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Zhouna Tang, [Takafumi Enomoto](https://orcid.org/0000-0001-5137-6129), [Takeshi Ueki](https://orcid.org/0000-0001-9317-6280), [Ryota Tamate](https://orcid.org/0000-0002-1704-1058), [Aya Mizutani Akimoto](https://orcid.org/0000-0003-1506-267X), [Ryo Yoshida](https://orcid.org/0000-0002-0558-2922)

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This document is the unedited Author’s version of a Submitted Manuscript subsequently accepted for publication in Langmuir, copyright © 2026 American Chemical Society. To access the final published article, see https://doi.org/10.1021/acs.langmuir.5c06076.[In Copyright](http://rightsstatements.org/vocab/InC/1.0/)

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[Cross-Hierarchical Transduction of Dynamic Behaviors from Self-Oscillating Microgels to Colloidosomes](https://mdr.nims.go.jp/datasets/a4cc1096-63f9-4fdb-afc1-781cff9fdf67)

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Template for Electronic Submission to ACS Journals 1 Cross-Hierarchical Transduction of Dynamic 1 Behaviors from Self-Oscillating Microgels to 2 Colloidosomes 3 Zhouna Tang1, Takafumi Enomoto1, Takeshi Ueki2,3, Ryota Tamate2, Aya M. Akimoto4, and Ryo 4 Yoshida1* 5 1Department of Materials Engineering, School of Engineering, The University of Tokyo 6 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan 7 2National Institute for Materials Science 8 1 Namiki, Tsukuba, Ibaraki 305-0044, Japan  9 3Graduate School of Life Science, Hokkaido University 10 Kita 10, Nishi 8, Kita-ku, Sapporo, Hokkaido, 060-0810, Japan 11 4Department of Human-Centered Engineering, Faculty of Transdisciplinary Engineering, 12 Ochanomizu University 13 2-1-1 Ohtsuka, Bunkyo-ku, Tokyo 112-8610, Japan 14  15  2 ABSTRACT 16 Life consists of many hierarchical levels, in which complex behaviors emerge from the interactions 17 among simpler components. Here we demonstrate the cross-hierarchical transduction of dynamic 18 behaviors in life-like autonomous materials by investigating self-oscillating colloidosomes as a 19 model system. Self-oscillating colloidosomes are composed of self-oscillating microgels, which 20 exhibit autonomous flocculation/dispersion oscillation driven by a self-promoted Belouzov-21 Zhabotinsky reaction at certain temperatures. We identified chemo-mechanical transduction across 22 hierarchical levels in self-oscillating colloidosomes under out-of-equilibrium conditions. The self-23 oscillating colloidosomes exhibited swelling/deswelling or shape deformation oscillations in a 24 stochastic manner, originating from flocculation/dispersion oscillation at the microgel level. We 25 found that the choice between these two oscillation modes is determined by the oscillation modes 26 of their constituent self-oscillating microgels. These findings pave the way for cross-hierarchical 27 design of chemically powered autonomous materials. 28  29 Introduction 30 Life is hierarchically organized, and each level has distinct functions and emergent properties. At 31 the molecular level, small molecules and proteins respond to external stimuli, modulating the 32 properties of their assembly states and thereby inducing the dynamic behaviors at the cellular 33 level1–3. For example, the intracellular signal leads to actin polymerization and actomyosin 34 contraction, thereby producing amoeboid migration of cells4. Understanding chemo-mechanical 35 transduction across hierarchical levels is key to engineering dynamic behavior of chemically 36 powered autonomous materials.  