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1. Nanoimprint Lithography for Next-Generation Carbon Nanotube-Based Devices

   https://doi.org/10.3390/nano14121011  

   Fialkova, Svitlana; Yarmolenko, Sergey; Krishnaswamy, Arvind; Sankar, Jagannathan; Shanov, Vesselin; Schulz, Mark J; Desai, Salil (June 2024, Nanomaterials)

   This research reports the development of 3D carbon nanostructures that can provide unique capabilities for manufacturing carbon nanotube (CNT) electronic components, electrochemical probes, biosensors, and tissue scaffolds. The shaped CNT arrays were grown on patterned catalytic substrate by chemical vapor deposition (CVD) method. The new fabrication process for catalyst patterning based on combination of nanoimprint lithography (NIL), magnetron sputtering, and reactive etching techniques was studied. The optimal process parameters for each technique were evaluated. The catalyst was made by deposition of Fe and Co nanoparticles over an alumina support layer on a Si/SiO2 substrate. The metal particles were deposited using direct current (DC) magnetron sputtering technique, with a particle ranging from 6 nm to 12 nm and density from 70 to 1000 particles/micron. The Alumina layer was deposited by radio frequency (RF) and reactive pulsed DC sputtering, and the effect of sputtering parameters on surface roughness was studied. The pattern was developed by thermal NIL using Si master-molds with PMMA and NRX1025 polymers as thermal resists. Catalyst patterns of lines, dots, and holes ranging from 70 nm to 500 nm were produced and characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Vertically aligned CNTs were successfully grown on patterned catalyst and their quality was evaluated by SEM and micro-Raman. The results confirm that the new fabrication process has the ability to control the size and shape of CNT arrays with superior quality. 

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2. Visualizing formation of high entropy alloy nanoparticles with liquid phase transmission electron microscopy

   https://doi.org/10.1039/D3NR01073B  

   Sun, Jiayue; Leff, Asher; Li, Yue; Woehl, Taylor J. (June 2023, Nanoscale)

   High entropy alloy (HEA) nanoparticles hold promise as active and durable (electro)catalysts. Understanding their formation mechanism will enable rational control over composition and atomic arrangement of multimetallic catalytic surface sites to maximize their activity. While prior reports have attributed HEA nanoparticle formation to nucleation and growth, there is a dearth of detailed mechanistic investigations. Here we utilize liquid phase transmission electron microscopy (LPTEM), systematic synthesis, and mass spectrometry (MS) to demonstrate that HEA nanoparticles form by aggregation of metal cluster intermediates. AuAgCuPtPd HEA nanoparticles are synthesized by aqueous co-reduction of metal salts with sodium borohydride in the presence of thiolated polymer ligands. Varying the metal : ligand ratio during synthesis showed that alloyed HEA nanoparticles formed only above a threshold ligand concentration. Interestingly, stable single metal atoms and sub-nanometer clusters are observed by TEM and MS in the final HEA nanoparticle solution, suggesting nucleation and growth is not the dominant mechanism. Increasing supersaturation ratio increased particle size, which together with observations of stable single metal atoms and clusters, supported an aggregative growth mechanism. Direct real-time observation with LPTEM imaging showed aggregation of HEA nanoparticles during synthesis. Quantitative analyses of the nanoparticle growth kinetics and particle size distribution from LPTEM movies were consistent with a theoretical model for aggregative growth. Taken together, these results are consistent with a reaction mechanism involving rapid reduction of metal ions into sub-nanometer clusters followed by cluster aggregation driven by borohydride ion induced thiol ligand desorption. This work demonstrates the importance of cluster species as potential synthetic handles for rational control over HEA nanoparticle atomic structure. 

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3. Size-dependent shape distributions of platinum nanoparticles

   https://doi.org/10.1039/D2NA00326K  

   Ding, Ruikang; Padilla Espinosa, Ingrid M.; Loevlie, Dennis; Azadehranjbar, Soodabeh; Baker, Andrew J.; Mpourmpakis, Giannis; Martini, Ashlie; Jacobs, Tevis D. (September 2022, Nanoscale Advances)

   While it is well established that nanoparticle shape can depend on equilibrium thermodynamics or growth kinetics, recent computational work has suggested the importance of thermal energy in controlling the distribution of shapes in populations of nanoparticles. Here, we used transmission electron microscopy to characterize the shapes of bare platinum nanoparticles and observed a strong dependence of shape distribution on particle size. Specifically, the smallest nanoparticles (<2.5 nm) had a truncated octahedral shape, bound by 〈111〉 and 〈100〉 facets, as predicted by lowest-energy thermodynamics. However, as particle size increased, the higher-energy 〈110〉 facets became increasingly common, leading to a large population of non-equilibrium truncated cuboctahedra. The observed trends were explained by combining atomistic simulations (both molecular dynamics and an empirical square-root bond-cutting model) with Boltzmann statistics. Overall, this study demonstrates experimentally how thermal energy leads to shape variation in populations of metal nanoparticles, and reveals the dependence of shape distributions on particle size. The prevalence of non-equilibrium facets has implications for metal nanoparticles applications from catalysis to solar energy. 

