Single-Particle Spectroelectrochemistry: Promoting the Electrocatalytic Activity of Gold Nanorods via Oxygen Plasma Treatment without Structural Deformation.

Understanding of the electrocatalytic activity enhancement in gold nanoparticles is still limited. Herein, we present the effect of the oxygen plasma treatment on the electrochemical activity of gold nanorods (AuNRs). Oxygen plasma treatment resulted in the blueshift and line width narrowing of the localized surface plasmon resonance (LSPR) spectra obtained from individual AuNRs immobilized on an indium tin oxide (ITO) surface. These changes can be attributed to increases in the surface charges of the AuNRs. The formation of a Au-ITO heterojunction provided structural stability to the immobilized AuNRs regardless of the duration of oxygen plasma exposure. The electrocatalytic oxidation of hydrogen peroxide (H2O2) was induced by increases in the free-electron densities on the surfaces of these AuNRs owing to oxygen plasma treatment, and Au did not dissolve under the experimental conditions. However, the potential-dependent LSPR spectra of the individual AuNRs showed similar patterns of LSPR behavior, irrespective of the duration of oxygen plasma treatment and the concentration of H2O2. Therefore, this study based on single-particle spectroelectrochemistry and cyclic voltammetry improves the understanding of the role of oxygen plasma treatment in promoting the catalytic activity of structurally stable AuNRs immobilized on an ITO surface.

Direct Observation of In-Focus Plasmonic Cargos via Breaking Angular Degeneracy in Differential Interference Contrast Microscopy.

Breaking the angular degeneracy arising from the 2-fold optical symmetry of plasmonic anisotropic nanoprobes is critical in biological studies. In this study, we propose differential interference contrast (DIC) microscopy-based focused orientation and position imaging (dFOPI) to break the angular degeneracy of single gold nanorods (AuNRs). Single in-focus AuNRs (39 nm × 123 nm) within a spherical mesoporous silica shell were characterized with high throughput and produced distinct doughnut-shaped DIC image patterns featuring two lobes in the peripheral region, attributed to the scattering contribution of the AuNRs with large scattering cross sections. Interestingly, rotation of the lobes was observed in the focal plane for a large AuNR (>100 nm) tilted by more than ∼20° from the horizontal plane as the rotational stage was moved by 10° in a rotational study. From the rotation-dependent characteristic patterns, we directly visualized counterclockwise/clockwise rotations without the angular degeneracy at the localized surface plasmon resonance wavelength. Therefore, our dFOPI method can be applied for in vivo studies of important biological systems. To validate this claim, we tracked the three-dimensional rotational behavior of transferrin-modified in-focus AuNRs during clathrin-mediated endocytosis in real time without sacrificing the temporal and spatial resolution. In the invagination and scission stage, one or two directed twist motions of the AuNR cargos detached the AuNR-containing vesicles from the cell membrane. Furthermore, the dFOPI method directly visualized and revealed the right-handed twisting action along the dynamin helix in dynamin-catalyzed fission in live cells.

Tuning Chemical Interface Damping: Competition between Surface Damping Pathways in Amalgamated Gold Nanorods Coated with Mesoporous Silica Shells.

The mechanism of mercury (Hg) amalgamation in gold nanorods coated with a mesoporous silica shell (AuNRs@mSiO2) and the effect of chemical treatments on the localized surface plasmon resonance (LSPR) spectral changes in single amalgamated AuNRs@mSiO2 remains unclear. In this study, we investigated Hg amalgamation and inward Hg diffusion in single AuNRs@mSiO2 without structural deformation via dark-field scattering spectroscopy and X-ray photoelectron spectroscopy. Then, we investigated the chemisorption of thiol molecules on single amalgamated AuNRs@Hg-mSiO2. Unlike previous studies on single AuNRs, the thiolation on single AuNRs@Hg-mSiO2 resulted in a redshift and line width narrowing of the LSPR peak within 1 h. To determine the chemical effect, we investigated the competition between two surface damping pathways: metal interface damping (MID) and chemical interface damping (CID). When we exposed amalgamated AuNRs@Hg-mSiO2 to 1-alkanethiols with three different carbon chain lengths for 1 h, we observed an increase in the line width broadening with longer chain lengths owing to enhanced CID, demonstrating the tunability of CID and LSPR properties upon chemical treatments. We also investigated the competition between the two surface damping pathways as a function of the time-dependent Au-Hg surface properties in AuNRs@Hg-mSiO2. The 24-h Hg treatment resulted in increased line width broadening compared to the 1-h treatment for the same thiols, which was attributed to the predominance of CID. This was in contrast to the predominance of MID under the 1-h treatment, which formed a core-shell structure. Therefore, this study provides new insights into the Hg amalgamation process, the effect of chemical treatments, competition between surface decay pathways, and LSPR control in AuNRs@mSiO2.

