Novel and Sensitive Core-Shell Nanoparticles Based on Surface Plasmon Resonance

In this paper, a rough silver core-shell nanoparticle with strong electric field enhancement in the vicinity of a bumpy structure on the silver core-shell surface is reported. A dipolar plasmonic mode of the silver nanoshell is investigated by using the quasi-static approach and plasmon hybridization theory, which analytical results identify the electric field enhancement spectra in which the enhancement is optimized. As the silver shell thickness is small, the hot spots play an important role in the plasmonic field enhancement. In addition, the deposition of a rough silver shell can generate a stronger near-field enhancement near the silver surface which is more desirable than that of a smooth silver shell for sensitive detection based on SPR and surface enhanced Raman scattering (SERS). The plasmonic field enhancement of a bumpy silver core-shell nanoparticle permits the detection and characterization of bovine serum albumin (BSA) protein molecule and hemoglobin solution with a high sensitivity.     

Surface Plasmon Enhancement of Optical Absorption in Thin-Film Silicon Solar Cells

Strong electromagnetic field enhancement that occurs under conditions of the surface plasmon excitation in metallic nanoparticles deposited on a semiconductor surface is a very efficient and promising tool for increasing the optical absorption within semiconductor solar cells and, hence, their photocurrent response. The enhancement of the optical absorption in thin-film silicon solar cells via the excitation of localized surface plasmons in spherical silver nanoparticles is investigated. Using the effective medium model, the effect of the nanoparticle size and the surface coverage on that enhancement is analyzed. The optimum configuration and the nanoparticle parameters leading to the maximum enhancement in the optical absorption and the photocurrent response in a single p-n junction silicon cell are obtained. The effect of coupling between the silicon layer and the surface plasmon fields on the efficiency of the above enhancement is quantified as well.     

The Effect of Spatial Inhomogeneity of the Cornea on the Deformation Properties of the Eyeball and the Results of Maklakoff Applanation Tonometry

A two-component model of the eyeball that represents the cornea as a momentless, linearly elastic deformable surface and the scleral region, as an elastic element that responds to intraocular pressure changes by volume changes, has been used to analyze the effect of spatial inhomogeneity in the distribution of effective corneal stiffness on the mechanical properties of the eye. The effective stiffness of the cornea characterized both the elastic properties and the thickness of the cornea within the framework of the model. Various axisymmetric forms of the effective stiffness distribution characterized by monotonic increase along the arc between a point on the corneal surface and the apex of the cornea were studied. The considered distributions simulated both natural inhomogeneity and apical region weakening due to surgical interventions. Numerical simulation yielded the dependences of deformation parameters on intraocular pressure changes. These parameters characterized the deformation properties of both the cornea (apex displacement) and the eyeball as a whole (intraocular volume change). In the case of moderate inhomogeneity, the dependences were only slightly different from those for a homogeneous cornea with an effective stiffness equal to the mean value for the corresponding inhomogeneous distribution. A noticeable increase in the integral response of the cornea and the eyeball as a whole to changes in pressure was observed if the effective stiffness amplitude was very high (two or more times higher than the mean value). The effect of inhomogeneity on the results of tonometric measurements with a Maklakoff tonometer (flat stamp) was studied. The tonometric difference, that is, the difference between the tonometric pressure (in the loaded eye) and the true pressure (before loading), mainly depended on the average stiffness of the cornea in this case as well, with a substantial increase observed at very high stiffness amplitudes only. Apical weakening of the cornea led to an increase (although not very pronounced) of the tonometric difference.     

An Integrated Multistage Nanofocusing System

We demonstrate an integrated multistage nanofocusing system which combines a conventional objective, a surface plasmonic lens, and a center-positioned rounded-tip cone nanoparticle. The surface plasmonic lens, fabricated on the cover glass which has been mounted on the biological microscopic objective, is composed of several concentric annular slits for exciting propagating surface plasmonic wave. The rounded-tip cone nanoparticle is for further generating non-propagating localized surface plasmonic wave. It is revealed that the enhancement of the nanoscale optical field can be improved by carefully choosing the appropriate numerical aperture of the objective to match the specific nanostructure of the surface plasmonic lens and choosing the relatively big cone angle of the nanoparticle. The investigation shows that a highly confined electric field as small as 20 nm and an enhancement factor of 5 orders of magnitude can be achieved through this multistage nanofocusing system when the system is illuminated with a uniform radially polarized beam.     

