Metal-enhanced Singlet Oxygen Generation: A Consequence of Plasmon Enhanced Triplet Yields

In this Rapid Communication, we report the first observation of Metal-Enhanced singlet oxygen generation (ME¹O₂). Rose Bengal in close proximity to Silver Island Films (SiFs) can generate more singlet oxygen, a three-fold increase observed, as compared to an identical glass control sample but containing no silver. The enhanced absorption of the photo-sensitizer, due to coupling to silver surface plasmons, facilitates enhanced singlet oxygen generation. The singlet oxygen yield can potentially be adjusted by modifying the choice of MEF (Metal-Enhanced Fluorescence) & MEP (Metal Enhance Phosphorescence) parameters, such as distance dependence for plasmon coupling and wavelength emission of the coupling fluorophore. This is a most helpful observation in understanding the interactions between plasmons and lumophores, and this approach may well be of significance for singlet oxygen based clinical therapy.     

纳米银对表面吸附核黄素分子光谱性质的影响

采用氧化还原法制备了纳米尺寸的银溶胶,研究了纳米银粒子对核黄素(Riboflavin,Ri)水溶液吸收光谱和荧光光谱的影响.Ri溶液中加入纳米银粒子,随着纳米银浓度的增大,吸收强度不断增强,372 nm处吸收峰红移,而444 nm处吸收峰蓝移,同时发生荧光猝灭现象.从无辐射通道增强、纳米银表面局域场减弱及Ri分子第一激...     

Characterization of the Plasmonic Fluorescence Enhancement of Poly (3-hexylthiophene) for Organic Solar Cell Applications

The dependence of surface-enhanced fluorescence of the semiconducting polymer poly (3-hexylthiophene) on the diameter of silver nanoparticles was studied. Particle suspensions with a high degree of monodispersity, ranging in diameter from 15 to 153 nm, were synthesized. Polymer films were spin-cast onto substrates containing immobilized silver particles. Fluorescence enhancement factors ranged from 0.9 to 4.9 and generally improved with increasing particle size. Normalization of the fluorescence enhancement to the number of interrogated particles showed an 800-fold increase in enhancement between the smallest and largest particles.     

Effect of temperature on the synthesis of silver nanoparticles with polyethylene glycol: new insights into the reduction mechanism

Polyethylene glycol (PEG) molecules act as a reducing and stabilizing agent in the formation of silver nanoparticles. PEG undergoes thermal oxidative degradation at temperatures over 70 °C in the presence of oxygen. Here, we studied how the temperature and an oxidizing atmosphere could affect the synthesis of silver nanoparticles with PEG. We tested different AgNO₃ concentrations for nanoparticles syntheses using PEG of low molecular weight, at 60 and 100 °C. At the higher temperature, the reducing action of PEG increased and the effect of PEG/Ag⁺ ratio on nanoparticles aggregation changed. These results suggest that different synthesis mechanisms operate at 60 and 100 °C. Thus, at 60 °C the reduction of silver ions can occur through the oxidation of the hydroxyl groups of PEG, as has been previously reported. We propose that the thermal oxidative degradation of PEG at 100 °C increases the number of both, functional groups and molecules that can reduce silver ions and stabilize silver nanoparticles. This degradation process could explain the enhancement of PEG reducing action observed by other authors when they increase the reaction temperature or use a PEG of higher molecular weight     

The Effect of L-Cysteine on Surface-Enhanced Raman Scattering of Malachite Green in Silver Colloids

ABSTRACT

Colloidal silver nanoparticles were prepared by a simple chemical reduction method. The effect of L-cysteine on the surface-enhanced Raman scattering activity of colloidal silver nanoparticles was investigated by using malachite green as a probe molecule. It was found that the surface-enhanced Raman scattering activity of colloidal silver nanoparticles was improved tremendously with the help of L-cysteine. The possible reasons for this enhancement effect were given. Specifically, in silver colloidal solution, no surface-enhanced Raman scattering spectrum of malachite green was observed at a relatively low concentration (≤2.5 × 10^?5 mol/L). However, well-resolved and high-quality surface-enhanced Raman scattering spectra of malachite green were successfully obtained after the addition of L-cysteine to silver colloids, and the minimum detection limit for malachite green was down to 10^?8 mol/L.     