Burst of hopping trafficking correlated reversible dynamic interactions between lipid droplets and mitochondria under starvation.

Dynamic membrane contacts between lipid droplets (LDs) and mitochondria play key roles in lipid metabolism and energy homeostasis. Understanding the dynamics of LDs under energy stimulation is thereby crucial to disclosing the metabolic mechanism. Here, the reversible interactions between LDs and mitochondria are tracked in real-time using a robust LDs-specific fluorescent probe (LDs-Tags). Through tracking the dynamics of LDs at the single-particle level, spatiotemporal heterogeneity is revealed. LDs in starved cells communicate and integrate their activities (i.e., lipid exchange) through a membrane contact site-mediated mechanism. Thus the diffusion is intermittently alternated between active and confined states. Statistical analysis shows that the translocation of LDs in response to starvation stress is non-Gaussian, and obeys nonergodic-like behavior. These results provide deep understanding of the anomalous diffusion of LDs in living cells, and also afford guidance for rationally designing efficient transporter.

Elucidating Surface Plasmon Damping and Fano Resonance Induced by Epitaxial Growth of Palladium on Single Gold Nanorods.

Plasmon damping and Fano resonance induced in the growth of palladium (Pd) on gold nanorods (AuNRs) have been poorly understood. Herein, we investigated the optical properties and morphologies of single AuNRs@Pd (core@shell) synthesized using epitaxial Pd growth at different Pd concentrations. The localized surface plasmon resonance (LSPR) spectra of single AuNRs@Pd showed characteristic subradiant and superradiant peaks as well as Fano resonance as a spectral dip, which was highly influenced by the Pd shell thickness. The occurrence of the Fano resonance during the Pd growth was further verified by in situ real-time observation experiments. We then elucidated time-dependent, real-time variations in LSPR peak wavelength, metal-induced surface damping, and Fano resonance mode of single AuNRs@Pd during Pd shell formation in three successive phases: Pd reduction, nucleation, and growth. Therefore, this study provides new insights into metal interface damping, the Fano resonance, and optical tunability by engineering the Fano resonance energy and Pd shell thickness.

In situ reversible tuning of chemical interface damping in mesoporous silica-coated gold nanorods via direct adsorption and removal of thiol.

Chemical interface damping (CID) is a recently proposed plasmon decay channel in gold nanoparticles. However, thus far, a very limited number of studies have focused on controlling CID in single gold nanoparticles. Herein, we describe a new simple method for reversible tuning of CID in single gold nanorods coated with a mesoporous silica shell (AuNRs@mSiO2). We used 1-alkanethiols with two different carbon chain lengths (1-butanethiol and 1-decanethiol) as adsorbates to induce CID. In addition, NaBH4 solution was used to remove the attached thiol from the AuNR surface. We confirmed the adsorption and removal of 1-alkanethiols on single AuNRs@mSiO2 and the corresponding changes in localized surface plasmon resonance (LSPR) peak wavelengths and linewidths. Furthermore, we investigated the effect of immersion time in NaBH4 solution on thiol removal from AuNRs@mSiO2. Therefore, the LSPR properties and CID can be controlled, thereby paving the way for in situ reversible tuning of CID by repeated adsorption and desorption of thiol molecules on single AuNRs@mSiO2.

