Nanoporous silk films with capillary action and size-exclusion capacity for sensitive glucose determination in whole blood.

In optical biosensing, silk fibroin (SF) appears as a promising alternative where other materials, such as paper, find limitations. Besides its excellent optical properties and unmet capacity to stabilize biomacromolecules, SF in test strips exhibits additional functions, i.e. capillary pumping activity of 1.5 mm s-1, capacity to filter blood cells thanks to its small, but tuneable, porosity and enhanced biosensing sensitivity. The bulk functionalization of SF with the enzymes glucose oxidase and peroxidase and the mediator ABTS produces colourless and transparent SF films that respond to blood glucose increasing 2.5 times the sensitivity of conventional ABTS-based assays. This enhanced sensitivity results from the formation of SF-ABTS complexes, where SF becomes part of the bioassay. Additionally, SF films triple the durability of most stable cellulose-based sensors. Although demonstrated for glucose, SF microfluidic test strips may incorporate other optical bioassays, e.g. immunoassays, with the aim of transferring them from central laboratories to the place of patient's care.

Understanding kinetics and thermodynamics of the interactions between amitriptyline or eosin yellow and aminosilane-modified cellulose.

A new adsorbent matrix (Cel-SiN) for the adsorption of the dye eosin yellow (EY) and the drug amitriptyline (AMI) from aqueous media has been synthesized. The Cel-SiN matrix was obtained via chemical modification of cellulose with (3-aminopropyl)trimethoxysilane. Successful modification was confirmed using Fourier transform infrared (FTIR) and 13C and 29Si solid state nuclear magnetic resonance (SSNMR) spectroscopies, thermal analysis (TG/DTG), X-ray diffraction (XRD), and elemental analysis. The effects of pH, contact time, concentration, and temperature were evaluated in batch adsorption tests. Cel-SiN efficiently adsorbed AMI and EY in aqueous media, with maximum adsorption capacities of 92.28 ±â€¯1.34 mg g-1 for AMI (pH = 7, time =240 min, and temperature = 318 K) and 61.0 ±â€¯0.36 mg g-1 for EY (pH = 5, time =80 min, and temperature = 298 K). The adsorption process occurs mainly via hydrogen bonding interactions for AMI and electrostatic interactions for EY.

Ion-Pair Complexes of Pyrylium and Tetraarylborate as New Host-Guest Dyes: Photoinduced Electron Transfer Promoting Radical Polymerization.

Ultrafast transient absorption spectroscopy, NOESY-NMR, and EPR spectroscopy shed light on how π-π stacking interactions combined with electrostatic interactions can be used to form stable ion-pair complexes between pyrylium and tetraarylborate ions in which the interaction of the π-delocalized clouds promotes the observation of new radiative processes and also electron transfer processes excitation using visible light. The results exhibit a striking combination of properties, chemical stability and photophysical and photochemical events, that make these ion-pair complexes as a step toward the realization of chromophore/luminescent materials and also their use as a new monophotoinitiator system in radical polymerization reactions.

Phosphate glasses via coacervation route containing CdFe2O4 nanoparticles: structural, optical and magnetic characterization.

CdFe2O4 nanoparticles of around 3.9 nm were synthesized using the coprecipitation method and protected by a silica layer. The nanoparticles were mixed with a coacervate and transformed into phosphate glasses with 1, 4 and 8% in mass of nanoparticles by the melt-quenching method. TEM images confirm that the nanoparticles were successfully incorporated into the matrix without inducing crystallization. 31P NMR and Raman spectral analyses show that new P-O-Si bonds are formed in the glasses containing nanoparticles. The glass transition increases as a function of the nanoparticle content due to an increase in the connectivity of the phosphate glass chains. The UV-Vis spectra show bands at 415 and 520 nm assigned to Fe3+ ions and at 1025 nm, characteristic of Fe2+ ions, indicating that some of the nanoparticles dissolve during the melting process. The sample with 8% CdFe2O4 presents a paramagnetic behavior. The glasses obtained are transparent, non-hygroscopic and possess enormous thermal stability which is important for the production of optical devices.

Fabrication of Biocompatible, Functional, and Transparent Hybrid Films Based on Silk Fibroin and Epoxy Silane for Biophotonics.

In this work we explored the fabrication of flexible and transparent hybrids of silk fibroin (SF) and epoxy-modified siloxane for photonic applications. It is well-known that regenerated SF solutions can form free-standing films with high transparency. Although SF has a restricted number of chemically reactive side groups, the main issues of as-cast pristine SF films regard the high solubility into aqueous media, brittleness, and low thermal stability. The design of SF films with enhanced functionality but high transparency triggers new opportunities on a broader range of applications in biophotonics. Here we present a simple, functional, yet remarkably versatile hybrid material derived from silica sol-gel process based on SF protein and (3-glycidyloxypropyl)trimethoxysilane (GPTMS), an organically modified silicon-alkoxide owning a reactive terminal epoxy group. Specifically, we investigated the effect of the addition of GPTMS into SF solutions on the processability, morphology, crystallinity, and mechanical and optical properties of the resulting hybrid films. Highly transparent (ca. 90%) and flexible free-standing hybrid films were achieved. Cell viability assays revealed that the hybrid films are noncytotoxic to rat osteoblast cells even at high GPTMS content (up to 70 wt %). The hybrid films showed enhanced thermal stability and were rich in organic (epoxy) and inorganic (silanol) functional groups according to the content of GPTMS. We also evaluated the successful preparation of high-quality optical red emissive SF hybrid films by loading YVO4:Eu3+ nanoparticles at low concentration (<5 wt %). A meaningful description of the hybrid film structure is reported from the combination of scanning electron and atomic force microscopies, vibrational spectroscopy, solid-state NMR, and X-ray diffraction analyses.

Preparation and characterization of new glassy system As2P2S8-Ga2S3.

Glasses having the composition (100 - x)As2P2S8-xGa2S3 with x ranging from 0 to 50% were investigated to determine the compositional effect on properties and local structure. The glass transition temperature (Tg) and the stability parameter against crystallization (Tx - Tg) increased with the addition of Ga2S3. The structure of these glasses was probed by Raman scattering, Fourier transform infrared (FT-IR) and 31P nuclear magnetic resonance. On the basis of the observed vibrations and the strength of the 31P-31P homonuclear magnetic dipolar coupling, two scenarios can be proposed for the structural evolution induced by the addition of Ga2S3. For x or= 30% we have depolymerization of the As2P2S8 units and the formation of a network of GaPS4 units with each PS 4/2 unit (Q4) species carrying a single positive formal charge.

Al3+ environments in nanostructured ZnAl2O4 and their effects on the luminescence properties.

Single-phase zinc aluminate (ZnAl2O4) with the spinel structure was successfully obtained by the Pechini method at different calcining temperatures for 4 hours. The nanoparticles are highly crystalline with no impurities related to ZnO or Al2O3 residues. The microstructural environment of aluminium ions changes with heat treatment temperature, as observed by Fourier transform infrared spectroscopy. The spinel structure might present two different AlO6 sites as evidenced by 27Al solid-state magic-angle-spinning nuclear magnetic resonance spectra. Some AlO4 sites were also detected for samples calcined at a temperature lower than 900 degrees C. The photoluminescence spectra show that the emission can be tuned depending on the calcining temperature. This effect was discussed on the basis of symmetry and oxygen vacancies.

Structural studies of NaPO3-MoO3 glasses by solid-state nuclear magnetic resonance and Raman spectroscopy.

Vitreous samples were prepared in the (100 - x)% NaPO(3)-x% MoO(3) (0