Visible and near-infrared luminescent Eu(3+) or Er(3+) doped laponite-derived xerogels and thick films: Structural and spectroscopic properties

Laponite-derived materials represent promising materials for optical applications. In this work, Eu(3+)- or Er(3+)-doped laponite xerogels and films were prepared from colloidal dispersion. Homogeneous, crack-free and transparent single layers were deposited on soda-lime substrates with a thickness of 10 mu m. Structural and spectroscopic properties were analyzed by thermal analyses, X-ray diffractometry, transmission electron microscopy, infrared spectroscopy, and luminescence spectroscopy. The addition of a rare earth ion to the laponite does not promote any changes in thermal stability or phase transition. Laponite clay was identified after annealing up to 500 degrees C, with a decrease in basal spacing when the annealing temperature is changed from 100 degrees C to 500 degrees C. Enstatite polymorphs and amorphous silicate phases were observed after heat treatment at 700 degrees C and 900 degrees C. Stationary and time-dependent luminescence spectra in the visible region for Eu(3+), and (5)D(0) lifetime are discussed in terms of thermal treatment and structural evolution. In the layered host, the Eu(3+) ions are distributed in many different local environments. However, Eu(3+) ions were found to occupy at least two symmetry sites, and the ions are preferentially incorporated into the crystalline enstatite for the materials annealed at 700 degrees C and 900 degrees C. A (5)D(0) lifetime of 1.3 ms and 3.1 ms was obtained for Eu(3+) ions in an amorphous silicate and crystalline MgSiO(3) local environment, respectively. Strong Er(3+) emission at the 1550 nm region was observed for the materials annealed at 900 degrees C, with a bandwidth of 44 nm. (C) 2008 Elsevier B.V. All rights reserved.

Photophysical and Complexation Studies of Chloro-Aluminum Phthalocyanine with Beta-Cyclodextrin and Hydroxypropyl-Beta-Cyclodextrin

A variety of nanostructures are being investigated as functional drug carriers for treatment of a wide range of diseases, most notably cardiovascular defects, autoimmune diseases, and cancer. The aim of this present contribution is to evaluate potentially applicable nanomaterials in the diagnosis and treatment of cancer due to their photophysical and photobiological properties and complexation behavior. The delivery systems consisted of chloro-aluminum phthalocyanine associated with beta-cyclodextrin and hydroxypropyl-beta-cyclodextrin. The preparation of the complex and its stoichiometry in an ethanol/buffer (3:1) solution were studied by spectroscopic techniques, which were defined as 1:2. The inclusion complex in the nanometer scale was observed on the basis of changes to the spectroscopic properties. The singlet oxygen production and complex photophysical parameters were determined by measuring luminescence at 1270 nm and by steady state and time resolved spectroscopic, respectively. The preparation of the complex was tested and analyzed with regard to cellular damage by visible light activation. The inclusion complex showed a higher singlet oxygen quantum yield compared with other systems and other photoactive dyes. There was also a reduction in the fluorescence quantum yield compared with the results obtained for zinc phthalocyanine in organic medium. The results reported clearly that the inclusion complex chloro-aluminum phthalocyanine/cyclodextrin showed some changes in its spectroscopy properties leading to better biodistribution and biocompatibility with a potential application in photodynamic therapy, especially in the case of neoplasy. Additionally, it also has non-oncological applications as a drug delivery system.

Evaluation of the Binding Properties of Maghemite Nanoparticle Surface-Coated with Meso-2-3-Dimercaptosuccinic Acid to Serum Albumin

In this study the interaction between magnetic nanoparticles (MNPs) surface-coated with meso-2,3-dimercaptosuccinic acid (DMSA) with both bovine serum albumin (BSA) and human serum albumin (HSA) was investigated. The binding of the MNP-DMSA was probed by the fluorescence quenching of the BSA and HSA tryptophan residue. Magnetic resonance and light microscopy analyses were carried out in in vivo tests using female Swiss mice. The binding constants (K(b)) and the complex stoichiometries (n) indicate that MNP-DMSA/BSA and MNP-DMSA/HSA complexes have low association profiles. After five minutes following intravenous injection of MNP-DMSA into mice`s blood stream we found the lung firstly target by the MNP-DMSA, followed by the liver in a latter stage. This finding suggests that the nanoparticle`s DMSA-coating process probably hides the thiol group, through which albumin usually binds. This indicates that biocompatible MNP-DMSA is a very promising material system to be used as a drug delivery system (DDS), primarily for lung cancer treatment.

