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1. Hybrid Metal–Ligand Interfacial Dipole Engineering of Functional Plasmonic Nanostructures for Extraordinary Responses of Optoelectronic Properties

   https://doi.org/10.1021/acsnano.3c06047  

   Hati, Sumon; Yang, Xuehui; Gupta, Prashant; Muhoberac, Barry B; Pu, Jingzhi; Zhang, Jing; Sardar, Rajesh (September 2023, ACS Nano)

   Programmable manipulation of inorganic–organic interfacial electronic properties of ligand-functionalized plasmonic nanoparticles (NPs) is the key parameter dictating their applications such as catalysis, photovoltaics, and biosensing. Here we report the localized surface plasmon resonance (LSPR) properties of gold triangular nanoprisms (Au TNPs) in solid state that are functionalized with dipolar, conjugated ligands. A library of thiocinnamate ligands with varying surface dipole moments were used to functionalize TNPs, which results in ∼150 nm reversible tunability of LSPR peak wavelength with significant peak broadening (∼230 meV). The highly adjustable chemical system of thiocinnamate ligands is capable of shifting the Au work function down to 2.4 eV versus vacuum, i.e., ∼2.9 eV lower than a clean Au (111) surface, and this work function can be modulated up to 3.3 eV, the largest value reported to date through the formation of organothiolate SAMs on Au. Interestingly, the magnitude of plasmonic responses and work function modulation is NP shape dependent. By combining first-principles calculations and experiments, we have established the mechanism of direct wave function delocalization of electrons residing near the Fermi level into hybrid electronic states that are mostly dictated by the inorganic–organic interfacial dipole moments. We determine that both interfacial dipole and hybrid electronic states, and vinyl conjugation together are the key to achieving such extraordinary changes in the optoelectronic properties of ligand-functionalized, plasmonic NPs. The present study provides a quantitative relationship describing how specifically constructed organic ligands can be used to control the interfacial properties of NPs and thus the plasmonic and electronic responses of these functional plasmonics for a wide range of plasmon-driven applications. 

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2. Protein Interactions with Nanoparticle Surfaces: Highlighting Solution NMR Techniques

   https://doi.org/10.1002/ijch.201900080  

   Randika Perera, Y.; Hill, Rebecca A.; Fitzkee, Nicholas C. (September 2019, Israel Journal of Chemistry)

   Abstract In the last decade, nanoparticles (NPs) have become a key tool in medicine and biotechnology as drug delivery systems, biosensors and diagnostic devices. The composition and surface chemistry of NPs vary based on the materials used: typically organic polymers, inorganic materials, or lipids. Nanoparticle classes can be further divided into sub‐categories depending on the surface modification and functionalization. These surface properties matter when NPs are introduced into a physiological environment, as they will influence how nucleic acids, lipids, and proteins will interact with the NP surface. While small‐molecule interactions are easily probed using NMR spectroscopy, studying protein‐NP interactions using NMR introduces several challenges. For example, globular proteins may have a perturbed conformation when attached to a foreign surface, and the size of NP‐protein conjugates can lead to excessive line broadening. Many of these challenges have been addressed, and NMR spectroscopy is becoming a mature technique forin situanalysis of NP binding behavior. It is therefore not surprising that NMR has been applied to NP systems and has been used to study biomolecules on NP surfaces. Important considerations include corona composition, protein behavior, and ligand architecture. These features are difficult to resolve using classical surface and material characterization strategies, and NMR provides a complementary avenue of characterization. In this review, we examine how solution NMR can be combined with other analytical techniques to investigate protein behavior on NP surfaces. 

