New infrared emitting d-f (ruthenium(II)-neodymium(III)) heterobimetallic complexes with alkoxy(silyl) functional groups have been prepared. Visible excitation evidenced energy transfer processes from the ruthenium(II) donor to neodymium(III) acceptors leading to infrared emission. Energy transfer rates (kEnT) and efficiency of energy transfer (ηEnT) are, respectively, 0.61 × 107s-1 and 44% for RuL1-NdL3 complex. Larger values of kEnT (3.04 × 107 s-1) and ηEnT (84%) were detected for RuL2-NdL4 complex. RuL1-NdL3 and RuL2-NdL4 complexes were fully characterized by elementary analysis (EA), mass spectrometry (MS), Fourier transform infrared spectroscopy (FTIR) and Fourier transform Raman spectroscopy (FT-Raman). Total correlation spectroscopy (TOCSY1D), 1H{13C} heteronuclear single quantum correlation (HSQC) and 1H{13C} heteronuclear multiple bond correlation (HMBC) nuclear magnetic resonance (NMR) analyses were also carried out to characterize NdL3 and RuL1-NdL3 complexes. The presence of trialkoxysilyl-substituted ligands would allow further grafting onto any silica or silicated surface aiming at applications as new luminescent near infrared (NIR)-emitting biosensors or biomarkers.

A bioanalytical method for HIV detection based on surface-enhanced Raman scattering (SERS) is described. The assay targeted the peptide p17-1. This peptide sequence is present in the protein p17, a structural protein essential in the life cycle of the human immunodeficiency retrovirus (HIV). The antibody anti-p17 was immobilized in a planar gold surface using self-assembled techniques. This planar platform was used to capture the target analyte (p17-1 peptide). The peptide detection was carried out using specially designed SERS probes, consisting of gold nanoparticles coated with a Raman reporter molecule (Nile Blue A) and functionalized with anti-p17. This sandwich assay led to the successful detection of the peptide p17-1 at 40.8 ng/mL levels. The sandwich assay described here demonstrated that the SERS technique can rival more common fluorescence methods, such as ELISA, in the detection HIV-type virus.

This paper reports the synthesis and characterization of Cr3+-doped alumina by the sol-gel non-hydrolytic methodology. The resulting sample was treated at different temperatures. X-ray diffraction revealed that the ruby phase emerged in the sample treated at 1100 ºC, which was later confirmed by absorption bands correspondent to Cr3+ ions allowed transitions at 4A2 → 4T1, 4T2, and forbidden at 4A2 → 2T1, 2E, observed by diffuse reflectance UV-Vis. The luminescence spectroscopy showed the intensity band at 694 nm in red region, characterized of the Cr3+ ion. The peaks at 702 and 705 nm correspond to N1 and N2 lines, respectively, which arose from the second and fourth nearest-neighbor exchange-coupled pairs of chromium(III) ion, respectively, ascribed to high chromium(III) concentration. The Cr3+ cluster formation was observed in electron paramagnetic resonance signal as discussed in this work. Nuclear magnetic resonance evidenced that the 27 Al symmetry changed in the samples treated between 900 and 1100 ºC.

Immunosensors based on impedance spectroscopy for diagnosing hepatitis C are reported where the sensing units were made with the antigenic peptide PPLLESWKDPDYVPPWHG (NS5A-1) derived from the NS5A protein of the hepatitis C virus (HCV) immobilized in layer-by-layer (LbL) films with silk fibroin (SF) and deposited on gold interdigitated electrodes. The electrical response of the sensing units varied upon immersion into solutions containing the antibody anti-HCV owing to the biomolecular recognition of NS5A-1. This was associated with morphological changes on the LbL films caused by adsorption of NS5A-1 and inferred from atomic force microscopy images. Buffer solutions with different anti-HCV concentrations down to 2 ng mL-1 could be clearly distinguished by analyzing the impedance spectroscopy data with a multidimensional projection technique. The specificity toward anti-HCV antibodies was confirmed in control experiments where no significant changes in the electrical response were measured by exposing the sensing units to solutions containing an anti-human immunodeficiency virus (HIV) antibody. The high sensitivity and selectivity of the units made with LbL films demonstrate the feasibility of measuring electrical impedance as an immunosensing strategy to detect hepatitis C.