37  3 To create life-like autonomous materials, we have established the concept of self-oscillating 38 polymer systems that exhibits dynamic behavior driven by self-promoted Belousov-Zhabotinsky 39 (BZ) reaction5. The systems are mainly composed of thermoresponsive poly(N-40 isopropylacrylamide) (PNIPAAm) main chain and tris(2,2'-bipyridyl)ruthenium complex 41 (Ru(bpy)32+), a catalyst of the BZ reaction. Since the hydrophilicity of the self-oscillating polymers 42 is different between the reduced state (Ru(bpy)32+) and the oxidized state (Ru(bpy)33+), the lower 43 critical solution temperature (LCST) also differs in each state. Therefore, between a certain 44 temperature range, these self-oscillating polymers undergo autonomous structural oscillations 45 driven by the self-promoted BZ reaction. To date, we have developed several forms of self-46 oscillating materials, including gels6–8, micelles and vesicles9–11, and microgels12,13. Based on this 47 driving mechanism, the self-oscillating materials provide a platform for investigating the cross-48 hierarchical transduction of chemical events. 49 In this context, we employed self-oscillating colloidosomes (SOCs) as a model system of 50 hierarchical autonomous materials. Colloidosomes are cell-like spherical hollow structures14, and 51 are formed from Pickering emulsions that are stabilized by the self-assembly of amphiphilic 52 colloid particles at the oil-water interface15. Because of their structures and flexible cell-like 53 membranes, they are favored as simplified artificial cell models. Many studies have shown that 54 silica particles16–18 and polystyrene latex particles19,20 can be used to fabricate the colloidosome 55 structures. Recently, microgels have attracted increasing interest as emulsifiers for Pickering 56 emulsions because of their unique deformability and stimuli responsiveness21–25. Our previous 57 study demonstrated that SOCs composed of microgels exhibited periodic autonomous shape 58 deformation in the presence of the BZ substrates26. 59  4 In this study, we investigated chemo-mechanical transduction of dynamic behaviors in SOCs 60 across two hierarchical levels, from microgels to colloidosomes (Scheme 1).  By modifying the 61 synthesis protocol for SOCs, we enabled independent characterization of the SOCs and their 62 constituent self-oscillating microgels (SOMGs). We found that the thermoresponsive behaviors of 63 the SOCs are inherited from the constituent SOMGs. Moreover, the dynamic behaviors of SOMGs 64 were transduced into that of the SOCs under out-of-equilibrium conditions. At the microgel level, 65 chemical redox oscillations of the Ru(bpy)3 complex were transduced into mechanical oscillations 66 between flocculated and dispersed states. Upon crosslinking SOMGs to form colloidosomes, these 67 oscillations were further transduced into swelling/deswelling or shape deformation oscillations. In 68 addition, the temperature dependence of SOC oscillations modes was inherited their constituent 69 SOMGs. These results established that the dynamic characteristics of the lower hierarchy were 70 transduced to the higher hierarchy.   71  72 Scheme 1. (a) Chemical structure of poly(NIPAAm-co-NAPMAm-co-NAPMAm(Ru(bpy)3)) 73 microgel (SOMG). (b) Schematic illustration of self-oscillating colloidosomes (SOCs) assembled 74 by self-oscillating microgels (SOMGs). 75  76  5 Experimental section 77 Materials. N-Isopropylacrylamide (NIPAAm) was generously donated by the KJ chemicals Co. 78 (Tokyo, Japan), and purified by recrystallization from toluene/hexane mixed solvent. N-(3-79 Aminopropyl)methacrylamide hydrochloride (NAPMAm) was purchased from Combi-Blocks 80 (San Diego, USA), and purified by reprecipitation in Tetrahydrofura. N-Succinimidyl acrylate 81 (NAS) was purchased from Tokyo Chemical Industry (Tokyo, Japan). Potassium peroxydisulfate 82 (KPS) was purchased from Kanto Chemical (Tokyo, Japan). N,N-Dimethylacrylamide (DMAAm) 83 was purchased from FUJIFILM Wako Pure Chemical Co. (Osaka, Japan), and was purified by 84 being passed through a column of basic alumina before using. Bis(2,2’-bipyridine)(1-(4’-methyl-85 2,2’-bipyridine-4-carbonyloxy)-2,5-pyrrolidinedione)-ruthenium(II) bis(hexafluorophosphate) 86 (NHH-Ru(bpy)3) was purchased from HangZhou Trylead Chemical Technology (Hangzhou, 87 China). All other chemical reagents were purchased from Wako Pure Chemical Corporation, and 88 used as received. 