Studies on the two-photon pumped upconverted fluorescence and superradiance of a new organic dye material in solutions

The linear and nonlinear optical properties of a new organic dye, trans-4-[p-(N-ethyl-N-ethylamino)-styryl]-N-methyl-pyridinium tris(thiocyanato) cadmates (II), are reported in this paper. When pumped with a picosecond laser at the wavelength range of 850-1200 nm, intense upconversion fluorescence can be obtained. The upconversion efficiencies at different pump energies were measured when pumped with a 1064-nm laser beam from a mode-locked Nd:YAG laser. The highest upconversion efficiencies were measured to be 5.8% and 7.6% in dimethyl formamide (DMF) and methanol. The lifetime of the dye in DMF was measured to be 75 ps. The strongest nonlinear absorption was at the wavelength of 940 nm, and the highest upconversion efficiency was at the wavelength of 1030 nm. The difference of the two wavelengths was caused by excited state absorption in the dye at wavelengths shorter than 1000 nm. The dye solution in DMF and methanol show a clear optical power limiting effect.     

R6G on graphene: high Raman detection sensitivity, yet decreased Raman cross-section

Several recent studies have demonstrated the use of single and few-layer graphene as a substrate for the enhancement of Raman scattering by adsorbed molecules in a method termed graphene-enhanced Raman spectroscopy (GERS). Here we determine the resonance Raman scattering cross-section for the dye molecule rhodamine 6G (R6G) adsorbed on bilayer graphene. For the 1650 cm(-1) R6G mode, we obtain a cross-section of 5.1 × 10(-24) cm(2)·molecule(-1), a greater than 3-fold reduction from the previously reported solution value. We show that the absorption spectrum of adsorbed R6G can be measured using micro-optical contrast spectroscopy, and we find that detuning of the molecular resonance explains the decreased Raman scattering cross-section. We find no evidence for a graphene Raman enhancement process. We also study the graphene thickness dependence of the adsorbed R6G Raman signal and show that a model incorporating electromagnetic interference effects can qualitatively explain the decrease in signal with increasing graphene thickness.     

High-resolution colocalization of single dye molecules by fluorescence lifetime imaging microscopy

Conventional fluorescence microscopy can be used to determine the positions of objects in space when those objects are separated by distances greater than several hundred nanometers, as restricted by the diffraction limit of light. Fluorescence microscopy/spectroscopy based on fluorescence resonance energy-transfer techniques can be used to measure separation distances below approximately 10 nm. To fill the gap between these fundamental limits, we have developed an alternative technique for high-resolution colocalization of fluorescent dyes. The technique is based on fluorescence lifetime imaging. Under favorable conditions, the method can be used to distinguish, and to measure the distance between, two dye molecules that are less than 30 nm apart. To demonstrate the method, lifetime images of a mixture of Cy5 and JF9 (rhodamine derivative) molecules statistically adsorbed on a glass surface were acquired and analyzed. Since these two molecular species differ in fluorescence lifetime (for Cy5, tau(f) = 2.0 ns, and for JF9, tau(f) = 4.0 ns), it is possible to assign the contribution of fluorescence of the two dye types to each image pixel using a pattern recognition technique. Since both dye types can be excited using the same laser wavelength, the measurement is free of chromatic aberrations. The results presented demonstrate the first high-precision distance measurements between single conventional fluorescent dyes based solely on fluorescence lifetime.     

High-resolution multiwavelength surface plasmon resonance spectroscopy for probing conformational and electronic changes in redox proteins

To date, surface plasmon resonance (SPR) spectroscopy identifies molecules via specific bindings with their ligands immobilized on a surface. We demonstrate here that a high-resolution multiwavelength SPR technique can measure the electronic states of the molecules and thus allow direct identification of the molecules. Using this new capability, we have studied the electronic and conformational differences between the oxidized and reduced states of cytochrome c immobilized on a modified gold electrode. When the wavelength of the incident light is far away from the optical absorption bands of the protein, a approximately 0.008 degree decrease in the resonance angle, due to a conformational change, occurs as the protein is switched from the oxidized to reduced states. When the wavelength is tuned to the absorption bands, the resonance angle oscillates at the wavelengths of the absorption peaks, which provides electronic signatures of the protein.     

