116) Bysell, H.; Malmsten, M. Interactions between Homopolypeptides and Lightly Cross-Linked Microgels. *Langmuir* **2009**, *25* (1), 522–528. https://doi.org/10.1021/la8029984.

(117) Coppi, G.; Iannuccelli, V.; Leo, E.; Bernabei, M. T.; Cameroni, R. Protein Immobilization in Crosslinked Alginate Microparticles. *J. Microencapsul.* **2002**, *19* (1), 37–44.
https://doi.org/10.1080/02652040110055621.

(118) Li, Y.; Kleijn, M.; Slaghek, T.; Timmermans, J.; Stuart, M. C.; Norde, W. Lysozyme Uptake and Release by Oxidized Starch Polymer Microgels. *J. Control. Release* **2010**, *148* (1), 1754–1762.
https://doi.org/10.1016/j.jconrel.2010.07.052.

(119) Welsch, N.; Wittemann, A.; Ballauff, M. Enhanced Activity of Enzymes Immobilized in Thermoresponsive Core-Shell Microgels. *J. Phys. Chem. B* **2009**, *113* (49), 16039–16045.
https://doi.org/10.1021/jp907508w.

(120) Zhang, Y.; Zhang, D.; Wang, J. T.; Zhang, X.; Yang, Y. Fabrication of Stimuli-Responsive Nanogels for Protein Encapsulation and Traceless Release without Introducing Organic Solvents, Surfactants, or Small-Molecule Cross-Linkers. *Polym. Chem.* **2021**, *12* (4), 554–563.
https://doi.org/10.1039/d0py01600d.

(121) Shao, P. G.; Bailey, L. C. Stabilization of PH-Induced Degradation of Porcine Insulin in Biodegradable Polyester Microspheres. *Pharm. Dev. Technol.* **1999**, *4* (4), 633–642.
https://doi.org/10.1081/PDT-100101402.

(122) Esser-Kahn, A. P.; Odom, S. A.; Sottos, N. R.; White, S. R.; Moore, J. S. Triggered Release from Polymer Capsules. *Macromolecules* **2011**, *44* (14), 5539–5553. https://doi.org/10.1021/ma201014n.

(123) Peyratout, C. S.; Dähne, L. Tailor-Made Polyelectrolyte Microcapsules: From Multilayers to Smart Containers. *Angew. Chemie - Int. Ed.* **2004**, *43* (29), 3762–3783.
https://doi.org/10.1002/anie.200300568.

(124) Gupta, N.; Kozlovskaya, V.; Dolmat, M.; Kharlampieva, E. Shape Recovery of Spherical Hydrogen-Bonded Multilayer Capsules after Osmotically Induced Deformation. *Langmuir* **2019**, *35* (33), 10910–10919. https://doi.org/10.1021/acs.langmuir.9b01795.

(125) Wang, Z.; Feng, Z.; Gao, C. Stepwise Assembly of the Same Poly Electrolytes Using Host-Guest Interaction to Obtain Microcapsules with Multiresponsive Properties. *Chem. Mater.* **2008**, *20* (13), 4194–4199. https://doi.org/10.1021/cm8003358.

(126) Gil, P. R.; de Koker, S.; de Geest, B. G.; Parak, W. J. Intracellular Processing of Proteins Mediated
by Biodegradable Polyelectrolyte Capsules. *Eur. Cells Mater.* **2010**, *20* (SUPPL.3), 213.

(127) Städler, B.; Price, A. D.; Zelikin, A. N. A Critical Look at Multilayered Polymer Capsules in Biomedicine: Drug Carriers, Artificial Organelles, and Cell Mimics. *Adv. Funct. Mater.* **2011**, *21* (1), 14–28. https://doi.org/10.1002/adfm.201001676.

(128) De Temmerman, M. L.; Demeester, J.; De Vos, F.; De Smedt, S. C. Encapsulation Performance of Layer-by-Layer Microcapsules for Proteins. *Biomacromolecules* **2011**, *12* (4), 1283–1289. https://doi.org/10.1021/bm101559w.

(129) Grigoriev, D. O.; Bukreeva, T.; Möhwald, H.; Shchukin, D. G. New Method for Fabrication of Loaded Micro- and Nanocontainers: Emulsion Encapsulation by Polyelectrolyte Layer-by-Layer Deposition on the Liquid Core. *Langmuir* **2008**, *24* (3), 999–1004. https://doi.org/10.1021/la702873f.

(130) Szczepanowicz, K.; Bazylińska, U.; Pietkiewicz, J.; Szyk-Warszyńska, L.; Wilk, K. A.; Warszyński, P. Biocompatible Long-Sustained Release Oil-Core Polyelectrolyte Nanocarriers: From Controlling Physical State and Stability to Biological Impact. *Adv. Colloid Interface Sci.* **2015**, *222*, 678–691. https://doi.org/10.1016/j.cis.2014.10.005.

(131) Atkin, R.; Davies, P.; Hardy, J.; Vincent, B. Preparation of Aqueous Core/Polymer Shell Microcapsules by Internal Phase Separation. *Macromolecules* **2004**, *37* (21), 7979–7985. https://doi.org/10.1021/ma048902y.

(132) Yu, X.; Zhao, Z.; Nie, W.; Deng, R.; Liu, S.; Liang, R.; Zhu, J.; Ji, X. Biodegradable Polymer Microcapsules Fabrication through a Template-Free Approach. *Langmuir* **2011**, *27* (16), 10265–10273. https://doi.org/10.1021/la201944s.

(133) Roux, R.; Sallet, L.; Alcouffe, P.; Chambert, S. P.; Sintes-Zydowicz, N.; Fleury, E.; Bernard, J. Facile and Rapid Access to Glyconanocapsules by CuAAC Interfacial Polyaddition in Miniemulsion Conditions. *ACS Macro Lett.* **2012**, *1* (8), 1074–1078. https://doi.org/10.1021/mz300281.

(134) Siebert, J. M.; Baier, G.; Musyanovych, A.; Landfester, K. Towards Copper-Free Nanocapsules Obtained by Orthogonal Interfacial “Click” Polymerization in Miniemulsion. *Chem. Commun.* **2012**, *48* (44), 5470–5472. https://doi.org/10.1039/c2cc30253e.

(135) Zhang, S.; Qin, B.; Huang, Z.; Xu, J. F.; Zhang, X. Supramolecular Emulsion Interfacial Polymerization. *ACS Macro Lett.* **2019**, *8* (2), 177–182. https://doi.org/10.1021/acsmacrolett.8b01003.

(136) Malzahn, K.; Marsico, F.; Koynov, K.; Landfester, K.; Weiss, C. K.; Wurm, F. R. Selective Interfacial Olefin Cross Metathesis for the Preparation of Hollow Nanocapsules. *ACS Macro Lett.* **2014**, *3* (1), 40–43. https://doi.org/10.1021/mz400578e.

(137) Breitenkamp, K.; Emrick, T. Novel Polymer Capsules from Amphiphilic Graft Copolymers and
Cross-Metathesis. **J. Am. Chem. Soc. 2003**, *125* (40), 12070–12071.
https://doi.org/10.1021/ja036561i.

(138) Scott, C.; Wu, D.; Ho, C. C.; Co, C. C. Liquid-Core Capsules via Interfacial Polymerization: A Free-Radical Analogy of the Nylon Rope Trick. **J. Am. Chem. Soc. 2005**, *127* (12), 4160–4161.
https://doi.org/10.1021/ja044532h.

(139) Sarkar, D.; El-Khoury, J.; Lopina, S. T.; Hu, J. An Effective Method for Preparing Polymer Nanocapsules with Hydrophobic Acrylic Shell and Hydrophilic Interior by Inverse Emulsion Radical Polymerization. **Macromolecules 2005**, *38* (20), 8603–8605.
https://doi.org/10.1021/ma050661m.

(140) Luo, Y.; Gu, H. A General Strategy for Nano-Encapsulation via Interfacially Confined Living/Controlled Radical Miniemulsion Polymerization. **Macromol. Rapid Commun. 2006**, *27* (1), 21–25.
https://doi.org/10.1002/marc.200500649.

(141) Sun, Q.; Deng, Y. In Situ Synthesis of Temperature-Sensitive Hollow Microspheres via Interfacial Polymerization. **J. Am. Chem. Soc. 2005**, *127* (23), 8274–8275.
https://doi.org/10.1021/ja051487k.

