Silver Nanostructures Research Articles

Influence of annealing on optical, morphological and electrophysical properties of granular silver nanostructures

The optical, morphological and electrophysical properties of silver nanostructures fabricated by electron beam evaporation and annealed at temperatures of 145 and 195 °C were studied. All samples are characterized by the presence of a pronounced surface plasmon absorption resonance band in the visible range and represent close-packed monolayers of nanoparticles, the average sizes of which increase from ~10 nm in the original samples to ~35–40 nm and ~45–60 nm in the annealed ones, depending on the annealing temperature. The influence of various factors on the spectral characteristics of samples, including the size of nanoparticles and electrodynamic interactions between nanoparticles, is discussed. It has been shown that all granular nanostructures studied, both initial and annealed, are highly resistive. It has been established that for the initial and annealed at 145 °C samples, near low values of the applied voltage, a dependence of the current on the irradiation wavelength can be traced, with its value changing up to two orders of magnitude for certain wavelengths.

Comparison of Survivin Determination by Surface-Enhanced Fluorescence and Raman Spectroscopy on Nanostructured Silver Substrates.

Survivin belongs to a family of proteins that promote cellular proliferation and inhibit cellular apoptosis. Its overexpression in various cancer types has led to its recognition as an important marker for cancer diagnosis and treatment. In this work, we compare two approaches for the immunochemical detection of survivin through surface-enhanced fluorescence or Raman spectroscopy using surfaces with nanowires decorated with silver nanoparticles in the form of dendrites or aggregates as immunoassays substrates. In both substrates, a two-step non-competitive immunoassay was developed using a pair of specific monoclonal antibodies, one for detection and the other for capture. The detection antibody was biotinylated and combined with streptavidin labeled with rhodamine for the detection of surface-enhanced fluorescence, while, for the detection via Raman spectroscopy, streptavidin labeled with peroxidase was used and the signal was obtained after the application of 3,3',5,5'-tetramethylbenzidine (TMB) precipitating substrate. It was found that the substrate with the silver dendrites provided higher fluorescence signal intensity compared to the substrate with the silver aggregates, while the opposite was observed for the Raman signal. Thus, the best substrate was used for each detection method. A detection limit of 12.5 pg/mL was achieved with both detection approaches along with a linear dynamic range up to 500 pg/mL, enabling survivin determination in human serum samples from both healthy and ovarian cancer patients for cancer diagnosis and monitoring purposes.

An Overview of the Anticancer Potential of Silver Nanostructures against Cervical Cancer.

Women are impacted by the extremely common cancer known as cervical cancer worldwide. Although preventive vaccines for cervical cancer are successful, treatment of cervical cancer is far less satisfactory because of multidrug resistance and side effects. There is an increasing need for alternative treatment modalities due to the rather aggressive and non-specific nature of conventional chemotherapeutics. With the advent of new technologies, scientists are working harder to create novel drug delivery strategies for chemotherapy of cervical cancer. Metal nanoparticles, and particularly silver nanoparticles, are a relatively new class with a lot of promise in the field of cancer biology. Nanoparticle therapeutics are attractive platforms for clinically relevant drug development because of their powerful anti-cancer properties, correspondingly attenuated side effects, and cancer-specific targeting. In this review, we provide an overview of the most recent uses of nanotechnology, particularly silver nanostructures, in the diagnosis and treatment of cervical cancer. The salient features of silver nanoparticle-based therapeutic concepts that are novel, viable, and attainable are emphasized in this review, along with those that pose a significant obstacle to their progress toward clinical application.