纳米银与表面吸附荧光素的荧光性能的影响

研究了纳米银粒子对表面吸附荧光素(fluorescein,Fl)的荧光性能的影响。Fl溶液中加入纳米银粒子,Fl分子包覆在纳米银粒子表面形成Fl_n-Ag复合物使纳米银相互桥连形成类似网络的结构,且Fl分子吸收峰随着纳米银浓度的增加发生红移。纳米银通过产生的强局域场将能量传输给Fl发光中心,实现了Fl的荧光增强,荧光增强效率随着纳米银浓度的增加具有最大值。较大粒径的纳米银使Fl获得最大荧光增强效率所需浓度较低且最大荧光增强效率值较高。研究结果表明,纳米银与Fl间的能量传输主要由Fl分子附近局域电磁场增强和分子到金属表面无辐射跃迁能量转移过程所决定并与纳米银的浓度、尺寸密切相关。     

Integral fluorescence enhancement by silver nanoparticles controlled via PMMA matrix

The metal-enhanced fluorescence is measured with different thickness of emission film. Silver nanoparticles are immobilized on glass slide by chemical self-assembly method. Rhodamine B molecules are dispersed in the polymer matrix of Poly(methyl methacrylate) (PMMA), then spin coated on prepared silver particles substrate with different thickness from 15 nm to 70 nm. The enhanced fluorescence is observed depending on the thickness of emission film since the average distance between rhodamine B molecules and silver nanoparticles is altered by the PMMA matrix. The 5-fold enhancement is attained. The experiment was explained qualitatively by an integral fluorescence enhancement.     

Surface‐enhanced Raman scattering of silylated graphite oxide sheets sandwiched between colloidal silver nanoparticles and silver piece

Graphite oxide (GO) was successfully silylated by 3‐mercaptopropyltrimethoxysilane. The surface‐enhanced Raman scattering spectrum of the silylated GO sheets sandwiched between colloidal silver nanoparticles and silver piece is presented. The Raman signal shows a 10⁴ enhancement compared to that of bulk GO. The large Raman enhancement is most likely a result of electromagnetic (EM) coupling between the colloidal silver nanoparticles (localized surface plasmon) and the silver piece (surface plasmon polariton), creating large localized EM fields at their interface, where the silylated GO sheets reside in this sandwich architecture. Copyright © 2009 John Wiley & Sons, Ltd.     

Novel Silicon Phthalocyanines Bearing Triethylene Glycol Groups: Photophysical and Photochemical Properties as well as pH-Induced Spectral Behaviour

Herein, novel silicon (IV) phthalocyanines peripherally substituted by triethylene glycol groups and bearing axial hydroxyl groups were synthesized and fully characterized by using different analyses techniques. The photophysical and photochemical properties of octa (2a) and tetra (2b) derivatives were investigated in DMF and DMSO. The effect of octa or tetra substitution on fluorescence quantum yield, singlet oxygen generation and photodegradation were examined, and the differences were evaluated regarding their potential efficiency in photodynamic therapy (PDT). Their pH-responses were investigated to determine the influence of protonation of azomethine nitrogen atoms on singlet oxygen generation efficiencies. Dramatic optical changes were observed by protonation of azomethine bridges of 2a and 2b. They exhibited signal decrease from pH 4.0 to 1.0 for 2a (pKa = 2.6) and pH 3.0 to 1.0 for 2b (pKa = 1.8). Besides, the compounds exhibited no aggregation tendency, moderate fluorescence quantum yield, solubility in common organic solvents, high singlet oxygen quantum yield and high photostability in DMF and in DMSO, these favorable properties making them good candidates as photosensitizer for PDT.     

