Surface Passivation of Nanoporous TiO2 via Atomic Layer Deposition of ZrO2 for Solid-State Dye-Sensitized Solar Cell Applications

We report here the utilization of atomid layer deposition to passivate surface map states in mosoporous TiO2 nanoparticles for solid state dye sensitized solar cells based on 9,9'-spirobifluorene (spiro-OMeTAD). By depositing ZrO2 films with angstrom-level precision, coating the mesoporous TiO2 produces over a two-fold enhancement in short-circuit current density, as compared to a control device. Impedance spectroscopy measurements provide evidence that the ZrO2 coating reduces recombination lossed at the TiO2/spiro-OMeTAD interface and passivates localized surface states. Low-frequency negative capacitances, frequently observed in nanocomposite solar cells, have been associated with the surface-state mediated charge transfer from TiO2 to the spiro-OMeTAD.

Tunable plasmon resonance modes on gold nanoparticles in Er 3 +-doped germanium-tellurite glass

Relative to the Er3 +:gold-nanoparticle (Er3 +:Au-NP) axis, the polarization of the gold nanoparticle can be longitudinal (electric dipole parallel to the Er3 +:Au-NP axis) or transverse (electric dipole perpendicular to the Er3 +:Au-NP axis). For longitudinal polarization, the plasmon resonance modes of gold nanoparticles embedded in Er3 +-doped germanium-tellurite glass are activated using laser lines at 808 and 488 nm in resonance with radiative transitions of Er3 + ions. The gold nanoparticles were grown within the host glass by thermal annealing over various lengths of time, achieving diameters lower than 1.6 nm. The resonance wavelengths, determined theoretically and experimentally, are 770 and 800 nm. The absorption wavelength of nanoparticles was determined by using the Frohlich condition. Gold nanoparticles provide tunable emission resulting in a large enhancement for the 2H11/2 → 4I13/2 (emission at 805 nm) and 4S 3/2 → 4I13/2 (emission at 840 nm) electronic transitions of Er3 + ions; this is associated with the quantum yield of the energy transfer process. The excitation pathways, up-conversion and luminescence spectra of Er3 + ions are described through simplified energy level diagrams. We observed that up-conversion is favored by the excited-state absorption due to the presence of the gold nanoparticles coupled with the Er3 + ions within the glass matrix. © 2013 Elsevier B.V.

Preparação de vidros e vitrocerâmicas de óxidos de metais pesados contendo prata: propriedades ópticas, estruturais e eletroquímicas

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Identification of Rv3852 as a nucleoid-associated protein in Mycobacterium tuberculosis

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Y2O3:Eu3+ (5 mol%) with Ag nanoparticles prepared by citrate precursor

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Nanoscale manipulation of CdSe quantum dots in layer-by-layer films: influence of the host polyelectrolyte on the luminescent properties

Thioglycolic acid-capped Use quantum dots (QDs) were assembled on glass substrates with two distinct polyelectrolytes, viz poly(allylamine hydrochloride) (PAH) and poly(amidoamine) (PAMAM), generation 4 dendrimer, via the layer-by-layer (LbL) technique. Films containing up to 30 polyelectrolyte/QD bilayers were prepared. The growth of the multilayers was monitored with UV-vis spectroscopy, which showed an almost linear increase in the absorbance of the 2.8 nm QDs at 535 nm with the number of deposited bilayers. AFM measurements estimated a film thickness of 3 nm per bilayer for the PAH/Cdse films. The adsorption process and the optical properties of the PAMAM/CdSe LbL films were further analyzed layer-by-layer using surface plasmon resonance (SPR), from which a thickness of 3.2 nm was found for a PAMAM/CdSe bilayer. Photoluminescence measurements revealed higher photooxidation of the quantum dots in PAH/CdSe than in PAMAM/CdSe films. (c) 2004 Elsevier B.V. All rights reserved.

Catechol biosensing using a nanostructured layer-by-layer film containing Cl-catechol 1,2-dioxygenase

dThe detection of aromatic compounds from pesticides and industrial wastewater has become of great interest, since these compounds withstand chemical oxidation and biological degradation, accumulating in the environment. In this work, a highly sensitive biosensor for detecting catechol was obtained with the immobilization of Cl-catechol 1,2-dioxygenase (CCD) in nanostructured films. CCD layers were alternated with poly(amidoamine) generation 4 (PAMAM G4) dendrimer using the electrostatic layer-by-layer (LbL) technique. Circular dichroism (CD) measurements indicated that the immobilized CCD preserved the same conformation as in solution. The thickness of the very first CCD layers in the LbL films was estimated at ca. 3.6 nm, as revealed by surface plasmon resonance (SPR). PAMAM/CCD 10-bilayer films were employed in detecting diluted catechol solutions using either an optical or electrical approach. Due to the mild immobilization conditions employed, especially regarding the pH and ionic strength of the dipping solutions, CCD remained active in the films for periods longer than 3 weeks. The optical detection comprised absorption experiments in which the formation of cis-cis muconic acid, resulting from the reaction between CCD and catechol, was monitored by measuring the absorbance at 260 nm after film immersion in catechol solutions. The electrical detection was carried out using LbL films deposited onto gold-interdigitated electrodes immersed in aqueous solutions at different catechol concentrations. Using impedance spectroscopy in a broad frequency range (1Hz-1kHz), we could detect catechol in solutions at concentrations as low as 10(-10) M. (c) 2005 Elsevier B.V. All rights reserved.

