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
Note: All glassware used in the syntheses are washed with aqua regia (CAUTION: highly acidic and corrosive, handle with caution and dispose following the regulations), thoroughly rinsed, and then dried in 60 &#176;C oven. Metal impurity or residue may lead to premature nucleation and failure of the nanoparticle synthesis.
<ol>
	<li>Synthesis of 16 and 32 nm Au nanoparticles (AuNPs)
	<ol>
		<li>Dissolve 10 mg of hydrogen tetrachloroaurate(III) hydrate (HAuCl4&#8729;3H2O) into 100 ml of deionized (DI) water in a round-bottom flask equipped with a condenser and a stir bar.</li>
		<li>With stirring on, heat the solution to reflux (boiling, 100 &#176;C). The yellow color of the HAuCl4 remains unchanged.</li>
		<li>Prepare a 1% sodium citrate solution by dissolving 30 mg of sodium citrate into 3 ml of DI water.</li>
		<li>To synthesize 16 nm AuNPs, inject 3 ml of 1% sodium citrate solution (1.1.3) into the boiling HAuCl4 solution (1.1.2). The solution turns grey within 1 min, and then gradually turns red.
		<ol>
			<li>To synthesize 32 nm Au NPs, use 1.5 ml of the sodium citrate solution instead. The smaller amount of reductant leads to less extensive homogeneous nucleation, so that each nucleus can grow larger.</li>
		</ol>
		</li>
		<li>Keep the solution at boiling for another 30 min, and then cool down to RT for use in the subsequent reactions.</li>
		<li>Confirm the size and morphology of the resulting AuNPs by transmission electron microscopy (TEM).
		<ol>
			<li>To prepare the TEM sample, first concentrate the AuNPs by transferring 1.5 ml of the as-synthesized solution into a microcentrifuge tube, and centrifuge it at 16,000 x g for 15 min. After removing the transparent supernatant, drop a 10 &#181;l aliquot of the residue solution onto a TEM copper grid. Wick off the excess liquid sample using a filter paper and dry the copper grid in air.</li>
			<li>To conduct the TEM characterization, load the copper grid sample into the TEM holder, secure the sample, and load the holder into the specimen chamber following the standard operation procedures (specific to the type/brand of instrument).22</li>
		</ol>
		</li>
	</ol>
	</li>
	<li>Synthesis of Au nanorods (AuNRs)
	<ol>
		<li>Prepare the seed solution. Under vigorous stirring, add 0.6 ml of 10 mM ice-cooled sodium borohydride (NaBH4) to 10 ml of 0.25 mM HAuCl4&#8729;3H2O prepared in 0.1 M hexadecyltrimethylammonium bromide (CTAB) solution. Continue stirring for 10 min.</li>
		<li>Add 95 ml of 0.1 M CTAB, 1 ml of 10 mM silver nitrate (AgNO3), 5 ml of 10 mM HAuCl4&#8729;3H2O in sequence into a 200 ml conical flask.</li>
		<li>Add 0.55 ml of 0.1 M L-ascorbic acid to the solution, and shake gently to homogenize the solution.</li>
		<li>Immediately add 0.12 ml of the seed solution (Step 1.2.1). Mix the solution by gentle shaking and leave it undisturbed O/N (14-16 hr).</li>
	</ol>
	</li>
	<li>Synthesis of t-Te nanowires (TeNWs)
	<ol>
		<li>Prepare 10 ml of N2H4 solution by mixing 1 ml of neat N2H4&#183;H2O with 9 ml of DI water.</li>
		<li>Add 16 mg of TeO2 powder slowly to the N2H4 solution (Step 1.3.1) in a beaker at RT under constant stirring. In about 10 min, the powder completely dissolves. The solution would change from colorless to amber, to purple, and eventually to blue, indicating the formation of t-Te nanowires.</li>
		<li>Dilute the solution 10 times with sodium dodecylsulfate (10 mM) to terminate the reaction. The blue color of the solution becomes less intense after the dilution.</li>
	</ol>
	</li>
</ol>
2. Synthesis of PSPAA Encapsulated Metal Nanoparticles (the Monomers)
Note: In the following, precise amounts are used to achieve a precise ratio of the final DMF/water solvent mixture. Because the residue volume after centrifugation and extraction of the supernatant is always different, roughly measure the residue volume by pipette and then compensate for this volume when adding DMF/water to make the final solutions. Small variations of the solvent ratio are usually not a problem.
<ol>
	<li>Encapsulate AuNPs (dAu= 16 nm, 32 nm) with PSPAA (AuNP@PSPAA)