89  90 Synthesis of poly(NIPAAm-co-NAS). Poly(NIPAAm-co-NAS) was synthesized by free radical 91 polymerization. NIPAAm (5.04 g, 44.6 mmol), NAS (0.381 g, 2.26 mmol), and 2,2’-92 azobis(isobutyronitrile) (AIBN) (34.8 mg, 0.212 mmol) were added into a 100 mL three-neck 93 round-bottom flask and methanol (30 mL) was added as a solvent. DMF (774 μL, 10.0 mmol) was 94 also added into the reaction solution as the NMR calculation standard. The solution was 95 deoxygenated by argon gas bubbling at room temperature for 30 min. The polymerization was 96 carried out at 60 °C for 24 h. The reaction was quenched by cooling down in an ice-water bath. 97 The reacted solution was evaporated by a rotary evaporator and was dissolved in a good solvent, 98 the mixture of toluene and acetone, and then was reprecipitated in a poor solvent, hexane. After 99  6 the suction filtration, the collected powders were redissolved into the mixture of toluene and 100 acetone, and then the reprecipitation in hexane was carried out. The collected polymers were dried 101 under vacuum for 48 h. Finally, white solid products were obtained. Poly(DMAAm-co-NAS) was 102 synthesized by the same procedure except the monomers were changed from NIPAAm to 103 DMAAm. 104  105 Synthesis of poly(NIPAAm-co-NAPMAm) microgel. poly(NIPAAm-co-NAPMAm) 106 microgels were synthesized by precipitation polymerization. NIPAAm (1.69 g, 14.9 mmol), 107 NAPMAm (0.268 g, 1.50 mmol), and N,N’-methylenebis(acrylamide) (MBAAm) (0.0568 g, 0.368 108 mmol) were added into a 300 mL three-neck round-bottom flask and deionized water (95 mL) was 109 added as a solvent. DMF (774 μL, 10.0 mmol) was also added into the reaction solution as the 110 NMR calculation standard. The solution was deoxygenated by argon gas bubbling at 70 °C for 30 111 min. KPS (0.0405 g, 0.150 mmol) was added into a 13.5 mL screw bottle and dissolved in 112 deionized water (5 mL). The initiator solution was deoxygenated by argon gas bubbling at room 113 temperature for 30 min. Then, the initiator solution was added into the flask through a PTFE tube. 114 The reaction was carried out at 70 °C for 1 h and the solution was stirred at 250 rpm during the 115 reaction. The reaction was quenched at room temperature with an open atmosphere. The reacted 116 solution was dialyzed against deionized water, and the dialysis solvent was exchanged one time. 117 Finally, white solid products were obtained by a freeze-dryer.  118  119 Synthesis of poly(NIPAAm-co-NAPMAm-co-NAPMAmRu(bpy)3) microgel (SOMG). 0.95 120 g of poly(NIPAAm-co-NAPMAm) microgel was dissolved into 50 mL of DMSO, and then NHS-121 Ru(bpy)3 (370 mg, 0.365 mmol), and triethylamine (TEA) (305 μL, 2.19 mmol) were also added. 122  7 The reaction was carried out at room temperature for 24 h. The solution was dialyzed against 123 DMSO, and the dialysis solvent was exchanged twice. Then, the dialysis solvent was changed to 124 deionized water, and was exchanged four times. Finally, orange solid products were obtained by a 125 freeze-dryer. 126  127 Fabrication of colloidosome. The fabrication scheme is shown in Scheme S1. 200 mg of 128 P(NIPAAm-co-NAPMAm-co-NAPMAmRu(bpy)3) microgel was dissolved into 5 mL of PBS(-), 129 and 100 mg of poly(NIPAAm-co-NAS) was dissolved into another 5 mL of PBS(-). Then, two 130 solutions were fully mixed. Next, 40 mL of 1-octanol was added into the mixed solution, and the 131 solution was vigorously mixed. The resulted dispersion was left overnight at 20 ℃ for the cross-132 linking reaction. Next day, the supernatant oil was eliminated, and 20 mL of ethanol was added to 133 dissolve the oil and water. After the colloidosomes precipitated in the bottle, the supernatant was 134 eliminated again, and 20 mL of ethanol was added. Next, the solution was dialyzed against ethanol, 135 and the dialysis solvent was exchanged twice. Then, the dialysis solvent was changed to deionized 136 water, and was exchanged three times. Finally, the colloidosomes were stored in the solution for 137 the following experiments. The colloidosomes whose crosslinkers were P(DMAAm-co-NAS), 138 were fabricated with the same procedure.  