Fluorescence enhancement of Ln doped nanoparticles

Fluorescence emission of Ln³⁺ doped nanoparticles is influenced by many factors. Enhancement of fluorescence emission of Ln³⁺ doped nanoparticles can be achieved either through an external approach or an internal adjustment. The external approaches mainly include application of core/shell configuration and metal or semiconductor nanoparticles. Varying the crystal phase of the nanoparticle or introducing a codopant sensitizer are the internal approaches frequently used to obtain fluorescence enhancement, which are through inner adjustments to change the local structure, local symmetry and interaction with active ions. In the current work, efforts to obtain luminescence enhancement in Ln³⁺ doped nanoparticles through external or internal approaches are reviewed. The important roles of local symmetry and asymmetric interactions with optically active ions are extensively discussed.     

甲基橙溶液的pH值对纳米银荧光增强效应的影响

研究了甲基橙溶液的pH对纳米银荧光增强效应的影响.当pH 1.5和2.1时,纳米银对溶液的吸收光谱影响甚小.当pH 3.1时,吸收峰蓝移26 nm,且强度明显降低.当pH值在3.8～8.2范围时,不仅吸收峰蓝移而且在426～456 nm出现宽吸收带.在任何pH值的甲基橙溶液中加入纳米银,S2→S0跃迁荧光发射带强度下降,但下降比率受pH值影响不大;S1→S0跃迁荧光发射带强度增强,其增强比率受pH值影响较大.当pH 2.1时,荧光增强比率最大;当pH 4.8时,荧光增强比率最小.分析认为,pH值对甲基橙溶液光谱性质的影响与不同pH值条件下甲基橙分子结构的改变以及分子在纳米银粒子表面不同的吸附方式、介质环境等因素相关,尤其与甲基橙分子与纳米银粒子间的距离密切相关.     

Enhancement of two-photon absorption and photoinduced birefringence in methyl orange by Au nanoparticles

Two-photon absorption and photoinduced anistropy of a methyl orange/Au nanoparticles composite system were investigated. Open aperture Z-scan measurements demonstrated that the absorption cross section of methyl orange in an Au colloid solution can increase 42-fold compared to purified that of a methyl orange aqueous solution. Meanwhile, a 2.6-fold enhancement of the photoinduced birefringence of methyl orange in the presence of Au was also observed. The mechanism accounting for the enhancement of two-photon absorption coefficient and photoinduced birefringence was discussed in terms of the localized field effect via surface plasmon resonance of Au nanoparticles, which was further confirmed using the fluorescence spectrum technique.     

Au的金属颗粒对二硫化钼发光增强

二硫化钼(MoS₂)是一种层状的二维过渡金属硫族化合物材料,从块体到单层,禁带由间接带隙变为直接带隙,由于通常机械剥落的单层MoS₂是n型掺杂的,使得其发光效率仍然很低. 在本文中,采用匀胶机旋涂的方法将共振吸收峰在514 nm附近的纳米金颗粒尽可能均匀的铺在单层、双层以及多层的MoS₂样品表面,发现单层和双层样品的光致发光谱(PL谱)分别增强了约30倍和2倍同时伴随着峰位的蓝移,而多层样品的发光强度也略有增强. 拉曼特性揭示了纳米金颗粒对单层和双层MoS₂样品产生了明显的p型掺杂,从而增强了发光;同时纳米金颗粒的表面等离子激元效应对激发光的天线作用也是增强MoS₂的光致发光的一个因素. 关键词： 二硫化钼 光致发光 p型掺杂 Au纳米颗粒     

Plasmonic enhancement of optical absorption of UV radiation by Au nanoparticles dispersed on ZnO thin film

Ultraviolet photoconductivity in sol gel-derived ZnO thin film loaded with gold (Au) nanoparticle (NPs) is investigated. Au-NPs loaded ZnO thin film (Au-NPs/ZnO) is found to exhibit high photoconducting gain (K) of about 4.12 × 10³ as compared to the bare ZnO thin film-based photodetector (4.9 × 10¹). The enhanced photoconductive gain of Au-NPs/ZnO detector has been achieved due to simultaneous lowering of dark current which occurs due to Schottky barrier effect originated after dispersing the Au NPs on the surface of ZnO thin film. The enhancement in photocurrent upon UV illumination is due to trapping of UV radiation via plasmonic effect caused by Au-NPs and subsequently coupling of absorbed light with the optical modes of underlying semiconducting ZnO surface.     