Near-infrared plasmonic sensors based on surface plasmon resonances in two-dimensional metasurfaces of silver nanostructures

Near-infrared plasmonic sensors based on surface plasmon resonances in two-dimensional metasurfaces of silver nanostructures

Enhanced SERS performance of cavity-hosting silver dendrites grown over TiO2 nanotubes

Silver nanostructures, utilized as SERS substrates, consistently exhibit exceptional performance in detecting organic compounds through Raman spectroscopy, primarily due to the electromagnetic enhancement mechanism. This study explores an advanced SERS substrate composed of cavities formed by silver dendrites (Ag-Ds) on TiO2 nanotubes (TiO2-NT), demonstrating exceptional performance in detecting organic compounds through Raman spectroscopy. TiO2-NT acts as a template, guiding the nucleation and growth of Ag-D to create the cavity structures. The deposition time of silver significantly influences substrate performance in detecting Rhodamine 6G (R6G) and Ibuprofen (IB). It has been observed that an extended deposition time diminishes the enhancement factor. In contrast, a shorter deposition time yields notable enhancement due to the combined effects of electromagnetic and chemical enhancement mechanisms. An optimum deposition time limits dendrite growth, forming cavities where the electric field couples with multiple light reflections, further amplifying the SERS enhancement. The cavity-hosted Ag-D/TiO2-NT substrate achieves an impressive analytic SERS enhancement factor of up to 2 × 109, enabling the detection of R6G and IB at a low detection limit of 10-12 M.

Quantification of Pectobacterium carotovorum subsp. carotovorum in kimchi cabbage using a surface-enhanced Raman scattering platform with silver nanostructures

Pectobacterium carotovorum subsp. carotovorum (PCC) is a notorious plant pathogen responsible for severe soft rot in kimchi cabbage, which results in significant economic losses. To detect PCC rapidly and accurately in kimchi cabbage, we developed a surface-enhanced Raman scattering (SERS) substrate on which silver nanospheres (AgNSs), nanowires (AgNWs), and nanoseeds are combined on a polydimethylsiloxane (PDMS) platform. The incorporation of Ag nanoseeds creates a higher density of hotspots, which ensures a low detection limit of 1.001 CFU/mL. Electron microscopy and spectroscopic analyses confirmed the successful fabrication of the substrate and its enhanced sensitivity. The SERS substrate exhibits excellent selectivity by effectively distinguishing PCC from other bacteria commonly found in kimchi cabbage. The substrate gives rise to strong Raman signals across PCC concentrations ranging from 101 to 106 CFU/mL. Additionally, a predictive model was developed for accurately detecting PCC in real kimchi cabbage samples, and the results were validated by polymerase chain reaction measurements. A sensitive, selective, and rapid approach for PCC detection in kimchi cabbage that offers a promising improvement over existing methodologies is presented.

Polyvinyl Alcohol Capped Silver Nanostructures for Fortified Apoptotic Potential Against Human Laryngeal Carcinoma Cells Hep-2 Using Extremely-Low Frequency Electromagnetic Field.

: Polyvinyl alcohol-capped silver nanostructures (cAgNSs) were investigated in order to enhance the cytotoxicity, pro-apoptotic, and oxidant patterns of in human laryngeal carcinoma Hep-2 cells by employing a 50 mT electromagnetic field (LEMF) for 30 min. Wet chemical reduction was used to synthesize the cAgNSs, and after they had been capped with polyvinyl alcohol, they were specifically examined for particle size analysis and structural morphology. To visualize how the silver may attach to the protein targets, a molecular docking study was conducted. Estimation of cytotoxicity, cell cycle progression supported by mRNA expression of three apoptotic-promoting genes and one apoptotic-resisting. Particle size analysis results were a mean particle size of 157.3±0.5 nm, zeta potential value of -29.6 mV±1.5 mV, and polydispersity index of 0.31±0.05. Significantly reduction of IC50 against Hep-2 cells by around 6-fold was concluded. Also, we obtained suppression of the proliferation of Hep-2 cells, especially in the G0/G1 and S phases. Significant enhanced mRNA expression revealed enhanced induced CASP3, p53, and Beclin-1 mediated pro-apoptosis and induced NF-κB mediated autophagy in Hep-2 cells. Augmented levels of GR, ROS and MDA as oxidative stress biomarkers were also obtained. HE staining of Hep-2 cells exposed to cAgNSs and LEMF confirmed the enhanced apoptotic potential comparatively. By conclusion, the developed nano-sized structures with the aid of extremely-low frequency electromagnetic field were successful to fortify the anti-cancer profile of cAgNSs in Hep-2 cells.

