Name: using polystyrene-block-poly(acrylic acid)-coated metal nanoparticles as monomers for their homo- and co-polymerization
Uploaded: 2015-07-09T15:00:00.000+00:00
Duration: 9 min 2 s
Description: Watch this Scientific Journal Video about Using Polystyrene-block-polyacrylic acid-coated Metal Nanoparticles as Monomers for Their Homo- and Co-polymerization at JoVE.com

The authors thank the NRF (CRP-4-2008-06), A*Star (SERC 112-120-2011) and MOE (RG14/13) Singapore for financial supports.

<ol>
	<li>Anker, J. N. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Biosensing+with+plasmonic+nanosensors.">Biosensing with plasmonic nanosensors.</a> Nat Mater. 7, 442-453 (2008).</li><li>Maier, S. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Plasmonics&#8212;A+Route+to+Nanoscale+Optical+Devices.">Plasmonics&#8212;A Route to Nanoscale Optical Devices.</a> Adv. Mater. 13, 1501-1505 (2001).</li><li>Zhu, Z. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Manipulation+of+Collective+Optical+Activity+in+One-Dimensional+Plasmonic+Assembly.">Manipulation of Collective Optical Activity in One-Dimensional Plasmonic Assembly.</a> ACS Nano. 6, 2326-2332 (2012).</li><li>Maier, S. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Local+detection+of+electromagnetic+energy+transport+below+the+diffraction+limit+in+metal+nanoparticle+plasmon+waveguides.">Local detection of electromagnetic energy transport below the diffraction limit in metal nanoparticle plasmon waveguides.</a> Nat. Mater. 2, 229-232 (2003).</li><li>Gong, J., Li, G., Tang, Z. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Self-assembly+of+noble+metal+nanocrystals:+Fabrication,+optical+property,+and+application.">Self-assembly of noble metal nanocrystals: Fabrication, optical property, and application.</a> Nano Today. 7, 564-585 (2012).</li><li>Wei, Q. H., Su, K. H., Durant, S., Zhang, X. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Plasmon Resonance of Finite One-Dimensional Au Nanoparticle Chains. Nano Lett. 4, 1067-1071 (2004).</li><li>Warner, M. G., Hutchison, J. E. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Linear+assemblies+of+nanoparticles+electrostatically+organized+on+DNA+scaffolds.">Linear assemblies of nanoparticles electrostatically organized on DNA scaffolds.</a> Nat Mater. 2, 272-277 (2003).</li><li>DeVries, G. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Divalent+Metal+Nanoparticles.">Divalent Metal Nanoparticles.</a> Science. 315, 358-361 (2007).</li><li>Kim, B. Y., Shim, I. -. B., Monti, O. L. A., Pyun, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Magnetic+self-assembly+of+gold+nanoparticle+chains+using+dipolar+core-shell+colloids.">Magnetic self-assembly of gold nanoparticle chains using dipolar core-shell colloids.</a> Chem. Commun. 47, 890-892 (2011).</li><li>Wang, L. B., Xu, L. G., Kuang, H., Xu, C. L., Kotov, N. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Dynamic+Nanoparticle+Assemblies.">Dynamic Nanoparticle Assemblies.</a> Acc. Chem. Res. 45, 1916-1926 (2012).</li><li>Tang, Z., Kotov, N. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=One-Dimensional+Assemblies+of+Nanoparticles:+Preparation,+Properties,+and+Promise.">One-Dimensional Assemblies of Nanoparticles: Preparation, Properties, and Promise.</a> Adv. Mater. 17, 951-962 (2005).</li><li>Keng, P. Y., Shim, I., Korth, B. D., Douglas, J. F., Pyun, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis+and+Self-Assembly+of+Polymer-Coated+Ferromagnetic+Nanoparticles.">Synthesis and Self-Assembly of Polymer-Coated Ferromagnetic Nanoparticles.</a> ACS Nano. 1, 279-292 (2007).</li><li>Shim, M., Guyot-Sionnest, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Permanent+dipole+moment+and+charges+in+colloidal+semiconductor+quantum+dots.">Permanent dipole moment and charges in colloidal semiconductor quantum dots.</a> J. Chem. Phys. 111, 6955-6964 (1999).</li><li>Nakata, K., Hu, Y., Uzun, O., Bakr, O., Stellacci, F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Chains+of+Superparamagnetic+Nanoparticles.">Chains of Superparamagnetic Nanoparticles.</a> Adv. Mater. 20, 4294-4299 (2008).</li><li>Tang, Z., Kotov, N. A., Giersig, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Spontaneous+Organization+of+Single+CdTe+Nanoparticles+into+Luminescent+Nanowires.">Spontaneous Organization of Single CdTe Nanoparticles into Luminescent Nanowires.</a> Science. 297, 237-240 (2002).</li><li>Zhang, H., Wang, D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Controlling+the+Growth+of+Charged-Nanoparticle+Chains+through+Interparticle+Electrostatic+Repulsion.">Controlling the Growth of Charged-Nanoparticle Chains through Interparticle Electrostatic Repulsion.</a> Angew. Chem. Int. Ed. 47, 3984-3987 (2008).</li><li>Yang, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Mechanistic+investigation+into+the+spontaneous+linear+assembly+of+gold+nanospheres.">Mechanistic investigation into the spontaneous linear assembly of gold nanospheres.