Single-Particle Spectroelectrochemistry: Electrochemical Approaches for Tuning Chemical Interfaces and Plasmon Damping in Single Gold Nanorods.

The strong adsorption of thiol molecules on gold nanorods (AuNRs) results in localized surface plasmon resonance (LSPR) energy loss via chemical interface damping (CID). This study investigated the CID effect induced by thiophenol (TP) adsorption on single AuNRs and the in situ tuning of LSPR properties and chemical interfaces through electrochemical potential manipulation. The potential-dependent LSPR spectrum of bare AuNRs exhibited redshifts and line width broadening owing to the characteristics of capacitive charging, Au oxidation, and oxidation dissolution. However, TP passivation provided stability to the AuNRs from oxidation in an electrochemical environment. Electrochemical potentials induced electron donation and withdrawal, causing changes in the Fermi level of AuNRs at the Au-TP interface, thereby controlling the LSPR spectrum. Additionally, the desorption of TP molecules from the Au surface was electrochemically achieved at the anodic potentials further away from the capacitive charging region, which can be used to tune chemical interfaces and the CID process in single AuNRs.

Bioactive Phytochemicals from Salix pseudolasiogyne Twigs: Anti-Adipogenic Effect of 2'-O-Acetylsalicortin in 3T3-L1 Cells.

Salix pseudolasiogyne (Salicaceae) is a willow tree and has been used as a medicinal herb in Korea to treat pain and fever. As a part of an ongoing study to identify bioactive natural products, potential anti-adipogenic compounds were investigated using the ethanol (EtOH) extract of S. pseudolasiogyne twigs. Phytochemical investigation of the EtOH extracts using liquid chromatography-mass spectrometry (LC/MS) led to the separation of two compounds, oregonin (1) and 2'-O-acetylsalicortin (2). The structures of the isolates were identified using nuclear magnetic resonance spectroscopy and LC/MS analysis. To the best of our knowledge, it is the first report identifying oregonin (1) in twigs of S. pseudolasiogyne. Here, we found that the isolated compounds, oregonin (1) and 2'-O-acetylsalicortin (2), showed anti-adipogenic effects during 3T3-L1 cell differentiation. Notably, 2'-O-acetylsalicortin (2), at a concentration of 50 µM, significantly suppressed lipid accumulation. Moreover, the mRNA and protein levels of lipogenic and adipogenic transcription factors were reduced in 2'-O-acetylsalicortin (2)-treated 3T3-L1 cells. Taken together, these results indicate that 2'-O-acetylsalicortin (2), isolated from S. pseudolasiogyne twigs, has the potential to be applied as a therapeutic agent to effectively control adipocyte differentiation, a critical stage in the progression of obesity.

Antitumor Potential of Withanolide Glycosides from Ashwagandha (Withania somnifera) on Apoptosis of Human Hepatocellular Carcinoma Cells and Tube Formation in Human Umbilical Vein Endothelial Cells.