Surface Plasmon Enhancement at a Liquid–Metal–Liquid Interface

Herein, we report the first experimental demonstration of surface plasmon enhancement at a liquid–metal–liquid interface using a pseudo-Kretschmann geometry. Pumping gold nanoparticle clusters at the interface of a p-xylene–water mixture, we were able to measure a fluorescence enhancement of three orders of magnitude in Rose Bengal at an excitation wavelength of 532 nm. The observed increase is due to the local electric field enhancement and the reduction of the fluorescence lifetime of dye molecules in the close vicinity of the metal surface. Theoretical modeling using the T-matrix method of the electric field intensity enhancement of emulated surfaces supports the experimental results. This new approach will open a new road for the study of dynamic systems using plasmonics.     

Novel thermal effect at nanoshell heating by pulsed laser irradiation: hoop‐shaped hot zone formation

Photonic nanotechnologies have good perspectives to be widely used in biophotonics. In this study we have developed an approach for calculation of nanoparticle temperature field accounting for absorbed local intensity at pulse laser radiation of composite spherical nanoparticles (nanoshells). This approach allowed us to analyze spatial inhomogeneities of light field diffracted into a nanoshell and corresponding distribution of the absorption energy and to provide numerical solution of time‐dependent heat conduction equation accounting for corresponding spatially inhomogeneous distribution of heating sources. We were able to predict the appearance of a novel thermal effect – hoop‐shaped hot zone on the nanoshell surface. The observed effect has potential applications in cell biology and medicine for controlled cell optoporation and nanosurgery, as well as cancer cell killing. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Surface Plasmon Effects Excited by the Dielectric Hole in a Silver-Shell Nanospherical Pair

Using the finite-element method, the surface plasmon effects in a three-dimensional silver-shell nanospherical pair with five different dielectric holes (DHs) that interact with a transverse magnetic mode incident plane wave are investigated. The proposed structure exhibits a red-shifted localized surface plasmon that can be tuned over an extended wavelength range by varying the dielectric constant and the radii in DHs. The increase in the near-field intensity is attributed to a larger effective size of DH that is filled with a higher refractive index medium. The predictive character of these calculations allows one to tailor the shape of the nanoparticle to achieve excitation spectra on demand with a controlled field enhancement.     

Optical Modeling of Plasmonic Nanoparticles Enhanced Light Emission of Silicon Light-Emitting Diodes

Significant enhancement of radiative efficiency of thin-film silicon light-emitting diodes achieved by placing the active layer in close proximity to silver (Ag) nanoparticles has been observed. In this paper, optical properties including transmission, reflection, and absorption of a random assembly of Ag nanoparticles are theoretically investigated using the effective medium model. Furthermore, the influence of Ag nanoparticles on light emission of silicon light-emitting diodes is studied by an improved effective mode volume model we propose here. The normalized line shape of dipole oscillation is calculated directly using Lorentz–Drude model without using any approximation. Thus, it results in more accurate calculation of the enhanced Purcell factor in comparison with the conventional approach. We show that an enhancement of radiative efficiency of silicon light-emitting diodes can be achieved by localized surface plasmons on metal nanoparticles. The calculated result of optimal Ag nanoparticle size to enhance light emission of silicon light-emitting diodes at 900 nm wavelength is in very good agreement with those obtained from the experimental result. The model is useful for the design of metallic nanoparticles enhanced light emitters.     