</a> Phys. Chem. Chem. Phys. 12, 11850-11860 (2010).</li><li>Keng, P. Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Colloidal+Polymerization+of+Polymer-Coated+Ferromagnetic+Nanoparticles+into+Cobalt+Oxide+Nanowires.">Colloidal Polymerization of Polymer-Coated Ferromagnetic Nanoparticles into Cobalt Oxide Nanowires.</a> ACS Nano. 3, 3143-3157 (2009).</li><li>Xia, H., Su, G., Wang, D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Size-Dependent+Electrostatic+Chain+Growth+of+pH-Sensitive+Hairy+Nanoparticles.">Size-Dependent Electrostatic Chain Growth of pH-Sensitive Hairy Nanoparticles.</a> Angew. Chem. Int. Ed. 52, 3726-3730 (2013).</li><li>Wang, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Unconventional+Chain-Growth+Mode+in+the+Assembly+of+Colloidal+Gold+Nanoparticles.">Unconventional Chain-Growth Mode in the Assembly of Colloidal Gold Nanoparticles.</a> Angew. Chem. Int. Ed. 51, 8021-8025 (2012).</li><li>Wang, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Homo-+and+Co-polymerization+of+Polysytrene-block-Poly(acrylic+acid)-Coated+Metal+Nanoparticles.">Homo- and Co-polymerization of Polysytrene-block-Poly(acrylic acid)-Coated Metal Nanoparticles.</a> ACS Nano. 8, 8063-8073 (2014).</li><li>Fred, G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Controlled+Nucleation+for+Regulation+of+Particle-size+in+Monodisperse+Gold+Suspensions.">Controlled Nucleation for Regulation of Particle-size in Monodisperse Gold Suspensions.</a> Nature-Phys. Sci. 241, 20-22 (1973).</li><li>Gole, A., Murphy, C. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Azide-Derivatized+Gold+Nanorods:+Functional+Materials+for+&#8220;Click&#8221;+Chemistry.">Azide-Derivatized Gold Nanorods: Functional Materials for &#8220;Click&#8221; Chemistry.</a> Langmuir. 24, 266-272 (2007).</li><li>Lin, Z. -. H., Yang, Z., Chang, H. -. T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Preparation+of+Fluorescent+Tellurium+Nanowires+at+Room+Temperature.">Preparation of Fluorescent Tellurium Nanowires at Room Temperature.</a> Cryst. Growth Des. 8, 351-357 (2007).</li><li>Xia, Y. N., Xiong, Y. J., Lim, B., Skrabalak, S. E. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Shape-Controlled+Synthesis+of+Metal+Nanocrystals.">Shape-Controlled Synthesis of Metal Nanocrystals.</a> Simple Chemistry Meets Complex Physics? Angew. Chem. Int. Ed. 48, 60-103 (2009).</li><li>Chen, H. Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Encapsulation+of+Single+Small+Gold+Nanoparticles+by+Diblock+Copolymers.">Encapsulation of Single Small Gold Nanoparticles by Diblock Copolymers.</a> ChemPhysChem. 9, 388-392 (2008).</li><li>Kang, Y., Taton, T. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Controlling+Shell+Thickness+in+Core&#8722;Shell+Gold+Nanoparticles+via+Surface-Templated+Adsorption+of+Block+Copolymer+Surfactants.">Controlling Shell Thickness in Core&#8722;Shell Gold Nanoparticles via Surface-Templated Adsorption of Block Copolymer Surfactants.</a> Macromolecules. 38, 6115-6121 (2005).</li><li>Kang, Y., Taton, T. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Core/Shell+Gold+Nanoparticles+by+Self-Assembly+and+Crosslinking+of+Micellar.+Block-Copolymer+Shells.">Core/Shell Gold Nanoparticles by Self-Assembly and Crosslinking of Micellar. Block-Copolymer Shells.</a> Angew. Chem. Int. Ed. 44, 409-412 (2005).</li><li>Chen, Y., Cui, H., Li, L., Tian, Z., Tang, Z. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Controlling+micro-phase+separation+in+semi-crystalline/amorphous+conjugated+block+copolymers.">Controlling micro-phase separation in semi-crystalline/amorphous conjugated block copolymers.</a> Polymer Chemistry. 5, 4441-4445 (2014).</li><li>Bates, F. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Polymer-Polymer+Phase+Behavior.">Polymer-Polymer Phase Behavior.</a> Science. 251, 898-905 (1991).</li><li>Zhang, L. F., Shen, H. W., Eisenberg, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Phase+separation+behavior+and+crew-cut+micelle+formation+of+polystyrene-b-poly(acrylic+acid)+copolymers+in+solutions.">Phase separation behavior and crew-cut micelle formation of polystyrene-b-poly(acrylic acid) copolymers in solutions.</a> Macromolecules. 30, 1001-1011 (1997).</li><li>Yu, Y., Zhang, L., Eisenberg, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Morphogenic+Effect+of+Solvent+on+Crew-Cut+Aggregates+of+Apmphiphilic+Diblock+Copolymers.">Morphogenic Effect of Solvent on Crew-Cut Aggregates of Apmphiphilic Diblock Copolymers.</a> Macromolecules. 31, 1144-1154 (1998).</li><li>Liu, C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Toroidal+Micelles+of+Polystyrene-block-Poly(acrylic+acid).">Toroidal Micelles of Polystyrene-block-Poly(acrylic acid).</a> Small. 7, 2721-2726 (2011).</li></ol>

