Facet‐Dependent Optical Properties Revealed through Investigation of Polyhedral Au–Cu2O and Bimetallic Core–Shell Nanocrystals

The ability to prepare Au–Cu₂O core–shell nanocrystals with precise control over particle size and shape has led to the discovery of facet‐dependent optical properties in cuprous oxide crystals. The use of Au cores not only allows the successful formation of Au–Cu₂O core–shell nanocrystals with tunable sizes, but also enables the observation of facet‐dependent optical properties in these crystals through the Au localized surface plasmon resonance (LSPR) absorption band. By tuning the Cu₂O shell morphology from rhombic dodecahedral to octahedral and cubic structures, and thus the exposed facets, the Au LSPR band position can be widely tuned. Such facet‐dependent optical effects are not observed in bimetallic Au–Ag and Au–Pd core–shell nanocrystals with the same precisely tuned particle sizes and shapes. It is believed that similar facet‐dependent optical properties could be observed in other ionic solids and other metal–metal oxide systems. The unusually large degree of plasmonic band tuning covering from the visible to the near‐infrared region in this type of nanostructure should be quite useful for a range of plasmonic applications.     

Rapid rotation of micron and submicron dielectric particles measured using optical tweezers

Abstract

We demonstrate the use of a laser trap (‘optical tweezers’) and back-focal-plane position detector to measure rapid rotation in aqueous solution of single particles with sizes in the vicinity of 1 μm. Two types of rotation were measured: electrorotation of polystyrene microspheres and rotation of the flagellar motor of the bacterium Vibrio alginolyticus. In both cases, speeds in excess of 1000 Hz (rev s^?1) were measured. Polystyrene beads of diameter about 1 μm labelled with smaller beads were held at the centre of a microelectrode array by the optical tweezers. Electrorotation of the labelled beads was induced by applying a rotating electric field to the solution using microelectrodes. Electrorotation spectra were obtained by varying the frequency of the applied field and analysed to obtain the surface conductance of the beads. Single cells of V. alginolyticus were trapped and rotation of the polar sodium-driven flagellar motor was measured. Cells rotated more rapidly in media containing higher concentrations of Na⁺, and photodamage caused by the trap was considerably less when the suspending medium did not contain oxygen. The technique allows single-speed measurements to be made in less than a second and separate particles can be measured at a rate of several per minute.     

Optical trapping of fluorescent beads

Optical tweezers have been successfully used to trap a variety of particles and biological specimens for numerous applications. Particles which are reflective as well as absorbing could be trapped using beams such as optical vortex. Here we give the details of our efforts to trap fluorescent microparticles. We have set up an optical trap for these fluorescent microparticles using holographic optical tweezers; we observe that it is not possible to trap fluorescent microparticles with a Gaussian laser beam or a hollow beam. However, as the fluorescence of these particles gets degraded they could be trapped in custom-made holographic tweezers. Moreover, when a fluorescent particle is brought in the trap containing stably trapped non-fluorescent particle, the stably trapped non-fluorescent particle also escapes from the trap.     

The applicability of dynamic light scattering to determination of nanoparticle dimensions in sols

It is shown that the use of the dynamic light scattering (DLS) method for determining nanoparticle dimensions in sols containing mixtures of particles with various sizes may lead to incorrect results, since the distribution of small particle sizes can remain unrecognized. The conditions and threshold of this phenomenon are established. It is indicated that the measurement of nanoparticle dimensions by DLS in these cases must be supplemented by auxiliary optical measurements.     

