Funding: This research is funded through the support of the Rowland Fellowship at the Rowland Institute at Harvard University, the Harvard PSE Accelerator Fund, and the Gordon and Betty Moore Foundation. A portion of this work was performed at the Harvard Center for Nanoscale Systems (CNS), a member of the National Nanotechnology Coordinated Infrastructure Network (NNCI), which is supported by the National Science Foundation under NSF, Award No. 1541959. A portion of this work was performed at the Stanford Nano Shared Facilities (SNSF), supported by the National Science Foundation under award ECCS-2026822. A portion of this work was performed at the Stanford ChEM-H Macromolecular Structure Knowledge Center.
Acknowledgements: THS and SNS acknowledge the support of Arnold O. Beckman Postdoctoral Fellowships. MS acknowledges financial support through a Doc. Mobility Fellowship from the Swiss National Science Foundation (Project No. P1SKP2 187676). PN acknowledges the support of a Stanford Graduate Fellowship in Science &#38; Engineering (SGF) as a Gabilan Fellow. MH was partially supported by the Defense Advanced Research Projects Agency under Grant No. HR00112220010. AOG acknowledges the support of a National Science Foundation Graduate Research Fellowship under Grant DGE-1656518 and a Stanford Graduate Fellowship in Science &#38; Engineering (SGF) as a Scott A. and Geraldine D. Macomber Fellow.

1. Large-scale upconversion nanocapsule synthesis
<ol>
	<li>In a glovebox (see Table of Materials) with an inert atmosphere under red lighting, prepare saturated solutions of the sensitizer (PdTPTBP) and annihilator (TIPS-anthracene) (see Table of Materials) in 99% oleic acid at room temperature (~22 &#176;C).
	<ol>
		<li>Add 2 mL of oleic acid to 20 mg of PdTPTBP in a vial with a stir bar. Then, cover the vial with foil to protect from ambient light. Add 2 mL of oleic acid to 25 mg of TIPS-anthracene in a vial with a stir bar.</li>
		<li>Stir the mixtures at 600 rpm for at least 4 h before filtering with a 0.45 &#181;m PTFE syringe filter. Each solution should visibly have undissolved solid to be removed by filtration, signifying that each solution is saturated.</li>
		<li>Using a syringe, prepare 1.75 mL of the upconversion material stock solution by mixing 0.7 mL of the filtered TIPS-anthracene solution, 0.35 mL of the filtered PdTPTBP solution, and 0.7 mL of oleic acid. 
		NOTE: The upconversion solution used for the nanocapsules has a ratio of 2:1:2 of TIPS-anthracene to PdTPTBP to oleic acid by volume.</li>
	</ol>
	</li>
	<li>Measure 4 g of 10K MPEG-silane in a clean 20 mL vial so that it is ready for use during synthesis. This can be conducted inside or outside of the glovebox. If this material is measured outside of the glovebox, secure the vial lid with sealing film or electrical tape before bringing it into the glovebox.</li>
	<li>In a 250 mL Erlenmeyer flask sealed with a septum, chill 200 mL of ultrapure deionized water in an ice bath for at least 1 h to reach ~5 &#176;C . Typically, this takes a few hours.</li>
	<li>Secure the septum to the flask using at least six pieces of sealing film. This is to ensure that the septum remains affixed when the flask is under vacuum in the glovebox antechamber.</li>
	<li>Bring the chilled water into the glovebox immediately before preparing the nanocapsules. Only pull a light vacuum on the antechamber when bringing in the water by pulling 20% vacuum based on the measurement on the antechamber pressure gauge.</li>
	<li>After bringing the water into the glovebox, immediately turn on the glovebox purge feature to bypass the column. This removes the oxygen introduced when bringing in the water under light vacuum and prolongs the life of the column. Keep the purge on until the synthesis is complete, and all waste has been removed from the glovebox.</li>
	<li>Ensure all chemicals and consumables are ready to use, including syringes and needles for dispensing (3-aminopropyl)triethoxysilane (APTES) and tetraethyl orthosilicate. Make sure the 10K MPEG-silane is within reach. For cleaning, nylon cloths are also useful to have available.</li>
	<li>Plug in the blender (see Table of Materials). Cover the electrical sockets with a plastic bin or nylon cloth. This barrier allows for protection in the case of an unexpected blender leak. Make sure the blender is powered off.</li>
	<li>Carefully pour the water into the blender. Add 1.45 mL of the upconversion material stock solution (prepared in step 1.1.3) in one portion with a syringe into the center of the water in the blender.</li>
	<li>Affix the lid and cover it with a nylon wipe in the case of an unexpected leak. Blend at the maximum speed (22,600 rpm) for exactly 60 s while holding the blender lid to prevent small leaks.</li>
	<li>Turn off the blender and move it out of the way to ensure adequate working space.</li>
	<li>Transfer the emulsion to a 500 mL round bottom flask. Secure the flask to a stir plate with a clamp. Mix the emulsion vigorously at 1200 rpm with an egg-shaped stir bar (see Table of Materials).</li>
	<li>Using a syringe, add 0.75 mL of APTES to the emulsion to generate a clear solution of micelles.</li>
	<li>Add 4 g of 10K MPEG-silane to prevent capsule aggregation. Shake the flask if needed to ensure it is dispersed. Stir at 1200 rpm for approximately 10 min.</li>
	<li>During this time, dry the blender and lid with a nylon cloth. Use tongs to keep hands far away from the sharp blender blades.</li>
	<li>After 10 min have passed, add 15 mL of tetraethyl orthosilicate in one portion using a 20 mL syringe. Add another 15 mL of tetraethyl orthosilicate in one portion using a 20 mL syringe for a total of 30 mL. Affix a septum to the flask and stir at 1200 rpm for 30 min.</li>
	<li>Remove the flask and waste from the glovebox and turn off the glovebox purge.</li>
	<li>Affix the flask to a stir plate with a heating element, such as an oil bath or aluminum heating block. Connect the flask to a Schlenk line so the reaction is held at a constant pressure under an inert gas such as nitrogen or argon.</li>
	<li>Stir and heat the reaction at 65 &#176;C at a speed of 1200 rpm for 40 h.</li>
	<li>After 40 h, disconnect the reaction from the Schlenk line to add 4 g of 10K MPEG-silane. Reconnect the reaction to the Schlenk line. Stir and heat the reaction at 65 &#176;C at 1200 rpm for 8 h.</li>
	<li>After 8 h, turn off the heat and allow the reaction to cool to room temperature while stirring at 1200 rpm.</li>
	<li>When the reaction is cool, transfer the reaction into centrifuge tubes.
	<ol>
