Modulation of Optical Properties of Gold Nanorods on Addition of KOH

Gold nanorods are known to exhibit two distinct surface plasmon oscillations namely, transverse and longitudinal bands corresponding to oscillations of conduction electrons along width and length of gold nanorods. Considerable changes in these surface plasmon resonance peak positions occurred when KOH was added to the nanorod solution. Nanorods with initial longitudinal plasmon band at 739, 796, and 895 nm are studied with variation in KOH concentration. While the longitudinal plasmon resonance peak showed blue shift, transverse plasmon resonance peak exhibited only intensity variations. Changes could be attributed to the shape transition of gold nanorods on variation of pH in the solution. Shape transition of gold nanorods is confirmed by transmission electron microscopy images.     

Gold Nanowire and Nanorod Plasmonic Mechanisms for Increasing Ultra-Thin Organic Photovoltaic Active Layer Absorption

We theoretically investigate the effect of incorporating gold cylindrical- and ellipsoidal-shaped nanowires and gold nanorods situated centrally within the active layer of organic bulk-heterojunction photovoltaic devices, on the optical absorption performance using finite element electromagnetic simulations. Gold cylindrical nanowire-embedded devices show increased active layer absorption enhancement with increasing radius; however, this effect decreases with the introduction of a polystyrene dielectric capping layer around the nanowires. Active layer absorption, with respect to changes in the orientation, aspect ratio, periodicity, and spacing between ellipsoidal nanowires were optimized. A maximum absorption enhancement weighted by AM 1.5 solar spectrum of 17 % is predicted for gold ellipsoidal nanowires of aspect ratio of 1.167 with in-plane horizontal orientation and arranged with periodicity of 35 nm within a 30-nm thin active layer. We attribute this enhancement primarily to interparticle electromagnetic coupling between adjacent nanowires, where, a maximum spatial and spectral overlap of the electromagnetic field with the absorption band of the active layer material is achieved. This effect increases with decreasing aspect ratio as well as decreasing periodicity with a trade-off observed between nanowire packing density and the active layer absorption enhancement. For gold nanorod-embedded organic photovoltaic devices, the inter-particle electromagnetic coupling effects are weaker and longitudinal surface–plasmon resonances supported by the nanorods are more pronounced. However, since the longitudinal surface–plasmon resonances occur at wavelengths greater than the absorption edge of the photovoltaic active layer, a mere 3.4 % increase in absorption enhancement is achieved for the photovoltaic device incorporating gold nanorods with aspect ratio of 1.167 and periodicity of 35 nm.     

金纳米棒的光学性质及其在生物医学领域的应用

简要介绍金纳米棒的光学性质和合成方法,重点阐述其在生物医学领域研究的最新进展,并对其今后的研究方向进行展望．金纳米棒是一种胶囊状的金纳米颗粒,具有一个横向等离子共振吸收峰和一个纵向等离子共振吸收峰,分别对应其横轴和纵轴两个特征尺寸．通过调节金纳米棒的长径比,纵向等离子共振吸收峰可由可见光区跨越至近红外光区．金纳米棒这一独特的光学性质在生物和化学传感方面有着广泛而重要的应用前景．     

金纳米棒的表面修饰及其应用于肿瘤诊疗的研究进展

金纳米棒具有独特的光学性质、表面易修饰性、较低的生物毒性和良好的生物相容性,因而在成像、光热治疗和药物载带等方面具有极高的潜在应用价值.本文综述了典型的金纳米棒表面修饰方法及其在生物成像、光热治疗和药物治疗中的应用,重点阐述了通过金纳米棒同时实现肿瘤诊断和治疗相结合的研究进展.     