(142) Lambert, G.; Fattal, E.; Pinto-Alphandary, H.; Gulik, A.; Couvreur, P. Polyisobutylcyanoacrylate Nanocapsules Containing an Aqueous Core as a Novel Colloidal Carrier for the Delivery of Oligonucleotides. **Pharm. Res. 2000**, *17* (6), 707–714.
https://doi.org/10.1023/A:1007582332491.

(143) Li, S.; He, Y.; Li, C.; Liu, X. In Vitro Release of Protein from Poly(Butylcyanoacrylate) Nanocapsules with an Aqueous Core. **Colloid Polym. Sci. 2005**, *283* (5), 480–485.
https://doi.org/10.1007/s00396-004-1173-5.

(144) Crespy, D.; Stark, M.; Hoffmann-Richter, C.; Ziener, U.; Landfester, K. Polymeric Nanoreactors for Hydrophilic Reagents Synthesized by Interfacial Polycondensation on Miniemulsion Droplets. **Macromolecules 2007**, *40* (9), 3122–3135.
https://doi.org/10.1021/ma0621932.

(145) Yiamsawas, D.; Baier, G.; Thines, E.; Landfester, K.; Wurm, F. R. Biodegradable Lignin Nanocontainers. **RSC Adv. 2014**, *4* (23), 11661–11663.
https://doi.org/10.1039/c3ra47971d.

(146) Jo, S. M.; Jiang, S.; Graf, R.; Wurm, F. R.; Landfester, K. Aqueous Core and Hollow Silica Nanocapsules for Confined Enzyme Modules. **Nanoscale 2020**, *12* (47), 24266–24272.
https://doi.org/10.1039/d0nr07148j.

(147) Monteillet, H.; Hagemans, F.; Sprakel, J. Charge-Driven Co-Assembly of Polyelectrolytes across Oil-Water Interfaces. **Soft Matter 2013**, *9* (47), 11270–11275.
https://doi.org/10.1039/c3sm52241e.

(148) Kaufman, G.; Boltyanskiy, R.; Nejati, S.; Thiam, A. R.; Loewenberg, M.; Dufresne, E. R.; Osuji, C. O. Single-Step Microfluidic Fabrication of Soft Monodisperse Polyelectrolyte Microcapsules by Interfacial Complexation. **Lab Chip 2014**, *14* (18), 3494–3497.
https://doi.org/10.1039/c4lc00482e.

(149) Ma, Q.; Song, Y.; Kim, J. W.; Choi, H. S.; Shum, H. C. Affinity Partitioning-Induced Self-Assembly
in Aqueous Two-Phase Systems: Templating for Polyelectrolyte Microcapsules. *ACS Macro Lett.* **2016**, *5* (6), 666–670. https://doi.org/10.1021/acsmacrolett.6b00228.

(150) Hann, S. D.; Niepa, T. H. R.; Stebe, K. J.; Lee, D. One-Step Generation of Cell-Encapsulating Compartments via Polyelectrolyte Complexation in an Aqueous Two Phase System. *ACS Appl. Mater. Interfaces* **2016**, *8* (38), 25603–25611. https://doi.org/10.1021/acsmami.6b07939.

(151) Ma, Q.; Yuan, H.; Song, Y.; Chao, Y.; Mak, S. Y.; Shum, H. C. Partitioning-Dependent Conversion of Polyelectrolyte Assemblies in an Aqueous Two-Phase System. *Soft Matter* **2018**, *14* (9), 1552–1558. https://doi.org/10.1039/c7sm02275a.

(152) Huang, X.; Tian, L.; Wang, Z.; Zhang, J.; Chan, Y. S.; Cheng, S. H.; Yao, X. Bioinspired Robust All-Aqueous Droplet via Diffusion-Controlled Interfacial Coacervation. *Adv. Funct. Mater.* **2020**, *30* (49), 1–9. https://doi.org/10.1002/adfm.202004166.

(153) Chao, Y.; Shum, H. C. Emerging Aqueous Two-Phase Systems: From Fundamentals of Interfaces to Biomedical Applications. *Chem. Soc. Rev.* **2020**, *49* (1), 114–142. https://doi.org/10.1039/c9cs00466a.

(154) Zhang, L.; Cai, L. H.; Lienemann, P. S.; Rossow, T.; Polenz, I.; Vallmajo-Martin, Q.; Ehrbar, M.; Na, H.; Mooney, D. J.; Weitz, D. A. One-Step Microfluidic Fabrication of Polyelectrolyte Microcapsules in Aqueous Conditions for Protein Release. *Angew. Chemie - Int. Ed.* **2016**, *55* (43), 13470–13474. https://doi.org/10.1002/anie.201606960.

(155) Hann, S. D.; Stebe, K. J.; Lee, D. All-Aqueous Assemblies via Interfacial Complexation: Toward Artificial Cell and Microniche Development. *Langmuir* **2017**, *33* (39), 10107–10117. https://doi.org/10.1021/acs.langmuir.7b02237.

(156) Kim, M.; Doh, J.; Lee, D. PH-Induced Softening of Polyelectrolyte Microcapsules without Apparent Swelling. *ACS Macro Lett.* **2016**, *5* (4), 487–492. https://doi.org/10.1021/acsmacrolett.6b00124.

(157) Duan, G.; Haase, M. F.; Stebe, K. J.; Lee, D. One-Step Generation of Salt-Responsive Polyelectrolyte Microcapsules via Surfactant-Organized Nanoscale Interfacial Complexation in Emulsions (SO NICE). *Langmuir* **2018**, *34* (3), 847–853. https://doi.org/10.1021/acs.langmuir.7b01526.

(158) Zou, Y.; Song, J.; You, X.; Yao, J.; Xie, S.; Jin, M.; Wang, X.; Yan, Z.; Zhou, G.; Shui, L. Interfacial Complexation Induced Controllable Fabrication of Stable Polyelectrolyte Microcapsules Using All-Aqueous Droplet Microfluidics for Enzyme Release. *ACS Appl. Mater. Interfaces* **2019**, *11* (23), 21227–21238. https://doi.org/10.1021/acsami.9b02788.

(159) Kim, B. J.; Han, S.; Lee, K. B.; Choi, I. S. Biphasic Supramolecular Self-Assembly of Ferric Ions and Tannic Acid across Interfaces for Nanofilm Formation. *Adv. Mater.* **2017**, *29* (28), 1–7. https://doi.org/10.1002/adma.201700784.
(160) Dupré De Baubigny, J.; Trégouët, C.; Salez, T.; Pantoustier, N.; Perrin, P.; Reyssat, M.; Monteux, C. One-Step Fabrication of PH-Responsive Membranes and Microcapsules through Interfacial H-Bond Polymer Complexation. *Sci. Rep.* **2017**, *7* (1), 1–7. https://doi.org/10.1038/s41598-017-01374-3.

(161) Wang, Y.; Chou, T.; Sukhishvili, S. A. Spontaneous, One-Pot Assembly of PH-Responsive Hydrogen-Bonded Polymer Capsules. *ACS Macro Lett.* **2016**, *5* (1), 35–39. https://doi.org/10.1021/acsmacrolett.5b00716.

(162) Trongsatitkul, T.; Budhlall, B. M. Microgels or Microcapsules? Role of Morphology on the Release Kinetics of Thermoresponsive PNIPAm-Co-PEGMa Hydrogels. *Polym. Chem.* **2013**, *4* (5), 1502–1516. https://doi.org/10.1039/c2py20889j.

(163) Gan, D.; Lyon, L. A. Tunable Swelling Kinetics in Core - Shell Hydrogel Nanoparticles. *J. Am. Chem. Soc.* **2001**, *123* (31), 7511–7517. https://doi.org/10.1021/ja010609f.

(164) Manuela Gaspar, M.; Blanco, D.; Cruz, M. E. M.; José Alonso, M. Formulation of L-Asparaginase-Loaded Poly(Lactide-Co-Glycolide) Nanoparticles: Influence of Polymer Properties on Enzyme Loading, Activity and in Vitro Release. *J. Control. Release* **1998**, *52* (1–2), 53–62. https://doi.org/10.1016/S0168-3659(97)00196-X.

