Colloidal Gold Nanorods Research Articles

Hybrid plasmonic gold-nanorod-platinum short-wave infrared photodetectors with fast response.

Short-wave infrared (SWIR) photodetectors, sensitive to the wavelength range between 1 and 3 μm, are essential components for various applications, which constantly demand devices with a lower cost, a higher responsivity and a faster response. In this work, a new hybrid device structure is presented for SWIR photodetection composing a coupling between solution-processed colloidal plasmonic gold (Au) NRs and a morphology-optimized resistive platinum (Pt) microwire. Pt microwires harvest efficiently the photothermal effect of Au NRs and in return generating a change of device resistance. A fast photon-heat-resistance conversion happens in these Au-NRs/Pt photodetectors exhibiting a response (rise) time of 97 μs under the illumination of a λ = 1.5 μm laser. Clear photoresponse can be observed in these devices at a laser illumination with a modulation frequency up to 50 kHz. The photoresponsivity of the current devices reached 4500 Ω W-1 under a laser power of 0.2 mW, which is equivalent to a responsivity of 340 mA W-1 under a DC bias of 1 V. A series of mapping experiments were performed providing a direct correlation between Au NRs and the device zone where resistance change happens under a laser illumination modulated at different frequencies.

Mechanisms and advanced photothermal modelling of laser-induced shape transformations of colloidal gold nanorods by nanosecond laser pulses.

We propose an advanced photothermal model based on a modified Takami model (MTM) to explain the mechanisms of shape changes of colloidal gold nanorods (NRs) induced by nanosecond laser pulses. This model takes into account the orientation of NRs, the radiative and convective losses, and the phase transitions of NRs. It was applied to the determination of the evolution of temperature and the shape and size transformations of NRs during the laser exposure. A series of measurements arising from the interaction between Au NRs and nanosecond laser pulses were analyzed by TEM measurements and the MTM model. We have demonstrated that the fragmentation and reshaping processes govern the nanoparticle (NP) shape. At high laser fluence, the complete fragmentation leads to a population of nearly spherical NPs, while at a moderate laser fluence, the partial fragmentation and reshaping processes generate a bimodal distribution. At low laser fluence, uncommon φ-shape NPs were produced as a result of the competition of cooling and reshaping processes. We also demonstrated that it is possible by the MTM model to determine the laser fluence required to suppress some specific NR shapes and to predict the NP size and shape distributions obtained after the laser exposure.

Seed-Mediated Growth of Gold Nanorods Using Silver Seeds: Effect of Silver Seeds Concentration and Growth Time

Seed-mediated growth method (SMGM) in preparation of gold nanoparticles becomes one of the most popular methods due to the simplicity of the experimental procedures and flexibility in structural modifications. In this paper, we report a new method for synthesizing gold nanoparticles using silver seeds. The effect of seed concentration and growth time are investigated in this work. By increasing the silver seed concentration, it is found that the color of the colloidal gold nanorods obtained are changed from light pink to reddish purple, the surface plasmon resonance band is shifted to the blue region whereas absorption spectra becomes narrower. The additional peak is also spotted when increasing silver seed concentration to 5 µl. Meanwhile, increasing the growth time from 5 to 240 minutes tends to increase the color concentration of the solution. Besides that, the absorbance of colloidal gold nanorods is also increased with an increase in the growth time whereas optimum growth time is found to be 45 minutes. FESEM characterization shows that gold nanoparticles shapes are dominated by nanorods with average length, width, and aspect ratio are 129.8 nm, 42.9 nm, and 3.4, respectively. The energy-dispersive x-ray spectroscopy (EDX) shows the chemical composition of the synthesized sample is Gold (Au) with weight % and atomic % are 32.23 and 5.98, respectively. Besides that, signals from Carbon (C), Oxygen (O), and Indium (In) atoms were also recorded from EDS spectra. The present approach thus provides new method for synthesis gold nanoparticles with additional plasmon resonance peak thus it has very potential for application in plasmonic sensing.

Designing Efficient Low-Cost Paper-Based Sensing Plasmonic Nanoplatforms.