Sensing capability of the localized surface plasmon resonance of gold nanorods

We demonstrate the feasibility of using the longitudinal component of gold nanorod's surface plasmon resonance in biomolecular sensing. The sensitive dependence of the absorption maximum on the dielectric constant of the particle interfacial region makes gold nanorods a promise for constructing a biomolecular sensing scheme. The sensor containing gold nanorods, with a mean aspect ratio of 5.2, exhibits a sensitivity of ca. 366 nm/RIU (refractive index unit), which increases accordingly with the increase of the particle mean aspect ratios. Such a biosensor was further modified to demonstrate its effectiveness in quantitative detection for selective binding events, such as biotin/streptavidin pairs, through a process in which biotin molecules were chemically attached to the gold nanorods' surface prior to detection measurements. Results showed that the spectral lambda(max) shifts linearly to the concentrations of the streptavidin. The results from both experiment and model calculations strongly indicate the efficacy of the longitudinal surface plasmon absorption band in biosensing.     

Tailoring of Localized Surface Plasmon Resonances of Core-Shell Au@Ag Nanorods by Changing the Thickness of Ag Shell

We report the synthesis and the characterization of core-shell Au@Ag nanorods through reduction by the wet chemical method. UV-visible absorption spectra of core-shell Au@Ag nanorods demonstrate the longitudinal mode of localized surface plasmon resonances (LSPRs) can be tailored from 724 to 786 nm by controlling the thickness of the silver shell, as is assessed by transmission electron microscope (TEM). Furthermore, the tunable and well-controlled LSPRs of core-shell Au@Ag nanorods are also investigated by numerical simulation using the finite difference time domain (FDTD) method, which strongly supports the experimental observations. The growth mechanism for core-shell Au@Ag nanorods is proposed, according to experimental observations and numerical calculations.     

SERS Properties of Gold Nanorods at Resonance with Molecular,Transverse, and Longitudinal Plasmon Excitations

The amplification of Raman signals of the heteroaromatic cation 1-(N-methylpyrid-4-yl)-2-(N-methylpyrrol-2-yl)ethylene (PEP+)) bound to Au nanorods (NRs) was investigated at different excitation wavelengths to study the effect of the laser resonance with the absorption band of the PEP+ moiety and with the two plasmon oscillation modes of the NR. Two different PEP+ derivatives, differing in the length of the alkyl chain bearing the anchoring group, were used as target molecules. Raman spectra obtained exciting at 514 or at 785 nm (i.e., exciting the transverse or the longitudinal plasmon band) present a higher intensity than that at 488 nm suggesting a higher Raman amplification when the laser excitation wavelength is resonant with one of the two plasmon modes. Moreover, considering results of Discrete Dipole Approximation (DDA) calculations of the local field generated at the NR surface when either the transverse or the longitudinal plasmon modes are excited, we deduced that the resonance condition of the 514-nm laser excitation with the absorption band of the dye strongly contributes to the amplification of the Raman signal.     

Fabrication of Gold Nanostructures and Studies of Their Morphological and Surface Plasmonic Properties

We report fabrication of gold nanostructures on glass and indium tin oxide (ITO)-coated glass substrates using high fluence and highly energetic gold ions generated by hot, dense, and strongly non-equilibrium plasma. Nanodots and nanorods are observed in scanning electron microscopy (SEM) of nanostructures grown on glass substrate with single and double shots of gold ions which is in conformity with the transmission electron microscopy image. SEM images for single and double shots of gold ions on ITO-coated glass substrate show only nanodots. The mean diameter of nanodots obtained on both glass and ITO-coated glass is found to increase with increase in the number of gold ions shot from one to two. The gold nanostructures exhibit red shift in surface plasmon resonance with increased interaction which is in agreement with other reported work.     

