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This work reports in situ (active) electrochemical control over the coupling strength between semiconducting nanoplatelets and a plasmonic cavity. We found that by applying a reductive bias to an Al nanoparticle lattice working electrode the number of CdSe nanoplatelet emitters that can couple to the cavity is decreased. Strong coupling can be reversibly recovered by discharging the lattice at oxidative potentials relative to the conduction band edge reduction potential of the emitters. By correlating the number of electrons added or removed with the measured coupling strength, we identified that loss and recovery of strong coupling are likely hindered by side processes that trap and/or inhibit electrons from populating the nanoplatelet conduction band. These findings demonstrate tunable, external control of strong coupling and offer prospects to tune selectivity in chemical reactions.
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ConspectusMany desirable and undesirable properties of semiconductor nanocrystals (NCs) can be traced to the NC surface due to the large surface-to-volume ratio. Therefore, precise control of the NC surface is imperative to achieve NCs with the desired qualities. Ligand-specific reactivity and surface heterogeneity make it difficult to accurately control and tune the NC surface. Without a molecular-level appreciation of the NC surface chemistry, modulating the NC surface is impossible and the risk of introducing deleterious surface defects is imminent. To gain a more comprehensive understanding of the surface reactivity, we have utilized a variety of spectroscopic techniques and analytical methods in concert.This Account describes our use of robust characterization techniques and ligand exchange reactions in effort to establish a molecular-level understanding of NC surface reactivity. The utility of NCs in target applications such as catalysis and charge transfer hangs on precise tunability of NC ligands. Modulating the NC surface requires the necessary tools to monitor chemical reactions. One commonly utilized analytical method to achieve targeted surface compositions is 1H nuclear magnetic resonance (NMR) spectroscopy. Here we describe our use of 1H NMR spectroscopy to monitor chemical reactions at CdSe and PbS NC surfaces to identify ligand specific reactivity. However, seemingly straightforward ligand exchange reactions can vary widely depending on the NC materials and anchoring group. Some non-native X-type ligands will irreversibly displace native ligands. Other ligands exist in equilibrium with native ligands. Depending on the application, it is important to understand the nature of exchange reactions. This level of understanding can be obtained by extracting exchange ratios, exchange equilibrium, and reaction mechanism information from 1H NMR spectroscopy to establish precise NC reactivity.Reactivity that occurs through multiple, parallel ligand exchange mechanisms can involve both the liberation of metal-based Z-type ligands in addition to reactivity of X-type ligands. In these reactions, 1H NMR spectroscopy fails to discern between an X-type oleate or a Z-type Pb(oleate)2 because only the alkene resonance of the organic constituent is probed by this method. Multiple, parallel reaction pathways occur when thiol ligands are introduced to oleate-capped PbS NCs. This necessitated the use of synergistic characterization methods including 1H NMR spectroscopy, Fourier-transform infrared (FTIR) spectroscopy, and inductively coupled plasma mass spectrometry (ICP-MS) to characterize both surface-bound and liberated ligands.Similar analytical methods have been employed to probe the NC topology, which is an important, but often overlooked, component to NC reactivity given the facet-specific reactivity of PbS NCs. Through the tandem use of NMR spectroscopy and ICP-MS, we have monitored the liberation of Pb(oleate)2 as an L-type ligand is titrated to the NC to determine the quantity and equilibrium of Z-type ligands. By studying a variety of NC sizes, we correlated the number of liberated ligands with the size-dependent topology of PbS NCs.Lastly, we incorporate redox-active chemical probes into our toolbox to study NC surface defects. We describe how the site-specific reactivity and relative energetics of redox-active surface-based defects are elucidated using redox probes and show that this reactivity is highly dependent on the surface composition. This Account is designed to encourage readers to consider the necessary characterization techniques needed establish a molecular-level understanding of NC surfaces in their own work.
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Serum transferrin (sTf) plays a pivotal role in regulating iron biodistribution and homeostasis within the body. The molecular details of sTf Fe(III) binding blood transport, and cellular delivery through transferrin receptor-mediated endocytosis are generally well-understood. Emerging interest exists in exploring sTf complexation of nonferric metals as it facilitates the therapeutic potential and toxicity of several of them. This review explores recent X-ray structural and physiologically relevant metal speciation studies to understand how sTf partakes in the bioactivity of key non-redox active hard Lewis acidic metals. It challenges preconceived notions of sTf structure function correlations that were based exclusively on the Fe(III) model by revealing distinct coordination modalities that nonferric metal ions can adopt and different modes of binding to metal-free and Fe(III)-bound sTf that can directly influence how they enter into cells and, ultimately, how they may impact human health. This knowledge informs on biomedical strategies to engineer sTf as a delivery vehicle for metal-based diagnostic and therapeutic agents in the cancer field. It is the intention of this work to open new avenues for characterizing the functionality and medical utility of nonferric-bound sTf and to expand the significance of this protein in the context of bioinorganic chemistry.
