Name: using polystyrene-block-poly(acrylic acid)-coated metal nanoparticles as monomers for their homo- and co-polymerization
Uploaded: 2015-07-09T15:00:00
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.

Caution: Please consult all relevant material safety data sheets (MSDS). Some chemicals used in these syntheses are corrosive, toxic and possibly carcinogenic. Nanomaterials may have unrecognized hazards as compared to their bulk counterparts. Please use appropriate safety practices when performing reaction, including the use of fume hood and personal protective equipment (safety glasses, gloves, lab coat, full length pants, closed-toe shoes, etc.).
1. Synthesis of Metal Nanoparticles
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The mechanistic details of the syntheses are reported and discussed in the previous publications.20,21 Here we focus on the rationales of the synthetic conditions. For the polymerization of nanoparticles, it is preferred that nanoparticles of uniform size are used. We follow literature procedures to obtain the uniform Au nanoparticles,23 Au nanorods,24 and Te nanowires.25 In general, better size uniformity can be obtained when the nucleation and growth stages are separated.<sup...

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 border="0" cellpadding="0" cellspacing="0">
	<tbody>
		<tr>
			<td>Gold(III) chloride trihydrate, ACS reagent, &#8805;49.0% Au basis 
			&#160;</td>
			<td>Sigma-Aldrich</td>
			<td>G4022</td>
			<td>HAuCl4</td>
		</tr>
		<tr>
			<td>Sodium citrate dihydrate, 99%</td>
			<td>Alfa Aesar</td>
			<td>A12274</td>
			<td></td>
		</tr>
		<tr>
			<td>Sodium borohydride, &#8805;99% 
			&#160;</td>
			<td>Sigma-Aldrich</td>
			<td>71321, Fluka</td>
			<td></td>
		</tr>
		<tr>
			<td>Hexadecyltrimethylammonium bromide,&#8805;98%&#160;</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, &#8805;99.0%, crystalline 
			&#160;</td>
			<td>Sigma-Aldrich</td>
			<td>A5960</td>
			<td></td>
		</tr>
		<tr>
			<td>Tellurium dioxide,&#8805;99%&#160;</td>
			<td>Sigma-Aldrich</td>
			<td>243450</td>
			<td></td>
		</tr>
		<tr>
			<td>Hydrazine monohydrate, 64-65 %, reagent grade, 98%&#160;</td>
			<td>Sigma-Aldrich</td>
			<td>207942</td>
			<td></td>
		</tr>
		<tr>
			<td>Poly(styrene-b-acrylic acid)(PS154-PAA49)</td>
			<td>Polymer Source</td>
			<td>P4673A-SAA</td>
			<td>PS16000-PAA3500</td>
		</tr>
		<tr>
			<td>Poly(styrene-b-acrylic acid)(PS144-PAA28)</td>
			<td>Polymer Source</td>
			<td>P4002-SAA</td>
			<td>PS15000-PAA1600</td>
		</tr>
		<tr>
			<td>2-Naphthalenethiol, 
			&#160;&#8805;99.0% (GC)&#160;</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%&#160; 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-sn-glycero-3-phosphothioethanol (sodium salt)&#160;</td>
			<td>Avanti polar lipids</td>
			<td>870160P</td>
			<td>PSH</td>
		</tr>
		<tr>
			<td>N,N-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 1M before use&#160;</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.

The nanoparticle monomers and chains are characterized by TEM. Figure 1 shows the representative TEM images of the PSPAA encapsulated monomers, confirming the morphologies and sizes (Figure 1). As some monomers typically remain in the sample after the &#8220;polymerization&#8221;, the sample is usually purified and concentrated before being used for TEM characterization. A stain was introduced during the preparation of the TEM samples by mixing the sample solution with 1% ammonium molybd...

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;.

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 ...

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