Superradiance and lasing properties of new two-photon absorption dye DEASPS

Pumped by picosecond pulses from a Nd:YAG laser, a new lasing dye, trans-4-[4′-(N,N-diethylamino)styryl]-N-methyl pyridinium methyl sulfate (abbreviated to DEASPS), shows both intense superradiance and strong lasing properties in benzyl alcohol solution. By using streak camera systems, the superradiance and lasing can be distinguished both spectrally and temporally. It has been found that the peak wavelength of lasing is at 620 nm with a red-shift of about 12 nm to the superradiance wavelength. The lasing pulse shows an oscillatory effect that it is not found in the superradiance pulse. The fluorescence lifetime is 529 ± 40 ps and the effective molecular two-photon absorption is (1.25 ± 0.1) × 10^?48 cm⁴ ·s·photon ^?1, measured using a nonlinear transmittance method. This dye shows effective optical limiting of the pumping wavelength.     

Optical detection in microscopic domains. 2. Inner filter effects for monitoring nonfluorescent molecules with fluorescence

In this research, we test whether optical detection techniques show different characteristics in microscopic solution volumes (nano-, pico-, and femtoliter range) compared to the usual macroscopic samples. In part 1 (Lu, H.; et al. Anal Chem. 2000, 72, 1569-1576.) absorption spectra of high quality were obtained, quantitatively obeying both Beer-Lambert's law and the law of superposition, despite the micrometer optical path lengths and the curvatures of the droplets studied. Addition and subtraction of absorbing molecules with diffusional microburets (DMBs), as well as more complex operations (simultaneous addition of one and subtraction of another molecule, and a consuming scheme), have been monitored with good spectral and temporal resolution. Despite the unexpectedly good performance of absorption microspectrometry, fluorescence-based detection schemes are considered more sensitive for microscopic studies (e.g., cell physiology). In this paper, we test whether fluorescence-based schemes can be used to indirectly measure nonfluorescent chemicals in microscopic domains. Absorption by such molecules will cause a corresponding decrease in overall fluorescence intensity of the added standard fluorescent dye. This phenomenon, the inner filter effect (IFE), was tested using Lucifer Yellow CH (LY) as the fluorescent standard dye. Its effective irradiation was absorbed by Orange G (primary IFE) or its emission by Bromophenol Blue (secondary IFE). By utilizing these phenomena, (1) we measured the concentration of absorbing molecules in microscopic samples by adding a standard amount of LY by a DMB, and (2) we monitored DMB delivery of nonfluorescent reagents into droplets preloaded with LY. The results prove that IFEs are sensitive indirect means of detection of absorbing molecules in microscopic domains. The techniques presented are expected to find applications in cellular studies where absorption spectrometry is usually not considered.     

Optical nonlinearities of gallium nitride

Luminescence, induced absorption and degenerate four wave mixing experiments are performed on GaN epilayers grown on a sapphire substrate by MOCVD. We measure the nonlinear behaviour of the luminescence spectra near the excitonic resonance, by using an excitation at 4.026 eV from an excimer laser. At low intensities of excitation, spectra show a saturation of the I₂ line due to the finite donor density in the sample. Higher intensities of excitation induce collision process between photo-created particles. Using a dye laser as a pump beam, we measure the induced variation of absorption of a probe beam as a function of the intensity and of the wavelength of the excitation. With increasing intensities of the pump beam, curves show a red-shift of the absorption edge and of the excitonic resonance. Pulsed degenerate four-wave mixing experiments were performed using the third harmonics of a picosecond Nd-YAG laser at 3.492 eV. A characteristic time of 16 ps has been measured, which is independent of the temperature, of the fringe spacing and of the intensity of the pump beams.     

Quantitative SERS Measurements on Dielectric-Overcoated Silver-Island Films by Solution-Deposition Control of Surface Concentrations

A simple method to control the dosing of small adsorbate molecules onto solid surfaces from liquid solution is applied to quantitative surface-enhanced Raman scattering measurements on dielectric-overcoated silver-island films. The deposition method, based on substrate withdrawal from solution, is evaluated by measuring fluorescence (ex situ) and optical absorption (in situ) of dye molecules deposited onto glass surfaces. Control of adsorbate surface concentrations was accomplished by varying the withdrawal rate and the concentration of the dye in solution. The dosing method was used to study the dependence of the electromagnetic contribution to SERS enhancement on surface coverage of scatterer. The sensitivity enhancement was found to be constant for adsorbate coverages up to 60-80% of a monolayer. Beyond a full monolayer, SERS enhancement for additional molecules deposited onto the surface was found to drop significantly, by as much as 1 order of magnitude.     