The authors have nothing to disclose.

Die mechanistischen Details der Synthesen berichtet und in den früheren Veröffentlichungen diskutiert. 20,21 Hier konzentrieren wir uns auf die Grundprinzipien der Synthesebedingungen. Für die Polymerisation von Nanopartikeln ist es bevorzugt, dass Nanopartikel von einheitlicher Größe verwendet. Wir folgen der Literatur beschriebenen Verfahren, um die gleichmäßige Au-Nanopartikeln, 23 Au-Nanostäbchen, 24 und Te-Nanodrähte. 25 In der Regel bessere Gleichmäßigkeit Gr?...

Despite great advances in the synthesis of nanoparticles over the past two decades, their orderly assembly remains a great challenge. Our synthetic capabilities in putting the basic building blocks together are of critical importance for the exploration and exploitation of their synergistic effects and collective properties. Thus, developing new reaction pathways and exploring the underlying mechanisms are the stepping stones towards the rational synthesis of complex nanodevices. 
Among the rich structural variety of possible nanoparticle assemblies, one-dimensional (1D) chains have shown useful applications in nanoelectronics, optoelectronics, and biosensors.1-4 Typically, self-assembly of nanoparticles into chain-like structures requires magnetic or electric dipole interactions, anisotropic electrostatic repulsion, or external templates.5-11 For dipole-induced assembly, one needs nanoparticles with permanent dipoles, such as magnetic nanoparticles and semiconductor nanoparticles under special environments.12-15 For nanoparticles with no permanent dipole, it has been shown that the relatively weaker electrostatic repulsion at the ends of the nanoparticle chains can promote the selective attachment of nanoparticle thereon and thus, 1D chain growth.16,17 Because the nanoparticles can aggregate with each other and with the oligomers, the aggregation often follows the intrinsic step-growth mode, leading to short chain length and the lack of control over branching. Lastly, nanoparticles can be adsorbed onto 1D templates to form chains, but usually it is very difficult to achieve secure anchoring and avoid gaps among the nanoparticles. 
With these existing methods, hetero-assembly or &#8220;co-polymerization&#8221; of nanoparticles is particularly difficult. A few pioneer works have demonstrated the &#8220;co-polymerization&#8221; of short nanoparticle chains exploiting magnetic dipole18 or electrostatic repulsion.19
Recently, we reported the homo- and co-polymerization of PSPAA-coated nanoparticles into chains.20,21 This new synthetic pathway involves facile colloidal synthesis and generic use of different types of nanoparticles. It affords ultralong chains without branching and allows ready control of their length and width (single-, double-, and triple-line chains). Most importantly, random- and co-polymers of nanoparticles can be synthesized with improved structural control. In this work, we provide video protocols for the related syntheses, intending to give a detailed demonstration and presentation.

