A Composite Substrate of Ag Nanoparticle-Decorated Inverse Opal Polydimethylsiloxane for Surface Raman Fluorescence Dual Enhancement

Herein, a transparent and reproducible substrate, fabricated using polydimethylsiloxane (PDMS) laminated with self-assembled Ag nanoparticles (Ag NPs), was employed as a universal surface-enhanced Raman scattering (SERS) substrate for the detection of targets with various matrices. The Ag NPs were assembled in a two-dimensional manner via a self-assembly technique. Due to the electrostatic interaction between the Ag NPs, the reproducibility of the assembly was ensured by the fixed density of the assembled Ag NPs at saturated assembly states. The assembled pattern and plasmon resonance of the Ag NPs were well preserved during the molding and curing of PDMS. As a result, the Ag NP laminated PDMS film exhibited a SERS effect to the adsorbed p-aminothiophenol comparable to that of the assembled Ag NPs on a glass slide. Extra SERS enhancement was achieved by construction of a Ag (PDMS)/molecule/Ag (glass) configuration due to the electromagnetic coupling between the Ag NPs. The Raman scattering of 4-mercaptobenzoic acid and benzotriazole modified on the surfaces of a smooth Au electrode and copper foil, respectively, was detected with the aid of the Ag NP-laminated PDMS film. Furthermore, malachite green dispersed in a KBr solid matrix was quantitatively determined with a detection limit of 0.5 μg/g. It is suggested that the SERS enhancement and consequential SERS detection sensitivity of the target molecules may be further maximized by adjusting the distance between the target molecules and the Ag NPs laminated on the PDMS film.

Surface-enhanced Raman spectroscopy (SERS) has been demonstrated as an ultrasensitive tool for various molecules. However, for the negatively charged molecules, the widely used SERS substrate [negatively charged Ag and Au nanoparticles (Ag or Au NPs (-)] showed either low sensitivity or poor stability. The best solution is to synthesize positively charged silver or gold nanoparticles [Ag or Au NPs (+)] with high stability and excellent SERS performance, which are currently unavailable. To this end, we revitalized the strategy of "charge reversal and seed growth". By selection of ascorbic acid as the reductant and surfactant, the surface charge of Ag or Au NP (-) seeds is adjusted to a balanced state, where the surface charge is negative enough to satisfy the stabilization of the NPs (-) but does not hinder the subsequent charge reversal. By optimization of the chain length and electric charge of polyamine molecules, the highly stable and size-controllable uniform Ag NPs (+) and Au NPs (+) were seed-growth synthesized with high reproducibility. More importantly, the SERS performance of both Ag NPs (+) and Au NPs (+) achieved the trace detection of negatively charged molecules at the level of 1 μg/L, demonstrating an improved SERS sensitivity of up to 3 orders of magnitude compared to the previously reported sensitivity. Promisingly, the introduction of polyamine-capped Ag NPs (+) and Au NPs (+) as SERS substrates with high stability (1 year shelf life) will significantly broaden the application of SERS.

In this work, MXene and Ag nanoparticle (Ag NP)–decorated aligned Ag nanowires (Ag NWs) are applied to achieve surface-enhanced Raman scattering (SERS). MXene/Ag NP–decorated aligned Ag NWs based PDMS (polydimethylsiloxane) (MAAP) substrate is fabricated following the order of oil–water–air interfacial self-assembly of aligned Ag NWs, then surface modification of Ag NPs, and drop-casting of MXene last. The synergistic effect of MXene and Ag NP–decorated Ag NWs confers the MAAP substrate with high sensitivity, universality (limit of detection of 10−10 M for rhodamine 6G and crystal violet, 10−9 M for malachite green), and reproducibility. Based on the existence of PDMS, the MAAP substrate exhibits a good flexibility, and it maintains a high Raman activity after stretching and bending for 100 times. In addition, the surface covering MXene prevents Ag NWs decorated by Ag NPs from oxidation, which made the MAAP substrate still have a relatively high Raman activity. The fabricated MAAP substrate enriches the family members of MXene-based SERS substrates and displays an application value in SERS on irregular surfaces.