Study of the conditions affecting dye adsorption on titania films and of their effect on dye photodegradation rates

Nanocrystalline titania films have been deposited on glass slides by the sol-gel technique in the presence of surfactant, which plays the role of template of the nanostructure. Several different dyes, both anionic and cationic, have been adsorbed on these films from aqueous solutions. Some of these dyes were adsorbed at large quantities some at lower quantities. Some of them were adsorbed in monomeric form and others formed aggregates. Aggregates are easily distinguished by absorption spectrophotometry, since absorption of light is observed at a different wavelength than monomer absorption in a dilute solution. In all cases, aggregation demonstrated a hypsochromic shift, indicating repulsive interactions, which are justified in view of the fact that titania surface is charged and that adsorbed molecules are aligned in parallel. The above titania films are hydroxylated. Therefore, cationic dyes were readily adsorbed. Anionic dyes could be adsorbed only from aqueous solutions brought at low pH. Photodegradation rates of adsorbed dyes were generally fast since these films are efficient photocatalysts. Nevertheless, photodegradation of an adsorbed dye was faster when the quantity of the dye was smaller. When the adsorbed dyes formed aggregates, aggregation had adverse effect on photodegradation rates.     

Plasmonic enhancement of molecular fluorescence

Metallic nanoparticles are known to dramatically modify the spontaneous emission of nearby fluorescent molecules and materials. Here we examine the role of the nanoparticle plasmon resonance energy and nanoparticle scattering cross section on the fluorescence enhancement of adjacent indocyanine green (ICG) dye molecules. We find that enhancement of the molecular fluorescence by more than a factor of 50 can be achieved for ICG next to a nanoparticle with a large scattering cross section and a plasmon resonance frequency corresponding to the emission frequency of the molecule.     

Exciton dephasing time in CuBr quantum dots

We perform degenerate four-wave mixing on CuBr quantum dot samples on a femtosecond time scale. Due to inhomogeneous broadening, we observe a so called photon-echo signal. The signal dynamics measured at different pump intensities provide information on the dephasing time. We study this dephasing time at 5 K as a function of the excitation wavelength. We also determine the homogeneous absorption linewidth by spectral hole burning measurements, in the same sample, at 5 K, using a nanosecond dye laser excitation. This is an alternative indirect method to determine dephasing times and we can compare both results. We then conclude on the difficulties of measuring dephasing times in confined systems by the latter method.     

Surface-plasmon resonance spectrometry and characterization of absorbing liquids

The effect of absorption of the sample medium on the surface-plasmon resonance (SPR) characteristics is analyzed by approximate analytical and exact numerical models. We show that absorption leads to specific changes in the value of reflectivity near the SPR angle and that these can be used for absorbance detection. The strongest absorption-induced change in reflectivity occurs at two values of metal film thickness (28 and 55 nm for a gold film and lambda = 632.8 nm). Using a sample solution of Rhodamine 700 in ethanol, we measured the characteristic changes in the SPR angle and in reflectivity over the wavelength interval encompassing the strong absorption band at 610-680 nm. The possibility of the simultaneous determination of the refractive index and absorption from SPR measurements is demonstrated and has the potential for substance-specific detection.     

Color-tuned FRET polystyrene microspheres by single wavelength excitation

Fluorescent monodisperse polystyrene microspheres were prepared by two-stage dispersion polymerization, which successfully covalently labeled microspheres with two dyes without disturbing the final particle size and size distribution. By varying the dye concentrations, microspheres show tuned colors with different fluorescent intensity under a single wavelength excitation. Fluorescence resonance energy transfer (FRET) between two labeled dyes was proved to contribute to the emission of the longer-wavelength dye at a shorter-wavelength excitation. There is no dye leakage for microspheres because of the covalent incorporation of dye molecules. The microsphere matrix provides good protection of dye molecules and blocks the influence of media outside on the fluorescence of microspheres. Single microsphere shows intense fluorescence due to a large number of encapsulated dye molecules. These uniform barcoding fluorescent microspheres have potential application in multiplexed bioanalysis.     

The interaction of indocyanine green dye with the human epidermis studied in vivo

A shift of the light wavelength corresponding to the optical absorption peak of Indocyanine Green used for staining the horny layer of the human epidermis was measured in vivo. It is established that the dye molecules occur in both free and chemically bound state at the skin surface and only in the bound state at a depth of ∼5 μ m.     

Study of nonlinear optical properties of organic dye by Z-scan technique using He–Ne laser

Laser induced nonlinear absorption coefficient of Brilliant Green solution was measured by single beam open aperture Z-scan technique using a continuous wave He–Ne laser at the wavelength of 632.8 nm. It was found that the material exhibits multiphoton absorption type optical nonlinearity. Significant optical nonlinearity is an indicative that Brilliant Green dye is prominent material for low power nonlinear applications. Ultraviolet–visible and photoluminescence (PL) spectra of Brilliant Green solutions are also recorded. A strong linear absorption band with a peak at 625 nm has been observed, while the PL intensity was found to decrease due to quenching effect on increasing the concentration.     

