Upconversion in NaYF(4):Yb, Er nanoparticles amplified by metal nanostructures

Upconversion (UC) fluorescence in NaYF(4):Yb, Er nanoparticles amplified by metal nanostructures was compared in two nanostructure geometries: gold nanoshells surrounding nanoparticles and silver nanostructures adjacent to the nanoparticles, both placed on a dielectric silica surface. Enhanced UC luminescence signals and modified lifetimes induced by these two metals were observed in our study. The UC luminescence intensities of green and red emissions were enhanced by Ag nanostructures by a factor of approximately 4.4 and 3.5, respectively. The corresponding UC lifetimes were reduced ～ 1.7-fold and ～ 2.4-fold. In NaYF(4):Yb, Er nanoparticles encapsulated in gold nanoshells, higher luminescence enhancement factors were obtained (～9.1-fold for the green emission and ～ 6.7-fold for the red emission). However, the Au shell coating extended the red emission by a factor of 1.5 and did not obviously change the lifetime of green emission. The responsible mechanisms such as plasmonic enhancement and surface effects are discussed.     

Metal-enhanced fluorescence of colloidal nanocrystals with nanoscale control

Engineering the spectral properties of fluorophores, such as the enhancement of luminescence intensity, can be achieved through coupling with surface plasmons in metallic nanostructures. This process, referred to as metal-enhanced fluorescence, offers promise for a range of applications, including LEDs, sensor technology, microarrays and single-molecule studies. It becomes even more appealing when applied to colloidal semiconductor nanocrystals, which exhibit size-dependent optical properties, have high photochemical stability, and are characterized by broad excitation spectra and narrow emission bands. Other approaches have relied upon the coupling of fluorophores (typically organic dyes) to random distributions of metallic nanoparticles or nanoscale roughness in metallic films. Here, we develop a new strategy based on the highly reproducible fabrication of ordered arrays of gold nanostructures coupled to CdSe/ZnS nanocrystals dispersed in a polymer blend. We demonstrate the possibility of obtaining precise control and a high spatial selectivity of the fluorescence enhancement process.     

Improving the signal sensitivity and photostability of DNA hybridizations on microarrays by using dye-doped core-shell silica nanoparticles

The development of new highly sensitive and selective methods for microarray-based analysis is a great challenge because, for many bioassays, the amount of genetic material available for analysis is extremely limited. Currently, imaging and detection of DNA microarrays are based primarily on the use of organic dyes. To overcome the problems of photobleaching and low signal intensities of organic dyes, we developed a new class of silica core-shell nanoparticles that encapsulated with cyanine dyes and applied the dye-doped nanoparticles as labeling in the DNA microarray-based bioanalysis. The developed nanoparticles have core-shell structure containing 15-nm Au colloidal cores with 95 dye-alkanethiol (dT)20 oligomers chemisorbed on the each Au particle surface and 10-15-nm silica coatings bearing thiol functional groups. To be utilized for microarray detection, the dye-doped nanoparticles were conjugated with DNA signaling probes by using heterobifunctional cross-linker. The prepared nanoparticle conjugates are stable in both aqueous electrolytes and organic solvents. Two-color DNA microarray-based detection was demonstrated in this work by using Cy3- and Cy5-doped nanoparticles in sandwich hybridization. The use of the fluorophore-doped nanoparticles in high-throughput microarray detection reveals higher sensitivity with a detection limit of 1 pM for target DNA in sandwich hybridization and greater photostable signals than the direct use of organic fluorophore as labeling. A wide dynamic range of approximately 4 orders of magnitude was also found when the dye-doped nanoparticles were applied in microarray-based DNA bioanalysis. In addition, the use of these dye-doped nanoparticles as the labeling in hybridization also improved the differentiation of single-nucleotide polymorphisms. This work offers promising prospects for applying dye-doped nanoparticles as labeling for gene profiling based on DNA microarray technology.     