<table><tbody><tr><td>Gold(III) chloride trihydrate, ACS reagent, &amp;ge;49.0% Au basis</td><td>Sigma-Aldrich</td><td>G4022</td><td>HAuCl&lt;sub&gt;4&lt;/sub&gt;</td></tr><tr><td>Sodium citrate dihydrate, 99%</td><td>Alfa Aesar</td><td>A12274</td><td></td></tr><tr><td>Sodium borohydride, &amp;ge;99%</td><td>Sigma-Aldrich</td><td>71321, Fluka</td><td></td></tr><tr><td>Hexadecyltrimethylammonium bromide, &amp;ge;98%</td><td>Sigma-Aldrich</td><td>H5882</td><td>CTAB</td></tr><tr><td>Silver Nitrate, 99.9999% trace metals basis</td><td>Sigma-Aldrich</td><td>204390</td><td></td></tr><tr><td>L-ascorbic acid, BioXtra, &amp;ge;99.0%, crystalline</td><td>Sigma-Aldrich</td><td>A5960</td><td></td></tr><tr><td>Tellurium dioxide, &amp;ge;99%&amp;nbsp;</td><td>Sigma-Aldrich</td><td>243450</td><td></td></tr><tr><td>Hydrazine monohydrate, 64-65%, reagent grade, 98%</td><td>Sigma-Aldrich</td><td>207942</td><td></td></tr><tr><td>Poly(styrene-&lt;em&gt;b&lt;/em&gt;-acrylic acid) (PS&lt;sub&gt;154&lt;/sub&gt;-PAA&lt;sub&gt;49&lt;/sub&gt;)</td><td>Polymer Source</td><td>P4673A-SAA</td><td>PS16000-PAA3500</td></tr><tr><td>Poly(styrene-&lt;em&gt;b&lt;/em&gt;-acrylic acid) (PS&lt;sub&gt;144&lt;/sub&gt;-PAA&lt;sub&gt;28&lt;/sub&gt;)</td><td>Polymer Source</td><td>P4002-SAA</td><td>PS15000-PAA1600</td></tr><tr><td>2-Naphthalenethiol, &amp;ge;99.0% (GC)</td><td>Sigma-Aldrich</td><td>88910, Fluka</td><td></td></tr><tr><td>Sodium dodecyl sulfate, 99%</td><td>Alfa Aesar</td><td>A11183</td><td></td></tr><tr><td>single wall carbon nanotubes, 99% ultra-pure</td><td>NanoIntegris</td><td>PC10344a</td><td></td></tr><tr><td>Sodium hydroxide</td><td>Sinopharm</td><td>S1900136</td><td></td></tr><tr><td>1,2-dipalmitoyl-&lt;em&gt;sn&lt;/em&gt;-glycero-3-phosphothioethanol (sodium salt)</td><td>Avanti polar lipids</td><td>870160P</td><td>PSH</td></tr><tr><td>&lt;em&gt;N,N&lt;/em&gt;-dimethylformamide</td><td>Merck</td><td>SA4s640012</td><td></td></tr><tr><td>Ethanol, absolute</td><td>Fischer</td><td>E/0650DF/17</td><td></td></tr><tr><td>Hydrochloric acid, 37%</td><td>Honey well</td><td>10189005</td><td>Dilute to 1&amp;nbsp;M before use</td></tr></tbody></table>

using polystyrene-block-poly(acrylic acid)-coated metal nanoparticles as monomers for their homo- and co-polymerization

We present a template-free method for &#8220;polymerizing&#8221; nanoparticles into long chains without side branches. A variety of nanoparticles are encapsulated in polystyrene-block-poly(acrylic acid) (PSPAA) shells and then used as monomers for their self-assembly. Spherical PSPAA micelles upon acid treatment are known to assemble into cylindrical micelles. Exploiting this tendency, the core-shell nanoparticles are induced to aggregate, coalesce, and then transform into long chains. When more than one type of nanoparticles are used, random and block &#8220;copolymers&#8221; of nanoparticles can be obtained. Detailed procedures are reported for the PSPAA encapsulation of nanoparticles, homo- and co-polymerization of the core-shell nanoparticles, separation and purification of the resulting nanoparticle chains. Transformations of single-line chains into double- and triple-line chains are also presented. The synergy between the polymer shell and the embedded nanoparticles leads to an unusual chain-growth polymerization mode, giving long nanoparticle chains that are distinct from the products of the traditional step-growth aggregation process.

Die Nanopartikelmonomere und Ketten durch TEM. 1 zeigt die repräsentative TEM-Bilder der PSPAA eingekapselt Monomeren und bestätigt die Morphologien und Größen (Abbildung 1). Da einige Monomere in der Regel in der Probe nach der &quot;Polymerisation&quot; bleiben, wird die Probe in der Regel gereinigt und vor dem für die TEM-Charakterisierung konzentriert. Ein Fleck wurde während der Herstellung der TEM-Proben durch Mischen der Probenlösung mit 1% Ammoniummolybdat, um die Polymer...

Watch this Scientific Journal Video about Using Polystyrene-block-polyacrylic acid-coated Metal Nanoparticles as Monomers for Their Homo- and Co-polymerization at JoVE.com

Using Polystyrene-block-polyacrylic acid-coated Metal Nanoparticles as Monomers for Their Homo- and Co-polymerization

We report protocols for &#8220;polymerizing&#8221; various types of polymer-encapsulated metal nanoparticles into long chains of &#8220;homo-&#8220; and &#8220;co-polymers&#8221;.