		<li>For a centrifuge (see Table of Materials) that holds 50 mL centrifuge tubes, split the reaction equally among 10 centrifuge tubes.</li>
		<li>For a centrifuge that holds 0.5 L centrifuge tubes, split the reaction equally among two centrifuge tubes.</li>
	</ol>
	</li>
	<li>Centrifuge the suspension at 8670 x g for 1 h at a temperature of 20-22 &#176;C. Discard the pellet and retain the supernatant containing the nanocapsules.</li>
	<li>Centrifuge the supernatant at 8670 x g for 14-16 h at 20-22 &#176;C.</li>
	<li>Discard the supernatant and collect the pellet containing upconversion nanocapsules.
	<ol>
		<li>Using a pipette, carefully rinse the top surface of the nanocapsule pellet with ultrapure deionized water (2 x 10 mL). This should be conducted at a low flow so the pellet is not dislodged from the centrifuge tube.</li>
		<li>Transfer the nanocapsule paste into two or three separate 20 mL scintillation vials with a spatula and immediately bring the vials into the glovebox. Approximately 7-10 g of nanocapsule paste should be recovered. 
		NOTE: For further use, it is recommended that the nanocapsules are dispersed into a solvent such as a monomer for 3D printing or deoxygenated ultrapure deionized water within 48 h of synthesis. Water will evaporate from the nanocapsule paste and leave the nanocapsules unusable after 48 h.</li>
	</ol>
	</li>
	<li>Perform scanning electron microscopy (SEM), dynamic light scattering (DLS), and upconversion photoluminescence to characterize the nanocapsule preparation.</li>
</ol>
2. Small-scale upconversion nanocapsule synthesis
<ol>
	<li>Prepare the stock solutions of the sensitizer and the annihilator as described in step 1.1. Scale down the volume of the solution used to make upconversion nanocapsules to 250 &#956;L instead of the 1.75 mL described in step 1.1. Mix 100 &#956;L of the filtered TIPS-an solution with 50 &#956;L of the filtered PdTPTBP solution and 100 &#956;L of oleic acid.</li>
	<li>Vigorously sparge 20 mL of ultrapure deionized water in a 40 mL scintillation vial (see Table of Materials) with an inert gas, such as nitrogen or argon, using a Schlenk line for at least 10 min. Affix the lid with electrical tape or sealing film prior to bringing the vial into the glovebox. 
	NOTE: If making multiple small-scale samples at once, larger volumes of water can be sufficiently degassed by blending 200 mL of chilled water as outlined in section 1 using a clean, unused blender pitcher. Sparging water with an inert gas on a Schlenk line is not effective at volumes greater than 20 mL.</li>
	<li>Measure 400 mg of 10K MPEG-silane so that it is ready for use during synthesis into a clean 10 mL vial. This can be conducted inside or outside of the glovebox. If this is measured outside of the glovebox, secure the vial&#39;s lid with sealing film or electrical tape before bringing it into the glovebox.</li>
	<li>Bring the sparged water into the glovebox, and immediately turn on the glovebox purge feature to bypass the column. This whisks away oxygen introduced when bringing in the water under light vacuum and prolongs the life of the column. The purge should remain on until the synthesis is complete, and all waste has been removed from the glovebox.</li>
	<li>Ensure all chemicals and consumables (5 mL syringes and a micropipette with tips) are ready to use.
	<ol>
		<li>Using a syringe, remove 1 mL of (3-aminopropyl)triethoxysilane from the bottle and dispense it into a clean, labeled 20 mL vial for later use.</li>
		<li>Using a syringe, remove 5 mL of tetraethyl orthosilicate and dispense it into a clean, labeled 20 mL vial for later use.</li>
		<li>Make sure the 10K MPEG-silane is within reach in the glovebox.</li>
		<li>For cleaning, extra nylon cloths are also useful to have available.</li>
	</ol>
	</li>
	<li>Plug in the vortex mixer (see Table of Materials) and set the speed to the highest setting (3200 rpm).</li>
	<li>Using a micropipette, add 145 &#181;L of sensitizer/annihilator stock solution to a vial of water (20 mL). Affix the lid with electrical tape or sealing film.</li>
	<li>Vortex the solution at the highest speed of the vortex mixer (3200 rpm) for 7 min to ensure nanodroplet formation similar to the large-scale synthesis. Hold the vial close to the base and never hold on to the vial lid during vortexing, as the lid can become loose and detach from the vial.</li>
	<li>Affix the vial to a stir plate. Stir the emulsion at 1200 rpm with an octagon-shaped stir bar (see Table of Materials).</li>
	<li>Using a micropipette, add 75 &#181;L of APTES to generate a clear solution of micelles.</li>
	<li>After generating the clear solution, immediately add 400 mg of 10K MPEG-silane. Affix the lid and shake the vial to efficiently mix the reaction. Return the vial to the stir plate.</li>
	<li>Using a syringe, add 3 mL of tetraethyl orthosilicate in sequence while the reaction is being stirred at 1200 rpm. Affix the lid and shake the vial to efficiently mix the reaction. Stir the reaction at 1200 rpm until it is removed from the glovebox.</li>
	<li>Seal the vial with electrical tape or sealing film and remove the vial from the glovebox.</li>
	<li>Heat the solution at 65 &#176;C using an oil bath or aluminum heating block. Stir the reaction at 1200 rpm for 40 h.</li>
	<li>After 40 h, add 400 mg of 10K MPEG-silane. Reseal the vial with electrical tape or sealing film. Stir the reaction at 1200 rpm for 8 h.</li>
	<li>Allow the reaction to cool to room temperature while stirring at 1200 rpm. When the reaction is cool, combine the reaction mixtures into one 50 mL centrifuge tube.</li>
	<li>Centrifuge the suspension at 8670 x g for 1 h at a temperature of 20-22 &#176;C. Discard the pellet and retain the supernatant containing the nanocapsules.</li>
	<li>Centrifuge the supernatant at 8670 x g for 14-16 h at 20-22 &#176;C.</li>
	<li>Discard the supernatant and retain the pellet containing upconversion nanocapsules. Using a pipette, carefully rinse the top surface of the nanocapsule pellet with 2 x 1 mL of ultrapure deionized water. This should be conducted at a low flow so the pellet is not dislodged from the centrifuge tube.</li>
	<li>Transfer the nanocapsule paste into a 20 mL scintillation vial with a spatula and bring the vials into the glovebox immediately. Approximately 700-1000 mg of nanocapsule paste should be recovered. 
	NOTE: For further use, it is recommended that the nanocapsules are dispersed into a solvent, such as a monomer for 3D printing or deoxygenated ultrapure deionized water, within 48 h. Water will evaporate from the nanocapsule paste and will leave the nanocapsules unusable after 48 h.</li>
</ol>