Bimodal functionality of highly conductive nanostructured silver film towards improved performance of photosystem I-based graphene photocathode

We present the novel design of photosystem I (PSI)-based biosolar cell, whereby conductive transparent electrode materials, such as ITO or FTO, are replaced with glass covered with silver island film. This nanostructured metallic layer combines high electric conductance with enhancing the absorption efficiency of the PSI biocatalyst via the plasmonic effect. We demonstrate strong enhancement of the photocurrent generated in the biohybrid electrode composed of oriented layers of PSI reaction centers due to plasmonic interactions of the PSI fluorophores and redox centres with the conductive silver island film.

Plasmonic Ag Nanoparticles on SiC for Use as SERS Substrate and in Integrated Optical Sensors for Bio-Chemical Applications

Development of optical chemical sensors for the detection of specific toxic chemicals at ultratrace levels and analysis of complex mixtures is crucial for new green and safe technologies [1, 2]. Metallic structures confined at the nanoscale acquire interesting properties such as strongly localizing E fields on their surfaces through Plasmonic Resonance under stimuli of light at certain wavelengths. This nanostructures are called plasmonic structures [3–5]. This effect is exploited to amplify the optical signal obtained by the molecules of interest, located near plasmonic structures [3, 6]. Purpose of the work is the development of innovative, easy to manufacture and cheap optical active layer consisting of Plasmonic Ag Nanoparticles on a Wide Band Gap semiconductor material such as Silicon Carbide to be used as substrate for Surface Enhanced Raman Scattering or for the fabrication of integrated optical sensor for remote chemical and biological applications. In this contest, the phenomenon of Ag thin film thermal dewetting on SiC substrate was implemented to develop a simple nanoparticles synthetic approach. Scanning Electron Microscopy confirmed the formation of Ag nanoparticles by thermal annealing of thin silver film. 4-MBA was used as probe molecule for SERS phenomenon investigation. The formation of a covalent bond between the silver nanostructures, acting as plasmonic "hot spots", and the species of interest enable its detection at very low concentrations, in the range of 10-5 M or less, in both Raman and UV-Vis configurations.

Nanostructure silver absorbance with polarized light spectroscopy (PLS) and mobile imaging

This study presents a novel interdisciplinary approach for characterizing the optical properties of nanostructured silver films, combining methodologies from polarized light spectroscopy (PLS) and mobile app-based spectroscopic image detection. Silver nanofilms were deposited using electron beam evaporation (EBE) and subsequently analyzed for their absorbance across the visible light spectrum through PLS spectroscopy. The innovative aspect of this study lies in the validation of PLS spectral data using a mobile application developed with MIT App Inventor, which analyzes the intensity of light beams captured in images taken by a smartphone. The findings indicate that the silver nanofilm exhibits peak absorbance at approximately 400 nm within the violet region, corroborated by the mobile app’s data, which shows the lowest light intensity. However, discrepancies were observed from 500 to 600 nm, likely due to ambient light interferences and inherent optical phenomena such as diffraction, reflection, and refraction. Despite these deviations, the app’s readings closely align with the PLS data, supporting the film’s selective absorption properties. This study demonstrates the potential of this multidisciplinary technique in nanomaterial research, highlighting the application of nanotechnology in material science and the transformative potential of integrating software engineering for in-depth material characterization. These findings open avenues for advancements in both academic and practical applications.

Engineering the apparent quantum yield and emission rate of fluorophore molecules by coupling fluorophore dipoles with plasmon modes of gold using low frequency electric fields

