Large emergent optoelectronic enhancement in molecularly cross-linked gold nanoparticle nanosheets.

A central goal in molecular electronics and optoelectronics is to translate tailorable molecular properties to larger materials and to the device level. Here, we present a method to fabricate molecularly cross-linked, self-assembled 2D nanoparticle sheets (X-NS). Our method extends a Langmuir approach of self-assembling gold nanoparticle (NP) arrays at an air-water interface by replacing the liquid sub-phase to an organic solvent to enable cross-linking with organic molecules, and then draining the sub-phase to deposit films. Remarkably, X-NS comprising conjugated oligophenylene dithiol cross-linkers (HS-(C6H4)n-SH, 1 ≤ n ≤ 3) exhibit increasing conductance with molecule length, ~6 orders of magnitude enhancement in UV-Vis extinction coefficients, and photoconductivity with molecule vs. NP contributions varying depending on the excitation wavelength. Finite difference time domain (FDTD) analyses and control measurements indicate that these effects can be modeled provided the local complex dielectric constant is strongly modified upon cross-linking. This suggests quantum hybridization at a molecule-band (q-MB) level. Given the vast number of molecules and nano-building blocks available, X-NS have potential to significantly increase the range of available 2D nanosheets and associated quantum properties.

Glucose oxidase kinetics using MnO2 nanosheets: confirming Michaelis-Menten kinetics and quantifying decreasing enzyme performance with increasing buffer concentration.

MnO2 nanosheets and ultraviolet-visible (UV-Vis) absorbance spectroscopy are used to study glucose oxidase (GOx) kinetics. Glucose oxidation by GOx produces H2O2, which rapidly decomposes the nanosheets and reduces their absorption. This direct approach for monitoring glucose oxidation enables simpler, real time kinetics analysis compared to methods that employ additional enzymes. Using this approach, the present study confirms that GOx kinetics is consistent with the Michaelis-Menten (MM) model, and reveals that the MM constant increases by an order of magnitude with increasing buffer concentration. Since larger MM constants imply higher enzyme substrate concentrations are required to achieve the same rate of product formation, increasing MM constants imply decreasing enzyme performance. These results demonstrate the facility of using MnO2 nanosheets to study GOx kinetics and, given the widespread applications of enzymes with buffers, the important sensitivity of enzyme-buffer systems on buffer concentration.

A Scalable, Solution-Based Approach to Tuning the Solubility and Improving the Photoluminescence of Chemically Exfoliated MoS2.

MoS2 are two-dimensional (2D) materials that exhibit emerging photoluminescence (PL) at the monolayer level and have potential optoelectronic applications. Monolayers of MoS2 typically achieved by mechanical exfoliation (Me), chemical vapor deposition (CVD), and chemical exfoliation (Ce) via lithium intercalation contain numerous defects that significantly reduce their PL efficiency. Several studies have reported overcoming poor PL in mechanically exfoliated and CVD-grown MoS2, but such studies for chemically exfoliated MoS2 (Ce-MoS2) have not been reported. Here, we report a solution-based method of enhancing the PL of Ce-MoS2 by reacting with molecules with suitable functional groups at high temperatures. Reaction with dodecanethiol (DDT) generates PL that is more intense than mechanically exfoliated MoS2 (Me-MoS2) with high crystallinity and has a significantly broader range of wavelengths. Based on ultraviolet-visible, Fourier transform infrared, X-ray photoemission, and PL spectroscopy as well as transmission electron and PL imaging, we propose that the present method modifies PL properties of Ce-MoS2 by simultaneously annealing, replacing molybdenum-oxygen with molybdenum-sulfur bonds, inducing strain, and generating a nanopolycrystalline structure. This work points to such defect engineering using molecules as an effective means to modify the properties of Ce-MoS2 and layered transition-metal dichalcogenides more generally.

Large Kondo effect in assemblies of Au nanoparticles linked with alkanedithiol electron bridges.

Using a prototypical nanoparticle-molecule assembly, namely alkanedithiol-linked gold nanoparticle films, we observe hallmark signatures of the Kondo effect in conductance vs. voltage as well as temperature measurements. Its contribution to temperature dependence of conductance is much larger than those from all other temperature-dependant effects up to 300 K by >20-fold - much larger than previous reports of the Kondo effect using other platforms. We find that previous models of the Kondo effect describe our data even in this regime. Given the synthetic control available over nanoparticle properties such as surface area, shape, and chemical composition, our work points to combining flexibility afforded by molecule + nanoparticle assemblies as a powerful way to generate materials exhibiting strong spin-electron interactions.

Controlled hierarchical assembly of gold nanoparticles in macroscopic films: from densely packed monolayers to networks of micropores and nanobundles.

The present study demonstrates the ability of excess, weakly amphiphilic n-alkanethiols (n = 4, 12, 18) and solvent composition to tune through a wide range of large-scale, macroscopic architectures formed by alkanethiol-capped Au nanoparticles (NPs). Both the alkanethiols and NPs are significantly hydrophobic species and compete for surface area at an air-water interface. When solutions of the two species are spread on a large (50 cm2) water surface in a Teflon well, a thin film forms and exhibits co-existing macroscopic regions with various distinct NP self-assembled architectures, namely a close packed monolayer, a network phase characterized by micron-sized pores (micropores) surrounded by quasi-linear bundles of nanoparticles, and finally aggregates. We hypothesize that the co-existence of various NP architectures results from fast, non-uniform evaporation across the large water surface. When solutions are instead deposited on a smaller (5 cm2) water surface contained within a Teflon ring to control the water surface curvature and the evaporation rate is slowed, we show for the first time that NPs form macroscopically uniform self-assemblies whose architectures can be tuned from monolayers → monolayers with micropores → extended micropore/NP bundle networks by varying excess alkanethiol concentration and solvent composition. We propose that competition between NPs and excess alkanethiols for water surface area, and alkanethiol self-assembly as well as solvent dewetting play important roles in the formation of the network phase, and discuss a potential mechanism for its formation.