(165) Pasparakis, G.; Tsitsilianis, C. LCST Polymers: Thermoresponsive Nanostructured Assemblies towards Bioapplications. *Polymer* (Guildf). **2020**, *211*, 123146. https://doi.org/10.1016/j.polymer.2020.123146.

(166) Seuring, J.; Agarwal, S. Polymers with Upper Critical Solution Temperature in Aqueous Solution. *Macromol. Rapid Commun.* **2012**, *33* (22), 1898–1920. https://doi.org/10.1002/marc.201200433.

(167) Halperin, A.; Kröger, M.; Winnik, F. M. Poly(N-Isopropylacrylamide) Phase Diagrams: Fifty Years of Research. *Angew. Chem. Int. Ed.* **2015**, *54* (51), 15342–15367. https://doi.org/10.1002/anie.201506663.

(168) Ma, Z.; Jia, X.; Hu, J.; Zhang, G.; Zhou, F.; Liu, Z.; Wang, H. Dual-Responsive Capsules with Tunable Low Critical Solution Temperatures and Their Loading and Release Behavior. *Langmuir* **2013**, *29* (19), 5631–5637. https://doi.org/10.1021/la400025j.

(169) Hoogenboom, R.; Schlaad, H. Thermoresponsive Poly(2-Oxazoline)s, Polypeptoids, and Polypeptides. *Polym. Chem.* **2017**, *8* (1), 24–40. https://doi.org/10.1039/c6py01320a.

(170) Cortez-Lemus, N. A.; Licea-Claverie, A. Poly(N-Vinylcaprolactam), a Comprehensive Review on a Thermoresponsive Polymer Becoming Popular. *Prog. Polym. Sci.* **2016**, *53*, 1–51. https://doi.org/10.1016/j.progpolymsci.2015.08.001.

(171) Nolan, C. M.; Gelbaum, L. T.; Lyon, L. A. 1H NMR Investigation of Thermally Triggered Insulin Release from Poly(N-Isopropylacrylamide) Microgels. *Biomacromolecules* **2006**, *7* (10), 2918–
2922. https://doi.org/10.1021/bm060718s.

(172) Qin, S.; Geng, Y.; Discher, D. E.; Yang, S. Temperature-Controlled Assembly and Release from Polymer Vesicles of Poly(Ethylene Oxide)-Block-Poly(N-Isopropylacrylamide). *Adv. Mater.* **2006**, *18* (21), 2905–2909. https://doi.org/10.1002/adma.200601019.

(173) Gao, H.; Yang, W.; Min, K.; Zha, L.; Wang, C.; Fu, S. Thermosensitive Poly(N-Isopropylacrylamide) Nanocapsules with Controlled Permeability. *Polymer (Guildf)*. **2005**, *46*, 1087–1093. https://doi.org/10.1016/j.polymer.2004.11.078.

(174) Liu, F.; Kozlovskaya, V.; Medipelli, S.; Xue, B.; Ahmad, F.; Saeed, M.; Cropek, D.; Kharlampieva, E. Temperature-Sensitive Polymersomes for Controlled Delivery of Anticancer Drugs. *Chem. Mater.* **2015**, *27* (23), 7945–7956. https://doi.org/10.1021/acs.chemmater.5b03048.

(175) Amstad, E.; Kim, S. H.; Weitz, D. A. Photo- and Thermoresponsive Polymersomes for Triggered Release. *Angew. Chemie - Int. Ed.* **2012**, *51* (50), 12499–12503. https://doi.org/10.1002/anie.201206531.

(176) Yu, Y. L.; Zhang, M. J.; Xie, R.; Ju, X. J.; Wang, J. Y.; Pi, S. W.; Chu, L. Y. Thermo-Responsive Monodisperse Core-Shell Microspheres with PNIPAM Core and Biocompatible Porous Ethyl Cellulose Shell Embedded with PNIPAM Gates. *J. Colloid Interface Sci.* **2012**, *376* (1), 97–106. https://doi.org/10.1016/j.jcis.2012.03.028.

(177) Seuring, J.; Agarwal, S. Polymers with Upper Critical Solution Temperature in Aqueous Solution: Unexpected Properties from Known Building Blocks. *ACS Macro Lett.* **2013**, *2* (7), 597–600. https://doi.org/10.1021/mz400227y.

(178) Fu, W.; Luo, C.; Morin, E. A.; He, W.; Li, Z.; Zhao, B. UCST-Type Thermosensitive Hairy Nanogels Synthesized by RAFT Polymerization-Induced Self-Assembly. *ACS Macro Lett.* **2017**, *6* (2), 127–133. https://doi.org/10.1021/acsmacrolett.6b00888.

(179) Wang, Y.; Hu, L.; Yin, Q.; Du, K.; Zhang, T.; Yin, Q. Multi-Responsive Hollow Nanospheres Self-Assembly by Amphiphilic Random Copolymer and Azobenzene. *Polymer (Guildf)*. **2019**, *175* (April), 235–242. https://doi.org/10.1016/j.polymer.2019.04.071.

(180) Morimoto, N.; Oishi, Y.; Yamamoto, M. The Design of Sulfobetaine Polymers with Thermoresponsiveness under Physiological Salt Conditions. *Macromol. Chem. Phys.* **2020**, *221* (5), 1–7. https://doi.org/10.1002/macp.201900429.

(181) Niskanen, J.; Tenhu, H. How to Manipulate the Upper Critical Solution Temperature (UCST)? *Polym. Chem.* **2017**, *8* (1), 220–232. https://doi.org/10.1039/c6py01612j.

(182) Seuring, J.; Bayer, F. M.; Huber, K.; Agarwal, S. Upper Critical Solution Temperature of Poly(N-Acryloyl Glycinamide) in Water: A Concealed Property. *Macromolecules* **2012**, *45* (1), 374–384. https://doi.org/10.1021/ma202059t.
(183) Yu, X.; Liu, J.; Xin, Y.; Zhan, M.; Xiao, J.; Lu, L.; Peng, S. Temperature and Salt Responsive Zwitterionic Polysulfamide-Based Nanogels with Surface Regeneration Ability and Controlled Drug Release. *Polym. Chem.* **2019**, *10* (47), 6423–6431. https://doi.org/10.1039/c9py01548e.

(184) Maji, T.; Banerjee, S.; Biswas, Y.; Mandal, T. K. Dual-Stimuli-Responsive L-Serine-Based Zwitterionic UCST-Type Polymer with Tunable Thermosensitivity. *Macromolecules* **2015**, *48* (14), 4957–4966. https://doi.org/10.1021/acs.macromol.5b01099.

(185) Seuring, J.; Agarwal, S. First Example of a Universal and Cost-Effective Approach: Polymers with Tunable Upper Critical Solution Temperature in Water and Electrolyte Solution. *Macromolecules* **2012**, *45* (9), 3910–3918. https://doi.org/10.1021/ma300355k.

(186) Asadujjaman, A.; Kent, B.; Bertin, A. Phase Transition and Aggregation Behaviour of an UCST-Type Copolymer Poly(Acrylamide-Co-Acrylonitrile) in Water: Effect of Acrylonitrile Content, Concentration in Solution, Copolymer Chain Length and Presence of Electrolyte. *Soft Matter* **2017**, *13* (3), 658–669. https://doi.org/10.1039/c6sm02262f.

(187) Bordat, A.; Soliman, N.; Ben Chraït, I.; Manerlax, K.; Yagoubi, N.; Boissenot, T.; Nicolas, J.; Tsapis, N. The Crucial Role of Macromolecular Engineering, Drug Encapsulation and Dilution on the Thermoresponsiveness of UCST Diblock Copolymer Nanoparticles Used for Hyperthermia. *Eur. J. Pharm. Biopharm.* **2019**, *142* (June), 281–290. https://doi.org/10.1016/j.ejpb.2019.07.001.

(188) Augé, A.; Fortin, D.; Tong, X.; Zhao, Y. Nanogel-like UCST Triblock Copolymer Micelles Showing Large Volume Expansion before Abrupt Dissolution. *Polym. Chem.* **2018**, *9* (37), 4660–4673. https://doi.org/10.1039/c8py00960k.

(189) Echeverria, C.; López, D.; Mijangos, C. UCST Responsive Microgels of Poly(Acrylamide-Acrylic Acid) Copolymers: Structure and Viscoelastic Properties. *Macromolecules* **2009**, *42* (22), 9118–9123. https://doi.org/10.1021/ma901316k.

