Optimization of plasmonic enhancement of fluorescence on plastic substrates

In this work, we report on the uniform deposition of tailored plasmonic coatings on polymer substrates and on the distance dependence of the plasmonic enhancement of a fluorescent dye. Silver, gold, and silver/gold alloy nanoparticles (NPs) with a range of diameters were synthesized using chemical techniques and characterized using UV-vis absorption spectroscopy, transmission electron microscopy (TEM), and atomic force microscopy (AFM). Reproducible polyelectrolyte (PEL) layers, which were deposited on plastic microwell plates using a layer-by-layer technique, served as both a stable and uniform substrate for deposition of the NPs as well as providing spacer layers of known thickness between the NPs and the fluorescent dye. A maximum enhancement factor of approximately 11 was measured for 60 nm diameter pure silver NPs, for a dye-NP separation of approximately 3 nm. A shift in the localized surface plasmon resonance (LSPR) wavelength as a function of the effective refractive index of the PEL layers was also observed, and the measured shifts show a similar trend with theoretical predictions. This work will contribute toward the rational design of optical biochip platforms based on plasmon-enhanced fluorescence.     

Amplified fluorescence polarization aptasensors based on structure-switching-triggered nanoparticles enhancement for bioassays

We have developed an amplified fluorescence polarization aptasensor that relies on aptamer structure-switching-triggered nanoparticles (NPs) enhancement for biomolecules detection. This new type of assay exhibits higher detection sensitivity over traditional homogeneous aptasensors by two orders of magnitude and high specificity for target molecules.     

Attomolar sensitivity in bioassays based on surface plasmon fluorescence spectroscopy

With the aid of a dextran matrix, the metal-induced fluorescence loss of bound fluorophores can be greatly reduced, and the distance dependence of the fluorescence yield could be largely convoluted. This is optimized for the limit of detection assessment of surface plasmon fluorescence spectroscopy. The model system was designed as a direct assay with mouse IgG covalently immobilized to the carboxymethyl dextran matrix of a CM5 sensor chip from Biacore. Time-resolved ultratrace detection of fluorophore (Alexa-Fluor 647)-labeled rabbit anti-mouse antibody down to 500 aM (10-18 M) was accomplished, corresponding to a binding rate of approximately 10 molecules mm-2 min-1.     

Optical enhancement effects of plasmonic nanostructures on organic photovoltaic cells

In this article, the optical enhancement effects of plasmonic nanostructures on OPV cells were reviewed as an effective way to resolve the mismatch problems between the short exciton diffusion length in organic semiconductors (around 10 nm) and the large thickness required to fully absorb sunlight (e.g. hundreds of nanometers). Especially, the performances of OPVs with plasmonic nanoparticles in photoactive and buffer layers and with periodic nanostructures were investigated. Furthermore, nanoimprint lithography-based nanofabrication processes that can easily control the dimension and uniformity of structures for large-area and uniform plasmonic nanostructures were demonstrated.     

Micellar enhancement of benzodiazepine fluorescence

The interactions that exist between benzodiazepines and surfactants provide micellar enhancement factors for their fluorimetric determination in the range 1.2-6.5, depending on the nature of both the benzodiazepine and the surfactant. A series of benzodiazepines and anionic surfactants were treated topologically to determine the influence of each benzodiazepine substituent on the basic benzodiazepine structure and the influence of both the hydrophobic moiety of the surfactant and its counter ion on the sensitisation process. Sensitisation parameters were used to quantify the effect of the chemical structures of both surfactants and drugs on their interaction.     

Mechanism of polarization-induced single-photon fluorescence enhancement

The single-photon fluorescence (SPF) of IR125 can be enhanced when the laser polarization changes from linear through elliptical to circular [A. Nag and D. Goswami, J. Chem. Phys. 132, 154508 (2010)]. In this paper, we further explain and discuss the physical control mechanism. Our theoretical and experimental results demonstrate that the SPF enhancement can be attributed to the nonresonant two-photon absorption of a higher excited state. We conclude that the SPF intensity involving the nonresonant multiphoton absorption of the higher excited state can be controlled by varying the laser polarization.     

A novel fluoride sensor based on fluorescence enhancement

A novel halide sensor, which yields greater fluorescence upon binding to fluoride, has been synthesized and characterized.     

