Tailoring Molecular Architectures with Cobalt Tetrasulfonated Phthalocyanine: Immobilization in Layer-by-Layer Films and Sensing Applications

In the field of organic thin films, manipulation at the nanoscale can be obtained by immobilization of different materials on platforms designed to enhance a specific property via the layer-by-layer technique. In this paper we describe the fabrication of nanostructured films containing cobalt tetrasulfonated phthalocyanine (CoTsPc) obtained through the layer-by-layer architecture and assembled with linear poly(allylamine hydrochloride) (PAH) and poly(amidoamine) dendrimer (PAMAM) polyelectrolytes. Film growth was monitored by UV-vis spectroscopy following the Q band of CoTsPc and revealed a linear growth for both systems. Fourier transform infrared (FTIR) spectroscopy showed that the driving force keeping the structure of the films was achieved upon interactions of CoTsPc sulfonic groups with protonated amine groups present in the positive polyelectrolyte. A comprehensive SPR investigation on film growth reproduced the deposition process dynamically and provided an estimation of the thicknesses of the layers. Both FTIR and SPR techniques suggested a preferential orientation of the Pc ring parallel to the substrate. The electrical conductivity of the PAH films deposited on interdigitated electrodes was found to be very sensitive to water vapor. These results point to the development of a phthalocyanine-based humidity sensor obtained from a simple thin film deposition technique, whose ability to tailor molecular organization was crucial to achieve high sensitivity.

Dendrimers/TiO2 nanoparticles layer-by-layer films as extended gate FET for pH detection

The layer-by-layer (LbL) technique combined with field-effect transistor (FET) based sensors has enabled the production of pH-sensitive platforms with potential application in biosensors. A variation of the FET architecture, so called separative extended gate FET (SEGFET) devices, are promise as an alternative to conventional ion sensitive FET (ISFET). SEGFET configuration exhibits the advantage of combining the field-effect concept with organic and inorganic materials directly adsorbed on the extended gate, allowing the test of new pH-sensitive materials in a simple and low cost way. In this communication, poly(propylene imine) dendrimer (PPI) and TiO2 nanoparticles (TiO2-np) were assembled onto gold-covered substrates via layer-by-layer technique to produce a low cost SEGFET pH sensor. The sensor presented good pH sensitivity, ca. 57 mV pH(-1), showing that our strategy has potential advantages to fabricate low cost pH-sensing membranes. (C) 2012 Elsevier B.V. All rights reserved.

A novel microdeletion syndrome at 3q13.31 characterised by developmental delay, postnatal overgrowth, hypoplastic male genitals, and characteristic facial features

Background Congenital deletions affecting 3q11q23 have rarely been reported and only five cases have been molecularly characterised. Genotype. phenotype correlation has been hampered by the variable sizes and breakpoints of the deletions. In this study, 14 novel patients with deletions in 3q11q23 were investigated and compared with 13 previously reported patients. Methods Clinical data were collected from 14 novel patients that had been investigated by high resolution microarray techniques. Molecular investigation and updated clinical information of one cytogenetically previously reported patient were also included. Results The molecular investigation identified deletions in the region 3q12.3q21.3 with different boundaries and variable sizes. The smallest studied deletion was 580 kb, located in 3q13.31. Genotype. phenotype comparison in 24 patients sharing this shortest region of overlapping deletion revealed several common major characteristics including significant developmental delay, muscular hypotonia, a high arched palate, and recognisable facial features including a short philtrum and protruding lips. Abnormal genitalia were found in the majority of males, several having micropenis. Finally, a postnatal growth pattern above the mean was apparent. The 580 kb deleted region includes five RefSeq genes and two of them are strong candidate genes for the developmental delay: DRD3 and ZBTB20. Conclusion A newly recognised 3q13.31 microdeletion syndrome is delineated which is of diagnostic and prognostic value. Furthermore, two genes are suggested to be responsible for the main phenotype.

Nerve fiber layer in glaucomatous hemifield loss: a case-control study with time- and spectral-domain optical coherence tomography

