Rômulo A. Ando

A facile approach to TiO2 colloidal spheres decorated with Au nanoparticles displaying well-defined sizes and uniform dispersion.

This paper describes a straightforward approach for the synthesis of hybrid materials composed of titanium dioxide (TiO(2)) colloidal spheres decorated with gold nanoparticles (Au NPs). In the reported method, monodisperse TiO(2) colloidal spheres (∼220 nm in diameter) could be directly employed as templates for the nucleation and growth of Au NPs over their surface using AuCl(4)(-)(aq) as the Au precursor, ascorbic acid as the reducing agent, PVP as the stabilizer, and water as the solvent. The Au NPs presented a uniform distribution over the TiO(2) surface. Interestingly, the size of the Au NPs could be controlled by performing sequential reduction steps with AuCl(4)(-)(aq). This method could also be adapted for the production of TiO(2) colloidal spheres decorated with other metal NPs including silver (Ag), palladium (Pd), and platinum (Pt). The catalytic activities of the TiO(2)-Au materials as a function of composition and NPs size were investigated toward the reduction of 4-nitrophenol to 4-aminophenol under ambient conditions. An increase of up to 10.3-fold was observed for TiO(2)-Au relative to TiO(2). A surface-enhanced Raman scattering application for TiO(2)-Au was also demonstrated employing 4-mercaptopyridine as the probe molecule. The results presented herein indicate that our approach may serve as a platform for the synthesis of hybrid materials containing TiO(2) and metal NPs displaying well-defined morphologies, compositions, and sizes. This can have important implications for the design of TiO(2)-based materials with improved performances for photocatalysis and photovoltaic applications.

L-Diphenylalanine Microtubes As a Potential Drug-Delivery System: Characterization, Release Kinetics, and Cytotoxicity

Microtubes obtained from the self-assembly of L-diphenylalanine (FF-MTs) were evaluated as potential vehicles for drug delivery. The biological marker Rhodamine B (RhB) was chosen as a model drug and conjugated to the peptide arrays during self-organization in the liquid phase. Microscopy and X-ray studies were performed to provide morphological and structural information. The data revealed that the cargo was distributed either in small aggregates at the hydrophobic surface of the FF-MTs or homogeneously embedded in the structure, presumably anchored at polar sites in the matrix. Raman spectroscopy revealed notable shifts of the characteristic RhB resonance peaks, demonstrating the successful conjugation of the fluorophore and peptide assemblies. In vitro assays were conducted in erythrocytes and fibroblast cells. Interestingly, FF-MTs were found to modulate the release of the load. The release of RhB from the FF-MTs followed first-order kinetics with a steady-state profile, demonstrating the potential of these carriers to deliver drugs at constant rates in the body. Cytotoxicity investigations revealed high cell viability up to concentrations of 5 mg mL(-1), demonstrating the low toxicity of the FF-MTs.

Controlling the Selectivity of the Surface Plasmon Resonance Mediated Oxidation of p-Aminothiophenol on Au Nanoparticles by Charge Transfer from UV-excited TiO2†

Although catalytic processes mediated by surface plasmon resonance (SPR) excitation have emerged as a new frontier in catalysis, the selectivity of these processes remains poorly understood. Here, the selectivity of the SPR-mediated oxidation of p-aminothiophenol (PATP) employing Au NPs as catalysts was controlled by the choice of catalysts (Au or TiO2-Au NPs) and by the modulation of the charge transfer from UV-excited TiO2 to Au. When Au NPs were employed as catalyst, the SPR-mediated oxidation of PATP yielded p,p-dimercaptobenzene (DMAB). When TiO2-Au NPs were employed as catalysts under both UV illumination and SPR excitation, p-nitrophenol (PNTP) was formed from PATP in a single step. Interestingly, PNTP molecules were further reduced to DMAB after the UV illumination was removed. Our data show that control over charge-transfer processes may play an important role to tune activity, product formation, and selectivity in SPR-mediated catalytic processes.

High performance gold nanorods and silver nanocubes in surface-enhanced Raman spectroscopy of pesticides.

