The desire for designing efficient synthetic methods that lead to industrially important nanomaterials has led a desire to more fully understand the mechanism of growth and how modern synthetic techniques can be employed. Microwave (MW) synthesis is one such technique that has attracted attention as a green, sustainable method. The reports of enhancement of formation rates and improved quality for MW driven reactions are intriguing, but the lack of understanding of the reaction mechanism and how coupling to the MW field leads to these observations is concerning. In this manuscript, the growth of a metal nanoparticles (NPs) in a microwave cavity is spectroscopically analyzed and compared with the classical autocatalytic method of NP growth to elucidate the underpinnings for the observed enhanced growth behavior for metal NPs prepared in a MW field. The study illustrates that microwave synthesis of nickel and gold NPs below saturation conditions follows the Finke-Watzky mechanism of nucleation and growth. The enhancement of the reaction arises from the size-dependent increase in MW absorption cross section for the metal NPs. For Ni, the presence of oxides is considered via theoretical computations and compared to dielectric measurements of isolated nickel NPs. The study definitively shows that MW growth can be modeled by an autocatalytic mechanism that directly leads to the observed enhanced rates and improved quality widely reported in the nanomaterial community when MW irradiation is employed.
Research over the past decade has identified several of the key limiting features of multidrug resistance (MDR) in cancer therapy applications, such as evolving glycoprotein receptors at the surface of the cell that limit therapeutic uptake, metabolic changes that lead to protection from multidrug resistant mediators which enhance degradation or efflux of therapeutics, and difficulty ensuring retention of intact and functional drugs once endocytosed. Nanoparticles have been demonstrated to be effective delivery vehicles for a plethora of therapeutic agents, and in the case of nucleic acid based agents, they provide protective advantages. Functionalizing cell penetrating peptides, also known as protein transduction domains, onto the surface of fluorescent quantum dots creates a labeled delivery package to investigate the nuances and difficulties of drug transport in MDR cancer cells for potential future clinical applications of diverse nanoparticle-based therapeutic delivery strategies. In this study, eight distinct cell penetrating peptides were used (CAAKA, HSV1-VP22, HIV-TAT, HIV-gp41, Ku-70, hCT(9-32), integrin-β3, and K-FGF) to examine the different cellular uptake profiles in cancer versus drug resistant melanoma (A375 & A375-R), mesothelioma (MSTO & MSTO-R), and glioma (rat 9L and 9L-R, and human U87 & LN18) cell lines. The results of this study demonstrate that cell penetrating peptide uptake varies with drug resistance status and cell type, likely due to changes in cell surface markers. This study provides insight into developing functional nanoplatform delivery systems in drug resistant cancer models.
Nanomaterial-loaded thermoplastics are attractive for applications in adaptive printing methods, as the physical properties of the printed materials are dependent on the nanomaterial type and degree of dispersion. This study compares the dispersion and the impact on the dielectric properties of two common nanoparticles, nickel and iron oxide, loaded into polystyrene. Comparisons between commercial and synthetically prepared samples indicate that well-passivated synthetically prepared nanomaterials are dispersed and minimize the impact on the dielectric properties of the host polymer by limiting particle–particle contacts. Commercial samples were observed to phase-segregate, leading to the loss of the low- k performance of polystyrene. The change in the real and imaginary dielectric was systematically studied in two earth abundant nanoparticles at the concentration between 0 and 13 vol % (0–50 wt %). By varying the volume percentage of fillers in the matrix, it is shown that one can increase the magnetic properties of the materials while minimizing unwanted contributions to the dielectric constant and dielectric loss. The well-dispersed nanoparticle systems were successfully modeled through the Looyenga dielectric theory, thus giving one a predictive ability for the dielectric properties. The current experimental work coupled with modeling could facilitate future material choices and guide design rules for printable polymer composite systems.
As the importance of anisotropic nanostructures and the role of surfaces continues to rise in applications including catalysis, magneto-optics, and electromagnetic interference shielding, there is a need for efficient and economical synthesis routes for such nanostructures. The article describes the application of cycled microwave power for the rapid synthesis of highly branched pure-phase face-centered cubic crystalline nickel multipod nanostructures with >99% multipod population. By controlling the power delivery to the reaction mixture through cycling, superior control is achieved over the growth kinetics of the metallic nanostructures, allowing formation of multipods consisting of arms with different aspect ratios. The multipod structures are formed under ambient conditions in a simple reaction system composed of nickel acetylacetonate (Ni(acac)), oleylamine (OAm), and oleic acid (OAc) in a matter of minutes by selective heating at the (111) overgrowth corners on Ni nanoseeds. The selective heating at the corners leads to accelerated autocatalytic growth along the ⟨111⟩ direction through a "lightning rod" effect. The length is proprtional to the length and number of microwave (MW)-on cycles, whereas the core size is controlled by continuous MW power delivery. The roles of heating mode (cycling versus variable power versus convective heating) during synthesis of the materials is explored, allowing a mechanism into how cycled microwave energy may allow fast multipod evolution to be proposed.
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