Plasmonic Nanomaterials Research Articles

Recent Development in Plasmonic Nanobiosensors for Viral DNA/RNA Biomarkers

Recently, due to the coronavirus pandemic, the need for early diagnosis of infectious diseases, including viruses, is emerging. Though early diagnosis is essential to prevent infection and progression to severe illness, there are few technologies that accurately measure low concentrations of biomarkers. Plasmonic nanomaterials are attracting materials that can effectively amplify various signals, including fluorescence, Raman, and other optical and electromagnetic output. In this review, we introduce recently developed plasmonic nanobiosensors for measuring viral DNA/RNA as potential biomarkers of viral diseases. In addition, we discuss the future perspective of plasmonic nanobiosensors for DNA/RNA detection. This review is expected to help the early diagnosis and pathological interpretation of viruses and other diseases.

Plasmonic Sensing and Switches Enriched by Tailorable Multiple Fano Resonances in Rotational Misalignment Metasurfaces.

Fano resonances that feature strong field enhancement in the narrowband range have motivated extensive studies of light-matter interactions in plasmonic nanomaterials. Optical metasurfaces that are subject to different mirror symmetries have been dedicated to achieving nanoscale light manipulation via plasmonic Fano resonances, thus enabling advantages for high-sensitivity optical sensing and optical switches. Here, we investigate the plasmonic sensing and switches enriched by tailorable multiple Fano resonances that undergo in-plane mirror symmetry or asymmetry in a hybrid rotational misalignment metasurface, which consists of periodic metallic arrays with concentric C-shaped- and circular-ring-aperture unit cells. We found that the plasmonic double Fano resonances can be realized by undergoing mirror symmetry along the X-axis. The plasmonic multiple Fano resonances can be tailored by adjusting the level of the mirror asymmetry along the Z-axis. Moreover, the Fano-resonance-based plasmonic sensing that suffer from mirror symmetry or asymmetry can be implemented by changing the related structural parameters of the unit cells. The passive dual-wavelength plasmonic switches of specific polarization can be achieved within mirror symmetry and asymmetry. These results could entail benefits for metasurface-based devices, which are also used in sensing, beam-splitter, and optical communication systems.

Engineering Plasmon-Enhanced Fluorescent Gold Nanoclusters Using Bovine Serum Albumin as a Novel Separation Layer for Improved Selectivity.

The combination of gold nanoclusters (AuNCs) with surface plasmonic metal nanomaterials is an effective and direct method to improve the photoluminescence efficiency of AuNCs. However, the plasmon-enhanced AuNC luminescence strategies usually utilize silica as the separation layer, which requires further functionalization because the silica layer has no functional groups for in situ bonding of AuNCs. Therefore, it appears as a crucial need to develop an appropriate separation layer for the preparation of plasmon-enhanced AuNC luminescent nanomaterials. In this work, employing bovine serum albumin (BSA) as a novel separation layer, we prepared gold nanoparticles (AuNPs)@BSA@Au35NCs by a controllable and in situ synthesis method. BSA can form a BSA layer on the surface of AuNPs through Au-S bonds. Meanwhile, BSA can reduce AuCl4- ions to generate Au35NCs. In comparison with pure BSA-AuNCs, the quantum yield of the AuNPs@BSA@Au35NCs was increased by nearly 7 times as a result of plasmonic coupling, and the time of in situ synthesis of Au35NCs was shortened by 8 h. More importantly, the preparation of the BSA layer was simple and time-saving without functionalization, in contrast to the previously reported silica layer. Moreover, the simulation calculation of different dimensions determined the optimal binding sites between Au35NCs and BSA, confirming that BSA can be an effective spatial spacer. Finally, it was found that the BSA layer between AuNPs and AuNCs can improve the specificity of AuNCs toward H2S, which is extremely difficult for pure BSA@AuNCs.

Nanoenzyme Reactor-Based Oxidation-Induced Reaction for Quantitative SERS Analysis of Food Antiseptics.