Infrared-to-visible upconversion in Yb3+/Er3+ co-doped PbO-GeO2 glass with silver nanoparticles

Enhanced frequency upconversion (UC) emission was studied in Yb3+/Er3+ co-doped PbO-GeO2 glass containing silver nanoparticles (NPs). Optical excitation was achieved with a laser operating at 980 nm in resonance with the Yb3+ transition F-4(5/2)-> F-4(7/2). The intensity of the whole UC spectrum from 400 to 700 nm was intensified due to the influence of silver NPs. The green and red emissions were enhanced by more than 300%. Emission bands centered at 408 nm and 480 nm were also detected corresponding to the H-2(9/2)-> I-4(15/2) and F-4(7/2)-> I-4(15/2) transitions of Er3+ ion. An intensity enhancement of approximate to 150% due to the NPs was measured. For the first time the influence of silver NPs on the blue emission of Yb3+/Er3+ co-doped PbO-GeO2 glass is reported. The large enhancement in the whole UC spectrum is due to the increased local field in the Er3+ ions locations and the proximity between the luminescence wavelengths and the NPs surface plasmon resonance. (C) 2010 Elsevier B.V. All rights reserved.

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

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Sensitive Affimer and Antibody Based Impedimetric Label-Free Assays for C-Reactive Protein

C-reactive protein (CRP) is an acute phase protein whose levels are increased in many disorders. Levels greater than 3 mu g/mL serum have hitherto been considered to indicate pathology, but there is increasing interest in assessments between 0.1 and 10 mu g/mL, which have been found to correlate with severity of risk for cardiovascular disease. We report herein the generation of both antibody and Affimer based impedance immunoassays for CRP that are substantially more sensitive than clinically utilized immunonephelometry and immunoturbidity assessments. Significant in this study is not only the use of a constrained peptide to detect a clinically important target but also that derived electrochemical impedance assays can be highly sensitive even with probes whose relatively weak (mu M) affinities are not amenable to target detection by surface plasmon resonance (SPR). Key to this finding is acknowledging that receptive surfaces of comparatively low initial steric bulk and charge transfer resistance are especially primed to be highly responsive to target binding in electroanalytical assays of this type.

Luminescence of Tb(3+) doped TeO(2)-ZnO-Na(2)O-PbO glasses containing silver nanoparticles

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Variable structure control of switched systems based on Lyapunov-Metzler-SPR systems

This paper presents two Variable Structure Controllers (VSC) for continuous-time switched plants. It is assumed that the state vector is available for feedback. The proposed control system provides a switching rule and also the variable structure control input. The design is based on Lyapunov-Metzler (LM) inequalities and also on Strictly Positive Real (SPR) systems stability results. The definition of Lyapunov-Metzler-SPR (LMS) systems and its direct application in the design of VSC for switched systems are introduced in this paper. Two examples illustrate the design of the proposed VSC, considering a plant given by a switched system with a switched-state control law and two linear time-invariant systems, that are not controllable and also can not be stabilized with state feedback. ©2008 IEEE.

Plasmonic structures fabricated by interference lithography for sensor applications

In this work we demonstrate the use of holographic lithography for generation of large area plasmonic periodic structures. Submicrometric array of holes, with different periods and thickness, were recorded in gold films, in areas of about 1 cm2, with homogeneity similar to that of samples recorded by Focused Ion Beam. In order to check the plasmonic properties, we measured the transmission spectra of the samples. The spectra exhibit the typical surface plasmon resonances (SPR) in the infrared whose position and width present the expected behavior with the period of the array and film thickness. The shift of the peak position with the permittivity of the surrounding medium demonstrates the feasebility of the sample as large area sensors. © 2009 SPIE.

Tethered DNA scaffolds on optical sensor platforms for detection of hipO gene from Campylobacter jejuni

DNA biosensors have gained increased attention over traditional diagnostic methods due to their fast and responsive operation and cost-effective design. The specificity of DNA biosensors relies on single-stranded oligonucleotide probes immobilized to a transduction platform. Here, we report the development of biosensors to detect the hippuricase gene (hipO) from Campylobacter jejuni using direct covalent coupling of thiol- and biotin-labeled single-stranded DNA (ssDNA) on both surface plasmon resonance (SPR) and diffraction optics technology (DOT, dotLab) transduction platforms. This is the first known report of the dotLab to detect targeted DNA. Application of 6-mercapto-1-hexanol as a spacer thiol for SPR gold surface created a self-assembled monolayer that removed unbound ssDNA and minimized non-specific detection. The detection limit of SPR sensors was shown to be 2.5 nM DNA while dotLab sensors demonstrated a slightly decreased detection limit of 5.0 nM (0.005 μM). It was possible to reuse the SPR sensor due to the negligible changes in sensor sensitivity (∼9.7 × 10 -7 ΔRU) and minimal damage to immobilized probes following use, whereas dotLab sensors could not be reused. Results indicated feasibility of optical biosensors for rapid and sensitive detection of the hipO gene of Campylobacter jejuni using specific ssDNA as a probe. © 2011 Elsevier B.V.

Nonlinear Optical Properties of Tungsten Lead-Pyrophosphate Glasses Containing Metallic Copper Nanoparticles

We have prepared heavy metal oxide glasses containing metallic copper nanoparticles with promising nonlinear optical properties which were determined by Z-scan and pump-probe measurements using femtosecond laser pulses. For the wavelengths within the plasmon band, we have observed saturable absorption and response times of 2.3 ps. For the other regions of the spectrum, reverse saturable absorption and lifetimes shorter than 200 fs were verified. The nonlinear refractive index is about 2.0 × 10-19 m2/W from visible to telecom region, thus presenting an enhancement effect at wavelengths near the plasmon and Cu+2 d-d band. © 2013 Springer Science+Business Media New York.