银纳米粒子的SERS效应和SEF效应在微流控芯片光学检测中的应用

银纳米离子的SERS技术和SEF技术的信号检测灵敏度非常高,可以用在微流控芯片的定量分析中。为了提高微流控芯片光学检测技术的检测精度,提出一种在微通道中添加银纳米粒子来增强SYBR GreenⅠ拉曼和荧光信号的方法,并对该方法的原理和增强效果进行了研究。首先,利用准分子激光器在PMMA基板上直写刻蚀出宽200 μm、深68 μm的微通道,接着将制备的银前体溶液加入微通道,通过加热制备出表面增强拉曼（SERS）和表面增强荧光（SEF）基板,接下来对添加银纳米粒子前后的拉曼和荧光信号分别进行对比,进一步研究了微通道中不同浓度银纳米粒子对SYBR GREEN I的拉曼和荧光信号增强效果。添加银纳米粒子后,表面增强拉曼（SERS）实验的增强因子为3.5×10³,添加银纳米粒子的样品的荧光信号强度与不含银纳米粒子样品的荧光信号强度相比,约增加了1倍。结果表明,在微通道中检测SYBR Green I时通过增加银纳米粒子显著地增强了拉曼和荧光信号,这种方法可以用在以SYBR GreenⅠ做染料的微流控芯片检测技术中。     

Surface-enhanced optical third-harmonic generation in Ag island films

Surface-enhanced optical third-harmonic generation (THG) is observed in silver island films. The THG intensity from Ag nanoparticles is enhanced by more than 2 orders of magnitude with respect to the THG intensity from a smooth and homogeneous silver surface. This enhancement is attributed to a local plasmon excitation and resonance of the local field at the third-harmonic wavelength. The diffuse and depolarized component of the enhanced THG is associated with the third-order hyper-Rayleigh scattering in a two-dimensional random array of silver nanoparticles.     

Localized Surface Plasmon Resonance Enhanced Singlet Oxygen Generation and Light Absorption Based on Black Phosphorus@AuNPs Nanosheet for Tumor Photodynamic/Thermal Therapy

Although photodynamic therapy is an efficient therapeutic strategy for cancer treatment, it always suffers from the low singlet oxygen (¹O₂) yields owing to the weak absorption in optical transparent window of biological tissues. Herein, the black phosphorus (BP) nanosheet is integrated with gold nanoparticles (AuNPs) to simultaneously enhance the singlet oxygen generation and hyperthermia by localized surface plasmon resonance (LSPR) in cancer therapy. In the design, BP nanosheet employed as two‐dimension (2D) inorganic photosensitizer is hybridized with AuNPs through polyetherimide (PEI) as bridge to form BP‐PEI/AuNPs hybrid nanosheet. Such hybridation not only significantly increases the ¹O₂ production of BP nanosheet through maximizing the local field enhancement of AuNPs, but also significantly enhances the light absorption of BP nanosheet to promote photothermal effect by LSPR. Accordingly, about 3.9‐fold enhancement of ¹O₂ production and 1.7‐fold increasement of photothermal conversion efficiency are achieved compared with BP‐PEI alone upon single 670 nm laser irradiation. As a proof‐of‐concept model, BP‐PEI/AuNPs hybrid nanosheet with simultaneous dual‐modal phototherapy functions result in effective suppression of tumor growth with minimized side effects both in vitro and in vivo, indicating the great potential of the BP‐PEI/AuNPs hybrid nanosheet as an effective strategy to enhance the cancer therapy efficiency.     

银纳米颗粒对胆固醇荧光的增强效用研究

在传统荧光光谱技术的基础上,结合金属纳米颗粒的增强荧光技术,探索提高荧光光谱技术检测人全血溶液中胆固醇含量的精度和分辨率的方法。实验研究方面,采用波长为407 nm的激光作为激发光,照射加入一定量银纳米颗粒作为荧光增强剂的人全血溶液,研究了银纳米颗粒对人全血溶液在可见光波段的荧光增强作用。结果表明,胶体状态的银纳米颗粒可以显著增强低浓度的人全血溶液荧光光谱的强度,且不同位置荧光发射峰的荧光增强效率随银胶加入量的增加均呈现先增后减的趋势,但不同峰位置的最强增强效率对应的银胶加入量不同。理论分析方面,根据实验结果及胆固醇分子和银纳米颗粒在溶液中的分布情况,建立了分子间距模型,并根据模型计算得出胆固醇分子和银纳米粒子之间的最佳增强荧光效果间距在12.19～25 nm范围内,这个结果和其他文献中的理论值吻合较好。综上所述,使用银纳米颗粒可实现全血溶液荧光的增强,研究结果为提高检测血液中多种物质的灵敏度和精度提供了有价值的参考作用。     