Optothermal escape of plasmonically coupled silver nanoparticles from a three-dimensional optical trap

We demonstrate that optical trapping of multiple silver nanoparticles is strongly influenced by plasmonic coupling of the nanoparticles. Employing dark-field Rayleigh scattering imaging and spectroscopy on multiple silver nanoparticles optically trapped in three dimensions, we experimentally investigate the time-evolution of the coupled plasmon resonance and its influence on the trapping stability. With time the coupling strengthens, which is observed as a gradual red shift of the coupled plasmon scattering. When the coupled plasmon becomes resonant with the trapping laser wavelength, the trap is destabilized and nanoparticles are released from the trap. Modeling of the trapping potential and its comparison to the plasmonic heating efficiency at various nanoparticle separation distances suggests a thermal mechanism of the trap destabilization. Our findings provide insight into the specificity of three-dimensional optical manipulation of plasmonic nanostructures suitable for field enhancement, for example for surface-enhanced Raman scattering.     

Temperature Determination of Resonantly Excited Plasmonic Branched Gold Nanoparticles by X‐ray Absorption Spectroscopy

The fields of bioscience and nanomedicine demand precise thermometry for nanoparticle heat characterization down to the nanoscale regime. Since current methods often use indirect and less accurate techniques to determine the nanoparticle temperature, there is a pressing need for a direct and reliable element‐specific method. In‐situ extended X‐ray absorption fine structure (EXAFS) spectroscopy is used to determine the thermo‐optical properties of plasmonic branched gold nanoparticles upon resonant laser illumination. With EXAFS, the direct determination of the nanoparticle temperature increase upon laser illumination is possible via the thermal influence on the gold lattice parameters. More specifically, using the change of the Debye–Waller term representing the lattice disorder, the temperature increase is selectively measured within the plasmonic branched nanoparticles upon resonant laser illumination. In addition, the signal intensity shows that the nanoparticle concentration in the beam more than doubles during laser illumination, thereby demonstrating that photothermal heating is a dynamic process. A comparable temperature increase is measured in the nanoparticle suspension using a thermocouple. This good correspondence between the temperature at the level of the nanoparticle and at the level of the suspension points to an efficient heat transfer between the nanoparticle and the surrounding medium, thus confirming the potential of branched gold nanoparticles for hyperthermia applications. This work demonstrates that X‐ray absorption spectroscopy‐based nanothermometry could be a valuable tool in the fast‐growing number of applications of plasmonic nanoparticles, particularly in life sciences and medicine.     

不同粒径超顺磁性氧化铁纳米粒子的合成及其在交变磁场中的磁热效应

采用多醇热解法制备3种不同粒径的超顺磁性氧化铁纳米粒子(SPIONs),合成的SPIONs含Fe_3O_4晶相,分散性好,平均粒径分别为8.7,12.6nm和15.3nm,且在300K下,3种SPIONs均呈超顺磁性。将不同粒径、不同浓度的SPIONs水分散液置于频率为425kHz、磁场强度为5.3kA·m^-1的交变磁场(ACMF)中进行升温实验。探讨比能量吸收率值与SPIONs粒径之间的关系,计算布朗弛豫时间及尼尔弛豫时间。结果表明:SPIONs水分散液的升温速率随SPIONs的粒径增大而增大,初始温度为20℃时,粒径为8.7,12.6nm和15.3nm的SPIONs水分散液(2mg·mL^-1)在480s内温度分别升高了25,27,35℃。尼尔弛豫时间比布朗弛豫时间小,说明磁热效应主要来自于尼尔弛豫损耗。SPIONs粒径越大,比能量吸收率SAR值越高,最高可达810W·g^-1,且SAR值与SPIONs水分散液的浓度呈负相关关系。     

Optically driven nanorotors: experiments and model calculations

We show that asymmetric nanorods rotate under the laser radiation pressure, irrespective of the polarization of the light, when trapped in laser tweezers. If a nanorod is not quite transparent to the trapping laser radiation, the radiation pressure force generates a non zero torque on the asymmetric nanorods making them rotate at a moderate speed. Our experimental observations on radiation pressure driven rotations of MgO and Si nanorods in optical trap show that the efficiency of the rotors depends directly on their transmittance at the trapping wavelength. We propose theoretical models to estimate the rotational speed at different laser powers for a rotor with shape asymmetries or surface irregularities.     

