Synergy of shaped-induced enhanced Raman scattering to improve surface-enhanced Raman scattering signal in the thiram molecule detection.

Herein, we explore the combined effect of Shaped-Induced Enhanced Raman Scattering (SIERS) and Surface-Enhanced Raman Scattering (SERS) for detecting thiram molecules. We fabricated V-shaped microchannels on a silicon (100) substrate through a standard lithography and etching process. The analysis of SIERS@SERS was performed for Si-V substrates modified with AuNRs with different thiram concentrations, 10-7 to 10-10 mol/L. The spectra were collected for different regions of the Si-V substrates, i.e., in the inside, edge, between (flat top), and far from Si-V (coffee-ring AuNRs aggregation) to assess the performance of Si-V microchannels obtained. The IDMAP statistical projection reveals a higher silhouette coefficient of 0.91 for the inside of Si-V, indicating a more excellent spectral reproducibility with closer relative intensities. The device platform used in this study stands out as a robust option for commercial sensors, demonstrating exceptional sensitivity in detecting a diverse range of molecules, even at low concentrations.

Self-Healing E-tongue.

Self-healing materials inspire the next generation of multifunctional wearables and Internet of Things appliances. They expand the realm of thin film fabrication, enabling seamless conformational coverage irrespective of the shape complexity and surface geometry for electronic skins, smart textiles, soft robotics, and energy storage devices. Within this context, the layer-by-layer (LbL) technique is versatile for homogeneously dispersing materials onto various matrices. Moreover, it provides molecular level thickness control and coverage on practically any surface, with poly(ethylenimine) (PEI) and poly(acrylic acid) (PAA) being the most used materials primarily employed in self-healing LbL structures operating at room temperature. However, achieving thin film composites displaying controlled conductivity and healing ability is still challenging under ambient conditions. Here, PEI and PAA are mixed with conductive fillers (gold nanorods, poly(3,4-ethylene dioxythiophene): polystyrenesulfonate (PEDOT:PSS), reduced graphene oxides, and multiwalled carbon nanotubes) in distinct LbL film architectures. Electrical (AC and DC), optical (Raman spectroscopy), and mechanical (nanoindentation) measurements are used for characterizing composite structures and properties. A delicate balance among electrical, mechanical, and structural characteristics must be accomplished for a controlled design of conductive self-healing composites. As a proof-of-concept, four LbL composites were chosen as sensing units in the first reported self-healing e-tongue. The sensor can easily distinguish basic tastes at low molar concentrations and differentiate trace levels of glucose in artificial sweat. The formed nanostructures enable smart coverages that have unique features for solving current technological challenges.

Reorganization Energy upon Controlled Intermolecular Charge-Transfer Reactions in Monolithically Integrated Nanodevices.

Intermolecular electron-transfer reactions are key processes in physics, chemistry, and biology. The electron-transfer rates depend primarily on the system reorganization energy, that is, the energetic cost to rearrange each reactant and its surrounding environment when a charge is transferred. Despite the evident impact of electron-transfer reactions on charge-carrier hopping, well-controlled electronic transport measurements using monolithically integrated electrochemical devices have not successfully measured the reorganization energies to this date. Here, it is shown that self-rolling nanomembrane devices with strain-engineered mechanical properties, on-a-chip monolithic integration, and multi-environment operation features can overcome this challenge. The ongoing advances in nanomembrane-origami technology allow to manufacture the nCap, a nanocapacitor platform, to perform molecular-level charge transport characterization. Thereby, employing nCap, the copper-phthalocyanine (CuPc) reorganization energy is probed, ≈0.93 eV, from temperature-dependent measurements of CuPc nanometer-thick films. Supporting the experimental findings, density functional theory calculations provide the atomistic picture of the measured CuPc charge-transfer reaction. The experimental strategy demonstrated here is a consistent route towards determining the reorganization energy of a system formed by molecules monolithically integrated into electrochemical nanodevices.

Silicon Microchannel-Driven Raman Scattering Enhancement to Improve Gold Nanorod Functions as a SERS Substrate toward Single-Molecule Detection.

The investigation of enhanced Raman signal effects and the preparation of high-quality, reliable surface-enhanced Raman scattering (SERS) substrates is still a hot topic in the SERS field. Herein, we report an effect based on the shape-induced enhanced Raman scattering (SIERS) to improve the action of gold nanorods (AuNRs) as a SERS substrate. Scattered electric field simulations reveal that bare V-shaped Si substrates exhibit spatially distributed interference patterns from the incident radiation used in the Raman experiment, resulting in constructive interference for an enhanced Raman signal. Experimental data show a 4.29 increase in Raman signal intensity for bare V-shaped Si microchannels when compared with flat Si substrates. The combination of V-shaped microchannels and uniform aggregates of AuNRs is the key feature to achieve detections in ultra-low concentrations, enabling reproducible SERS substrates having high performance and sensitivity. Besides SIERS effects, the geometric design of V-shaped microchannels also enables a "trap" to the molecule confinement and builds up an excellent electromagnetic field distribution by AuNR aggregates. The statistical projection of SERS spectra combined with the SIERS effect displayed a silhouette coefficient of 0.83, indicating attomolar (10-18 mol L-1) detection with the V-shaped Si microchannel.

