A correlative optical microscopy and scanning electron microscopy approach to locating nanoparticles in brain tumors

The growing use of nanoparticles in biomedical applications, including cancer diagnosis and treatment, demands the capability to exactly locate them within complex biological systems. In this work a correlative optical and scanning electron microscopy technique was developed to locate and observe multi-modal gold core nanoparticle accumulation in brain tumor models. Entire brain sections from mice containing orthotopic brain tumors injected intravenously with nanoparticles were imaged using both optical microscopy to identify the brain tumor, and scanning electron microscopy to identify the individual nanoparticles. Gold-based nanoparticles were readily identified in the scanning electron microscope using backscattered electron imaging as bright spots against a darker background. This information was then correlated to determine the exact location of the nanoparticles within the brain tissue. The nanoparticles were located only in areas that contained tumor cells, and not in the surrounding healthy brain tissue. This correlative technique provides a powerful method to relate the macro- and micro-scale features visible in light microscopy with the nanoscale features resolvable in scanning electron microscopy.     

Structural and Optical Properties of Gold/Silica “Mushroom” Particles Prepared by Interfacial Templating

Complex shaped nanoparticles featuring structural or surface chemical patchiness are of special interest in both fundamental and applied research areas. This study reports the preparation and optical properties of gold/silica “mushroom” nanoparticles, where a gold particle is only partially covered by the silica cap. The synthetic approach allows precise control over the particle structure. The interfacial preparation method relies on partially embedding the gold particles in a polystyrene layer that masks the immersed part of the gold particle during silica shell growth from an aqueous solution. By adjusting sacrificial polystyrene film thickness and silica growth time, precise control over the coverage and cap thickness can be achieved. Correlative electron microscopy and single particle scattering spectroscopy measurements underline the high precision and reproducibility of the method. The good agreement between the measured and simulated single particle spectra supported by near‐field calculations indicates that the observed changes in the dipolar plasmon resonance are influenced by the extent of coverage of the gold core by the silica cap. The straightforward methods readily available for gold and silica surface modification using range of different (bio)molecules make these well‐defined nanoscale objects excellent candidates to study fundamental processes of programmed self‐assembly or application as theranostic agents.     

Application of metal nanoparticles in confocal laser scanning microscopy: improved resolution by optical field enhancement

We describe experiments in which the field enhancement by metal nanoparticles that accompanies surface plasmon excitation has been exploited in confocal laser scanning microscopy. The objective was to make use of the rapid decay of the enhanced light field with distance from the nanoparticles to increase the longitudinal resolution, by confining the emission of fluorescence light to the immediate vicinity of the contact area between the substrate and the objects under study. We demonstrate that the increased longitudinal resolution is accompanied by a better lateral resolution if the imaged objects have a curved surface.     

A Correlative Analysis of Gold Nanoparticles Internalized by A549 Cells

Fluorescently labeled nanoparticles are widely used to investigate nanoparticle cell interactions by fluorescence microscopy. Owing to limited lateral and axial resolution, nanostructures (<100 nm) cannot be resolved by conventional light micro­scopy techniques. Especially after uptake into cells, a common fate of the fluorescence label and the particle core cannot be taken for granted. In this study, a correlative approach is presented to image fluorescently labeled gold nanoparticles inside whole cells by correlative light and electron microscopy (CLEM). This approach allows for detection of the fluorescently labeled particle shell as well as for the gold core in one sample. In this setup, A549 cells are exposed to 8 nm Atto 647N‐labeled gold nanoparticles (3.3 × 10⁹ particles mL^?1, 0.02 μg Au mL^?1) for 5 h and are subsequently imaged by confocal laser scanning microscopy (CLSM) and transmission electron microscopy (TEM). Eight fluorescence signals located at different intracellular positions are further analyzed by TEM. Five of the eight fluorescence spots are correlated with isolated or agglomerated gold nanoparticles. Three fluorescence signals could not be related to the presence of gold, indicating a loss of the particle shell.     

Radiation induced synthesis of gold/iron-oxide composite nanoparticles using high-energy electron beam

Composite nanoparticles consisting of gold and iron oxide were synthesized in aqueous solution systems by using a high-energy electron beam. The electron irradiation induces radiation-chemical reaction to form metallic gold nanoparticles. These gold nanoparticles were firmly immobilized on the surface of the support iron oxide nanoparticles. Surface of the support iron oxide nanoparticles are almost fully coated with fine gold nanoparticles. The size of these gold nanoparticles depended on the concentrations of gold ions, polymers and iron oxide nanoparticles in the solutions before the irradiation.     