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4. Copper oxide nanoparticle dissolution at alkaline pH is controlled by dissolved organic matter: influence of soil-derived organic matter, wheat, bacteria, and nanoparticle coating

   https://doi.org/10.1039/d0en00574f  

   Hortin, J. M.; Anderson, A. J.; Britt, D. W.; Jacobson, A. R.; McLean, J. E. (January 2020, Environmental Science: Nano)

   Dissolution of CuO nanoparticles, releasing Cu ions, is a primary mechanism of Cu interaction in the rooting zone of plants. CuO dissolution is sometimes incorrectly considered negligible at high pH, since complexation of Cu with dissolved organic matter may enhance nanoparticle dissolution. Therefore data on the effects of plant-microbial-soil interactions on nanoparticle dissolution, particularly in alkaline soils, are needed. Dissolution of CuO nanoparticles (100 mg kg −1 Cu) was studied in sand supplemented with factorial combinations of wheat growth, a root-colonizing bacterium, and saturated paste extracts (SPEs) from three alkaline, calcareous soils. In control sand systems with 3.34 mM Ca(NO 3 ) 2 solution, dissolved Cu was low (266 μg L −1 Cu). Addition of dissolved organic matter via wheat root metabolites and/or soil SPEs increased dissolved Cu to 795–6250 μg L −1 Cu. Dissolution was correlated with dissolved organic carbon ( R = 0.916, p < 0.0001). Ligands >3 kDa, presumably fulvic acid from the SPEs, complexed Cu driving solubility; the addition of plant exudates further increased solubility 1.5–3.5×. The root-colonizing bacterium decreased dissolved Cu in sand pore waters from planted systems due to metabolism of root exudates. Batch solubility studies (10 mg L −1 Cu) with the soil SPEs and defined solutions containing bicarbonate or fulvic acid confirmed elevated CuO nanoparticle solubility at >7.5 pH. Nanoparticle dissolution was suppressed in batch experiments compared to sand, via nanoparticle organic matter coating or homoconjugation of dissolved organic matter. Alterations of CuO nanoparticles by soil organic matter, plant exudates, and bacteria will affect dissolution and bioavailability of the CuO nanoparticles in alkaline soils. 

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5. Self-Assembly of pH-Labile Polymer Nanoparticles for Paclitaxel Prodrug Delivery: Formulation, Characterization, and Evaluation

   https://doi.org/10.3390/ijms21239292  

   Levit, Shani L.; Gade, Narendar Reddy; Roper, Thomas D.; Yang, Hu; Tang, Christina (December 2020, International Journal of Molecular Sciences)

   null (Ed.)

   The efficacy of paclitaxel (PTX) is limited due to its poor solubility, poor bioavailability, and acquired drug resistance mechanisms. Designing paclitaxel prodrugs can improve its anticancer activity and enable formulation of nanoparticles. Overall, the aim of this work is to improve the potency of paclitaxel with prodrug synthesis, nanoparticle formation, and synergistic formulation with lapatinib. Specifically, we improve potency of paclitaxel by conjugating it to α-tocopherol (vitamin E) to produce a hydrophobic prodrug (Pro); this increase in potency is indicated by the 8-fold decrease in half maximal inhibitory concentration (IC50) concentration in ovarian cancer cell line, OVCA-432, used as a model system. The efficacy of the paclitaxel prodrug was further enhanced by encapsulation into pH-labile nanoparticles using Flash NanoPrecipitation (FNP), a rapid, polymer directed self-assembly method. There was an 1100-fold decrease in IC50 concentration upon formulating the prodrug into nanoparticles. Notably, the prodrug formulations were 5-fold more potent than paclitaxel nanoparticles. Finally, the cytotoxic effects were further enhanced by co-encapsulating the prodrug with lapatinib (LAP). Formulating the drug combination resulted in synergistic interactions as indicated by the combination index (CI) of 0.51. Overall, these results demonstrate this prodrug combined with nanoparticle formulation and combination therapy is a promising approach for enhancing paclitaxel potency. 

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