Hepatocellular carcinoma (HCC) is the fastest-growing tumor capable of spreading to other organs via blood vessels formed by endothelial cells. Apoptosis and angiogenesis-targeting therapies are attractive for cancer treatment. In this study, we aimed to study the in vitro cytotoxicity of Withania somnifera against human HCC (HepG2) cells, identify potential antitumoral withanolide glycosides from the active fraction, and elucidate cytotoxic molecular mechanisms of identified bioactive compounds. W. somnifera (Solanaceae), well-known as 'ashwagandha', is an Ayurvedic medicinal plant used to promote health and longevity, and the MeOH extract of W. somnifera root exhibited cytotoxicity against HepG2 cells during initial screening. Bioactivity-guided fractionation of the MeOH extract and subsequent phytochemical investigation of the active n-BuOH-soluble fraction resulted in the isolation of five withanolide glycosides (1-5), including one new metabolite, withanoside XIII (1), aided by liquid chromatography-mass spectrometry-based analysis. The new compound structure was determined by 1D and 2D nuclear magnetic resonance spectroscopy, high-resolution electrospray ionization mass spectroscopy, electronic circular dichroism, and enzymatic hydrolysis. In addition, withanoside XIIIa (1a) was identified as the new aglycone (1a) of 1. Isolated withanolide glycosides 1-5 and 1a were cytotoxic toward HepG2 cells; withagenin A diglucoside (WAD) (3) exhibited the most potent cytotoxicity against HepG2 cells, with cell viability less than 50% at 100 µM. WAD cytotoxicity was mediated by both extrinsic and intrinsic apoptosis pathways. Treatment with WAD increased protein expression levels of cleaved caspase-8, cleaved caspase-9, cleaved caspase-3, Bcl-2-associated X protein (Bax), and cleaved poly(ADP-ribose) polymerase (cleaved PARP) but decreased expression levels of B-cell lymphoma 2 (Bcl-2). Moreover, WAD inhibited tubular structure formation in human umbilical vein endothelial cells (HUVECs) by inhibiting the protein expression of vascular endothelial growth factor receptor 2 and its downstream pathways, including extracellular signal-regulated kinase (ERK), phosphoinositide 3-kinase (PI3K), Akt, and mammalian target of rapamycin (mTOR). These effects were also enhanced by co-treatment with ERK and PI3K inhibitors. Overall, these results indicate that WAD (3) induced HepG2 apoptosis and inhibited HUVEC tube formation, suggesting its potential application in treating liver cancers.

Influence of oxygen plasma treatment on structural and spectral changes in gold nanorods immobilized on indium tin oxide surfaces.

Oxygen plasma treatment is commonly used to sterilize gold nanoparticles by removing chemical contaminants from their surface while simultaneously inducing surface activation and functionalization of nanoparticles for biological, electrocatalytic, or electrochemical studies. In this study, we investigate the influence of oxygen plasma treatment on structural and localized surface plasmon resonance (LSPR) spectral changes of anisotropic gold nanorods (AuNRs) immobilized on an indium tin oxide (ITO) glass substrate. Unlike AuNRs deposited on a glass slide, no noticeable structural change or deformation of AuNRs on ITO was observed while increasing the oxygen plasma treatment time. This result indicates that ITO provides structural stability to AuNRs immobilized on its surface. Additionally, single-particle scattering spectra of AuNRs showed the broadening of LSPR linewidth within 60 s of oxygen plasma treatment as a result of the plasmon energy loss contributed from plasmon damping to ITO due to the removal of capping material from the AuNR surface. Nevertheless, an increase in the surface charge on the AuNR surface was observed by narrowing the LSPR linewidth after 180 s of plasma treatment. The electrochemical study of AuNRs immobilized on ITO electrodes revealed the surface activation and functionalization of AuNRs by increasing plasma treatment. Hence, in this study, a significant understanding of oxygen plasma treatment on AuNRs immobilized on ITO surfaces is provided.

Tuning plasmonic properties by promoting the inward Hg diffusion via oxygen plasma treatment in gold nanorods coated with a mesoporous silica shell.

This paper describes a new strategy using oxygen plasma treatment to tune the localized surface plasmon resonance (LSPR) of gold nanorods coated with a mesoporous silica shell (AuNRs@mSiO2) exposed to mercury (Hg) solution. Dark-field (DF) microscopy and spectroscopy were used to reveal the effects of oxygen plasma treatment on the structural and LSPR spectral changes of single amalgamated AuNRs@mSiO2. Due to the structural stability provided by the mesoporous silica shell, the amalgamated AuNRs@mSiO2 exposed to oxygen plasma treatment showed no morphological transformation. Furthermore, real-time monitoring of single AuNRs@mSiO2 showed slow Hg inward diffusion into AuNR cores in air over a long timeframe (24 h), as revealed by the redshift and linewidth narrowing of the LSPR peak. However, the oxygen plasma treatment resulted in faster inward diffusion of Hg into AuNR cores within 20 min, almost 60 times faster than the amalgamated AuNRs@mSiO2 untreated with oxygen plasma. Thus, oxygen plasma treatment was further presented as a new effective approach to control the LSPR properties by promoting the inward Hg diffusion in amalgamated AuNRs@mSiO2 without structural deformation.

