Enhanced luminescence from lanthanide complex by silver nanoparticles

Photoluminescence of europium complex, Eu(III)DPA, where DPA is dipicolinic acid, in the presence of 5 nm-diameter Ag nanoparticles, was studied. Pronounced enhancement of Eu(III) luminescence was observed in the complex solution containing Ag nanoparticle with a concentration below 3.0 × 10¹³/ml. The dependencies of emission intensity of ⁵D₀ → ⁷F₂ and ⁵D₀ → ⁷F₁ transition on the concentration of Ag nanoparticles are quite different, the enhancement of electric dipole transition is stronger than that of magnetic dipole transition. There is no significant change in fluorescence lifetime in enhanced luminescence. The enhancement was attributed to a strong coupling between the radiation transition and surface plasmon resonance.     

Synthesis and luminescence of nano-insulators doped with lanthanide ions

This paper reviews the syntheses, particle-size measurements and various aspects of the optical spectra of lanthanide ion doped insulating nanomaterials, with the focus upon the sesquioxides, and it contrasts their behaviour with bulk materials.     

Homogeneous single-label biochemical Ras activation assay using time-resolved luminescence

Mutations of the small GTP-binding protein Ras have been commonly found in tumors, and Ras oncogenes have been established to be involved in the early steps of cancerogenesis. The detection of Ras activity is critical in the determination of the cell signaling events controlling cell growth and differentiation. Therefore, development of improved methods for primary screening of novel potential drugs that target small GTPase or their regulators and their signaling pathways is important. Several assays have been developed for small GTPases studies, but all these methods have limitations for a high-throughput screening (HTS) use. Multiple steps including separation, use of radioactive labels or time-consuming immunoblotting, and a need of large quantities of purified proteins are decreasing the user-friendliness of these methods. Here, we have developed a homogeneous H-Ras activity assay based on a single-label utilizing the homogeneous quenching resonance energy transfer technique (QRET). In the QRET method, the binding of a terbium-labeled GTP (Tb-GTP) to small GTPase protein H-Ras protects the signal of the label from quenching, whereas the signal of the nonbound fraction of Tb-GTP is quenched by a soluble quencher. This enables a rapid determination of the changes in the activity status of Ras. The assay optimization showed that only 60 nM concentration of purified H-Ras protein was needed. The functionality of the assay was proved by detecting the effect of H-Ras guanine nucleotide exchange factor, Son of Sevenless. The signal-to-background ratio up to 7.7 was achieved with an average assay coefficient of variation of 9.1%. The use of a low concentration of purified protein is desirable and the signal-to-background ratio of 3.4 was achieved in the assay at a concentration of 60 nM for H-Ras and SOS proteins. The need of only one labeled molecule and the ability to decrease the quantities of purified proteins used in the experiments are valuable qualities in HTS showing the potential of the QRET method.     

Enhanced luminescence of lanthanide complexes by silver nanoparticles for ciprofloxacin determination

We present the enhancement of luminescence of europium complex, Eu(3+)-ciprofloxacin (CIP), in the presence of silver nanoparticles (Ag NPs) for the CIP determination. The increment of the luminescence intensity of the Eu(3+)-CIP complex with Ag NPs was obtained due to the transfer of resonance energy to the fluorophores through the interaction of the excited-state fluorophores and surface plasmon electron in the metal nano surface. The luminescence intensity of Eu3+ was enhanced by complexation with CIP at 614 nm after excitation at 373 nm corresponding to the 5D0-7F2 transitions of Eu3+ ion. Based on the above phenomenon, a sensitive and rapid spectrofluorimetric method has been developed for the CIP determination. Linearity of the calibration curve was obtained in the range of 2.0 x 10(-10)-1.0 x 10(-8) g mL(-1) with correlation coefficient of 0.9992. The limit of detection of CIP was found to be 1.9 x 10(-11) g mL(-1) with the relative standard deviation (RSD) of 1.19% for 5 replicate measurements of 5.0 x 10(-7) g mL(-1) of CIP. The present method has been successfully applied for CIP determination in pharmaceutical and biological samples.     