Location-Dependent Local Field Enhancement Along the Surface of the Metal–Dielectric Core–Shell Nanostructure

A theoretical study based on quasi-static approximation is performed to investigate the location-dependent local field enhancement around the dielectric shell-coated gold nanosphere. Our calculation results show that the local field distribution near a gold nanoparticle can be altered greatly by coating with a dielectric shell. Because of the polarizability of the dielectric shell, increasing azimuth angle along the inner surface leads to the increase of the local field, which is opposite to that of the outer surface. Furthermore, the location-dependent local field enhancement and resonance frequency at both the inner and outer surfaces can also be modulated by varying the shell thickness and shell dielectric constant. These calculation results about the location-dependent local field enhancement show the potential of dielectric-coated metallic nanostructure for single-molecule detection based on surface-enhanced Raman scattering and surface enhanced fluorescence.     

纳米磁性粒子在DNA分离与纯化中的应用进展

纳米磁性粒子是一种新型的亲和纯析固相载体 ,其粒径小 ,具有超顺磁性 ,表面积大 ,表面可赋予多种反应基团如链霉亲和素、抗体等 ,或DNA片段 ,在磁场作用下可分离目的DNA ,已逐步应用于分子生物学领域中 ,有着极为广泛的应用前景。     

A Surface Design for Enhancement of Light Trapping Efficiencies in Thin Film Silicon Solar Cells

We report on a surface design of thin film silicon solar cells based on silver nanoparticle arrays and blazed grating arrays. The light transmittance is increased at the front surface of the cells, utilizing the surface plasmon resonance effect induced by silver nanoparticle arrays. As a reflection layer structure, blazed gratings are placed at the rear surface to increase the light reflectance at bottom of the thin film cells. With the combination of the silver nanoparticle arrays and the blazed gratings, the light trapping efficiency of the thin film solar cell is characterized by its light absorptance, which is determined from the transmittance at front surface and the reflectance at bottom, via the finite-difference time-domain (FDTD) numerical simulation method. The results reveal that the light trapping efficiency is enhanced as the structural parameters are optimized. This work also shows that the surface plasmon resonance effect induced by the silver nanoparticles and the grating characteristics of the blazed gratings play crucial roles in the design of the thin film silicon solar cells.     

Position Dependent Plasmonic Interaction Between a Single Nanoparticle and a Nanohole Array

The interaction of surface plasmons supported on a nanohole array and a single nanoparticle affixed to an atomic force microscopy (AFM) probe was studied for optimizing gap mode enhancement of the plasmonic field. Scanning probe microscopy controlled the AFM probe position, and the location specific interaction of the single nanoparticle (SNP) probe-nanohole array surface plasmons, was measured by darkfield spectroscopy. Raster-scanned darkfield imaging of the surface plasmons on the nanohole array is demonstrated, as well as image formation from measuring the SNP interaction at various (X, Y) locations relative to the nanohole. Coupling of the nanoparticle to the nanohole array exhibited maximal coupling when the SNP resided within a nanohole, resulting in a maximum SPR wavelength shift of 17 nm and an increase in scatter intensity of 137×. This technique may be expanded to mapping nanostructure coupling across three dimensions to determine optimal coupling conditions for applications in biosensing and surface enhanced spectroscopy. This contribution presents the first empirical observations of scanning probe microscopy (SPM) controlled gap mode enhancement of more complex nanostructures, a method for positioning optimization prior to sensing applications and experimental evidence for optimal lateral SNP-nanohole array positioning.     

Tumor-specific hybrid polyhydroxybutyrate nanoparticle: surface modification of nanoparticle by enzymatically synthesized functional block copolymer

A new approach to functionalize the surface of hydrophobic nanocarrier through enzymatic polymerization was demonstrated. The effective coupling between the hydrophobic surface of PHB nanoparticle and PHB chain grown from the enzyme fused with a specific ligand provided a simple way of functionalizing nanoparticles with active protein layers in aqueous environment. PHB nanoparticles loaded with model drug molecule, Nile red, were prepared through oil-in-water emulsion solvent evaporation method and the surface of nanoparticles were functionalized with tumor-specific ligand, RGD4C, fused with PHA synthase that drove the coupling reaction. The functionalized PHB nanoparticles showed a specific affinity to MDA-MB 231 breast cancer cells indicating that the tumor-specific ligand, RGD4C, was effectively displayed on the surface of PHB nanoparticles through enzymatic modification and confers targeting capability on the drug carrier.     