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3. N‐Heterocyclic Carbene‐Based Copolymers for Templated Synthesis and Stabilization of Gold Nanoparticles

   https://doi.org/10.1002/chem.202500596  

   Nguyen, Suong T; Brown, Christopher M; Zhang, Wenxu; Kilgallon, Landon J; Johnson, Jeremiah A (April 2025, Chemistry – A European Journal)

   Abstract Surface functionalization and colloidal stability are pivotal for numerous applications of gold nanoparticles (Au‐NPs). Over the past decade, N‐heterocyclic carbenes (NHCs) have emerged as promising ligands for stabilizing Au‐NPs owing to their ease of synthesis, structural diversity, and strong metal‐ligand bonds. Here, we introduce new Au(I)–NHCcopolymer scaffolds as precursors to multidentate NHC‐protected Au‐NPs. Ring‐opening metathesis copolymerization of a norbornene‐appended Au(I)−NHC complex with another functionalized norbornene comonomer provides NHC–Au(I) copolymers with modular compositions and structures. Upon reduction, these copolymers yield multidentate polyNHC‐coated Au‐NPs with varied properties and corona functionalities dictated by the secondary monomer. These nanoparticles exhibit excellent size homogeneity and stability against aggregation in various buffers, cell culture media, and under exposure to electrolytes, oxidants, and exogenous thiols over extended periods. Moreover, we demonstrate post‐synthetic surface functionalization reactions of polyNHC−Au‐NPs while maintaining colloidal stability, highlighting their robustness and potential for applications such as bioconjugation. Overall, these findings underscore the potential of ROMP‐derived NHC‐containing copolymers as highly tunable and versatile multidentate ligands that may be suitable for other inorganic colloids and flat surfaces. 

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4. Inorganic nitrogen and organic matter jointly regulate ectomycorrhizal fungi‐mediated iron acquisition

   https://doi.org/10.1111/nph.20394  

   Wang, Haihua; Zhang, Kaile; Tappero, Ryan; Victor, Tiffany W; Bhatnagar, Jennifer M; Vilgalys, Rytas; Liao, Hui‐Ling (January 2025, New Phytologist)

   Summary Ectomycorrhizal fungi (EMF) play a crucial role in facilitating plant nutrient uptake from the soil although inorganic nitrogen (N) can potentially diminish this role. However, the effect of inorganic N availability and organic matter on shaping EMF‐mediated plant iron (Fe) uptake remains unclear.To explore this, we performed a microcosm study onPinus taedaroots inoculated withSuillus cothurnatustreated with +/−Fe‐coated sand, +/−organic matter, and a gradient of NH₄NO₃concentrations.Mycorrhiza formation was most favorable under conditions with organic matter, without inorganic N. Synchrotron X‐ray microfluorescence imaging on ectomycorrhizal cross‐sections suggested that the effect of inorganic N on mycorrhizal Fe acquisition largely depended on organic matter supply. With organic matter, mycorrhizal Fe concentration was significantly decreased as inorganic N levels increased. Conversely, an opposite trend was observed when organic matter was absent. Spatial distribution analysis showed that Fe, zinc, calcium, and copper predominantly accumulated in the fungal mantle across all conditions, highlighting the mantle's critical role in nutrient accumulation and regulation of nutrient transfer to internal compartments.Our work illustrated that the liberation of soil mineral Fe and the EMF‐mediated plant Fe acquisition are jointly regulated by inorganic N and organic matter in the soil. 

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5. PolyMOF Nanoparticles: Dual Roles of a Multivalent polyMOF Ligand in Size Control and Surface Functionalization

   https://doi.org/10.1002/anie.201910542  

   Gu, Yuwei; Huang, Mingjun; Zhang, Wenxu; Pearson, Matthew A.; Johnson, Jeremiah A. (September 2019, Angewandte Chemie International Edition)

   Abstract Metal–organic framework nanoparticles (MOF NPs) have emerged as an important class of materials that display significantly enhanced performance in many applications compared to bulk MOF materials; their synthesis, however, commonly involves a tedious sequence that controls particle size and surface properties in separate steps. Now, a simple strategy to access functional MOF NPs in one pot is reported that uses a polyMOF ligand possessing a polymer block for surface functionalization and a coordination block with tunable multivalency for size control. This strategy produces uniform polyMOF‐5 NPs with sizes down to 20 nm, displaying exceptional structural and colloidal stability upon exposure to ambient conditions. A detailed time‐dependent study revealed that the polyMOF NPs were formed following an aggregation‐confined crystallization mechanism. Generality was demonstrated through the synthesis of well‐defined polyUiO‐66 NPs. 

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