Homogeneous luminescence decay time-based assay using energy transfer from nanospheres

Following a study on the feasibility of resonance energy transfer (RET) from carboxylated nanospheres with an incorporated phosphorescent donor to a cationic polyelectrolyte/acceptor aggregate on their surface, a novel scheme for homogeneous assays is presented that is based on RET from phosphorescent biotinylated nanospheres to fluorescently labeled streptavidin (SA). The phosphorescent nanospheres, with a diameter of well below 50 nm, are made from carboxylated polyacrylonitrile and dyed with ruthenium(II)-tris-4,7-diphenyl-1,10-phenanthroline dichloride (Ru(dpp)). Due to the small size of the nanospheres and the complete extraction of the ruthenium dye into the nanospheres during the precipitation process, RET occurs from Ru(dpp) to the label if labeled SA binds to the surface of the nanospheres. Luminescence quenching by oxygen or other species present in the sample can be neglected due to the shielding effect of the polymer matrix. Based on this finding, a competitive binding assay was established, where avidin and labeled SA compete for the biotin binding sites on the nanosphere. The process of binding to the surface can be detected by measurement of the luminescence intensity or the apparent decay time which is in the order of 2.5-4.5 micros.     

Dual-mode luminescence from lanthanide tri-doped NaYF4 nanocrystals

Silica-coated NaYF₄:Yb/Er(Tm)/Eu nanocrystals (NCs) with a mean size of 35 nm were prepared and characterized. Each of the core/shell NCs can be dispersed in ethanol and water to form stable colloidal solutions and emit bright visible light of two colors (blue and red, green and red) by up- and down-converting excitation modes. As we know, this is the first time to obtain the distinct dual-color photos of NaYF₄:Yb/Er(Tm)/Eu NCs which were dispersed in deionized water. In particular, the ability to optically manipulate luminescence color of NCs doped with RE ions opens the door to multiplexed detection for high precision in more complex biotic environment.     

Sensitized room-temperature luminescence in reverse micelles using lanthanide counterions as acceptors

The analytical usefulness of sensitized room-temperature luminescence in reverse micelles using lanthanide counterions is examined. The technique is based on the unique luminescent properties of tripositive lanthanide metal ions as counterions for the surfactant and the molecular organization produced by reverse micelles. After excitation, the analyte molecule transfers its triplet-state energy to an acceptor molecule (lanthanide), which subsequently emits luminescence. Two surfactants with different lanthanide counterions have been synthesized and characterized by spectroscopic and mass spectrometric techniques. When compared to the lanthanide salt, the sensitized luminescence of the lanthanide surfactant is substantially enhanced. The exact locations of the analyte and the counterion in the micellar system are discussed. The efficiencies of energy transfer for the two surfactants are compared.     

Synthesis and luminescence properties of lanthanide (III)-doped YF3 nanoparticles

Synthesis process and luminescence properties of trivalent lanthanide ions (Ln3+) doped YF3 nanoparticles have been investigated. To synthesis Ln(3+)-doped YF3 nanoparticles, the mixture of (YCl3 x nH2O + LnCl3 x nH2O), and NH4F was hydrothermal treated at 180 degrees C in a Teflon-liner auto-clave or heated at higher temperatures (400 degrees C - 600 degrees C) in a stove. The XRD patterns showed that the Ln(3+)-doped orthorhombic YF3 nanoparticles with no second phase have been prepared. The solid solution Y(1-x)Eu(x)F3 (x = 0 - 0.4) nanoparticles have been synthesized. The luminescence concentration quenching resulted from resonance energy transfer between neighboring Eu3+ ions occurred at higher Eu3+ concentrations (30 mol%). The upconversion luminescence of Er(3+)-Yb3+ codoped YF3 nanoparticles under 980 nm excitation has also been observed. With increase of heated temperature, the size of the Er(3+)-Yb3+ codoped YF3 nanoparticles increased gradually, and upconversion luminescence intensity increased significantly.     

Ferroelectric liquid-crystal waveguide modulation based on a switchable uniaxial-uniaxial interface

Liquid crystals have effective electro-optic coefficients that are orders of magnitude larger than other integrated optical materials such as lithium niobate. However, previous studies of liquid-crystal waveguides have mainly focused on nematic liquid crystals, which exhibit impractically large scattering losses as waveguides. Studies of smectic liquid crystals and liquid crystals under strong confinement suggest the losses in these materials may be more manageable. In this study, the possibility of using ferroelectric liquid crystals in active waveguide modulators is explored through the analysis of several modulator configurations: a cutoff modulator, a deflection modulator, and an input coupler. As a way to study these structures, a mode-matching technique was developed to analyze the effects of a discontinuity in a uniaxial slab waveguide whose optic axis is in the plane of the waveguide. The results from the mode-matching technique were compared with those from simple bulk models. The analysis shows that ferroelectric liquid-crystal modulators have many desirable performance characteristics and could form the basis for practical waveguide modulators.     

