Specific and reversible DNA-directed self-assembly of oil-in-water emulsion droplets

Higher-order structures that originate from the specific and reversible DNA-directed self-assembly of microscopic building blocks hold great promise for future technologies. Here, we functionalized biotinylated soft colloid oil-in-water emulsion droplets with biotinylated single-stranded DNA oligonucleotides using streptavidin as an intermediary linker. We show the components of this modular linking system to be stable and to induce sequence-specific aggregation of binary mixtures of emulsion droplets. Three length scales were thereby involved: nanoscale DNA base pairing linking microscopic building blocks resulted in macroscopic aggregates visible to the naked eye. The aggregation process was reversible by changing the temperature and electrolyte concentration and by the addition of competing oligonucleotides. The system was reset and reused by subsequent refunctionalization of the emulsion droplets. DNA-directed self-assembly of oil-in-water emulsion droplets, therefore, offers a solid basis for programmable and recyclable soft materials that undergo structural rearrangements on demand and that range in application from information technology to medicine.

[1]  D Needham,et al.  Avidin-biotin interactions at vesicle surfaces: adsorption and binding, cross-bridge formation, and lateral interactions. , 1996, Biophysical journal.

[2]  E. Evans,et al.  ENERGETICS OF MEMBRANE DEFORMATION AND ADHESION IN CELL AND VESICLE AGGREGATION a , 1983, Annals of the New York Academy of Sciences.

[3]  Carolyn R Bertozzi,et al.  Programmed assembly of 3-dimensional microtissues with defined cellular connectivity , 2009, Proceedings of the National Academy of Sciences.

[4]  J. Crocker,et al.  Reversible self-assembly and directed assembly of DNA-linked micrometer-sized colloids. , 2005, Proceedings of the National Academy of Sciences of the United States of America.

[5]  Hiroyuki Fujita,et al.  Active transport of oil droplets along oriented microtubules by kinesin molecular motors. , 2009, Lab on a chip.

[6]  D. Leckband,et al.  A neutron reflectivity study of polymer-modified phospholipid monolayers at the solid-solution interface: polyethylene glycol-lipids on silane-modified substrates. , 1998, Biophysical journal.

[7]  Yutaka Sumino,et al.  Blebbing dynamics in an oil-water-surfactant system through the generation and destruction of a gel-like structure. , 2007, Physical review. E, Statistical, nonlinear, and soft matter physics.

[8]  T. Vanderlick,et al.  Specific binding of different vesicle populations by the hybridization of membrane-anchored DNA. , 2007, The journal of physical chemistry. A.

[9]  I. Bekersky,et al.  AmBisome (Liposomal Amphotericin B): A Comparative Review , 1998, Journal of clinical pharmacology.

[10]  Fredrik Höök,et al.  Characterization of DNA immobilization and subsequent hybridization on a 2D arrangement of streptavidin on a biotin-modified lipid bilayer supported on SiO2. , 2003, Analytical chemistry.

[11]  J. Baudry,et al.  Specific wetting probed with biomimetic emulsion droplets , 2008 .

[12]  S. Alexander,et al.  Adsorption of chain molecules with a polar head a scaling description , 1977 .

[13]  M. Prentiss,et al.  Demonstration that the shear force required to separate short double-stranded DNA does not increase significantly with sequence length for sequences longer than 25 base pairs. , 2008, Physical review. E, Statistical, nonlinear, and soft matter physics.

[14]  Takashi Ikegami,et al.  Fatty acid chemistry at the oil-water interface: self-propelled oil droplets. , 2007, Journal of the American Chemical Society.

[15]  D. Leckband,et al.  Modulation of interaction forces between bilayers exposing short-chained ethylene oxide headgroups. , 1994, Biophysical journal.

[16]  V. Viasnoff,et al.  Biomimetic emulsions reveal the effect of mechanical forces on cell–cell adhesion , 2012, Proceedings of the National Academy of Sciences.

[17]  T. Allen,et al.  Insertion of poly(ethylene glycol) derivatized phospholipid into pre‐formed liposomes results in prolonged in vivo circulation time , 1996, FEBS letters.

[18]  W. Meier.  Reversible cell aggregation induced by specific ligand-receptor coupling , 2000 .

