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.

The rapid heating rates (ΔT/δt) achieved in a microwave (MW) reactor has been shown to accelerate reaction rates due to the direct power absorbed (P abs ) into the reactants leading to faster kinetics. The P abs is proportional to the dielectric cross section of the materials as defined by the real (ε′) and imaginary (ε″) components. In a nanocrystal, the dielectric cross-section will be frequency dependent as well as size dependent. In this work, the frequency dependent growth of nickel nanocrystals at frequencies of 2.45, 15.50, and 18.00 GHz at constant ΔT/δt was studied to evaluate the frequency dependence on MW growth of Ni. A scaling law behavior for growth rates is observed that is shown to depend on the MW electric field strength. A relationship is derived between the "configurational energy" of the precursor molecules and the final nanoparticle size. The study provides a clear description of a microwave effect that is dependent on the frequency and power of the microwave and offers further insight into the physical chemistry of microwave applications to nanomaterial synthesis.

There are no adequate vaccines against some of the new or reemerged infectious scourges such as HIV and TB. They may require strong and enduring cell-mediated immunity to be elicited. This is quite a task, as the only known basis of protection by current commercial vaccines is antibody. As DNA or RNA vaccines may induce both cell-mediated and humoral immunity, great interest has been shown in them. However, doubt remains whether their efficacy will suffice for their clinical realization. We look at the various tactics to increase the potency of nucleic acid vaccines and divided them broadly under those affecting delivery and those affecting immune induction. For delivery, we have considered ways of improving uptake and the use of bacterial, replicon or viral vectors. For immune induction, we considered aspects of immunostimulatory CpG motifs, coinjection of cytokines or costimulators and alterations of the antigen, its cellular localization and its anatomical localization including the use of ligand-targeting to lymphoid tissue. We also thought that mucosal application of DNA deserved a separate section. In this review, we have taken the liberty to discuss these enhancement methods, whenever possible, in the context of the underlying mechanisms that might argue for or against these strategies.

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