Abstract Localized surface plasmons produced by gold and silver nanostructures have been utilized to enhance the intensity of fluorophore molecules. The issue with using nanostructure plasmons for fluorescence enhancement is their short-range nature (5–50 nm from the nanostructures), which limits accessibility to a few molecules. In addition, fluorophore dipoles needed to be aligned with the plasmon electric fields to maximize the fluorescence enhancement. To address these issues, we used low-frequency electric fields (<5 MHz) and commercially available nanorod and nanosphere samples and studied their effectiveness in enhancing the fluorescence of fluorophore-labeled short single-stranded DNA molecules (22 bases). We demonstrated that DNA molecules and nanorod particles can effectively be manipulated around the charging frequency of DNA molecules (∼3 MHz). Nanorod particles enhanced the fluorescence emission rate by ∼50-fold. When the 3 MHz electric field was introduced, the emission rate increased to over 700-fold. We also found that the introduction of a 3 MHz electric field aided the enhancement of the intrinsic quantum yield fluorophore molecules, which resulted in over a 1000-fold fluorescence enhancement. This enhancement was due to the very high electric produced by polarized DNA dipoles at 3 MHz, which resulted in a torque on fluorophore dipoles and subsequently aligning the fluorophore dipole axis with the plasmon electric field. At a fundamental level, our results demonstrate the role of the low-frequency electric field in the fluorophore–plasmon coupling. These findings can directly be applied to many fluorescence detection systems, including the development of biosensors.

(Invited) Mie Resonant Silicon Nanosphere Nanoantenna for Fluorescence Enhancement

A nanoantenna is a device that manipulates light propagation and enhances light-matter interaction at the nanoscale. Integration of an emitter into a nanoantenna capable of increasing local density of photonic states at the emission wavelength results in the enhancement of the spontaneous emission rate (Purcell effect) and modifies the emission spectrum. A nanoantenna can also control the directionality and radiation pattern of an emitter. Traditionally, plasmonic nanoantennas made from gold or silver nanostructures supporting localized surface plasmon resonances had been the main stream of the nanoantenna research. Recently, high refractive index nanoparticles having low-order Mie resonances have been attracting attention as a new type of dielectric nanoantennas. Advantages of a dielectric nanoantenna compared to a plasmonic one are the smaller loss and the possession of magnetic type Mie resonances arising from light-induced displacement current. By properly controlling the overlap of the magnetic and electric multipole resonances, radiation patters of an emitter placed nearby can be tailored with high degree of freedom. Furthermore, magnetic-type Mie resonances can couple with higher-order optical transitions of an emitter such as a magnetic-dipole transition, and thus can enhance and control radiation from otherwise weak forbidden transitions.Recently, we have succeeded in producing perfectly spherical nanoparticles of crystalline silicon (Si) in 100-300 nm in diameters. These Si nanospheres exhibit the electric and magnetic multipole resonances at the optical frequency [1]. In this presentation, we first show scattering and absorption properties of the Mie resonant Si nanospheres. Especially, we show that solutions of size-purified Si nanospheres exhibit vivid structural color and the solutions can be used as structural color inks. We then show that the solutions can preserve helicity of incoming circularly-polarized light and can enhance local chiral fields around nanospheres [2, 3]. This property can be used to improve the sensitivity of enantiomer-selective chiral molecular sensing. We then show some examples of enhanced light-matter interaction by Si nanoparticles. These include enhancement of magnetic dipole transitions of an emitter by magnetic-type Mie resonances of Si nanospheres (magnetic Purcell effect) [4, 5], enhancement of excitation and emission processes of in-plane dipoles of monolayer transition metal dichalcogenides (TMDC) [6], and enhancement of a spin forbidden singlet-to-triplet absorption transition of a molecule by Si nanodisks [7, 8].

Fabrication of multifunctional wool textile using the synthesis of silver-modified N-doped ZnO/TiO2 photocatalysts