(190) Wolf, T.; Rheinberger, T.; Simon, J.; Wurm, F. R. Reversible Self-Assembly of Degradable Polymersomes with Upper Critical Solution Temperature in Water. **2017**. https://doi.org/10.1021/jacs.7b02723.

(191) Huang, X.; Mutlu, H.; Lin, S.; Theato, P. Oxygen-Switchable Thermo-Responsive Polymers with Unprecedented UCST in Water. *Eur. Polym. J.* **2021**, *142* (August 2020), 110156. https://doi.org/10.1016/j.eurpolymj.2020.110156.

(192) Jacques, S. L. Optical Properties of Biological Tissues: A Review. *Phys. Med. Biol.* **2013**, *58* (14), 5007–5008. https://doi.org/10.1088/0031-9155/58/14/5007.

(193) Bertrand, O.; Gohy, J. F. Photo-Responsive Polymers: Synthesis and Applications. *Polym. Chem.* **2017**, *8* (1), 52–73. https://doi.org/10.1039/c6py01082b.

(194) Patnaik, S.; Sharma, A. K.; Garg, B. S.; Gandhi, R. P.; Gupta, K. C. Photoregulation of Drug Release
in Azo-Dextran Nanogels. *Int. J. Pharm.* **2007**, *342* (1-2), 184-193.
https://doi.org/10.1016/j.ijpharm.2007.04.038.

(195) Lin, H.; Xiao, W.; Qin, S. Y.; Cheng, S. X.; Zhang, X. Z. Switch on/off Microcapsules for Controllable Photosensitive Drug Release in a “release-Cease-Recommence” Mode. *Polym. Chem.* **2014**, *5* (15), 4437-4440. https://doi.org/10.1039/c4py00564c.

(196) Wang, X.; Hu, J.; Liu, G.; Tian, J.; Wang, H.; Gong, M.; Liu, S. Reversibly Switching Bilayer Permeability and Release Modules of Photochromic Polymersomes Stabilized by Cooperative Noncovalent Interactions. *J. Am. Chem. Soc.* **2015**, *137* (48), 15262-15275.
https://doi.org/10.1021/jacs.5b10127.

(197) Rifaie-Graham, O.; Ulrich, S.; Galensowske, N. F. B.; Balog, S.; Chami, M.; Rentsch, D.; Hemmer, J. R.; Read De Alaniz, J.; Boesel, L. F.; Bruns, N. Wavelength-Selective Light-Responsive DASA-Functionalized Polymersome Nanoreactors. *J. Am. Chem. Soc.* **2018**, *140* (25), 8027-8036.
https://doi.org/10.1021/jacs.8b04511.

(198) Lin, L.; Yan, Z.; Gu, J.; Zhang, Y.; Feng, Z.; Yu, Y. UV-Responsive Behavior of Azopyridine-Containing Diblock Copolymeric Vesicles: Photoinduced Fusion, Disintegration and Rearrangement. *Macromol. Rapid Commun.* **2009**, *30* (13), 1089-1093.
https://doi.org/10.1002/marc.200900105.

(199) Mabrouk, E.; Cuvelier, D.; Brochard-Wyart, F.; Nassoy, P.; Li, M. H. Bursting of Sensitive Polymersomes Induced by Curling. *Proc. Natl. Acad. Sci. U. S. A.* **2009**, *106* (18), 7294-7298.
https://doi.org/10.1073/pnas.0813157106.

(200) Han, D.; Tong, X.; Zhao, Y. Fast Photodegradable Block Copolymer Micelles for Burst Release. *Macromolecules* **2011**, *44* (3), 437-439. https://doi.org/10.1021/ma102778d.

(201) Cabane, E.; Malinova, V.; Meier, W. Synthesis of Photocleavable Amphiphilic Block Copolymers: Toward the Design of Photosensitive Nanocarriers. *Macromol. Chem. Phys.* **2010**, *211* (17), 1847-1856. https://doi.org/10.1002/macp.201000151.

(202) Lee, J. S.; Deng, X.; Han, P.; Cheng, J. Dual Stimuli-Responsive Poly(β-Amino Ester) Nanoparticles for On-Demand Burst Release. *Macromol. Biosci.* **2015**, *15* (9), 1314-1322.
https://doi.org/10.1002/mabi.201500111.

(203) Cao, Z.; Li, Q.; Wang, G. Photodegradable Polymer Nanocapsules Fabricated from Dimethyldiethoxysilane Emulsion Templates for Controlled Release. *Polym. Chem.* **2017**, *8* (44), 6817-6823. https://doi.org/10.1039/c7py01153a.

(204) Zhu, K.; Liu, G.; Zhang, G.; Hu, J.; Liu, S. Engineering Cross-Linkable Plasmonic Vesicles for Synergistic Chemo-Photothermal Therapy Using Orthogonal Light Irradiation. *Macromolecules* **2018**, *51* (21), 8530-8538. https://doi.org/10.1021/acs.macromol.8b01653.
(205) Fomina, N.; McFearin, C.; Sermsakdi, M.; Edigin, O.; Almutairi, A. UV and Near-IR Triggered Release from Polymeric Nanoparticles. *J. Am. Chem. Soc.* **2010**, *132* (28), 9540–9542. https://doi.org/10.1021/ja102595j.

(206) Liu, G.; Wang, X.; Hu, J.; Zhang, G.; Liu, S. Self-Immolative Polymersomes for High-Efficiency Triggered Release and Programmed Enzymatic Reactions. *J. Am. Chem. Soc.* **2014**, *136* (20), 7492–7497. https://doi.org/10.1021/ja5030832.

(207) Peyret, A.; Ibarboure, E.; Tron, A.; Beauté, L.; Rust, R.; Sandre, O.; McClenaghan, N. D.; Lecommandoux, S. Polymersome Popping by Light-Induced Osmotic Shock under Temporal, Spatial, and Spectral Control. *Angew. Chemie - Int. Ed.* **2017**, *56* (6), 1566–1570. https://doi.org/10.1002/anie.201609231.

(208) Paret, N.; Trachsel, A.; Berthier, D. L.; Herrmann, A. Controlled Release of Encapsulated Bioactive Volatiles by Rupture of the Capsule Wall through the Light-Induced Generation of a Gas. *Angew. Chemie - Int. Ed.* **2015**, *54* (7), 2275–2279. https://doi.org/10.1002/anie.201410778.

(209) Brongersma, M. L.; Halas, N. J.; Nordlander, P. Plasmon-Induced Hot Carrier Science and Technology. *Nat. Nanotechnol.* **2015**, *10* (1), 25–34. https://doi.org/10.1038/nnano.2014.311.

(210) Baffou, G. *Thermoplasmonics: Heating Metal Nanoparticles Using Light*; Cambridge University Press, 2017. https://doi.org/10.1017/9781108289801.

(211) Liz-Marzan, L. M. Tailoring Surface Plasmons through the Morphology and Assembly of Metal Nanoparticles. *Langmuir* **2006**, *22* (1), 32–41.

(212) Baffou, G.; Quidant, R.; Girard, C. Heat Generation in Plasmonic Nanostructures: Influence of Morphology. *Appl. Phys. Lett.* **2009**, *94* (15). https://doi.org/10.1063/1.3116645.

(213) Attia, Y. A.; Buceta, D.; Requejo, F. G.; Giovanetti, L. J.; López-Quintela, M. A. Photostability of Gold Nanoparticles with Different Shapes: The Role of Ag Clusters. *Nanoscale* **2015**, *7* (26), 11273–11279. https://doi.org/10.1039/c5nr01887k.

(214) Mathiyazhakan, M.; Wiraja, C.; Xu, C. A Concise Review of Gold Nanoparticles-Based Photo-Responsive Liposomes for Controlled Drug Delivery. *Nano-Micro Lett.* **2018**, *10* (1), 1–10. https://doi.org/10.1007/s40820-017-0166-0.

(215) Disalvo, G. M.; Robinson, A. R.; Aly, M. S.; Hoglund, E. R.; O’malley, S. M.; Griepenburg, J. C. Polymersome Poration and Rupture Mediated by Plasmonic Nanoparticles in Response to Single-Pulse Irradiation. *Polymers (Basel)*. **2020**, *12* (10), 1–14. https://doi.org/10.3390/polym12102381.

