Mapping the Energy Distribution of SERRS Hot Spots from Anti-Stokes to Stokes Intensity Ratios

The anomalies in the anti-Stokes to Stokes intensity ratios in single-molecule surface-enhanced resonance Raman scattering were investigated. Brilliant green and crystal violet dyes were the molecular probes, and the experiments were carried out on an electrochemically activated Ag surface. The results allowed new insights into the origin of these anomalies and led to a new method to confirm the single-molecule regime in surface-enhanced Raman scattering. Moreover, a methodology to estimate the distribution of resonance energies that contributed to the imbalance in the anti-Stokes to Stokes intensity ratios at the electromagnetic hot spots was proposed. This method allowed the local plasmonic resonance energies on the metallic surface to be spatially mapped.

Changes in a nanoparticle's spectroscopic signal mediated by the local environment

Using a first-principles theoretical model the adsorption of a methyl radical on different sized silver nanoparticles is compared to the adsorption of the same radical on model surfaces. Calculations of our structural, dynamical and electronic properties indicated that small changes in the local environment will lead to small changes in infrared (IR) wavenumbers, but in dramatic changes in the IR signal. Our calculations indicate the lower the adsorption site coordination, the higher is the signal strength, suggesting that small changes in the electronic charge distribution will result in bigger changes in the polarizability and hence in the spectroscopic signal intensity. This effect explains, among others, the signal magnification observed for nanoparticles in surface enhanced Raman spectroscopic (SERS) experiments.

Gold nanoparticle formation in diamond-like carbon using two different methods: Gold ion implantation and co-deposition of gold and carbon

We describe work in which gold nanoparticles were formed in diamond-like carbon (DLC), thereby generating a Au-DLC nanocomposite. A high-quality, hydrogen-free DLC thin film was formed by filtered vacuum arc plasma deposition, into which gold nanoparticles were introduced using two different methods. The first method was gold ion implantation into the DLC film at a number of decreasing ion energies, distributing the gold over a controllable depth range within the DLC. The second method was co-deposition of gold and carbon, using two separate vacuum arc plasma guns with suitably interleaved repetitive pulsing. Transmission electron microscope images show that the size of the gold nanoparticles obtained by ion implantation is 3-5 nm. For the Au-DLC composite obtained by co-deposition, there were two different nanoparticle sizes, most about 2 nm with some 6-7 nm. Raman spectroscopy indicates that the implanted sample contains a smaller fraction of sp(3) bonding for the DLC, demonstrating that some sp(3) bonds are destroyed by the gold implantation. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4757029]

Synthesis and characterization of silver/alanine nanocomposites for radiation detection in medical applications: the influence of particle size on the detection properties

Silver/alanine nanocomposites with varying mass percentage of silver have been produced. The size of the silver nanoparticles seems to drive the formation of the nanocomposite, yielding a homogeneous dispersion of the silver nanoparticles in the alanine matrix or flocs of silver nanoparticles segregated from the alanine crystals. The alanine crystalline orientation is modified according to the particle size of the silver nanoparticles. Concerning a mass percentage of silver below 0.1%, the nanocomposites are homogeneous, and there is no particle aggregation. As the mass percentage of silver is increased, the system becomes unstable, and there is particle flocculation with subsequent segregation of the alanine crystals. The nanocomposites have been analyzed by transmission electron microscopy (TEM), UV-Vis absorption spectroscopy, X-ray diffraction (XRD), and Fourier transform infrared (FTIR) spectroscopy and they have been tested as radiation detectors by means of electron spin resonance (ESR) spectroscopy in order to detect the paramagnetic centers created by the radiation. In fact, the sensitivity of the radiation detectors is optimized in the case of systems containing small particles (30 nm) that are well dispersed in the alanine matrix. As the agglomeration increases, particle growth (up to 1.5 mu m) and segregation diminish the sensitivity. In conclusion, nanostructured materials can be used for optimization of alanine sensitivity, by taking into account the influence of the particles size of the silver nanoparticles on the detection properties of the alanine radiation detectors, thus contributing to the construction of small-sized detectors.