<ol>
	<li>High Resolution SLA and SLS 3D Printers for Professionals. Formlabs Available from: <a target="_blank" href="https://formlabs.com">https://formlabs.com</a> (2022)</li><li>Zhang, D., Liu, X., Qiu, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=3D+printing+of+glass+by+additive+manufacturing+techniques:+a+review.">3D printing of glass by additive manufacturing techniques: a review.</a> Frontiers of Optoelectronics. 14 (3), 263-277 (2021).</li><li>Chen, Z., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=3D+printing+of+ceramics:+A+review.">3D printing of ceramics: A review.</a> Journal of the European Ceramic Society. 39 (4), 661-687 (2019).</li><li>Zhang, F., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+review+of+3D+printed+porous+ceramics.">A review of 3D printed porous ceramics.</a> Journal of the European Ceramic Society. 42 (8), 3351-3373 (2022).</li><li>Frazier, W. E. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Metal+additive+manufacturing:+A+review.">Metal additive manufacturing: A review.</a> Journal of Materials Engineering and Performance. 23 (6), 1917-1928 (2014).</li><li>Ligon, S. C., Liska, R., Stampfl, J., Gurr, M., M&#252;lhaupt, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Polymers+for+3D+printing+and+customized+additive+manufacturing.">Polymers for 3D printing and customized additive manufacturing.</a> Chemical Reviews. 117 (15), 10212-10290 (2017).</li><li>Bagheri, A., Jin, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Photopolymerization+in+3D+printing.">Photopolymerization in 3D printing.</a> ACS Applied Polymer Materials. 1 (4), 593-611 (2019).</li><li>Geng, Q., Wang, D., Chen, P., Chen, S. -. C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ultrafast+multi-focus+3-D+nano-fabrication+based+on+two-photon+polymerization.">Ultrafast multi-focus 3-D nano-fabrication based on two-photon polymerization.</a> Nature Communications. 10 (1), 2179 (2019).</li><li>LaFratta, C. N., Li, L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Making+two-photon+polymerization+faster.">Making two-photon polymerization faster.</a> Three-dimensional Microfabrication using Two-Photon Polymerization. , 221-241 (2016).</li><li>Sanders, S. N., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Triplet+fusion+upconversion+nanocapsules+for+volumetric+3D+printing.">Triplet fusion upconversion nanocapsules for volumetric 3D printing.</a> Nature. 604 (7906), 474-478 (2022).</li><li>Anscombe, N. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Direct+laser+writing.">Direct laser writing.</a> Nature Photonics. 4 (1), 22-23 (2010).</li><li>Xiong, W., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Simultaneous+additive+and+subtractive+three-dimensional+nanofabrication+using+integrated+two-photon+polymerization+and+multiphoton+ablation.">Simultaneous additive and subtractive three-dimensional nanofabrication using integrated two-photon polymerization and multiphoton ablation.</a> Light: Science &amp; Applications. 1 (4), 6 (2012).</li><li>Singh-Rachford, T. N., Castellano, F. N. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Photon+upconversion+based+on+sensitized+triplet-triplet+annihilation.">Photon upconversion based on sensitized triplet-triplet annihilation.</a> Coordination Chemistry Reviews. 254 (21), 2560-2573 (2010).</li><li>Rauch, M. P., Knowles, R. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Applications+and+prospects+for+triplet-triplet+annihilation+photon+upconversion.">Applications and prospects for triplet-triplet annihilation photon upconversion.</a> CHIMIA International Journal for Chemistry. 72 (7), 501-507 (2018).</li><li>Seo, S. E., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Recent+advances+in+materials+for+and+applications+of+triplet-triplet+annihilation-based+upconversion.">Recent advances in materials for and applications of triplet-triplet annihilation-based upconversion.</a> Journal of Materials Chemistry C. 10 (12), 4483-4496 (2022).</li><li>Ahmad, W., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Strategies+for+combining+triplet-triplet+annihilation+upconversion+sensitizers+and+acceptors+in+a+host+matrix.">Strategies for combining triplet-triplet annihilation upconversion sensitizers and acceptors in a host matrix.</a> Coordination Chemistry Reviews. , 439-213944 (2021).</li><li>Stetefeld, J., McKenna, S. A., Patel, T. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Dynamic+light+scattering:+a+practical+guide+and+applications+in+biomedical+sciences.">Dynamic light scattering: a practical guide and applications in biomedical sciences.</a> Biophysical Reviews. 8 (4), 409-427 (2016).</li><li>Speckbacher, M., Yu, L., Lindsey, J. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Formation+of+porphyrins+in+the+presence+of+acid-labile+metalloporphyrins:+A+new+route+to+mixed-metal+multiporphyrin+arrays.">Formation of porphyrins in the presence of acid-labile metalloporphyrins: A new route to mixed-metal multiporphyrin arrays.</a> Inorganic Chemistry. 42 (14), 4322-4337 (2003).</li><li>Congrave, D. G., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Suppressing+aggregation+induced+quenching+in+anthracene+based+conjugated+polymers.">Suppressing aggregation induced quenching in anthracene based conjugated polymers.</a> Polymer Chemistry. 12 (12), 1830-1836 (2021).</li><li>Titration: Principles, volumetric analysis | General Chemistry. JoVE Available from: <a target="_blank" href="https://jove.unicartagenaproxy.elogim.com/v/5699/introduction-to-titration">https://jove.unicartagenaproxy.elogim.com/v/5699/introduction-to-titration</a> (2022)</li><li>Cushing, B. L., Kolesnichenko, V. L., O'Connor, 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=Recent+advances+in+the+liquid-phase+syntheses+of+inorganic+nanoparticles.">Recent advances in the liquid-phase syntheses of inorganic nanoparticles.</a> Chemical Reviews. 104 (9), 3893-3946 (2004).</li><li>Han, L., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Anionic+surfactants+templating+route+for+synthesizing+silica+hollow+spheres+with+different+shell+porosity.">Anionic surfactants templating route for synthesizing silica hollow spheres with different shell porosity.</a> Solid State Sciences. 13 (4), 721-728 (2011).</li><li>Kwon, O. S., Kim, J. -. H., Cho, J. K., Kim, J. -. H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Triplet-triplet+annihilation+upconversion+in+CdS-decorated+SiO2+nanocapsules+for+sub-bandgap+photocatalysis.">Triplet-triplet annihilation upconversion in CdS-decorated SiO2 nanocapsules for sub-bandgap photocatalysis.</a> ACS Applied Materials &amp; Interfaces. 7 (1), 318-325 (2015).</li><li>Brinker, C. J., Scherer, G. W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Sol-Gel Science: the Physics and Chemistry of Sol-Gel Processing. , (2014).</li><li>. G Force Calculator - RCF to RPM Available from: <a target="_blank" href="https://www.sigmaaldrich.com/US/en/support/calculators-and-apps/g-force-calculator">https://www.sigmaaldrich.com/US/en/support/calculators-and-apps/g-force-calculator</a> (2022)</li><li>. Acrylic acid (HSG 104, 1997) Available from: <a target="_blank" href="https://inchem.org/documents/hsg/hsg/v104hsg.htm">https://inchem.org/documents/hsg/hsg/v104hsg.htm</a> (2022)</li><li>de Mello, J. C., Wittmann, H. F., Friend, R. H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=An+improved+experimental+determination+of+external+photoluminescence+quantum+efficiency.">An improved experimental determination of external photoluminescence quantum efficiency.</a> Advanced Materials. 9 (3), 230-232 (1997).</li></ol>