(216) Radt, B.; Smith, T. A.; Caruso, F. Optically Addressable Nanostructured Capsules. *Adv. Mater.* **2004**, *16* (23–24), 2184–2189. https://doi.org/10.1002/adma.200400920.

(217) Shao, J.; Xuan, M.; Si, T.; Dai, L.; He, Q. Biointerfacing Polymeric Microcapsules for in Vivo Near-Infrared Light-Triggered Drug Release. *Nanoscale* **2015**, *7* (45), 19092–19098.
https://doi.org/10.1039/c5nr06350g.

(218) Lee, M. H.; Hribar, K. C.; Brugarolas, T.; Kamat, N. P.; Burdick, J. A.; Lee, D. Harnessing Interfacial Phenomena to Program the Release Properties of Hollow Microcapsules. *Adv. Funct. Mater.* **2012**, *22* (1), 131–138. https://doi.org/10.1002/adfm.201101303.

(219) Sershen, S. R.; Westcott, S. L.; Halas, N. J.; West, J. L. Temperature-Sensitive Polymer-Nanoshell Composites for Photothermally Modulated Drug Delivery. *J. Biomed. Mater. Res. 2000*, *51* (3), 293–298. https://doi.org/10.1002/1097-4636(20000905)51:3<293::AID-JBM1>3.0.CO;2-T.

(220) Kang, H.; Trondoli, A. C.; Zhu, G.; Chen, Y.; Chang, Y. J.; Liu, H.; Huang, Y. F.; Zhang, X.; Tan, W. Near-Infrared Light-Responsive Core-Shell Nanogels for Targeted Drug Delivery. *ACS Nano* **2011**, *5* (6), 5094–5099. https://doi.org/10.1021/nn201171r.

(221) Jeong, W. C.; Kim, S. H.; Yang, S. M. Photothermal Control of Membrane Permeability of Microcapsules for On-Demand Release. *ACS Appl. Mater. Interfaces* **2014**, *6* (2), 826–832. https://doi.org/10.1021/am4037993.

(222) Lin, Y. C.; Fang, T. Y.; Kao, H. Y.; Tseng, W. C. Nanoassembly of UCST Polypeptide for NIR-Modulated Drug Release. *Biochem. Eng. J.* **2021**, *176*, 108194. https://doi.org/10.1016/j.bej.2021.108194.

(223) Zhang, H.; Guo, S.; Fu, S.; Zhao, Y. A Near-Infrared Light-Responsive Hybrid Hydrogel Based on UCST Triblock Copolymer and Gold Nanorods. *Polymers (Basel)*. **2017**, *9* (6). https://doi.org/10.3390/polym9060238.

(224) Hui, L.; Qin, S.; Yang, L. Upper Critical Solution Temperature Polymer, Photothermal Agent, and Erythrocyte Membrane Coating: An Unexplored Recipe for Making Drug Carriers with Spatiotemporally Controlled Cargo Release. *ACS Biomater. Sci. Eng.* **2016**, *2* (12), 2127–2132. https://doi.org/10.1021/acsbiomaterials.6b00459.

(225) Deng, Y.; Käfer, F.; Chen, T.; Jin, Q.; Ji, J.; Agarwal, S. Let There Be Light: Polymeric Micelles with Upper Critical Solution Temperature as Light-Triggered Heat Nanogenerators for Combating Drug-Resistant Cancer. *Small* **2018**, *14* (37), 1–10. https://doi.org/10.1002/smll.201802420.

(226) Augé, A.; Camerel, F.; Benoist, A.; Zhao, Y. Near-Infrared Light-Responsive UCST-Nanogels Using an Efficient Nickel-Bis(Dithiolene) Photothermal Crosslinker. *Polym. Chem.* **2020**, *11* (23), 3863–3875. https://doi.org/10.1039/d0py00567c.

(227) Huang, X.; Brazel, C. S. On the Importance and Mechanisms of Burst Release in Matrix-Controlled Drug Delivery Systems. *J. Control. Release* **2001**, *73* (2–3), 121–136. https://doi.org/10.1016/S0168-3659(01)00248-6.

(228) Mai, X.; Chang, Y.; You, Y.; He, L.; Chen, T. Designing Intelligent Nano-Bomb with on-Demand Site-Specific Drug Burst Release to Synergize with High-Intensity Focused Ultrasound Cancer
Ablation. **J. Control. Release** **2021**, **331** (September 2020), 270-281.
https://doi.org/10.1016/j.jconrel.2020.09.051.

(229) Zhu, T. F.; Szostak, J. W. Exploding Vesicles. *J. Syst. Chem.* **2011**, *2* (1), 2-7.
https://doi.org/10.1186/1759-2208-2-4.

(230) Zhang, W.; Qu, L.; Pei, H.; Qin, Z.; Didier, J.; Wu, Z.; Bobe, F.; Ingber, D. E.; Weitz, D. A. Controllable Fabrication of Inhomogeneous Microcapsules for Triggered Release by Osmotic Pressure. *Small* **2019**, *15* (42), 1-7. https://doi.org/10.1002/smll.201903087.

(231) Liu, L.; Wang, W.; Ju, X. J.; Xie, R.; Chu, L. Y. Smart Thermo-Triggered Squirting Capsules for Nanoparticle Delivery. *Soft Matter* **2010**, *6* (16), 3759-3763. https://doi.org/10.1039/c002231d.

(232) Sankaranarayanan, J.; Mahmoud, E. a; Kim, G.; Morachis, M.; Almutairi, A. Multiresponse Strategies To Modulate Nanoparticles. *ACS Nano* **2010**, *4* (10), 5930-5936.

(233) Scott, R. L. The Solubility of Fluorocarbons. *J. Am. Chem. Soc.* **1948**, *70* (12), 4090-4093.
https://doi.org/10.1021/ja01192a036.

(234) Bai, Y.; He, X.; Liu, D.; Patil, S. N.; Bratton, D.; Huebner, A.; Hollfelder, F.; Abell, C.; Huck, W. T. S. A Double Droplet Trap System for Studying Mass Transport across a Droplet-Droplet Interface. *Lab Chip* **2010**, *10* (10), 1281-1285. https://doi.org/10.1039/b925133b.

(235) Gruner, P.; Riechers, B.; Chacòn Orellana, L. A.; Brosseau, Q.; Maes, F.; Beneyton, T.; Pekin, D.; Baret, J. C. Stabilisers for Water-in-Fluorinated-Oil Dispersions: Key Properties for Microfluidic Applications. *Curr. Opin. Colloid Interface Sci.* **2015**, *20* (3), 183-191.
https://doi.org/10.1016/j.cocis.2015.07.005.

(236) Lowe, K. C.; Davey, M. R.; Power, J. B. Perfluorochemicals: Their Applications and Benefits to Cell Culture. *Trends Biotechnol.* **1998**, *16* (6), 272-277. https://doi.org/10.1016/S0167-7799(98)01205-0.

(237) Giaever, I.; Keese, C. R. Behavior of Cells at Fluid Interfaces. *Proc. Natl. Acad. Sci. U. S. A.* **1983**, *80* (11), 2191-222. https://doi.org/10.1073/pnas.80.1.219.

(238) Lowe, K. C. Fluorinated Blood Substitutes and Oxygen Carriers. *J. Fluor. Chem.* **2001**, *109* (1), 59-65. https://doi.org/10.1016/S0022-1139(01)00374-8.

(239) Roach, L. S.; Song, H.; Ismagilov, R. F. Controlling Nonspecific Protein Adsorption in a Plug-Based Microfluidic System by Controlling Interfacial Chemistry Using Fluorous-Phase Surfactants. *Anal. Chem.* **2005**, *77* (3), 785-796. https://doi.org/10.1021/ac049061w.

(240) Holtze, C.; Rowat, A. C.; Agresti, J. J.; Hutchison, J. B.; Angilè, F. E.; Schmitz, C. H. J.; Köster, S.; Duan, H.; Humphry, K. J.; Scanga, R. A.; Johnson, J. S.; Pisignano, D.; Weitz, D. A. Biocompatible Surfactants for Water-in-Fluorocarbon Emulsions. *Lab Chip* **2008**, *8* (10), 1632-1639.
https://doi.org/10.1039/b806706f.
(241) Wagner, O.; Thiele, J.; Weinhart, M.; Mazutis, L.; Weitz, D. A.; Huck, W. T. S.; Haag, R. Biocompatible Fluorinated Polyglycerols for Droplet Microfluidics as an Alternative to PEG-Based Copolymer Surfactants. *Lab Chip* **2016**, 16 (1), 65–69. https://doi.org/10.1039/c5lc00823a.