PbO-GeO2 rare earth doped glasses with silver nanoparticles as materials for IR laser triggers

We have shown the possibility of operation by the piezooptical response of PbO-GeO2 glasses doped with rare earth ions and silver nanoparticles by illumination of double frequency CO2 nanosecond laser. Substantial influence of thermoannealing on the output photoinduced elastooptical susceptibilities was established. The effect is very sensitive to temperature and to the corresponding tensor components. The effect of thermoannealing leads to enhanced long-range ordering with the occurrence of corresponding trapping levels within the forbidden gaps. The discovered effects may be used for creation of low-temperature IR laser triggers.

Film based on Y2O3: Eu3+ (5 mol% of Eu3+) for flat panel display

This paper reports on Y2O3:Eu3+ containing 1 mol% of Ag-0 nanoparticle films recovered with a SiO2 layer by using glass foil as a substrate for a possible optical display device application. The obtained film showed an intense emission at 612 nm due to the Eu3+ 5D0 -> F-7(2) hypersensitive transition, a high transmittance in that emission range, an excellent optical quality, and a high absorption only below 300 nm. Moreover, despite the presence of the SiO2 layer used to improve the phosphor adhesion on Corning (R) foil substrates, the intensity ratios between the emissions assigned to Eu3+ D-5(0) -> F-7(2) (dipole electric transition) and D-5(0) -> F-7(1) (dipole magnetic transition) were not affected by it. The x and y coordinate values found in the 1931 Commission Internationale de l'Eclairage Chromaticity Diagram for this film reveal that it has a suitable pure red color emission for optical displays devices. (C) 2012 Elsevier B. V. All rights reserved.

Frequency upconversion properties of Tm3+ doped TeO2-ZnO glasses containing silver nanoparticles

Frequency upconversion (UC) properties of Tm3+ doped TeO2-ZnO glasses containing silver nanoparticles (NPs) were investigated. Infrared-to-visible and infrared-to-infrared UC processes associated to the Tm3+ ions were studied by exciting the samples with a cw 1050 nm ytterbium laser. The luminescence intensity as a function of laser intensity was also measured using a pulsed 1047 nm Nd3+:YVO laser in order to determine the number of photons participating in the UC processes. Enhancement of the UC signals for samples heat-treated during various time intervals is attributed to the growth of the local field in the vicinity of the NPs. PL enhancement by one-order of magnitude was observed in the whole spectrum of the samples heat-treated during 48 h. On the other hand PL quenching was observed for the samples heat-treated more than 48 h. (c) 2011 Elsevier B.V. All rights reserved.

Monoclonal antibodies anti-TGF beta 1 and anti-VEGF inhibit the experimental pleurodesis induced by silver nitrate

Background. The mechanisms underlying pleural inflammation and pleurodesis are poorly understood. We hypothesized that the cytokines transforming growth factor beta (TGF beta 1) and vascular endothelial growth factor (VEGF) play a major role in pleurodesis after intrapleural silver nitrate (SN) injection. Method. Forty rabbits received intrapleurally 0.5% SN alone or 0.5% SN + anti-TGF beta 1, anti-IL-8, or anti-VEGF. After 28 days, the animals were euthanized and macroscopic pleural adhesions, microscopic pleural fibrosis, and collagen deposition were analyzed for characterization of the degree of pleurodesis (scores 0-4). Results. Scores of pleural adhesions, pleural fibrosis, total collagen, and thin collagen fibers deposition after 28 days were significantly lower for 0.5% SN + anti-TGF beta 1 and 0.5% SN + anti-VEGF. Significant correlations were found between macroscopic adhesion and microscopic pleural fibrosis with total collagen and thin collagen fibers. Conclusions. We conclude that both TGF beta 1 and VEGF, but not IL-8, mediate the pleural inflammatory response and pleurodesis induced by SN.