Polyethyleneimine-Functionalized Carbon Nanotube/Graphene Oxide Composite: A Novel Sensing Platform for Pb(II) Acetate in Aqueous Solution.

Heavy metal pollution is posing a severe health risk on living organisms. Therefore, significant research efforts are focused on their detection. Here, we developed a sensing platform sensor for the selective detection of lead(II) acetate. The sensor is based on self-assembled polyethyleneimine-functionalized carbon nanotubes (PEI-CNTs) and graphene oxide films deposited onto gold interdigitated electrodes. The graphene-based nanostructure showed a resistive behavior, and the fabricated layer-by-layer film was used to detect Pb(II) acetate in an aqueous solution by comparison of three electrochemical methods: impedance spectroscopy, amperometry, and potentiometry stripping analysis. The results obtained from different methods show that the detection limit was down to 36 pmol/L and the sensitivity up to 4.3 µAL/µmol, with excellent repeatability. The detection mechanism was associated with the high affinity of heavy metal ions with the functional groups present in the PEI-CNTs and GO, allowing high performance and sensitivity. The achieved results are important for the research toward integrated monitoring and sensing platforms for Pb(II) contamination in drinking water.

Influence of the Flow Rate in an Automated Microfluidic Electronic Tongue Tested for Sucralose Differentiation.

Incorporating electronic tongues into microfluidic devices brings benefits as dealing with small amounts of sample/discharge. Nonetheless, such measurements may be time-consuming in some applications once they require several operational steps. Here, we designed four collinear electrodes on a single printed circuit board, further comprised inside a straight microchannel, culminating in a robust e-tongue device for faster data acquisition. An analog multiplexing circuit automated the signal's routing from each of the four sensing units to an impedance analyzer. Both instruments and a syringe pump are controlled by dedicated software. The automated e-tongue was tested with four Brazilian brands of liquid sucralose-based sweeteners under 20 different flow rates, aiming to systematically evaluate the influence of the flow rate in the discrimination among sweet tastes sold as the same food product. All four brands were successfully distinguished using principal component analysis of the raw data, and despite the nearly identical sucralose-based taste in all samples, all brands' significant distinction is attributed to small differences in the ingredients and manufacturing processes to deliver the final food product. The increasing flow rate improves the analyte's discrimination, as the silhouette coefficient reaches a plateau at ~3 mL/h. We used an equivalent circuit model to evaluate the raw data, finding a decrease in the double-layer capacitance proportional to improvements in the samples' discrimination. In other words, the flow rate increase mitigates the formation of the double-layer, resulting in faster stabilization and better repeatability in the sensor response.

Synergy between polyaniline and OMt clay mineral in Langmuir-Blodgett films for the simultaneous detection of traces of metal ions.

We report on Langmuir-Blodgett (LB) films made with emeraldine salt polyaniline (PAni-ES) and organophilic montmorillonite clay mineral (OMt), where synergy between the components was reached to yield an enhanced performance in detecting trace levels of cadmium (Cd(2+)), lead (Pb(2+)) and copper (Cu(2+)). Detection was carried out using square wave anodic stripping (SWAS) voltammetry with indium tin oxide (ITO) electrodes modified with LB films of PAni-ES/OMt nanocomposite, whose data were compared to those obtained with electrodes coated with neat PAni-ES and neat OMt LB films. The enhanced performance in the nanocomposite may be attributed to the stabilizing and ordering effect promoted by OMt in PAni-ES Langmuir films, which then led to more homogeneous LB films. According to X-ray diffraction data, the stacking of OMt layers was preserved in the LB films and therefore the PAni-ES chains did not cause clay mineral exfoliation. Instead, OMt affected the polaronic state of PAni-ES as indicated in UV-vis, Raman and FTIR spectra, also consistent with the changes observed for the Langmuir films. Taken together these results do indicate that semiconducting polymers and clay minerals may be combined for enhancing the electrical properties of nanostructures for sensing and related applications.

Layer-by-layer films based on carbon nanotubes and polyaniline for detecting 2-chlorophenol.

Electrochemical sensors made with layer-by-layer (LbL) films of functionalized multi-walled carbon nanotubes (MWCNTs-COO-) and polyaniline (PAni) deposited onto ITO substrates were used to detect 2-chlorophenol. Concentrations down to ppm level could be detected with square wave voltammetry (SWV), owing to synergistic effects between PAni and nanotubes, whose molecular-level interactions in the LbL films were inferred using FTIR and Raman spectroscopy. Significantly, the Raman spectra of MWCNTs-COO-/PAni LbL films indicated that the conducting properties of PAni were preserved upon adsorption on the ITO substrates, with homogeneous nanocomposites being formed according to Scanning Electron Microscopy (SEM) images.