Confinement of Dyes inside Boron Nitride Nanotubes: Photostable and Shifted Fluorescence down to the Near Infrared

Fluorescence is ubiquitous in life science and used in many fields of research ranging from ecology to medicine. Among the most common fluorogenic compounds, dyes are being exploited in bioimaging for their outstanding optical properties from UV down to the near IR (NIR). However, dye molecules are often toxic to living organisms and photodegradable, which limits the time window for in vivo experiments. Here, it is demonstrated that organic dye molecules are passivated and photostable when they are encapsulated inside a boron nitride nanotube (dyes@BNNT). The results show that the BNNTs drive an aggregation of the encapsulated dyes, which induces a redshifted fluorescence from visible to NIR-II. The fluorescence remains strong and stable, exempt of bleaching and blinking, over a time scale longer than that of free dyes by more than 10⁴. This passivation also reduces the toxicity of the dyes and induces exceptional chemical robustness, even in harsh conditions. These properties are highlighted in bioimaging where the dyes@BNNT nanohybrids are used as fluorescent nanoprobes for in vivo monitoring of Daphnia Pulex microorganisms and for diffusion tracking on human hepatoblastoma cells with two-photon imaging.     

Co–Fe Alloy/N‐Doped Carbon Hollow Spheres Derived from Dual Metal–Organic Frameworks for Enhanced Electrocatalytic Oxygen Reduction

Metal–organic framework (MOF) composites have recently been considered as promising precursors to derive advanced metal/carbon‐based materials for various energy‐related applications. Here, a dual‐MOF‐assisted pyrolysis approach is developed to synthesize Co–Fe alloy@N‐doped carbon hollow spheres. Novel core–shell architectures consisting of polystyrene cores and Co‐based MOF composite shells encapsulated with discrete Fe‐based MOF nanocrystallites are first synthesized, followed by a thermal treatment to prepare hollow composite materials composed of Co–Fe alloy nanoparticles homogeneously distributed in porous N‐doped carbon nanoshells. Benefitting from the unique structure and composition, the as‐derived Co–Fe alloy@N‐doped carbon hollow spheres exhibit enhanced electrocatalytic performance for oxygen reduction reaction. The present approach expands the toolbox for design and preparation of advanced MOF‐derived functional materials for diverse applications.     

Coherent acoustic vibration of metal nanoshells

Using time-resolved pump-probe spectroscopy, we have performed the first investigation of the vibrational modes of gold nanoshells. The fundamental isotropic mode launched by a femtosecond pump pulse manifests itself in a pronounced time-domain modulation of the differential transmission probed at the frequency of nanoshell surface plasmon resonance. The modulation amplitude is significantly stronger, and the period is longer than that in a gold nanoparticle of the same overall size, in agreement with theoretical calculations. This distinct acoustical signature of nanoshells provides a new and efficient method for identifying these versatile nanostructures and for studying their mechanical and structural properties.     

Porous Gold Nanoshells on Functional NH2‐MOFs: Facile Synthesis and Designable Platforms for Cancer Multiple Therapy

AuroShell nanoparticles (sealed gold nanoshell on silica) are the only inorganic materials that are approved for clinical trial for photothermal ablation of solid tumors. Based on that, porous gold nanoshell structures are thus critical for cancer multiple theranostics in the future owing to their inherent cargo‐loading ability. Nevertheless, adjusting the diverse experimental parameters of the reported procedures to obtain porous gold nanoshell structures is challenging. Herein, a series of amino‐functionalized porous metal–organic frameworks (NH₂‐MOFs) nanoparticles are uncovered as superior templates for porous gold nanoshell deposition (NH₂‐MOFs@Au_shell) by means of a more facile and general one‐step method, which combines the enriched functionalities of NH₂‐MOFs with those of porous gold nanoshells. Moreover, in order to illustrate the promising applications of this method in biomedicine, platinum nanozymes‐encapsulated NH₂‐MOFs are further designed with porous gold nanoshell coating and photosensitizer chlorin e6 (Ce6)‐loaded nanoparticles with continuous O₂‐evolving ability (Pt@UiO‐66‐NH₂@Au_shell‐Ce6). The combination of photodynamic and photothermal therapy is then carried out both in vitro and in vivo, achieving excellent synergistic therapeutic outcomes. Therefore, this work not only presents a facile strategy to fabricate functionalized porous gold nanoshell structures, but also illustrates an excellent synergistic tumor therapy strategy.     

