Pseudomonas aeruginosa is an opportunistic, biofilm-forming pathogen. P. aeruginosa produces pyocyanin, a secondary metabolite as part of its quorum sensing signaling system activated during biofilm formation. Self-organized plasmonic nanogaps provide enhancements to Raman scattering signals to achieve 10 ng/mL limit of detection of pyocyanin that enables early detection of biofilm formation. We report, for the first time, in-line biofilm detection in microfluidic channels as early as three hours from the onset of bacterial culturing and quantification spanning five-orders of magnitude of pyocyanin concentration during biofilm formation of PA14.

We propose a novel multi-length-scale architecture for giant electric field enhancement. We investigate the capability of our structure to boost the electric field analytically and using fullwave simulations and verify our results with surface-enhanced Raman spectroscopy experiment.

We propose a two-scale architecture by simultaneously exploiting both the Rayleigh anomaly and localized surface plasmon resonance in colloidal directly assembled oligomers to achieve giant field enhancement, overcoming limitations by losses and the intrinsic nonlocality of the dielectric response of metal nanoparticles. We show that the total field enhancement in the nanogap hotspots of this two-scale structure is the product of the enhancements of each individual geometrical scale. Under this scheme, chemically assembled metallic oligomers enable strong enhancement of the near-field in resultant few-nanometer gaps at their plasmonic resonance. An extra enhancement factor results from combining the plasmonic resonance enhancement of these oligomers (nanometer scale) with a Rayleigh anomaly caused by a one-dimensional (1D) periodic set of nanorods (micrometer scale) fabricated using a lithographic method. This extra field enhancement cannot be obtained by further reducing the nanoantennas' gaps, since they are already in the few-nm ranges thanks to direct chemical assembly of oligomers. Experimental results verify that surface-enhanced Raman spectroscopy (SERS) signal is enhanced by more than one order of magnitude due to the Rayleigh anomaly as compared to the signal taken by using only metallic oligomers without periodic nanorods. The proposed two-scale structure could serve as a substrate for different spectroscopy techniques including SERS and can improve the sensitivity of spectroscopy for ultrasensitive biomolecule detection and single molecule spectroscopy studies.

Abstract: Mechanical gradients are often employed in nature to prevent biological materials from damage by creating a smooth transition from strong to weak that dissipates large forces. Synthetic mimics of these natural structures are highly desired to improve distribution of stresses at interfaces and reduce contact deformation in manmade materials. Current synthetic gradient materials commonly suffer from non‐continuous transitions, relatively small gradients in mechanical properties, and difficult syntheses. Inspired by the polychaete worm jaw, we report a novel approach to generate stiffness gradients in polymeric materials via incorporation of dynamic monodentate metal–ligand crosslinks. Through spatial control of metal ion content, we created a continuous mechanical gradient that spans over a 200‐fold difference in stiffness, approaching the mechanical contrast observed in biological gradient materials.

Mechanical gradients are often employed in nature to prevent biological materials from damage by creating a smooth transition from strong to weak that dissipates large forces. Synthetic mimics of these natural structures are highly desired to improve distribution of stresses at interfaces and reduce contact deformation in manmade materials. Current synthetic gradient materials commonly suffer from non-continuous transitions, relatively small gradients in mechanical properties, and difficult syntheses. Inspired by the polychaete worm jaw, we report a novel approach to generate stiffness gradients in polymeric materials via incorporation of dynamic monodentate metal-ligand crosslinks. Through spatial control of metal ion content, we created a continuous mechanical gradient that spans over a 200-fold difference in stiffness, approaching the mechanical contrast observed in biological gradient materials.

Surface enhanced Raman scattering (SERS) is a vibrational spectroscopy method that enables the quantification of the concentration of small molecules. SERS sensing has been demonstrated in a wide variety of applications, from explosive and drug detection, to monitoring of bacteria growth. Underpinning SERS sensing are the sensor surfaces that are composed of vast quantities of metal nanostructures which confine light into small gaps called "hotspots", enhancing Raman scattering. While these surfaces are essential for increasing Raman scattering intensity so that analyte signal may be observed in small concentrations, they introduce signal variations due to spatial distributions of Raman enhancement and hotspot volume. In this work, we introduce a convolutional neural network model that improves concentration regressions in SERS sensors by learning the distributions of sensor surface dependent latent variables. We demonstrate that this model significantly improves predictions compared to a traditional multilayer perceptron approach, and that the model uses analyte spectral information and is capable of reasonable interpolations.

Nanoparticles from colloidal solution-with controlled composition, size, and shape-serve as excellent building blocks for plasmonic devices and metasurfaces. However, understanding hierarchical driving forces affecting the geometry of oligomers and interparticle gap spacings is still needed to fabricate high-density architectures over large areas. Here, electrohydrodynamic (EHD) flow is used as a long-range driving force to enable carbodiimide cross-linking between nanospheres and produces oligomers exhibiting sub-nanometer gap spacing over mm² areas. Anhydride linkers between nanospheres are observed via surface-enhanced Raman scattering (SERS) spectroscopy. The anhydride linkers are cleavable via nucleophilic substitution and enable placement of nucleophilic molecules in electromagnetic hotspots. Atomistic simulations elucidate that the transient attractive force provided by EHD flow is needed to provide a sufficient residence time for anhydride cross-linking to overcome slow reaction kinetics. This synergistic analysis shows assembly involves an interplay between long-range driving forces increasing nanoparticle-nanoparticle interactions and probability that ligands are in proximity to overcome activation energy barriers associated with short-range chemical reactions. Absorption spectroscopy and electromagnetic full-wave simulations show that variations in nanogap spacing have a greater influence on optical response than variations in close-packed oligomer geometry. The EHD flow-anhydride cross-linking assembly method enables close-packed oligomers with uniform gap spacings that produce uniform SERS enhancement factors. These results demonstrate the efficacy of colloidal driving forces to selectively enable chemical reactions leading to future assembly platforms for large-area nanodevices.