Recent Advances in the Development of Magnetically Recoverable Metal Nanoparticle Catalysts

The aim of this Account is to provide an overview of our current research activities on the design and modification of superparamagnetic nanomaterials for application in the field of magnetic separation and catalysis. First, an introduction of magnetism and magnetic separation is done. Then, the synthetic strategies that have been developed for generating superparamagnetic nanoparticles spherically coated by silica and other oxides, with a focus on well characterized systems prepared by methods that generate samples of high quality and easy to scale- up, are discussed. A set of magnetically recoverable catalysts prepared in our research group by the unique combination of superparamagnetic supports and metal nanoparticles is highlighted. This Account is concluded with personal remarks and perspectives on this research field.

Comparative study on the far-field spectra and near-field amplitudes for silver and gold nanocubes irradiated at 514, 633 and 785 nm as a function of the edge length

We describe a systematic investigation by the discrete dipole approximation on the optical properties of silver (Ag) and gold (Au) nanocubes as a function of the edge length in the 20-100 nm range. Our results showed that, as the nanocube size increased, the plasmon resonance modes shifted to higher wavelengths, the contribution from scattering to the extinction increased, and the quadrupole modes became more intense in the spectra. The electric field amplitudes at the surface of the nanocubes were calculated considering 514, 633 and 785 nm as the excitation wavelengths. While Ag nanocubes displayed the highest electric field amplitudes (vertical bar E vertical bar(max)) when excited at 514 nm, the Au nanocubes displayed higher vertical bar E vertical bar(max) values than Ag, for all sizes investigated, when the excitation wavelength was either 633 or 785 nm. The variations in vertical bar E vertical bar(max) as a function of size for both Ag and Au nanocubes could be explained based on the relative position of the surface plasmon resonance peak relative to the wavelength of the incoming electromagnetic wave. Our results show that not only size and composition, but also the excitation wavelength, can play an important role over the maximum near-field amplitudes values generated at the surface of the nanocubes.

Infrared-to-visible upconversion emission in Er3+ doped TeO2-WO3-Bi2O3 glasses with silver nanoparticles

The influence of silver nanoparticles (NPs) on the frequency upconversion luminescence in Er3+ doped TeO2-WO3-Bi2O3 glasses is reported. The effect of the NPs on the Er3+ luminescence was controlled by appropriate heat-treatment of the samples. Enhancement up to 700% was obtained for the upconverted emissions at 527, 550, and 660 nm, when a laser at 980 nm is used for excitation. Since the laser frequency is far from the NPs surface plasmon resonance frequency, the luminescence enhancement is attributed to the local field increase in the proximity of the NPs and not to energy transfer from the NPs to the emitters as is usually reported. This is the first time that the effect is investigated for tellurite-tungstate-bismutate glasses and the enhancement observed is the largest reported for a tellurium oxide based glass. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4754468]

Femtosecond third-order nonlinear spectra of lead-germanium oxide glasses containing silver nanoparticles

This work reports on the spectral dependence of both nonlinear refraction and absorption in lead-germanium oxide glasses (PbO-GeO2) containing silver nanoparticles. We have found that this material is suitable for all-optical switching at telecom wavelengths but at the visible range it behaves either as a saturable absorber or as an optical limiter. (C) 2012 Optical Society of America

Synthesis of silver nanoparticles using DL-alanine for ESR dosimetry applications

The potential use of alanine for the production of nanoparticles is presented here for the first time. Silver nanoparticles were synthesized using a simple green method, namely the thermal treatment of silver nitrate aqueous solutions with in-alanine. The latter compound was employed both as a reducing and a capping agent. Particles with average size equal to 7.5 nm, face-centered cubic crystalline structure, narrow size distribution, and spherical shape were obtained. Interaction between the silver ions present on the surface of the nanoparticles and the amine group of the DL-alanine molecule seems to be responsible for reduction of the silver ions and for the stability of the colloid. The bio-hybrid nanocomposite was used as an ESR dosimeter. The amount of silver nanoparticles in the nanocomposite was not sufficient to cause considerable loss of tissue equivalency. Moreover, the samples containing nanoparticles presented increased sensitivity and reduced energetic dependence as compared with pure DL-alanine, contributing to the construction of small-sized dosimeters. (C) 2011 Elsevier Ltd. All rights reserved.