Verwendung Polystyrol-<em&gt; Block</em&gt; -Poly (Acrylsäure) beschichteten Metallnanopartikel als Monomere für ihre Homo- und Polymerisation

We present a template-free method for &#8220;polymerizing&#8221; nanoparticles into long chains without side branches. A variety of nanoparticles are ...

using-polystyrene-block-poly-acrylic-acid-coated-metal-nanoparticles

Universidad de Cartagena UDEC

Research

JoVE Journal

Chemistry

Using Polystyrene-block-poly(acrylic acid)-coated Metal Nanoparticles as Monomers for Their Homo- and Co-polymerization

12.1K Aufrufe.  Nanyang Technological University. We report protocols for “polymerizing” various types of polymer-encapsulated metal nanoparticles into long chains of “homo-“ and “co-polymers”. 

Serie: Using Polystyrene-block-polyacrylic acid-coated Metal Nanoparticles as Monomers for Their Homo- and Co-polymerization

Gyroid Nickel Nanostructures from Diblock Copolymer Supramolecules

Nanoporous metal foams possess a unique combination of properties - they are catalytically active, thermally and electrically conductive, and furthermore, have high porosity, high surface-to-volume and strength-to-weight ratio. Unfortunately, common approaches for preparation of metallic nanostructures render materials with highly disordered architecture, which might have an adverse effect on their mechanical properties. Block copolymers have the ability to self-assemble into ordered nanostructures and can be applied as templates for the preparation of well-ordered metal nanofoams. Here we describe the application of a block copolymer-based supramolecular complex - polystyrene-block-poly(4-vinylpyridine)(pentadecylphenol) PS-b-P4VP(PDP) - as a precursor for well-ordered nickel nanofoam. The supramolecular complexes exhibit a phase behavior similar to conventional block copolymers and can self-assemble into the bicontinuous gyroid morphology with two PS networks placed in a P4VP(PDP) matrix. PDP can be dissolved in ethanol leading to the formation of a porous structure that can be backfilled with metal. Using electroless plating technique, nickel can be inserted into the template&#39;s channels. Finally, the remaining polymer can be removed via pyrolysis from the polymer/inorganic nanohybrid resulting in nanoporous nickel foam with inverse gyroid morphology.

This article describes the preparation of well-ordered nickel nanofoams via electroless metal deposition onto nanoporous templates obtained from self-assembled diblock copolymer based supramolecules.

Gyroid Nickel Nanostrukturen aus Diblockcopolymer Übermolekülen

Nanoporous metal foams possess a unique combination of properties - they are catalytically active, thermally and electrically conductive, and furthermore, ...

Forschung

Chemie

Formulation of Diblock Polymeric Nanoparticles through Nanoprecipitation Technique

Nanotechnology is a relatively new branch of science that involves harnessing the unique properties of particles that are nanometers in scale (nanoparticles). Nanoparticles can be engineered in a precise fashion where their size, composition and surface chemistry can be carefully controlled. This enables unprecedented freedom to modify some of the fundamental properties of their cargo, such as solubility, diffusivity, biodistribution, release characteristics and immunogenicity. Since their inception, nanoparticles have been utilized in many areas of science and medicine, including drug delivery, imaging, and cell biology1-4. However, it has not been fully utilized outside of "nanotechnology laboratories" due to perceived technical barrier. In this article, we describe a simple method to synthesize a polymer based nanoparticle platform that has a wide range of potential applications. 
The first step is to synthesize a diblock co-polymer that has both a hydrophobic domain and hydrophilic domain. Using PLGA and PEG as model polymers, we described a conjugation reaction using EDC/NHS chemistry5 (Fig 1). We also discuss the polymer purification process. The synthesized diblock co-polymer can self-assemble into nanoparticles in the nanoprecipitation process through hydrophobic-hydrophilic interactions.
The described polymer nanoparticle is very versatile. The hydrophobic core of the nanoparticle can be utilized to carry poorly soluble drugs for drug delivery experiments6. Furthermore, the nanoparticles can overcome the problem of toxic solvents for poorly soluble molecular biology reagents, such as wortmannin, which requires a solvent like DMSO. However, DMSO can be toxic to cells and interfere with the experiment. These poorly soluble drugs and reagents can be effectively delivered using polymer nanoparticles with minimal toxicity. Polymer nanoparticles can also be loaded with fluorescent dye and utilized for intracellular trafficking studies. Lastly, these polymer nanoparticles can be conjugated to targeting ligands through surface PEG. Such targeted nanoparticles can be utilized to label specific epitopes on or in cells7-10.