We report on the synthesis of single-crystalline tellurium nanowires with different aspect-ratios prepared via facile surfactant-assisted synthesis under mild conditions. Short and long Te nanowires were synthesized by the reduction of tellurium dioxide by hypophosphorous acid with the assistance of polyoxyethylene (23) laurylether and cetyltrimethylammonium bromide, respectively. We obtained uniform single-crystal Te nanowires with diameter below 30 nm and tunable length from 600 nm to 5 µm. Short and long Te nanowires showed remarkable nonlinear absorption and their third-order nonlinear optical properties were investigated by the Z-scan technique with single 80 ps laser pulses at 532 nm. For the first time, it was observed a distinguished switching behavior from saturated absorption to reverse saturated absorption as a function of the laser intensity in one-dimensional Te nanostructures. Although both short and long Te nanowires display such interesting behavior, the short ones exhibited superior optical limiting performance.

The development of drug delivery systems for photodynamic therapy (PDT) is increasingly demanded due to the hydrophobicity presented by most of photosensitizers molecules. Bacterial cellulose (BC), a highly pure cellulose produced by bacteria, possesses the essential features for applications in drug delivery systems, such as large surface area and excellent loading capacity. BC membranes prepared containing a photosensitizer, chloroaluminum phthalocyanine (ClAlPc), were tested aiming applications as a drug delivery system for PDT skin cancer protocols. BC membranes production was optimized regarding thickness and optical transmission. Thinner membranes lead to higher relative incorporation efficiencies. Skin permeation and retention in vitro tests were performed by using pig's ears as a skin model. ClAlPc was retained at stratum corneum and epidermis/dermis, showing adequate properties for topical administration of ClAlPc. Photophysical studies showed that singlet oxygen production was not affected for ClAlPc compartmentalized in the BC array. BC-ClAlPc membranes did not present cytotoxic effects in vitro.

In this second part it will be discussed some photonic applications of glassy and glass ceramic thin films which can be used as planar waveguides. Some photonic applications require certain specifications of glass, which can be quantified by studying the nonlinear optical properties of the materials. Therefore, a brief introduction of these phenomena is discussed, as well as the use of femtosecond lasers to manipulate the composition or for the preparation of waveguides into glasses. Finally, the article will address a brief introduction on microstructured optical fibers and commercial application prospects for these devices.

2015 is the Year of Light, according to UNESCO. Chemistry has a close relationship with light and one of the materials that allows such synergy is glass. Depending on the chemical composition of the glass, it is possible to achieve technological applications for the whole range of wavelengths extending from the region of the microwave to gamma rays. This diversity of applications opens a large range of research where chemistry, as a central science, overlaps the fields of physics, engineering, medicine, etc., generating a huge amount of knowledge and technological products used for humanity. This review article aimed at discussing some families of glasses, illustrating some applications. Due to the extension of the theme, and all points raised, we thought it would be good to divide the article into two parts. In the first part we focus on the properties of heavy metal oxide glasses, fluoride glasses and chalcogenide glasses. In the second part we emphasize the properties of glassy thin films prepared by sol-gel methodology and some applications, of both glasses as the films in photonics, and more attention was given to the nonlinear properties and uses of photonic fibers.

New luminescent organic-inorganic hybrid particles based on Tb-doped aluminates and asparagine (Asn) surface modifiers were investigated. The Tb3+ doped inorganic core was obtained by spray pyrolysis, at 200 ºC γ-AlOOH (BOE:Tbx%) or at 700 ºC γ-Al2O3 (γTA:Tbx%). The reaction of Asn with boehmite in water disaggregated the sub-micronic boehmite particles to give stable dispersion of surface modified nanoparticles Asn:BOE:Tbx% (x = 1 or 5). Concerning the Asn:γTA:Tbx% system, an Asn film wrapping alumina particles was observed. Photoluminescence spectra exhibited the bands assigned to Tb3+5D4 → 7FJ = 6-3 transitions. A broad absorption band (240 nm) was assigned to the host (aluminate) to ion (Tb3+) energy transfer. Efficient energy transfer was observed when active ions are incorporated in the defect-spinel structure of γTA, whereas it was relatively weak for BOE:Tb where Tb3+ are bonded to the hydroxyls groups at nanocrystals surface. It is noticeable that Asn strengthens the linkage of Tb3+ with the aluminate matrix, enhancing the host to dopant energy transfer.

The influence of silver nanoparticles (Ag-NPs) on the optical properties of Bi2O3-GeO2 glasses was investigated aiming the characterization of their potential for applications in photonic devices. The samples were prepared by the melt-quenching technique starting from high purity oxides (GeO2, Bi2O3 and AgNO3). Heat-treatment during different times was performed to nucleate Ag-NPs. A transmission electron microscope was used to confirm the presence of Ag-NPs and to determine their sizes and composition. The glass network was studied by spontaneous Raman scattering. The optical absorption spectra showed an absorption band at ca. 500 nm associated to the bismuth ions, and a 7-fold enhancement of absorption was observed in the samples with Ag-NPs. Photoluminescence (PL) spectra were obtained by exciting the samples with a 808 nm laser. Maximum enhancements of ca. 100% of the PL band centered at 1300 nm and ca. 70% of the Raman spectrum were observed due to the nucleation of the Ag-NPs. The enhanced optical response of the samples with Ag-NPs is attributed to the growth of the local field on the isolated bismuth ions and clusters that are located in the vicinity of the nanoparticles. The results illustrate the large potential of Bi2O3-GeO2 with Ag-NPs to be used in photonic devices.