The behavior of Au nanorods and Ag nanocubes as analytical sensors was evaluated for three different classes of herbicides. The use of such anisotropic nanoparticles in surface-enhanced Raman scattering (SERS) experiments allows the one to obtain the spectrum of crystal violet dye in the single molecule regime, as well as the pesticides dichlorophenoxyacetic acid (2,4-D), trichlorfon and ametryn. Such metallic substrates show high SERS performance at low analyte concentrations making them adequate for use as analytical sensors. Density functional theory (DFT) calculations of the geometries and vibrational wavenumbers of the adsorbates in the presence of silver or gold atoms were used to elucidate the nature of adsorbate-nanostructure bonding in each case and support the enhancement patterns observed in each SERS spectrum.

Azo−Hydrazone Tautomerism in Protonated Aminoazobenzenes: Resonance Raman Spectroscopy and Quantum-Chemical Calculations

The protonation effect on the vibrational and electronic spectra of 4-aminoazobenzene and 4-(dimethylamino)azobenzene was investigated by resonance Raman spectroscopy, and the results were discussed on the basis of quantum-chemical calculations. Although this class of molecular systems has been investigated in the past concerning the azo-hydrazone tautomerism, the present work is the first to use CASSCF/CASPT2 calculations to unveil the structure of both tautomers as well the nature of the molecular orbitals involved in chromophoric moieties responsible for the resonance Raman enhancement patterns. More specifically both the resonance Raman and theoretical results show clearly that in the neutral species, the charge transfer transition involves mainly the azo moiety, whereas in the protonated forms there is a great difference, depending on the tautomer. In fact, for the azo tautomer the transition is similar to that observed in the corresponding neutral species, whereas in the hydrazone tautomer such a transition is much more delocalized due to the contribution of the quinoid structure. The characterization of protonated species and the understanding of the tautomerization mechanism are crucial for controlling molecular properties depending on the polarity and pH of the medium.

Intracellular biosynthesis and removal of copper nanoparticles by dead biomass of yeast isolated from the wastewater of a mine in the Brazilian Amazonia.

In this study was developed a natural process using a biological system for the biosynthesis of nanoparticles (NPs) and possible removal of copper from wastewater by dead biomass of the yeast Rhodotorula mucilaginosa. Dead and live biomass of Rhodotorula mucilaginosa was used to analyze the equilibrium and kinetics of copper biosorption by the yeast in function of the initial metal concentration, contact time, pH, temperature, agitation and inoculum volume. Dead biomass exhibited the highest biosorption capacity of copper, 26.2 mg g−1, which was achieved within 60 min of contact, at pH 5.0, temperature of 30°C, and agitation speed of 150 rpm. The equilibrium data were best described by the Langmuir isotherm and Kinetic analysis indicated a pseudo-second-order model. The average size, morphology and location of NPs biosynthesized by the yeast were determined by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and transmission electron microscopy (TEM). The shape of the intracellularly synthesized NPs was mainly spherical, with an average size of 10.5 nm. The X-ray photoelectron spectroscopy (XPS) analysis of the copper NPs confirmed the formation of metallic copper. The dead biomass of Rhodotorula mucilaginosa may be considered an efficiently bioprocess, being fast and low-cost to production of copper nanoparticles and also a probably nano-adsorbent of this metal ion in wastewater in bioremediation process.

Spectroscopic, structural, and functional characterization of the alternative low-spin state of horse heart cytochrome C.

The alternative low-spin states of Fe(3+) and Fe(2+) cytochrome c induced by SDS or AOT/hexane reverse micelles exhibited the heme group in a less rhombic symmetry and were characterized by electron paramagnetic resonance, UV-visible, CD, magnetic CD, fluorescence, and Raman resonance. Consistent with the replacement of Met(80) by another strong field ligand at the sixth heme iron coordination position, Fe(3+) ALSScytc exhibited 1-nm Soret band blue shift and epsilon enhancement accompanied by disappearance of the 695-nm charge transfer band. The Raman resonance, CD, and magnetic CD spectra of Fe(3+) and Fe(2+) ALSScytc exhibited significant changes suggestive of alterations in the heme iron microenvironment and conformation and should not be assigned to unfold because the Trp(59) fluorescence remained quenched by the neighboring heme group. ALSScytc was obtained with His(33) and His(26) carboxyethoxylated horse cytochrome c and with tuna cytochrome c (His(33) replaced by Asn) pointing out Lys(79) as the probable heme iron ligand. Fe(3+) ALSScytc retained the capacity to cleave tert-butylhydroperoxide and to be reduced by dithiothreitol and diphenylacetaldehyde but not by ascorbate. Compatible with a more open heme crevice, ALSScytc exhibited a redox potential approximately 200 mV lower than the wild-type protein (+220 mV) and was more susceptible to the attack of free radicals.