Use of ZnO:Tb down‐conversion phosphor for Ag nanoparticle plasmon absorption using a He–Cd ultraviolet laser

Although noble metal nanoparticles (NPs) have attracted some attention for potentially enhancing the luminescence of rare earth ions for phosphor lighting applications, the absorption of energy by NPs can also be beneficial in biological and polymer applications where local heating is desired, e.g. photothermal applications. Strong interaction between incident laser light and NPs occurs only when the laser wavelength matches the NP plasmon resonance. Although lasers with different wavelengths are available and the NP plasmon resonance can be tuned by changing its size and shape or the dielectric medium (host material), in this work, we consider exciting the plasmon resonance of Ag NPs indirectly with a He–Cd UV laser using the down‐conversion properties of Tb³⁺ ions in ZnO. The formation of Ag NPs was confirmed by X‐ray diffraction, transmission electron microscopy and UV–vis diffuse reflectance measurements. Radiative energy transfer from the Tb³⁺ ions to the Ag NPs resulted in quenching of the green luminescence of ZnO:Tb and was studied by means of spectral overlap and lifetime measurements. The use of a down‐converting phosphor, possibly with other rare earth ions, to indirectly couple a laser to the plasmon resonance wavelength of metal NPs is therefore successfully demonstrated and adds to the flexibility of such systems. Copyright © 2016 John Wiley & Sons, Ltd.     

Surface Plasmon Dynamics of High-Aspect-Ratio Gold Nanorods

Ultrafast transient absorption studies are reported for high-aspect-ratio gold nanorods that were fabricated by electrochemical deposition in polycarbonate templates. The nanorods are 60 nm in diameter with distribution of lengths of up to 6 μm. The average aspect ratio was ∼50, resulting in a longitudinal surface plasmon resonance (SPR_L) band in the mid-IR, as well as a transverse (SPR_T) band in the visible. The rods were excited at 400 nm and probed at a range of wavelengths from the visible to the mid-IR to interrogate both SPR bands. The dynamics observed, including the electron–phonon coupling time and coherent acoustic breathing mode oscillations, closely resemble those previously reported for gold spherical nanoparticles and smaller-aspect-ratio nanorods. The electron–phonon coupling time was similarly determined to be 3.3 ± 0.2 ps for both of the SPR bands. Also, oscillations with a 32-ps period were observed for probing near the SPR_T band in the visible region due to impulsive coherent excitation of the acoustic breathing mode, which are consistent with the 60-nm diameter of the nanorods determined by scanning electron microscopy. The results demonstrate that the dynamics for long gold nanorods are similar to those for smaller nanoparticles. Gerald M. Sando is a NRL-ASEE Research Associate     

Sensitive and Robust Colorimetric Sensing of Sulfide Anion by Plasmonic Nanosensors Based on Quick Crystal Growth

A highly sensitive and selective method for colorimetric sensing of sulfide anions in aqueous solutions is illustrated. The sensing mechanism is based on quick crystallization from Ag to Ag₂S in the presence of sulfide anions which alter the dielectric properties of the Au/Ag core/shell nanorods. The longitudinal surface plasmon resonance peak of the Au/Ag nanorods at about 686 nm undergoes a redshift and the color of the nanorod solution also changes from light green to purple. Sulfide ions at a concentration of 4.0 μM (1.3 ppb) can be detected visually and a sensitivity of 0.5 μM (167 ppt) is achieved by Vis–near-infrared spectrophotometry. Compared to other plasmonic sensors, our Au/Ag nanorod probe does not require surface modification while exhibiting high stability and robustness under different pH conditions. This simple and cost-effective sensing platform provides a rapid and convenient detection for sulfide anions at concentrations far below the hazardous limit in aqueous media.     

Association of gold nanorods in water solutions: influence of globular proteins

By absorption spectroscopy method optical properties of gold nanorods (10x38 nm) and their interaction with globular protein bovine hemoglobin and bovine serum albumin were investigated. Nanorods behavior was studied in water solution and in solution of 97 mM NaCl under ultrasound action during 90 min and results were then compared. In water solutions nanorods coagulation (aggregation) was observed with reduced optical density of the longitudinal plasmon band widening at lamda>800 nm. In NaCI solution absorption spectra evolution had complex character and was in some degree analogous to the result that was obtained for two-dimensional grids of gold nanoparticles when changing the distance between them. By interacting with serum albumin stabilization of colloid solution and dissociation of nanorods aggregates were observed.     