Hydrothermal synthesis and luminescence properties of multiform lanthanide ions doped YVO4 architectures

YVO4 flowerlike architectures with well-aligned microneedles and urchin-like architectures with nanorods have been synthesized using a facile hydrothermal method in the presence of disodium ethylenediamine tetraacetate (Na2H2L). The morphology of the YVO4 flowerlike architectures can be easily controlled by adjusting the pH value of the reaction system. Proper reaction temperature and the basic source ammonia are key requirements for the fabrication of the flowerlike architectures. The additive Na2H2L can coordinate with metal ions to form strong complexes and be absorbed on specific crystal surfaces of the initial colloidal precipitates, which serve as seeds for the anisotropic growth. The formation mechanism for the YVO4 assemblies has been discussed on the basis of time-dependent experiments. YVO4:Ln3+ (Ln = Eu, Dy and Sm) phosphors preserved the architecture morphologies show strong light emissions with different colors coming from different activated ions under ultraviolet excitation.     

Homogeneous assay technology based on upconverting phosphors

Upconversion photoluminescence can eliminate problems associated with autofluorescence and scattered excitation light in homogeneous luminescence-based assays without need for temporal resolution. We have demonstrated a luminescence resonance energy-transfer-based assay utilizing inorganic upconverting (UPC) lanthanide phosphor as a donor and fluorescent protein as an acceptor. UPC phosphors are excited at near-infrared and they have narrow-banded anti-Stokes emission at visible wavelengths enabling measurement of the proximity-dependent sensitized emission with minimal background. The acceptor alone does not generate any direct emission at shorter wavelengths under near-infrared excitation. A competitive model assay for biotin was constructed using streptavidin-conjugated Er3+,Yb3+-doped UPC phosphor as a donor and biotinylated phycobiliprotein as an acceptor. UPC phosphor was excited at near-infrared (980 nm) and sensitized acceptor emission was measured at red wavelength (600 nm) by using a microtitration plate fluorometer equipped with an infrared laser diode and suitable excitation and emission filters. Lower limit of detection was in the subnanomolar concentration range. Compared to time-resolved fluorometry, the developed assay technology enabled simplified instrumentation. Excitation at near-infrared and emission at red wavelengths render the technology also suitable to analysis of strongly colored and fluorescent samples, which are often of concern in clinical immunoassays and in high-throughput screening.     

Application of avidin-biotin technology and adsorptive transfer stripping square-wave voltammetry for detection of DNA hybridization and avidin in transgenic avidin maize

The proteins streptavidin and avidin were electrochemically detected in solution by adsorptive transfer stripping square wave voltammetry (AdTS SWV) at a carbon paste electrode (CPE). AdTS SWV was used to quantify biotinylated oligonucleotides, DNA hybridizations, and avidin in extracts of transgenic avidin maize. The detection limits of denatured and native streptavidin were 6 pM and 120 nM, respectively. The results demonstrated that streptavidin/avidin AdTS SWV is a sensitive and specific method for quantifying DNA and proteins in biological samples such as foods and tissue extracts, including genetically modified crops (avidin maize) and other plants in neighboring fields.     

Homogeneous detection of nucleic acids based upon the light scattering properties of silver-coated nanoparticle probes

Herein we report the development of a simple, rapid, homogeneous, and sensitive detection system for DNA based on the scattering properties of silver-amplified gold nanoparticle probes. The assay uses DNA-functionalized magnetic particle probes that act as scavengers for target DNA, which can be collected via a magnetic field. Once the DNA targets are isolated from the initial sample, they are sandwiched via hybridization by a second set of probes. The latter probes are 13-nm gold nanoparticles modified with a different target complementary DNA. Excess probes are removed through repetitive washing steps. The gold particles are dispersed in solution by dehybridization, corresponding to an assumed 1:1 ratio with the target DNA. Electroless deposition of silver on the surface of the gold probes results in particle growth, which increases their scattering efficiency with time. The scattering efficiency and the extinction signatures of the particle sizes are monitored as a function of time and correlated with target concentration. The limit of detection for this novel assay was determined to be 10 fM.     