Nanoenzyme reactors based on shell-isolated colloidal plasmonic nanomaterials are well-established and widely applied in catalysis and surface-enhanced Raman scattering (SERS) sensing. In this study, a "double wing with one body" strategy was developed to establish a reduced food antiseptic sensing method using shell-isolated colloidal plasmonic nanomaterials. Gold nano particles (Au NPs) were used to synthesize the colloidal plasmonic nanomaterials, which was achieved by attaching ferrous ions (Fe2+), ferric ions (Fe3+), nitroso (NO-) group, cyanogen (CN-) group, and dopamine (DA) via coordinative interactions. The oxidation-induced reaction was utilized to generate •OH following the Fe2+-mediated Fenton reaction with the shell-isolated colloidal plasmonic nanomaterials. The •OH generated in the cascade reactor had a high oxidative capacity toward acid preservatives. Importantly, with the introduction of the signal molecule DA, the cascade reactor exhibited also induced a Raman signal change by reaction with the oxidation product (malondialdehyde) which improved the sensitivity of the analysis. In addition, the stable shell-isolated structure was effective in realizing a reproducible and quantitative SERS analysis method, which overcomes previous limitations and could extend the use of nanoenzymes to various complex sensing applications.

Colloidal titanium nitride nanobars for broadband inexpensive plasmonics and photochemistry from visible to mid-IR wavelengths

Developing colloidal plasmonic nanomaterials with high carrier density that show optical resonances and photochemical activity extending from the visible to the mid-infrared (MIR) ranges remains a challenging pursuit. Here, we report the fabrication of titanium nitride (TiN) nanobars obtained using a two–step procedure based on a wet chemical route synthesis of TiO2 nanowires and their subsequent high temperature annealing in ammonia flow. Electromagnetic simulations of the resulting TiN nanobars reveal a rich set of optical resonances featuring transverse, longitudinal and mixed transverse–longitudinal plasmonic modes that cover energies from the visible to MIR region. TiN nanobars decorated with Pt co-catalyst nanocrystals show enhanced photocatalytic hydrogen evolution activity in comparison to both isotropic TiN nanospheres of similar size and TiN nanocubes under near infrared excitation at 940 nm due to the enhanced hot electron generation. We also demonstrate that plasmonic TiN nanobars can be used for the detection of furfural molecular vibrations by providing a strong surface enhanced infrared absorption (SEIRA) effect in the MIR region.

Hydrophobic Gold Nanoparticles with Intrinsic Chirality for the Efficient Fabrication of Chiral Plasmonic Nanocomposites.

The development of plasmonic nanomaterials with chiral geometry has drawn extensive attention owing to their practical implications in chiral catalysis, chiral metamaterials, or enantioselective biosensing and medicine. However, due to the lack of effective synthesis methods of hydrophobic nanoparticles (NPs) showing intrinsic, plasmonic chirality, their applications are currently limited to aqueous systems. In this work, we resolve the problem of achieving hydrophobic Au NPs with intrinsic chirality by efficient phase transfer of water-soluble NPs using low molecular weight, liquid crystal-like ligands. We confirmed that, after the phase transfer, Au NPs preserve strong, far-field circular dichroism (CD) signals, attesting their chiral geometry. The universality of the method is exemplified by using different types of NPs and ligands. We further highlight the potential of the proposed approach to realize chiral plasmonic, inorganic/organic nanocomposites with block copolymers, liquid crystals, and compounds forming physical gels. All soft matter composites sustain plasmonic CD signals with electron microscopies confirming well-dispersed nanoinclusions. The developed methodology allows us to expand the portfolio of plasmonic NPs with intrinsic structural chirality, thereby broadening the scope of their applications toward soft-matter based systems.

