Tunable-wavelength nanosecond laser tailoring of plasmon resonance spectra of gold nanoparticle colloids.

Metal nanoparticles have applications across a range of fields of science and industry. While there are numerous existing methods to facilitate their large-scale production, most face limitations, particularly in achieving reproducible processes and minimizing undesirable impurities. Common issues are varying particle sizes and aggregates with unfavorable spectral properties. Researchers are currently developing methods to separate or modify nanoparticle sizes and shapes post-synthesis and to eliminate impurities. One promising approach involves laser light irradiation and enables the changing of nanoparticle sizes and shapes while controlling crucial spectral parameters. In this work, we present a novel extension of this method by irradiating nanoparticle colloids with variable-wavelength nanosecond laser pulses on both sides of the extinction band. Our results demonstrate the use of gradual laser wavelength tuning to optimize the photothermal reshaping of gold nanorods and achieve precise control over the plasmon resonance band. By irradiating both sides of the plasmon resonance band, we execute a multistep tuning process, controlling the band's width and spectral position. A statistical analysis of SEM images reveals differences in the nanorod morphology when irradiated on the long- or short-wavelength side of the plasmon resonance band. The fine-tuning of plasmonic spectral properties is desirable for various applications, including the development of sensors and filters and the exploitation of the photothermal effect. The findings of this study can be extended to other plasmonic nanostructures.

MCR-ALS with sample insertion constraint to enhance the sensitivity of surface-enhanced Raman scattering detection.

The multivariate curve resolution-alternative least squares (MCR-ALS) algorithm was modified with sample insertion constraint to deconvolute the overlapping peaks in SERS spectra. The developed method was evaluated by the spectral data simulated using a Gaussian distribution function to generate two independent peaks corresponding to a capping agent and an analyte. The spectra were generated with different overlapping levels and various intensity ratios of the analyte to the capping agent. By using MCR-ALS with the sample insertion constraint, the peak of the capping agent was completely excluded to obtain a calibration model of the analyte with R2 > 0.95 under all conditions. Furthermore, our developed method was later applied to a real SERS measurement to quantify carbofuran (analyte) using the azo-coupling reaction with p-ATP (capping agent) on silver nanoparticles as a SERS substrate. A calibration model of derivative carbofuran phenol was generated with R2 = 0.99 and LOD = 28.19 ppm. To assess the performance of the calibration model, the model was used to estimate the concentration of carbofuran in an external validation set. It was found that the RMSE of prediction was only 2.109 with a promising R2 = 0.97.

Distinguishing Enantiomers by Tip-Enhanced Raman Scattering: Chemically Modified Silver Tip with an Asymmetric Atomic Arrangement.

Discrimination between enantiomers is achieved by tip-enhanced Raman scattering (TERS) using a silver tip that is chemically modified by an achiral para-mercaptopyridine (pMPY) probe molecule. Differences in the relative intensities of the pMPY spectra were monitored for three pairs of enantiomers containing hydroxy (-OH) and/or amino (-NH2 ) groups. The N: or N+ -H functionality of the pMPY-modified tip participates in hydrogen-bond interactions with a particular molecular orientation of each chiral isomer. The asymmetric arrangement of silver atoms at the apex of the tip induces an asymmetric electric field, which causes the tip to become a chiral center. Differences in the charge-transfer (CT) states of the metal-achiral probe system in conjunction with the asymmetric electric field produce different enhancements in the Raman signals of the two enantiomers. The near-field effect of the asymmetric electric field, which depends on the number of analyte functional groups capable of hydrogen-bond formation, improves the degree of discrimination.

Silver nanoparticle/bacterial nanocellulose paper composites for paste-and-read SERS detection of pesticides on fruit surfaces.

This study aimed to develop an eco-friendly flexible surface-enhanced Raman scattering (SERS) substrate for in-situ detection of pesticides using biodegradable bacterial nanocellulose (BNC). Plasmonic silver nanoparticle- bacterial nanocellulose paper (AgNP-BNCP) composites were prepared by vacuum-assisted filtration. After loading AgNPs into BNC hydrogel, AgNPs were trapped firmly in the network of nanofibrous BNCP upon ambient drying process, resulting in 3D SERS hotspots within a few-micron depth on the substrate. The fabricated AgNP-BNCPs exhibited high SERS activity with good reproducibility and stability as demonstrated by the detection of 4-aminothiophenol and methomyl pesticide. Due to the optical transparency of BNCP, a direct and rapid detection of methomyl on fruit peels using AgNP-BNCPs can be achieved, demonstrating a simple and effective 'paste-and-read' SERS approach. These results demonstrate potential of AgNP-BNCP composites for user-friendly in-situ SERS analysis.

Oxidized Carbon Black: Preparation, Characterization and Application in Antibody Delivery across Cell Membrane.

Modulating biomolecular networks in cells with peptides and proteins has become a promising therapeutic strategy and effective biological tools. A simple and effective reagent that can bring functional proteins into cells can increase efficacy and allow more investigations. Here we show that the relatively non-toxic and non-immunogenic oxidized carbon black particles (OCBs) prepared from commercially available carbon black can deliver a 300 kDa protein directly into cells, without an involvement of a cellular endocytosis. Experiments with cell-sized liposomes indicate that OCBs directly interact with phospholipids and induce membrane leakages. Delivery of human monoclonal antibodies (HuMAbs, 150 kDa) with specific affinity towards dengue viruses (DENV) into DENV-infected Vero cells by OCBs results in HuMAbs distribution all over cells' interior and effective viral neutralization. An ability of OCBs to deliver big functional/therapeutic proteins into cells should open doors for more protein drug investigations and new levels of antibody therapies and biological studies.

Paper-based chemical reaction arrays as an effective tool for geographical indication of turmerics.

Geographical indications have gained increasing importance as a powerful marketing tool for highly valuable products especially foods. In this study, a unique and synergistic combination of chemical reaction arrays on paper and chemometric analysis was used to uncover geographical indication of turmerics, an important food ingredient in several cultures. The key to effective differentiation was based on the subtle differences in the compositions of compounds found in each sample, mainly curcumin and derivatives. When these compounds reacted with various reagents in the form of paper arrays, different optical and fluorescence profiles were generated, which can then be exploited by chemometrics. As a result, our strategy could provide up to 94% prediction accuracy without the need for any sophisticated instruments.

Facile and Sensitive Detection of Carbofuran Carbamate Pesticide in Rice and Soybean Using Coupling Reaction-based Surface-Enhanced Raman Scattering.

In this research, a sensitive and selective method for detecting one of the most toxic insecticides, "carbofuran", in rice and soybean is presented. This method is based on the coupling reaction of diazonium ion combined with a surface-enhanced Raman scattering technique. Diazonium ion produced from p-aminothiophenol reacts specifically with carbofuran phenol from the hydrolysis of carbofuran. The generated azo compounds attach to the surface of silver nanoparticles via the Ag-S bond. Therefore, a strong Raman intensity can be obtained. The concentration of carbofuran can be determined by following the intensity of the peak at 1201 cm-1, attributed to the C-N stretching vibration of the azo compound. The result shows a good linear correlation (R2 = 0.9786) against carbofuran concentrations (0.1 - 5 ppm) with a detection limit of 0.452 ppm. Our proposed protocol is insignificantly influenced by various common interferences. Moreover, this method has been successfully validated to determine carbofuran concentrations in rice and soybean with detection limits of 0.446 and 0.520 ppm, respectively.