Retraction: Single gold nanostars with multiple branches as multispectral orientation probes in single-particle rotational tracking.

Retraction of 'Single gold nanostars with multiple branches as multispectral orientation probes in single-particle rotational tracking' by Geun Wan Kim et al., Chem. Commun., 2021, 57, 3263-3266, https://doi.org/10.1039/D1CC00731A.

Single-particle spectroelectrochemistry: electrochemical tuning of plasmonic properties via mercury amalgamation in mesoporous silica coated gold nanorods without structural deformation.

This paper elucidates the mercury (Hg) amalgamation induced by electrochemical reduction on gold nanorods coated with mesoporous silica shell (AuNRs@mSiO2) using single-particle spectroelectrochemistry. First, the silica shell significantly enhanced the structural stability of AuNR cores after Hg amalgamation with the application of linear sweep voltages (LSVs). Thus, we were able to focus on the spectral changes of AuNRs@mSiO2 induced by the deposition of Hg without the disturbance of structural deformation, which also strongly affects localized surface plasmon resonance (LSPR) properties. Second, following the application of LSVs in the presence of Hg2+, a remarkable blueshift of the LSPR peak was observed, caused by the lowering of the work function due to the Hg adsorption, donating electron density to Au. Furthermore, the LSPR linewidth also dramatically increased after the Hg deposition with LSV. Lastly, the evolution of the Hg amalgamation process was directly observed by monitoring real-time LSPR peaks and LSPR linewidth shifts of a single AuNRs@mSiO2 in the Hg solution according to the application of the electrochemical potential. Moreover, the results showed the possibility of the in situ tuning of the LSPR properties of AuNRs@mSiO2 by Hg deposition via electrochemical potential manipulations without the disturbance of the structural variations of AuNR cores.

Effects of Amine Linkers with Different Carbon Chain Lengths at Guanine-Rich Polynucleotides on Chemical Interface Damping in Single Gold Nanorods.

DNA-functionalized gold nanoparticles (AuNPs) are used for various bioapplications, such as biosensor development and drug delivery. Nevertheless, no study has reported the effect of polynucleotide chains on chemical interface damping (CID), the most recently proposed plasmon damping pathway in single AuNPs. In this study, we conducted total internal reflection scattering measurements of gold nanorods (AuNRs) to reveal the CID effect induced by amine (NH2)-linked polynucleotides (or DNA) with guanine-rich sequences through the interaction between nitrogen and Au surfaces. Additionally, we elucidated the effect of a linear hydrocarbon chain length between NH2 and DNA (NH2-Cn-DNA, n = 6, 12, 18, 24) on spectral changes in single AuNRs. The localized surface plasmon resonance (LSPR) linewidth increased with an increasing number of linear carbon, from 6 to 24, due to the increase in van der Waals forces. Second, the effect of the direction (5' or 3' ends) of DNA attachment to the AuNR surfaces on LSPR spectral changes was investigated, and there was no significant difference in LSPR wavelength and full linewidth at half-maximum shifts caused by the DNA attachment directions (5' or 3' ends). Third, guanine-rich DNA can fold into four-stranded secondary structures called G-quadruplexes (GQs). We demonstrated the effect of linear carbon chain length, between NH2 and GQs, on CID in single AuNRs. Lastly, a label-free detection of DNA hybridization events on single AuNRs was demonstrated for sensing applications. Thus, we provide an insight into the effect of amine-functionalized guanine-rich DNA with different carbon chains on LSPR spectral changes, including CID in single AuNRs.

Enhanced refractive index sensitivity of localized surface plasmon resonance inflection points in single hollow gold nanospheres with inner cavity.