Kinetic Monte Carlo simulation of nanoparticle film formation via nanocolloid drying

A kinetic Monte Carlo simulation of nanoparticle film formation via nanocolloid drying is presented. The proposed two-dimensional model addresses the dynamics of nanoparticles in the vertical plane of a drying nanocolloid film. The gas–liquid interface movement due to solvent evaporation was controlled by a time-dependent chemical potential, and the resultant particle dynamics including Brownian diffusion and aggregate growth were calculated. Simulations were performed at various Peclet numbers defined based on the rate ratio of solvent evaporation and nanoparticle diffusion. At high Peclet numbers, nanoparticles accumulated at the top layer of the liquid film and eventually formed a skin layer, causing the formation of a particulate film with a densely packed structure. At low Peclet numbers, enhanced particle diffusion led to significant particle aggregation in the bulk colloid, and the resulting film structure became highly porous. The simulated results showed some typical characteristics of a drying nanocolloid that had been reported experimentally. Finally, the potential of the model as well as the remaining challenges are discussed.     

Quantitative atomic-scale analysis of interface structures: transmission electron microscopy and local density functional theory

Transmission electron microscopy (TEM) and local density functional theory (LDFT) are combined to analyze the microscopic structure of the rhombohedral twin interface in alpha-Al2O3. LDFT provides interfacial energetics and atomic and electronic structures for three competing models. With high-resolution TEM the atomic structure at the interface is imaged quantitatively along two orthogonal zone axes. Electron energy loss spectroscopy in TEM with nanoscale spatial resolution yields the interfacial electronic structure. Both experiments confirm the theoretically preferred model quantitatively.     

Surface plasmon microscopy using an energy-filtered low energy electron microscope

We present low energy electron microscope (LEEM) spectromicroscopy studies of surface plasmons, localized on micro- and nanoscale epitaxial Ag islands. Excellent agreement is found in a direct comparison of wave vector dependent plasmon intensity with theory, demonstrating that high quality quantitative data can be obtained with a large improvement in both spatial and temporal resolution over traditional electron scattering experiments. The plasmon signal from Ag islands is successfully imaged with a spatial resolution of less than 35 nm. LEEM based plasmon spectromicroscopy promises to be a powerful tool for furthering our understanding of nanoplasmonics.     

Laser-assisted generation of gold nanoparticles and nanostructures in liquid and their plasmonic luminescence

Nanoparticles (NPs) and surface nanostructures (NS) are produced via laser ablation of a bulk gold target in liquid using second harmonics of 10 ps Nd:YAG laser (532 nm) with repetition rate of 50 kHz. The morphology and plasmon photoluminescence (PL) properties of obtained nanoscale objects are described. Transmission electron microscopy and field emission scanning electron microscopy are used for morphology characterization of NPs and NS, respectively. Plasmon PL of both gold NPs and NS is experimentally studied using the third harmonics of the Nd:YAG picosecond laser (355 nm) as a pump. The wavelength of intensity maximum of PL of Au NPs colloidal solution virtually coincides with the position of Au NPs plasmon absorption peak. Real-time excitation of both plasmon PL and Raman scattering of surrounding liquid by picosecond laser pulses in aqueous colloidal solution is also investigated. The efficient cross section of plasmon PL of Au NPs colloid is evaluated using Raman scattering of water as a comparative parameter. The results are in good agreement with values obtained in previous works. Plasmon PL from self-organized NS on the Au surface produced via laser ablation is observed for the first time. Its spectrum is compared to PL spectra of both aqueous colloidal solutions of NPs and of NPs deposited on a Si wafer. The obtained experimental data are discussed with reference to the band structure of bulk Au.     

Surface plasmon resonance-induced tunable polarization filters based on nanoscale gold film-coated photonic crystal fibers

Surface plasmon resonance induced tunable polarization filters based on nanoscale gold film-coated photonic crystal fibers were proposed and analyzed. The characteristics of the polarization filter were calculated by finite element method(FEM). The gold film was selectively coated on the inner wall of one cladding air hole which was located near the fiber core along the y-axis direction. When the phase of core fundamental mode and surface plasmon polaritons(SPPs) mode matches,the two modes couple with each other intensely. Numerical results show that the resonance wavelength and strength vary with fiber structural parameters and the index of the infilling liquid. The fiber parameters were optimized to achieve specific functions. Under the optimal structure, we realized a dual channel filter at the communication wavelength of 1.31 μm and1.55 μm for y polarization direction and x polarization direction. Then a single channel polarized filter at the communication wavelength of 1.55 μm is also achieved by adjusting the refractive index of the infilling liquid. The proposed polarization filters realized dual channel filtering and single channel filtering simultaneously under the same structure for the first time to the best of our knowledge.     