139  140 Dynamic light scattering (DLS) measurement. DLS measurements were carried out on a zeta-141 potential & particle size analyzer (Otsuka ELSZ–2000, Japan). The sample solution was 142 equilibrated for 10 min at each temperature. The hydrodynamic radius (Rh) was calculated using 143 the CONTIN analysis. 144  145  8 UV-vis absorption measurement. UV-vis measurement was carried out on a UV-vis 146 spectrophotometer (SHIMADZU UV-1900i, Japan) with a thermoelectric cell holder 147 (SHIMADZU S-1700, Japan). For the measurement of oscillatory behaviors, the time course mode 148 was used. The wavelength was set as a certain wavelength and the measurement time was set as 149 3600 s.  150  151 Optical microscopic observation. The microscopic observation was conducted on the digital 152 microscope (Keyence, VHX-900, Japan) equipped with a high-resolution 1000x zoom lens 153 (Keyence, VH-Z100R). A 24 mm × 24 mm glass slide (thickness: 0.12 – 0.17 mm) was used for 154 holding the sample solution. An appropriate size circle was drawn on the glass slide using high 155 vacuum grease to avoid the leakage of the solution. Then, the sample solution was added to the 156 circular range and another glass slide was used as a cover. 157  158 Confocal microscopic observation. Confocal laser scanning microscopy was conducted using 159 FLUOVIEW FV3000 Confocal Microscope (Olympus, Japan) with a 100× oil immersion 160 objective lens and a differential interference contrast (DIC) prism. The lens was immersed in oil 161 (IMMOIL-F30CC, Olympus, Japan) to obtain clear image. The excitation wavelength was 488 nm. 162 A 24 mm × 24 mm glass slide (thickness: 0.12 – 0.17 mm) was used for holding the sample solution. 163 An appropriate size circle was drawn on the glass slide using high vacuum grease to avoid the 164 leakage of the solution. Then, the sample solution was added to the circular range and another 165 glass slide was used as a cover. 166   167  9 Results and discussion 168 The microgels were synthesized by the precipitation copolymerization of NIPAAm and NAPMAm. 169 Then, BZ catalyst was introduced into the microgels to fabricate SOMGs through a condensation 170 reaction between the NHS esters of Ru(bpy)3 complex and the primary amine groups of NAPMAm 171 units. According to the previous study, by using 1-octanol as the oil phase, it is possible to fabricate 172 the water-in-oil (W/O) Pickering emulsion stabilized by PNIPAAm microgels27. Based on this 173 procedure, we fabricated the colloidosome structures using SOMGs through the W/O emulsion 174 method. The polymer crosslinker, poly(NIPAAm-co-NAS), was used to maintain the 175 colloidosome structure after redispersing into the aqueous solution. After the dialysis, the obtained 176 SOCs were stored in the aqueous solution. 177 First, we examined the internal structure of the SOCs, which are assembled from the SOMGs. 178 Because of the phosphorescence of the Ru(bpy)3 complex, the internal structure of the SOCs could 179 be visualized using the confocal laser scanning microscopy. Figure 1 shows that the SOCs have a 180 hollow structure with a membrane thickness around 2-3 μm. According to the DLS results, Rh of 181 the SOMGs is around 635 nm in water at 24 ℃ (Figure S1). These results suggest that the 182 membrane of the SOCs is not composed of a monolayer of the SOMGs. A similar phenomenon 183 was also reported in a previous study using 1-octanol as the oil phase in the W/O emulsion 184 method27. Uptake of 1-octanol by microgels increases the attractive interaction between microgels, 185 resulting in greater adsorption at the interface layer and formation of heterogeneous membranes. 186 We also assumed that the size distribution of the SOMG and the broad molecular weight 187 distribution of the polymer crosslinker contributed to the inhomogeneity of the membrane (Figure 188 S2a). 