Modification-related porosity formation in hypoeutectic aluminum-silicon alloys

A series of aluminum-10 wt pet silicon castings were produced in sand molds to investigate the effect of modification on porosity formation. Modification with individual additions of either strontium or sodium resulted in a statistically significant increase in the level of porosity compared to unmodified castings. The increase in porosity with modification is due to the presence of numerous dispersed pores, which were absent in the unmodified casting. It is proposed that these pores form as a result of differences in size of the aluminum-silicon eutectic grains between unmodified and modified alloys. A geometric model is developed to show how the size of eutectic grains can influence the amount and distribution of porosity. Unlike traditional feeding-based models, which incorporate the effect: of microstructure on permeability, this model considers what happens when liquid is isolated from the riser and can no longer flow. This simple isolation model complements rather than contradicts existing theories on modification-related porosity formation and should be considered in the development of future comprehensive models.

Photophysical and photobiological studies of a silicon tribenzonaphthoporphyrazinato incorporated into liposomes for photodynamic therapy use

Nanostructured drug delivery systems (NDDS), such as liposomes, represent a growing area in biomedical research. These microheterogeneous media can be used in many biological systems to provide appropriate drug levels with a specific biodistribution. The photophysical properties of a silicon derivative of tribenzonaphthoporphyrazinato (Si-tri-PcNc) incorporated into liposome were studied by steady-state techniques, time-resolved fluorescence and laser flash photolysis. All the spectroscopy measurements performed allowed us to conclude that Si-tri-PcNc in liposome is a promising NDDS for PDT The in vitro experiments with liposomal NDDS showed that the system is not cytotoxic in darkness, but exhibits a substantial phototoxicity at 1 mu M of photosensitizer concentration and 10.0 J/cm(2) of light. These conditions are sufficient to kill about 80% of the cells.

Dynamic susceptibility investigation of maghemite nanoparticles incorporated in bovine serum albumin template

Room-temperature measurements of the magnetic susceptibility of Bovine Serum Albumin-based nanocapsules (50 to 300 nm in size) loaded with different amounts of maghemite nanoparticles (7.6 nm average diameter) have been carried out in this study The field (H) dependence of the imaginary peak susceptibility (f(P)) of the nanocomposite samples was investigated in the range of 0 to 4 kOe. From the analysis of the f(P) x H curves the concentration (N) dependence of the effective maghemite magnetocrystalline energy barrier (E) was obtained. Analysis of the E x N data was performed using a modified Morup-Tronc [Phys. Rev. Lett. 72, 3278 (1994)] model, from which a huge contribution from the magnetocrystalline surface anisotropy was observed.

Erbium-activated silica-zirconia planar waveguides prepared by sol-gel route

Er(3+) doped (100-x)SiO(2)-xZrO(2) planar waveguides were prepared by the sol-gel route, with x ranging from 10 up to 30 mol%. Multilayer films doped with 0.3 mol% Er(3+) ions were deposited on fused quartz substrates by the dip-coating technique. The thickness and refractive index were measured by m-line spectroscopy at different wavelengths. The fabrication protocol was optimized in order to confine one propagating mode at 1.5 mu m. Photoluminescence in the near and visible region indicated a crystalline local environment for the Er(3+) ion. (c) 2007 Elsevier B.V. All rights reserved.