Thermally and electrically switchable gratings based on polymer-ball-type polymer-dispersed liquid-crystal films

We focus on the fabrication and study of controllable holographic gratings based on azo-dye-doped and undoped polymer-ball-type polymer-dispersed liquid-crystal films. Experimental results indicate that the next step of photopolymerization of the sample with the illumination of Ar+ laser beams after UV curing causes a latent density grating to be recorded. This grating is formed by a selective secondary photopolymerization. Heating and applying a voltage change the structure of the liquid crystal and induce the appearance of the latent grating. Diffraction efficiencies versus temperature, voltage, and state of polarization are studied for both dye-doped and undoped cells and are found to be quite different. This discrepancy is attributable to the reorientation effect of liquid crystals through their interaction with the photo-induced adsorption of the doped dyes on the surface of polymer balls in the dye-doped cell.     

All-optical switchable holographic Fresnel lens based on azo-dye-doped polymer-dispersed liquid crystals

Fabrication of an all-optical switchable holographic liquid crystal (LC) Fresnel lens based on azo-dye-doped polymer-dispersed LCs is reported using a Michelson interferometer. It is found that, upon circularly polarized photoirradiation, the diffraction efficiency of the fabricated Fresnel lens was increased significantly in a reversible manner. We believe this is due to the anisotropy induced by reorientation of the LC molecules coupled with azo-dye molecule orientation due to trans-cis-trans photoisomerization, which modulates the refractive index of the LC-rich regions. We also studied the effect of azo dye on the polarization dependency of the fabricated lens.     

Full-color persistent luminescence tuning: A marriage of perovskite quantum dots and lanthanide ions

In modern society,the developments of luminescent materials capable of emitting various colored lights are critically important for lighting and display systems[1–3].As a typical kind of luminescent materials,the persistent luminescence phosphors have been widely investigated as night-light vision materials due to their many significant applications such as emergency route signage and security signals,biolabels,photocatalysts,anti-counterfeiting,optical sensors,and optical data storage[4–6].     

Homogeneous detection of single rolling circle replication products

We describe a simple and straightforward approach for homogeneous and isothermal detection of individual rolling circle replication (RCR) products, which represent individual padlock probe circularization events. The RCR products constitute tens of kilobases long single-stranded tandem repeated copies of the probe sequence, and in solution, they fold into micrometer-sized random coils. The method is based on the local enrichment of fluorescence-labeled probes that hybridize to the coiled RCR products compared to the concentration of free probes in solution. We present a detailed characterization of the fluorescence-labeled products using a highly sensitive and fast microscopy setup. At a 10(4)-fold excess of free label, we were able to detect and follow individual RCR products at a signal-to-background noise ratio of 27. This high signal-to-background noise ratio leaves room for analysis in a simple detection device at higher speeds or at lower labeling ratios.     

Gadolinium nanoparticle based switchable mirrors: quenching of hydrogenation-dehydrogenation hysteresis

A continuous and reversible 'structural, optical, and electronic' transition between the reflecting metallic dihydride and transparent semiconducting trihydride states observed in rare earth metals on hydrogenation make these materials and their hydrides suitable for switchable mirror, sensing, and other technological applications. Recently Pd capped Gd nanoparticle based 'new generation' switchable mirrors have been fabricated with extended color neutrality, better optical contrast, and faster kinetics in comparison to the polycrystalline, epitaxial, alloy, and multilayer films. The present report aims at investigating the effect of nanoparticle nature on the hydrogenation-dehydrogenation hysteresis in switchable mirrors by carrying out in situ measurement of optical transmittance and electrode potentials during electrochemical hydrogen loading-deloading of Gd nanoparticle samples. Interestingly, Gd nanoparticle samples were observed to exhibit quenched hysteresis. The quenching of hysteresis in hydrogen-induced properties has been attributed to the absence of structural transition upon hydrogenation, reduction in topographical interlocking of the grains and elimination of lateral clamping of the slack nanoparticle layer to the substrate.