	<ol>
		<li>Purification of the AuNP solution. Add 3 ml of the as-synthesized AuNP solution (Step 1.1) to two microcentrifuge tubes (1.5 ml each), centrifuge at 16,000 x g for 15 min and remove the supernatant. Dilute the concentrated solution (~20 &#181;l) with 160 &#181;l of DI water.</li>
		<li>Prepare the PSPAA stock solution by dissolving 8 mg of PSPAA (PS154-b-PAA49 or PS144-b-PAA22) in 1 ml of DMF.</li>
		<li>Prepare a PSPAA solution by mixing 740 &#181;l of DMF with 80 &#181;l of PS154-b-PAA49 stock solution. For encapsulating the AuNPs in PS144-b-PAA22 shells, use 80 &#181;l of PS144-b-PAA22 stock solution.</li>
		<li>In a glass vial, add the AuNPs (~180 &#181;l solution, step 2.1.1) to 820 &#181;l of the PSPAA solution (Step 2.1.3). The final mixture has a volume of 1 ml with VDMF/VH2O = 4.5:1.</li>
		<li>Add 40 &#181;l solution of 1,2-dipalmitoyl-sn-glycero-3-phosphothioethanol (P-SH) in ethanol (2 mg/ml).</li>
		<li>Incubate the mixture at 110 &#176;C for 2 hr to allow polymer self-assembly.</li>
		<li>Slowly cool the solution to RT in the oil bath. The sample can be stored at this state for weeks.</li>
		<li>Confirm the formation of AuNP@PSPAA with TEM.
		<ol>
			<li>To prepare the TEM sample, concentrate the AuNP@PSPAA by transferring 200 &#181;l of the as-synthesized solution into a microcentrifuge tube, add 1.3 ml of DI water and centrifuge it at 16,000 x g for 15 min.</li>
			<li>Mix a 5 &#181;l aliquot of concentrated sample solution with 5 &#181;l of 1% ammonium molybdate stain solution (Note: stain is used for samples containing PSPAA to improve the contrast of the polymers), and drop the mixture onto a TEM copper grid. Wick off the excess liquid sample using a filter paper and dry the copper grid in air.</li>
		</ol>
		</li>
	</ol>
	</li>
	<li>Encapsulate AuNRs with PSPAA (AuNR@PS154-b-PAA49)
	<ol>
		<li>Purify the as-synthesized AuNR solution (Step 1.2) twice to remove the excess CTAB. Add 3 ml of the AuNR solution into two microcentrifuge tubes, and then centrifuge them at 8,100 x g for 15 min. After removing the supernatant, add 1.5 ml of DI water and centrifuge again to remove the supernatant.</li>
		<li>Combine the concentrated AuNR solutions, and add 160 &#181;l of DI water.</li>
		<li>In a glass vial, add the AuNR solution (~180 &#181;l) to 820 &#181;l of the PS154-b-PAA49 solution (Step 2.1.3). The final mixture has a volume of 1 ml with VDMF/VH2O = 4.5:1.</li>
		<li>Add 40 &#181;l solution of 2-naphthalenethiol (NpSH) in ethanol (2 mg/ml) into the mixture.</li>
		<li>Incubate the mixture at 110 &#176;C for 2 hr to allow polymer self-assembly.</li>
		<li>Slowly cool the solution to RT.</li>
	</ol>
	</li>
	<li>Encapsulate TeNWs with PSPAA (TeNW@PS154-b-PAA49)
	<ol>
		<li>Purify the as-synthesized TeNWs (Step 1.3) to remove the excess SDS. Add 3 ml of the TeNW solution into two microcentrifuge tubes, and centrifuge them at 2,900 x g for 10 min. After removing the supernatant, add 1.5 ml of ethanol and centrifuge the tubes again. Repeat this purification process once more (total 3 rounds of centrifugation).</li>
		<li>Combine the concentrated TeNWs solutions, and add 160 &#181;l of DI water.</li>
		<li>Add the TeNWs solution (~180 &#181;l) to 820 &#181;l of PS154-b-PAA49 solution (Step 2.1.3). The final mixture has a volume of 1 ml with VDMF/VH2O = 4.5:1.</li>
		<li>Incubate the mixture at 110 &#176;C for 2 hr.</li>
		<li>Slowly cool the solution to RT.</li>
	</ol>
	</li>
	<li>Encapsulate carbon nanotubes (CNTs) with PSPAA (CNT@PS154-b-PAA49)
	<ol>
		<li>Mix 730 &#181;l DMF with 80 &#181;l of the PS154-b-PAA49 stock solution (Step 2.1.2).</li>
		<li>Disperse about 0.05 mg of single-wall CNTs into the PS154-b-PAA49 solution. 
		Note: It is hard to measure the small weight of the CNTs; usually 0.2 mg of CNTs is weighed and about &#188; of the sample (by estimated volume) is added.</li>
		<li>Sonicate the mixture in an ice-water bath until it becomes a transparent dark solution. Use the clear solution and discard the insoluble residue CNTs.</li>
		<li>Add 180 &#181;l of DI H2O drop-wise to the solution. The final mixture has a volume of 990 &#181;l with VDMF/VH2O = 4.5:1.</li>