(242) Dejournette, C. J.; Kim, J.; Medlen, H.; Li, X.; Vincent, L. J.; Easley, C. J. Creating Biocompatible Oil-Water Interfaces without Synthesis: Direct Interactions between Primary Amines and Carboxylated Perfluorocarbon Surfactants. *Anal. Chem.* **2013**, 85 (21), 10556–10564. https://doi.org/10.1021/ac4026048.

(243) O’Neal, K. L.; Geib, S.; Weber, S. G. Extraction of Pyridines into Fluorous Solvents Based on Hydrogen Bond Complex Formation with Carboxylic Acid Receptors. *Anal. Chem.* **2007**, 79 (8), 3117–3125. https://doi.org/10.1021/ac062287+.

(244) O’Neal, K. L.; Weber, S. G. Molecular and Ionic Hydrogen Bond Formation in Fluorous Solvents. *J. Phys. Chem. B* **2009**, 113 (1), 149–158. https://doi.org/10.1021/jp8084155.

(245) Parker, R. M.; Zhang, J.; Zheng, Y.; Coulston, R. J.; Smith, C. A.; Salmon, A. R.; Yu, Z.; Scherman, O. A.; Abell, C. Electrostatically Directed Self-Assembly of Ultrathin Supramolecular Polymer Microcapsules. *Adv. Funct. Mater.* **2015**, 25 (26), 4091–4100. https://doi.org/10.1002/adfm.201501079.

(246) Yu, Z.; Zhang, J.; Coulston, R. J.; Parker, R. M.; Biedermann, F.; Liu, X.; Scherman, O. A.; Abell, C. Supramolecular Hydrogel Microcapsules via Cucurbit[8]Uril Host-Guest Interactions with Triggered and UV-Controlled Molecular Permeability. *Chem. Sci.* **2015**, 6 (8), 4929–4933. https://doi.org/10.1039/c5sc01440a.

(247) Dalier, F.; Eghiaian, F.; Scheuring, S.; Marie, E.; Tribet, C. Temperature-Switchable Control of Ligand Display on Adlayers of Mixed Poly(Lysine)-g-(PEO) and Poly(Lysine)-g-(Ligand-Modified Poly-N-Isopropylacrylamide). *Biomacromolecules* **2016**, 17 (5), 1727–1736. https://doi.org/10.1021/acs.biomac.6b00136.

(248) Doan, V.; Köppe, R.; Kasai, P. H. Dimerization of Carboxylic Acids and Salts: An IR Study in Perfluoropolyether Media. *J. Am. Chem. Soc.* **1997**, 119 (41), 9810–9815. https://doi.org/10.1021/ja970304u.

(249) Boswell, P. G.; Lugert, E. C.; Rábai, J.; Amin, E. A.; Bühlmann, P. Coordinative Properties of Highly Fluorinated Solvents with Amino and Ether Groups. *J. Am. Chem. Soc.* **2005**, 127 (48), 16976–16984. https://doi.org/10.1021/ja055816k.

(250) Riechers, B. Dynamics of Surfactants at Soft Interfaces Using Droplet-Based Microfluidics Dissertation Birte Riechers. *PhD thesis* **2015**.

(251) Riechers, B.; Maes, F.; Akoury, E.; Semin, B.; Gruner, P.; Baret, J. C. Surfactant Adsorption Kinetics in Microfluidics. *Proc. Natl. Acad. Sci. U. S. A.* **2016**, 113 (41), 11465–11470.
https://doi.org/10.1073/pnas.1604307113.

(252) Csucs, G.; Michel, R.; Lussi, J. W.; Textor, M.; Danuser, G. Microcontact Printing of Novel Co-Polymers in Combination with Proteins for Cell-Biological Applications. *Biomaterials* **2003**, *24* (10), 1713–1720. https://doi.org/10.1016/S0142-9612(02)00568-9.

(253) Gruner, P.; Riechers, B.; Semin, B.; Lim, J.; Johnston, A.; Short, K.; Baret, J. C. Controlling Molecular Transport in Minimal Emulsions. *Nat. Commun.* **2016**, *7*. https://doi.org/10.1038/ncomms10392.

(254) Etienne, G.; Vian, A.; Biočanin, M.; Deplancke, B.; Amstad, E. Cross-Talk between Emulsion Drops: How Are Hydrophilic Reagents Transported across Oil Phases? *Lab Chip* **2018**, *18* (24), 3903–3912. https://doi.org/10.1039/c8lc01000e.

(255) Ali, S.; Prabhu, V. Relaxation Behavior by Time-Salt and Time-Temperature Superpositions of Polyelectrolyte Complexes from Coacervate to Precipitate. *Gels* **2018**, *4* (1), 11. https://doi.org/10.3390/gels4010011.

(256) Sing, C. E.; Perry, S. L. Recent Progress in the Science of Complex Coacervation. *Soft Matter* **2020**, *16* (12), 2885–2914. https://doi.org/10.1039/d0sm00001a.

(257) Chen, Y.; Yang, M.; Schlenoff, J. B. Glass Transitions in Hydrated Polyelectrolyte Complexes. *Macromolecules* **2021**, *54* (8), 3822–3831. https://doi.org/10.1021/acs.macromol.0c02682.

(258) Hawe, A.; Sutter, M.; Jiskoot, W. Extrinsic Fluorescent Dyes as Tools for Protein Characterization. *Pharm. Res.* **2008**, *25* (7), 1487–1499. https://doi.org/10.1007/s11095-007-9516-9.

(259) Gasymov, O. K.; Glasgow, B. J. ANS Fluorescence: Potential to Augment the Identification of the External Binding Sites of Proteins. *Biochim. Biophys. Acta - Proteins Proteomics* **2007**, *1774* (3), 403–411. https://doi.org/10.1016/j.bkapap.2007.01.002.

(260) Winnik, F. M.; Regismond, S. T. A. Fluorescence Methods in the Study of the Interactions of Surfactants with Polymers. *Colloids Surfaces A Physicochem. Eng. Asp.* **1996**, *118* (1–2), 1–39. https://doi.org/10.1016/0927-7757(96)03733-8.

(261) Hirokawa, Y.; Jinnai, H.; Nishikawa, Y.; Okamoto, T.; Hashimoto, T. Direct Observation of Internal Structures in Poly(N-Isopropylacrylamide) Chemical Gels. *Macromolecules* **1999**, *32* (21), 7093–7099. https://doi.org/10.1021/ma990437v.

(262) Liu, X.; Gao, H.; Huang, F.; Pei, X.; An, Y.; Zhang, Z.; Shi, L. Structure Change of Mixed Shell Polymeric Micelles and Its Interaction with Bio-Targets as Probed by the 1-Anilino-8-Naphthalene Sulfonate (ANS) Fluorescence. *Polymer* (*Guildf*). **2013**, *54* (14), 3633–3640. https://doi.org/10.1016/j.polymer.2013.05.001.

(263) Pramanik, P.; Ghosh, S. Thermoresponsive Polymersome from a Double Hydrophilic Block Copolymer. *J. Polym. Sci. Part A Polym. Chem.* **2015**, *53* (21), 2444–2451.
https://doi.org/10.1002/pola.27735.

(264) Longmire, M. R.; Ogawa, M.; Hama, Y.; Kosaka, N.; Regino, C. A. S.; Choyke, P. L.; Kobayashi, H. Determination of Optimal Rhodamine Fluorophore for in Vivo Optical Imaging. *Bioconjug. Chem.* **2008**, *19* (8), 1735–1742. https://doi.org/10.1021/bc800140c.

(265) Capito, R. M.; Azevedo, H. S.; Velichko, Y. S.; Mata, A.; Stupp, S. I. Self-Assembly of Large and Small Molecules into Hierarchically Ordered Sacs and Membranes. *Science* (80-). **2008**, *319* (5871), 1812–1816. https://doi.org/10.1126/science.1154586.

(266) Gasteiger, E.; Hoogland, C.; Gattiker, A.; Duvaud, S.; Wilkins, M. R.; Appel, R. D.; Bairoch, A. Protein Identification and Analysis Tools on the ExPASy Server. In *The Proteomics Protocols Handbook*; Walker, J. M., Ed.; Humana Press, 2005; pp 571–608. https://doi.org/10.1385/1592598900.

