Light-controlled self-assembly of non-photoresponsive nanoparticles.

The ability to guide the assembly of nanosized objects reversibly with external stimuli, in particular light, is of fundamental importance, and it contributes to the development of applications as diverse as nanofabrication and controlled drug delivery. However, all the systems described to date are based on nanoparticles (NPs) that are inherently photoresponsive, which makes their preparation cumbersome and can markedly hamper their performance. Here we describe a conceptually new methodology to assemble NPs reversibly using light that does not require the particles to be functionalized with light-responsive ligands. Our strategy is based on the use of a photoswitchable medium that responds to light in such a way that it modulates the interparticle interactions. NP assembly proceeds quantitatively and without apparent fatigue, both in solution and in gels. Exposing the gels to light in a spatially controlled manner allowed us to draw images that spontaneously disappeared after a specific period of time.

[1]  M. Pileni,et al.  Effect of the Structure of Cobalt Nanocrystal Organization on the Collective Magnetic Properties , 2003 .

[2]  Bartosz A Grzybowski,et al.  Photoswitchable catalysis mediated by dynamic aggregation of nanoparticles. , 2010, Journal of the American Chemical Society.

[3]  T. Santa,et al.  A photoinduced electron-transfer reagent for peroxyacetic acid, 4-ethylthioacetylamino-7-phenylsulfonyl-2,1,3-benzoxadiazole, based on the method for predicting the fluorescence quantum yields. , 2002, Analytical chemistry.

[4]  J. T. Mayo,et al.  Low-Field Magnetic Separation of Monodisperse Fe3O4 Nanocrystals , 2006, Science.

[5]  F. Glorius,et al.  Superparamagnetic nanoparticles for asymmetric catalysis—a perfect match , 2011 .

[6]  M. El-Sayed,et al.  Catalysis with Transition Metal Nanoparticles in Colloidal Solution: Nanoparticle Shape Dependence and Stability , 2005 .

[7]  Jelle E. Stumpel,et al.  Photoswitchable hydrogel surface topographies by polymerisation-induced diffusion. , 2013, Chemistry.

[8]  Sunghoon Kwon,et al.  Magnetic assembly of nonmagnetic particles into photonic crystal structures. , 2010, Nano letters.

[9]  T. Rajh,et al.  In situ visualization of self-assembly of charged gold nanoparticles. , 2013, Journal of the American Chemical Society.

[10]  Mingsheng Wang,et al.  Magnetic assembly route to colloidal responsive photonic nanostructures. , 2012, Accounts of chemical research.

[11]  Sanjib Das,et al.  Tailoring the properties of surface-immobilized azobenzenes by monolayer dilution and surface curvature. , 2015, Langmuir : the ACS journal of surfaces and colloids.

[12]  Kaoru Tamada,et al.  Optimized Photoisomerization on Gold Nanoparticles Capped by Unsymmetrical Azobenzene Disulfides , 2003 .

[13]  M. Fox,et al.  Photoreactivity of Self-assembled Monolayers of Azobenzene or Stilbene Derivatives Capped on Colloidal Gold Clusters , 2001 .

[14]  Dayang Wang,et al.  Size-dependent electrostatic chain growth of pH-sensitive hairy nanoparticles. , 2013, Angewandte Chemie.

[15]  Bartosz A Grzybowski,et al.  How and why nanoparticle's curvature regulates the apparent pKa of the coating ligands. , 2011, Journal of the American Chemical Society.

[16]  Jinwoo Cheon,et al.  Critical enhancements of MRI contrast and hyperthermic effects by dopant-controlled magnetic nanoparticles. , 2009, Angewandte Chemie.

[17]  Benjamin J. Wiley,et al.  Imaginary magnetic tweezers for massively parallel surface adhesion spectroscopy. , 2011, Nano letters.

[18]  R. Eelkema,et al.  Spatial structuring of a supramolecular hydrogel by using a visible-light triggered catalyst. , 2015, Angewandte Chemie.

[19]  E. Kumacheva,et al.  Properties and emerging applications of self-assembled structures made from inorganic nanoparticles. , 2010, Nature nanotechnology.

[20]  Christina Graf,et al.  Multivalency as a chemical organization and action principle. , 2012, Angewandte Chemie.

[21]  M. El-Sayed,et al.  Catalysis with transition metal nanoparticles in colloidal solution: nanoparticle shape dependence and stability. , 2005, The journal of physical chemistry. B.