Quantum Dot‐Based Thermal Spectroscopy and Imaging of Optically Trapped Microspheres and Single Cells

Laser‐induced thermal effects in optically trapped microspheres and single cells are investigated by quantum dot luminescence thermometry. Thermal spectroscopy has revealed a non‐localized temperature distribution around the trap that extends over tens of micrometers, in agreement with previous theoretical models besides identifying water absorption as the most important heating source. The experimental results of thermal loading at a variety of wavelengths reveal that an optimum trapping wavelength exists for biological applications close to 820 nm. This is corroborated by a simultaneous analysis of the spectral dependence of cellular heating and damage in human lymphocytes during optical trapping. This quantum dot luminescence thermometry demonstrates that optical trapping with 820 nm laser radiation produces minimum intracellular heating, well below the cytotoxic level (43 °C), thus, avoiding cell damage.     

Preparation of highly water-dispersible titanium-silicon binary oxide materials by sol-gel method

The preparation of highly water-dispersible titanium-silicon binary oxide materials was performed by the following two-stage sol-gel reactions. First, the mixture of titanium tetraisopropoxide and 3-aminopropyltrimethoxysilane was stirred in a mixed solvent of isopropyl alcohol and 0.5 mol/L methanolic hydrochloric acid at room temperature, followed by heating in an open system until the solvent was evaporated. Then, the aqueous solution obtained by adding water to the resulting product was heated in the open system until the water was completely reevaporated. The resulting product was dispersed well in water, and its aqueous dispersion was highly transparent and cut off UV light, confirmed by UV-Vis measurements. The solid product obtained by lyophilization of its aqueous dispersion was redispersed in water. The average particle size of the product was assessed to be < 10 nm by dynamic light scattering (DLS) in water and transmission electron microscopy (TEM) measurements, indicating that the product was a water-dispersible spherical nanoparticle. It was assumed that the water-dispersible property of the product probably originated from the TiO2/SiO1.5(CH2)3NH3 x Cl core/shell structure. In addition, highly transparent films can be prepared from the aqueous dispersion of the product, and these films also cut off the UV light, evaluated by UV-Vis measurements.     

An on-line measurement and control system for submerged arc spray synthesis of TiO2 nanoparticles

This article presents the development of an on-line measurement and control system for process characterization and optimization of the nanoparticle manufacturing process, called the submerged arc-spray nanoparticle synthesis system (SANSS). To achieve optimized control of particle uniformity, this research investigates the feasibility of employing optical fiber probe and the dynamic light scattering (DLS) technique to monitor and control particle sizes. According to the theory of DLS, an on-line nanoparticle sampling and measurement system was developed and integrated with the SANSS as an important step to verify the measurement performance of the proposed method. To examine the measurement accuracy of the developed system, calibrated polystyrene latex particles with known accurate sizes were employed to verify the particle sizing accuracy of the proposed system. The data conformity between the measurement results of TiO, nanoparticles obtained by various methods, including TEM, a calibrated commercial particle sizing system and the on-line measurement system, has indicated that the developed method was feasible and effective.     

Controlled synthesis and optical properties of Au and Au@PS nanoparticles

In this study, uniform gold (Au) nanoparticles (NPs) were prepared using seed-mediated growth method. The particle size was controlled by tuning the dosage of seed solution. Au@PS core–shell NPs were then synthesized by introducing a polystyrene (PS) shell (2–3 nm thick) around the core of Au NPs (115 nm). Evaluation of the surface plasmon (SP) optical properties indicated that wavelength of SP resonance of Au NPs increased gradually with increase in the particle size. This red shift was about 0.92 nm per 1 nm increase in particle size. The results also indicated that the zeta potential and optical properties of Au NPs could be adjusted by coating PS on the outside. Therefore, surface modifications and surface coating were effective ways to control the optical properties of Au NPs.     