		<li>Sonicate the solution at about 50 &#176;C for 2 hr.</li>
		<li>Slowly cool the solution to RT.</li>
	</ol>
	</li>
	<li>Prepare spherical micelles of PS154-b-PAA49.
	<ol>
		<li>Add 80 &#181;l of the PS154-b-PAA49 stock solution (Step 2.1.1) to 740 &#181;l of DMF, then add 180 &#181;l water, making a solution of VDMF/VH2O = 4.5:1.</li>
		<li>Incubate the polymer solution at 110 &#176;C for 2 hr.</li>
		<li>Slowly cool the solution to RT.</li>
	</ol>
	</li>
</ol>
3. Homo-polymerization of the PSPAA Encapsulated Metal Nanoparticles
<ol>
	<li>Synthesis of single-line chains from the AuNP@PSPAA
	<ol>
		<li>Purify the AuNP@PSPAA.
		<ol>
			<li>Dilute 800 &#181;l of the as-synthesized AuNP@PSPAA (section 2.1) with 11.2 ml of water, divide the solution into individual microcentrifuge tubes (1.5 ml each), and centrifuge them at 16,000 x g for 30 min. Carry out two separate reactions, using the 16 nm AuNPs encapsulated in PS154-b-PAA49 and the 32 nm AuNPs encapsulated in PS144-b-PAA22 as the monomers.</li>
			<li>Remove and discard the supernatant, add 1.5 ml of 0.1 mM NaOH (pH = 10) to each tube and centrifuge them again at 16,000 x g for 30 min to remove the supernatant. 
			Note: The pH of the NaOH used for centrifugation in the purification process should not be too high. Higher pH would lead to aggregation during the centrifugation, and the residue base would comprise the effects of acid in the chain-growth step, leading to globular aggregates.</li>
		</ol>
		</li>
		<li>Disperse the concentrated AuNP@PSPAA (combine all the tubes) in 1 ml of DMF/H2O (VDMF/VH2O = 6:1) in a glass vial, and add 5 &#181;l of 1 M HCl. 
		Note: It is important to control the residue NaOH and loss of the AuNP@PSPAA in the previous steps, so that the HCl amount required in the assembly process is consistent among the different batches. Vortex the reaction mixture before incubation to ensure complete mixing of the components.</li>
		<li>Incubate the mixture at 60 &#176;C for 2 hr to allow the aggregation, coalescence, and morphological transformation of the core-shell nanoparticles.</li>
		<li>Cool the mixture to RT.</li>
		<li>For homo-polymerization of the AuNR@PS154-b-PAA49 and TeNW@PS154-b-PAA49, follow the same procedures, including the purification processes. 
		Note: In the experiments, plastic microcentrifuge tubes are typically used for purification and centrifugation, and glass vials are used for the reactions at elevated temperature. The PSPAA-coated nanoparticles are usually stable in solutions, except that when dispersed in high-DMF content solution in microcentrifuge tubes, they will stick to the plastic surface. To avoid this situation, high-DMF content solutions of the nanoparticles are only prepared in glass vials.</li>
	</ol>
	</li>
	<li>Synthesis of double-line chains from the AuNP@PSPAA
	<ol>
		<li>Purify the AuNP@PSPAA (by following Step 3.1.1). Only the 16 nm AuNPs encapsulated in PS154-b-PAA49 shells have been tested.</li>
		<li>Disperse the concentrated AuNP@PSPAA in 1 ml of DMF/H2O (VDMF/VH2O = 7:3) in a glass vial, and add 5 &#181;l of 1 M HCl.</li>
		<li>Incubate the mixture at 60 &#176;C for 2 hr.</li>
		<li>Cool the mixture to RT.</li>
	</ol>
	</li>
	<li>Purification of the nanoparticle chains 
	Note: The as-synthesize solutions contain the product nanoparticle chains, small chains/clusters, large agglomerates, AuNP@PSPAA monomers, empty PSPAA micelles, DMF and excess acid.
	<ol>
		<li>Remove the empty PSPAA micelles, DMF and acid.
		<ol>
			<li>Dilute 800 &#181;l of the as-synthesized solution with 11.2 ml of 0.1 mM NaOH, divide the solution into individual microcentrifuge tubes (1.5 ml each), and centrifuge them at 16,000 x g for 30 min.</li>
			<li>Add 1.5 ml of 0.1 mM NaOH to dilute the concentrated solutions, and centrifuge the tubes again at 16,000 x g for 30 min. Repeat this step once more.</li>
		</ol>
		</li>
		<li>Enrich the AuNPs chains 
		Note: The purified solution contains the product nanoparticle chains, small chains/clusters, and AuNP@PSPAA monomers. They were separated by differential centrifugation.