Paper-based platforms can be a promising choice as portable sensors due to their low-cost and facile fabrication, ease of use, high sensitivity, specificity and flexibility. By combining the qualities of these 3D platforms with the optical properties of gold nanoparticles, it is possible to create efficient nanodevices with desired biosensing functionalities. In this work, we propose a new plasmonic paper-based dual localized surface plasmon resonance–surface-enhanced Raman scattering (LSPR-SERS) nanoplatform with improved detection abilities in terms of high sensitivity, uniformity and reproducibility. Specifically, colloidal gold nanorods (GNRs) with a well-controlled plasmonic response were firstly synthesized and validated as efficient dual LSPR-SERS nanosensors in solution using the p-aminothiophenol (p-ATP) analyte. GNRs were then efficiently immobilized onto the paper via the immersion approach, thus obtaining plasmonic nanoplatforms with a modulated LSPR response. The successful deposition of the nanoparticles onto the cellulose fibers was confirmed by LSPR measurements, which demonstrate the preserved plasmonic response after immobilization, as well as by dark-field microscopy and scanning electron microscopy investigations, which confirm their uniform distribution. Finally, a limit of detection for p-ATP as low as 10−12 M has been achieved by our developed SERS-based paper nanoplatform, proving that our optimized plasmonic paper-based biosensing design could be further considered as an excellent candidate for miniaturized biomedical applications.

Morphological control of gold nanorods via thermally driven bi-surfactant growth and application for detection of heavy metal ions

We report a modified synthesis route of colloidal gold nanorods (AuNRs) by combining the thermal re-shaping treatment and bi-surfactant modification using hexadecyltrimethylammonium bromide (CTAB) and sodium oleate (NaOL). Aspect ratios down to 1.3 ± 0.1 can be achieved in addition to good monodispersity, uniformity, and chemical stability of the materials. Furthermore, without needing post-treatment, metal ions directly interact with the AuNRs efficiently, allowing rapid and sensitive colorimetric detection of heavy metal ions such as Pb2+ and Cu2+ with a low concentration down to 2.5 μM. The detection performance in terms of selectivity, sensitivity and stability is systematically evaluated. The AuNRs with tunable aspect ratios as well as chemical stability have potential in surface-plasmon-based applications such as biochemical sensing, biochemical imaging, medical diagnostics, and cancer therapy.

Sensitive and simple determination of zwitterionic morphine in human urine based on liquid-liquid micro-extraction coupled with surface-enhanced Raman spectroscopy

Morphine, a kind of illicit drugs, is also one of the main heroin metabolites. In consideration of a noninvasive way to monitor and identify drug abuse during forensic cases, the urine samples are usually detected. Here, colloidal gold nanorods (Au NRs) were introduced to act as active substrate, because of the strong optical extinction and spectral tunability of the longitudinal surface plasmon resonance (SPR). Thus, well surface-enhanced Raman spectra of morphine even at low concentrations could be obtained by portable Raman spectrometer. For the complex matrix environment of urine, liquid-liquid micro-extraction (LLME), a simple and inexpensive pretreatment, was employed to avoid the interferences. And then, the coupled surface-enhanced Raman spectroscopy (SERS) can give full play to the advantages of high sensitivity and unique spectroscopic fingerprint. According to the zwitterionic structure and physicochemical parameters of morphine molecules, the pH value of urine sample was adjusted to about 9 by buffer solution (KOH/NaB4O7) and the mixture of chloroform and isopropyl alcohol (V/V=9:1) was chosen as extractant. Moreover, such pretreatment was proved to be appropriate for separation and concentration of morphine from urine. The developed LLME-SERS method could provide a detection limit less than 1 ppm in the human urine environment and the whole process of detection just needed take 5–6 min. What's more, the results of urine samples from heroin users exhibited application value of the proposed technique. The excellent performance makes it promising to become a rapid, reliable, and on-spot analyzer, especially for public safety and healthcare.

Short-Wave Infrared Sensor by the Photothermal Effect of Colloidal Gold Nanorods.