Photocatalysts and noble metals have attracted considerable attention for their potential in addressing global environmental pollution through photochemical processes. At low temperatures, multifunctional self-cleanable wool fabric was developed through green photo-sonosynthesis of N–Ag/TiO2/ZnO. A narrower bandgap of the hybrid photocatalyst, the surface plasmonic resonance effect of silver nanostructures, and nitrogen doping resulted in synergistically enhanced self-cleaning activity. The self-cleaning activity was evaluated by monitoring the discoloration of methylene blue stains on the wool fabric exposed to natural sunlight, using CIELAB color space and ΔE measurements. The ΔE value of the N–Ag/TiO2/ZnO-sonicated wool was superior, showing a value of 45.9 compared to 15.7 for the control and 28.7 for the sample coated by the stirrer. Furthermore, the nanocomposite construction improved tensile strength, enhanced fabric hydrophilicity, and reduced the yellowness index. Additionally, the synthesis of TiO2 and silver particles on ZnO particles increased surface resistance to acid, reducing ZnO acid solubility. The reflectance of the non-treated wool ranged from 5 to 20 % within 200–380 nm, while the reflectance of the Ag/TiO2/ZnO-sonicated sample remained constant at 4 %, exhibiting protection against UV rays. AATCC test revealed 100 % bacteria reduction against E. coli and S. aureus and 99 % against C. albicans fungus for N–Ag/TiO2/ZnO-sonicated sample. Moreover, cell culture assays demonstrated a viability of over 70 %, indicating non-cytotoxicity.

Effect of blue light irradiation on the formation of silver nanostructures in polyvinyl alcohol nanocomposite films

Effect of blue light irradiation on the formation of silver nanostructures in polyvinyl alcohol nanocomposite films

Rapid, microwave-assisted deposition of anisotropic silver nanostructures on various substrates.

A facile, rapid, and scalable in situ microwave-assisted solvothermal technique (MAST) has been developed to deposit anisotropic silver nanoparticles (AgNP) on various substrates in a solution medium. SEM-EDS and XRD were used to characterize the morphology and structure of the deposits. Deposition on non-patterned aluminium led to near-spherical AgNP agglomerates all across the surface. Deposition on the glass at optimum solution concentration led to mirror-like coatings comprising spherical ∼50 nm particles, whereas no coating occurred at lower concentrations. AgNPs decorated the hexagonal pattern formed on a nano-patterned aluminium (NPA) substrate. Among various precursor concentrations used for deposition on NPA, the 10 μM concentration resulted in conformal deposition, with nanoparticles decorating the hexagons in NPA. In contrast, AgNP density was lower in the concave dimples on NPA. Our work demonstrates a quick and easy approach for the AgNPs' deposition, with control over size, and morphology. It can be used for deposition on large substrates, potentially making it suitable for surface-enhanced spectroscopic applications.

Plasmon-Exciton Interaction at the Nanoscale: Silver Is More "Precious" than Gold!

Predictive understanding of factors affecting plasmon-exciton coupling is crucial for the successful realization of the exciting potentials of plexcitonic nanostructures. Here, we systematically investigate the role of plasmonic metals in controlling the plasmon-exciton coupling strength. We use gold and silver nanoprisms, having identical LSPR maxima, as the plasmonic components and form two plexciton hybrids with the J-aggregates of a cyanine dye. Single-particle spectroscopy is employed to study and compare the abilities of gold and silver in influencing plasmon-exciton interaction at the nanoscale. Despite much faster plasmon dephasing than its gold counterpart, the silver nanoprism exhibits greater Rabi splitting. We reveal that the smaller plasmon mode-volume despite having larger physical volume, superior local electric-field enhancement, and smaller Ohmic losses compared to gold, enables the silver nanoprism to defy the pronounced plasmon decoherence effects and to show stronger plasmon-exciton coupling. These findings suggest that silver nanostructures should be the unequivocal choice over gold when "strong coupling" is desired for any application.

Combined Electrochemical Deposition and Photo-Reduction to Fabricate SERS-Active Silver Substrates: Characterization and Application for Malachite Green Detection in Aquaculture Water.

This research introduces a novel approach using silver (Ag) nanostructures generated through electrochemical deposition and photo-reduction of Ag on fluorine-doped tin oxide glass substrates (denoted as X-Ag-AgyFTO, where 'X' and 'y' represent the type of light source and number of deposited cycles, respectively) for surface-enhanced Raman spectroscopy (SERS). This study used malachite green (MG) as a Raman probe to evaluate the enhancement factors (EFs) in SERS-active substrates under varied fabrication conditions. For the substrates produced via electrochemical deposition, we determined a Raman EF of 6.15 × 104 for the Ag2FTO substrate. In photo-reduction, the impact of reductant concentration, light source, and light exposure duration were examined on X-Ag nanoparticle formation to achieve superior Raman EFs. Under optimal conditions (9.0 mM sodium citrate, 460 nm blue-LED at 10 W for 90 min), the combination of blue-LED-reduced Ag (B-Ag) and an Ag2FTO substrate (denoted as B-Ag-Ag2FTO) exhibited the best Raman EF of 2.79 × 105. This substrate enabled MG detection within a linear range of 0.1 to 1.0 µM (R2 = 0.98) and a detection limit of 0.02 µM. Additionally, the spiked recoveries in aquaculture water samples were between 90.0% and 110.0%, with relative standard deviations between 3.9% and 6.3%, indicating the substrate's potential for fungicide detection in aquaculture.