		<ol>
			<li>Centrifuge the tube at 300 x g for 25 min to isolate and remove the large agglomerates.</li>
			<li>Collect the supernatant, centrifuge it at 2,000 x g for 30 min. Remove the supernatant containing mostly monomers and small chains/clusters.</li>
			<li>Collect the bottom solution, dilute it in 1.5 ml of 0.1 mM NaOH, and centrifuge at 2,000 x g for 20 min to remove excess monomers. Repeat the process once more. 
			Note: The pH of the NaOH used in the centrifugation in the all purification process should not be too high. Higher pH would lead to aggregation during the centrifugation, causing the formation of globular aggregates.</li>
		</ol>
		</li>
	</ol>
	</li>
	<li>Transformation of single-line nanoparticle chains to double-/triple-line chains
	<ol>
		<li>Purify the single-line chains (Step 3.3.1, without the enriching step).</li>
		<li>Concentrate 800 &#181;l of the purified solution to ~20 &#181;l by centrifugation.</li>
		<li>To transform to double-line chains, disperse the solution in 1 ml of DMF/H2O mixture solvent (VDMF/VH2O = 7:3) and add 2.5 &#181;l of 1 M HCl, [HCl]final = 2.5 mM. To transform to triple-line chains, use 1 ml of DMF/H2O (VDMF/VH2O = 3:2) and 2.5 mM [HCl]final.</li>
		<li>Incubate the solution at 70 &#176;C for 1 hr to allow the transformation of the nanostructures.</li>
		<li>Slowly cool the solution to RT.</li>
	</ol>
	</li>
</ol>
4. Co-polymerization of the PSPAA Encapsulated Metal Nanoparticles
<ol>
	<li>Random co-polymerization of the 16 nm AuNP@PS154-b-PAA49 and the 32 nm AuNP@PS144-b-PAA22. The process is very similar to Step 3.1 except that two monomers are used.
	<ol>
		<li>Purify the two types of the as-synthesized AuNP@PSPAA separately (Step 3.1.1).</li>
		<li>Disperse the concentrated 16 nm AuNP@PS154-b-PAA49 and 32 nm AuNP@PS144-b-PAA22 in 1:1 ratio into 1 ml of DMF/H2O mixture (VDMF/VH2O = 6:1).</li>
		<li>Add 5 &#181;l of 1 M HCl, [HCl]final = 5 mM.</li>
		<li>Incubate the solution at 60 &#176;C for 2 hr to allow co-assembly of the nanoparticles.</li>
		<li>Cool the solution to RT.</li>
	</ol>
	</li>
	<li>Random co-polymerization of the 16 nm AuNP@PS154-b-PAA49 and AuNR@PS154-b-PAA49
	<ol>
		<li>Purify the AuNP@ PS154-b-PAA49 and AuNR@ PS154-b-PAA49 separately (Step 3.1.1).</li>
		<li>Disperse the AuNP@PS154-b-PAA49 and AuNR@PS154-b-PAA49 in 1:1 ratio into 1 ml of DMF/H2O mixture (VDMF/VH2O = 6:1).</li>
		<li>Add 5 &#181;l of 1 M HCl, [HCl]final = 5 mM.</li>
		<li>Incubate the solution at 60 &#176;C for 2 hr to allow co-assembly of the nanoparticles.</li>
		<li>Cool the solution to RT.</li>
	</ol>
	</li>
	<li>Random co-polymerization of the 16 nm AuNP@PS154-b-PAA49 and PS154-b-PAA49 micelles
	<ol>
		<li>Purification of the 16 nm AuNP@PS154-b-PAA49 (Step 3.1.1).</li>
		<li>Add the concentrated AuNP@PS154-b-PAA49 and 60 &#181;l of the spherical PS154-b-PAA49 micelles (Step 2.5) into 940 ml of DMF/H2O. In the final solution, VDMF/VH2O = 6:1.</li>
		<li>Add 5 &#181;l of 1 M HCl, [HCl]final = 5 mM.</li>
		<li>Incubate the solution at 60 &#176;C for 1.5 hr.</li>
		<li>Cool the solution to RT.</li>
	</ol>
	</li>
	<li>Random co-polymerization of AuNP@PS154-b-PAA49 and PS154-b-PAA49 vesicles
	<ol>
		<li>Follow the same procedures as Step 4.3.1-4.3.3.</li>
		<li>Incubate the solution at 60 &#176;C for 6 hr to allow shape transformation of the PSPAA cylinders to vesicles.</li>
		<li>Cool the solution to RT.</li>
	</ol>
	</li>
	<li>Block-copolymerization of TeNWs with AuNPs
	<ol>
		<li>Purify the 16 nm AuNP@PS154-b-PAA49 and TeNW@PS154-b-PAA49 (Step 3.1.1)</li>
		<li>Disperse the concentrated TeNW@PS154-b-PAA49 in 1 ml of DMF/H2O mixture (VDMF/VH2O = 6:1)</li>
		<li>Add 2 &#181;l of 1 M HCl.</li>
		<li>Incubate the mixture at 60 &#176;C for 20 min.</li>
		<li>Add the concentrated 16 nm AuNP@PS154-b-PAA49 and 3 &#181;l of 1 M HCl.</li>
		<li>Incubate the mixture at 60 &#176;C for 2 hr.</li>
		<li>Cool the solution to RT.</li>
		<li>For block-copolymerization of CNTs with AuNPs, follow the same procedures as Step 4.5.1-4.5.7 by using CNT@PS154-b-PAA49 (Step 2.4).</li>
	</ol>
	</li>
</ol>