Wafer-scale surface-enhanced Raman scattering (SERS) substrates fabricated using maskless lithography are important for scalable production targets. Large-area, leaning silver-capped silicon nanopillar (Ag NP) structures suitable for SERS molecular detection at extremely low analyte concentrations are investigated. Theoretical results show that isolated Ag NPs essentially support two localized surface plasmon (LSP) modes. The most prominent LSP resonance is observed in the near-infrared region (∼800 nm) and can be tuned by changing the diameter of the silicon nanopillars (Si NPs). The corresponding electric field distribution maps indicate that the maximum E-field enhancement is found at the Ag cavity, i.e., the bottom part of the Ag cap. We argue that the plasmon coupling between the resonant Ag cap cavities contributes most to the enhancement of the Raman signal. We experimentally evaluate these findings and show that by exposing Si NPs to an O2-plasma the average Ag NP cluster size, and thus the overall interpillar coupling, can be systematically reduced. We show that deposition of Cr adhesion layers on Si NPs (>3 nm) introduces plasmon coupling loss to the Ag NP LSP cavity mode that significantly reduces the SERS intensity. Results also show that short exposures to the O2-plasma and the use of 1–3 nm Cr adhesion layers are advantageous for reducing the signal background noise from Ag NPs. In addition, the influence of the Ag NP height and Ag metal thickness on SERS intensities is investigated and optimal fabrication process parameters are evaluated. Finally, the SERS spectrum from 100 pM trans-1,2-bis(4-pyridyl) ethylene (BPE) is recorded, showing distinct characteristic Raman vibrational modes. The calculated enhancement factor is of the order of 108, and the SERS signal intensity exhibits a standard deviation of around 14% (660 data points) across a 5 × 5 mm2 surface area.

In the textile industry, textile materials are dyed and multi-functionalised by multi-step treatments that considerably increase the environmental impacts by increasing water and energy usage along with increasing the generation of volume of effluent. In this work, Ag nanoparticles (Ag NPs) were in situ formed and stabilised with gallnut, feijoa fruit skin, and mango seed kernel-derived tannins, and wool fabrics were coated simultaneously with these Ag NPs in the same bath. The Ag NP treatment produced dark to light olive-brown shades on wool fabrics. The treatment conditions for the treatment with Ag NPs were optimised to achieve the best results. The colour intensity, UV radiation absorption, antibacterial activity, surface electrical resistance, and durability of the treatment to washing were assessed by various methods. The gallnut-derived tannin (GNT)-stabilised Ag NP-coated wool fabrics showed overall the best results including excellent antibacterial activity against various types of bacteria. The treatment was durable to at least 20 cycles of IWS 7A washes (equivalent to 80 domestic washes). For the 0.5% Ag NPs on the weight of fibre (owf) dosage, the UV light transmission through the trisodium citrate-stabilised Ag NP-coated fabric at 365 and 311 nm was 6.37 and 0.95% respectively, which reduced to 1.63 and 0.20% for the fabric coated with GNT-stabilised Ag NPs providing excellent protection against UV radiation. The surface resistivity of wool fabric reduced from 1.1 × 1012 ohm cm-1 for the untreated fabric to 1.1 × 109 ohm cm-1 for the fabric coated with 2.0% owf GNT-stabilised Ag NPs. The stabilisation of Ag NPs with GNT prolonged the wash-durability by reducing the leaching of Ag NPs from the treated fabric. The developed method could be a sustainable alternative to traditional multi-stage treatments conducted in the textile industry with toxic synthetic dyes and finishing agents for the colouration and multifunctionalisation of wool fabrics.

