Light-induced dynamic shaping and self-division of multipodal polyelectrolyte-surfactant microarchitectures via azobenzene photomechanics

Light-induced shape transformations represent a fundamental step towards the emergence of adaptive materials exhibiting photomechanical behaviours. Although a range of covalent azobenzene-based photoactive materials has been demonstrated, the use of dynamic photoisomerization in mesostructured soft solids involving non-covalent co-assembly has received little attention. Here we prepare discrete micrometre-sized hydrated particles of a hexagonally ordered polyelectrolyte-surfactant mesophase based on the electrostatically induced co-assembly of poly(sodium acrylate) (PAA) and trans-azobenzene trimethylammonium bromide (trans-azoTAB), and demonstrate unusual non-equilibrium substrate-mediated shape transformations to complex multipodal microarchitectures under continuous blue light. The microparticles spontaneously sequester molecular dyes, functional enzymes and oligonucleotides, and undergo self-division when transformed to the cis state under UV irradiation. Our results illustrate that weak bonding interactions in polyelectrolyte-azobenzene surfactant mesophases can be exploited for photo-induced long-range molecular motion, and highlight how dynamic shape transformations and autonomous division can be activated by spatially confining azobenzene photomechanics in condensed microparticulate materials.

[1]  R. Azumi,et al.  Light-induced crawling of crystals on a glass surface , 2015, Nature Communications.

[2]  H. Stone,et al.  Pumping-out photo-surfactants from an air–water interface using light , 2011 .

[3]  C. Faul.  Ionic self-assembly for functional hierarchical nanostructured materials. , 2014, Accounts of chemical research.

[4]  Dirk J. Broer,et al.  New insights into photoactivated volume generation boost surface morphing in liquid crystal coatings , 2015, Nature Communications.

[5]  Dirk J. Broer,et al.  A chaotic self-oscillating sunlight-driven polymer actuator , 2016, Nature Communications.

[6]  Jung-Ki Park,et al.  Directional Photofluidization Lithography: Micro/Nanostructural Evolution by Photofluidic Motions of Azobenzene Materials , 2012, Advanced materials.

[7]  N. K. Mani,et al.  Photosensitive surfactants with various hydrophobic tail lengths for the photocontrol of genomic DNA conformation with improved efficiency. , 2010, Chemistry.

[8]  S. Ferrari,et al.  Author contributions , 2021 .

[9]  H. Koshima,et al.  Mechanical motion of azobenzene crystals upon photoirradiation. , 2009, Journal of the American Chemical Society.

[10]  Guichao Kuang,et al.  A ferrocene-azobenzene derivative showing unprecedented phase transition and better solubility upon UV irradiation. , 2016, Physical chemistry chemical physics : PCCP.

[11]  S. Takeda,et al.  Dissipative and Autonomous Square-Wave Self-Oscillation of a Macroscopic Hybrid Self-Assembly under Continuous Light Irradiation. , 2016, Angewandte Chemie.

[12]  S. Kanazawa,et al.  Photochemically reversible liquefaction and solidification of multiazobenzene sugar-alcohol derivatives and application to reworkable adhesives. , 2014, ACS applied materials & interfaces.

[13]  C. Faul,et al.  A Supramolecular Approach to Optically Anisotropic Materials: Photosensitive Ionic Self‐Assembly Complexes , 2006 .

[14]  J. Eastoe,et al.  Self-assembly of light-sensitive surfactants. , 2005, Soft matter.

[15]  S. Santer,et al.  A comparative study of photoinduced deformation in azobenzene containing polymer films. , 2016, Soft matter.

[16]  J. Santamarina,et al.  Closure of "Particle Shape Effects on Packing Density, Stiffness, and Strength: Natural and Crushed Sands" , 2006 .

[17]  T. Asahi,et al.  Mechanical Motion of Chiral Azobenzene Crystals with Twisting upon Photoirradiation. , 2016, Chemistry.

[18]  J. Cornelissen,et al.  Conversion of light into macroscopic helical motion. , 2014, Nature chemistry.

[19]  Pascal Royer,et al.  Multiscale model for photoinduced molecular motion in azo polymers. , 2009, ACS nano.

[20]  Richard LeSar,et al.  The random-walk model , 2013 .

[21]  Haifeng Yu,et al.  Photocontrollable Liquid‐Crystalline Actuators , 2011, Advanced materials.

[22]  T. Ikeda,et al.  Photomechanics: Directed bending of a polymer film by light , 2003, Nature.