Self-Cleaning Antibacterial Composite Coating of Fluorinated Acrylic Resin and Ag/SiO2 Nanoparticles with Quaternary Ammonium.

With improvements in living standards, the demand for antibacterial self-cleaning coatings has significantly increased. In this work, self-cleaning coatings with antibacterial properties were fabricated by spray-coating a composite of fluorinated acrylic resin and Ag/SiO2 nanoparticles with quaternary ammonium salts. The synergistic action of the quaternary ammonium salts and silver nanostructures caused the coating to show a dual antibacterial effect. The Ag/SiO2 nanoparticles roughened the coating's surface and, in combination with the fluorinated chains, provided the surface a superhydrophobic self-cleaning property with a contact angle of 156° and a sliding angle of less than 2°. Notably, the composite coating withstood 100 abrasion cycles without losing its superhydrophobicity and the contact angle is still exceeded 150° after 60 h of immersion solutions with different pH values, demonstrating outstanding wear resistance and acid/alkali stability. The incorporation of nanostructured antibacterial agents was effective in improving the roughness and antibacterial properties of the low-surface-energy resin, resulting in a self-cleaning antibacterial composite coating. This method may pave a new route for the design of functional coating materials with excellent overall performance.

Eu-doped chitosan carbon dot/dendritic silver nanostructure-based biosensor for BRAF detection in thyroid cancer exosome

In this work, a novel electrochemiluminescence (ECL) biosensor has been constructed with Eu-doped chitosan carbon dot (Eu: Cs dot) and dendritic silver nanostructure. Firstly, Eu: Cs dots were synthesized as ECL tags, which not only possessed exceptional electrochemical characters and intense luminescence, but also can reacted with H2O2 as co-reactant to generate ECL signal. Furthermore, dendritic silver nanostructure with conductive gel was successfully prepared as sensing interface. The dendritic silver nanostructure with conductive gel displayed the ideal conductivity, good electrochemical stability, which can enhance the ECL intensity of Eu: CS dots. Finally, BRAF V600E from thyroid cancer exosome in the clinic eluate can be captured and detected. The results indicated the relative association between BRAF V600E mutation and lymphatic metastasis, which can be used in assessing thyroid cancer progression for advancing clinical diagnosis applications.

Unveiling the industrial photocatalytic dye degradation of textile effluents using tailored eco-friendly AgO Nanoparticles

<p>In this study, tamarind leaf extract was used to effectively produce silver oxide (AgO) nanoparticles. Crystal violet (CV), Alizarin red (AR), Reactive black (RB), and rhodamine b (Rh B) degradation were examined to evaluate the effectiveness of AgO NPs. XRD patterns, UV-visible spectroscopy, Fourier transform infrared spectroscopy, and scanning electron microscope was used to analyze the AgO NPs. SEM observations showed spherical morphology size ranging at an average of 58.17 nm. Silver and oxygen were the only elements in the nanostructure, as shown by EDS chemical maps. The synthetic silver nanostructure, with a crystal size of 38 nm, was verified by X-ray diffraction to have the usual cubic structure. The nanostructure showed degradation efficiencies in Crystal violet, Alizarin red, Reactive black, and Rhodamine B, indicating excellent degradation efficiency. All of these results point to the effective production of AgO NPs without the use of any hazardous chemicals, and they point to this material as a potentially beneficial substance for eliminating toxic dye from wastewater made by commercial colouring processes.</p>