Molecular Mechanisms of ZnO Nanoparticle Dispersion in Solution: Modeling of Surfactant Association,Electrostatic Shielding and Counter Ion Dynamics

Molecular models of 5 nm sized ZnO/Zn(OH)2 core-shell nanoparticles in ethanolic solution were derived as scale-up models (based on an earlier model created from ion-by-ion aggregation and self-organization) and subjected to mechanistic analyses of surface stabilization by block-copolymers. The latter comprise a poly-methacrylate chain accounting for strong surfactant association to the nanoparticle by hydrogen bonding and salt-bridges. While dangling poly-ethylene oxide chains provide only a limited degree of sterical hindering to nanoparticle agglomeration, the key mechanism of surface stabilization is electrostatic shielding arising from the acrylates and a halo of Na⁺ counter ions associated to the nanoparticle. Molecular dynamics simulations reveal different solvent shells and distance-dependent mobility of ions and solvent molecules. From this, we provide a molecular rationale of effective particle size, net charge and polarizability of the nanoparticles in solution.     

Radio frequency magnetic field effects on molecular dynamics and iron uptake in cage proteins

The protein ferritin has a natural ferrihydrite nanoparticle that is superparamagnetic at room temperature. For native horse spleen ferritin, we measure the low field magnetic susceptibility of the nanoparticle as 2.2 × 10^?6 m³ kg^?1 and its Néel relaxation time at about 10^?10 s. Superparamagnetic nanoparticles increase their internal energy when exposed to radio frequency magnetic fields due to the lag between magnetization and applied field. The energy is dissipated to the surrounding peptidic cage, altering the molecular dynamics and functioning of the protein. This leads to an increased population of low energy vibrational states under a magnetic field of 30 µT at 1 MHz, as measured via Raman spectroscopy. After 2 h of exposure, the proteins have a reduced iron intake rate of about 20%. Our results open a new path for the study of non‐thermal bioeffects of radio frequency magnetic fields at the molecular scale. Bioelectromagnetics 31:311–317, 2010. © 2010 Wiley‐Liss, Inc.     

Folate-conjugated iron oxide nanoparticles for solid tumor targeting as potential specific magnetic hyperthermia mediators: synthesis, physicochemical characterization, and in vitro experiments

New folate-conjugated superparamagnetic maghemite nanoparticles have been synthesized for the intracellular hyperthermia treatment of solid tumors. These ultradispersed nanosystems have been characterized for their physicochemical properties and tumor cell targeting ability, facilitated by surface modification with folic acid. Preliminary experiments of nanoparticles heating under the influence of an alternating magnetic field at 108 kHz have been also performed. The nanoparticle size, surface charge, and colloidal stability have been assessed in various conditions of ionic strength and pH. The ability of these folate "decorated" maghemite nanoparticles to recognize the folate receptor has been investigated both by surface plasmon resonance and in folate receptor expressing cell lines, using radiolabeled folic acid in competitive binding experiments. The specificity of nanoparticle cellular uptake has been further investigated by transmission electron microscopy after incubation of these nanoparticles in the presence of three cell lines with differing folate receptor expression levels. Qualitative and quantitative determinations of both folate nanoparticles and nontargeted control nanoparticles demonstrated a specific cell internalization of the folate superparamagnetic nanoparticles.     