This article describes a nanoprecipitation method to synthesize polymer-based nanoparticles using diblock co-polymers. We will discuss the synthesis of diblock co-polymers, the nanoprecipitation technique, and potential applications.

Formulierung von Diblock Polymernanopartikel durch Nanopräzipitation Technik

Nanotechnology is a relatively new branch of science that involves harnessing the unique properties of particles that are nanometers in scale ...

Biotechnik

Polymer Microarrays for High Throughput Discovery of Biomaterials

The discovery of novel biomaterials that are optimized for a specific biological application is readily achieved using polymer microarrays, which allows a combinatorial library of materials to be screened in a parallel, high throughput format1. Herein is described the formation and characterization of a polymer microarray using an on-chip photopolymerization technique 2. This involves mixing monomers at varied ratios to produce a library of monomer solutions, transferring the solution to a glass slide format using a robotic printing device and curing with UV irradiation. This format is readily amenable to many biological assays, including stem cell attachment and proliferation, cell sorting and low bacterial adhesion, allowing the ready identification of 'hit' materials that fulfill a specific biological criterion3-5. Furthermore, the use of high throughput surface characterization (HTSC) allows the biological performance to be correlated with physio-chemical properties, hence elucidating the biological-material interaction6. HTSC makes use of water contact angle (WCA) measurements, atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). In particular, ToF-SIMS provides a chemically rich analysis of the sample that can be used to correlate the cell response with a molecular moiety. In some cases, the biological performance can be predicted from the ToF-SIMS spectra, demonstrating the chemical dependence of a biological-material interaction, and informing the development of hit materials5,3.

A description of the formation of a polymer microarray using an on-chip photopolymerization technique. The high throughput surface characterization using atomic force microscopy, water contact angle measurements, X-ray photoelectron spectroscopy and time of flight secondary ion mass spectrometry and a cell attachment assay is also described.

Polymer Microarrays für High Throughput Discovery of Biomaterials

The discovery of novel biomaterials that are optimized for a specific biological application is readily achieved using polymer microarrays, which allows a ...

Facile Synthesis of Worm-like Micelles by Visible Light Mediated Dispersion Polymerization Using Photoredox Catalyst

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins with the synthesis of a hydrophilic poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) homopolymer using reversible addition-fragmentation chain-transfer (RAFT) polymerization. Under mild visible light irradiation (&#955; = 460 nm, 0.7 mW/cm2), this macro-chain transfer agent (macro-CTA) in the presence of a ruthenium based photoredox catalyst, Ru(bpy)3Cl2 can be chain extended with a second monomer to form a well-defined block copolymer in a process known as Photoinduced Electron Transfer RAFT (PET-RAFT). When PET-RAFT is used to chain extend POEGMA with benzyl methacrylate (BzMA) in ethanol (EtOH), polymeric nanoparticles with different morphologies are formed in situ according to a polymerization-induced self-assembly (PISA) mechanism. Self-assembly into nanoparticles presenting POEGMA chains at the corona and poly(benzyl methacrylate) (PBzMA) chains in the core occurs in situ due to the growing insolubility of the PBzMA block in ethanol. Interestingly, the formation of highly pure worm-like micelles can be readily monitored by observing the onset of a highly viscous gel in situ due to nanoparticle entanglements occurring during the polymerization. This process thereby allows for a more reproducible synthesis of worm-like micelles simply by monitoring the solution viscosity during the course of the polymerization. In addition, the light stimulus can be intermittently applied in an ON/OFF manner demonstrating temporal control over the nanoparticle morphology.

This article describes a process for producing polymeric self-assembled nanoparticles using visible light mediated dispersion polymerization. Using low energy visible light to control the polymerization allows for the reproducible formation of self-assembled worm-like micelles at high solids content.

Einfache Synthese von wurmartigen Mizellen durch sichtbares Licht Mediated Dispersion Polymerisation mit Photoredox Katalysator

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins ...

Anionic Polymerization of an Amphiphilic Copolymer for Preparation of Block Copolymer Micelles Stabilized by &#960;-&#960; Stacking Interactions

In this study, an amphiphilic copolymer that includes a core-forming block with phenyl groups was synthesized by living anionic polymerization of phenyl glycidyl ether (PheGE) on methoxy-polyethylene glycol (mPEG-b-PPheGE). Characterization of the copolymer revealed a narrow molecular distribution (PDI &#60; 1.03) and confirmed the degree of polymerization of mPEG122-b-(PheGE)15. The critical micelle concentration of the copolymer was evaluated using an established fluorescence method with the aggregation behavior evaluated by dynamic light scattering and transmission electronic microscopy. The potential of the copolymer for use in drug delivery applications was evaluated in a preliminary manner including in vitro biocompatibility, loading and release of the hydrophobic anti-cancer drug doxorubicin (DOX). A stable micelle formulation of DOX was prepared with drug loading levels up to 14% (wt%), drug loading efficiencies &#62; 60% (w/w) and sustained release of drug over 4 days under physiologically relevant conditions (acidic and neutral pH, presence of albumin). The high drug loading level and sustained release is attributed to stabilizing &#960;-&#960; interactions between DOX and the core-forming block of the micelles.