Introduction: Silver nanoparticles (Ag NPs) are pivotal in advancing surface-enhanced Raman scattering (SERS) due to their exceptional plasmonic properties. Yet, conventional synthesis methods often fail to precisely control their shape and size, impacting SERS efficiency. This study introduces a novel synthesis approach using hydrogen peroxide (H2O2) to tailor Ag NP morphologies, aiming to optimize their plasmonic resonance for improved SERS detection of hazardous substances. Methods: We utilized a chemical reduction process with H2O2 to etch and shape Ag NPs, adjusting H2O2 concentrations to control nanoparticle morphology. The characterization of the nanoparticles involved SEM, TEM, and XRD for morphology and structure, with UV-Vis spectroscopy determining their absorption spectra. Results: The approach yielded Ag NPs with variable shapes and absorption wavelengths (330 nm to 740 nm), directly correlating H2O2 concentration with morphological changes. SEM and TEM showed diverse nanoparticle shapes, and XRD confirmed their crystalline structure. Notably, nanoparticles tuned to specific absorption wavelengths significantly enhanced SERS detection of Rhodamine B. Conclusion: Our method effectively produces multi-shaped Ag NPs with tunable optical properties, enhancing SERS application in detecting trace organic compounds. This streamlined synthesis process offers new possibilities for environmental monitoring and safety assessments.

Silver nanoparticles (Ag NPs) have been used widely for antibacterial applications; however, the effects of their sizes on antibacterial activities and toxicities to human cells, particularly for the laser‐generated Ag NPs, are not fully understood. In this study, sucrose gradient centrifugation was used to separate laser‐generated Ag NPs into different fractions by size. Transmission electron microscopy was used to analyze the size distribution of the Ag NPs, and well diffusion method was used to evaluate the antibacterial activity of the Ag NP fractions against the Escherichia coli. Results showed that the antibacterial effects of laser‐generated Ag NPs inversely correlated to the particle size. Among Ag NP fractions with average sizes ranging 19–47 nm, the 19‐nm Ag NPs presented the highest bactericidal effect. The smaller sized laser Ag NPs also significantly induced the generation of reactive oxygen species when applied to E. coli, compared with that of the larger sized laser Ag NPs. Cytotoxicity analysis revealed that the different sized laser‐generated Ag NPs were not significantly toxic to the human fibroblasts and lung epithelial cells in a 72‐h in vitro cell culture period. Understanding the size‐dependent functional properties of the laser‐generated Ag NPs helps informing the designs for future applications of the laser‐generated Ag NPs.

Bacterial biofilms are most likely confronted with silver nanoparticles (Ag NPs) as a pollutant stressor in aquatic systems. In this study, biofilms of Aquabacterium citratiphilum were exposed for 20h to 30 and 70nm citrate stabilized Ag NPs in low-dose concentrations ranging from 600 to 2400μgl-1, and the Ag NP-mediated effects on descriptive, structural, and functional biofilm characteristics, including viability, protein content, architecture, and mechanical stability, were investigated. Viability, based on the bacterial cell membrane integrity of A. citratiphilum, as determined by epifluorescence microscopy, remained unaffected after Ag NP exposure. Moreover, in contrast to information in the current literature, protein contents of cells and extracellular polymeric substances (EPS) and biofilm architecture, including dry mass, thickness, and density, were not significantly impacted by exposure to Ag NPs. However, the biofilms themselves served as effective sinks for Ag NPs, exhibiting enrichment factors from 5 to 8. Biofilms showed a greater capacity to accumulate 30nm sized Ag NPs than 70nm Ag NPs. Furthermore, Ag NPs significantly threatened the mechanical stability of biofilms, as determined by a newly developed assay. For 30nm Ag NPs, the mechanical stability of biofilms decreased as the Ag NP concentrations applied to them increased. In contrast, 70nm Ag NPs produced a similar decrease in mechanical stability for each applied concentration. Overall, this finding demonstrates that exposure to Ag NPs triggers remarkable changes in biofilm adhesion and/or cohesiveness. Because of biofilm-mediated ecological services, this response raises environmental concerns regarding Ag NP release into freshwater systems, even in sublethal concentrations.