Light-driven fluorescence enhancement of phenylazo indazole-terminated polystyrene

The well-defined phenylazo indazole-terminated polystyrene (PS) was successfully prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization of styrene (St) mediated by a novel chain transfer agent (CTA) bearing phenylazo indazole moieties in the Z group, benzyl-5-(4-(dimethylamino)phenylazo) indazole-1-carbodithioate (BPCD). The fluorescence emission of BPCD and the phenylazo indazole-terminated PS in chloroform (CHCl₃) before and after the 365 nm ultraviolet irradiation was investigated. Interestingly, the fluorescence intensities of BPCD and the phenylazo indazole-terminated PS in CHCl₃ were both sensitive to the 365 nm ultraviolet irradiation. The fluorescence intensities of these solutions increased with the irradiation time and reached maximum at 110 min. The light-driven fluorescence enhancement of BPCD and the phenylazo indazole-terminated PS were both attributed to the formation of spherical aggregate originated from the trans-cis isomerization of azobenzene moieties in BPCD and PS chain, which was confirmed by transmission electron microscopy (TEM), ¹H NMR, UV and dynamic light scattering (DLS) spectra.     

A bis-guanidine-based multisignaling sensor molecule that displays redox-ratiometric behavior or fluorescence enhancement in the presence of anions and cations

[structure: see text]The guanidine bridge in the new structural motif [3,3]ferrocenophane acts as a dual binding site for anions and metal ions. Sensing of anions (Cl(-), F(-), NO(3)(-), HSO(4)(-), and H(2)PO(4)(-)) takes place by redox-ratiometric measurements, whereas metal ion (Zn(2+), Ni(2+), and Cd(2+)) recognition is achieved by fluorescence measurements.     

Selective recognition iodide in aqueous solution based on fluorescence enhancement chemosensor

A novel and simple fluorescence enhancement method for selectively sensing iodide was proposed based on metal complex formation between mercuric(II) ion with fluorophore (p-((dimethylamino)benzylidene)thiosemicarbazide, 1) and with anion in aqueous solution. The 1-Hg complex was found to show selectively and sensitively fluorescence enhancement response toward iodide over than S(2-), EDTA, SCN-, CH(3)CO(2-), Br-, Cl-, F-, H2PO4- and SO4(2-), which was attributed to the higher stability of inorganic complex between iodide and mercuric(II).     

Efficiency enhancement in PbS/CdS quantum dot-sensitized solar cells by plasmonic Ag nanoparticles

Journal of Solid State Electrochemistry - Semiconductor quantum dots (Q-dots) are attractive nanomaterials to be used in numerous research areas and device fabrication such as sensors,...     

Properties of Ni-W alloy coatings on steel substrate

Ni-W alloy coatings were prepared on the steel substrate at the temperature of 60°C. The content of tungsten in coatings was increased with the growing cathodic current density. The increase of the corrosion resistance of Ni-W alloy coatings with the rising content of tungsten was confirmed by the measurement of anodic polarization curves. Annealed coatings showed better antioorrosion properties than the non-annealed ones. The properties of annealed coatings including their corrosion resistance depend on the tungsten content, too.     

Direct detection of ion pairs by fluorescence enhancement

Sensor 1 signals the simultaneous presence of sodium and phosphate with an increased fluorescence signal in the manner of a photoionic AND logic gate.     

Effective enhancement of fluorescence signals in rotaxane-doped reversible hydrosol-gel systems

Rotaxane-based nanoscale architectures have a huge potential to be processed into widely applied devices. In this work, light-driven rotaxanes with fluorescent chromophores based on alpha-cyclodextrin (alpha-CyD) have been doped into amphoteric thermoreversible hydrosol-gels to form a new type of disperse system with reversible optical signals. The photoisomerizations with alpha-CyD shuttling have been studied by induced circular dichroism (ICD). Compared with their corresponding solutions, the rotaxane-doped hydrosol-gel systems produce much more obvious fluorescent binary signals.     

The influence of oxygen on the fluorescence enhancement of fatty-acid-capped CdS nanocrystals

CdS nanocrystals were synthesized in 1-octadecene (ODE) solution with oleic acid (OA) as a capping agent. Freshly prepared CdS nanocrystals showed a weak orangelike fluorescence due to defects on the particle surface. After several weeks' storage, the bulk fluorescence of CdS nanocrystals was dramatically enhanced, which gave the nanocrystals a blue or violet appearance. UV and photoluminescence (PL) measurements were employed to investigate this process. It has been found that the oxygen in the air played the most important role. The oxygen atoms could absorb on the surface of particles and a layer of oxide was gradually formed, which effectively passivated the surface of CdS nanocrystals. Interestingly, this oxidative process had no relation to UV illumination.     