189  10  190 Figure 1. (a) Confocal microscopic image of single SOC and the zoom in part of the membrane 191 of the SOC (yellow dash line rectangle). (T = 24 ℃, solvent: water) (b) Plot correspond to the 192 intensity profile along the white respective dash line on the confocal image. 193 The thermoresponsive behaviors of the SOMGs were then studied. In high salt concentration 194 solutions, PNIPAAm microgels aggregate above a certain temperature due to increased 195 hydrophobicity of the microgel network28. This temperature is determined as critical flocculation 196 temperature (CFT). Figure 2 shows the temperature dependence of the SOMG dispersion from 197 DLS measurements under reduced and oxidized conditions. The hydrodynamic radius (Rh) 198 increases sharply above a specific temperature in each case, indicating the CFTs for reduced and 199 oxidized states at TF,red = 15 ºC and TF,ox = 25 ºC, respectively. We also found that the Rh of the 200 oxidized state is bigger than that of the reduced state below the TF,red, which is attributed to the 201 higher hydrophilicity of SOMGs in the oxidized state. In addition, the SOMG was slightly shrunk 202 as the temperature increased below the TF, which is attributed to the thermoresponsive volume 203 phase transition of PNIPAAm based microgels, similar to a previous report29. 204  11  205  206 Figure 2. (a) Temperature dependence of the hydrodynamic radius (Rh) for the SOMG dispersions 207 under reduced and oxidized conditions, and (b) enlarged view of panel (a). ([SOMG] = 0.5 g/L, 208 reduced condition: [HNO3] = 800 mM, [NaCl] = 50 mM; oxidized condition: [HNO3] = 800 mM, 209 [NaBrO3] = 50 mM) 210 The equilibrium swelling ratio for the SOCs under both reduced and oxidized conditions were 211 also determined, with the projected area at 10 ℃ normalized to 1 (Figure 3). As the temperature 212 increased, the equilibrium swelling ratio gradually decreased, indicating the deswelling of the 213 SOCs. One of the reasons for this phenomenon is the thermoresponsiveness of the SOMGs, the 214 main component of the SOCs. Although the SOMGs on the SOCs are fixed by the polymer 215 crosslinker and cannot move freely, they still tend to move closer together due to the flocculation 216 above the CFT, leading to deswelling of the SOCs. Additionally, consistent with the volume phase 217 transition behavior of self-oscillating gels6, the SOMGs also deswell with increasing temperature 218 under the CFT as shown in Figure 2b, thereby contributing to the deswelling of the SOCs. Note 219 that thermoresponsive deswelling was also observed for the SOCs crosslinked with the non-220 thermoresponsive polymer, poly(DMAAm-co-NAS) (Figure S3), indicating that the deswelling 221 and flocculation at the microgel level are transduced into deswelling at the colloidosome level. 222  12 Another reason comes from the thermoresponsive property of the polymer crosslinker 223 poly(NIPAAm-co-NAS), which has a lower critical solution temperature (LCST) at 20 ºC (Figure 224 S2b). Contraction of the crosslinker polymer chains shortens the distance between microgels, 225 leading to a more compact structure. As a result, the temperature dependent deswelling of the 226 SOCs arises from both the thermoresponsive property of the SOMGs and the crosslinker. In 227 addition, the swelling ratio of the SOCs also differs between redox states (Figure 3). This arises 228 from differences in the flocculation temperatures of the constituent SOMGs in redox states (TF,red 229 < TF,ox). Overall, these results clearly indicate that the thermoresponsive behaviors of the SOMGs 230 were successfully inherited by the SOCs. 231  232 Figure 3. Equilibrium swelling ratio of the SOC under the reduced and oxidized conditions. The 233 values are the average of three different SOCs. (reduced condition: [HNO3] = 800 mM, [NaCl] = 234 50 mM; oxidized condition: [HNO3] = 800 mM, [NaBrO3] = 50 mM) 235 Thus far, we have investigated the thermoresponsive behaviors of the SOMGs and SOCs. We 236 next focus on dynamic chemo-mechanical transduction