[23]  Zahid Mahimwalla,et al.  Azobenzene photomechanics: prospects and potential applications , 2012, Polymer Bulletin.

[24]  Tomiki Ikeda,et al.  Photomobile polymer materials with crosslinked liquid-crystalline structures: molecular design, fabrication, and functions. , 2014, Angewandte Chemie.

[25]  Jörg Ackermann,et al.  Light-induced molecular motion of azobenzene-containing molecules: a random-walk model , 2006 .

[26]  S. Monti,et al.  cis .dblharw. trans Photoisomerization of azobenzene-cyclodextrin inclusion complexes , 1987 .

[27]  R. Haag,et al.  Photoresponsive amphiphiles based on azobenzene-dendritic glycerol conjugates show switchable transport behavior. , 2011, Chemical communications.

[28]  A. Schenning,et al.  Regulating the modulus of a chiral liquid crystal polymer network by light† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6sm00114a Click here for additional data file. Click here for additional data file. , 2016, Soft matter.

[29]  Alberto Credi,et al.  Light-powered autonomous and directional molecular motion of a dissipative self-assembling system. , 2015, Nature nanotechnology.

[30]  T. C. Huang,et al.  X‐ray powder diffraction analysis of silver behenate, a possible low‐angle diffraction standard , 1993 .

[31]  Mina Han,et al.  Rational design of light-directed dynamic spheres. , 2012, Chemical communications.

[32]  M. Shelley,et al.  Fast liquid-crystal elastomer swims into the dark , 2004, Nature materials.

[33]  S. Adachi,et al.  Crystal melting by light: X-ray crystal structure analysis of an azo crystal showing photoinduced crystal-melt transition. , 2014, Journal of the American Chemical Society.

[34]  Paul Rochon,et al.  Optically induced surface gratings on azoaromatic polymer films , 1995 .

[35]  C. Bazuin,et al.  Submolecular Plasticization Induced by Photons in Azobenzene Materials. , 2015, Journal of the American Chemical Society.

[36]  B. Cabane,et al.  How To Concentrate an Aqueous Polyelectrolyte/Surfactant Mixture by Adding Water , 1998 .

[37]  Jianbin Huang,et al.  Adaptive soft molecular self-assemblies. , 2016, Soft matter.

[38]  I Pagonabarraga,et al.  Controlled drop emission by wetting properties in driven liquid filaments. , 2011, Nature materials.

[39]  T. Ikeda,et al.  Photomobile polymer materials: towards light-driven plastic motors. , 2008, Angewandte Chemie.

[40]  T. Narayanan,et al.  Kinetics of Photocontrollable Micelles: Light-Induced Self-Assembly and Disassembly of Azobenzene-Based Surfactants Revealed by TR-SAXS. , 2016, Langmuir : the ACS journal of surfaces and colloids.

[41]  Qibin Chen,et al.  Hierarchical Assembly of a Dual-responsive Macroscopic Insulated Molecular Wire Bundle in a Gradient System , 2015, Scientific Reports.

[42]  R. Al‐Kaysi,et al.  Reversible photoinduced twisting of molecular crystal microribbons. , 2011, Journal of the American Chemical Society.

[43]  D. Cholakova,et al.  Self-shaping of oil droplets via the formation of intermediate rotator phases upon cooling , 2015, Nature.

[44]  R. Haag,et al.  Supramolecular Architectures of Dendritic Amphiphiles in Water. , 2016, Chemical reviews.

[45]  Paul Rochon,et al.  Photoinduced motions in azo-containing polymers. , 2002, Chemical reviews.

[46]  R. von Klitzing,et al.  Light‐Controlled Reversible Manipulation of Microgel Particle Size Using Azobenzene‐Containing Surfactant , 2012 .

[47]  F. Fabbri,et al.  Evidence of two distinct mechanisms driving photoinduced matter motion in thin films containing azobenzene derivatives. , 2011, The journal of physical chemistry. B.

[48]  D. Wiersma,et al.  Structured light enables biomimetic swimming and versatile locomotion of photoresponsive soft microrobots. , 2016, Nature materials.

[49]  S. Hecht,et al.  Light-Controlled “Molecular Zippers” Based on Azobenzene Main Chain Polymers , 2015 .

[50]  O. Ikkala,et al.  Structurally Controlled Dynamics in Azobenzene-Based Supramolecular Self-Assemblies in Solid State , 2016 .

[51]  S. Hecht,et al.  Cooperative Switching in Nanofibers of Azobenzene Oligomers , 2016, Scientific Reports.