Photothermally enhanced catalytic activity of partially aggregated gold nanoparticles

In the present study, a facile, rapid, and environmentally friendly method was used for the preparation of metal oxide nanoparticles in an ionic liquid medium. This technique involves mixing and heating the corresponding powder material (cadmium oxide, anatase, and hematite) and the selected ionic liquid (trihexyl(tetradecyl)phosphonium chloride, [P_6,6,6,14]Cl), without any other precursors or solvents. The confirmation of the existence of nanoparticles in the ionic liquid was carried out using UV?CVis absorption spectroscopy, and its concentration was determined by X-ray fluorescence. In order to analyze the shape and size distribution, transmission electron microscopy and a ZetaSizer (DLS technique) were used; finding out that the size of the hematite nanoparticles was 10?C55?nm. Nevertheless, for the cadmium oxide and the anatase nanoparticles, the size was between 2 and 15?nm. The composition of the prepared nanoparticles was studied by Raman spectroscopy. The structure of solids did not suffer any modification in their transformation to the nanoscale, as concluded from the X-ray powder diffraction analysis.     

Scattering lens resolves sub-100 nm structures with visible light

The smallest structures that conventional lenses are able to optically resolve are of the order of 200 nm. We introduce a new type of lens that exploits multiple scattering of light to generate a scanning nanosized optical focus. With an experimental realization of this lens in gallium phosphide we imaged gold nanoparticles at 97 nm optical resolution. Our work is the first lens that provides a resolution better than 100 nm at visible wavelengths.     

Synthesis and characterization of stable Co and Cd doped nickel hydroxide nanoparticles for electrochemical applications

The present paper describes the physical-chemical characterization and electrochemical behavior of a new nanomaterial formed by the addition of cadmium and cobalt atoms into the structure of nickel hydroxide nanoparticles, these ones synthesized by an easy sonochemical method. Particles of about 5nm diameter were obtained and characterized by high resolution transmission electron microscopy (HRTEM), X-ray diffraction and Raman spectroscopy. Different nickel hydroxide nanoparticles were immobilized onto transparent conducting substrates by using electrostatic layer-by-layer providing thin films at the nanoscale and the electrochemical behavior was investigated. The formation of a mixed hydroxide was corroborated by observation of very interesting properties as redox potential shifting to less positive potentials and high stability when submitted to long electrochemical cycling or high times of ultrasonic synthesis, suggesting practical applications.     

Size‐Dependence of the Melting Temperature of Individual Au Nanoparticles

Nanoparticles have an immense importance in various fields, such as medicine, catalysis, and various technological applications. Nanoparticles exhibit a significant depression in melting point as their size goes below ≈10 nm. However, nanoparticles are frequently used in high temperature applications such as catalysis where temperatures often exceed several 100 degrees which makes it interesting to study not only the melting temperature depression, but also how the melting progresses through the particle. Using high‐resolution transmission electron microscopy, the melting process of gold nanoparticles in the size range of 2–20 nm Au nanoparticles combined with molecular dynamics studies is investigated. A linear dependence of the melting temperature on the inverse particle size is confirmed; electron microscopy imaging reveals that the particles start melting at the surface and the liquid shell formed then rapidly expands to the particle core.     

Observation of Undamped 3D Brownian Motion of Nanoparticles Using Liquid-Cell Scanning Transmission Electron Microscopy

In theory, liquid-cell (scanning) transmission electron microscopy (LC(S)TEM) is the ideal method to measure 3D diffusion of nanoparticles (NPs) on a single particle level, beyond the capabilities of optical methods. However, particle diffusion experiments have been especially hard to explain in LC(S)TEM as the observed motion thus far has been slower than theoretical predictions by 3–8 orders of magnitude due to electron beam effects. Here, direct experimental evidence of undamped diffusion for two systems is shown; charge-neutral 77 nm gold nanoparticles in glycerol and negatively charged 350 nm titania particles in glycerol carbonate. The high viscosities of the used media and a low electron dose rate allow observation of Brownian motion that is not significantly altered by the electron beam. The resulting diffusion coefficient agrees excellently with a theoretical value assuming free diffusion. It is confirmed that the particles are also moving in the direction parallel to the electron beam by simulating STEM images using Monte Carlo simulations. Simulations and experiments show blurring of the particles when these move out of focus. These results make clear that direct observation of 3D diffusion of NPs is possible, which is of critical importance for the study of interparticle interactions or in situ colloidal self-assembly using LC(S)TEM.     