under out-of-equilibrium conditions. Since 237 the flocculation of the SOMGs decreases the optical transmittance of their dispersions30, the self-238 oscillating behaviors of the SOMGs can be observed by UV-vis absorption spectroscopy. The self-239 oscillating profiles at different temperatures were observed at 583 nm, an isosbestic point between 240  13 the reduced and oxidized SOMGs, as shown in Figure 4a. All samples exhibited periodic 241 oscillations in optical transmittance, indicating the flocculation/dispersion oscillation of the 242 SOMG driven by the BZ reaction. At 15 ℃, only slight flocculation occurred in the reduced state 243 as shown in Figure 2. Consequently, the amplitude of the transmittance oscillations was much 244 smaller than the other two temperatures. At 20 ℃, the SOMGs in the reduced state drastically 245 flocculated, and a clear transmittance oscillation was observed. Note that the oscillation became 246 unstable overtime, and transmittance did not completely recover to its initial value, which implies 247 the incomplete dispersion of SMOGs during the oxidized regime. When the temperature was 248 increased to 25 ℃, the optical transmittance decreased sharply at the outset, indicating the 249 formation of large aggregates. However, the oscillation amplitudes at 25 ℃ were smaller than 250 those at 20 ℃, because the SOMGs in the oxidized state already flocculated slightly at 25 ºC 251 (Figure 2), and redispersion during the oxidized regime was less complete. We also found that the 252 SOMGs precipitated over time (Figure S4), leading to an increase in transmittance at the later 253 times. Then, the average oscillation periods were calculated using the 4th to 8th cycles. As shown 254 in Figure 4b, the average oscillation period decreased as the temperature increased, which is 255 consistent to Arrhenius equation31. Based on these results, we speculate that the precipitation 256 observed at 25 ℃ was induced by the faster oscillation rate at higher temperatures. The increased 257 oscillation rate leads to a shorter oscillation period. During this period, the flocculated SOMGs in 258 the reduced state lack sufficient time to fully disperse upon the oxidized regime. As a result, the 259 SOMG dispersion oscillated between a flocculated reduced state and an incompletely dispersed 260 oxidized state at 25 ℃. 261  14  262 Figure 4. (a) Oscillation profiles of optical transmittance for the SOMG dispersions at different 263 temperatures. (BZ reaction condition: [SOMG] = 0.38 g/L, [HNO3] = 800 mM, [NaBrO3] = 50 264 mM, [Malonic Acid] = 100 mM, wavelength: 583 nm) (b) Average oscillation period for the 265 SOMG dispersions at different temperatures. 266 Next, we examined the self-oscillating behaviors of the SOCs. At 20 ℃ in the presence of BZ 267 substrates, the SOC exhibited the autonomous swelling/deswelling oscillations (Figure 5a, Movie 268 S1). Because Ru(bpy)3 catalysts are tethered only within the SOMGs, the constituent SOMGs drive 269 these oscillations via the self-promoted BZ reaction. The redox oscillations induce 270 flocculation/dispersion oscillation at microgel level, and these oscillations were transduced into 271 volumetric oscillations at colloidosome level. This result is also consistent with a higher 272 equilibrium swelling ratio of the SOCs in the oxidized state than in the reduced state.  273 Another mode of self-oscillations was also observed for the SOC at 20 ℃ in the presence of BZ 274 substrates (Figure 5b, Movie S2). The shape of the SOC periodically changed between a circular 275 shape and an irregular shape, that is the buckling/unbuckling shape deformation oscillation. This 276 behavior is similar to our previous report26. Same as the swelling/deswelling oscillation mentioned 277 above, the SOC tends to swell in the oxidized state during the BZ reaction. However, since the 278 SOC is crosslinked, the volume change is restricted. Therefore, the membrane buckled inside to 279  15 accommodate swelling by increasing surface area. Upon returning to the reduced state, the SOC 280 deswelled and recovered a circular shape. We discuss the occurrence of the volume and the shape 281 deformation oscillations in the SOCs later.  