Purpose: To evaluate the retinal nerve fiber layer measurements with time-domain (TD) and spectral-domain (SD) optical coherence tomography (OCT), and to test the diagnostic ability of both technologies in glaucomatous patients with asymmetric visual hemifield loss. Methods: 36 patients with primary open-angle glaucoma with visual field loss in one hemifield (affected) and absent loss in the other (non-affected), and 36 age-matched healthy controls had the study eye imaged with Stratus-OCT (Carl Zeiss Meditec Inc., Dublin, California, USA) and 3 D OCT-1000 (Topcon, Tokyo, Japan). Peripapillary retinal nerve fiber layer measurements and normative classification were recorded. Total deviation values were averaged in each hemifield (hemifield mean deviation) for each subject. Visual field and retinal nerve fiber layer "asymmetry indexes" were calculated as the ratio between affected versus non-affected hemifields and corresponding hemiretinas. Results: Retinal nerve fiber layer measurements in non-affected hemifields (mean [SD] 87.0 [17.1] mu m and 84.3 [20.2] mu m, for TD and SD-OCT, respectively) were thinner than in controls (119.0 [12.2] mu m and 117.0 [17.7] mu m, P<0.001). The optical coherence tomography normative database classified 42% and 67% of hemiretinas corresponding to non-affected hemifields as abnormal in TD and SD-OCT, respectively (P=0.01). Retinal nerve fiber layer measurements were consistently thicker with TD compared to SD-OCT. Retinal nerve fiber layer thickness asymmetry index was similar in TD (0.76 [0.17]) and SD-OCT (0.79 [0.12]) and significantly greater than the visual field asymmetry index (0.36 [0.20], P<0.001). Conclusions: Normal hemifields of glaucoma patients had thinner retinal nerve fiber layer than healthy eyes, as measured by TD and SD-OCT. Retinal nerve fiber layer measurements were thicker with TD than SD-OCT. SD-OCT detected abnormal retinal nerve fiber layer thickness more often than TD-OCT.

Optical chemical sensors using polythiophene derivatives as active layer for detection of volatile organic compounds

Several studies on polythiophene gas sensors, based mainly on electrochemical and gravimetric principles can be found in the literature. However, other principles of gas detection, such as optical and thermal, are still little studied. Optical sensing is suitable for remote detection and offers great versatility at low cost. Here,we report on the use of thin films of seven polythiophene derivatives as active layer in optical sensors for the detection of six volatile organic compounds (n-hexane, toluene, tetrahydrofuran, chloroform, dichloromethane and methanol) and water vapor, in concentration range of 500-30,000 ppm. The results showed that it is possible to use different polythiophene derivatives to differentiate VOCs by optical sensing. Differentiation can be performed based on the presence or not of response to an analyte and the sensitivity value of the sensors for the analytes. Another important feature is the lack of the effect of humidity on the response of most films, which could be a major drawback in the application of these sensors. (C) 2011 Elsevier B.V. All rights reserved.

Spectroscopic, morphological and electrochromic characterization of layer-by-layer hybrid films of polyaniline and hexaniobate nanoscrolls

The combination of semiconducting oxides and polyaniline in the nanoscale range may result in hybrid materials having enhanced properties, such as electrochromism and charge capacity. This paper reports the spectroscopic, morphological and electrochromic characterization of hybrid films made up of hexaniobate one-dimensional (1D) nanoscrolls and polyaniline prepared by the layer-by-layer assembly technique (LbL). Secondary electron imaging and backscattered electron imaging techniques performed using a scanning electron microscope showed that polyaniline is adsorbed on the hexaniobate nanoscrolls, which confirms the combination of the components in the nanoscale domain. UV-VIS-NIR electronic spectra of the LbL hybrid films showed the absorption tail in the NIR region, assigned to delocalized polarons of the polyaniline. Resonance Raman spectra in the 1000-1700 cm(-1) range indicated that hybrid films present a higher relative intensity of polaron bands at 1337 and 1508 cm(-1) than pristine polyaniline in the emeraldine salt form. These results suggest that hexaniobate nanoscrolls induce a secondary doping of polyaniline. The cyclic voltammetry (CV) data for the hybrid film showed a specific capacity of 870 C cm(-3). According to CV results, the synergistic effect on charge storage properties of the hybrid material is attributed to the enhanced electroactivity of the hexaniobate component in the LbL film. Spectroelectrochemical experiments showed that the electrochromic efficiencies at 420 nm are ca. -41 and 24 cm(2) C-1 as the potential changes from 0.8 to -0.9 V and from -0.9 to -1.8 V, respectively, whereas at 800 nm the efficiencies are ca. -55 and 8 cm(2) C-1 for the same potential ranges. The electrochromic efficiencies and multi-colour character of the LbL film of hexaniobate nanoscrolls and polyaniline indicate that this novel hybrid material is an interesting modified electrode for electrochromic devices.