Hollow gold nanoparticles have great potential for localized surface plasmon resonance (LSPR) sensing. In this study, we investigated the refractive index (RI) sensitivities of single hollow gold nanosphere (HAuNS) with thin Au shell and inner cavity and single solid gold nanosphere (AuNS) in media with different RIs. The HAuNS exhibited a remarkable improvement in the RI sensitivity than the AuNS of similar size. The increased RI sensitivity of HAuNSs was ascribed to plasmon coupling between the inner and outer surface of the Au nanoshell. We then investigated the homogeneous LSPR scattering inflection points (IFs) to better understand the RI sensitivity of single HAuNS. The LSPR IF at the long wavelength side exhibited a better RI sensitivity compared to the wavelength shift of its counterpart LSPR maximum peak. Furthermore, the single HAuNS showed a remarkable improvement in the RI sensitivity at the LSPR IFs when compared to the AuNS of similar size. Therefore, we provided a new insight into the effect of inner cavity of HAuNS on the RI sensitivity of homogeneous LSPR IFs for use in LSPR-based biosensors.

Structural Characterization of Withanolide Glycosides from the Roots of Withania somnifera and Their Potential Biological Activities.

Withania somnifera (Solanaceae), commonly known as "ashwagandha", is an ayurvedic medicinal plant that has been used for promoting good health and longevity. As part of our ongoing natural product research for the discovery of bioactive phytochemicals with novel structures, we conducted a phytochemical analysis of W. somnifera root, commonly used as an herbal medicine part. The phytochemical investigation aided by liquid chromatography-mass spectrometry (LC/MS)-based analysis led to the isolation of four withanolide glycosides (1-4), including one new compound, withanoside XII (1), from the methanol (MeOH) extract of W. somnifera root. The structure of the new compound was determined by nuclear magnetic resonance (NMR) spectroscopic data, high-resolution (HR) electrospray ionization (ESI) mass spectroscopy (MS), and electronic circular dichroism (ECD) data as well as enzymatic hydrolysis followed by LC/MS analysis. In addition, enzymatic hydrolysis of 1 afforded an aglycone (1a) of 1, which was identified as a new compound, withanoside XIIa (1a), by the interpretation of NMR spectroscopic data, HR-ESIMS, and ECD data. To the best of our knowledge, the structure of compound 2 (withagenin A diglucoside) was previously proposed by HRMS and MS/MS spectral data, without NMR experiment, and the physical and spectroscopic data of withagenin A diglucoside (2) are reported in this study for the first time. All the isolated compounds were evaluated for their anti-Helicobacter pylori, anti-oxidant, and anti-inflammatory activities. In the anti-Helicobacter pylori activity assay, compound 2 showed weak anti-H. pylori activity with 7.8% inhibition. All the isolated compounds showed significant ABTS radical scavenging activity. However, all isolates failed to show inhibitory activity against nitric oxide (NO) production in lipopolysaccharide-stimulated RAW 264.7 macrophage cells. This study demonstrated the experimental support that the W. somnifera root is rich in withanolides, and it can be a valuable natural resource for bioactive withanolides.

Single-particle study: effects of mercury amalgamation on morphological and spectral changes in anisotropic gold nanorods.

This study investigated the amalgamation of gold nanorods (AuNRs) exposed to Hg(II) solution and its effects on structural and spectral changes in single AuNRs using scanning electron microscopy and total internal reflection scattering microscopy. First, Hg adsorption on AuNR surfaces formed AuNRs@Hg core-shell structures. Afterwards, they transformed to AuNRs@AuHg alloy shell structures in air due to the slow inward diffusion of Hg over time. The aspect ratio (AR) of the AuNRs@AuHg formed by the amalgamation was significantly decreased compared to that of bare AuNRs. Furthermore, the Hg coating on AuNRs induced a dramatic blue shift of the localized surface plasmon resonance (LSPR) peak and linewidth broadening, followed by a red shift and linewidth narrowing of the LSPR peak due to inward diffusion of Hg into the AuNR core. Finally, we investigated the effects of oxygen plasma treatment on the structural changes of AuNRs@AuHg and found that their AR was a decreasing function of the plasma treatment time. More notably, a major structural change was observed 5 min after the plasma treatment. Therefore, fundamental information on the relationship among amalgamation process, plasma treatment time, structural change, and LSPR peak and linewidth is provided at the single-particle level.

