Nanoporous Gold Disk Research Articles

Directed Concentrating of Micro-/Nanoparticles via Near-Infrared Laser Generated Plasmonic Microbubbles.

Directed concentrating of micro- and nanoparticles via laser-generated plasmonic microbubbles in a liquid environment is an emerging technology. For effective heating, visible light has been primarily employed in existing demonstrations. In this paper, we demonstrate a new plasmonic platform based on nanoporous gold disk (NPGD) array. Thanks to the highly tunable localized surface plasmon resonance of the NPGD array, microbubbles of controlled size can be generated by near-infrared (NIR) light. Using NIR light provides several key advantages over visible light in less interference with standard microscopy and fluorescence imaging, preventing fluorescence photobleaching, less susceptible to absorption and scattering in turbid biological media, and much reduced photochemistry, phototoxicity, and so forth. The large surface-to-volume ratio of NPGD further facilitates the heat transfer from these gold nanoheaters to the surroundings. While the microbubble is formed, the surrounding liquid circulates and direct microparticles randomly dispersed in the liquid to the bottom NPGD surface, which can be made to yield a unique collection of 3D hollow dome microstructures with bubbles larger than 5 μm. Such capability can also be employed in concentrating suspended colloidal nanoparticles at desirable sites and with the preferred configuration enhancing the sensor performance. Specifically, the interaction among concentrated nanoparticles and their interactions with the underlying substrate have been investigated for the first time. These collections have been characterized using optical microscopy, scanning electron microscopy, hyperspectral localized surface plasmon resonance imaging, and hyperspectral Raman imaging. In addition to various micro- and nanoparticles, the plasmonic microbubbles are also shown to collect biological cells and extracellular nanovesicles such as exosomes. By using a spatial light modulator to project the laser in arbitrary patterns, parallel concentrating can be achieved to fabricate an array of clusters.

10×-Enhanced Heterogeneous Nanocatalysis on a Nanoporous Gold Disk Array with High-Density Hot Spots.

Certain noble metal nanostructures as heterogeneous photocatalysts have drawn significant attention in the recent past because of their unique optical properties which lead to the excitation of localized surface plasmon resonance (LSPR). The LSPR concentrates electromagnetic fields to the surfaces and its relaxation processes can convert photon energy to energetic charge carriers or heat, which can be subsequently harvested to enhance surface catalysis. Here, we report the catalytic performance of a novel plasmonic nanostructure, disk-shaped nanoporous gold (NPG) nanoparticles or simply NPG disks, using a well-tested reduction pathway of resazurin to resorufin. We show that the catalytic reaction rate of NPG disks is enhanced by 10-fold upon external light illumination because of the excitation of LSPR. The plasmon-enhanced catalytic reaction follows a linear-to-superlinear transition in the rate dependence on the input light power. In addition, the light input results in a room temperature reaction rate equivalent to that of an ambient temperature of 70 °C. Together, the results support that hot charge carriers play the dominant role in the enhancement.

Photothermal generation of programmable microbubble array on nanoporous gold disks.

We present a novel technique to generate microbubbles photothermally by continuous-wave laser irradiation of nanoporous gold disk (NPGD) array covered microfluidic channels. When a single laser spot is focused on the NPGDs, a microbubble can be generated with controlled size by adjusting the laser power. The dynamics of both bubble growth and shrinkage are studied. Using computer-generated holography on a spatial light modulator (SLM), simultaneous generation of multiple microbubbles at arbitrary locations with independent control is demonstrated. A potential application of flow manipulation is demonstrated using a microfluidic X-shaped junction. The advantages of this technique are flexible bubble generation locations, long bubble lifetimes, no need for light-adsorbing dyes, high controllability over bubble size, and relatively lower power consumption.

Nanoporous Gold Disks Functionalized with Stabilized G-Quadruplex Moieties for Sensing Small Molecules.

We report label-free small molecule sensing on nanoporous gold disks functionalized with stabilized Guanine-quadruplex (G4) moieties using surface-enhanced Raman spectroscopy (SERS). By utilizing the unique G4 topological structure, target molecules can be selectively captured onto nanoporous gold (NPG) disk surfaces via π-π stacking and electrostatic attractions. Together with high-density plasmonic "hot spots" of NPG disks, the captured molecules produce a remarkable SERS signal. Our strategy represents the first example of the detection of foreign molecules conjugated to nondouble helical DNA nanostructures using SERS while providing a new technique for studying the formation and evolution of G4 moieties. The molecular specificity of G4 is known to be controlled by its unit sequence. Without losing generality, we have selected d(GGT)7GG sequence for the sensing of malachite green (MG), a known carcinogen frequently abused illegally in aquaculture. The newly developed technique achieved a lowest detectable concentration at an impressive 50 pM, two orders of magnitude lower than the European Union (EU) regulatory requirement, with high specificity against potential interferents. To demonstrate the translational potential of this technology, we achieved a lowest detectable concentration of 5.0 nM, meeting the EU regulatory requirement, using a portable probe based detection system.