Fluorescence enhancement of the conjugated polymer films based on well-ordered Au nanoparticle arrays

In this paper, well-ordered Au nanoparticle arrays on silicon substrates were employed as efficient metal-enhanced fluorescence (MEF) substrates for investigating the fluorescence properties of the conjugated polymer poly(3-hexylthiophene) (P3HT). The ordered Au nanoparticle arrays were fabricated by block copolymer self-assembly technology, and the particle sizes were controlled by adjusting the molar ratios of HAuCl₄ precursor to vinyl pyridine units. The approach is economical and suitable to fabricate large-area MEF substrates. The results about fluorescence properties of P3HT showed that the fluorescence intensities of the P3HT films were improved on ordered Au nanoparticle arrays compared to those on bare silicon substrate and were significantly enhanced with the Au nanoparticle sizes increasing. The mechanism is based on localized surface plasmon resonances, coupling and propagating surface plasmons, and the emission enhancement mainly resulted from the increase of the excitation rate. This work provides a new way to prepare efficient MEF substrates for high-performance fluorescence-based devices.     

Fluorescence of nanoparticles of organic matter dissolved in natural water

The fluorescence of nanoparticles of dissolved organic matter under 270-, 310-, and 355-nm excitation is studied for different molecular fractions. The fluorescence quantum yield of the colloidal (molecules of size 5–200 nm) and low-molecular-weight (molecules smaller than 5 nm) fractions are obtained. It is shown that the spectral position of the fluorescence peak depends on both the size of the molecules and the excitation wavelength.     

Sound absorption by a solution of nanoparticles

Absorption of an acoustic wave in a colloidal solution via two mechanisms: due to viscous friction in the liquid and due to energy dissipation on nanoparticles is studied. The dependence of the imaginary part of the wave vector on the frequency is estimated in both cases. It is shown that in typical colloidal solutions, the first absorption mechanism dominates at low frequencies, and the second one, at higher, ultrasonic frequencies.     

Fluorescence resonance energy transfer between acridine orange and rhodamine 6G and analytical application in micelles of dodecyl benzene sodium sulfonate

A new method for the determination of erythromycin by energy transfer fluorescence quenching of acridine orange (AO)—rhodamine 6G (R6G) in micelles solution studied and established. It was found that the effective energy transfer could occur between AO and R6G in the dodecyl benzene sodium sulfonate at and Britton-Robinson buffer (BR, pH=5.72). The fluorescence intensity of R6G had been increased sharply. Erythromycin diminished the fluorescence intensity of R6G. The detection limit was up to 0.316 mg l⁻¹. The range of determining concentration of erythromycin was 0.75-15 mg l⁻¹. The relative standards deviation were 0.66-1.38% for six parallel determinations of erythromycin. The recoveries of erythromycin were 96.95-101.41%. The measurement was applied to the determination of capsules of erythromycin with good results.     

Large enhancement of Faraday rotation by localized surface plasmon resonance in Au nanoparticles embedded in Bi:YIG film

A large enhancement of the Faraday rotation, which is associated with localized surface plasmon resonance (LSPR), was obtained in a sample with Au nanoparticles embedded in a Bi-substituted yttrium iron garnet (Bi:YIG) film. On a quartz substrate, Au nanoparticles were formed by heating an Au thin film, and a Bi:YIG film was then deposited on them. A sample containing the Au nanoparticles produced by 1000 °C heating showed a resonant attenuation with narrower bandwidth in the transmission spectrum than nanoparticles of other samples formed by low-temperature heating. The sharp resonant Faraday rotation angle was 4.4 times larger than the estimated intrinsic Bi:YIG film at the LSPR wavelength; the angular difference was 0.14°. A discrepancy in the bandwidth between the transmission attenuation and the resonant Faraday rotation is discussed.     