Synthesis of silicon nanocomposite for printable photovoltaic devices on flexible substrate

Renewed interest has been established in the preparation of silicon nanoparticles for electronic device applications. In this work, we report on the production of silicon powders using a simple ball mill and of silicon nanocomposite ink for screen-printable photovoltaic device on a flexible substrate. Bulk single crystalline silicon was milled for 25 h in the ball mill. The structural properties of the produced silicon nanoparticles were investigated using X-ray diffraction (XRD) and transmission electron microscopy. The results show that the particles remained highly crystalline, though transformed from their original single crystalline state to polycrystalline. The elemental composition using energy dispersive X-ray florescence spectroscopy (EDXRF) revealed that contamination from iron (Fe) and chromium (Cr) of the milling media and oxygen from the atmosphere were insignificant. The size distribution of the nanoparticles follows a lognormal pattern that ranges from 60 nm to about 1.2 μm and a mean particle size of about 103 nm. Electrical characterization of screen-printed PN structures of the nanocomposite formed by embedding the powder into a suitable water-soluble polymer on Kapton sheet reveals an enhanced photocurrent transport resulting from photo-induced carrier generation in the depletion region with energy greater that the Schottky barrier height at the metal-composite interface.     

自组装银膜增强8-羟基喹啉铝(Alq_3)光致发光的实验和理论研究

实验和理论研究了不同自组装密度的银纳米颗粒膜对8-羟基喹啉铝(Alq_3)光致发光的影响,结果表明:Alq_3光致发光的表观增强和发射增强因子与银纳米颗粒膜密度呈正相关关系,最大值约为3.2和13;理论计算表明银纳米颗粒膜对Alq_3光致发光的量子效率和发射的最大增强因子约为1.4和15,对比实验和理论结果,金属纳米颗粒膜的近场场强增强是导致Alq3光致发光发射强度增强的主要因素,且Alq_3光致发光效率与Alq_3相对银纳米颗粒的分布和"热点"区域面积覆盖率有关。     

Green synthesis of gold and silver nanoparticles using gallic acid: catalytic activity and conversion yield toward the 4-nitrophenol reduction reaction

In the present report, gallic acid was used as both a reducing and stabilizing agent to synthesize gold and silver nanoparticles. The synthesized gold and silver nanoparticles exhibited characteristic surface plasmon resonance bands at 536 and 392 nm, respectively. Nanoparticles that were approximately spherical in shape were observed in high-resolution transmission electron microscopy and atomic force microscopy images. The hydrodynamic radius was determined to be 54.4 nm for gold nanoparticles and 33.7 nm for silver nanoparticles in aqueous medium. X-ray diffraction analyses confirmed that the synthesized nanoparticles possessed a face-centered cubic structure. FT-IR spectra demonstrated that the carboxylic acid functional groups of gallic acid contributed to the electrostatic binding onto the surface of the nanoparticles. Zeta potential values of ?41.98 mV for the gold nanoparticles and ?53.47 mV for the silver nanoparticles indicated that the synthesized nanoparticles possess excellent stability. On-the-shelf stability for 4 weeks also confirmed that the synthesized nanoparticles were quite stable without significant changes in their UV–visible spectra. The synthesized nanoparticles exhibited catalytic activity toward the reduction reaction of 4-nitrophenol to 4-aminophenol in the presence of sodium borohydride. The rate constant of the silver nanoparticles was higher than that of the gold nanoparticles in the catalytic reaction. Furthermore, the conversion yield (%) of 4-nitrophenol to 4-aminophenol was determined using reversed-phase high-performance liquid chromatography with UV detection at 254 nm. The silver nanoparticles exhibited an excellent conversion yield (96.7–99.9 %), suggesting that the synthesized silver nanoparticles are highly efficient catalysts for the 4-nitrophenol reduction reaction.     

