Marcos J. L. Santos

Attomolar Protein Detection Using in-Hole Surface Plasmon Resonance

An in-hole nanohole surface plasmon resonance sensing scheme is demonstrated. Arrays of periodic nanoholes milled through thin layers of SiO(x) and gold were used to detect the binding of organic and biological molecules inside the nanoholes, while blocking the gold surfaces outside the holes. This new approach is more efficient than the previous nanohole array method, where the response was related to binding events taking place inside of the holes and on the top gold surface. The improved sensitivity to binding events and lower detection limit are related to resonant surface plasmon enhanced transmission through the arrays of nanoholes. The sensitivity was found to be 650 nm/RIU and the detection of three attomoles of proteins was estimated from this scheme.

TiO2 and TiO2/SiO2 nanoparticles obtained by sol–gel method and applied on dye sensitized solar cells

AbstractnIn this work we show the synthesis and characterization of TiO2 and TiO2/SiO2 nanoparticles synthesized by sol–gel method using HF and HCl as catalysts. The obtained nanoparticles were analyzed by N2 adsorption–desorption isotherms, transmission electronic microscopy, Ultraviolet–visible spectroscopy and X-ray diffractometry. Mesoporous, homogeneously polycondensed TiO2/SiO2 materials, containing nanocrystalline anatase phase with band gap similar to pure titania were obtained. Films of the powdered oxides were applied to assemble dye sensitized solar cells that presented electrical parameters, Fill Factor and efficiencies similar to devices obtained by only TiO2. The sol–gel route arises as an alternative way to prepare TiO2/SiO2 materials for solar cells.n

Polymorphic phase study on nitrogen-doped TiO2 nanoparticles: effect on oxygen site occupancy, dye sensitized solar cells efficiency and hydrogen production

In this work we show that phase formation and oxygen substitution can be controlled by the source of nitrogen used during the synthesis of TiO2 nanoparticles. By performing a thorough study on the structure of the nanoparticles, the use of NH4+ or NO3− was found to influence not only the N-doping level but also the formation of the polymorphic phase. Structural and microstructural refinement obtained by XRD pattern and data processing performed by the Rietveld refinement revealed that TiO2 obtained with HNO3 presents ca. 98% of anatase and ca. 2% for rutile. Meanwhile TiO2 nanoparticles synthesized with NH4F and NH4Cl presents a single anatase phase with ca. 7.0% and 4.4% of nitrogen substitutional oxygen sites, respectively. The local structure of N-doped TiO2 around the Ti atoms was investigated by X-ray absorption spectroscopy. The XANES spectra show that N-doped TiO2 possesses a characteristic pre-edge of a single anatase structure. The coordination number decreased and the shrinking Ti–O bond distances are due to the N-doping in the TiO2 structure. The most efficient dye sensitized solar cell and the higher hydrogen production was obtained from the TiO2/NH4Cl, which was obtained as a single anatase phase with intermediary concentration of N substitutional oxygen sites.

Surface Plasmon-Induced Band Gap in the Photocurrent Response of Organic Solar Cells

A 260 nm layer of organic bulk heterojunction blend of the polymer poly(3-hexylthiophene) (P3HT) and the fullerene [6,6]-phenyl C61-butyric (PCBM) was spin-coated in between aluminum and gold electrodes, respectively, on top of a laser inscribed azo polymer surface-relief diffraction grating. Angle-dependent surface plasmons (SPs) with a large band gap were observed in the normalized photocurrent by the P3HT-PCBM layer as a function of wavelength. The SP-induced photocurrents were also investigated as a function of the grating depth and spacing.

Development of plasmonic substrates for biosensing

The transmission of normally incident light through arrays of subwavelength holes (nanoholes) in gold thin films is enhanced at the wavelengths that satisfy the surface plasmon resonance (SPR) condition. Our group has been active on the implementation of schemes for the application of this phenomenon for chemical sensing. For instance, we have shown that the interaction between adsorbates with nanoholes modified the SP resonance conditions, leading to a shift in the wavelength of maximum transmission. The output sensitivity of this substrate was found to be 400 nm RIU-1 (refractive index units), which is comparable to other grating-based surface plasmon resonance devices. The array of nanoholes was also integrated into a microfluidic system and the characteristics of the solution flow and detection systems were evaluated. In this work, we will concentrate on improving the efficiency of the nanohole arrays for applications in chemical in chemical sensing. Attempts to improve the sensitivity of the device will be discussed. In-hole sensing is suggested as an alternative to decrease the number of probe molecules, and enhance sensitivity. A biaxial sensing scheme will also be introduced. The biaxial scheme allows for polarization-modulation detection that can account for background fluctuations. A flow-through approach should lead to an optimized transport situation of the analytes to the immobilized species at the surface, which should significantly improve the time and sensitivity of the analysis. Finally, we will discuss the implementation of multiplexing detection using these arrays. Multiplexing detection in zero-order transmission is simpler to implement than the common multiplexing imaging from angle-resolved SPR.

Probing the functionalization of gold surfaces and protein adsorption by PM-IRRAS.

The control of morphology and coating of metal surfaces is essential for a number of organic electronic devices including photovoltaic cells and sensors. In this study, we monitor the functionalization of gold surfaces with 11-mercaptoundecanoic acid (MUA, HS(CH(2) )(10) CO(2) H) and cysteamine, aiming at passivating the surfaces for application in surface plasmon resonance (SPR) biosensors. Using polarization-modulated infrared reflection-absorption spectroscopy (PM-IRRAS), cyclic voltammetry, atomic force microscopy and quartz crystal microbalance, we observed a time-dependent organization process of the adsorbed MUA monolayer with alkyl chains perpendicular to the gold surface. Such optimized condition for surface passivation was obtained with a systematic search for experimental parameters leading to the lowest electrochemical signal of the functionalized gold electrode. The ability to build supramolecular architectures was also confirmed by detecting with PM-IRRAS the adsorption of streptavidin on the MUA-functionalized gold. As the approaches used for surface functionalization and its verification with PM-IRRAS are generic, one may now envisage monitoring the fabrication of tailored electrodes for a variety of applications.