Programmable Negative Differential Resistance Effects Based on Self‐Assembled Au@PPy Core–Shell Nanoparticle Arrays

The negative differential resistance (NDR) effect observed in conducting polymer/Au nanoparticle composite devices is not yet fully clarified due to the random and disordered incorporation of Au nanoparticles into conducting polymers. It remains a formidable challenge to achieve the sequential arrangement of various components in an optimal manner during the fabrication of Au nanoparticle/conducting polymer composite devices. Here, a novel strategy for fabricating Au nanoparticle/conducting polymer composite devices based on self‐assembled Au@PPy core–shell nanoparticle arrays is demonstrated. The interval between the two Au nanoparticles can be precisely programmed by modulating the thickness of the shell and the size of the core. Programmable NDR is achieved by regulating the spacer between two Au nanoparticles. In addition, the Au/conducting polymer composite device exhibits a reproducible memory effect with read–write–erase characteristics. The sequentially controllable assembly of Au@PPy core–shell nanoparticle arrays between two microelectrodes will simplify nanodevice fabrication and will provide a profound impact on the development of new approaches for Au/conducting polymer composite devices.     

Particle-size and velocity measurements in flowing conditions using dynamic light scattering

The noninvasive optical technique of dynamic light scattering (DLS) is routinely used to characterize dilute and transparent submicrometer particle dispersions in laboratory environments. A variety of industrial and biological applications would, however, greatly benefit from on-line monitoring of dispersions under flowing conditions. We present a model experiment to study flowing dispersions of polystyrene latex particles of varying sizes under varying flow conditions by using a newly developed fiber-optic DLS probe. A modified correlation function proposed in an earlier study is applied to the analysis of extracting the size and velocity of laminar flowing particulate dispersions. The complementary technique of laser Doppler velocimetry is also used to measure the speed of moving particles to confirm the DLS findings.     

Characterization of silica-coated Ag nanoparticles synthesized using a water-soluble nanoparticle micelle

This article describes the synthesis of silica-coated Ag nanoparticles using a water-soluble nanoparticle micelle under basic conditions. Monodispersed Ag nanoparticles with a mean particle size of 7 nm were synthesized using AgNO₃ in the presence of ascorbic acid as a reducing agent. The Ag nanoparticles were easily re-dispersed into an aqueous solution by surface adsorption of surfactant molecules, indicating formation of water-soluble nanoparticle micelles. Silica-coated Ag nanoparticles ranging in size from 50 to 100 nm were obtained by controlling the surfactant, Ag nanoparticle and tetraethylortho silicate (TEOS) concentrations. Adsorbed surfactant monolayers on Ag nanoparticles were used as a template for the silica shell because of the hydrophobicity of TEOS. In all cases, the size of the resulting particles increased linearly as these concentrations increased. Based on transmission electron microscopy, all the Ag nanoparticles were completely covered with a silica shell. In most samples, however, Ag nanoparticle size increased from 7 to 50 nm due to evaporation of hexane by heating. Although mean particle size of silica-coated Ag nanoparticles was drastically altered, characteristic absorption peaks were observed at approximately 410 nm.     

Multiphoton fluorescence excitation in continuous-wave infrared optical traps

The multiphoton fluorescence excitation observed in acontinuous-wave (cw) single-beam gradient force optical trap(optical tweezers) is reported for latex beads labeled with ayellow-green fluorescent dye (BODIPY). The fluorescenceemission spectra of the yellow-green beads trapped and excited by thesame 1064-nm laser light are identical to the spectra excited by the365-nm UV light. The influence of the numerical aperture of theobjective on the slope of the log-log power-dependence has beendemonstrated for BODIPY-Oil solution under cw and pulsed-laserconditions. The possibility that three-photon excitation processoccurs is discussed within the context of a dog-bone saturationmodel. Other possibilities for the observed fluorescence excitationhave been discussed.     