Role of polyfunctional organic molecules in the synthesis and assembly of metal nanoparticles

The role of polyfunctional organic molecules in the synthesis of differently shaped metallic nanostructures and their assembly is investigated. These molecules could be used as spacer ligands and also for surface passivation of nanoparticles, especially with the objective of controlling their electronic and optical properties depending on their length scales. We investigate the role of several such molecules, such as 4-aminothiophenol, tridecylamine, Bismarck brown R and Y, mordant brown, fat brown, chrysoidin (basic orange), and 3-aminobenzoic acid in the synthesis and assembly of various nanoparticles of gold and silver. For example, the use of 4-ATP helps in the formation of rod shaped micelles in aqueous acetonitrile as confirmed by transmission electron microscopy (TEM) suggesting their role as soft templates. In addition, 4-ATP has also been used for the formation of heteroassembly of spherical nanoparticles of gold and silver at controlled pH. Significantly, triangular and hexagonal gold nanoplates are formed at room temperature by similar polyfunctional dye molecule, Bismarck brown R (BBR), while other analogous dye molecules give only arbitrary shaped gold nanoparticles. Further confirmation of their role in shape determination comes from linear amine molecules such as tridecylamine, which give only spherical nanoparticles both for silver and gold. In essence, our study confirms the role of various such organic molecules in shape controlled synthesis of nanoparticles. We also report optical and electrochemical properties of few of these nanostructures as a function of their shape.     

Multicolor FRET silica nanoparticles by single wavelength excitation

Fluorescent nanoparticles with multiple emission signatures by a single wavelength excitation are needed in multiplex bioanalysis and molecular imaging. We have prepared silica nanoparticles encapsulated with three organic dyes using a modified St?ber synthesis method. By varying the doping ratio of the three tandem dyes, fluorescence resonance energy transfer (FRET)-mediated emission signatures can be tuned to have the nanoparticles exhibit multiple colors under one single wavelength excitation. These nanoparticles are intensely fluorescent, highly photostable, uniform in size, and biocompatible. The acceptor emission of the FRET nanoparticles has generated a large Stokes shift, which implicates broad applications in biological labeling and imaging. Molecular recognition moieties, such as biotin, can be covalently attached to the nanoparticle surface to allow for specific binding to target molecules. These multicolor FRET silica nanoparticles can be used as barcoding tags for multiplexed signaling. By using these NPs, one can envision a dynamic, multicolor, colocalization methodology to follow proteins, nucleic acids, molecular machines, and assemblies within living systems.     

Voltage regulation of fluorescence emission of single dyes bound to gold nanoparticles

An organic dye, SAMSA, bound to gold nanoparticles, displays random photoactivated fluorescence blinking whose rate depends on the size of the nanoparticles. We report experiments indicating that (1) the dye emission wavelength is red-shifted (10-30 nm) by applying an external low voltage (1-10 V) and that (2) the fluorescence emission of single dyes can be resonantly driven by tuning the alternating external bias frequency from 1 to 3 Hz, depending on the nanoparticle size. These properties appear highly valuable and promising for devising light emitting nanostructures.     

Metal nanoshell assembly on a virus bioscaffold

Chilo iridescent virus is demonstrated as a useful core substrate in the fabrication of metallodielectric, plasmonic nanostructures. A gold shell is assembled around the wild-type viral core by attaching small, 2-5-nm gold nanoparticles to the virus surface by means of the chemical functionality found inherently on the surface of the proteinaceous viral capsid. The density of these nucleation sites was maximized by reducing the repulsive forces between the gold particles through electrolyte addition. These gold nanoparticles then act as nucleation sites for the electroless deposition of gold ions from solution around the biotemplate. The optical extinction spectra of the metalloviral complex is in quantitative agreement with Mie scattering theory. Overall, the utilization of a native virus and the inherent chemical functionality of the capsid afford the ability to grow and harvest biotemplates for metallodielectric nanoshells in large quantities, potentially providing cores with a narrower size distribution and smaller diameters (below 80 nm) than for currently used silica.     