Bacterial infections are one of the leading causes of death worldwide. In the case of topical bacterial infections such as wound infections, silver (Ag) has historically been one of the most widely used antibacterials. However, scientific publications have demonstrated the adverse effects of silver on human cells, ecotoxicity and insufficient antibacterial effect for the complete elimination of bacterial infections. The use of Ag in the form of nanoparticles (NPs, 1–100 nm) allows to control the release of antibacterial Ag ions but is still not sufficient to eliminate infection and avoid cytotoxicity. In this study, we tested the potency of differently functionalized copper oxide (CuO) NPs to enhance the antibacterial properties of Ag NPs. The antibacterial effect of the mixture of CuO NPs (CuO, CuO–NH2 and CuO–COOH NPs) with Ag NPs (uncoated and coated) was studied. CuO and Ag NP combinations were more efficient than Cu or Ag (NPs) alone against a wide range of bacteria, including antibiotic-resistant strains such as gram-negative Escherichia coli and Pseudomonas aeruginosa as well as gram-positive Staphylococcus aureus, Enterococcus faecalis and Streptococcus dysgalactiae. We showed that positively charged CuO NPs enhanced the antibacterial effect of Ag NPs up to 6 times. Notably, compared to the synergy of CuO and Ag NPs, the synergy of respective metal ions was low, suggesting that NP surface is required for the enhanced antibacterial effect. We also studied the mechanisms of synergy and showed that the production of Cu+ ions, faster dissolution of Ag+ from Ag NPs and lower binding of Ag+ by proteins of the incubation media in the presence of Cu2+ were the main mechanisms of the synergy. In summary, CuO and Ag NP combinations allowed increasing the antibacterial effect up to 6 times. Thus, using CuO and Ag NP combinations enables to retain excellent antibacterial effects due to Ag and synergy and enhances beneficial effects, since Cu is a vital microelement for human cells. Thus, we suggest using combinations of Ag and CuO NPs in antibacterial materials, such as wound care products, to increase the antibacterial effect of Ag, improve safety and prevent and cure topical bacterial infections.

Microwave mediated synthesis of catalytic fluorescent carbon dots (Cdots) has been reported using biodegradable starch as precursor. The as-synthesized Cdots were then characterized using various techniques such as fluorescence spectroscopy, fourier-transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM) and x-ray photoelectron spectroscopy (XPS) analysis. Interestingly, Cdots showed high catalytic activity in the photo-reduction of Ag+ to silver nanoparticles (Ag NPs). During the photo-reduction process, no additional surface passivating agents was needed to stabilize the Ag NPs. Further, TEM results indicated the formation of Cdot–Ag NP nanocomposite i.e. Ag NPs surrounded with Cdots, and the emission intensity of Cdots was significantly decreased whereas the lifetime of Cdots remained almost unaltered in the presence of Ag NPs following static quenching. Finally, combination therapy of Cdots and Ag NPs using Cdot–Ag NP nanocomposite was performed which indicated synergistic bactericidal activity against antibiotic resistant recombinant E. coli bacteria. The treatment elevated the reactive oxygen species (ROS) level as compared to its individual components. Additionally, the flow cytometer study demonstrated that combination therapy causing bacterial cell wall perforation that was possibly leading to synergistic bactericidal activity against both Gram positive and Gram negative bacteria. The presence of Cdots on the surface of the Ag NPs due to their ground state complexation, possibly facilitated electrons towards Ag NPs which enhanced the ROS production in comparison to only Ag NPs.

The high antibiotic resistance of Pseudomonas aeruginosa (PA) makes it critical to develop alternative antimicrobial agents that are effective and affordable. One of the many applications of silver nanoparticles (Ag NPs) is their use as an antimicrobial agent against bacteria resistant to common antibiotics. The key purpose of this research was to assess the antibacterial and antibiofilm effectiveness of biosynthesized Ag NPs against six biofilm-forming clinically isolated strains of PA and one reference strain (ATCC 27853). Ag NPs were biosynthesized using a seed extract of Peganum harmala as a reducing agent. Ag NPs were characterized by Ultraviolet–visible (UV–Vis) spectroscopy and scanning transmission electron microscopy (STEM). The effect of Ag NPs on biofilm formation and eradication was examined through micro-titer plate assays, and the minimal inhibitory (MIC) and minimum bactericidal (MBC) concentrations determined. In addition, real-time polymerase chain reactions (RT-PCR) were performed to examine the effects of Ag NPs on the expression of seven PA biofilm-encoding genes (LasR, LasI, LssB, rhIR, rhII, pqsA and pqsR). The biosynthesized Ag NPs were spherically-shaped with a mean diameter of 11 nm. The MIC for each PA strain was 15.6 µg/ml, while the MBC was 31.25 µg/ml. All PA strains exposed to Ag NPs at sub-inhibitory concentrations (0.22–7.5 µg/ml) showed significant inhibitory effects on growth and biofilm formation. Biomass and biofilm metabolism were reduced dependent on Ag NP concentration. The expression of the quorum-sensing genes of all strains were significantly reduced at an Ag NP concentration of 7.5 µg/ml. The results demonstrate the extensive in-vitro antibacterial and antibiofilm performance of Ag NPs and their potential in the treatment of PA infection. It is recommended that future studies examine the possible synergy between Ag NPs and antibiotics.