Plasmon-induced charge transfer desorption/ionization for mass spectrometric analysis of small biomolecules

Laser desorption/ionization (LDI) has been an essential ionization means for biological mass spectrometry (MS). It relies on an energy transfer medium to adsorb the light energy and convert it into other forms of energy to desorb and ionize analyte molecules. Noble metal nanomaterials, which are well-known as plasmonic nanomaterials and exhibit unique plasmonic effects, have been increasingly used in LDI. Various mechanisms were proposed; however, the mechanisms remain to be elucidated and verified, especially for biomolecules. Herein, we proposed a plasmon-induced charge transfer desorption/ionization (PICTDI) mechanism. Upon being shined with a laser beam, plasmonic nanoparticles, such as gold nanoparticles (AuNPs), silver nanoparticles (AgNPs) or their mixture, transfer charges (electrons, protons or other cations) from the nanoparticles to surrounding analytes through surface plasmon, leading to analyte desorption and ionization. Hybrid plasmon-excited LDI surpassed single plasmon-excited mode, which can be proved in both positive and negative ion mode and confirmed by a variety of biomolecules, from nucleosides to saccharides to short peptides. This mechanism provides a sound understanding and a useful guideline for rational design of new plasmonic charge transfer nanomedia.

(Invited) Ultrafast Reducing Power of a Plasmonic Photocatalyst

Plasmonic nanomaterials are promising catalysts for selective, green, and efficient photo-driven processes, however currently the mechanisms involved in plasmon-driven catalysis are under debate. Contributions from processes such as vibrational and electronic energy transfer, electron transfer, or electromagnetic field enhancement could all lead to modified potential energy landscapes in the plasmon-molecule system. We have developed ultrafast and electrochemical surface-enhanced Raman spectroscopic (SERS) techniques to probe the contribution of these processes on the nanometer length scale and femtosecond timescale. This talk will highlight the use of these approaches in quantifying the rate, yield, and lifetime of plasmon-to-molecule charge transfer. We monitor changes in the vibrational spectra of adsorbed molecular species following plasmon excitation with picosecond time resolution, and quantify how many molecules are reduced and how quickly they undergo back electron transfer. Overall, these methods allow for quantification of the ultrafast reducing power of a plasmonic surface, and suggest routes for optimizing plasmonic systems for efficient and selective photochemistry.

Plasmonic Nanostructures-Decorated ZIF-8-Derived Nanoporous Carbon for Surface-Enhanced Raman Scattering

Surface-enhanced Raman scattering (SERS) is considered to be a highly sensitive platform for chemical and biological sensing. Recently, owing to their high porosity and large surface area, metal–organic frameworks (MOFs) have attracted considerable attention in sensing applications. Porous carbon nanostructures are promising SERS substrates due to their strong broadband charge-transfer resonance and reproducible fabrication. Furthermore, an extraordinarily large enhancement of the electromagnetic field enables plasmonic nanomaterials to be ideal SERS substrates. Here, we demonstrate the porous Au@Ag nanostructure-decorated MOF-derived nanoporous carbon (NPC) for highly efficient SERS sensing. Specifically, this plasmonic nanomaterial–NPC composite offers high Raman signal enhancement with the ability to detect the model Raman reporter 2-naphthalenethiol (2-NT) at picomolar concentration levels.

Plasmon-Induced Semiconductor-Based Photo-Thermal Catalysis: Fundamentals, Critical Aspects, Design, and Applications

Photo-thermal catalysis is among the most effective alternative pathways used to perform chemical reactions under solar irradiation. The synergistic contributions of heat and light during photo-thermal catalytic processes can effectively improve reaction efficiency and alter design selectivity, even under operational instability. The present review focuses on the recent advances in photo-thermal-driven chemical reactions, basic physics behind the localized surface plasmon resonance (LSPR) formation and enhancement, pathways of charge carrier generation and transfer between plasmonic nanostructures and photo-thermal conversion, critical aspects influencing photo-thermal catalytic performance, tailored symmetry, and morphology engineering used to design efficient photo-thermal catalytic systems. By highlighting the multifield coupling benefits of plasmonic nanomaterials and semiconductor oxides, we summarized and discussed several recently developed photo-thermal catalysts and their catalytic performance in energy production (CO2 conversion and H2 dissociation), environmental protection (VOCs and dyes degradation), and organic compound synthesis (Olefins). Finally, the difficulties and future endeavors related to the design and engineering of photo-thermal catalysts were pointed out to draw the attention of researchers to this sustainable technology used for maximum solar energy utilization.