Oligonucleotide-coated metallic nanoparticles as a flexible platform for molecular imaging agents

Targeted metallic nanoparticles have shown promise as contrast agents for molecular imaging. To obtain molecular specificity, the nanoparticle surface must be appropriately functionalized with probe molecules that will bind to biomarkers of interest. The aim of this study was to develop and characterize a flexible approach to generate molecular imaging agents based on gold nanoparticles conjugated to a diverse range of probe molecules. We present two complementary oligonucleotide-based approaches to develop gold nanoparticle contrast agents which can be functionalized with a variety of biomolecules ranging from small molecules, to peptides, to antibodies. The size, biocompatibility, and protein concentration per nanoparticle are characterized for the two oligonucleotide-based approaches; the results are compared to contrast agents prepared using adsorption of proteins on gold nanoparticles by electrostatic interaction. Contrast agents prepared from oligonucleotide-functionalized nanoparticles are significantly smaller in size and more stable than contrast agents prepared by adsorption of proteins on gold nanoparticles. We demonstrate the flexibility of the oligonucleotide-based approach by preparing contrast agents conjugated to folate, EGF peptide, and anti-EGFR antibodies. Reflectance images of cancer cell lines labeled with functionalized contrast agents show significantly increased image contrast which is specific for the target biomarker. To demonstrate the modularity of this new bioconjugation approach, we use it to conjugate both fluorophore and anti-EGFR antibodies to metal nanoparticles, yielding a contrast agent which can be probed with multiple imaging modalities. This novel bioconjugation approach can be used to prepare contrast agents targeted with biomolecules that span a diverse range of sizes; at the same time, the bioconjugation method can be adapted to develop multimodal contrast agents for molecular imaging without changing the coating design or material.     

Proximity-activated nanoparticles: in vitro performance of specific structural modification by enzymatic cleavage

The development and in vitro performance of a modular nanoscale system capable of specific structural modification by enzymatic activity is described in this work. Due to its small physical size and adaptable characteristics, this system has the potential for utilization in targeted delivery systems and biosensing. Nanoparticle probes were synthesized containing two distinct fluorescent species including a quantum dot base particle and fluorescently labeled cleavable peptide substrate. Activity of these probes was monitored by gel electrophoresis with quantitative cleavage measurements made by fluorometric analysis. The model proximity-activated nanoparticles studied here exhibit significant susceptibility to cleavage by matrix metalloprotease-7 (MMP-7) at physiologically relevant concentrations, with nearly complete cleavage of available substrate molecules after 24 hours. This response is specific to MMP-7 enzyme activity, as cleavage is completely inhibited with the addition of EDTA. Utilization of enzyme-specific modification is a sensitive approach with broad applications for targeted therapeutics and biosensing. The versatility of this nanoparticle system is highlighted in its modular design, as it has the capability to integrate characteristics for detection, biosensing, targeting, and payload delivery into a single, multifunctional nanoparticle structure.     

Light scattering in TIRF microscopy: A theoretical study of the limits to surface selectivity

In TIRF microscopy, the sample resides near a surface in an evanescent optical field that, ideally, decreases in intensity with distance from the surface in a pure exponential fashion. In practice, multiple surfaces and imperfections in the optical system and refractive index (RI) inhomogeneities in the sample (often living cells) produce propagating scattered light that degrades the exponential purity. RI inhomogeneities cannot easily be avoided. How severe is the consequent optical degradation? Starting from Maxwell’s equations, we derive a first-order perturbative approximation of the electric field strength of light scattered by sample RI inhomogeneities of several types under coherent evanescent field illumination. The approximation provides an expression for the scattering field of any arbitrary RI inhomogeneity pattern. The scattering is not all propagating; some is evanescent and remains near the scattering centers. The results presented here are only a first-order approximation, and they ignore multiple scattering and reflections off the total internal reflection (TIR) surface. For simplicity, we assume that the RI variations in the z direction are insignificant within the depth of the evanescent field and consider only scattering of excitation light, not fluorescence emission light. The general conclusion of most significance from this study is that TIR scattering from a sample with RI variations typical of those on a cell culture alters the effective thickness of the illumination to only ∼50% greater than it would be without scattering. The qualitative surface selectivity of TIR fluorescence is largely retained even in the presence of scattering. Quantitatively, however, scattering will cause a deviation from the incident exponential decay at shorter distances, adding a slower decaying background. Calculations that assume a pure exponential decay will be approximations, and scattering should be taken into account. TIR scattering is only slightly dependent on polarization but is strongly reduced for the highest accessible incidence angles.