Harvard University has filed several patents based on this work. SNS, RCS, and DNC are co-founders of Quadratic3D, Inc.

There are several considerations when preparing bright upconverting nanocapsules. First, the synthesis is completed in a glovebox because the upconversion materials must be protected from oxygen-it is well established that upconverted light output is reduced in the presence of oxygen13,14,15,16. Additionally, the sensitizer and annihilator stock solutions should be prepared fresh for every batch. PdTPTBP and other metalated porphyrins have been shown to demetalate in ambient lighting in the presence of acid18, and anthracenes are known to aggregate over time19. These effects can be minimized by preparing fresh solutions under red lighting for each synthesis. The authors note that rigorous red lighting is no longer required once the metalated porphyrin and anthracene are mixed, and ambient lighting is acceptable to use after this step. Finally, for the large-scale synthesis, it is recommended that at least 1.75 mL of the upconverting stock solution is prepared, since adding less than 1.45 mL of this solution to make UCNCs will alter the proportions of all other required reagents as well as the concentration-dependent nanodroplet formation. Similarly, for the small-scale synthesis, it is recommended that 250 &#181;L of the upconverting stock solution is prepared in the same proportions. Finally, when using a micropipette for dispensing the oleic acid stock solutions, slowly release the plunger and wait for it to fully rise to dispense the desired volume. The oleic acid will slowly fill the pipette tip due to its high viscosity and it is easy to inadvertently dispense less solution than expected.
It is important to understand that the oleic acid nanodroplet generation is sensitive to blending time, speed, and significant temperature changes. For instance, the blender selection is significant and can impact the formation of oleic acid nanodroplets. Multiple blender brands were tested in the initial development stages. The blender recommended in the Table of Materials led to the generation of relatively superior and reproducible nanocapsules described in this protocol. Notably, powerful blending increases the temperature of the emulsion and reduces the oleic acid nanodroplet formation efficiency. The blender blades must be completely submerged in water to best control the temperature, which was one consideration for determining the required water volume presented here10. Additionally, chilling the water in advance reduces droplet aggregation in the emulsion, which ultimately improves the nanocapsule yield for the large-scale synthesis. On the other hand, for the small-scale synthesis, chilling the water does not significantly alter the oleic nanodroplet formation, probably because holding the 40 mL vial does not increase the temperature of the water as much as the blender blades.
The APTES addition is a significant synthetic step, as APTES stabilizes the oleic acid nanodroplets generated by blending or vortexing. The initial nanodroplet emulsion is a cloudy, turbid dispersion. Upon addition of APTES, the solution becomes clear and transparent as the nanodroplets are stabilized. On average, the APTES volumes required are very close to what is presented in the protocol, but sometimes slightly less or slightly more APTES is required for the solution to become clear. Thus, the APTES addition should be treated in an analogous manner to conducting other titrations20. Adding too much APTES (i.e., beyond a &#34;just clear&#34; solution) will disrupt nanocapsule shell formation and decrease yield. To that end, if significantly different volumes of APTES are required to produce a clear suspension, or a clear suspension is never reached, this indicates troubleshooting is required to optimize the oleic acid nanodroplet formation. For instance, if the nanodroplet generation is inefficient, the droplet volume and thus surface area of the nanodroplet will be larger than expected and may require more APTES. This has been observed in the small-scale synthesis, and can be remedied in a variety of ways, such as the force used to hold a vial against the vortex mixer or by increasing the vortexing time.
Additionally, the 10K MPEG-silane must be added immediately after APTES to prevent aggregation and cannot be omitted10. Without the addition of 10K MPEG-silane, irreversible aggregation is observed within ~30 min in the form of precipitate generation. Although 5K MPEG-silane can be substituted for 10K MPEG-silane, lower molecular weight MPEG-silanes do not sufficiently prevent aggregation at a constant concentration.
The silica shell formation is key to impart UCNC durability when dispersed in various solutions. While silica shell growth is generally well studied21,22,23, the often-used21 acid or base catalysis to promote silica growth is not used here, as the heating is sufficient for generating a durable, cross-linked silica shell. To monitor the silica shell formation over time, bright upconversion should be observed after 100x dilution of a nanocapsule reaction aliquot in an organic solvent, such as acetone, with minimal sensitizer phosphorescence for the PdTPTBP/TIPS-an system (Figure 2D and reference10). Typically, bright upconversion is observable after about 24 h, but 48 h will increase the relative emission, signifying that a larger population of the UCNCs possess a durable shell. Note that the UC emission is dependent upon the irradiation power and sufficient power densities should be employed. For instance, in the system described here, power densities on the order of ~65 W cm-2 are required to see bright upconverted PL.
The second addition of 10K MPEG-silane after 40 h of silica growth improves nanocapsule dispersibility in organic solvents. While the UCNCs will still be dispersible in multiple solvents without this second 10K MPEG-silane addition, the second addition is highly recommended to increase the UCNC loadings by mass in solution. For instance, for use in a 3D printing resin, 0.67 g mL-1 of nanocapsule paste was dispersed in acrylic acid10.
Exposing the UCNCs to oxygen during the entire multi-day fabrication process results in the ingress of oxygen in concentrations that significantly reduce upconversion photoluminescence. To ensure an inert atmosphere is maintained during the 48 h of stirring in an ambient atmosphere, different protocols are invoked depending upon the reaction scale. At large scales, the ethanol generated during silica growth can produce significant pressures which can lead to the removal of an affixed septum or the loss in structural integrity of the reaction vessel24. Thus, the 500 mL flask should be connected to a Schlenk line to allow for a pressure release in an inert atmosphere. At small scales, sealing a 40 mL glass vial with sealing film or electrical tape maintains the seal&#39;s structural integrity. Without sealing the vial&#39;s lid, the increase in pressure will slowly unthread the lid and allow for the ingress of oxygen.
The reaction purification by centrifugation separates the UCNCs from other undesired side products. Multiple centrifuge brands and rotors are compatible with this purification if the g force provided in the protocol is accessible. The g force can be converted to rotations per minute based upon the centrifuge rotor dimensions25. Exposing the UCNCs to an ambient atmosphere briefly during centrifugation is acceptable as long as they are stored in an inert atmosphere after purification. One limitation of this synthesis is that atom yield is difficult to quantify in relation to the input chemicals. After centrifugation, this large-scale nanocapsule synthesis should yield roughly 10 g of paste and the small-scale synthesis should yield roughly 1.0 g of capsule paste. It is unclear how much of the TEOS is incorporated into making the UCNC shell. The pellet discarded after the first centrifugation is comprised of large molecular weight silica that is not incorporated into the UCNCs. After the second centrifugation, the supernatant can be centrifuged again to increase the mass collected. It is not recommended to increase the centrifugation time beyond 16 h, as the soft capsule paste will solidify into a compact film that cannot be dispersed in other solvents. Even so, the capsule paste masses collected from batch to batch are consistent and are sufficient for subsequent use and characterization.
The UCNC durability can vary from solvent to solvent as well as with storage conditions. While the UCNC paste collected by centrifugation is unusable after 48 h as water evaporates, the nanocapsules are durable in a variety of solvents. In water, the UCNC durability is in the order of several months. In acrylic acid, the durability is reduced to days mostly because the acrylic acid solvent is unstable and can undergo polymerization when stored in oxygen-free conditions10,26. Further solvent-dependent investigations of UCNC durability are ongoing.
The small-scale synthesis is especially useful for relative comparisons of upconversion photoluminescence among different formulations. The NC paste collected after the second centrifugation should be dispersed in water at concentration of 100-200 mg mL-1 and diluted in acetone (or another solvent as desired). A minimum of 25% of the solution volume must contain water (e.g., 25/75 water/acetone v/v) to keep the NCs suspended and prevent precipitates from forming. Comparing the relative upconversion emission among batches was required to determine the concentrations of sensitizer and annihilator in this protocol. Perhaps counterintuitively, the ratio of sensitizer to annihilator required to maximize the light output in UC nanocapsules for 3D printing may not be equivalent to the ratio that maximizes the UC quantum yield27 in oleic acid stock solutions.
In conclusion, a detailed protocol and best practices for synthesizing upconversion nanocapsules is expanded upon in a step-by-step fashion10. Since other methods to encapsulate upconversion materials for use in real-life applications are only compatible with aqueous environments16, this synthesis is significant because it allows for upconversion materials to be deployed into diverse chemical environments, such as organic solvents. These methods will serve to increase approaches to access volumetric 3D printing for precision additive manufacturing and in any application requiring high-energy light beyond the surface.