Site-selective introduction of MnO2 co-catalyst onto gold nanocubes via plasmon-induced charge separation and galvanic replacement for enhanced photocatalysis.

For energy harvesting with plasmonic photocatalysis, it is important to optimize geometrical arrangements of plasmonic nanomaterials, electron (or hole) acceptors, and co-catalysts so as to improve the charge separation efficiency and suppress charge recombination. Here, we employ a photocatalytic system with Au nanocubes on TiO2 and introduce MnO2 as an oxidation co-catalyst onto the nanocubes via site-selective oxidation based on plasmon-induced charge separation (PICS). However, it has been known that PbO2 is the only material that can be deposited onto Au nanomaterials through PICS with sufficient site-selectivity. Here we addressed this issue by introducing an indirect approach for MnO2 deposition via site-selective PbO2 deposition and subsequent galvanic replacement of PbO2 with MnO2. The indirect approach gave nanostructures with MnO2 introduced at around the top part, bottom part, or entire surface of the Au nanocubes on a TiO2 electrode. The activity of those plasmonic photocatalysts was strongly dependent on the location of MnO2. The key to improving the activity is to separate MnO2 from TiO2 to prevent recombination of the positive charges in MnO2 with the negative ones in TiO2.

Chemical Mechanism-Dominated and Reporter-Tunable Surface-Enhanced Raman Scattering via Directional Supramolecular Assembly.

Molecular resonance can be strengthened by charge transfer, profiting chemical mechanism (CM)-related surface-enhanced Raman scattering (SERS). Herein a supramolecular assembly enabled SERS system is established by functionalizing para-sulfonatocalix[4]arene (pSC4) onto Au3Cu nanocrystals (NCs). Due to the cooperation of Au and Cu, pSC4 is directionally assembled on the surface of Au3Cu NCs via van der Waals force, enabling photoinduced and hydrogen bond-induced charge transfer, which remarkably enhances the Raman scattering of methylene blue (MB) captured by pSC4. In particular, for the C-N and C-C stretching of MB, the contributions of resonance Raman scattering increase up to 80%. In addition, the SERS system is able to display affinities of different host-guest interactions, and further employed to evaluate effects of drugs for Alzheimer's disease. In this work, charge transfer is realized by performing supramolecular assembly on the surface of plasmonic nanomaterials, providing an avenue to design CM-related and reporter-tunable SERS systems.

Recent Advances in Silver Nanostructured Substrates for Plasmonic Sensors.

Noble metal nanostructures are known to confine photon energies to their dimensions with resonant oscillations of their conduction electrons, leading to the ultrahigh enhancement of electromagnetic fields in numerous spectroscopic methods. Of all the possible plasmonic nanomaterials, silver offers the most intriguing properties, such as best field enhancements and tunable resonances in visible-to-near infrared regions. This review highlights the recent developments in silver nanostructured substrates for plasmonic sensing with the main emphasis on surface plasmon resonance (SPR) and surface-enhanced Raman spectroscopy (SERS) over the past decade. The main focus is on the synthesis of silver nanostructured substrates via physical vapor deposition and chemical synthesis routes and their applications in each sensing regime. A comprehensive review of recent literature on various possible silver nanostructures prepared through these methodologies is discussed and critically reviewed for various planar and optical fiber-based substrates.

Noble-metal free plasmonic nanomaterials for enhanced photocatalytic applications—A review

Plasmonic nanomaterial catalysis is currently at the frontier of photocatalysis, overcoming the limitations of wide bandgap semiconductors for light absorption. Its localized surface plasmon resonance (LSPR) properties allow broad ultraviolet—visible—near infrared ray (UV—vis—NIR) absorption, making it an ideal material for solar energy conversion. Most plasmonic nanostructures rely on precious metals. Although noble metal plasmonic nanomaterials have proven to be one of the strategies for enhancing photocatalytic activity, their expensive cost and limitations in light absorption range have hindered their practical application. As a result, noble-metal free plasmonic nanomaterials have risen to the top of the research priority list. Therefore, this paper reviews the fundamental principles and classification of the LSPR effect of noble-metal free plasmonic nanomaterials in photocatalytic and their recent applications in hydrogen generation, carbon dioxide reduction, and pollutant degradation. Specific cases elucidate the possible working mechanism of enhanced photocatalysis by noble-metal free plasmonic nanomaterials. Finally, the challenges and future opportunities for noble-metal free plasmonic nanomaterials in energy conversion and storage are discussed and envisioned.