Silver nanoparticles: Green synthesis and their antimicrobial activities

The topic of this investigation was to evaluate the microbial contamination of household sponges, biosynthesize of silver nanoparticles (Ag NPs) by Gliocladium deliquescens cell-free supernatant, and estimate the efficiency of Ag NPs as an acceptable disinfectant. The 23 factorial design was applied for the optimization of Ag NPs synthesis. Silver nitrate (AgNO3) concentration was the main positive impact on Ag NP biosynthesis. Various gamma irradiation doses were used in Ag NP production where the highest yield production was at 25.0 kGy. Ag NPs were characterized by UV-Vis. spectroscopy, The Fourier-transform infrared spectroscopy analysis (FTIR), dynamic light scattering (DLS), X-ray diffraction (XRD), and transmission electron microscope (TEM). Ag NPs were monodispersed spherical-shaped with 9.68 nm mean size. Two hundred sponge samples that were collected from different Egyptian household furniture and kitchens were highly contaminated by various contaminants including Salmonella spp., Staphylococcus spp., coliform bacteria, Gram-negative bacteria, yeasts, and molds. Ag NPs showed functional antimicrobial activity against all the microbial contaminants; Salmonella spp. was completely inhibited by Ag NP (50.0 μg/mL) treatment. The Ag NPs have the maximum inhibition zone against Salmonella spp. (14 mm) compared with the Staphylococcus spp. (12.3 mm). The minimum inhibitory concentration (MIC) of Ag NPs against Salmonella spp. and Staphylococcus spp. were 6.25 μg/ mL and 12.5 μg/ mL, respectively. The antibiofilm activity of Ag NPs was the highest at the concentration of 50.0 μg/mL recording 63.3 % for Salmonella spp. and 54.5 % for Staphylococcus spp. Ag NPs may find potent disinfectant applications for household purposes.

Comparison of nanosilver removal by flocculent and granular sludge and short- and long-term inhibition impacts

The rapidly increasing use of silver nanoparticles (Ag NPs) in consumer products and medical applications has raised ecological and human health concerns. A key question for addressing these concerns is whether Ag NP toxicity is mechanistically unique to nanoparticulate silver, or if it is a result of the release of silver ions. Furthermore, since Ag NPs are produced in a large variety of monomer sizes and coatings, and since their physicochemical behavior depends on the media composition, it is important to understand how these variables modulate toxicity. We found that a lower ionic strength medium resulted in greater toxicity (measured as growth inhibition) of all tested Ag NPs to Caenorhabditis elegans and that both dissolved silver and coating influenced Ag NP toxicity. We found a linear correlation between Ag NP toxicity and dissolved silver, but no correlation between size and toxicity. We used three independent and complementary approaches to investigate the mechanisms of toxicity of differentially coated and sized Ag NPs: pharmacological (rescue with trolox and N-acetylcysteine), genetic (analysis of metal-sensitive and oxidative stress-sensitive mutants), and physicochemical (including analysis of dissolution of Ag NPs). Oxidative dissolution was limited in our experimental conditions (maximally 15% in 24 h) yet was key to the toxicity of most Ag NPs, highlighting a critical role for dissolved silver complexed with thiols in the toxicity of all tested Ag NPs. Some Ag NPs (typically less soluble due to size or coating) also acted via oxidative stress, an effect specific to nanoparticulate silver. However, in no case studied here was the toxicity of a Ag NP greater than would be predicted by complete dissolution of the same mass of silver as silver ions.