Moving away from subtractive manufacturing processes (i.e., complex shapes made by carving blocks of raw material) can reduce waste and increase production rates. Accordingly, many industries are moving toward additive manufacturing processes, where objects are built layer-by-layer1 by means of three-dimensional (3D) printing. Many are working to develop additive manufacturing processes for numerous classes of materials (e.g., glass2, ceramics3,4, metals5, and plastics6,7).
This layer-by-layer curing limits resin selection and impacts the print&#39;s mechanical properties6,7. Considering light-based 3D printing for making plastics, two-photon absorption (2PA)-based printing moves away from the layer-by-layer processes by printing volumetrically8. The 2PA process requires simultaneous absorption of two photons to initiate polymerization. This not only increases the requisite power inputs, but also increases the complexity and cost of the printing system, limiting the print sizes to the mm3 scale or smaller9.
Recently, a new 3D printing methodology using triplet fusion upconversion (UC) has made volumetric 3D printing with UC possible on the cm3 scale10. Excitingly, this process requires relatively low power density irradiation10 as compared to 2PA-based printing9,11,12. The upconversion process converts two low energy photons into one high energy photon13, and the upconverted light is absorbed by the photoinitiator to initiate polymerization. Deploying triplet fusion UC materials has traditionally been challenging due to high material concentration requirements, poor solubility, and oxygen sensitivity13,14,15. Encapsulating UC materials using a variety of nanoparticle schemes has been well studied16 but falls short of the durability required in organic solvents. The silica-coated oleic acid upconversion nanocapsule (UCNC) synthetic protocol described here overcomes this durability challenge for dispersion of UC materials in a wide variety of organic solvents, including 3D printing resins10. The upconverted light generated from materials inside of the nanocapsules is patterned in multiple dimensions to generate support structure-free solid objects, which allows for printing high resolution structures with a resolution as small as 50 &#181;m10. By removing support structures and printing in an oxygen-free environment, new resin chemistries are accessible to achieve both improved and novel material properties inaccessible with traditional stereolithography.
Here, the UCNC synthetic protocol is outlined for encapsulating the sensitizer (palladium (II) meso-tetraphenyl tetrabenzoporphine, PdTPTBP) and the annihilator (9,10-bis((triisopropylsilyl)ethynyl)anthracene, TIPS-an) at two different scales. Synthesis on a large scale provides material to provide ~10 g of upconversion nanocapsule paste for use in 3D printing resins. Synthesis on a small scale for ~1 g of upconversion nanocapsule paste allows for the optimization of new nanocapsule contents. This protocol will support the successful integration of triplet fusion UCNCs into a variety of 3D printing workflows and other applications.

<table border="1" fo:keep-together.within-page="1" fo:keep-with-next.within-page="always">
	<tbody>
		<tr>
			<td>Chemicals</td>
			<td></td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>(3-aminopropyl)triethoxysilane, anhydrous</td>
			<td>Acros Organic/Fisher Scientific&#160;</td>
			<td>AC430941000</td>
			<td></td>
		</tr>
		<tr>
			<td>10K MPEG-Silane</td>
			<td>Nanosoft Polymers</td>
			<td>2526</td>
			<td></td>
		</tr>
		<tr>
			<td>Oleic acid (99%)</td>
			<td>Beantown Chemical</td>
			<td>126125</td>
			<td></td>
		</tr>
		<tr>
			<td>Pd (II) meso-tetraphenyl tetrabenzoporphine (PdTBTP)</td>
			<td>Frontier Scientific&#160;</td>
			<td>41217</td>
			<td></td>
		</tr>
		<tr>
			<td>tetraethyl orthosilicate, anhydrous</td>
			<td>Millipore Sigma</td>
			<td>86578</td>
			<td></td>
		</tr>
		<tr>
			<td>TIPS-Anthracene</td>
			<td>Millipore Sigma</td>
			<td>731439</td>
			<td></td>
		</tr>
		<tr>
			<td>Representative Ultracentrifuge for Nanocapsule Purification</td>
			<td></td>
			<td></td>
			<td>While a smaller centrifuge can be used, the ultracentrifuge is convenient for the 12-14 h centrifugation to isolate upconversion nanocapsule paste.</td>
		</tr>
		<tr>
			<td>500 mL, Polycarbonate Bottle with Cap Assembly, 69 x 160 mm - 6Pk</td>
			<td>Beckman-Coulter</td>
			<td>355605</td>
			<td></td>
		</tr>
		<tr>
			<td>Avanti J-26S XP High-Performance Centrifuge</td>
			<td>Beckman-Coulter</td>
			<td>Avanti J-26S XP</td>
			<td></td>
		</tr>
		<tr>
			<td>JA-10 Fixed-Angle Aluminum Rotor- 6 x 500 mL; 10,000 rpm; 17,700 x g</td>
			<td>Beckman-Coulter</td>
			<td>369687</td>
			<td></td>
		</tr>
		<tr>
			<td>Specialized Fabrication Equipment and Consumable Materials</td>
			<td></td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>3M 03429NA 051131034297 Scotch Electrical Tape, 3/4-in by 66-ft, Black, 1-Roll, 3/4 Foot</td>
			<td>Amazon</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>40 mL scintillation vials (28 mm OD x 95 mm Height, 24-400 thread size)</td>
			<td>Fisher Scientific</td>
			<td>CG490006</td>
			<td>Small-scale synthesis</td>
		</tr>
		<tr>
			<td>500 mL Single Neck RBF, 24/40 Outer Joint</td>
			<td>Chemglass</td>
			<td>CG-1506-20</td>
			<td>Large-scale synthesis</td>
		</tr>
		<tr>
			<td>Egg-shaped stir bar for use in a 500 mL round bottom flask (6.35 mm diameter, 16 mm length)</td>
			<td>Fisher Scientific</td>
			<td>14-512-122</td>
			<td>Large-scale synthesis</td>
		</tr>
		<tr>
			<td>Glovebox</td>
			<td>Mbraun</td>
			<td>LabStar Pro</td>
			<td>This is the glovebox used by the authors. However, as long as the oxygen can be maintained at levels below ~10 ppm, any model is acceptable.</td>
		</tr>
		<tr>
			<td>Magnetic stir plate - inside of glovebox</td>
			<td>Any brand</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>Magnetic stir plate with temperature control (oil bath or heating blocks) - outside of glovebox</td>
			<td>Any brand</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>Octagon-shaped stir bar for use in a 40 mL scintillation vial (3 mm diameter, 12 mm length)</td>
			<td>VWR</td>
			<td>58947-140</td>
			<td>Small-scale synthesis</td>
		</tr>
		<tr>
			<td>Parafilm M Wrapping Film</td>
			<td>Fisher Scientific</td>
			<td>&#160;S37440</td>
			<td></td>
		</tr>
		<tr>
			<td>Precision Seal rubber septa</td>
			<td>Millipore Sigma</td>
			<td>Z554103-10EA</td>
			<td>Large-scale synthesis</td>
		</tr>
		<tr>
			<td>Vitamix Blender</td>
			<td>Vitamix.com</td>
			<td>E310</td>
			<td>Large-scale synthesis</td>
		</tr>
		<tr>
			<td>Vortex Genie 2</td>
			<td>Millipore Sigma</td>
			<td>Z258415</td>
			<td>Small-scale synthesis</td>
		</tr>
		<tr>
			<td>Representative Characterization Instrumentation and Accessories</td>
			<td></td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>Brookhaven Instruments 90Plus Nanoparticle Size Analyzer</td>
			<td>Brookhaven Instruments</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>M Series 635nm Laser 300-500mW</td>
			<td>Dragon Lasers</td>
			<td></td>
			<td>Incident wavelength for upconversion photoluminescence characterization. The laser should only be used by trained researchers in a dedicated optics space with appropriate safety protocols. The laser should be focused using a lens to increase the incident power density.</td>
		</tr>
		<tr>
			<td>P50-1-UV-VIS</td>
			<td>Ocean Insight</td>
			<td>P50-1-UV-VIS</td>
			<td>Patch cord for QE Pro</td>
		</tr>
		<tr>
			<td>QE Pro Spectrometer</td>
			<td>Ocean Insight</td>
			<td>QEPRO-VIS-NIR</td>
			<td>Spectrometer for collecting upconversion photoluminescence.</td>
		</tr>
		<tr>
			<td>Supra55VP Field Emission Scanning Electron Microscope (FESEM)</td>
			<td>Zeiss</td>
			<td></td>
			<td></td>
		</tr>
	</tbody>
</table>