Photothermal heating of titanium nitride nanomaterials for fast and uniform laser warming of cryopreserved biomaterials.

Titanium nitride (TiN) is presented as an alternative plasmonic nanomaterial to the commonly used gold (Au) for its potential use in laser rewarming of cryopreserved biomaterials. The rewarming of vitrified, glass like state, cryopreserved biomaterials is a delicate process as potential ice formation leads to mechanical stress and cracking on a macroscale, and damage to cell walls and DNA on a microscale, ultimately leading to the destruction of the biomaterial. The use of plasmonic nanomaterials dispersed in cryoprotective agent solutions to rapidly convert optical radiation into heat, generally supplied by a focused laser beam, proposes a novel approach to overcome this difficulty. This study focuses on the performance of TiN nanoparticles (NPs), since they present high thermal stability and are inexpensive compared to Au. To uniformly warm up the nanomaterial solutions, a beam splitting laser system was developed to heat samples from multiple sides with equal beam energy distribution. In addition, uniform laser warming requires equal distribution of absorption and scattering properties in the nanomaterials. Preliminary results demonstrated higher absorption but less scattering in TiN NPs than Au nanorods (GNRs). This led to the development of TiN clusters, synthetized by nanoparticle agglomeration, to increase the scattering cross-section of the material. Overall, this study analyzed the heating rate, thermal efficiency, and heating uniformity of TiN NPs and clusters in comparison to GNRs at different solution concentrations. TiN NPs and clusters demonstrated higher heating rates and solution temperatures, while only clusters led to a significantly improved uniformity in heating. These results highlight a promising alternative plasmonic nanomaterial to rewarm cryopreserved biological systems in the future.

Mechanistic Insights into Graphene Oxide Driven Photocatalysis as Co-Catalyst and Sole Catalyst in Degradation of Organic Dye Pollutants

Photocatalysis is a promising route to utilize sunlight, which has been potentially used to solve energy as well as environmental problems with an emphasis on fundamental understanding and technological applications in society. Semiconductors are excellent photocatalysts but often show less efficient activities due to the fast recombination of photogenerated charge carriers and very slow kinetics of surface photochemical reactions. However, recent advancements show promising strategies to improve their photocatalytic activities, including surface modifications using suitable co-catalysts and the development of novel efficient photocatalysts. Graphene oxide (GO) is one of such nanomaterials which shows multifarious roles in photocatalysis with a great potential to act as an independent solar-driven sole photocatalyst. In this minireview, the photochemistry of GO has been discussed in view of its multifarious roles/mechanisms in improving the photocatalytic activity of metal oxide semiconductors, plasmonic nanomaterials, and also their nanocomposites. In addition, recent advancements and applications of such GO-based photocatalysts in photocatalytic degradation of organic dye pollutants, including engineering of GO as the sole photocatalyst, have been discussed. Furthermore, the challenges and future prospects for the development of GO-based photocatalysts are discussed.

Direct and Water-Mediated Adsorption of Stabilizers on SERS-Active Colloidal Bimetallic Plasmonic Nanomaterials: Insight into Citrate-AuAg Interactions from DFT Calculations.

