Since the first report in the early 2000s, there have been several experimental configurations that have demonstrated enhancement and spatial resolution of tip-enhanced Raman spectroscopy (TERS). The combination of a plasmonic substrate and a metallic tip is one suitable approach to achieve even higher enhancement and lateral resolution. In this contribution, we demonstrate TERS on a monolayer of MoS₂ on an array of Au nanodisks. The Au nanodisks were prepared by electron beam writing. Thereafter, MoS₂ was transferred onto the plasmonic substrate via the exfoliation technique. We witness an unprecedented enhancement and spatial resolution in the experiments. In the TERS image a ring-like shape is observed that matches the edges of the nanodisks. TERS enhancement at the edges is about 170 times stronger than at the center of the nanodisks. For a better understanding of the experimental results, finite element method (FEM) simulations were employed to simulate the TERS image of the MoS₂/plasmonic heterostructure. Our calculations show a higher electric field concentration at the edges that exponentially decays to the center. Therefore, it reproduces the ring-like shape of the experimental image. Moreover, the calculations suggest a TERS enhancement of 135 at the edges compared to the center, which is in very good agreement with the experimental data. According to our calculations, the spatial resolution is also increased at the edges. For comparison, FEM simulations of a tip–flat metal substrate system (conventional gap-mode TERS) were carried out. The calculations confirmed a 110 times stronger enhancement at the edges of the nanodisks than that of conventional gap-mode TERS and explained the experimental maps. Our results provide not only a deeper understanding of the TERS mechanism of this heterostructure, but can also help in realizing highly efficient TERS experiments using similar systems.

It has been widely shown that biomaterial surface topography can modulate host immune response, but a fundamental understanding of how different topographies contribute to pro‐inflammatory or anti‐inflammatory responses is still lacking. To investigate the impact of surface topography on immune response, we undertook a systematic approach by analyzing immune response to eight grades of medical grade polyurethane of increasing surface roughness in three in vitro models of the human immune system. Polyurethane specimens were produced with defined roughness values by injection molding according to the VDI 3400 industrial standard. Specimens ranged from 0.1 μm to 18 μm in average roughness (Ra), which was confirmed by confocal scanning microscopy. Immunological responses were assessed with THP‐1‐derived macrophages, human peripheral blood mononuclear cells (PBMCs), and whole blood following culture on polyurethane specimens. As shown by the release of pro‐inflammatory and anti‐inflammatory cytokines in all three models, a mild immune response to polyurethane was observed, however, this was not associated with the degree of surface roughness. Likewise, the cell morphology (cell spreading, circularity, and elongation) in THP‐1‐derived macrophages and the expression of CD molecules in the PBMC model on T cells (HLA‐DR and CD16), NK cells (HLA‐DR), and monocytes (HLA‐DR, CD16, CD86, and CD163) showed no influence of surface roughness. In summary, this study shows that modifying surface roughness in the micrometer range on polyurethane has no impact on the pro‐inflammatory immune response. Therefore, we propose that such modifications do not affect the immunocompatibility of polyurethane, thereby supporting the notion of polyurethane as a biocompatible material.

Graphene oxide (GO) films are deposited on flexible Kapton substrates and selectively modified to conductive reduced graphene oxide (rGO) electrodes using laser patterning. Based on this, we design, fabricate, and test a flexible sensor integrating laser-reduced GO with silver plasmonic nanostructures. The fabricated device results in dual transduction channels: for electrochemical and plasmonic nanostructure-based surface-enhanced Raman spectroscopy (SERS) detection. The spectroscopic analysis verifying the formation of rGO and the modification by silver nanostructures is performed by Raman, energy dispersive X-ray (EDX), and X-ray photoelectron spectroscopy (XPS). The morphological investigation is followed by optical and scanning electron microscopy imaging. In addition to pristine silver nanostructures, the Raman spectroscopy results show the formation of species such as Ag₂O, Ag₂CO₃, and Ag₂SO_x. A dual-channel sensor device based on electrochemical and plasmonic detection is fabricated as a demonstration of our Ag–rGO flexible concept architecture. The dual-channel device performance is successfully demonstrated in the electrochemical and SERS detection of 4-nitrobenzenethiol (4-NBT) using the same device. Our results show that without Ag nanostructures the sensitivity in the electrochemical and optical channels is not sufficient to detect 4-NBT. The performance and stability of the silver modified device are also verified. This work demonstrates an inexpensive, highly efficient, and greener way that is compatible with solution-processing technology for the production of flexible GO-based electrochemical and SERS detection devices integrated with plasmonic nanostructures.