Mike and Joseph's paper using N-heterocyclic carbenes for SERS was accepted by JACS!


Surface-enhanced Raman spectroscopy (SERS) underpins a wide range of commercial and fundamental applications. SERS often relies on ligands, usually thiols, bound to a noble metal surface. The difficulty of straightforward thiol synthesis combined with their instability on surfaces highlights the need for alternative ligand design. We present the first example of SERS utilizing N-heterocyclic carbene ligands. A general three step synthesis is presented for functionalized NHC-CO2 adducts. These ligands are deposited on SERS-active gold film-over-nanosphere substrates (AuFONs) in solvent-free and base-free conditions, which prevents fouling. The resulting films are found to be robust and capable of postsynthetic modifications.

DOI: 10.1021/jacs.7b12779

Guoliang's paper on multipolar plasmon mode mixing has been published at The Journal of Physical Chemistry Letters!


Facile control of the radiative and nonradiative properties of plasmonic nanostructures is of practical importance to a wide range of applications in the biological, chemical, optical, information, and energy sciences. For example, the ability to easily tune not only the plasmon spectrum but also the degree of coupling to light and/or heat, quality factor, and optical mode volume would aid the performance and function of nanophotonic devices and molecular sensors that rely upon plasmonic elements to confine and manipulate light at nanoscopic dimension. While many routes exist to tune these properties, identifying new approaches---especially when they are simple to apply experimentally---is an important task. Here, we demonstrate the significant and underappreciated effects that substrate thickness and dielectric composition can have upon plasmon hybridization as well as downstream properties that depend upon this hybridization. We find that even substrates as thin as ~10 nm can nontrivially mix free-space plasmon modes, imparting bright character to those that are dark (and vice versa) and, thereby, modifying the plasmonic density of states as well as the system's near- and far-field optical properties. A combination of electron energy-loss spectroscopy (EELS) experiment, numerical simulation, and analytical modeling is used to elucidate this behavior in the finite substrate-induced mixing of dipole, quadrupole, and octupole corner-localized plasmon resonances of individual silver nanocubes.

DOI: 10.1021/acs.jpclett.7b03271

Yueying, Guoliang, and Jon's review on probing nanoparticle plasmons with electron energy loss spectroscopy is published at Chemical Reviews!


Electron energy loss spectroscopy (EELS) performed in a scanning transmission electron microscope (STEM) has demonstrated unprecedented power in the characterization of surface plasmons. The subangstrom spatial resolution achieved in EELS and its capability of exciting the full set of localized surface plasmon resonance (LSPR) modes supported by a metallic nanostructure makes STEM/EELS an ideal tool in the study of LSPRs. The plasmonic properties characterized using EELS can be associated with geometric or structural features collected simultaneously in a STEM to achieve a deeper understanding of the plasmonic response. In this review, we provide the reader a thorough experimental description of EELS as a LSPR characterization tool and summarize the exciting recent progress in the field of STEM/EELS plasmon characterization.


DOI: 10.1021/acs.chemrev.7b00354

Xin's Paper On Utilizing Light-Triggered Plasmon-Driven Catalysis Reactions as a Template for Molecular Delivery and Release Has Been Published In Chemical Science!


Due to the facile manipulation and non-invasive nature of light-triggered release, it is one of the most potent ways to selectively and remotely deliver a molecular target. Among the various carrier platforms, plasmonic nanoparticles possess advantages such as enhanced cellular uptake and easy loading of “cargo” molecules. Two general strategies are currently utilized to achieve light-induced molecule release from plasmonic nanoparticles. The first uses femtosecond laser pulses to directly break the bond between the nanoparticle and the loaded target. The other requires significant photo-thermal effects to weaken the interaction between the cargo molecules and nanoparticle-attached host molecules. Different from above mechanisms, herein, we introduce a new light-controlled molecular-release method by taking advantage of a plasmon-driven catalytic reaction at the particle surface. In this strategy, we link the target to a plasmon responsive molecule, 4-aminobenzenethiol (4-ABT), through the robust and simple EDC coupling reaction and subsequently load the complex onto the particles via the strong Au–thiol interaction. Upon continuous-wave (CW) laser illumination, the excited surface plasmon catalyzes the formation of 4,4′-dimercaptoazobenzenethiol (DMAB) and simultaneously releases the loaded molecules with high efficiency. This method does not require the use of high-power pulsed lasers, nor does it rely on photo-thermal effects. We believe that plasmon-driven release strategies open a new direction for the designing of next-generation light-triggered release processes.

DOI: 10.1039/C7SC02089A

Hobbie's paper on probing molecular orientation with surface-enhanced hyper-Raman scattering has been published in The Journal of Physical Chemistry Letters!


Herein, we utilize surface-enhanced hyper-Raman scattering (SEHRS) under resonance conditions to probe the adsorbate geometry of rhodamine 6G (R6G) on silver colloids. Our results show resonance SEHRS is highly sensitive to molecular orientation due to non-Condon effects, which do not appear in its linear counterpart surface-enhanced Raman scattering. Comparisons between simulated and measured SEHRS spectra reveal R6G adsorbs mostly perpendicular to the nanoparticle surface along the ethylamine groups with the xanthene ring oriented edgewise. Our results expand upon previous studies that rely on indirect, qualitative probes of R6G’s orientation on plasmonic substrates. More importantly, this work represents the first determination of adsorbate geometry by SEHRS and opens up the possibility to study the orientation of single molecules in complex, plasmonic environments.

DOI: 10.1021/acs.jpclett.7b00498

Mike's paper on uranium detection is published and will be featured on the cover of Analytical Methods!


A surface-enhanced Raman scattering (SERS) method, based on functionalized silver colloids, is developed for the detection of uranyl ions that yields a limit of detection of 24 ppb. The signal is obtained from functionalized colloids three months after preparation and in the presence of interferents likely to be present in groundwater. Additionally, our method is transferrable to a hand-held Raman spectrometer with comparable sensitivity, exhibiting potential for field analysis of uranium.


DOI: 10.1039/C7AY00183E

Sarah's paper on imaging energy transfer in decorated nanoparticles is published in The Journal of Physical Chemistry Letters!


Driven by the desire to understand energy transfer between plasmonic and catalytic metals for applications such as plasmon-mediated catalysis, we examine the spatially resolved electron energy-loss spectra (EELS) of both pure Au nanoprisms and Pt-decorated Au nanoprisms. The EEL spectra and the resulting surface-plasmon mode maps reveal detailed near-field information on the coupling and energy transfer in these systems, thereby elucidating the underlying mechanism of plasmon-driven chemical catalysis in mixed-metal nanostructures. Through a combination of experiment and theory we demonstrate that although the location of the Pt decoration greatly influences the plasmons of the nanoprism, simple spatial proximity is not enough to induce significant energy transfer from the Au to the Pt. What matters more is the spectral overlap between the intrinsic plasmon resonances of the Au nanoprism and Pt decoration, which can be tuned by changing the composition or morphology of either component.