The key steps of living anionic polymerization of phenyl glycidyl ether (PheGE) on methoxy-polyethylene glycol (mPEG-b-PPheGE) are described. The resulting block copolymer micelles (BCMs) were loaded with doxorubicin 14% (wt%) and sustained release of drug over 4 days under physiologically relevant conditions was obtained.

Die anionische Polymerisation eines amphiphilen Copolymer zur Herstellung von Blockcopolymermicellen Stabilisiert durch π-π-Stapelwechselwirkungen

In this study, an amphiphilic copolymer that includes a core-forming block with phenyl groups was synthesized by living anionic polymerization of phenyl ...

Grafting Multiwalled Carbon Nanotubes with Polystyrene to Enable Self-Assembly and Anisotropic Patchiness

We demonstrate a straightforward protocol to graft pristine multiwalled carbon nanotubes (MWCNTs) with polystyrene (PS) chains at the sidewalls through a free-radical polymerization strategy to enable the modulation of the nanotube surface properties and produce supramolecular self-assembly of the nanostructures. First, a selective hydroxylation of the pristine nanotubes through a biphasic catalytically mediated oxidation reaction creates superficially distributed reactive sites at the sidewalls. The latter reactive sites are subsequently modified with methacrylic moieties using a silylated methacrylic precursor to create polymerizable sites. Those polymerizable groups can address further polymerization of styrene to produce a hybrid nanomaterial containing PS chains grafted to the nanotube sidewalls. The polymer-graft content, amount of silylated methacrylic moieties introduced and hydroxylation modification of the nanotubes are identified and quantified by Thermogravimetric Analysis (TGA). The presence of reactive functional groups hydroxyl and silylated methacrylate are confirmed by Fourier Transform Infrared Spectroscopy (FT-IR). Polystyrene-grafted carbon nanotube solutions in tetrahydrofuran (THF) provide wall-to-wall collinearly self-assembled nanotubes when cast samples are analyzed by transmission electron microscopy (TEM). Those self-assemblies are not obtained when suitable blanks are similarly cast from analogous solutions containing non-grafted counterparts. Therefore, this method enables the modification of the nanotube anisotropic patchiness at the sidewalls which results into spontaneous auto-organization at the nanoscale.

A procedure for the synthesis of polystyrene-grafted multiwalled carbon nanotubes using successive chemical modification steps to selectively introduce the polymer chains to the sidewalls and their self-assembly via anisotropic patchiness is presented.

Pfropfen Multiwalled Carbon Nanotubes mit Polystyrol Selbstmontage ermöglichen und anisotropen führt

We demonstrate a straightforward protocol to graft pristine multiwalled carbon nanotubes (MWCNTs) with polystyrene (PS) chains at the sidewalls through a ...

Preparation of Hollow Polystyrene Particles and Microcapsules by Radical Polymerization of Janus Droplets Consisting of Hydrocarbon and Fluorocarbon Oils

In this article, we have demonstrated a method for producing hollow particles and microcapsules using oil droplets consisting of hydrocarbon oil (styrene) and fluorocarbon oil (perfluoro-n-octane, PFO) in aqueous surfactant (sodium dodecylsulfate, SDS) solutions. Since fluorocarbon oils are immiscible with hydrocarbon oils, the two oils are separated. Emulsions are prepared by stirring styrene/PFO/aqueous SDS solution mixtures at 80 &#176;C. The type of emulsions and the morphology of droplets in the emulsions are observed by light microscope and scanning confocal fluorescence microscope. It is found that oil droplets with Janus-type morphologies consisting of mutually immiscible styrene and PFO are formed in aqueous SDS solutions. Polystyrene particles are fabricated by radical polymerization of the ternary mixtures of styrene/PFO/aqueous SDS solution at 80 &#176;C. The morphologies of the polystyrene are confirmed by scanning electron microscopy and scanning transmission electron microscopy observations. These observations show the preparation of hollow polystyrene particles with a single hole on the surface. To our knowledge, this method is a novel strategy using the immiscibility of hydrocarbon and fluorocarbon oils. The hollow particles can also be applied to the preparation of microcapsules.

A protocol for the fabrication of hollow polymer particles and microcapsules by radical polymerization using emulsions consisting of styrene, perfluoro-n-octane, and aqueous SDS (sodium dodecylsulfate) solution is presented.