282 Besides 20 ℃, the SOCs were also observed under 15 ℃ and 25 ℃. The self-oscillating profiles 283 and movies were in the Supporting Information (Figure S5-8 and Movie S3-6). The self-284 oscillating profile of the SOC that shows shape deformation was used for the calculation of the 285 average oscillation period. Figure 5c shows that, when the reaction temperature increased, the 286 average oscillation period of the SOC decreased, which is similar to the result of the SOMG 287 dispersion. As a consequence, the self-oscillating behaviors of the SOC at different temperatures 288 is also consistent to Arrhenius equation31.  289  290 Figure 5. (a) Autonomous swelling/deswelling oscillation and (b) shape deformation oscillation 291 of colloidosomes at 20 ℃ during the BZ reaction. (BZ reaction condition: [HNO3] = 800 mM, 292 [NaBrO3] = 50 mM, [Malonic Acid] = 100 mM) (a1) (b1) Snapshots of the colloidosome at 293 different moments under the optical microscope. (a2) (b2) Oscillation profiles of projected areas 294 and projected area ratios for the colloidosome. The projected area ratio (-) is defined as the 295  16 projected area at time t normalized by the projected area at time t = 0. (c) Average oscillation 296 period for the SOC dispersion at different temperatures. 297 Table 1 summarizes of the occurrence percentages for each oscillation mode at different 298 temperatures. The occurrence of the swelling/deswelling oscillation and the shape deformation 299 oscillation on SOCs appears random (Table S1), which may be attributed to the heterogeneity in 300 membrane thickness of the SOCs. Then, according to our previous study 26, larger SOCs exhibit 301 higher probability of shape deformation oscillations. As shown in Table S1, the SOCs had larger 302 diameters at 15 ℃ compared with those in higher temperature. However, the occurrence for shape 303 deformation oscillations was only 26.7%, which is less than that at 20 ºC, and the deformation 304 amplitude was small (Figure S6 and Movie S4). These results are likely linked to the self-305 oscillation behaviors of the SOMGs. At 15 ℃, the SOMGs exhibited autonomous oscillations 306 between dispersion and slight flocculation with small amplitudes (Figure 4a). We assumed that 307 the small flocculation/dispersion oscillation was transduced into the swelling/deswelling 308 oscillation in the SOCs with small amplitudes, leading to a lower probability of shape deformation 309 oscillations (Figure 6a). When the temperature was increased to 20 ℃, the average diameter for 310 the SOCs decreased compared to that at 15 ℃ (Table S1). On the other hand, deformation was 311 much more obvious, and the occurrence percentage of shape deformation oscillations increased. 312 This is likely because of the drastic transitions of the SOMGs between flocculation and dispersion 313 states at 20 ℃ (Figure 4a), thereby driving shape deformation oscillations of the SOCs across 314 hierarchy (Figure 6b). At 25 ℃, deformation on the SOCs became slight again (Figure S8 and 315 Movie S6), and the occurrence percentage of deformation oscillations was lower than that at 20 ℃.  316 Additionally, nearly half of the SOCs did not show volumetric oscillations. As mentioned earlier, 317 the SOMG exhibited the flocculation/incomplete dispersion oscillations at 25 ℃ due to the higher 318  17 oscillation rate (Figure 4a). We speculated that the incomplete oscillation in the microgel level 319 was transduced into smaller oscillation amplitudes in the colloidosome level (Figure 6c). Together, 320 these observations indicate that the dynamic behaviors of the SOMGs are also inherited by the 321 higher hierarchical level. 322 Table 1. Summary of the percentage of occurrence of each oscillation type at each temperature. 