Controlled thermal nitridation resulting in improved structural and photoelectrochemical properties from Ta3N5 nanotubular photoanodes

Ta3N5 nanotubular photoanodes were synthesized by thermal nitridation of anodized Ta2O5 nanotubes (NTs) in a temperature range from 650 °C to 1000 °C. XRD diffractograms and Rietveld refinements show that the crystalline structure is strongly dependent on thermal nitridation that triggers defects in the orthorhombic structure of Ta3N5 NTs. A non-stoichiometric TaN0.1 phase was observed at the bottom of the Ta3N5 NTs at the Ta–Ta3N5 interface. Electrochemical impedance spectroscopy revealed that nitridation conditions such as temperature and time strongly influence the interfacial charge transportation; affecting the photoelectrochemical (PEC) activities of the photoanodes. Improved PEC performance was obtained from the NTs synthesized at higher temperature for shorter nitridation time. This result is related to the preservation of the tubular morphology obtained at short nitridation time, high crystallinity and lower charge transfer resistance across the semiconductor–electrolyte interface.

Structural stability of photodegradable poly(l-lactic acid)/PE/TiO2 nanocomposites through TiO2 nanospheres and TiO2 nanotubes incorporation

Photodegradation of PLA/PE, PLA/PE/TiO2 nanospheres and PLA/PE/TiO2 nanotubes was obtained under simulated sunlight. The nanocomposites were analyzed by infrared spectroscopy, scanning electron microscopy and tensile-deformation measurements. TiO2 nanospheres and TiO2 nanotubes were found to present different effects on the crystallinity of PLA and a straight correlation between structural organization and photostability was observed. According to the results, TiO2 promotes the degradation of PLA and PE, affecting the organizational level of the polymers. By adding TiO2 nanoparticles to the PLA/PE films, vibration modes characteristic of degradation products were promptly observed and the lifetime of the polymer decreased when compared to the PLA/PE without TiO2 nanoparticles. Mechanical measurements showed an improvement of the mechanical properties when adding the TiO2 nanoparticles.

Pristine Ta3N5 Nanotubes: Trap-Driven High External Biasing Perspective in Semiconductor/Electrolyte Interfaces

Ta3 N5 is a promising photoelectrode for solar hydrogen production; however, to date pristine Ta3 N5 electrodes without loading co-catalysts have presented limited photoelectrochemical (PEC) performance. In particular, large external biasing has been required to run water oxidation, the origin of which is investigated herein. Ta3 N5 nanotubes (NTs) prepared by nitridation were characterized by a wide range of techniques. The bandgap was confirmed by a novel PEC technique. Nondestructive synchrotron-excited XPS has shown the presence of reduced Ta species deeper in the Ta3 N5 surface. Lower photocurrent and transient spikes that were intense at lower applied biasing were observed under water oxidation; however, spikes were inhibited in the presence of a sacrificial agent and photocurrent was improved even at low biasing. It was observed for the first time that the lower PEC performance under water oxidation can be attributed to the presence of interband trapping states associated with pristine Ta3 N5 NTs/electrolyte junction. These states correspond to the structural defects in Ta3 N5 , devastate PEC performance, and present the necessity to apply higher biasing. The key to circumvent them is to use a sacrificial agent in the electrolyte or to load a suitable co-catalyst to avoid hole accumulation under water oxidation, thereby improving the phootocurrent. The findings on the interband states could also provide guidance for the investigation of PEC properties of new types of semiconducting devices.

Quinolines by Three-Component Reaction: Synthesis and Photophysical Studies

The synthesis of five quinolines 8-octyloxy-4-[4-(octyloxy)phenyl]quinoline and 6-alkoxy- 2-(4-alkoxyphenyl)-4-[(4-octyloxy)aryl]quinolines are described by three-component coupling reaction mediated by Lewis acid FeCl3 and Yb(OTf)3. 4-n-octyloxybenzaldehyde, anisaldehyde, 4-n-octyloxyaniline p-anisidine, and 1-ethynyl-4-heptyloxybenzene, 1-ethynyl-4-octyloxybenzene and 2-ethynyl-6-heptyloxynaphthalene are the reagents in this protocol. A Yb3+ catalyst resulted in higher yields of quinolines than Fe3+. Polarizing optical microscopy (POM) revealed that none of the quinolines were liquid crystals, even the more anisotropic. UV-Vis measurements of one of the quinolines in polar solvent show two absorption bands at 280 and 350 nm related to π,π* and n,π* transitions. No changes were observed to lower-energy absorption band (e < 104 mol L-1 cm-1) related to n,π* transition. A laser flash photolysis study for one of the quinolines relates a main transient band at 450 nm with a lifetime of 2.6 µs in ethanol, which is completely quenched in the presence of oxygen. This transient band was assigned to triplet-triplet absorption of one of the quinolines, which is semi-oxidised in the presence of phenol. Radiative rate constants have been determined along singlet and triplet excited state energies (3.39 and 3.10 eV, respectively). The chemical structure of one of the quinolines was also unequivocally confirmed by single-crystal X-ray analysis.