Enhancement of luminescence of Rhodamine B by gold nanoparticles in thin films on glass for active optical materials applications

Fluorescent dyes in solid matrices have many potential applications provided that their high optical efficiencies are achieved. We present here gold nanoparticles formed and incorporated together with fluorescent dye Rhodamine B into a film of polyvinyl alcohol (PVA). The increase of fluorescence of the dye results from its interaction with surface plasmons. The electric charge on the gold nanoparticles and the distance between them and the dye molecules has a significant effect on the fluorescence intensity. Fluorescence enhancement of 74% was achieved for the negatively charged particles. Dynamic measurements reveal decrease of fluorescent lifetimes of the dye in presence of gold nanoparticles. Our findings enable utilization of films with enhanced fluorescence in optical materials such as luminescence solar concentrators, solid state tunable laser and active waveguides.     

Energy absorption of gold nanoshells in hyperthermia therapy

The unique optical characteristics of a gold nanoshell motivate the application of nanoshell-based hyperthermia in drug delivery and cancer treatment. However, most of our understanding on energy absorption and heat transfer is still focused on individual particles, which may not be accurate for nanoshell aggregates in a real application due to the strong optical interaction of nanoshells. This paper investigates the relationship between the optical interaction and the interparticle distance in the visible and near-infrared regions by means of a finite-difference time-domain (FDTD) method. The objective is to explore the energy transportation mechanism, which is critical for hyperthermia therapy. From the numerical simulation results of different forms of nanoshell aggregates, including individual nanoshells, 1-D chains, 2-D arrays, and 3-D clusters, it was found that the interparticle distance plays a crucial role from the maximal absorption point of view. The interparticle distance affects both field enhancement and surface plasmon resonance position. The accurate prediction of energy absorption also helps the way nanoshells are populated in the tumor cell so as to prevent heat damage to healthy tissues in clinic applications. In the case of 3-D clusters, the laser energy decays exponentially along the wave propagation, and the penetration depth greatly depends on the interparticle distance. The closer the nanoshells are placed, the shorter the penetration depth is. The maximal total length for the laser penetration through the shell of gold nanoparticles is about a few hundred to several nanometers. The actual penetration depth primarily depends not only on the interparticle distance, but also on the size of the nanoshells as well as other factors. Since the absorption energy is concentrated on the surface clusters of nanoparticles, heat transfer mechanisms in metal-nanoparticles-based hyperthermia will differ from that in other hyperthermia. The information obtained from this paper will serve as a basis for further study of heat transfer in metal-nanoparticles-based hyperthermia.     

Plasmonic Elastic Capsules as Colorimetric Reversible pH‐Microsensors

There is a crucial need for effective and easily dispersible colloidal microsensors able to detect local pH changes before irreversible damages caused by demineralization, corrosion, or biofilms occur. One class of such microsensors is based on molecular dyes encapsulated or dispersed either in polymer matrices or in liquid systems exhibiting different colors upon pH variations. They are efficient but often rely on sophisticated and costly syntheses, and present significant risks of leakage and photobleaching damages, which is detrimental for mainstream applications. Another approach consists of exploiting the distance‐dependent plasmonic properties of metallic nanoparticles. Still, assembling nanoparticles into dispersible colloidal pH‐sensitive sensors remains a challenge. Here, it is shown how to combine optically active plasmonic gold nanoparticles and pH‐responsive thin shells into “plasmocapsules.” Upon pH change, plasmocapsules swell or shrink. Concomitantly, the distance between the gold nanoparticles embedded in the polymeric matrix varies, resulting in an unambiguous color change. Billions of micron‐size sensors can thus be easily fabricated. They are nonintrusive, reusable, and sense local pH changes. Each plasmocapsule is an independent reversible microsensor over a large pH range. Finally, their potential use for the detection of bacterial growth is demonstrated, thus proving that plasmocapsules are a new class of sensing materials.     

Fluorescence‐Encoded Gold Nanoparticles: Library Design and Modulation of Cellular Uptake into Dendritic Cells

In order to harness the unique properties of nanoparticles for novel clinical applications and to modulate their uptake into specific immune cells we designed a new library of homo‐ and hetero‐functional fluorescence‐encoded gold nanoparticles (Au‐NPs) using different poly(vinyl alcohol) and poly(ethylene glycol)‐based polymers for particle coating and stabilization. The encoded particles were fully characterized by UV‐Vis and fluorescence spectroscopy, zeta potential and dynamic light scattering. The uptake by human monocyte derived dendritic cells in vitro was studied by confocal laser scanning microscopy and quantified by fluorescence‐activated cell sorting and inductively coupled plasma atomic emission spectroscopy. We show how the chemical modification of particle surfaces, for instance by attaching fluorescent dyes, can conceal fundamental particle properties and modulate cellular uptake. In order to mask the influence of fluorescent dyes on cellular uptake while still exploiting its fluorescence for detection, we have created hetero‐functionalized Au‐NPs, which again show typical particle dependent cellular interactions. Our study clearly prove that the thorough characterization of nanoparticles at each modification step in the engineering process is absolutely essential and that it can be necessary to make substantial adjustments of the particles in order to obtain reliable cellular uptake data, which truly reflects particle properties.     