Simultaneous Chemical and Refractive Index Sensing in the 1–2.5 μm Near-Infrared Wavelength Range on Nanoporous Gold Disks

Near-infrared (NIR) absorption spectroscopy provides molecular and chemical information based on overtones and combination bands of the fundamental vibrational modes in the infrared wavelengths. However, the sensitivity of NIR absorption measurement is limited by the generally weak absorption and the relatively poor detector performance compared to other wavelength ranges. To overcome these barriers, we have developed a novel technique to simultaneously obtain chemical and refractive index sensing in 1-2.5 μm NIR wavelength range on nanoporous gold (NPG) disks, which feature high-density plasmonic hot-spots of localized electric field enhancement. For the first time, surface-enhanced near-infrared absorption (SENIRA) spectroscopy has been demonstrated for high sensitivity chemical detection. With a self-assembled monolayer (SAM) of octadecanethiol (ODT), an enhancement factor (EF) of up to ∼10(4) has been demonstrated for the first C-H combination band at 2400 nm using NPG disk with 600 nm diameter. Together with localized surface plasmon resonance (LSPR) extinction spectroscopy, simultaneous sensing of sample refractive index has been achieved for the first time. The performance of this technique has been evaluated using various hydrocarbon compounds and crude oil samples.

Cover Picture: Label‐free, zeptomole cancer biomarker detection by surface‐enhanced fluorescence on nanoporous gold disk plasmonic nanoparticles (J. Biophotonics 10/2015)

Cover Picture: Label‐free, zeptomole cancer biomarker detection by surface‐enhanced fluorescence on nanoporous gold disk plasmonic nanoparticles (J. Biophotonics 10/2015)

Label-free, zeptomole cancer biomarker detection by surface-enhanced fluorescence on nanoporous gold disk plasmonic nanoparticles.

We experimentally demonstrate a label-free biosensor for the ERBB2 cancer gene DNA target based on the distance-dependent detection of surface-enhanced fluorescence (SEF) on nanoporous gold disk (NPGD) plasmonic nanoparticles. We achieve detection of 2.4 zeptomole of DNA target on the NPGD substrate with an upper concentration detection limit of 1 nM. Without the use of molecular spacers, the NPGD substrate as an SEF platform was shown to provide higher net fluorescence for visible and NIR fluorophores compared to glass and non-porous gold substrates. The enhanced fluorescence signals in patterned nanoporous gold nanoparticles make NPGD a viable material for further reducing detection limits for biomolecular targets used in clinical assays. With patterned nanoporous gold disk (NPGD) plasmonic nanoparticles, a label-free biosensor that makes use of distance-dependent detection of surface-enhanced fluorescence (SEF) is constructed and tested for zeptomole detection of ERBB2 cancer gene DNA targets.

Reagent- and separation-free measurements of urine creatinine concentration using stamping surface enhanced Raman scattering (S-SERS).

We report a novel reagent- and separation-free method for urine creatinine concentration measurement using stamping surface enhanced Raman scattering (S-SERS) technique with nanoporous gold disk (NPGD) plasmonic substrates, a label-free, multiplexed molecular sensing and imaging technique recently developed by us. The performance of this new technology is evaluated by the detection and quantification of creatinine spiked in three different liquids: creatinine in water, mixture of creatinine and urea in water, and creatinine in artificial urine within physiologically relevant concentration ranges. Moreover, the potential application of our method is demonstrated by creatinine concentration measurements in urine samples collected from a mouse model of nephritis. The limit of detection of creatinine was 13.2 nM (0.15 µg/dl) and 0.68 mg/dl in water and urine, respectively. Our method would provide an alternative tool for rapid, cost-effective, and reliable urine analysis for non-invasive diagnosis and monitoring of renal function.

Morphological control and plasmonic tuning of nanoporous gold disks by surface modifications

We report a surface modification protocol to control nanoporous gold (NPG) disk morphology and tune its plasmonic resonance.

Microfluidic surface-enhanced Raman scattering sensor with monolithically integrated nanoporous gold disk arrays for rapid and label-free biomolecular detection.

We present a microfluidic surface-enhanced Raman scattering (SERS) sensor for rapid and label-free biomolecular detection. Our sensor design mitigates a common limiting factor in microfluidic SERS sensors that utilize integrated nanostructures: low-efficiency transport of biomolecules to nanostructured surface which adversely impacts sensitivity. Our strategy is to increase the total usable nanostructured surface area, which provides more adsorption sites for biomolecules. Specifically, a nanoporous gold disk (NPGD) array, a highly effective SERS substrate, has been monolithically integrated inside a microfluidic chip. Individual NPGD is known to feature an order of magnitude larger surface area than its projected disk area. The increased surface area arises from nanoscale pores and ligaments three-dimensionally distributed in the NPGD, which manifest themselves as high-density SERS hot-spots. High-density NPGD arrays further guarantee large coverage of these hot-spots on the microchannel floor. The sensor performance has been demonstrated using Rhodamine 6G to quantify spatial uniformity and determine the shortest detection time. Next, the sensor is applied to detect two biomolecules, dopamine and urea, with unprecedented detection limit and speed compared to other existing microfluidic SERS sensors. The sensor holds great promise in point-of-care applications for various biomolecular detections.

Surface-enhanced Raman spectroscopy with monolithic nanoporous gold disk substrates

Monolithic hierarchical nanoporous gold disks, 500 nm in diameter, 75 nm in thickness and 3.5 nm in pore radius, have been fabricated by hybrid processes. A surface-enhanced Raman scattering enhancement factor of at least 10(8) has been obtained on individual disks using benzenethiol self-assembled monolayer with 785 nm laser excitation.