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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.

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 ...

using-polystyrene-block-polyacrylic-acid-coated-metal-nanoparticles

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JoVE Journal

Chemistry

12.0K Views.  Nanyang Technological University. We report protocols for “polymerizing” various types of polymer-encapsulated metal nanoparticles into long chains of “homo-“ and “co-polymers”. 

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

Structure and Coordination Determination of Peptide-metal Complexes Using 1D and 2D 1H NMR

Copper (I) binding by metallochaperone transport proteins prevents copper oxidation and release of the toxic ions that may participate in harmful redox reactions. The Cu (I) complex of the peptide model of a Cu (I) binding metallochaperone protein, which includes the sequence MTCSGCSRPG (underlined is conserved), was determined in solution under inert conditions by NMR spectroscopy.
NMR is a widely accepted technique for the determination of solution structures of proteins and peptides. Due to difficulty in crystallization to provide single crystals suitable for X-ray crystallography, the NMR technique is extremely valuable, especially as it provides information on the solution state rather than the solid state. Herein we describe all steps that are required for full three-dimensional structure determinations by NMR. The protocol includes sample preparation in an NMR tube, 1D and 2D data collection and processing, peak assignment and integration, molecular mechanics calculations, and structure analysis. Importantly, the analysis was first conducted without any preset metal-ligand bonds, to assure a reliable structure determination in an unbiased manner.

Structure and Coordination Determination of Peptide-metal Complexes Using 1D and 2D 1H NMR

The NMR-solution structure of a metallochaperone model peptide with Cu (I) was determined, and a detailed protocol from sample preparation and 1D and 2D data collection to a three-dimensional structure is described.

Copper (I) binding by metallochaperone transport proteins prevents copper oxidation and release of the toxic ions that may participate in harmful redox ...

Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents

Amide coupling reactions can be used to synthesize bispyridine-based ligands for use as bridging linkers in multinuclear platinum anticancer drugs. Isonicotinic acid, or its derivatives, are coupled to variable length diaminoalkane chains under an inert atmosphere in anhydrous DMF or DMSO with the use of a weak base, triethylamine, and a coupling agent, 1-propylphosphonic anhydride. The products precipitate from solution upon formation or can be precipitated by the addition of water. If desired, the ligands can be further purified by recrystallization from hot water. Dinuclear platinum complex synthesis using the bispyridine ligands is done in hot water using transplatin. The most informative of the chemical characterization techniques to determine the structure and gross purity of both the bispyridine ligands and the final platinum complexes is 1H NMR with particular analysis of the aromatic region of the spectra (7-9 ppm). The platinum complexes have potential application as anticancer agents and the synthesis method can be modified to produce trinuclear and other multinuclear complexes with different hydrogen bonding functionality in the bridging ligand.

This protocol describes the use of amide coupling reactions of isonicotinic acid and diaminoalkanes to form bridging ligands suitable for use in the synthesis of multinuclear platinum complexes, which combine aspects of the anticancer drugs BBR3464 and picoplatin.