Single-Particle Study on Hg Amalgamation Mechanism and Slow Inward Diffusion in Mesoporous Silica-Coated Gold Nanorods without Structural Deformation.

This paper presents the structural and spectral variations of individual mesoporous silica-coated gold nanorods (AuNRs@mSiO2) compared to bare AuNRs upon Hg-Au amalgamation. First, the aspect ratio of AuNRs@mSiO2 exposed to Hg solutions was unchanged because the deformation related to the cores of AuNR was suppressed by the silica shell. Second, dark-field microscopy and spectroscopy revealed a blue shift of the localized surface plasmon resonance (LSPR) wavelength peak and strong plasmon damping in the individual AuNRs@mSiO2 scattering spectra, exposed to Hg solutions. Furthermore, we investigated time-dependent adsorption kinetics and spectral changes during the formation of Au-Hg amalgam in single AuNRs@mSiO2 over a long time frame without any disturbance from the structural deformation. The inward Hg diffusion into the AuNR core caused a gradual red shift and line width narrowing of the LSPR peak when AuNRs@mSiO2 were withdrawn from Hg solution. Thus, this paper provides new insights into the relationship among amalgamation process, morphological change, the role of silica shell, Hg inward diffusion, LSPR peak, and line width at the single-particle level.

Localized surface plasmon resonance inflection points for improved detection of chemisorption of 1-alkanethiols under total internal reflection scattering microscopy.

Plasmonic gold nanoparticles are widely used in localized surface plasmon resonance (LSPR) sensing. When target molecules adsorb to the nanoparticles, they induce a shift in the LSPR scattering spectrum. In conventional LSPR sensing, this shift is monitored at the maximum of the LSPR scattering peak. Herein, we describe the sensitivity of detecting chemisorption of 1-alkanethiols with different chain lengths (1-butanethiol and 1-haxanethiol) on single gold nanorods (AuNRs) of fixed diameter (25 nm) and three different aspect ratios under a total internal reflection scattering microscope. For single AuNRs of all sizes, the inflection point (IF) at the long-wavelength side (or low-energy side) of the LSPR scattering peak showed higher detection sensitivity than the traditionally used peak maximum. The improved sensitivity can be ascribed to the shape change of the LSPR peak when the local refractive index is increased by chemisorption. Our results demonstrate the usefulness of tracking the curvature shapes by monitoring the homogeneous LSPR IF at the red side of the scattering spectrum of single AuNRs.

Influence of oxygen plasma treatment on structural and spectral changes in silica-coated gold nanorods studied using total internal reflection microscopy and spectroscopy.

This paper shows how oxygen plasma treatment affects the structural, localized surface plasmon resonance (LSPR) spectral, and spatial orientation changes in single gold nanorods coated with a mesoporous silica shell (AuNRs@SiO2) in comparison with bare AuNRs with the same aspect ratio (AR). Single AuNRs@SiO2 subjected to different plasma treatment times were characterized using scanning electron microscopy and total internal reflection scattering (TIRS) microscopy and spectroscopy. The AR of the single AuNRs without a silica shell was decreased by structural deformation, while their LSPR linewidth was increased with increasing plasma treatment time. In contrast, single AuNRs@SiO2 showed much higher structural and spectral stability due to the silica shell under the energetic plasma treatment. Furthermore, there was no noticeable variation in the three-dimensional (3D) orientations of single AuNR cores in the silica shell before and after the plasma treatment. The results support that no significant structural and spectral changes occur in single AuNRs@SiO2 and that the silica coating enhances the stability of AuNR cores against oxygen plasma treatment. Therefore, fundamental information on the relationship among plasma treatment time, structural change, LSPR damping, and defocused orientation patterns is provided at the single-particle level.