Photodetection in the short-wave infrared (SWIR) spectrum is a challenging task achieved often by costly low bandgap compound semiconductors involving highly toxic elements. In this work, an alternative low-cost approach is reported for SWIR sensors that rely on the plasmonic-induced photothermal effect of solution-processed colloidal gold nanorods (Au NRs). A series of uniform solution-processed Au NRs of various aspect ratios are prepared exhibiting a strong and well-defined longitudinal localized surface plasmon resonance (L-LSPR) maximum from 900 nm to 1.3 µm. A hybrid device structure is fabricated by applying Au NRs on the surface of a thermistor. Under a monochromatic illumination, hybrid Au-NR/thermistor devices exhibit a clear photoresponse in the form of photoinduced resistance drop in the wavelength window from 1.0 to 1.8 µm. The photoresponsivity of such hybrid devices reaches a maximum value of 4.44 × 107 Ω W-1 at λ = 1.4 µm (intensity = 0.28 mW cm-2 ), a wavelength in agreement with the L-LSPR of the Au NRs applied. Colloidal Au NRs, capable to perform fast conversion between photon absorption and thermal energy, thus open an interesting avenue for alternative low-cost SWIR photodetection.

Gold nanorods or nanospheres? Role of particle shape on tuning the shape memory effect of semicrystalline poly(ε-caprolactone) networks.

In this study, modified poly(ε-caprolactone) (PCL) tri-block copolymers were successfully synthesized through ring opening polymerization. The nanocomposite films containing either colloidal gold nanorods (AuNRs) or gold nanospheres (AuNSs) in the polymer matrix were fabricated without chemical modification to realize light-responsive shape memory behaviors. The localized surface plasmon resonance of AuNPs was utilized by irradiating the selective wavelength of light to create a photothermal effect. The polymer microstructures were investigated by NMR, and the thermal properties of the polymer networks were studied by TGA and DSC. The addition of AuNPs did not change the melting temperature, (Tm) of the SMP. The AuNRs were fairly well dispersed within the PCL matrix as observed using SEM-EDAX analysis and as indicated from the uniform shape memory transitions of the SMP/AuNR nanocomposites. The shape memory behavior was quantitatively analyzed by cyclic thermomechanical tests using DMA. The laser-triggered shape memory properties of the nanocomposites were analyzed and the shape recovery process from a rectangular shaped film to a helical coil was demonstrated. The speed of SMP recovery was found to be dependent on the geometry and concentration of the AuNPs in the nanocomposite, as well as on the laser wavelength and intensity.

Mode Evolution in Strongly Coupled Plasmonic Dolmens Fabricated by Templated Assembly

Plasmonic antennas have enabled a wealth of applications that exploit tailored near-fields and radiative properties, further endowed by the bespoke interactions of multiple resonant building blocks. Specifically, when the interparticle distances are reduced to a few nanometers, coupling may be greatly enhanced leading to ultimate near-field intensities and confinement along with a large energy splitting of resonant modes. While this concept is well-known, the fabrication and characterization of suitable multimers with controlled geometries and few-nanometer gaps remains highly challenging. In this article, we present the topographically templated assembly of single-crystal colloidal gold nanorods into trimers, with a dolmen geometry. This fabrication method enables the precise positioning of high-quality nanorods, with gaps as small as 1.5 nm, which permits a gradual and controlled symmetry breaking by tuning the arrangement of these strongly coupled nanostructures. To characterize the fabricated structures, we perform electron energy loss spectroscopy (EELS) near-field hyperspectral imaging and geometrically accurate EELS, plane wave, and eigenmode full-wave computations to reveal the principles governing the electromagnetic response of such nanostructures that have been extensively studied under plane wave excitation for their Fano resonant properties. These experiments track the evolution of the multipolar interactions with high accuracy as the antenna geometry varies. Our results provide new insights in strongly coupled single-crystal building blocks and open news opportunities for the design and fabrication of plasmonic systems.

Optical Asymmetry and Nonlinear Light Scattering from Colloidal Gold Nanorods.