Biosynthesis and uptake of copper nanoparticles by dead biomass of Hypocrea lixii isolated from the metal mine in the Brazilian Amazon Region.

A biological system for the biosynthesis of nanoparticles (NPs) and uptake of copper from wastewater, using dead biomass of Hypocrea lixii was analyzed and described for the first time. The equilibrium and kinetics investigation of the biosorption of copper onto dead, dried and live biomass of fungus were performed as a function of initial metal concentration, pH, temperature, agitation and inoculum volume. The high biosorption capacity was observed for dead biomass, completed within 60 min of contact, at pH 5.0, temperature of 40°C and agitation speed of 150 rpm with a maximum copper biosorption of 19.0 mg g−1. The equilibrium data were better described using the Langmuir isotherm and kinetic analysis indicated that copper biosorption follows a pseudo-second-order model. The average size, morphology and location of NPs biosynthesized by the fungus were determined by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and transmission electron microscopy (TEM). NPs were mainly spherical, with an average size of 24.5 nm, and were synthesized extracellularly. The X-ray diffraction (XRD) analysis confirms the presence of metallic copper particles. Infrared spectroscopy (FTIR) study revealed that the amide groups interact with the particles, which was accountable for the stability of NPs. This method further confirmed the presence of proteins as stabilizing and capping agents surrounding the copper NPs. These studies demonstrate that dead biomass of Hypocrea lixii provides an economic and technically feasible option for bioremediation of wastewater and is a potential candidate for industrial-scale production of copper NPs.

Plasmonic Nanorattles as Next-Generation Catalysts for Surface Plasmon Resonance-Mediated Oxidations Promoted by Activated Oxygen

Nanorattles, comprised of a nanosphere inside a nanoshell, were employed as the next generation of plasmonic catalysts for oxidations promoted by activated O2 . After investigating how the presence of a nanosphere inside a nanoshell affected the electric-field enhancements in the nanorattle relative to a nanoshell and a nanosphere, the SPR-mediated oxidation of p-aminothiophenol (PATP) functionalized at their surface was investigated to benchmark how these different electric-field intensities affected the performances of Au@AgAu nanorattles, AgAu nanoshells and Au nanoparticles having similar sizes. The high performance of the nanorattles enabled the visible-light driven synthesis of azobenzene from aniline under ambient conditions. As the nanorattles allow the formation of electromagnetic hot spots without relying on the uncontrolled aggregation of nanostructures, it enables their application as catalysts in liquid phase under mild conditions using visible light as the main energy input.

Raman, IR, UV–vis and EPR characterization of two copper dioxolene complexes derived from L-dopa and dopamine

The anionic complexes [Cu(L(1-))3](1-), L(-)=dopasemiquinone or L-dopasemiquinone, were prepared and characterized. The complexes are stable in aqueous solution showing intense absorption bands at ca. 605 nm for Cu(II)-L-dopasemiquinone and at ca. 595 nm for Cu(II)-dopasemiquinone in the UV-vis spectra, that can be assigned to intraligand transitions. Noradrenaline and adrenaline, under the same reaction conditions, did not yield Cu-complexes, despite the bands in the UV region showing that noradrenaline and adrenaline were oxidized during the process. The complexes display a resonance Raman effect, and the most enhanced bands involve ring modes and particularly the nuCC+nuCO stretching mode at ca. 1384 cm(-1). The free radical nature of the ligands and the oxidation state of the Cu(II) were confirmed by the EPR spectra that display absorptions assigned to organic radicals with g=2.0005 and g=2.0923, and for Cu(II) with g=2.008 and g=2.0897 for L-dopasemiquinone and dopasemiquinone, respectively. The possibility that dopamine and L-dopa can form stable and aqueous-soluble copper complexes at neutral pH, whereas noradrenaline and adrenaline cannot, may be important in understanding how Cu(II)-dopamine crosses the cellular membrane as proposed in the literature to explain the role of copper in Wilson disease.