Amide coupling reactions can be used to synthesize bispyridine-based ligands for use as bridging linkers in multinuclear platinum anticancer drugs. ...

Reverse Microemulsion-mediated Synthesis of Monometallic and Bimetallic Early Transition Metal Carbide and Nitride Nanoparticles

A reverse microemulsion is used to encapsulate monometallic or bimetallic early transition metal oxide nanoparticles in microporous silica shells. The silica-encapsulated metal oxide nanoparticles are then carburized in a methane/hydrogen atmosphere at temperatures over 800 &#176;C to form silica-encapsulated early transition metal carbide nanoparticles. During the carburization process, the silica shells prevent the sintering of adjacent carbide nanoparticles while also preventing the deposition of excess surface carbon. Alternatively, the silica-encapsulated metal oxide nanoparticles can be nitridized in an ammonia atmosphere at temperatures over 800 &#176;C to form silica-encapsulated early transition metal nitride nanoparticles. By adjusting the reverse microemulsion parameters, the thickness of the silica shells, and the carburization/nitridation conditions, the transition metal carbide or nitride nanoparticles can be tuned to various sizes, compositions, and crystal phases. After carburization or nitridation, the silica shells are then removed using either a room-temperature aqueous ammonium bifluoride solution or a 0.1 to 0.5 M NaOH solution at 40-60 &#176;C. While the silica shells are dissolving, a high surface area support, such as carbon black, can be added to these solutions to obtain supported early transition metal carbide or nitride nanoparticles. If no high surface area support is added, then the nanoparticles can be stored as a nanodispersion or centrifuged to obtain a nanopowder.

A &#8220;removable ceramic coating method&#8221; is presented in visual format for the synthesis of non-sintered and metal-terminated monometallic and bimetallic early transition metal carbide and nitride nanoparticles with tunable sizes and crystal structures.

A reverse microemulsion is used to encapsulate monometallic or bimetallic early transition metal oxide nanoparticles in microporous silica shells. The ...

Generation of Zerovalent Metal Core Nanoparticles Using n-(2-aminoethyl)-3-aminosilanetriol

In this work, a facile one-pot reaction for the formation of metal nanoparticles in a water solution through the use of n-(2-aminoethyl)-3-aminosilanetriol is presented. This compound can be used to effectively reduce and complex metal salts into metal core nanoparticles coated with the compound. By controlling the concentrations of salt and silane one is able to control reaction rates, particle size, and nanoparticle coating. The effects of these changes were characterized through transmission electron microscopy (TEM), UV-Vis spectrometry (UV-Vis), Nuclear Magnetic Resonance spectroscopy (NMR) and Fourier Transform Infrared spectroscopy (FTIR). A unique aspect to this reaction is that usually silanes hydrolyze and cross-link in water; however, in this system the silane is water-soluble and stable. It is known that silicon and amino moieties can form complexes with metal salts. The silicon is known to extend its coordination sphere to form penta- or hexa-coordinated species. Furthermore, the silanol group can undergo hydrolysis to form a Si-O-Si silica network, thereby transforming the metal nanoparticles into a functionalized nanocomposites.

Generation of Zerovalent Metal Core Nanoparticles Using n-2-aminoethyl-3-aminosilanetriol

A novel method for metal core nanoparticle synthesis using a water stable silanol is described.

In this work, a facile one-pot reaction for the formation of metal nanoparticles in a water solution through the use of ...

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst

A standardized technique for atom transfer radical polymerization of vinyl monomers using perylene as a visible-light photocatalyst is presented. The procedure is performed under an inert atmosphere using air- and water-exclusion techniques. The outcome of the polymerization is affected by the ratios of monomer, initiator, and catalyst used as well as the reaction concentration, solvent, and nature of the light source. Temporal control over the polymerization can be exercised by turning the visible light source off and on. Low dispersities of the resultant polymers as well as the ability to chain-extend to form block copolymers suggest control over the polymerization, while chain end-group analysis provides evidence supporting an atom-transfer radical polymerization mechanism.

A method for the atom transfer radical polymerization of functionalized vinyl monomers using perylene as a visible-light photocatalyst is described.

A standardized technique for atom transfer radical polymerization of vinyl monomers using perylene as a visible-light photocatalyst is presented. The ...

