Mechanistic Insight into Supramolecular Polymerization in Water Tunable by Molecular Geometry

Open AccessCCS ChemistryCOMMUNICATION14 Jul 2022Mechanistic Insight into Supramolecular Polymerization in Water Tunable by Molecular Geometry Fan Xu, Stefano Crespi†, Lukas Pfeifer†, Marc C. A. Stuart and Ben L. Feringa Xu Stratingh Institute for Chemistry, University of Groningen, Groningen 9747 AG Google Scholar More articles this author , Crespi† †Stefano Crespi’s present address is: Ångstrom Laboratory, Department Uppsala University, 751 20. Pfeifer’s Laboratory Photonics Interfaces, Chemistry Chemical Engineering, École Polytechnique Fédérale de Lausanne, Lausanne CH-1015.Google Pfeifer† *Corresponding author: E-mail Address: [email protected] Key Advanced Materials Joint International Research Precision Nobel Prize Scientist Center, Frontiers Science Center Materiobiology Dynamic Fine Chemicals, School East China Technology, Shanghai 200237 https://doi.org/10.31635/ccschem.022.202201821 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail self-assembly water based on non-covalent bonding is attracting major attention due the potential hydrogels aqueous polymers biomedical applications. Although supramolecular polymerization organic solvents well established, key design features, assembly mechanisms achieving control over aggregate structures remain challenging. Here, we disassembly geometrical isomers a stiff-stilbene bis-urea amphiphile ( SA) pure water. A remarkable feature system that (E)-isomer forms both solvents. Taking advantage unique property, hydrophobic effect was studied comparing systems. The process follows an enthalpy-driven nucleation-elongation (cooperative) mechanism with standard Gibbs free energy (?G° = ?53 kJ mol?1) double value one found toluene. We attributed distinctive Furthermore, discovered isomer-dependent process, which can be used aggregation media. Due substantial geometric difference between (E)- SA (Z)- SA, compared their study influence different driving forces involved process. cooperatively influenced hydrogen bonding, ?-stacking, effects, whereas mainly driven effects. As result, fiber length much longer than presenting opportunities Download figure PowerPoint Introduction are highly ordered assemblies held together bonds.1–7 reversible interaction monomers confers bountiful these as smart materials, opening new avenues fascinating opportunities, ranging from material recycling applications.3,8–11 solute-solute interactions well-established,1,2,4 solute-solvent interplay has recently attracted interest chemists.12–14 medium nature, many exquisite assemblies,15–24 low-molecular-weight gels,25–29 polymers30–36 have been developed media various applications, such biomolecular materials37,38 soft actuators.39–41 However, detailed insight far being understood it solvents.12,14 Equally challenging elucidating structural features enable aggregates Forming requires delicate amphiphilic monomers: balance hydrophilicity hydrophobicity sufficient directional (non-covalent bonding) induce formation linear instead micellar aggregates.32,42,43 It notoriously thermodynamic temperature-dependent experiments strong when exposed water.44–46 principal methods investigate properties computational simulations or inferring conclusions water-organic solvent mixtures.46–50 Meijer coworkers revealed controls growth using molecular dynamics (MD) simulations.49 Würthner signature ?-amphiphile, oligo(ethylene glycol) (OEG) functionalized perylene bisimides, water/tetrahydrofuran mixture, revealing entropically-driven process.46 Interestingly, its analog characterized methylene spacer bisimide core phenyl substituent bearing OEG followed water.45 resulting show opposite reactions temperature changes: heating induces former structures, latter assemble during cooling.45,46 These studies indicate minimal changes structure resulted fundamentally processes.45–47,51–53 Noting multiparameter nature water, question how effects affect remains largely unanswered. also particularly interested assembly. Stiff-stilbene five-membered ring stilbene54 example, switchable receptors ligands,55–58 force probes,59 aggregation-induced emission.60 C–Ph torsion angle nearly zero,61 imposing planar ? facilitating assemblies,54,62–64 (Z)-isomer loses planarity.65 huge differences (Z)-isomers offer opportunity ?