A molecular spectroscopic description of optical spectra of J-aggregated dyes on gold nanoparticles

The extinction spectra of J-aggregated dyes on gold nanoparticles, which exhibit interferences between the plasmonic and dye resonances, are simulated by a quantum mechanical model that considers the dye transition to interact through transition-dipole coupling with a continuum of nanoparticle states. This alternative to the classical core-shell dielectric model provides the wavefunctions of the coupled molecule-nanoparticle system and qualitatively explains the enhancement of resonance Raman, fluorescence, and other light-driven processes of molecules adsorbed to nanoparticles.     

Determination of hydrodynamic properties of bare gold and silver nanoparticles as a fluorescent probe using its surface-plasmon-induced photoluminescence by fluorescence correlation spectroscopy

Noble-metal nanoparticles labeled with fluorescent molecules are used in a variety of applications requiring the measurement of size and diffusion properties of single nanoprobes. We have successfully used intrinsic surface-plasmon-induced photoluminescence (SPPL) signatures of monodispersed bare gold and silver nanoparticles in water to detect and measure their precise diffusion coefficient, concentration and hydrodynamic radius by fluorescence correlation spectroscopy (FCS). Measurement of the effective hydrodynamic radius confirms particle size to be 80 ± 8 and 64 ± 14 nm for gold and silver, respectively, which is in excellent agreement with scanning electron microscopic measurements made on the same particles. Detection of bare gold and silver nanoparticles at the single-molecule level with moderately high value of "per particle brightness" (PPB) confirms those particles to be used as fluorescent probes in biological research and in different medical and biotechnology applications where fluorescence detection plays a vital role. Additionally, these results demonstrate an alternative method for measuring hydrodynamic properties, particularly the size-distribution of bare noble-metal nanoparticles in solution using data-fitting algorithm for FCS based on the maximum entropy method (MEMFCS).     

Thermal energy transfer by plasmon-resonant composite nanoparticles at pulse laser irradiation

Heating of composite plasmon-resonant nanoparticles (spherical gold nanoshells) under pulse laser illumination is considered. The numerical solution of the time-dependent heat conduction equation accounting for spatial inhomogeneities of absorbed laser radiation is performed. Important features of temperature kinetics and thermal flux inside nanoparticles are analyzed. Possible applications of the observed effects in nanotechnology and medicine are discussed.     

Selective separation of fluorescent-magnetic nanoparticles with different magnetite-doping levels

Fluorescent-labeled magnetic nanoparticles were explored as a biomedical agent for selective magnetic separation. By adjusting the loading volume of citrate-stabilized magnetites during a sol-gel reaction with silicon alkoxide, magnetites were simultaneously embedded into both the surface and inside the silica matrix, consequently leading to magnetic nanoparticles with different doping levels of magnetites. For endowing them with multifunctional tools in biomedical fields, magnetic nanoparticles were further encapsulated with silica thin layer labeled with fluorescent organic dyes (such as Alexa Fluor 488 and 594). Fluorescent-magnetic nanoparticles with different magnetism successfully displayed the differential separation of fluorescence spectra under an external magnetic field.     

Nanoscale films of organic dyes for broadband environmental sensing

Two types of suitably substituted organic dye molecules namely copper phthalocyanine and Rose Bengal were electrostatically self-assembled on gold-coated glass substrates, the gold surface being modified with poly(allylaminehydrochloridethe). The surface plasmon resonance technique was employed to investigate the sensing properties of organic dyes on exposure to three different volatile organic compounds. The films using phthalocyanine molecules were considered to be an optimal material because of its fast response and full recovery. This behaviour is attributed to the film surface morphology, molecular orientation in the film architecture, and sizes and dipole moments of vapours.