(267) Quérard, J.; Zhang, R.; Kelemen, Z.; Plamont, M. A.; Xie, X.; Chouket, R.; Roemgens, I.; Korepina, Y.; Albright, S.; Ipendey, E.; Volovitch, M.; Sladitschek, H. L.; Neveu, P.; Gissot, L.; Gautier, A.; Faure, J. D.; Croquette, V.; Le Saux, T.; Jullien, L. Resonant Out-of-Phase Fluorescence Microscopy and Remote Imaging Overcome Spectral Limitations. *Nat. Commun.* **2017**, *8* (1), 1–8. https://doi.org/10.1038/s41467-017-00847-3.

(268) Bédard, M. F.; Munoz-Javier, A.; Mueller, R.; Del Pino, P.; Fery, A.; Parak, W. J.; Skirtach, A. G.; Sukhorukov, G. B. On the Mechanical Stability of Polymeric Microcontainers Functionalized with Nanoparticles. *Soft Matter* **2009**, *5* (1), 148–155. https://doi.org/10.1039/b812553h.

(269) Fu, J.; Liang, L.; Qiu, L. In Situ Generated Gold Nanoparticle Hybrid Polymersomes for Water-Soluble Chemotherapeutics: Inhibited Leakage and PH-Responsive Intracellular Release. *Adv. Funct. Mater.* **2017**, *27* (18). https://doi.org/10.1002/adfm.201604981.

(270) Hasan, A. S.; Socha, M.; Lamprecht, A.; Ghazouani, F. El; Sapin, A.; Hoffman, M.; Maincent, P.; Ubrich, N. Effect of the Microencapsulation of Nanoparticles on the Reduction of Burst Release. *Int. J. Pharm.* **2007**, *344* (1–2), 53–61. https://doi.org/10.1016/j.ijpharm.2007.05.066.

(271) Katagiri, K.; Imai, Y.; Koumoto, K. Variable On-Demand Release Function of Magnetoresponsive Hybrid Capsules. *J. Colloid Interface Sci.* **2011**, *361* (1), 109–114. https://doi.org/10.1016/j.jcis.2011.05.035.

(272) Wu, T.; Ge, Z.; Liu, S. Fabrication of Thermoresponsive Cross-Linked Poly(N-Isopropylacrylamide) Nanocapsules and Silver Nanoparticle-Embedded Hybrid Capsules with Controlled Shell Thickness. *Chem. Mater.* **2011**, *23* (9), 2370–2380. https://doi.org/10.1021/cm200102g.

(273) Shi, S.; Chang, C.; Wang, T.; Ren, S.; Gao, Y.; Wang, N. A Novel Route to the Preparation of Polymer Hollow Particles Decorated with Gold Nanoparticles in the Shell. *J. Polym. Res.* **2015**, *22*
(1). https://doi.org/10.1007/s10965-014-0632-z.

(274) Yun, G.; Hassan, Z.; Lee, J.; Kim, J.; Lee, N. S.; Kim, N. H.; Baek, K.; Hwang, I.; Park, C. G.; Kim, K. Highly Stable, Water-Dispersible Metal-Nanoparticle-Decorated Polymer Nanocapsules and Their Catalytic Applications. *Angew. Chemie - Int. Ed.* **2014**, *53* (25), 6414–6418.
https://doi.org/10.1002/anie.201403438.

(275) Liu, D.; Jiang, X.; Yin, J. One-Step Interfacial Thiol-Ene Photopolymerization for Metal Nanoparticle-Decorated Microcapsules (MNP@MCs). *Langmuir* **2014**, *30* (24), 7213–7220.

(276) Shi, S.; Wang, Q.; Wang, T.; Ren, S.; Gao, Y.; Wang, N. Thermo-, PH-, and Light-Responsive Poly(N-Isopropylacrylamide- Co -Methacrylic Acid)-Au Hybrid Microgels Prepared by the in Situ Reduction Method Based on Au-Thiol Chemistry. *J. Phys. Chem. B* **2014**, *118* (25), 7177–7186.
https://doi.org/10.1021/jp5027477.

(277) Hitchcock, J. P.; Tasker, A. L.; Stark, K.; Leeson, A.; Baxter, E. A.; Biggs, S.; Cayre, O. J. Adsorption of Catalytic Nanoparticles onto Polymer Substrates for Controlled Deposition of Microcapsule Metal Shells. *Langmuir* **2018**, *34* (4), 1473–1480.
https://doi.org/10.1021/acs.langmuir.7b02874.

(278) Gorelikov, I.; Field, L. M.; Kumacheva, E. Hybrid Microgels Photoresponsive in the Near-Infrared Spectral Range. *J. Am. Chem. Soc.* **2004**, *126* (49), 15938–15939.
https://doi.org/10.1021/ja0448869.

(279) Das, M.; Mordoukhovski, L.; Kumacheva, E. Sequestering Gold Nanorods by Polymer Microgels. *Adv. Mater.* **2008**, *20* (12), 2371–2375. https://doi.org/10.1002/adma.200702860.

(280) De Geest, B. G.; Skirtach, A. G.; De Beer, T. R. M.; Sukhorukov, G. B.; Bracke, L.; Baeyens, W. R. G.; Demeester, J.; De Smedt, S. C. Stimuli-Responsive Multilayered Hybrid Nanoparticle/Polyelectrolyte Capsules. *Macromol. Rapid Commun.* **2007**, *28* (1), 88–95.
https://doi.org/10.1002/marc.200600631.

(281) Chen, T.; Colver, P. J.; Bon, S. A. F. Organic-Inorganic Hybrid Hollow Spheres Prepared from TiO 2-Stabilized Pickering Emulsion Polymerization. *Adv. Mater.* **2007**, *19* (17), 2286–2289.
https://doi.org/10.1002/adma.200602447.

(282) Tian, J.; Yuan, L.; Zhang, M.; Zheng, F.; Xiong, Q.; Zhao, H. Interface-Directed Self-Assembly of Gold Nanoparticles and Fabrication of Hybrid Hollow Capsules by Interfacial Cross-Linking Polymerization. *Langmuir* **2012**, *28* (25), 9365–9371. https://doi.org/10.1021/la301453n.

(283) Wu, Y.; Shen, J.; Larcinese-Hafner, V.; Erni, P.; Ouali, L. Hybrid Microcapsules with Tunable Properties: Via Pickering Emulsion Templates for the Encapsulation of Bioactive Volatiles. *RSC Adv.* **2016**, *6* (104), 102595–102602. https://doi.org/10.1039/c6ra21338c.

(284) Doyen, M.; Goole, J.; Bartik, K.; Bruylants, G. Amino Acid Induced Fractal Aggregation of Gold
(285) Kenausis, G. L.; Vörös, J.; Elbert, D. L.; Huang, N.; Hofer, R.; Ruiz-Taylor, L.; Textor, M.; Hubbell, J. A.; Spencer, N. D. Poly(L-Lysine)-g-Poly(Ethylene Glycol) Layers on Metal Oxide Surfaces: Attachment Mechanism and Effects of Polymer Architecture on Resistance to Protein Adsorption. *J. Phys. Chem. B* **2000**, *104* (14), 3298–3309. https://doi.org/10.1021/jp993359m.

(286) Singh, H. D.; Wang, G.; Uludağ, H.; Unsworth, L. D. Poly-L-Lysine-Coated Albumin Nanoparticles: Stability, Mechanism for Increasing in Vitro Enzymatic Resilience, and SiRNA Release Characteristics. *Acta Biomater.* **2010**, *6* (11), 4277–4284.
https://doi.org/10.1016/j.actbio.2010.06.017.

(287) Louguet, S.; Kumar, A. C.; Sigaud, G.; Duguet, E.; Lecommandoux, S.; Schatz, C. A Physico-Chemical Investigation of Poly(Ethylene Oxide)-Block-Poly(l-Lysine) Copolymer Adsorption onto Silica Nanoparticles. *J. Colloid Interface Sci.* **2011**, *359* (2), 413–422.
https://doi.org/10.1016/j.jcis.2011.03.093.