–? polymerization.64 Recently, reported photoinduced cooperative bis-ureas toluene taking intramolecular intermolecular hydrogen-bonding isomers.63 In study, investigated photoswitchable experimental parameters gain insights role (Figure 1). showed rather ability form To best our knowledge, limited focus solvent-adaptive polymers66; hence, findings provide excellent compare processes distinct environments additional benefit geometry controlled demand light. Figure 1 | schematic illustrations (E)-SA (Z)-SA Both follow mechanism, where (?G°) monomerically dissolved toluene, short fibers Results Discussion behavior (see Supporting Information Figures S10–S16 NMR high resolution MS data)in monitored UV–vis absorption spectrum (12.5 ?M) upon cooling range 310 370 K at rate 1.0 K/min details). characteristic band maximum centered 371 nm 2a), comparable toluene.63 Upon heating, decreased intensity, accompanied two local maxima 340 357 nm, closely resembles monomeric [e.g., dimethyl sulfoxide (DMSO)].63 polymer heating. K, gradually disappeared concomitant 2b), suggesting transition well-defined aggregates. steep increase critical 358.5 (inset 2b). non-sigmoidal curve sharp reflects process.53,67–69 2 Temperature-dependent (a) (b) K/min. Inset: nm. (c) Cryo-TEM image (0.4 mM) (d) Hexamer optimized GFN-FF level identify structure, performed cryo-transmission electron microscopy (TEM) measurements formed images nanofibers hundreds nanometers (?500 nm) uniform diameter 6.8 ± 0.5 2c S1), indicating 1D polymer. support hexamer modeled employing GFN field (GFN-FF).70 preliminary MD run 100 ps 398 Berendsen thermostat implicit (GBSA model). molecule then same theory 2d).70,71 (E)-stiff-stilbene units stacked distance 3.5–4.0 Å, main hold molecules nucleation stage ?-interactions cores, propagated along fiber. While H-bonding ureas strengthens side chains neighboring final polymer, random orientation, they seem contribution stage. bonds assembly, added concentration competing H-bond forming compounds solution (5.0 S9). remained stable after adding 105 equiv urea, evidenced consistent S9a). Aiming break formic acid stronger reagent S9b).72 even 3 × acid. stability pockets C6 alkyl chain.66,73 results hypothesis increased thanks cannot easily disrupted, excess reagent. Consequently, favorable urea interactions, is, H-bonding, facilitate water.49 recorded ? samples increasing total (cT) S4 S5). curves representing degree (?agg, estimated function shown 3a 3b. processes, shape combination intense transitions temperatures Te Te? confirm (nucleation-elongation) polymerization.53,67–69 higher (Te) (Te?) thermal hysteresis 3c), under kinetic control.68 contrast, heating-induced control, observation confirmed unaltered K·min?1 S6). further analyzed melting obtain Van’t Hoff plot.68 natural logarithm cT relationship reciprocal 3d). enthalpy ?H° ?124 mol?1 more negative (?77 obtained (Table Possibly, contributions stacking, while non-classical effect74 leads enthalpy.45 entropy (?S°) ?244 J K?1, ?165 K?1 organized decrease degrees freedom contribute enhanced almost robust equilibrium constants 2.8 109 M?1 9.8 104 1), respectively, mass model Markvoort et al.75 overall suggest contributing significantly ?G°. (?agg) apparent coefficients concentrations Values observed cT. Natural (Van’t plot). Table Thermodynamic Parameters Describing Assembly Toluene Solvent (kJ ?S° (J K?1) ?G° (293 K) (M?1) ?77 ?28 gelated relatively low (1 mg/mL), following heating–cooling cycle S3), failed hydrogel conditions. cryo-TEM above sample had undergone (annealing) were similar S3 entanglement suggests fibrous network contributes gelation. photo-isomerization S7). After irradiating 30 min, 1H same, assembled (aggregate) state possibly hampered room temperature, but happed S7 S10). By feasible,63 speculate reason impeded isomerization consequence aggregation,22 ?G°water ?G°toluene. aggregating abilities broadened proton resonances spectra (298 500 MHz, D2O) S17).76 measured SA. hypsochromic shift DMSO 4a), fibers, approximately 50 8.0 0.6 4b S2). ones less bonds.63 dihedral plane group Ph1 ethylene atom C1 14.3° 4a); not susceptible stacking.65 Therefore, shorter might related lack stacking bonds. direct situ irradiation feasible, external photochemical allows controlling fiber, tenfold diameter. 4 (10.0 (Z)-SA. Conclusions analysis adaptive determined impact ?G°, displays presence drastically polymers. will enrich fundamental understanding polymers, materials bottom-up strategy. available including preparation, characterization, UV–vis, cryo-TEM, NMR, studies. Conflict Interest There no conflict report. Funding Financial Netherlands Organization Scientific (NWO-CW), European Council (ERC; advanced grant no. 694345 B.L.F.), Dutch Ministry Education, Culture (Gravitation program 024.001.035), Scholarship (CSC; 201707040064 F.X.), Marie Sk?odowska-Curie Actions (Individual Fellowships 838280 S.C. 793082 L.P.) gratefully acknowledged. Acknowledgments authors wish acknowledge Dr. Sander J. Wezenberg Franco King-Chi Leung helpful discussions. References 1. Lehn M.Supramolecular Chemistry; John Wiley & Sons: Strasbourg, 1995. 2. Brunsveld L.; Folmer B. B.; E. W.; Sijbesma R. P.Supramolecular Polymers.Chem. Rev.2001, 101, 4071–4098. 3. Aida T.; Stupp S. I.Functional Polymers.Science2012, 335, 813–817. 4. Greef T. F. A.; Smulders M. J.; Wolffs M.; Schenning P. H. P.; W.Supramolecular Polymerization.Chem. Rev.2009, 109, 5687–5754. 5. Schmuck C.; Wienand W.Self-Complementary Quadruple Hydrogen-Bonding Motifs Functional Principle: From Dimeric Supramolecules Polymers.Angew. Chem. Int. 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