A systematic study is presented of the intensity-dependent nonlinear light scattering spectra of gold nanorods under resonant excitation of the longitudinal surface plasmon resonance (SPR). The spectra exhibit features due to coherent second and third harmonic generation as well as a broadband feature that has been previously attributed to multiphoton photoluminescence arising primarily from interband optical transitions in the gold. A detailed study of the spectral dependence of the scaling of the scattered light with excitation intensity shows unexpected scaling behavior of the coherent signals, which is quantitatively accounted for by optically induced damping of the SPR mode through a Fermi liquid model of the electronic scattering. The broadband feature is shown to arise not from luminescence, but from scattering of the second-order longitudinal SPR mode with the electron gas, where efficient excitation of the second order mode arises from an optical asymmetry of the nanorod. The electronic-temperature-dependent plasmon damping and the Fermi-Dirac distribution together determine the intensity dependence of the broadband emission, and the structure-dependent absorption spectrum determines the spectral shape through the fluctuation-dissipation theorem. Hence a complete self-consistent picture of both coherent and incoherent light scattering is obtained with a single set of physical parameters.

Exploring gold nanoparticle interactions with proteins and the tumor microenvironment in biological systems.

Gold nanoparticles (AuNPs) have been widely studied as a theranostics agent, especially in the field of cancer treatment and diagnosis, due to their versatile physical and chemical properties (1). Their physical properties make them a good imaging enhancer under different modalities, including x-ray and computed tomography. Their surface plasmon resonance enables them to be combined with newer technologies, including photoacoustic imaging and thermal ablation. Their versatility in synthesis means that AuNPs can be different sizes and shapes, including colloidal gold nanoparticles, nanorods, nanostars, and nanoshells. Common surface modifications are achieved via gold-thiol bond conjugation, and this is a widely applied method of delivering anticancer drugs.

Two-Photon Luminescence of Single Colloidal Gold Nanorods: Revealing the Origin of Plasmon Relaxation in Small Nanocrystals

The two-photon luminescence (TPL) of small 10 nm × 40 nm colloidal gold nanorods (GNR) is investigated at the single object level, combining polarization-resolved TPL and simultaneously acquired topography. A very high dependence of the TPL signal with both the nanorods longitudinal axis and the incident wavelength is observed, confirming the plasmonic origin of the signal and pointing to the limit of the analogy between GNRs and molecules. The maximum two-photon brightness of a single GNR is measured to be a few millions higher than the two-photon brightness of fluorescein molecules. The spectral analysis of the TPL evidence two emission bands peaks: in the visible (in direct connection with the gold band structure) and in the infrared (IR). In both bands, the TPL signal is observed to vary quadratically with the excitation beam; the signal emitted in either the visible or the IR exhibits, however, different polarization properties. We show that the important TPL observed in these small gold nanorods res...

Two-Step Mechanism of Cellular Uptake of Cationic Gold Nanoparticles Modified by (16-Mercaptohexadecyl)trimethylammonium Bromide.

Cationic colloidal gold nanorods (GNRs) have a great potential as a theranostic tool for diverse medical applications. GNRs' properties such as cellular internalization and stability are determined by physicochemical characteristics of their surface coating. GNRs modified by (16-mercaptohexadecyl)trimethylammonium bromide (MTAB), MTABGNRs, show excellent cellular uptake. Despite their promise for biomedicine, however, relatively little is known about the cellular pathways that facilitate the uptake of GNRs, their subcellular fate and intracellular persistence. Here we studied the mechanism of cellular internalization and long-term fate of GNRs coated with MTAB, for which the synthesis was optimized to give higher yield, in various human cell types including normal diploid versus cancerous, and dividing versus nondividing (senescent) cells. The process of MTABGNRs internalization into their final destination in lysosomes proceeds in two steps: (1) fast passive adhesion to cell membrane mediated by sulfated proteoglycans occurring within minutes and (2) slower active transmembrane and intracellular transport of individual nanorods via clathrin-mediated endocytosis and of aggregated nanorods via macropinocytosis. The expression of sulfated proteoglycans was the major factor determining the extent of uptake by the respective cell types. Upon uptake into proliferating cells, MTABGNRs were diluted equally and relatively rapidly into daughter cells; however, in nondividing/senescent cells the loss of MTABGNRs was gradual and very modest, attributable mainly to exocytosis. Exocytosed MTABGNRs can again be internalized. These findings broaden our knowledge about cellular uptake of gold nanorods, a crucial prerequisite for future successful engineering of nanoparticles for biomedical applications such as photothermal cancer therapy or elimination of senescent cells as part of the emerging rejuvenation approach.