triplet fusion upconversion nanocapsule synthesis

Triplet fusion upconversion (UC) allows for the generation of one high energy photon from two low energy input photons. This well-studied process has significant implications for producing high energy light beyond a material's surface. However, the deployment of UC materials has been stymied due to poor material solubility, high concentration requirements, and oxygen sensitivity, ultimately resulting in reduced light output. Toward this end, nanoencapsulation has been a popular motif to circumvent these challenges, but durability has remained elusive in organic solvents. Recently, a nanoencapsulation technique was engineered to tackle each of these challenges, whereupon an oleic acid nanodroplet containing upconversion materials was encapsulated with a silica shell. Ultimately, these nanocapsules (NCs) were durable enough to enable triplet fusion upconversion-facilitated volumetric three-dimensional (3D) printing. By encapsulating upconversion materials with silica and dispersing them in a 3D printing resin, photopatterning beyond the surface of the printing vat was made possible. Here, video protocols for the synthesis of upconversion NCs are presented for both small-scale and large-scale batches. The outlined protocols serve as a starting point for adapting this encapsulation scheme to multiple upconversion schemes for use in volumetric 3D printing applications.

Figure 1 shows a cartoon depiction of the upconversion nanocapsule synthesis protocol. The parallels among the small scale and large-scale UCNC preparation are emphasized, such as the oil in water emulsion generation and the addition of chemicals to synthesize the silica shell. From the small-scale synthesis, 700-1000 mg of UCNC paste is typically collected, while 7-10 g of the UCNC is typically collected from the large-scale synthesis.
The nanocapsules were characterized using a combination of spectroscopic and microscopy techniques10. To prepare samples for SEM, a film was drop-cast from a solution of 100 mg mL-1 nanocapsule paste dispersed in water onto an appropriate conductive SEM substrate and allowed to dry. The conductivity of the nanocapsules is inherently low, but still sufficient for characterization without the addition of another conductive material. A representative SEM image (Figure 2A) shows the relatively monodisperse nanocapsules with diameters of ~50 nm obtained with this protocol. One limitation of using SEM to characterize the morphology of the UCNCs is that they are unstable under ultrahigh vacuum for long periods of time. Under ultrahigh vacuum necessary for SEM measurements, the UCNCs can be successfully imaged if working efficiently, typically within 30 min. UCNCs fuse under high vacuum after approximately 30 min under ultrahigh vacuum (Figure 2B). This fusion is not observed under ambient conditions following the procedure outlined in this protocol (vide infra). Even in light of the stability considerations under vacuum, electron microscopy is still a beneficial method to assess the typical morphology of the UCNCs.
Dynamic light scattering (DLS) is another useful technique to characterize the average nanocapsule hydrodynamic diameter in solution. The samples for DLS can be easily prepared with a sample of diluted UCNCs. Here, a sample of the supernatant recovered after the first centrifuge (step 1.23 or 2.17) was characterized by DLS. The supernatant was diluted by a factor of 10x with ultrapure deionized water and filtered with a 0.2 &#956;m PVDF filter to remove large particulates and dust. Alternatively, one can characterize the UCNC paste at a concentration of 100 mg mL-1 in ultrapure deionized water diluted 10x and filtered with a 0.2 &#956;m PVDF filter. The hydrodynamic diameter was measured using DLS to be &#60;100 nm from batch to batch, typically in the range of 65-90 nm10. Nanoparticle aggregation is not observed under these characterization conditions, removing the need for an additional electrolyte10. Similar UCNC diameters can be generated from large scale or small-scale protocols; representative traces from one scan are presented in Figure 2C.&#160;Due to Brownian motion and the mathematical fitting process to the Stokes-Einstein equation, many scans are averaged together to determine the average hydrodynamic diameters17. The average hydrodynamic diameters for the samples shown in Figure 2C are ~75 nm for the large batch (polydispersity, PDI: 0.21) and ~66 nm (PDI: 0.15) for the small batch presented. This variation in hydrodynamic diameter is typical from batch to batch, irrespective of the reaction scale.
Finally, optical characterization is vital to assess the integrity of the silica shell encapsulation (Figure 2D). Here, a sample of the supernatant recovered after the first centrifuge was diluted by 10x in deoxygenated acetone in the glovebox. The sample was diluted in acetone to test the structural integrity of the UCNCs. In Figure 2D, the anthracene upconversion emission is clearly present upon irradiation with a 635 nm laser, signifying the average silica shell remains intact. If the silica shells are too thin, bright upconversion is extremely low upon irradiation with a 635 nm laser. This is due to the upconversion contents being dissolved and diluted in acetone to a concentration too low to generate bright upconverted emission10.
<img alt="Figure 1" class="xfigimg" src="/files/ftp_upload/64374/64374fig01.jpg" /> 
Figure 1: A cartoon depiction of the upconversion nanocapsule synthetic process on the small and large scale. This figure was created with Biorender.com. <a href="https://jove.unicartagenaproxy.elogim.com/files/ftp_upload/64374/64374fig01large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 2" class="xfigimg" src="/files/ftp_upload/64374/64374fig02v2.jpg" /> 
Figure 2: Representative nanocapsule characterization using microscopy and spectroscopy. (A) SEM of the UCNCs shows the scale and uniformity of the upconversion nanocapsule synthesis. Scale bar = 200 nm. (B) SEM of the UCNCs that have fused under ultra-high vacuum over the course of ~30 min. SEM samples were prepared by drop-casting solutions of UCNCs in deionized ultrapure water. Scale bar = 20 &#956;m. (C) Representative DLS traces of upconversion nanocapsules prepared on a small scale and large scale. UCNCs were diluted in deionized ultrapure water. (D) The upconversion emission of TIPS-an in UCNCs diluted in acetone was generated upon irradiation with a 635 nm laser at ~65 W cm-2. This bright upconversion signifies the silica shells are thick enough to prevent the nanocapsule contents from spilling out. <a href="https://jove.unicartagenaproxy.elogim.com/files/ftp_upload/64374/64374fig02largev2.jpg" target="_blank">Please click here to view a larger version of this figure.</a>

Watch this Scientific Journal Video about Triplet Fusion Upconversion Nanocapsule Synthesis at JoVE.com

Triplet Fusion Upconversion Nanocapsule Synthesis

This protocol details the synthesis of upconversion nanocapsules for subsequent use in photopolymerizable resins for triplet fusion upconversion-facilitated volumetric 3D printing.

Triplet fusion upconversion (UC) allows for the generation of one high energy photon from two low energy input photons. This well-studied process has ...

triplet-fusion-upconversion-nanocapsule-synthesis

Universidad de Cartagena UDEC

Research

JoVE Journal

Engineering

2.3K Views.  Harvard University. This protocol details the synthesis of upconversion nanocapsules for subsequent use in photopolymerizable resins for triplet fusion upconversion-facilitated volumetric 3D printing.