Molecular boxes on a molecular printboard: encapsulation of anionic dyes in immobilized dendrimers

Fifth-generation poly(propylene imine) dendrimers, modified with 64 apolar adamantyl groups, have been immobilized on cyclodextrin host monolayers ("molecular printboards") on glass by supramolecular microcontact printing. The immobilized dendrimers retain their guest-binding properties and function as "molecular boxes" that can be filled with fluorescent dye molecules from solution. Alternatively, part of the immobilized dendrimers were filled with dye molecules by cross-microcontact printing while the remaining, empty dendrimers were filled with a different dye from solution, resulting in alternating patterns of dye molecules. In addition, we demonstrate that encapsulation of dyes in immobilized dendrimers is reversible: immobilized molecular boxes can be filled with a dye, emptied, and subsequently refilled with a different dye.     

Resonance Excitation of Photoluminescence in an Aqueous Uranyl Chloride Solution

We have measured photoluminescence spectra of an aqueous uranyl chloride solution under excitation by various light sources: semiconductor light-emitting diodes and cw laser. The excitation wavelength lay within a resonance absorption band of uranyl chloride, which ensured photoluminescence detection at exposure times of 10^–3 s using an extremely small volume of the substance (10^–9 cm³). The photoluminescence spectra were measured using a small minispectrometer, which allowed us to analyze the spectra in the range 200–1000 nm.     

Extending the continuous tuning range of an external-cavity diode laser

The continuous tuning range of an external-cavity diode laser can be extended by making small corrections to the external-cavity length through an electronic feedback loop so that the cavity resonance condition is maintained as the laser wavelength is tuned. By maintaining the cavity resonance condition as the laser is tuned, the mode hops that typically limit the continuous tuning range of the external-cavity diode laser are eliminated. We present the design of a simple external-cavity diode laser based on the Littman-Metcalf external-cavity configuration that has a measured continuous tuning range of 1 GHz without an electronic feedback loop. To include the electronic feedback loop, a small sinusoidal signal is added to the drive current of the laser diode creating a small oscillation of the laser power. By comparing the phase of the modulated optical power with the phase of the sinusoidal drive signal using a lock-in amplifier, an error signal is created and used in an electronic feedback loop to control the external-cavity length. With electronic feedback, we find that the continuous tuning range can be extended to over 65 GHz. This occurs because the electronic feedback maintains the cavity resonance condition as the laser is tuned. An experimental demonstration of this extended tuning range is presented in which the external-cavity diode laser is tuned through an absorption feature of diatomic oxygen near 760 nm.     

Effect of pulsed dye-laser wavelength stabilization on spectral overlap in atmospheric NO fluorescence studies

We introduce an inexpensive application of a Fabry-Perot etalon to control long-term UV-laser line drift in atmospheric NO laser-induced fluorescence (LIF) measurements by monitoring the visible fundamental of a pulsed dye laser. A linear image sensor captures the interference pattern, and the dye grating can be adjusted to maintain a fixed wavelength through an interface with labview software. Results indicate that the laser wavelength can be fixed to an accuracy of +/-0.0001 nm in the dye fundamental and +/-0.00003 nm in the UV beam. Hence the average error in the LIF signal owing to fluctuations in spectral overlap between the laser and the NO absorption transition decreases from ~5 to ~0.05%, which results in improved measurement accuracy.     

Surface enhanced absorption and transmission from dye coated gold nanoparticles in thin films

Absorption spectra of gold nanoisland thin film and the composite film of gold having thin coating of Methylene Blue and Rh6G dyes have been studied. Thin gold nanoisland film shows surface plasmon resonance (SPR) peak in the visible wavelength range, which shifts to near infrared with an increase in the thickness of the film. It was found that thin film of gold consists of nanoparticles of different size and shape, particularly nanorods of noncylindrical shapes. A linear relation was found between SPR peak wavelength and the aspect ratio of the nanoparticles in gold thin film. Effective medium refractive index of the gold film is estimated to be ~2.5, which decreases with an increase in film thickness. The coating of dyes on gold films splits the SPR peak with an enhanced absorption. Enhancement in absorption of composite film is maximal when the dye absorption peak coincides with the SPR peak; otherwise enhancement in transmission is observed for all the wavelength range. Absorption amplitude of composite film peaks increase with an increase in the gold film thickness, which tend toward saturation for film thickness of ≥6 nm. A correlation shows that absorption spectra can be described by the Maxwell Garnett theory, when the gold nanoparticles have a nearly spherical shape for very thin film (≤6 nm).