323 15 different colloidosomes were counted at each temperature. Conditions of BZ substrates were 324 the same as Figure 4. 325 Temperature (℃) No volume oscillation (%) Swelling/deswelling oscillation (%) Shape deformation oscillation (%) 15 0 73.3 26.7 20 0 53.3 46.7 25 46.7 33.3 20.0  326  18   327 Figure 6. Schematic illustration of the self-oscillating behaviors of SOMGs and SOCs at (a) 15 ℃, 328 (b) 20 ℃, and (c) 25 ℃. 329  330 Conclusion 331 In this study, the independent characterization of the SOMGs and the SOCs revealed the cross-332 hierarchical transduction of dynamic behaviors. This was realized by modifying the synthesis 333 protocol, that is first synthesizing SOMGs and then fabricating SOCs using the SOMGs. Under 334 equilibrium conditions, thermoresponsive deswelling and flocculation at the microgel level were 335 transduced into deswelling at the colloidosome level. Beyond these thermoresponsive behaviors, 336 dynamic behaviors under out-of-equilibrium conditions were also inherited across the hierarchy. 337  19 The SOMGs exhibited flocculation/dispersion oscillations driven by the self-promoted BZ 338 reaction, and the oscillation modes depended on temperature. We found that 339 flocculation/dispersion oscillation at the microgel level were transduced into the 340 swelling/deswelling or shape deformation oscillations at the colloidosome level. Moreover, 341 difference in the oscillation modes of the SOMGs determined the oscillation modes of the SOCs. 342 These results show how dynamic behaviors are transduced from the lower hierarchical level, the 343 SOMGs, to the higher hierarchical level, the SOCs. These findings pave the way for cross-344 hierarchical design of chemically powered autonomous materials via a bottom-up approach. 345  346  347 ASSOCIATED CONTENT 348 Additional experimental details, materials, and methods, including image of the SOMG 349 dispersion, dynamic light scattering result of the microgel, GPC trace and the dynamic light 350 scattering result of the polymer crosslinker, equilibrium swelling ratio of the SOC with the non-351 responsive crosslinker, self-oscillating profiles of the SOC during the BZ reaction at 15 and 352 25 ℃, summary of the percentage of occurrence of each oscillation type at each temperature, 353 Average diameter of SOCs at different temperatures (.PDF) 354 Video for the optical microscopic observation of the autonomous oscillation behaviors of the 355 SOC during the BZ reaction (.mp4) 356  357 AUTHOR INFORMATION 358 Corresponding Author 359  20 Ryo Yoshida 360 Department of Materials Engineering, School of Engineering, The University of Tokyo, Tokyo, 361 113-8656, Japan; orcid.org/0000-0002-0558-2922; Email: ryo@cross.t.u-tokyo.ac.jp 362  363 Author Contributions 364 Conceptualization: ZT, TE, RY 365 Methodology: ZT 366 Investigation: ZT 367 Visualization: ZT 368 Supervision: TE, RY 369 Writing—original draft: ZT 370 Writing—review & editing: ZT, TE, TU, RT, AMA, RY 371 The manuscript was written through contributions of all authors. All authors have given approval 372 to the final version of the manuscript. 373  374 Notes 375 The authors declare no competing financial interest. 376  377 ACKNOWLEDGMENT 378 mailto:ryo@cross.t.u-tokyo.ac.jp 21 This work was partially supported by Grants-in-Aid for Scientific Research Grant Numbers 379 24H00471, JP20H00388 and JP20K20563 to R.Y. from the Ministry of Education, Culture, 380 Sports, Science, and Technology of Japan. 381  382 REFERENCES 383 (1) Lim, C. M.; Díaz, A. G.; Fuxreiter, M.; Pun, F. W.; Zhavoronkov, A.; Vendruscolo, M. 384 Multiomic Prediction of Therapeutic Targets for Human Diseases Associated with Protein Phase 385 Separation. Proc. Natl. Acad. Sci. U. S. A. 2023, 120, e2300215120. 386 (2) Saad, S.; Cereghetti, G.; Feng, Y.; Picotti, P.; Peter, M.; Dechant, R. Reversible Protein 387 Aggregation Is a Protective Mechanism to Ensure Cell Cycle Restart after Stress. Nat. Cell Biol. 388 2017, 19, 1202–1213. 389 (3) Marijan, D.; Momchilova, E. 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