Surface‐enhanced Raman scattering on colloid gels originated from low molecular weight gelator

Surface‐enhanced Raman scattering (SERS) on silver and gold colloid gels formed by a low molecular weight organic gelator, bis‐(S‐phenylalanine) oxalyl amide, was obtained. Strong Raman signals dominate in the SERS spectra of hydrogels containing silver nanoparticles prepared by citrate and borohydride reduction methods, whereas broad bands of low intensity are detected in the spectra of gold colloid gels. Resemblance between Raman spectrum of the crystalline substance and the SERS spectra of the silver nanoparticle–hydrogel composites implies the electromagnetic nature of the signal enhancement. A change in Raman intensity of the benzene and amide II bands caused by an increase in temperature and concentration indicates that the gelling molecules are strongly attached through the benzene moieties to the metal nanoparticles while participating in gel formation by intermolecular hydrogen bonding between the adjacent oxalyl amide groups. Transmission electron microscopy reveals a dense gel structure in the close vicinity of the enhancing metal particles for both silver colloid gels. Copyright © 2008 John Wiley & Sons, Ltd.     

Strong Photoluminescence Enhancement from Colloidal Quantum Dot Near Silver Nano-Island Films

We present the fabrication and optical investigation of highly random self-assembled, nano-scale films, probing their influence on the luminescence properties of near surface CdSe/ZnS colloidal quantum dots. When compared to quantum dots distributed on unstructured quartz substrates, the average luminescence intensity is found to be enhanced by a factor of 160×. The silver nanoparticles are prepared using slow thermal evaporation on quartz substrates and post-deposition annealing to produce a randomly-arranged layer of smooth nano-islands. Clear polarization dependent hot spots are observed. Such hot spots deliver a maximal enhancement of the emission intensity of 240× and have a spatial density of (0.050±0.002) μm^− 2. The results show that silver nano-island films strongly enhance the optical efficiency of near quantum dots emitters.     

Plasmonic Enhancement of Single-Molecule Fluorescence Near a Silver Nanoparticle

In this short paper, we reported the enhanced fluorescence from a single fluorophore bound to a 50nm silver nanoparticle. We found that on average the Cy5 molecules bound to metal nanoparticles are approximately 15-fold brighter than that of free dyes, and that single molecule lifetimes are shorter as compared to free fluorophores. The increased emission rate is primarily the result of local plasmon enhancement. These results demonstrate that the use of fluorophore-metal interactions can increase the brightness and photostability of fluorophores for single molecule detection.     

Fabrication and characterization of SERS‐active silver clusters on glassy carbon

In this article, a novel technique for the fabrication of surface enhanced Raman scattering (SERS) active silver clusters on glassy carbon (GC) has been proposed. It was found that silver clusters could be formed on a layer of positively charged poly(diallyldimethylammonium) (PDDA) anchored to a carbon surface by 4‐aminobenzoic acid when a drop containing silver nanoparticles was deposited on it. The characteristics of the obtained silver clusters have been investigated by atomic force microscopy (AFM), SERS and an SERS‐based Raman mapping technique in the form of line scanning. The AFM image shows that the silver clusters consist of several silver nanoparticles and the size of the clusters is in the range 80–100 nm. The SERS spectra of different concentrations of rhodamine 6G (R6G) on the silver clusters were obtained and compared with those from a silver colloid. The apparent enhancement factor (AEF) was estimated to be as large as 3.1 × 10⁴ relative to silver colloid, which might have resulted from the presence of ‘hot‐spots’ at the silver clusters, providing a highly localized electromagnetic field for the large enhancement of the SERS spectra of R6G. The minimum electromagnetic enhancement factor (EEF) is estimated to be 5.4 × 10⁷ by comparison with the SERS spectra of R6G on the silver clusters and on the bare GC surface. SERS‐based Raman mapping technique in the form of line scanning further illustrates the good SERS activity and reproducibility on the silver clusters. Finally, 4‐mercaptopyridine (4‐Mpy) was chosen as an analyte and the lowest detected concentration was investigated by the SERS‐active silver clusters. A concentration of 1.6 × 10⁻¹⁰ M 4‐Mpy could be detected with the SERS‐active silver clusters, showing the great potential of the technique in practical applications of microanalysis with high sensitivity. Copyright © 2006 John Wiley & Sons, Ltd.