Samples of (1 – x)SiO2:xGeO2 compositions, containing x = 10 and 20, and doped with Er3+, were prepared by a simple sol-gel route. Homogeneous and transparent gels were synthesized and xerogels were obtained by gel annealing from 700 ºC to 1100 ºC. Films exhibiting high transmittance in the visible and near infrared were deposited by spin-coating technique using the colloidal precursors. The materials were characterized structurally and microstructurally by some techniques. Spherical completely amorphous and tetragonal GeO2 nanocrystals from 3.7 nm to 25.0 nm in diameter embedded in silica-rich amorphous phase materials were obtained. The optical properties were studied by transmission spectra from ultraviolet to near infrared region, photoluminescence measurements in the infrared region, and the average lifetime of the metastable state 4I13/2 of Er3+ ions were determined. The 1 mol% Er3+ doped host with x = 20 have an infrared emission 4.9 times higher than the compound containing x = 10, and the Er3+4I13/2 level present lifetime between 15.0 ms and 7.5 ms. The optical band gap and refractive index values were determined, as well as the Sellmeier parameters. Finally, rib channel waveguides using femtosecond laser etching technique on silica substrates were obtained with width of 15 mm. The 1 mol% Er3+ doped 80SiO2:20GeO2 compounds can be applicable in integrated optical systems.

Energy conversion, involving UV and Vis absorption to generate near infrared (NIR) emission at 1000 nm from nanostructured Pr3+/Yb3+ co-doped SiO2-Nb2O5 for solar cell application was the main focus of this work. The synthesis, structural and optical characterization of Pr3+/Yb3+ co-doped 70SiO2-30Nb2O5 nanocomposites and planar waveguides prepared by the sol gel method are reported. The influence of the rare earth content and thermal annealing on the crystallization process and the luminescence properties was studied. The excitation spectra revealed the energy transfer between the Pr3+ and Yb3+, involving mainly the 3P2 level of Pr3+ ions. Multiphonon decay and cross relaxation processes take place at higher rare earth concentration and annealing temperature, which increases the 1D2 level population and consequently the NIR emission from the Pr3+ ions. The nanostructured Pr3+/Yb3+ co-doped SiO2-Nb2O5 nanocomposites and waveguides show interesting NIR emission and optical properties for photonic applications.

Bacterial cellulose produced from Gluconacetobacter xilinus was used to produce cellulose nanocrystals by sulfuric acid hydrolysis. Hydrolysis was performed with 64% sulfuric acid at 50 ºC with the hydrolysis time ranging between 5 and 90 min. The production of nanocrystals was observed to have size distributions that were dependent on hydrolysis times up to 10 min, after which time the suspensions showed distributions closer in size. Results from thermal analysis and X-ray diffraction showed that the amorphous cellulose was removed, leaving only the crystalline portion. Self-supported films were formed from the suspension of nanocrystals and had iridescence characteristics. The films were characterized by microscopy measures and specular reflectance.

In this work, methylcellulose (MC) was produced from bacterial cellulose (BC), using dimethyl sulfate in a 3 h (MC3h) or 5 h (MC5h) reaction under heterogeneous conditions, with reagent substitution at each hour. MC3h showed a degree of substitution (DS) of 2.26 ± 0.13 and MC5h showed a DS of 2.33 ± 0.05. The two samples were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray powder diffraction (XRD), differential thermal analysis (DTA), thermal gravimetric analysis (TGA), 13C nuclear magnetic ressonance (NMR) and 1H NMR techniques. The FTIR spectra of the BC and MC samples present significant differences in the regions from 3750 to 2750 cm−1 and from 1500 to 750 cm−1, which evidence the methylation of the samples. Solid state NMR spectroscopy of the MC samples was used to identify the 13C NMR signals of substitution at sites C-2, C-3 or C-6 in the glucopyranose units. The modification of bacterial cellulose produced a material with a high DS, determined by three different techniques (chemically and using the liquid 1H and solid 13C NMR spectra). These samples also demonstrate high crystallinity and thermal stability. With the MC samples synthesized in this work, transparent and resistant films were prepared and also a highly porous sponge like material.