Green synthesis of gold and silver nanoparticles using gallic acid: catalytic activity and conversion yield toward the 4-nitrophenol reduction reaction

In the present report, gallic acid was used as both a reducing and stabilizing agent to synthesize gold and silver nanoparticles. The synthesized gold and silver nanoparticles exhibited characteristic surface plasmon resonance bands at 536 and 392 nm, respectively. Nanoparticles that were approximately spherical in shape were observed in high-resolution transmission electron microscopy and atomic force microscopy images. The hydrodynamic radius was determined to be 54.4 nm for gold nanoparticles and 33.7 nm for silver nanoparticles in aqueous medium. X-ray diffraction analyses confirmed that the synthesized nanoparticles possessed a face-centered cubic structure. FT-IR spectra demonstrated that the carboxylic acid functional groups of gallic acid contributed to the electrostatic binding onto the surface of the nanoparticles. Zeta potential values of ?41.98 mV for the gold nanoparticles and ?53.47 mV for the silver nanoparticles indicated that the synthesized nanoparticles possess excellent stability. On-the-shelf stability for 4 weeks also confirmed that the synthesized nanoparticles were quite stable without significant changes in their UV–visible spectra. The synthesized nanoparticles exhibited catalytic activity toward the reduction reaction of 4-nitrophenol to 4-aminophenol in the presence of sodium borohydride. The rate constant of the silver nanoparticles was higher than that of the gold nanoparticles in the catalytic reaction. Furthermore, the conversion yield (%) of 4-nitrophenol to 4-aminophenol was determined using reversed-phase high-performance liquid chromatography with UV detection at 254 nm. The silver nanoparticles exhibited an excellent conversion yield (96.7–99.9 %), suggesting that the synthesized silver nanoparticles are highly efficient catalysts for the 4-nitrophenol reduction reaction.     

纳米流体介质导热机理初探

纳米流体导热行为具有许多奇异的特性，结合纳米流体的特点和微尺度传热学原理，研究了 热流在纳米颗粒内波动式及非限域的热传导特性、纳米颗粒在悬浮液内的布朗运动、颗粒- 液体界面上液膜层原子的有规则排列、以及纳米颗粒的团簇形成及移动等四方面因素对纳米 流体导热系数的影响. 关键词： 纳米流体 导热     

基于金刚石NV色心的纳米尺度磁场测量和成像技术

纳米级分辨率的磁场测量和成像是磁学中的一种重要研究手段.金刚石中的单个氮-空位点缺陷电子自旋作为一种量子传感器,具有灵敏度高、原子级别尺寸、可工作在室温等诸多优势,灵敏度可以达到单核自旋级别,空间分辨率达到亚纳米.将这种磁测量技术与扫描成像技术结合,能够实现高灵敏度和高分辨率的磁场成像,定量地重构出杂散场.这种新型的磁成像技术可以给出磁学中多种重要的研究对象如磁畴壁、反铁磁序、磁性斯格明子的结构信息.随着技术的发展,基于氮-空位点缺陷的磁成像技术有望成为磁性材料研究的重要手段.     

Thermo- and pH-responsive hydrogel-coated gold nanoparticles prepared from rationally designed surface-confined initiators

Gold nanoparticles (~40 nm in diameter) were encapsulated by a hydrogel overlayer generated by the free radical polymerization of N-isopropylacrylamide-co-acrylic acid (NIPAM-co-AA), which was promoted by a specifically designed radical initiator covalently anchored to the surface of the gold core. The size and morphology of the shell/core nanoparticles were characterized by scanning electron microscopy and transmission electron microscopy. In addition, the optical properties of the nanoparticles were characterized by UV–Visible spectroscopy. Separately, the particle size was evaluated as a function of temperature and pH using dynamic light scattering. The shell/core hydrogel nanoparticles undergo reversible volume changes in water at a lower critical solution temperature (LCST) of ~34 °C as well as at pH values between 3 and 4. The unique composition and properties of these shell/core hydrogel nanoparticles make them attractive for use as nanoscale drug-delivery vehicles.     

A Photonic Nanojet as Tunable and Polarization‐Sensitive Optical Tweezers

The ability to manipulate small objects with focused laser beams has opened a venue for investigating dynamical phenomena relevant to both fundamental and applied sciences. However, manipulating nano‐sized objects requires subwavelength field localization, provided by auxiliary nano‐ and microstructures. Particularly, dielectric microparticles can be used to confine light to an intense beam with a subwavelength waist, called a photonic nanojet (PNJ), which can provide sufficient field gradients for trapping nano‐objects. Herein, the scheme for wavelength‐tunable and nanoscale‐precise optical trapping is elaborated, and the possibility of lateral nanoparticle movement using the PNJ's side lobes is shown for the first time. In addition, the possibility of subwavelength positioning using polarization switching is shown. The estimated stability with respect to Brownian motion is higher compared to conventional optical trapping schemes.