Surface modification of metals by calcium carbonate thin films on a layer-by-layer polyelectrolyte matrix

A multilayer organic film containing poly(acrylic acid) and chitosan was fabricated on a metallic support by means of the layer-by-layer technique. This film was used as a template for calcium carbonate crystallization and presents two possible binding sites where the nucleation may be initiated, either calcium ions acting as counterions of the polyelectrolyte or those trapped in the template gel network formed by the polyelectrolyte chains. Calcium carbonate formation was carried out by carbon dioxide diffusion, where CO, was generated from ammonium carbonate decomposition. The CaCO3 nanocrystals obtained, formed a dense, homogeneous, and continuous film. Vaterite and calcite CaCO3 crystalline forms were detected. (c) 2007 Elsevier B.V All rights reserved.

Surface miscibility of EPC/DOTAP/DOPE in binary and ternary mixed monolayers

Surface pressure (pi)-molecular area (A) curves were used to characterize the packing of pseudo-ternary mixed Langmuir monolayers of egg phosphatidylcholine (EPC), 1,2-dioleoyl-3-trimethylammonium propane (DOTAP) and L-alpha-dioleoyl phosphatidylethanolamine (DOPE). This pseudo-ternary mixture EPC/DOPE/DOTAP has been successfully employed in liposome formulations designed for DNA non-viral vectors. Pseudo-binary mixtures were also studied as a control. Miscibility behavior was inferred from pi-A curves applying the additivity rule by calculating the excess free energy of mixture (Delta G(Exc)). The interaction between the lipids was also deduced from the surface compressional modulus (C(s)(-1)). The deviation from ideality shows dependence on the lipid polar head type and monolayer composition. For lower DOPE concentrations, the forces are predominantly attractive. However, if the monolayer is DOPE rich, the DOTAP presence disturbs the PE-PE intermolecular interaction and the net interaction is then repulsive. The ternary monolayer EPC/DOPE/DOTAP presented itself in two configurations, modulated by the DOPE content, in a similar behavior to the DOPE/DOTAP monolayers. These results contribute to the understanding of the lipid interactions and packing in self-assembled systems associated with the in vitro and in vivo stability of liposomes. (C) 2010 Elsevier B.V. All rights reserved.

Investigation of the electrical and electrochemical properties of nanocomposites from V2O5, polypyrrole, and polyaniline

In this work, an investigation of the electrical and electrochemical properties responsible for the energy storage capability of nanocomposites has been carried out. We demonstrate that, in the case of the V2O5 xerogel and the nanocomposites polypyrrole (Ppy)/V2O5 and polyaniline (PANI)/V2O5, the quadratic logistic equation (QLE) can be used to fit the inverse of the resistance values as a function of the injected charge in non-steady-state conditions. This contributes to a phenomenological understanding of the lithium ion and electron transport. The departure of the experimental curve from the fitting observed for the V2O5 xerogel can be attributed to the trapping sites formed during the lithium electroinsertion, which was observed by electrochemical impedance spectroscopy. The amount of trapping sites was obtained on the basis of the QLE. Similar values used to fit the inverse of the resistance were also used to fit the absorbance changes, which is also associated with the small polaron hopping from the V(IV) to the V(V) sites. On the other hand, there was good agreement between the experimental and the theoretical data when the profile of the inverse of the resistance as a function of the amount of inserted lithium ions of the nanocomposites Ppy/V2O5 and PANI/ V2O5 was concerned. We suggest that the presence of the conducting polymers is responsible for the different electrical profile of the V2O5 xerogel compared with those of the nanocomposites. In the latter case, interactions between the lithium ions and oxygen atoms from V2O5 are shielded, thus decreasing the trapping effect of lithium ions in the V2O5 sites. The different values of the lithium ion diffusion coefficient into these intercalation materials are in agreement with this hypothesis.

A technique to produce thin cucurbit[6]uril films

We report a methodology to obtain thin films of cucurbit[6]uril, starting from ammoniacal solutions. This technique is very useful for the obtention of modified electrodes or other substrates for sensor purposes. Cucurbit[6]uril is insoluble in most media, and film formation was impossible until now.