In previous studies, AuAg colloidal nanostar formulations were developed with the two-fold aim of producing optimized surface-enhanced Raman spectroscopy (SERS) substrates and investigating the nature of the capping process itself. Findings demonstrated that the nanoparticle metals are alloyed and neutral, and capping by stabilizers occurs via chemisorption. This study utilizes citrate as the model stabilizer and investigates the mechanistic aspects of its interaction with mono- (Au20) and bimetallic (Au19Ag) surfaces by density functional theory (DFT) calculations. Citrate was modeled according to the colloid's pH and surrounded by a water and sodium first solvation shell. A population of stable cluster-citrate structures was obtained, and energies were refined at the uB3LYP//LANL2TZ(f)/cc-pVTZ level of theory. Solvation was accounted for both explicitly and implicitly by the application of the continuum model SMD. Results indicate that both direct binding and binding by water proxy through the charge-transfer complex formation are thermodynamically favorable. Water participation in citrate adsorption is supported by the adsorption behavior observed experimentally and the comparison between experimental and DFT-simulated IR spectra. Vibrational mode analysis suggests the possible presence of water within a crystal in dried nanostar residues. All ΔGads(aq) indicate a weak chemisorptive process, leading to the hypothesis that citrate could be displaced by analytes during SERS measurements.

High-Density-Nanotips-Composed 3D Hierarchical Au/CuS Hybrids for Sensitive, Signal-Reproducible, and Substrate-Recyclable SERS Detection.

Surface-enhanced Raman scattering (SERS) provides an unprecedented opportunity for fingerprinting identification and trace-level detection in chemistry, biomedicine, materials, and so on. Although great efforts have been devoted to fabricating sensitive plasmonic nanomaterials, it is still challenging to batch-produce a SERS substrate with high sensitivity, good reproducibility, and perfect recyclability. Here, we describe a facile fabrication of three-dimensional (3D) hierarchical Au/CuS nanocomposites, in which high-density Au nanotips enable highly SERS-active sensing, and the well-defined microflower (MF) geometry produces perfect signal reproducibility (RSD < 5%) for large laser spot excitations (>50 μm2), which is particularly suitable for practical on-site detection with a handheld Raman spectrometer. In addition, a self-cleaning ability of this Au/CuS Schottky junction photocatalyst under sunlight irradiation allows complete removal of the adsorbed analytes, realizing perfect regeneration of the SERS substrates over many cycles. The mass-production, ultra-sensitive, high-reproducibility, and fast-recyclability features of hierarchical Au/CuS MFs greatly facilitate cost-effective and field SERS detection of trace analytes in practice.

Anchoring branched Ag nano-islands on Au@CuxO mesoporous nanospheres as dual plasmonic absorbers for efficient photothermal conversion

Plasmonic semiconductor nanomaterials have been widely accepted as promising candidates for photothermal conversion, while the efficiency is yet to optimize. Herein, we report a facile synthesis of Au@CuxO mesoporous nanospheres anchored with branched Ag nano-islands on the surface and explore their applications as photothermal conversion agent. Due to the intimate hybridization of two materials, the Au@CuxO-Ag hybrid nanocomposites display a unique dual-plasmonic absorption that covers the visible-NIR range, benefiting the utilization efficiency of light energy. The synthesis is realized by reacting Au@CuxO with Ag+, the galvanic replacement reaction between them enables a preferential depletion of Cu phase, leaving Ag and Cu2O as dominate crystal phases. The resulting hybrid nanocomposites are featured with a core-shell structure but incomplete coverage, as well as the mesoporous interior and dendritic outer shell. In addition to the enhanced photothermal conversion efficiency, the current nano-hybrids show excellent structural stability and no decay in conversion after five successive rounds of measurement. The advantages in both morphological and electronic structure aspects are discussed. The present study validates the promising synergetic use of distinct hot charge carriers originating from metal and semiconductor that are photoexcited in the same hybrid nanoparticle for photothermal conversion, shedding light on rational design of photothermal materials based on metal-semiconductor hybrid nanocomposites.

Hybrid composite based on conducting polymers and plasmonic nanomaterials applied to catalysis and sensing

Combining plasmonic and semiconductors offers significant potential in creating sensing and photocatalytic devices. Nanocomposites including both metals and semiconductors can control the charge states in the metals that can enhance catalysis activity along with plasmon-enhanced spectroscopy. Here we demonstrate the use of conducting polymer materials with plasmonic nanomaterials to boost up to five-fold plasmon-enhanced Raman scattering spectroscopy signal strength and support oxidation of target molecules through supporting charge transfer processes. This work demonstrates the use of conducting polymers as a semiconductor platform to support plasmonic catalysis and sensing.