Determination of melamine in milk powder based on the fluorescence enhancement of Au nanoparticles

We have developed a new analytical method to detect melamine (MA) in milk powder based on the fluorescence enhancement of Au nanoparticles (AuNPs). AuNPs with the average diameter of ～16 nm can emit stable fluorescence at 370 nm when the excitation wavelength was selected at 252 nm. The AuNPs could assemble with melamine to form larger aggregates (AuNPs-MA) through electrostatic interaction and coordinating interaction in acidic conditions, which led to the significant enhancement of the fluorescence intensity. Under the optimized conditions, the enhancement of the fluorescence intensity exhibited a good linear dependence on melamine concentration in the range from 8.0 × 10(-10) to 8.0 × 10(-8) M, and the detection limit is 6.1 × 10(-10) M (3σ). This proposed method showed high precision and accuracy when applied to the real sample analyses. In conclusion, a simple, rapid, accurate and sensitive method to detect melamine has been suggested.     

Determination of 6-mercaptopurine based on the fluorescence enhancement of Au nanoparticles

A novel method for the determination of 6-mercaptopurine (6MP) has been developed based on fluorescence enhancement of Au nanoparticles (AuNPs). The fluorescent AuNPs with mean diameter of ∼15 nm were synthesized in aqueous solution, exhibiting the stable maximum emission at 367 nm, under the excitation at wavelength of 264 nm. The AuNPs self-assembly with 6MP were characterized with transmission electron microscopy (TEM), ultraviolet-visible (UV-vis) absorption, fluorescence and surface-enhanced Raman scattering (SERS) spectroscopy. The results revealed that the surface attachment through versatile binding sites of S10, N3, N9 and N7 atoms in 6MP produced the interparticle coupling and formed aggregates of AuNPs. As a result, the fluorescence emission enhancement was significantly observed upon AuNPs self-assembly with 6MP. The fluorimetric determination under optimal conditions indicated that 6MP could be quantified in good linearity range of 6.35 × 10⁻⁸ to 3.05 × 10⁻⁷ M, with a low detection limit of 4.82 × 10⁻¹⁰ M. The relative standard deviation (n = 11) was 1.8% at 2.54 × 10⁻⁸ M 6MP concentration level. The proposed method was successfully applied for the determination of 6MP in spiked human urine. The probable fluorescence enhancement mechanism was also discussed there.     

Separate K-line contributions to fluorescence enhancement in electron probe microanalysis

The behaviour of the fluorescence enhancement correction factor in electron probe microanalysis, as a function of incident electron energy and take-off angle, is assessed for different binary samples in a wide range of compositions. Monte Carlo simulations are employed to validate Reed's correction algorithm [S.J.B. Reed, Characteristic fluorescence corrections in electron-probe microanalysis, Br. J. Appl. Phys. 16 (1965) 913-926], by means of estimating the primary excited radiation volume and the volume corresponding to secondary fluorescence generation. Then, Reed's expression for the fluorescence enhancement has been modified to account for Kα and Kβ line contributions separately. It is clearly shown that in certain cases the assignment of all fluorescent contribution to the Kα lines may be inadequate, particularly when trace element analysis imposes an accurate determination of elemental concentrations.     

Flipping the light switch 'on'--the design of sensor molecules that show cation-induced fluorescence enhancement with heavy and transition metal ions

Real-time and real-space analysis of heavy and transition metal ions employing fluorescent sensor molecules has received much attention over the past few years. Since many of these cations possess intrinsic properties that usually quench the fluorescence of organic dye molecules, a lot of research has lately been devoted to designing fluorescent probes that show complexation-induced fluorescence enhancement. Such an analytical reaction would be highly desirable in terms of increased sensitivity and selectivity. However, in this particular field of sensor research, the photophysical and photochemical mechanisms involved as well as the chemical constitutions of the sensor molecules employed are rather diverse and up to now, very few attempts have been made to establish some general concepts for rational probe design. By analyzing various systems published by other researchers as well as own work, this contribution aims at an elucidation of some of the underlying principles of heavy and transition metal ion-enhanced emission.     

Thermodynamic analysis of fluorescence enhancement and Quenching theory equations

The action of the three kinds of new third generation cephalosporin-class drugs, cefepime hydrochroride, cefpiramide and ceftizoxime with HSA and BSA was studied at different temperatures through the fluorescence method. First, the binding constants were calculated by using fluorescence quenching and enhancement theoretical equations. Their thermodynamic functions were also calculated. Because the K _A corresponding to the different theoretical equations are not completely the same, the thermodynamic parameters calculated are also different. In this paper, the differences among these thermodynamic data obtained from the different theoretical equations were analyzed and the results show that the thermodynamic data deduced from fluorescence enhancement are more reasonable. Thus, we propose that even when the fluorescence quenching action of the acceptorsubstrate is studied, more realistic data can be obtained by using the fluorescence enhancement equation. __________ Translated from Acta Chimica Sinica, 2007, 65(19): 2109–2116 [译自: 化学学报]