(288) Malinge, J.; Mousseau, F.; Zanchi, D.; Brun, G.; Tribet, C.; Marie, E. Tailored Stimuli-Responsive Interaction between Particles Adjusted by Straightforward Adsorption of Mixed Layers of Poly(Lysine)-g-PEG and Poly(Lysine)-g-PNIPAM on Anionic Beads. *J. Colloid Interface Sci.* **2016**, *461*, 50–55. https://doi.org/10.1016/j.jcis.2015.09.016.

(289) Wang, X. D.; Wolfbeis, O. S.; Meier, R. J. Luminescent Probes and Sensors for Temperature. *Chem. Soc. Rev.* **2013**, *42* (19), 7834–7869. https://doi.org/10.1039/c3cs60102a.

(290) Baffou, G. Quantitative Phase Microscopy Using Quadriwave Lateral Shearing Interferometry (QLSI): Principle, Terminology, Algorithm and Grating Shadow Description. *J. Phys. D. Appl. Phys.* **2021**, *54* (29). https://doi.org/10.1088/1361-6463/abfbf9.

(291) Bon, P.; Lécart, S.; Fort, E.; Lévêque-Fort, S. Fast Label-Free Cytoskeletal Network Imaging in Living Mammalian Cells. *Biophys. J.* **2014**, *106* (8), 1588–1595.
https://doi.org/10.1016/j.bpj.2014.02.023.

(292) Park, Y. K.; Depeursinge, C.; Popescu, G. Quantitative Phase Imaging in Biomedicine. *Nat. Photonics* **2018**, *12* (10), 578–589. https://doi.org/10.1038/s41566-018-0253-x.

(293) Baffou, G.; Bon, P.; Savatier, J.; Polleux, J.; Zhu, M.; Merlin, M.; Rigneault, H.; Monneret, S. Thermal Imaging of Nanostructures by Quantitative Optical Phase Analysis. *ACS Nano* **2012**, *6* (3), 2452–2458. https://doi.org/10.1021/nn2047586.

(294) Mann, C. J.; Yu, L.; Lo, C.-M.; Kim, M. K. High-Resolution Quantitative Phase-Contrast Microscopy by Digital Holography. *Opt. Express* **2005**, *13* (22), 8693.
https://doi.org/10.1364/opex.13.008693.
(295) Bon, P.; Maucort, G.; Wattellier, B.; Monneret, S. Quadriwave Lateral Shearing Interferometry for Quantitative Phase Microscopy of Living Cells. *Opt. Express* **2009**, *17* (15), 13080. https://doi.org/10.1364/oe.17.013080.

(296) Khadir, S.; Andrén, D.; Chaumet, P. C.; Monneret, S.; Bonod, N.; Käll, M.; Sentenac, A.; Baffou, G. Full Optical Characterization of Single Nanoparticles Using Quantitative Phase Imaging. *Optica* **2020**, *7* (3), 243. https://doi.org/10.1364/optica.381729.

(297) Bon, P.; Belaid, N.; Lagrange, D.; Bergaud, C.; Rigneault, H.; Monneret, S.; Baffou, G. Three-Dimensional Temperature Imaging around a Gold Microwire. *Appl. Phys. Lett.* **2013**, *102* (24), 1–5. https://doi.org/10.1063/1.4811557.

(298) Qiu, X. P.; Winnik, F. M. Facile and Efficient One-Pot Transformation of RAFT Polymer End Groups via a Mild Aminolysis/Michael Addition Sequence. *Macromol. Rapid Commun.* **2006**, *27* (19), 1648–1653. https://doi.org/10.1002/marc.200600436.

(299) He, W.; Graf, R.; Vieth, S.; Ziener, U.; Landfester, K.; Crespy, D. The Cushion Method: A New Technique for the Recovery of Hydrophilic Nanocarriers. *Langmuir* **2016**, *32* (51), 13669–13674. https://doi.org/10.1021/acs.langmuir.6b02880.

(300) Zhang, H.; Guo, S.; Fan, W.; Zhao, Y. Ultrasensitive PH-Induced Water Solubility Switch Using UCST Polymers. *Macromolecules* **2016**, *49* (4), 1424–1433. https://doi.org/10.1021/acs.macromol.5b02522.

(301) Lai, J. T.; Filla, D.; Shea, R. Functional Polymers from Novel Carboxyl-Terminated Trithiocarbonates as Highly Efficient RAFT Agents. *Am. Chem. Soc. Polym. Prepr. Div. Polym. Chem.* **2002**, *43* (2), 122–123.

(302) Andreas, J. M.; Hauser, E. A.; Tucker, W. B. Boundary Tension by Pendant Drops. *J. Phys. Chem.* **1938**, *42* (7), 1001–1019. https://doi.org/10.1021/j100903a002.

(303) Berry, J. D.; Neeson, M. J.; Dagastine, R. R.; Chan, D. Y. C.; Tabor, R. F. Measurement of Surface and Interfacial Tension Using Pendant Drop Tensiometry. *J. Colloid Interface Sci.* **2015**, *454*, 226–237. https://doi.org/10.1016/j.jcis.2015.05.012.
Design of stimuli-responsive polymer capsules by interfacial complexation

**Abstract:** The encapsulation of molecules or nanomaterials at microscales has become a major topic in many research fields, ranging from catalysis to therapeutic treatments. The development of highly functional encapsulation systems has become crucial for these applications but are likely to involve formulation steps that may be incompatible with the presence of the payloads of interest (such as fragile biomacromolecules, including proteins or nucleic acids). In this thesis, we describe and explore a formulation approach of polymer microcapsules that exhibit a mild aqueous core and a functional polymer shell. These microcapsules are formed by interfacial complexation between a functional cationic copolymer and an anionic surfactant in inverse emulsions, namely at the surface of water droplets dispersed in a fluorinated oil. The use of thermosensitive grafts on the cationic polymer led to the formation of polymer membranes with a lower or upper critical solution temperature (depending on the nature of the strands), hence paving the way to thermoresponsive delivery systems. We demonstrate that the thermoresponsiveness of the polymers used in this study can be leveraged to (i) change the physicochemical properties of the polymer shells and (ii) straightforwardly incorporate nanoparticles within these shells, hence providing new functionalities to the microcapsules. As an illustration, we used gold nanoparticles as thermoplasmonic nanoheaters to trigger the thermal response of the polymer shells under light irradiation. In this system, the temperature rise induced in the microcapsules by thermoplasmonic excitation of gold nanoparticles was precisely measured *in situ* using quantitative phase microscopy.

**Key words:** Polymer capsules, thermoresponsive polymers, inverse emulsions, interfacial complexation, thermoplasmonics.

Formulation de capsules polymères stimulables par complexation interfaciale

**Résumé** : L'encapsulation à l'échelle microscopique de molécules ou de nanomatériaux est un sujet de recherche particulièrement actif dans de nombreux domaines, allant de la catalyse aux traitements thérapeutiques. Le développement de systèmes d'encapsulation hautement fonctionnels est devenu un enjeu crucial pour ces applications mais peut nécessiter des voies de formulation potentiellement incompatibles avec la présence des molécules d'intérêt à encapsuler (notamment certaines biomacromolécules fragiles comme les protéines ou les acides nucléiques). Dans cette thèse, nous explorons une voie de formulation « douce » de microcapsules polymères fonctionnelles à cœur aqueux, prometteuses pour l'encapsulation et la libération contrôlée de biomacromolécules. Notre approche repose sur la complexation interfaciale entre un copolymère cationique fonctionnel et un tensioactif anionique en émulsion inverse, à savoir à la surface de gouttes d'eau dispersées dans une huile fluorée. L'utilisation d'un polycation greffé par des brins thermosensibles (possédant une température de solution critique supérieure ou inférieure en fonction de leur nature) permet de former une membrane polymère dont les propriétés physico-chimiques varient sensiblement avec la température, ouvrant la voie à des systèmes de délivrance thermo-contrôlée. De plus, nous montrons que le caractère thermosensible des membranes polymères permet d'y incorporer facilement des nanoparticules, permettant ainsi d'ajouter de nouvelles fonctionnalités aux capsules. Nous montrons par exemple que des nanoparticules d'or peuvent être introduites pour rendre les capsules photo-stimulables par effet thermoplasmonique. Dans ce système, nous avons notamment mesuré par microscopie de phase quantitative l'élévation de température induite *in situ* par excitation lumineuse.

**Mots-clés** : Capsules polymères, polymères thermosensibles, émulsions inverses, complexation interfaciale, thermoplasmonique.