Peptide-conjugated gold nanorods for nuclear targeting

Resonant electron oscillations on the surface of noble metal nanoparticles (Au, Ag, Cu) create the surface plasmon resonance (SPR) that greatly enhances the absorption and Rayleigh (Mie) scattering of light by these particles. By adjusting the size and shape of the particles from spheres to rods, the SPR absorption and scattering can be tuned from the visible to the near-infrared region (NIR) where biologic tissues are relatively transparent. Further, gold nanorods greatly enhance surface Raman scattering of adsorbed molecules. These unique properties make gold nanorods especially attractive as optical sensors for biological and medical applications. In the present work, gold nanorods are covalently conjugated with a nuclear localization signal peptide through a thioalkyl-triazole linker and incubated with an immortalized benign epithelial cell line and an oral cancer cell line. Dark field light SPR scattering images demonstrate that nanorods are located in both the cytoplasm and nucleus of both cell lines. Single cell micro-Raman spectra reveal enhanced Raman bands of the peptide as well as molecules in the cytoplasm and the nucleus. Further, the Raman spectra reveal a difference between benign and cancer cell lines. This work represents an important step toward both imaging and Raman-based intracellular biosensing with covalently linked ligand-nanorod probes.     

Surface Plasmon as a Probe of Local Field Enhancement

New method of experimental determination of local field enhancement at metal nanoparticles is suggested. It uses surface plasmon as a probe. Alternating-sign shift of surface plasmon resonance in copper nanoparticles incorporated in silica matrix has been observed under irradiation by intense femtosecond laser pulse. The red shift of plasmon observed during the action of pump pulse is interpreted as a result of change of dielectric constant of silica matrix due to optical Kerr effect in electric field of pump pulse enhanced in a vicinity of metal nanoparticles. The field enhancement factor is estimated from the value of the observed red shift of plasmon resonance.     

Blue-Shifted SPR of Au Nanoparticles with Ordering of Carbon by Dense Ionization and Thermal Treatment

Thin films of carbon-containing Au nanoparticles (NPs), prepared by the co-sputtering using a neutral Ar atom beam, were irradiated by 120 MeV Ag ions and also annealed, separately, at increasing temperatures in inert atmosphere. The surface plasmon resonance (SPR) band of the nanocomposite film was observed to be blue shifted (～50 nm) in both cases, with increasing fluence and temperature. The structural changes of Au NPs embedded in amorphous carbon matrix were investigated using X-ray diffraction and transmission electron microscopy. A growth of Au NPs was observed with increasing fluence and also with increasing temperature. A percolation of Au NPs was observed at 500 °C. A growth of Au NPs with ion irradiation is explained in the framework of a thermal spike model. Raman spectroscopy revealed the ordering of a-C thin films with increasing fluence and temperature, which is ascribed to a change of refractive index and the blue shift of the SPR band.     

Far-Field Raman Imaging of Short-Wavelength Particle Plasmons on Gold Nanorods

The surface plasmon fields of gold nanorods with a diameter of 100 nm and lengths of 1–5 m are imaged by using far-field Raman scattering of methylene blue adsorbed on the rods. When optically exciting the nanorods under total internal reflection with wave vector and electric field vector orientations along the rod axis, the plasmon field intensity along this axis is observed to be periodically modulated. This modulation is attributable to a beating of the exciting light wave and the nanorod plasmon mode. The plasmon wavelength deduced from the beat frequency is 379 nm, which is considerably smaller than the exciting laser wavelength of 647 nm. In general, Raman imaging is shown to be a powerful technique to probe local plasmon fields using far-field spectroscopy.     