Fluorescence properties of Ag nanoparticles in water, methanol and hexane

Ag nanoparticles, synthesized employing the electro-exploding wire technique, are reported. Absorption in the UV-visible region by these particles is characterized by the features reported in the literature, namely, a possible plasmon peak at ∼404 nm. For Ag nanoparticles dispersed in water, photo-excitation in the ranges 210-235 and 255-280 nm produces similar fluorescence emission at ∼300 nm, whose corresponding resonant absorption takes place at 215 and 270 nm in the excitation spectra. Further, we study the effect of the surrounding medium (solvent effect) on fluorescence from these nanoparticles by comparing fluorescence emission in methanol and hexane for photo-excitation in the same range. Compared to water, fluorescence emission in methanol is observed red-shifted at ∼310 nm, which further red-shifts to ∼325 nm in hexane. The corresponding resonant absorptions in methanol are at 225 and 275 nm. Consequence of this red-shift in a less polar solvent is discussed.     

Fluorescence enhancement of the aqueous solution of terephthalate ion after bi-frequency sonication

The fluorescence enhancement of the aqueous solution of terephthalate ion (TA) under orthogonal sonication of 28 kHz and 1.7 MHz ultrasonic wave has been studied. It has been found that the fluorescence intensity of TA solution after bi-frequency ultrasonic irradiation is obviously higher than the sum of those under two individual ultrasonic irradiations.     

Characterization of Ag and Au nanoparticles created by nanosecond pulsed laser ablation in double distilled water

Pulsed laser ablation of Ag and Au targets, immersed in double-distilled water is used to synthesize metallic nanoparticles (NPs). The targets are irradiated for 20 min by laser pulses at different wavelengths—the fundamental and the second harmonic (SHG) (λ = 1064 and 532 nm, respectively) of a Nd:YAG laser system. The ablation process is performed at a repetition rate of 10 Hz and with pulse duration of 15 ns. Two boundary values of the laser fluence for each wavelength under the experimental conditions chosen were used—it varied from several J/cm² to tens of J/cm². Only as-prepared samples were measured not later than two hours after fabrication. The NPs shape and size distribution were evaluated from transmission electron microscopy (TEM) images. The suspensions obtained were investigated by optical transmission spectroscopy in the near UV and in the visible region in order to get information about these parameters. Spherical shape of the NPs at the low laser fluence and appearance of aggregation and building of nanowires at the SHG and high laser fluence was seen. Dependence of the mean particle size at the SHG on the laser fluence was established. Comments on the results obtained have been also presented.     

Sonochemical activation-assisted biosynthesis of Au/Fe3O4 nanoparticles and sonocatalytic degradation of methyl orange

In this research, a sonochemical activation-assisted biosynthesis of Au/Fe₃O₄ nanoparticles is proposed. The proposed synthesis methodology incorporates the use of Piper auritum (an endemic plant) as reducing agent and in a complementary way, an ultrasonication process to promote the synthesis of the plasmonic/magnetic nanoparticles (Au/Fe₃O₄). The synergic effect of the green and sonochemical synthesis favors the well-dispersion of precursor salts and the subsequent growth of the Au/Fe₃O₄ nanoparticles.The hybrid green/sonochemical process generates an economical, ecological and simplified alternative to synthesizing Au/Fe₃O₄ nanoparticles whit enhanced catalytic activity, pronounced magnetic properties. The morphological, chemical and structural characterization was carried out by high- resolution Scanning electron microscopy (HR-SEM), Energy Dispersive X-Ray Spectroscopy (EDS) and X-Ray diffraction (XRD), respectively. Ultraviolet–visible (UV–vis) and X-ray photoelectron (XPS) spectroscopy confirm the Au/Fe₃O₄ nanoparticles obtention. The magnetic properties were evaluated by a vibrating sample magnetometer (VSM). Superparamagnetic behavior, of the Au/ Fe₃O₄ nanoparticles was observed (M_s = 51 emu/g and H_c = 30 Oe at 300 K). Finally, the catalytic activity was evaluated by sonocatalytic degradation of methyl orange (MO). In this stage, it was possible to achieve a removal percentage of 91.2% at 15 min of the sonocatalytic process (160 W/42 kHz). The initial concentration of the MO was 20 mg L⁻¹, and the Fe3O4-Au dosage was 0.075 gL⁻¹. The MO degradation process was described mathematically by four kinetic adsorption models: Pseudo-first order model, Pseudo-second order model, Elovich and intraparticle diffusion model.     