Post-receptor IGF1 insensitivity restricted to the MAPK pathway in a Silver-Russell syndrome patient with hypomethylation at the imprinting control region on chromosome 11

Background: Hypomethylation of the paternal imprinting center region 1 (ICR1) is the most frequent molecular cause of Silver-Russell syndrome (SRS). Clinical evidence suggests that patients with this epimutation have mild IGF1 insensitivity. Objective: To assess in vitro IGF1 action in fibroblast culture from a patient with SRS and IGF1 insensitivity. Methods: Fibroblast cultures from one patient with SRS due to ICR1 demethylation and controls were established. The SRS patient has severe growth failure, elevated IGF1 level, and poor growth rate during human recombinant GH treatment. IGF1 action was assessed by cell proliferation, AKT, and p42/44-MAPK phosphorylation. Gene expression was determined by real-time PCR. Results: Despite normal IGF1R sequence and expression, fibroblast proliferation induced by IGF1 was 50% lower in SRS fibroblasts in comparison with controls. IGF1 and insulin promoted a p42/44-MAPK activation in SRS fibroblasts 40 and 36%, respectively, lower than that in control fibroblasts. On the other hand, p42/44-MAPK activation induced by EGF stimulation was only slightly reduced (75% in SRS fibroblasts in comparison with control), suggesting a general impairment in MAPK pathway with a greater impairment of the stimulation induced by insulin and IGF1 than by EGF. A PCR array analysis disclosed a defect in MAPK pathway characterized by an increase in DUSP4 and MEF2C gene expressions in patient fibroblasts. Conclusion: A post-receptor IGF1 insensitivity was characterized in one patient with SRS and ICR1 hypomethylation. Although based on one unique severely affected patient, these results raise an intriguing mechanism to explain the postnatal growth impairment observed in SRS patients that needs confirmation in larger cohorts.

Functionalization of gold and silver nanoparticles with diphenyl dichalcogenides probed by surface enhanced Raman scattering

This paper describes a surface-enhanced Raman scattering (SERS) systematic investigation regarding the functionalization of gold (Au) and silver (Ag) nanoparticles with diphenyl dichalcogenides, i.e. diphenyl disulfide, diphenyl diselenide, and diphenyl ditelluride. Our results showed that, in all cases, functionalization took place with the cleavage of the chalcogenchalcogen bond on the surface of the metal. According to our density functional theory calculations, the molecules assumed a tilted orientation with respect to the metal surface for both Au and Ag, in which the angle of the phenyl ring relative to the metallic surface decreased as the mass of the chalcogen atom increased. The detected differences in the ordinary Raman and SERS spectra were assigned to the distinct stretching frequencies of the carbonchalcogen bond and its relative contribution to the ring vibrational modes. In addition, the SERS spectra showed that there was no significant interaction between the phenyl ring and the surface, in agreement with the tilted orientation observed from our density functional theory calculations. The results described herein indicate that diphenyl dichalcogenides can be successfully employed as starting materials for the functionalization of Au nanoparticles with organosulfur, organoselenium, and organotellurium compounds. On the other hand, diphenyl disulfide and diphenyl diselenide could be employed for the functionalization of Ag nanoparticles, while the partial oxidation of the organotellurium unit could be detected on the Ag surface. Copyright (C) 2011 John Wiley & Sons, Ltd.