Vorbereitung der hohlen Polystyrol Partikel und Mikrokapseln durch radikalische Polymerisation von Janus Tröpfchen bestehend aus Kohlenwasserstoff und Fluorcarbon-Öle

In this article, we have demonstrated a method for producing hollow particles and microcapsules using oil droplets consisting of hydrocarbon oil (styrene) ...

Synthesis of Monodisperse Cylindrical Nanoparticles via Crystallization-driven Self-assembly of Biodegradable Block Copolymers

The production of monodisperse cylindrical micelles is a significant challenge in polymer chemistry. Most cylindrical constructs formed from diblock copolymers are produced by one of three techniques: thin film rehydration, solvent switching or polymerization-induced self-assembly, and produce only flexible, polydisperse cylinders. Crystallization-driven self-assembly (CDSA) is a method which can produce cylinders with these properties, by stabilizing structures of a lower curvature due to the formation of a crystalline core. However, the living polymerization techniques by which most core-forming blocks are formed are not trivial processes and the CDSA process may yield unsatisfactory results if carried out incorrectly. Here, the synthesis of cylindrical nanoparticles from simple reagents is shown. The drying and purification of reagents prior to a ring-opening polymerization of &#949;-caprolactone catalyzed by diphenyl phosphate is described. This polymer is then chain extended by methyl methacrylate (MMA) followed by N,N-dimethyl acrylamide (DMA) using reversible addition&#8722;fragmentation chain-transfer (RAFT) polymerization, affording a triblock copolymer that can undergo CDSA in ethanol. The living CDSA process is outlined, the results of which yield cylindrical nanoparticles up to 500 nm in length and a length dispersity as low as 1.05. It is anticipated that these protocols will allow others to produce cylindrical nanostructures and elevate the field of CDSA in the future.

Crystallization-driven self-assembly (CDSA) displays the unique ability to fabricate cylindrical nanostructures of narrow length distributions. The organocatalyzed ring-opening polymerization of &#949;-caprolactone and subsequent chain extensions of methyl methacrylate and N,N-dimethyl acrylamide are demonstrated. A living CDSA protocol that produces monodisperse cylinders up to 500 nm in length is outlined.

Synthese von monodispersen zylindrischen Nanopartikeln durch kristallisationsgesteuerte Selbstmontage von biologisch abbaubaren Blockcopolymeren

The production of monodisperse cylindrical micelles is a significant challenge in polymer chemistry. Most cylindrical constructs formed from diblock ...

Selbstorganisation von polymergepfropften metallorganischen Gerüst-Monoschichten

Synthesis and Characterization of Self-Assembled Metal-Organic Framework Monolayers Using Polymer-Coated Particles

Metal-organic frameworks (MOFs) are materials with potential applications in fields such as gas adsorption and separation, catalysis, and biomedicine. Attempts to enhance the utility of MOFs have involved the preparation of various composites, including polymer-grafted MOFs. By directly grafting polymers to the external surface of MOFs, issues of incompatibility between polymers and MOFs can be overcome. Polymer brushes grafted from the surface of MOFs can serve to stabilize the MOF while enabling particle assembly into self-assembled metal-organic framework monolayers (SAMMs) via polymer-polymer interactions.
Control over the chemical composition and molecular weight of the grafted polymer can allow for tuning of the SAMM characteristics. In this work, instructions are provided on how to immobilize a chain transfer agent (CTA) onto the surface of the MOF UiO-66 (UiO = Universitetet i Oslo). The CTA&#160;serves as initiation sites for the growth of polymers. Once polymer chains are grown from the MOF surface, the formation of SAMMs is achieved through self-assembly at an air-water interface. The resulting SAMMs are characterized and shown to be freestanding by scanning electron microscopy imaging. The methods presented in this paper are expected to make the preparation of SAMMs more accessible to the research community and thereby expand their potential use as a&#160;MOF-polymer composite.

Autor im Rampenlicht: Erforschung selbstorganisierter MOF-Polymer-Verbundwerkstoffe

A protocol for the synthesis and characterization of self-assembled metal-organic framework monolayers is provided using polymer-grafted, metal-organic framework (MOF) crystals. The procedure shows that polymer-grafted MOF particles can be self-assembled at an air-water interface resulting in well-formed, free-standing, monolayer structures as evidenced by scanning electron microscopy imaging.

Synthese und Charakterisierung von selbstorganisierten metallorganischen Gerüstmonolagen unter Verwendung polymerbeschichteter Partikel

Metal-organic frameworks (MOFs) are materials with potential applications in fields such as gas adsorption and separation, catalysis, and biomedicine. ...

Verwendung Polystyrol-

Zusammenfassung

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