[19]  P. E. Hotz,et al.  A Quantitative Analytical Method to Test for Salt Effects on Giant Unilamellar Vesicles , 2011, Scientific reports.

[20]  P. G. de Gennes,et al.  Polymer solutions near an interface. Adsorption and depletion layers , 1981 .

[21]  S. Mann,et al.  Organization of Inorganic Nanoparticles Using Biotin−Streptavidin Connectors , 1999 .

[22]  B Montgomery Pettitt,et al.  Coulomb blockage of hybridization in two-dimensional DNA arrays. , 2002, Physical review. E, Statistical, nonlinear, and soft matter physics.

[23]  Joakim Lundeberg,et al.  The biotin‐streptavidin interaction can be reversibly broken using water at elevated temperatures , 2005, Electrophoresis.

[24]  R. Carbonell,et al.  Affinity Precipitation of Proteins by Surfactant‐Solubilized, Ligand‐Modified Phospholipids , 1992, Biotechnology progress.

[25]  U. Seifert,et al.  Force-induced growth of adhesion domains is controlled by receptor mobility , 2008, Proceedings of the National Academy of Sciences.

[26]  B. Grzybowski,et al.  Self-division of macroscopic droplets: partitioning of nanosized cargo into nanoscale micelles. , 2010, Angewandte Chemie.

[27]  Christopher K. Tison,et al.  Reversing DNA-mediated adhesion at a fixed temperature. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[28]  Maik Hadorn,et al.  DNA-Mediated Self-Assembly of Artificial Vesicles , 2010, PloS one.

[29]  John F. Nagle,et al.  Structure of Fully Hydrated Fluid Phase Lipid Bilayers with Monounsaturated Chains , 2006, The Journal of Membrane Biology.

[30]  H. Gaub,et al.  Adhesion forces between individual ligand-receptor pairs. , 1994, Science.

[31]  P. G. de Gennes,et al.  Polymers at an interface; a simplified view , 1987 .

[32]  J. Storhoff,et al.  A DNA-based method for rationally assembling nanoparticles into macroscopic materials , 1996, Nature.

[33]  D. Leckband,et al.  Higher order self-assembly of vesicles by site-specific binding. , 1994, Science.

[34]  J. Crocker,et al.  Direct measurements of DNA-mediated colloidal interactions and their quantitative modeling , 2011, Proceedings of the National Academy of Sciences.

[35]  N. Seeman,et al.  Simple quantitative model for the reversible association of DNA coated colloids. , 2009, Physical review letters.

[36]  Andrew I Cooper,et al.  Polymer-mediated hierarchical and reversible emulsion droplet assembly. , 2009, Angewandte Chemie.

[37]  K. Yoshikawa,et al.  Spontaneous deformation of an oil droplet induced by the cooperative transport of cationic and anionic surfactants through the interface. , 2009, The journal of physical chemistry. B.

[38]  V. N. Paunov,et al.  Adsorption and hybridisation of DNA-surfactants at fluid surfaces and lipid bilayers , 2005 .

[39]  Jérôme Bibette,et al.  Emulsions: basic principles , 1999 .

[40]  Warren A. Kibbe,et al.  The issue of amalgams. , 1996, Nucleic Acids Res..

[41]  Fook Chiong Cheong,et al.  Switchable self-protected attractions in DNA-functionalized colloids. , 2009, Nature Materials.

[42]  J. Weaver,et al.  The role of responsive branched copolymer composition in controlling pH-triggered aggregation of “engineered” emulsion droplets: towards selective droplet assembly , 2011 .

[43]  Needham,et al.  PEG-covered lipid surfaces: bilayers and monolayers. , 2000, Colloids and surfaces. B, Biointerfaces.

[44]  A. Cooper,et al.  Controlling responsive emulsion properties via polymer design. , 2009, Chemical communications.

[45]  Valeria T Milam,et al.  DNA-mediated phase behavior of microsphere suspensions. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[46]  Predicting DNA-mediated colloidal pair interactions , 2012, Proceedings of the National Academy of Sciences.

[47]  G. Whitesides,et al.  Self-Assembly at All Scales , 2002, Science.