Synthesis of Colloidal Gold Nanorods with Plasmon Absorbance Wavelength in the Near Infrared Region

We report preparation and characterization of colloidal gold nanorods (AuNR) with plasmon absorbance over 950 nm and an aspect ratio of 7.2 by tuning silver nitrate concentration and the CTAB/BDAC ratio during growth. Samples were analyzed by scanning transmission electron microscopy, X-ray diffraction, UV-vis absorption spectroscopy and measurement of zeta potential. Addition of 170 μM silver nitrate to the CTAB-containing reaction mixture allowed preparation of AuNRs with a maximum absorbance peak at 941.8 nm and a yield around 96%. Optimization of the BDAC/CTAB ratio allowed for a further redshift of the absorbance maximum to 954.0 nm, but with poorer yields.

Tuning the EDTA-induced self-assembly and plasmonic spectral properties of gold nanorods: application in surface-enhanced Raman scattering

Self-assembly of cetyl trimethyl ammonium bromide-protected colloidal gold nanorods with different aspect ratios has been studied by adding the ethylene diamine tetraacetic acid (EDTA). Both the assembly strength and assembly configuration fashion of the gold nanorods could be tuned by changing the aspect ratio. For gold nanorods with small aspect ratio, side-by-side assembly takes the major role in the aggregation. In this case, the blue shift of the longitudinal absorption and the increase of the transverse absorption lead to the great uplift of the middle spectrum dip as the EDTA is increased. For gold nanorods with large aspect ratio, end-to-end assembly takes the major role in the aggregation. In this case, the longitudinal absorption peak fades down rapidly and a tailing absorption peak at longer wavelength uplifts greatly as the EDTA is increased. The surface-enhanced Raman scattering (SERS) activity of the assembled gold nanorods has been studied using alpha-fetoprotein (AFP) as the Raman active probe. It has been found that both the side-by-side assembly and end-to-end assembly of the gold nanorods could effectively improve the Raman signal of the AFP. And the gold nanorod substrate with side-by-side assembly has higher SERS activity. Side-by-side assembly of gold nanorods leads to the middle spectrum dip of LSPR uplift greatly as the EDTA is increased, which also effectively improves the SERS activity.

End-to-end self-assembly of gold nanorods in isopropanol solution: experimental and theoretical studies.

We describe here a modification of properties of colloidal gold nanorods (NRs) resulting from the chemical treatment used to carry out their transfer into isopropanol (IPA) solution. The NRs acquire a tendency to attach one to another by their ends (end-to-end assembly). We focus on the investigation of the change in position and shape of the longitudinal surface plasmon (l-SPR) band after self-assembly. The experimental results are supported by a theoretical calculation, which rationalizes the dramatic change in optical properties when the NRs are positioned end-to-end at short distances. The detailed spectroscopic characterization performed at the consecutive stages of transfer of the NRs from water into IPA solution revealed the features of the interaction between the polymers used as ligands and their contribution to the final stage, when the NRs were dispersed in IPA solution. The efficient method of aligning the NRs detailed here may facilitate applications of the self-assembled NRs as building blocks for optical materials and biological sensing.Graphical

Tunable Electromagnetic Coupling in Plasmonic Nanostructures Mediated by Thermoresponsive Polymer Brushes.