Video: Triplet Fusion Upconversion Nanocapsule Synthesis

Synthesis of Phase-shift Nanoemulsions with Narrow Size Distributions for Acoustic Droplet Vaporization and Bubble-enhanced Ultrasound-mediated Ablation

High-intensity focused ultrasound (HIFU) is used clinically to thermally ablate tumors. To enhance localized heating and improve thermal ablation in tumors, lipid-coated perfluorocarbon droplets have been developed which can be vaporized by HIFU. The vasculature in many tumors is abnormally leaky due to their rapid growth, and nanoparticles are able to penetrate the fenestrations and passively accumulate within tumors. Thus, controlling the size of the droplets can result in better accumulation within tumors. In this report, the preparation of stable droplets in a phase-shift nanoemulsion (PSNE) with a narrow size distribution is described. PSNE were synthesized by sonicating a lipid solution in the presence of liquid perfluorocarbon. A narrow size distribution was obtained by extruding the PSNE multiple times using filters with pore sizes of 100 or 200 nm. The size distribution was measured over a 7-day period using dynamic light scattering. Polyacrylamide hydrogels containing PSNE were prepared for in vitro experiments. PSNE droplets in the hydrogels were vaporized with ultrasound and the resulting bubbles enhanced localized heating. Vaporized PSNE enables more rapid heating and also reduces the ultrasound intensity needed for thermal ablation. Thus, PSNE is expected to enhance thermal ablation in tumors, potentially improving therapeutic outcomes of HIFU-mediated thermal ablation treatments.

Phase-shift nanoemulsions (PSNE) can be vaporized using high intensity focused ultrasound to enhance localized heating and improve thermal ablation in tumors. In this report, the preparation of stable PSNE with a narrow size distribution is described. Furthermore, the impact of vaporized PSNE on ultrasound-mediated ablation is demonstrated in tissue-mimicking phantoms.

High-intensity  focused ultrasound (HIFU) is used clinically to thermally ablate tumors. To  enhance localized heating and improve thermal ablation in ...

Synthesis and Operation of Fluorescent-core Microcavities for Refractometric Sensing

This paper discusses fluorescent core microcavity-based sensors that can operate in a microfluidic analysis setup. These structures are based on the formation of a fluorescent quantum-dot (QD) coating on the channel surface of a conventional microcapillary. Silicon QDs are especially attractive for this application, owing in part to their negligible toxicity compared to the II-VI and II-VI compound QDs, which are legislatively controlled substances in many countries. While the ensemble emission spectrum is broad and featureless, an Si-QD film on the channel wall of a capillary features a set of sharp, narrow peaks in the fluorescence spectrum, corresponding to the electromagnetic resonances for light trapped within the film. The peak wavelength of these resonances is sensitive to the external medium, thus permitting the device to function as a refractometric sensor in which the QDs never come into physical contact with the analyte. The experimental methods associated with the fabrication of the fluorescent-core microcapillaries are discussed in detail, as well as the analysis methods. Finally, a comparison is made between these structures and the more widely investigated liquid-core optical ring resonators, in terms of microfluidic sensing capabilities.

Fluorescent-core microcavity sensors employ a high-index quantum-dot coating in the channel of silica microcapillaries. Changes in the refractive index of fluids pumped into the capillary channel cause shifts in the microcavity fluorescence spectrum that can be used to analyze the channel medium.

This paper discusses  fluorescent core microcavity-based sensors that can operate in a microfluidic  analysis setup. These structures are based on the ...

Synthesis and Functionalization of Nitrogen-doped Carbon Nanotube Cups with Gold Nanoparticles as Cork Stoppers

Nitrogen-doped carbon nanotubes consist of many cup-shaped graphitic compartments termed as nitrogen-doped carbon nanotube cups (NCNCs). These as-synthesized graphitic nanocups from chemical vapor deposition (CVD) method were stacked in a head-to-tail fashion held only through noncovalent interactions. Individual NCNCs can be isolated out of their stacking structure through a series of chemical and physical separation processes. First, as-synthesized NCNCs were oxidized in a mixture of strong acids to introduce oxygen-containing defects on the graphitic walls. The oxidized NCNCs were then processed using high-intensity probe-tip sonication which effectively separated the stacked NCNCs into individual graphitic nanocups. Owing to their abundant oxygen and nitrogen surface functionalities, the resulted individual NCNCs are highly hydrophilic and can be effectively functionalized with gold nanoparticles (GNPs), which preferentially fit in the opening of the cups as cork stoppers. These graphitic nanocups corked with GNPs may find promising applications as nanoscale containers and drug carriers.

We discussed the synthesis of individual graphitic nanocups using a series of techniques including chemical vapor deposition, acid oxidation and probe-tip sonication. By citrate reduction of HAuCl4, the graphitic nanocups were effectively corked with gold nanoparticles due to the chemically reactive edges of the cups.

Nitrogen-doped carbon  nanotubes consist of many cup-shaped graphitic compartments termed as  nitrogen-doped carbon nanotube cups (NCNCs).  These ...

Synthesis and Microdiffraction at Extreme Pressures and Temperatures

High pressure compounds and polymorphs are investigated for a broad range of purposes such as determine structures and processes of deep planetary interiors, design materials with novel properties, understand the mechanical behavior of materials exposed to very high stresses as in explosions or impacts. Synthesis and structural analysis of materials at extreme conditions of pressure and temperature entails remarkable technical challenges. In the laser heated diamond anvil cell (LH-DAC), very high pressure is generated between the tips of two opposing diamond anvils forced against each other; focused infrared laser beams, shined through the diamonds, allow to reach very high temperatures on samples absorbing the laser radiation. When the LH-DAC is installed in a synchrotron beamline that provides extremely brilliant x-ray radiation, the structure of materials under extreme conditions can be probed in situ. LH-DAC samples, although very small, can show highly variable grain size, phase and chemical composition. In order to obtain the high resolution structural analysis and the most comprehensive characterization of a sample, we collect diffraction data in 2D grids and combine powder, single crystal and multigrain diffraction techniques. Representative results obtained in the synthesis of a new iron oxide, Fe4O5 1 will be shown.

The laser heated diamond anvil cell combined with synchrotron micro-diffraction techniques allows researchers to explore the nature and properties of new phases of matter at extreme pressure and temperature (PT) conditions. Heterogeneous samples can be characterized in situ under high pressure by 2D mapping and combined powder, single-crystal and multigrain diffraction approaches.

High pressure compounds and polymorphs are investigated for a broad range of purposes such as determine structures and processes of deep planetary ...

Integrating a Triplet-triplet Annihilation Up-conversion System to Enhance Dye-sensitized Solar Cell Response to Sub-bandgap Light

The poor response of dye-sensitized solar cells (DSCs) to red and infrared light is a significant impediment to the realization of higher photocurrents and hence higher efficiencies. Photon up-conversion by way of triplet-triplet annihilation (TTA-UC) is an attractive technique for using these otherwise wasted low energy photons to produce photocurrent, while not interfering with the photoanodic performance in a deleterious manner. Further to this, TTA-UC has a number of features, distinct from other reported photon up-conversion technologies, which renders it particularly suitable for coupling with DSC technology. In this work, a proven high performance TTA-UC system, comprising a palladium porphyrin sensitizer and rubrene emitter, is combined with a high performance DSC (utilizing the organic dye D149) in an integrated device. The device shows an enhanced response to sub-bandgap light over the absorption range of the TTA-UC sub-unit resulting in the highest figure of merit for up-conversion assisted DSC performance to date.

An integrated device, incorporating a dye-sensitized solar cell and triplet-triplet annihilation up-conversion unit was produced, affording enhanced light harvesting, from a wider section of the solar spectrum. Under modest irradiation levels a significantly enhanced response to low energy photons was demonstrated, yielding a record figure of merit for dye-sensitized solar cells.