SERS quantitative detection of trace human chorionic gonadotropin using a label‐free Victoria blue B as probe in the aggregated immunonanogold sol substrate

Nanogold particles (NG) were modified by anti‐rabbit antibody (RAb) against human chorionic gonadotropin to obtain an immunonanogold probe (ING). In pH 7.0 Na₂HPO₄‐citrate buffer solution containing KCl, ING probes formed large aggregates in which Victoria blue B (VBB) molecules were adsorbed on the surface and which exhibited strong surface‐enhanced Raman scattering (SERS) at a peak of 1612 cm^–1. After addition of human chorionic gonadotropin (hCG) an immune reaction with the ING probe occurred to form dispersive ING–hCG complexes with non‐SERS activity that led to a decreased SERS peak at 1612 cm^–1. The decreased SERS intensity was linear to the concentration of hCG over 2.4–73.2 ng/mL. The ING reaction was studied in detail by SERS, scanning electron microscope (SEM), resonance Rayleigh scattering (RRS), surface plasmon resonance (SPR) absorption and laser scattering techniques. SERS quenching was observed and discussed. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis of gold nanotriangles and silver nanoparticles using Aloe vera plant extract

Biogenic gold nanotriangles and spherical silver nanoparticles were synthesized by a simple procedure using Aloe vera leaf extract as the reducing agent. This procedure offers control over the size of the gold nanotriangle and thereby a handle to tune their optical properties, particularly the position of the longitudinal surface plasmon resonance. The kinetics of gold nanotriangle formation was followed by UV-vis-NIR absorption spectroscopy and transmission electron microscopy (TEM). The effect of reducing agent concentration in the reaction mixture on the yield and size of the gold nanotriangles was studied using transmission electron microscopy. Monitoring the formation of gold nanotriangles as a function of time using TEM reveals that multiply twinned particles (MTPs) play an important role in the formation of gold nanotriangles. It is observed that the slow rate of the reaction along with the shape directing effect of the constituents of the extract are responsible for the formation of single crystalline gold nanotriangles. Reduction of silver ions by Aloe vera extract however, led to the formation of spherical silver nanoparticles of 15.2 nm +/- 4.2 nm size.     

Surface Plasmon Resonance Study of Au Nanorod Structures Templated in Mesoporous Silicon

Au nanorods forming carpet-like structures have been fabricated by electrochemical methods in mesoporous silicon templates. The anodically grown monodisperse pores on Si (100) were used to cathodically grow the Au structures from complexated Au solutions. Such structures feature selective absorption of light in the visible/near infrared wavelength range that can be tuned by controlling the aspect ratio and dielectric surrounding media. In the present work, the visible light absorption of Au structures has been studied and correlated with the light absorption of ideal structures with increasing complexity. According to these simulations, the observed selective light absorption arises from the anisotropic surface plasmon resonance (SPR) of the rods and a secondary SPR of isolated Au nanoparticles adsorbed on the rods.     

Optimized Synthesis of PEG-Encapsulated Gold Nanorods for Improved Stability and Its Application in OCT Imaging with Enhanced Contrast

Gold nanorods (GNRs) are synthesized with a surfactant template, which often poses toxicity issues for biomedical applications. In addition, blue shift of longitudinal surface plasmon resonance (LSPR) peak of GNR is an inherent problem that needs to be addressed for time-course studies. In this work, we resolve these issues by optimizing the encapsulation of GNRs with polyethylene glycol (PEG) where biocompatibility is improved by ～20 % and blue shift over a period of 8 days is reduced from 20 nm in the case of CTAB-GNR to 2 nm for PEG-encapsulated GNR. The encapsulated GNRs were then bioconjugated for targeted dark-field imaging of cancer cells. As an application, we also demonstrate the contrast-enhancing capability of GNRs in optical coherence tomography (OCT) imaging of tumor xenograft where the LSPR closely matches the OCT excitation wavelength. Our study proves that incorporating GNRs enhances the contrast of tumor tissue interfaces along with a considerable broadening in OCT depth profile by six times.