Au-Interaction of Slp1 Polymers and Monolayer from Lysinibacillus sphaericus JG-B53 - QCM-D, ICP-MS and AFM as Tools for Biomolecule-metal Studies

In this publication the gold sorption behavior of surface layer (S-layer) proteins (Slp1) of Lysinibacillus sphaericus JG-B53 is described. These biomolecules arrange in paracrystalline two-dimensional arrays on surfaces, bind metals, and are thus interesting for several biotechnical applications, such as biosorptive materials for the removal or recovery of different elements from the environment and industrial processes. The deposition of Au(0) nanoparticles on S-layers, either by S-layer directed synthesis 1 or adsorption of nanoparticles, opens new possibilities for diverse sensory applications. Although numerous studies have described the biosorptive properties of S-layers 2-5, a deeper understanding of protein-protein and protein-metal interaction still remains challenging. In the following study, inductively coupled mass spectrometry (ICP-MS) was used for the detection of metal sorption by suspended S-layers. This was correlated to measurements of quartz crystal microbalance with dissipation monitoring (QCM-D), which allows the online detection of proteinaceous monolayer formation and metal deposition, and thus, a more detailed understanding on metal binding.
The ICP-MS results indicated that the binding of Au(III) to the suspended S-layer polymers is pH dependent. The maximum binding of Au(III) was obtained at pH 4.0. The QCM-D investigations enabled the detection of Au(III) sorption as well as the deposition of Au(0)-NPs in real-time during the in situ experiments. Further, this method allowed studying the influence of metal binding on the protein lattice stability of Slp1. Structural properties and protein layer stability could be visualized directly after QCM-D experiment using atomic force microscopy (AFM). In conclusion, the combination of these different methods provides a deeper understanding of metal binding by bacterial S-layer proteins in suspension or as monolayers on either bacterial cells or recrystallized surfaces.

Au-Interaction of Slp1 Polymers and Monolayer from Lysinibacillus sphaericus JG-B53 - QCM-D, ICP-MS and AFM as Tools for Biomolecule-metal Studies

To obtain basic information on the sorption and recycling of gold from aqueous systems the interaction of Au(III) and Au(0) nanoparticles on S-layer proteins were investigated. The sorption of protein polymers was investigated by ICP-MS and that of proteinaceous monolayers by QCM-D. Subsequent AFM enables the imaging of the nanostructures.

In this publication the gold sorption behavior of surface layer (S-layer) proteins (Slp1) of Lysinibacillus sphaericus JG-B53 is described. These ...

In Situ Detection and Single Cell Quantification of Metal Oxide Nanoparticles Using Nuclear Microprobe Analysis

Micro-analytical techniques based on chemical element imaging enable the localization and quantification of chemical composition at the cellular level. They offer new possibilities for the characterization of living systems and are particularly appropriate for detecting, localizing and quantifying the presence of metal oxide nanoparticles both in biological specimens and the environment. Indeed, these techniques all meet relevant requirements in terms of (i) sensitivity (from 1 up to 10 &#181;g.g-1 of dry mass), (ii) micrometer range spatial resolution, and (iii) multi-element detection. Given these characteristics, microbeam chemical element imaging can powerfully complement routine imaging techniques such as optical and fluorescence microscopy. This protocol describes how to perform a nuclear microprobe analysis on cultured cells (U2OS) exposed to titanium dioxide nanoparticles. Cells must grow on and be exposed directly in a specially designed sample holder used on the optical microscope and in the nuclear microprobe analysis stages. Plunge-freeze cryogenic fixation of the samples preserves both the cellular organization and the chemical element distribution. Simultaneous nuclear microprobe analysis (scanning transmission ion microscopy, Rutherford backscattering spectrometry and particle induced X-ray emission) performed on the sample provides information about the cellular density, the local distribution of the chemical elements, as well as the cellular content of nanoparticles. There is a growing need for such analytical tools within biology, especially in the emerging context of Nanotoxicology and Nanomedicine for which our comprehension of the interactions between nanoparticles and biological samples must be deepened. In particular, as nuclear microprobe analysis does not require nanoparticles to be labelled, nanoparticle abundances are quantifiable down to the individual cell level in a cell population, independently of their surface state.

In Situ Detection and Single Cell Quantification of Metal Oxide Nanoparticles Using Nuclear Microprobe Analysis

We describe a procedure for the detection of chemical elements present in situ in human cells as well as their in vitro quantification. The method is well-suited to any cell type and is particularly useful for quantitative chemical analyses in single cells following in vitro metal oxide nanoparticles exposure.

Micro-analytical techniques based on chemical element imaging enable the localization and quantification of chemical composition at the cellular level. ...