Cerium-based phosphors: blue luminescent properties for applications in optical displays

In this paper, we describe the blue photoluminescence (PL) observed in the multi-component oxosalt phosphor GdVO(4)center dot Ce(3+). Different doping concentrations (0.25-1 mol%) and heat treatment (900-1100 degrees C) were used to evaluate which conditions would lead to the most suitable blue phosphor for optimal display performance. The cerium doping concentration influences the profile of the emission spectrum (broad peak at 412 nm under UV excitation at 330 nm), as reflected on the values of chromaticity coordinates. On the basis of luminescent properties, we can conclude that, among the phosphors prepared in this work the most adequate for a blue display is the one obtained via the combustion method using glycine as fuel, a 0.50 mol% cerium doping concentration, and heat treatment at 1000 degrees C.

PHBHV/PCL microspheres as biodegradable drug delivery systems (DDS) for photodynamic therapy (PDT)

Unloaded microspheres were prepared from polyhydroxybutyrate-co-valerate (PHBHV) and poly(epsilon-caprolactone) (PCL) polymers using the emulsification-solvent evaporation method (EE). The study was conducted to determine the ideal polymeric composition and ideal molecular weight for the microspheres preparation to be used as a Drug Delivery System (DDS) for cancer therapy. In this work, NzPC, a new photosensitizer, has been investigated when incorporated into microspheres of PHBHV/PCL evaluating its application for Photodynamic Therapy (PDT) of neoplastic tissue. The biodegradation studies were conducted to analyze the effects of the incorporation of the NzPC and also to determine the release profiles in vitro condition. We also evaluated the dark toxicity and the photobiological effect of the PHBHV-PCL microspheres in cutaneous melanoma cell line (B-16-A1) used as a biological neoplastic medium.

In Vitro Antifungal Activity and Toxicity of Itraconazole in DMSA-PLGA Nanoparticles

Itraconazole (ITZ) is a drug used to treat various fungal infections and may cause side effects. The aim of this study was to develop and evaluate the in vitro activity of DMSA-PLGA nanoparticles loaded with ITZ against Paracoccidioides brasiliensis, as well as their cytotoxicity. Nanoparticles were prepared using the emulsification-evaporation technique and characterized by their encapsulation efficiency, morphology (TEM), size (Nanosight) and charge (zeta potential). Antifungal efficacy in P brasiliensis was determined by minimal inhibition concentration (MIC), and cytotoxicity using MU assay. ITZ was effectively incorporated in the PLGA-DMSA nanoparticles with a loading efficiency of 72.8 +/- 3.50%. The shape was round with a solid polymeric structure, and a size distribution of 174 +/- 86 nm (Average +/- SD). The particles were negatively charged. ITZ-NANO presented antifungal inhibition (MIC = 6.25 ug/mL) against P brasiliensis and showed lower in vitro cytotoxicity than free drug (ITZ).

Rare Earth Doped SnO(2) Nanoscaled Powders and Coatings: Enhanced Photoluminescence in Water and Waveguiding Properties

Luminescent Eu(3+) and Er(3+) doped SnO(2) powders have been prepared by Sn(4+) hydrolysis followed by a controlled growth reaction using a particle`s surface modifier in order to avoid particles aggregation. The powders so obtained doped with up to 2 mol% rare earth ions are fully redispersable in water at pH > 8 and present the cassiterite structure. Particles size range from 3 to 10 nm as determined by Photon Correlation Spectroscopy. Rare earth ions were found to be essentially incorporated into the cassiterite structure, substituting for Sn(4+), for doping concentration smaller than 0.05 mol%. For higher concentration they are also located at the particles surface. The presence of Eu(3+) ions at the surface of the particles hinder their growth and has therefore allowed the preparation of new materials consisting of water redispersable powders coated with Eu(3+)-beta dike-tonate complexes. Enhanced UV excited photoluminescence was observed in water. SnO(2) single layers with thickness up to 200 nm and multilayer coatings were spin coated on borosilicate glass substrates from the colloidal suspensions. Waveguiding properties were evaluated by the prism coupling technique. For a 0.3 mu m planar waveguide single propagating mode was observed with attenuation coefficient of 3.5 dB/cm at 632.8 nm.