Photochromic Spatiotemporal Control of Bubble-Propelled Micromotors by a Spiropyran Molecular Switch.

Controlling the environment in which bubble-propelled micromotors operate represents an attractive strategy to influence their motion, especially when the trigger is as simple as light. We demonstrate that spiropyrans, which isomerize to amphiphilic merocyanines under UV irradiation, can act as molecular switches that drastically affect the locomotion of the micrometer-sized engines. The phototrigger could be either a point or a field source, thus allowing different modes of control to be executed. A whole ensemble of micromotors was repeatedly activated and deactivated by just altering the spiropyran-merocyanine ratio with light. Moreover, the velocity of individual micromotors was altered using a point irradiation source that caused only localized changes in the environment. Such selective manipulation, achieved here with an optical microscope and a photochromic additive in the medium, reveals the ease of the methodology, which can allow micro- and nanomotors to reach their full potential of not just stochastic, but directional controlled motion.

[1]  J. Eastoe,et al.  Dynamic surface tension and adsorption mechanisms of surfactants at the air-water interface. , 2000, Advances in colloid and interface science.

[2]  R. Becker,et al.  Photochromic spiropyrans. I. Absorption spectra and evaluation of the .pi.-electron orthogonality of the constituent halves , 1970 .

[3]  Martin Pumera,et al.  Crucial Role of Surfactants in Bubble-Propelled Microengines , 2014 .

[4]  T. Satoh,et al.  Isomerization of spirobenzopyrans bearing electron-donating and electron-withdrawing groups in acidic aqueous solutions. , 2011, Physical chemistry chemical physics : PCCP.

[5]  Samuel Sánchez,et al.  Chemically powered micro- and nanomotors. , 2015, Angewandte Chemie.

[6]  O. Schmidt,et al.  Effect of surfactants on the performance of tubular and spherical micromotors - a comparative study. , 2014, RSC advances.

[7]  Estrella Alvarez,et al.  Surface Tension of Alcohol Water + Water from 20 to 50 .degree.C , 1995 .

[8]  Samuel Sanchez,et al.  Stimuli-Responsive Microjets with Reconfigurable Shape , 2014, Angewandte Chemie.

[9]  Y. Mei,et al.  Dynamics of catalytic tubular microjet engines: dependence on geometry and chemical environment. , 2011, Nanoscale.

[10]  G. Giusti,et al.  Comparative photodegradation study between spiro[indoline—oxazine] and spiro[indoline—pyran] derivatives in solution , 1993 .

[11]  Martin Pumera,et al.  Challenges of the movement of catalytic micromotors in blood. , 2013, Lab on a chip.

[12]  S. Balasubramanian,et al.  Template-assisted fabrication of salt-independent catalytic tubular microengines. , 2010, ACS nano.

[13]  I. Cabrera,et al.  Photocontraction of Liquid Spiropyran-Merocyanine Films , 1984, Science.

[14]  A. Bose,et al.  Formation of molecular H- and J-stacks by the spiropyran-merocyanine transformation in a polymer matrix , 1987 .

[15]  Wei Gao,et al.  Synthetic micro/nanomotors in drug delivery. , 2014, Nanoscale.

[16]  Martin Pumera,et al.  Influence of real-world environments on the motion of catalytic bubble-propelled micromotors. , 2013, Lab on a chip.

[17]  Garry Berkovic,et al.  Spiropyrans and Spirooxazines for Memories and Switches , 2000 .

[18]  E. Berman,et al.  Photochromic Spiropyrans. I. The Effect of Substituents on the Rate of Ring Closure , 1959 .

[19]  Elias I. Franses,et al.  Adsorption dynamics of surfactants at the air/water interface: a critical review of mathematical models, data, and mechanisms , 1995 .

[20]  Martin Pumera,et al.  Enhanced diffusion of pollutants by self-propulsion. , 2011, Physical chemistry chemical physics : PCCP.

[21]  Feng Shi,et al.  Design of a UV-responsive microactuator on a smart device for light-induced ON-OFF-ON motion , 2014 .

[22]  X. Qu,et al.  Optically switchable organic hollow nanocapsules. , 2010, Journal of colloid and interface science.