A smart and highly SERS-active plasmonic platform was designed by coupling regular arrays of nanotriangles to colloidal gold nanorods via a thermoresponsive polymer spacer (poly(N-isopropylacrylamide), PNIPAM). The substrates were prepared by combining a top-down and a bottom-up approach based on nanosphere lithography, surface-initiated controlled radical polymerization, and colloidal assembly. This multistep strategy provided regular hexagonal arrays of nanotriangles functionalized by polymer brushes and colloidal gold nanorods, confined exclusively on the nanotriangle surface. Interestingly, one could finely tune the gold nanorod impregnation on the polymer-coated nanostructures by adjusting the polymer layer thickness, leading to highly coupled plasmonic systems for intense SERS signal. Moreover, the thermoresponsive properties of the PNIPAM brushes could be wisely handled in order to monitor the SERS activity of the nanostructures coupled via this polymer spacer. The coupled hybrid plasmonic nanostructures designed in this work are therefore very promising smart platforms for the sensitive detection of analytes by SERS.

Interactions of Bacterial Lipopolysaccharides with Gold Nanorod Surfaces Investigated by Refractometric Sensing.

The interface between nanoparticles and bacterial surfaces is of great interest for applications in nanomedicine and food safety. Here, we demonstrate that interactions between gold nanorods and bacterial surface molecules are governed by the nanoparticle surface coating. Polymer-coated gold nanorod substrates are exposed to lipopolysaccharides extracted from Pseudomonas aeruginosa, Salmonella enterica and Escherichia coli, and attachment is monitored using localized surface plasmon resonance refractometric sensing. The number of lipopolysaccharide molecules attached per nanorod is calculated from the shift in the plasmon maximum, which results from the change in refractive index after analyte binding. Colloidal gold nanorods in water are also incubated with lipopolysaccharides to demonstrate the effect of lipopolysaccharide concentration on plasmon shift, ζ-potential, and association constant. Both gold nanorod surface charge and surface chemistry affect gold nanorod-lipopolysaccharide interactions. In general, anionic lipopolysaccharides was found to attach more effectively to cationic gold nanorods than to neutral or anionic gold nanorods. Some variation in lipopolysaccharide attachment is also observed between the three strains studied, demonstrating the potential complexity of bacteria-nanoparticle interactions.

Two step continuous method to synthesize colloidal spheroid gold nanorods

This research investigated a two-step continuous process to synthesize colloidal suspension of spheroid gold nanorods. In the first step; gold precursor was reduced to seed-like particles in the presence of polyvinylpyrrolidone and ascorbic acid. In continuous second step; silver nitrate and alkaline sodium hydroxide produced various shape and size Au nanoparticles. The shape was manipulated through weight ratio of ascorbic acid to silver nitrate by varying silver nitrate concentration. The specific weight ratio of 1.35–1.75 grew spheroid gold nanorods of aspect ratio ∼1.85 to ∼2.2. Lower weight ratio of 0.5–1.1 formed spherical nanoparticle. The alkaline medium increased the yield of gold nanorods and reduced reaction time at room temperature. The synthesized gold nanorods retained their shape and size in ethanol. The surface plasmon resonance was red shifted by ∼5nm due to higher refractive index of ethanol than water.

Optical Resonances of Colloidal Gold Nanorods: From Seeds to Chemically Thiolated Long Nanorods

Following an adapted three-step seed-mediated method, we synthesize colloidal Au thin and long (L > 100 nm) nanorods (NRs) and characterize the metallic nanostructures evolving from the initial Au nanoparticle (NPs) seeds to thiolate-functionalized NRs, using HRTEM and ultraviolet, visible, and near-infrared absorption spectroscopy (UV–vis–NIR). For the long NRs we analyze the role of several solvents and rod concentration on the spectral features of the assembled products, which are further studied with simulated spectra. Superimposed to a broad resonance in the range 700–900 nm, which corresponds to short (L < 100 nm) interacting nanorods, the growth of long nanorods is clearly identified with the emergence of a robust resonance at 960 nm, linked to the three half-wavelength antenna plasmon mode. This mode is enhanced when the nanorod concentration decreases and splits into two peaks when the thiolate coverage chemically modifies the rod surface by a thin layer of nanometer size. This behavior is explained with a dielectric model based on ab initio calculations of thiolate–gold cluster surfaces.