Ligand-Mediated Nucleation and Growth of Palladium Metal Nanoparticles

The size, size distribution and stability of colloidal nanoparticles are greatly affected by the presence of capping ligands. Despite the key contribution of capping ligands during the synthesis reaction, their role in regulating the nucleation and growth rates of colloidal nanoparticles is not well understood. In this work, we demonstrate a mechanistic investigation of the role of trioctylphosphine (TOP) in Pd nanoparticles in different solvents (toluene and pyridine) using in situ SAXS and ligand-based kinetic modeling. Our results under different synthetic conditions reveal the overlap of nucleation and growth of Pd nanoparticles during the reaction, which contradicts the LaMer-type nucleation and growth model. The model accounts for the kinetics of Pd-TOP binding for both, the precursor and the particle surface, which is essential to capture the size evolution as well as the concentration of particles in situ. In addition, we illustrate the predictive power of our ligand-based model through designing the synthetic conditions to obtain nanoparticles with desired sizes. The proposed methodology can be applied to other synthesis systems and therefore serves as an effective strategy for predictive synthesis of colloidal nanoparticles.

The main goal of this work is to elucidate the role of capping agents in regulating the size of palladium nanoparticles by combining in situ small angle x-ray scattering (SAXS) and ligand-based kinetic modeling.

The size, size distribution and stability of colloidal nanoparticles are greatly affected by the presence of capping ligands. Despite the key contribution ...

Surface Functionalization of Metal-Organic Frameworks for Improved Moisture Resistance

Metal-organic frameworks (MOFs) are a class of porous inorganic materials with promising properties in gas storage and separation, catalysis and sensing. However, the main issue limiting their applicability is their poor stability in humid conditions. The common methods to overcome this problem involve the formation of strong metal-linker bonds by using highly charged metals, which is limited to a number of structures, the introduction of alkylic groups to the framework by post-synthetic modification (PSM) or chemical vapour deposition (CVD) to enhance overall hydrophobicity of the framework. These last two usually provoke a drastic reduction of the porosity of the material. These strategies do not permit to exploit the properties of the MOF already available and it is imperative to find new methods to enhance the stability of MOFs in water while keeping their properties intact. Herein, we report a novel method to enhance the water stability of MOF crystals featuring Cu2(O2C)4&#160;paddle-wheel units, such as HKUST (where HKUST stands for Hong Kong University of Science &#38; Technology), with the catechols functionalized with alkyl and fluoro-alkyl chains. By taking advantage of the unsaturated metal sites and the catalytic catecholase-like activity of CuII ions, we are able to create robust hydrophobic coatings through the oxidation and subsequent polymerization of the catechol units on the surface of the crystals under anaerobic and water-free conditions without disrupting the underlying structure of the framework. This approach not only affords the material with improved water stability but also provides control over the function of the protective coating, which enables the development of functional coatings for the adsorption and separations of volatile organic compounds. We are confident that this approach could also be extended to other unstable MOFs featuring open metal sites.

Robust functional catechol coatings were produced in one step by direct reaction of the material known as HKUST with synthetic catechols under anaerobic conditions. The formation of homogeneous coatings surrounding the entire crystal is ascribed to the biomimetic catalytic activity of Cu(II) dimers on the external surface of the crystals.

Metal-organic frameworks (MOFs) are a class of porous inorganic materials with promising properties in gas storage and separation, catalysis and sensing. ...

Molten-Salt Synthesis of Complex Metal Oxide Nanoparticles

The development of feasible synthesis methods is critical for the successful exploration of novel properties and potential applications of nanomaterials. Here, we introduce the molten-salt synthesis (MSS) method for making metal oxide nanomaterials. Advantages over other methods include its simplicity, greenness, reliability, scalability, and generalizability. Using pyrochlore lanthanum hafnium oxide (La2Hf2O7) as a representative, we describe the MSS protocol for the successful synthesis of complex metal oxide nanoparticles (NPs). Furthermore, this method has the unique ability to produce NPs with different material features by changing various synthesis parameters such as pH, temperature, duration, and post-annealing. By fine-tuning these parameters, we are able to synthesize highly uniform, non-agglomerated, and highly crystalline NPs. As a specific example, we vary the particle size of the La2Hf2O7&#160;NPs by changing the concentration of the ammonium hydroxide solution used in the MSS process, which allows us to further explore the effect of particle size on various properties. It is expected that the MSS method will become a more popular synthesis method for nanomaterials and more widely employed in the nanoscience and nanotechnology community in the upcoming years.

Here, we demonstrate a unique, relatively low-temperature, molten-salt synthesis method for preparing uniform complex metal oxide lanthanum hafnate nanoparticles.

The development of feasible synthesis methods is critical for the successful exploration of novel properties and potential applications of nanomaterials. ...