[23]  Martin Pumera,et al.  Blood proteins strongly reduce the mobility of artificial self-propelled micromotors. , 2013, Chemistry.

[24]  M. Moyá,et al.  Conductometric, surface tension, and kinetic studies in mixed SDS-Tween 20 and SDS-SB3-12 micellar solutions. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[25]  Martin Pumera,et al.  Magnetotactic artificial self-propelled nanojets. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[26]  Sharp spherical focal spot by dark ring 4Pi-confocal microscopy , 2001 .

[27]  Wei Gao,et al.  Catalytically propelled micro-/nanomotors: how fast can they move? , 2012, Chemical record.

[28]  R. A. Campbell,et al.  Effects of ionic strength on the surface tension and nonequilibrium interfacial characteristics of poly(sodium styrenesulfonate)/dodecyltrimethylammonium bromide mixtures. , 2014, Langmuir : the ACS journal of surfaces and colloids.

[29]  Sirilak Sattayasamitsathit,et al.  Water-driven micromotors for rapid photocatalytic degradation of biological and chemical warfare agents. , 2014, ACS nano.

[30]  Oliver G Schmidt,et al.  Thermal activation of catalytic microjets in blood samples using microfluidic chips. , 2013, Lab on a chip.

[31]  W. D. Harkins,et al.  The effect of salts on the critical concentration for the formation of micelles in colloidal electrolytes. , 1947, Journal of the American Chemical Society.

[32]  Wei Gao,et al.  Ultrasound-modulated bubble propulsion of chemically powered microengines. , 2014, Journal of the American Chemical Society.

[33]  I. Karube,et al.  Photocontrol of affinity chromatography: Purification of asparaginase by photosensitive AHA‐gel , 1978 .

[34]  A. Holtzer,et al.  On the ionic strength dependence of micelle number. II. , 1965, The Journal of physical chemistry.

[35]  Martin Pumera,et al.  Chemical energy powered nano/micro/macromotors and the environment. , 2015, Chemistry.

[36]  Martin Pumera,et al.  Biomimetic artificial inorganic enzyme-free self-propelled microfish robot for selective detection of Pb(2+) in water. , 2014, Chemistry.

[37]  Ayusman Sen,et al.  Fantastic voyage: designing self-powered nanorobots. , 2012, Angewandte Chemie.

[38]  David S. Jones,et al.  Synthesis and characterisation of polymerisable photochromic spiropyrans: towards photomechanical biomaterials , 2007 .

[39]  Sirilak Sattayasamitsathit,et al.  Efficient bubble propulsion of polymer-based microengines in real-life environments. , 2013, Nanoscale.

[40]  Wei Li,et al.  Single-Component TiO2 Tubular Microengines with Motion Controlled by Light-Induced Bubbles. , 2015, Small.

[41]  Hui Zhao,et al.  Light-controlled self-assembly of non-photoresponsive nanoparticles. , 2015, Nature chemistry.

[42]  O. Schmidt,et al.  Catalytic microtubular jet engines self-propelled by accumulated gas bubbles. , 2009, Small.

[43]  Chen Yu,et al.  Elucidating the mechanisms of acidochromic spiropyran-merocyanine interconversion. , 2007, The journal of physical chemistry. A.

[44]  R. Lemieux,et al.  Thermal Racemization of Substituted Indolinobenzospiropyrans: Evidence of Competing Polar and Nonpolar Mechanisms , 2000 .

[45]  J. K. Hurst,et al.  Spiropyran-based photochromic polymer nanoparticles with optically switchable luminescence. , 2006, Journal of the American Chemical Society.

[46]  T. Kunitake,et al.  Acid-Base Equilibria of Merocyanine Air-Water Monolayers , 1994 .

[47]  Martin Pumera,et al.  Blood metabolite strongly suppresses motion of electrochemically deposited catalytic self-propelled microjet engines , 2014 .

[48]  Wei Gao,et al.  The environmental impact of micro/nanomachines: a review. , 2014, ACS nano.

[49]  Krzysztof Matyjaszewski,et al.  Light-induced reversible formation of polymeric micelles. , 2007, Angewandte Chemie.

[50]  Shi-Yow Lin,et al.  Diffusion‐controlled surfactant adsorption studied by pendant drop digitization , 1990 .