Effect of ultrasonic wave on the syntheses of Au and ZnO nanoparticles by laser ablation in water

We synthesized Au and ZnO nanoparticles by laser ablation in distilled water with the superposition of an ultrasonic wave. The effect of the ultrasonic wave was examined on the optical absorbance of colloidal solution and the crystallinity of synthesized nanoparticles. The absorbance of colloidal solution was enhanced by the ultrasonic wave, indicating more efficient production rate of nanoparticles. In addition, the ultrasonic wave enhanced the crystallinity of synthesized nanoparticles. These enhancements are attributed to the fact that the ultrasonic wave drives the repetitive formations and collapses of cavitation bubbles.     

基于石墨烯的Au纳米颗粒增强染料随机激光

石墨烯和纳米颗粒的复合材料具有新颖的光学和电学特性,被广泛应用于信息传感、光电转换、医学诊断等领域,具有十分广阔的发展前景.虽然石墨烯拥有优异的光电性能,可以实现对随机激光性质的调控,但目前实现特殊结构的石墨烯与金属纳米结构的复合过程复杂繁琐,利用石墨烯有效降低随机激光阈值仍存在挑战.本文利用便捷的化学还原及吸附法制备Au/石墨烯结构,以染料DCJTB为增益介质,使用旋涂法制备了均匀的薄膜样品;研究对比Au纳米颗粒和Au/石墨烯结构随机激光特性,分析了石墨烯的作用机理.研究结果表明,Au/石墨烯复合材料透射峰与增益介质的光致发光光谱峰最为接近,对于染料分子的能级迁跃起到了促进作用.在相同的增益介质中,石墨烯的加入不仅使得光子在无序介质中散射频次增加,促进了增益效果,而且增强了Au纳米颗粒表面的等离子体共振效应.二者相互协同,展现出了优异的随机激光特性,阈值降低至2.8μJ/mm~2;对样品重复测量可得样品的激射重复性较强、品质较高.本研究对促进随机激光应用、实现高性能的光电器件起到了一定的推动作用.     

Monitoring the non-radiative relaxation time of PpIX solution with Au nanoparticles using Photoacoustic Spectroscopy

In this work we have used the Photoacoustic Spectroscopy (PAS) to determine in vitro the non-radiative relaxation time (NRRT) of a protoporphyrin IX (PpIX) standard solution and samples of PpIX(1), PpIX(2) and PpIX(3) with Au nanoparticle concentrations of 0.001008, 0.00504 and 0.01008 mmol in 25 mL of water respectively. We have used PpIX disodium salt (DS) solution of 25% HCl. The results show that the NRRT average values, obtained for each one of the solution were: τ = 29 ± 0.001, 84 ± 0.001 and 62 ± 0.009 ms for PpIX(1), PpIX(2) and PpIX(3), respectively. These values were compared with some NRRT of triplet states reported in the literature for molecules with tetrapyrrolic structure, increasing the NRRT considerably. From each solution it was obtained its PAS signal phase as a function of the light modulation frequency from 17 to 80 Hz. UV-vis spectrophotometer, photoluminescence spectroscopy and Transmission Electron Microscopy (TEM) were used in order to obtain the optical absorption spectra, the photoluminescence intensities, and the gold nanoparticle sizes respectively. Our investigations are devoted to improve the thermal treatments of drugs the porphyrins as photosensitizers used in image photodynamic therapy.     

On-line monitoring of Au nanoparticles formation by optical spectroscopy

X-Ray Magnetic Circular Dichroism experiments have been conducted on a vanadium inorganic salt and a vanadium enamino-ketone complex. Measurements at the K edge of oxygen and nitrogen reveal the amount of magnetic moment transferred in the 2p orbitals of the ligand atoms from the magnetic V ion. Measurements at the L edge of vanadium show that the orbital moment is small and that J = L + S, contrary to the expected J = L-S coupling for a 3d metal with less than five d-electrons. This surprising inobservance of Hunds third rule emphasizes the need for more detailed studies and calculations on such hybrid molecules.Received: 19 November 2003, Published online: 20 April 2004PACS: 75.20.-g Diamagnetism, paramagnetism, and superparamagnetism - 75.70.Ak Magnetic properties of monolayers and thin films - 78.70.Dm X-ray absorption spectra