DNA‐Directed Gold Nanodimers with Tunable Sizes and Interparticle Distances and Their Surface Plasmonic Properties

A quantitative understanding of the localized surface plasmon resonances (LSPRs) of metallic nanostructures has received tremendous interest. However, most of the current studies are concentrated on theoretical calculation due to the difficulty in experimentally obtaining monodisperse discrete metallic nanostructures with high purity. In this work, endeavors to assemble symmetric and asymmetric gold nanoparticle (AuNP) dimer structures with exceptional purity are reported using a DNA self‐assembly strategy through a one‐step gel electrophoresis, which greatly facilitates the preparation process and improves the final purity. In the obtained Au nanodimers, the sizes of AuNPs (13, 20, and 40 nm) and the interparticle distances (5, 10, and 15 nm) are tunable. The size‐ and distance‐dependent plasmon coupling of ensembles of single, isolated dimers in solution are subsequently investigated. The experimental measurements are correlated with the modeled plasmon optical properties of Au nanodimers, showing an expected resonance shift with changing particle sizes and interparticle distances. This new strategy of constructing monodisperse metallic nanodimers will be helpful for building more complicated nanostructures, and our theoretical and experimental understanding of the intrinsic dependence of plasmon property of metallic nanodimer on the sizes and interparticle distances will benefit the future investigation and exploitation of near‐field plasmonic properties.     

Determination of the size of water-soluble nanoparticles and quantum dots by field-flow fractionation

Field flow fractionation (FFF) technique is used to determine the size of water-soluble Au, ZnS, ZnS-Mn2+ nanoparticles, and CdSe, CdSe-DNA quantum dots (QDs). The results of the FFF measurements are compared with the particle size analysis using conventional techniques like scanning electron microscopy (SEM), transmission electron microscopy (TEM), and dynamic light scattering (DLS) studies. Water-soluble gold nanoparticles (AuNPs) stabilized by mercaptosuccinic acid (MSA) as the ligand when analyzed by the SEM and DLS showed evidence of extensive aggregation, preventing an accurate determination of the average particle size. The TEM analyses without staining offered a facile measurement of the nanoparticle core but average particle size determination required analysis of the TEM image using image analysis software. On the other hand the FFF is seemingly a convenient and easy method for the determination of the average particle size of the AuNPs. In case of the ZnS and ZnS-Mn2+ nanoparticles with mercaptopropionic acid (MPA) as the capping agent severe aggregation prevented accurate estimation of particle sizes even by the high resolution TEM (HRTEM), where as the size determination by the FFF was very facile. Analysis of the CdSe-DNA conjugate by the TEM was difficult as the sample got damaged upon exposure to the electron beam. The FFF cross-flow condition is apparently noninvasive and hence the technique was very effective in characterizing the CdSe-DNA QDs. Furthermore, using this simple technique it was possible to fractionate a sample of the AuNPs. The FFF measurement of water-soluble nanoparticles is an excellent complement to characterization of such particles by the conventional tools.     

Massively Multiplexed Submicron Particle Patterning in Acoustically Driven Oscillating Nanocavities

Nanoacoustic fields are a promising method for particle actuation at the nanoscale, though THz frequencies are typically required to create nanoscale wavelengths. In this work, the generation of robust nanoscale force gradients is demonstrated using MHz driving frequencies via acoustic‐structure interactions. A structured elastic layer at the interface between a microfluidic channel and a traveling surface acoustic wave (SAW) device results in submicron acoustic traps, each of which can trap individual submicron particles. The acoustically driven deformation of nanocavities gives rise to time‐averaged acoustic fields which direct suspended particles toward, and trap them within, the nanocavities. The use of SAWs permits massively multiplexed particle manipulation with deterministic patterning at the single‐particle level. In this work, 300 nm diameter particles are acoustically trapped in 500 nm diameter cavities using traveling SAWs with wavelengths in the range of 20–80 µm with one particle per cavity. On‐demand generation of nanoscale acoustic force gradients has wide applications in nanoparticle manipulation, including bioparticle enrichment and enhanced catalytic reactions for industrial applications.