[22]  N. Bell,et al.  Photophysical effects between spirobenzopyran-methyl methacrylate-functionalized colloidal particles. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[23]  J. Fraser Stoddart,et al.  Metal nanoparticles functionalized with molecular and supramolecular switches. , 2009, Journal of the American Chemical Society.

[24]  Bartosz A. Grzybowski,et al.  Colloidal assembly directed by virtual magnetic moulds , 2013, Nature.

[25]  Paul S Weiss,et al.  Surface-enhanced Raman spectroscopy to probe photoreaction pathways and kinetics of isolated reactants on surfaces: flat versus curved substrates. , 2012, Nano letters.

[26]  R. Varma,et al.  Nano-magnetite (Fe3O4) as a support for recyclable catalysts in the development of sustainable methodologies. , 2013, Chemical Society reviews.

[27]  Toshiyuki Kanamori,et al.  Fast-reversible light-driven hydrogels consisting of spirobenzopyran-functionalized poly(N-isopropylacrylamide) , 2011 .

[28]  K. Ichimura,et al.  Photocontrolled aggregation of colloidal silica , 1994 .

[29]  M. Pileni,et al.  Van der Waals versus dipolar forces controlling mesoscopic organizations of magnetic nanocrystals , 2004, Nature materials.

[30]  Rafal Klajn,et al.  Spiropyran-based dynamic materials. , 2014, Chemical Society reviews.

[31]  P. Braun,et al.  Patterned colloid assembly by grafted photochromic polymer layers. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[32]  R. Klajn,et al.  Dual-responsive nanoparticles that aggregate under the simultaneous action of light and CO2. , 2015, Chemical communications.

[33]  Jerry S. H. Lee,et al.  Magnetic nanoparticles in MR imaging and drug delivery. , 2008, Advanced drug delivery reviews.

[34]  Using light to covalently immobilize and pattern nanoparticles onto surfaces. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[35]  Yasuhiro Shiraishi,et al.  Spiropyran-modified gold nanoparticles: reversible size control of aggregates by UV and visible light irradiations. , 2014, ACS applied materials & interfaces.

[36]  J. Cheon,et al.  Artificial control of cell signaling and growth by magnetic nanoparticles. , 2010, Angewandte Chemie.

[37]  Y. Kang,et al.  Investigation of Co nanoparticle assemblies induced by magnetic field , 2008 .

[38]  R. Klajn,et al.  Dynamically self-assembling carriers enable guiding of diamagnetic particles by weak magnets. , 2012, Journal of the American Chemical Society.

[39]  Christian Bergemann,et al.  Iron oxide nanoparticles as a drug delivery vehicle for MRI monitored magnetic targeting of brain tumors. , 2008, Biomaterials.

[40]  R. Klajn Immobilized azobenzenes for the construction of photoresponsive materials , 2010 .

[41]  Rafal Klajn Spiropyran‐Based Dynamic Materials , 2014 .

[42]  R. Klajn,et al.  Support curvature and conformational freedom control chemical reactivity of immobilized species. , 2014, Journal of the American Chemical Society.

[43]  Vincent M. Rotello,et al.  Magnetic assembly of colloidal superstructures with multipole symmetry , 2009, Nature.

[44]  Eric Bakker,et al.  Photocurrent generation based on a light-driven proton pump in an artificial liquid membrane. , 2014, Nature chemistry.

[45]  Bartosz A Grzybowski,et al.  Writing self-erasing images using metastable nanoparticle "inks". , 2009, Angewandte Chemie.

[46]  Jinwoo Cheon,et al.  A magnetic switch for the control of cell death signalling in in vitro and in vivo systems. , 2012, Nature materials.

[47]  D. Diamond,et al.  Photo‐Chemopropulsion – Light‐Stimulated Movement of Microdroplets , 2014, Advanced materials.

[48]  D. Strohecker,et al.  Long-lived photoacid based upon a photochromic reaction. , 2011, Journal of the American Chemical Society.

[49]  Kang Sun,et al.  Resettable, multi-readout logic gates based on controllably reversible aggregation of gold nanoparticles. , 2011, Angewandte Chemie.

[50]  P. Král,et al.  Self‐Assembly of Magnetite Nanocubes into Helical Superstructures. , 2014 .

[51]  Gurvinder Singh,et al.  Dual‐Responsive Nanoparticles and their Self‐Assembly , 2013, Advanced materials.

[52]  Fang Qian,et al.  Light‐Directed Electrophoretic Deposition: A New Additive Manufacturing Technique for Arbitrarily Patterned 3D Composites , 2013, Advanced materials.