The poor response of dye-sensitized solar cells (DSCs) to red and infrared light is a significant impediment to the realization of higher photocurrents ...

Visible-light Induced Reduction of Graphene Oxide Using Plasmonic Nanoparticle

Present work demonstrates the simple, chemical free, fast, and energy efficient method to produce reduced graphene oxide (r-GO) solution at RT using visible light irradiation with plasmonic nanoparticles. The plasmonic nanoparticle is used to improve the reduction efficiency of GO. It only takes 30 min&#160;at RT by illuminating the solutions with Xe-lamp, the r-GO solutions can be obtained by completely removing gold nanoparticles through simple centrifugation step. The spherical gold nanoparticles (AuNPs) as compared to the other nanostructures is the most suitable plasmonic nanostructure for r-GO preparation. The reduced graphene oxide prepared using visible light and AuNPs was equally qualitative as chemically reduced graphene oxide, which was supported by various analytical techniques such as UV-Vis spectroscopy, Raman spectroscopy, powder XRD and XPS. The reduced graphene oxide prepared with visible light shows excellent quenching properties over the fluorescent molecules modified on ssDNA and excellent fluorescence recovery for target DNA detection. The r-GO prepared by recycled AuNPs is found to be of same quality with that of chemically reduced r-GO. The use of visible light with plasmonic nanoparticle demonstrates the good alternative method for r-GO synthesis.

A simple protocol for the preparation of reduced graphene oxide using visible light and plasmonic nanoparticle is described.

Present work demonstrates the simple, chemical free, fast, and energy efficient method to produce reduced graphene oxide (r-GO) solution at RT using ...

Synthesis and Functionalization of 3D Nano-graphene Materials: Graphene Aerogels and Graphene Macro Assemblies

Efforts to assemble graphene into three-dimensional monolithic structures have been hampered by the high cost and poor processability of graphene. Additionally, most reported graphene assemblies are held together through physical interactions (e.g., van der Waals forces) rather than chemical bonds, which limit their mechanical strength and conductivity. This video method details recently developed strategies to fabricate mass-producible, graphene-based bulk materials derived from either polymer foams or single layer graphene oxide. These materials consist primarily of individual graphene sheets connected through covalently bound carbon linkers. They maintain the favorable properties of graphene such as high surface area and high electrical and thermal conductivity, combined with tunable pore morphology and exceptional mechanical strength and elasticity. This flexible synthetic method can be extended to the fabrication of polymer/carbon nanotube (CNT) and polymer/graphene oxide (GO) composite materials. Furthermore, additional post-synthetic functionalization with anthraquinone is described, which enables a dramatic increase in charge storage performance in supercapacitor applications.

This video method describes the synthesis of high surface area, monolithic 3D graphene-based materials derived from polymer precursors as well as single layer graphene oxide.

Efforts to assemble graphene into three-dimensional monolithic structures have been hampered by the high cost and poor processability of graphene. ...

Colloidal Synthesis of Nanopatch Antennas for Applications in Plasmonics and Nanophotonics

We present a method for colloidal synthesis of silver nanocubes and the use of these in combination with a smooth gold film, to fabricate plasmonic nanoscale patch antennas. This includes a detailed procedure for the fabrication of thin films with a well-controlled thickness over macroscopic areas using layer-by-layer deposition of polyelectrolyte polymers, namely poly(allylamine) hydrochloride (PAH) and polystyrene sulfonate (PSS). These polyelectrolyte spacer layers serve as a dielectric gap in between silver nanocubes and a gold film. By controlling the size of the nanocubes or the gap thickness, the plasmon resonance can be tuned from about 500 nm to 700 nm. Next, we demonstrate how to incorporate organic sulfo-cyanine5 carboxylic acid (Cy5) dye molecules into the dielectric polymer gap region of the nanopatch antennas. Finally, we show greatly enhanced fluorescence of the Cy5 dyes by spectrally matching the plasmon resonance with the excitation energy and the Cy5 absorption peak. The method presented here enables the fabrication of plasmonic nanopatch antennas with well-controlled dimensions utilizing colloidal synthesis and a layer-by-layer dip-coating process with the potential for low cost and large-scale production. These nanopatch antennas hold great promise for practical applications, for example in sensing, ultrafast optoelectronic devices and for high-efficiency photodetectors.

A protocol for the colloidal synthesis of silver nanocubes and fabrication of plasmonic nanoscale patch antennas with sub-10 nm gaps is presented.

We present a method for colloidal synthesis of silver nanocubes and the use of these in combination with a smooth gold film, to fabricate plasmonic ...

Applying X-ray Imaging Crystal Spectroscopy for Use as a High Temperature Plasma Diagnostic

X-ray spectra provide a wealth of information on high temperature plasmas; for example electron temperature and density can be inferred from line intensity ratios. By using a Johann spectrometer viewing the plasma, it is possible to construct profiles of plasma parameters such as density, temperature, and velocity with good spatial and time resolution. However, benchmarking atomic code modeling of X-ray spectra obtained from well-diagnosed laboratory plasmas is important to justify use of such spectra to determine plasma parameters when other independent diagnostics are not available. This manuscript presents the operation of the High Resolution X-ray Crystal Imaging Spectrometer with Spatial Resolution (HIREXSR), a high wavelength resolution spatially imaging X-ray spectrometer used to view hydrogen- and helium-like ions of medium atomic number elements in a tokamak plasma. In addition, this manuscript covers a laser blow-off system that can introduce such ions to the plasma with precise timing to allow for perturbative studies of transport in the plasma.

X-ray spectra provide a wealth of information on high temperature plasmas. This manuscript presents the operation of a high wavelength resolution spatially imaging X-ray spectrometer used to view hydrogen- and helium-like ions of medium atomic number elements in a tokamak plasma.

X-ray spectra provide a wealth of information on high temperature plasmas; for example electron temperature and density can be inferred from line ...

Synthesis of Ionic Liquid Based Electrolytes, Assembly of Li-ion Batteries, and Measurements of Performance at High Temperature

The chemical instability of the traditional electrolyte remains a safety issue in widely used energy storage devices such as Li-ion batteries. Li-ion batteries for use in devices operating at elevated temperatures require thermally stable and non-flammable electrolytes. Ionic liquids (ILs), which are non-flammable, non-volatile, thermally stable molten salts, are an ideal replacement for flammable and low boiling point organic solvent electrolytes currently used today. We herein describe the procedures to: 1) synthesize mono- and di-phosphonium ionic liquids paired with chloride or bis(trifluoromethane)sulfonimide (TFSI) anions; 2) measure the thermal properties and stability of these ionic liquids by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA); 3) measure the electrochemical properties of the ionic liquids by cyclic voltammetry (CV); 4) prepare electrolytes containing lithium bis(trifluoromethane)sulfonamide; 5) measure the conductivity of the electrolytes as a function of temperature; 6) assemble a coin cell battery with two of the electrolytes along with a Li metal anode and LiCoO2 cathode; and 7) evaluate battery performance at 100 &#176;C. We additionally describe the challenges in execution as well as the insights gained from performing these experiments.

Here, we describe protocols to prepare phosphonium-based ionic liquid and lithium bis(trifluoromethane)sulfonimide salt electrolytes, and assemble a non-flammable and high temperature functioning lithium-ion coin cell battery.

The chemical instability of the traditional electrolyte remains a safety issue in widely used energy storage devices such as Li-ion batteries. Li-ion ...