[51]  Martin Pumera,et al.  External-energy-independent polymer capsule motors and their cooperative behaviors. , 2011, Chemistry.

[52]  Rohit Rosario,et al.  Lotus Effect Amplifies Light-Induced Contact Angle Switching , 2004 .

[53]  T. Seki,et al.  Formation of head-to-tail and side-by-side aggregates of photochromic spiropyrans in bilayer membrane , 1990 .

[54]  Devens Gust,et al.  Control of nanopore wetting by a photochromic spiropyran: a light-controlled valve and electrical switch. , 2006, Nano letters.

[55]  Michael R. Newton,et al.  Light-controlled ion transport through spiropyran-modified nanoporous silica colloidal films , 2010 .

[56]  D. Gust,et al.  Solvatochromic Study of the Microenvironment of Surface-Bound Spiropyrans , 2003 .

[57]  G. Giusti,et al.  Dealkylation of N-substituted indolinospironaphthoxazine photochromic compounds under UV irradiation , 1994 .

[58]  Samuel Sanchez,et al.  Light-controlled propulsion of catalytic microengines. , 2011, Angewandte Chemie.

[59]  F. Raymo,et al.  Signal processing at the molecular level. , 2001, Journal of the American Chemical Society.

[60]  M. Nakajima,et al.  Effects of surfactant and electrolyte concentrations on bubble formation and stabilization. , 2009, Journal of colloid and interface science.

[61]  T. Itoh,et al.  Photochromism of spiropyrans in organized molecular assemblies. Formation of J- and H-aggregates of photomerocyanines in bilayers–clay matrices , 1991 .

[62]  Jinwei Zhou,et al.  Correlations between solvatochromism, Lewis acid-base equilibrium and photochromism of an indoline spiropyran , 1995 .

[63]  G. Fernando,et al.  Photoresponsive polymers: An investigation of their photoinduced temperature changes during photoviscosity measurements , 2007 .

[64]  V. Krongauz,et al.  Quasi-crystals from irradiated photochromic dyes in an applied electric field , 1978, Nature.

[65]  Martin Pumera,et al.  Blood electrolytes exhibit a strong influence on the mobility of artificial catalytic microengines. , 2013, Physical chemistry chemical physics : PCCP.

[66]  Sung-Hoon Kim,et al.  Solvatochromic behavior of non-activated indolinobenzospiropyran 6-carboxylates in aqueous binary solvent mixtures. Part II , 2007 .

[67]  Thomas E Mallouk,et al.  Schooling behavior of light-powered autonomous micromotors in water. , 2009, Angewandte Chemie.

[68]  Byeong‐Su Kim,et al.  Light-responsive micelles of spiropyran initiated hyperbranched polyglycerol for smart drug delivery. , 2014, Biomacromolecules.

[69]  Jason Locklin,et al.  Formation of photochromic spiropyran polymer brushes via surface-initiated, ring-opening metathesis polymerization: reversible photocontrol of wetting behavior and solvent dependent morphology changes. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[70]  Qiang He,et al.  Near-infrared light-triggered "on/off" motion of polymer multilayer rockets. , 2014, ACS nano.

[71]  Martin Pumera,et al.  Magnetic Control of Tubular Catalytic Microbots for the Transport, Assembly, and Delivery of Micro‐objects , 2010 .

[72]  N. Abbott,et al.  Spatial and temporal control of surfactant systems. , 2009, Journal of colloid and interface science.

[73]  Lluís Soler,et al.  Catalytic nanomotors for environmental monitoring and water remediation , 2014, Nanoscale.

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

[75]  Martin Pumera,et al.  Concentric bimetallic microjets by electrodeposition , 2013 .

[76]  V. Minkin Photo‐, Thermo‐, Solvato‐, and Electrochromic Spiroheterocyclic Compounds , 2004 .

[77]  O. Schmidt,et al.  Superfast motion of catalytic microjet engines at physiological temperature. , 2011, Journal of the American Chemical Society.

[78]  Frank Jahnke,et al.  Photon-Modulated Wettability Changes on Spiropyran-Coated Surfaces , 2002 .

[79]  R. Becker,et al.  Photophysics, photochemistry, kinetics, and mechanism of the photochromism of 6'-nitroindolinospiropyran , 1986 .