Effect of the root canal final rinse protocols on the debris and smear layer removal and on the push-out strength of an epoxy-based sealer

The aim of the present study was to evaluate the efficacy of QMiX, SmearClear, and 17% EDTA for the debris and smear layer removal from the root canal and its effects on the push-out bond strength of an epoxy-based sealer by scanning electron microscopy (SEM). Forty extracted human canines (n = 10) were assigned to the following final rinse protocols: G1-distilled water (control), G2–17% EDTA, G3-SmearClear, and G4-QMiX. The specimens were submitted to a SEM analysis to evaluate the presence of debris and smear layer, respectively, in the apical or cervical segments. In sequence, forty extracted human maxillary canines with the root canals instrumented were divided into four groups (n = 10) similar to the SEM analysis study. After the filling with AH Plus, the roots were transversally sectioned to obtain dentinal slices. The specimens were submitted to a push-out bond strength test using an electromechanical testing machine. The statistical analysis for the SEM and push-out bond strength studies were performed using the Kruskal–Wallis and Dunn tests (α = 5%). There was no difference among the G2, G3, and G4 efficacy in removing the debris and smear layer (P > 0.05). The efficacy of these groups was superior to the control group. The push-out bond strength values of G2, G3, and G4 were superior to the control group. The ability to remove the debris and smear layer by SmearClear and QMiX was as effective as the 17% EDTA. The final rinse with these solutions promoted similar push-out bond strength values.

Effect of passive ultrassonic instrumentation as a final irrigation protocol on debris and smear layer removal

This study sought to evaluate the efficacy of passive ultrasonic irrigation (PUI) on removing the smear layer and debris from root dentin using scanning electron microscopy (SEM). Twenty-five bovine incisors were manually prepared and divided into three groups according to the final irrigation protocol: EDTA, final irrigation with 12 mL of 17% EDTA for 3 minutes followed by 5 mL of 2.5% NaOCl; EDTA=PUI, final flush with 4 mL of 17% EDTA and PUI for 30 seconds. These procedures were repeated three times to standardize the volume of the irrigant. Control group, after preparation, the specimens were irrigated only with 17 mL of 2.5% NaOCl. The roots were fractured and analyzed using SEM. The intragroup analysis revealed that the EDTA=PUI protocol removed a higher amount of debris at the cervical third (P 5 0.03). The intergroup analysis revealed that EDTA=PUI presented the lowest amount of debris at the cervical third (P 5 0.007). Smear layer scores were higher in the control group compared with the EDTA and EDTA=PUI groups, but only at the cervical third (P 50.02). None of the final irrigant protocols completely removed the smear layer and debris. EDTA=PUI only improved the removal of debris at the cervical third.

Flexural strengthening of reinforced concrete beams with carbon fibers reinforced polymer (CFRP) sheet bonded to a transition layer of high performance cement-based composite

Resistance to corrosion, high tensile strength, low weight, easiness and rapidity of application, are characteristics that have contributed to the spread of the strengthening technique characterized by bonding of carbon fibers reinforced polymer (CFRP). This research aimed to develop an innovate strengthening method for RC beams, based on a high performance cement-based composite of steel fibers (macro + microfibers) to be applied as a transition layer. The purpose of this transition layer is better control the cracking of concrete and detain or even avoid premature debonding of strengthening. A preliminary study in short beams molded with steel fibers and strengthened with CFRP sheet, was carried out where was verified that the conception of the transition layer is valid. Tests were developed to get a cement-based composite with adequate characteristics to constitute the layer transition. Results showed the possibility to develop a high performance material with a pseudo strain-hardening behavior, high strength and fracture toughness. The application of the strengthening on the transition layer surface had significantly to improve the performance levels of the strengthened beam. It summary, it was proven the efficiency of the new strengthening technique, and much information can be used as criteria of projects for repaired and strengthened structures.

Intravital microscopy technique to study parasite dynamics in the labyrinth layer of the mouse placenta

Intravital imaging techniques are the best approach to investigate in situ cellular behavior under physiological conditions. Many techniques have emerged during these last few years for this purpose. We recently described an intravital imaging technique that allows for the observation of placenta physiological responses at the labyrinth layer of this tissue. This technique will be very useful to study many placental opportunistic infections and in this article we reinforce its usefulness by analyzing placental physiological entrapment of beads and parasites. In particular, our results show that small beads (1.0 μm) or Plasmodium chabaudi-GFP-infected-Red Blood Cells (Pc-GFP-iRBCs) cannot get trapped inside small or large blood vessels of popliteal lymph nodes (PLNs). Inside the placenta, clusters of beads could only be found inside the maternal blood vessels. However, Pc-GFP-iRBCs were found inside and outside the maternal blood vessels. We observed that trophoblasts can ingest infected-Red Blood Cells (iRBCs) in vitro and immunofluorescence of placenta revealed Pc-GFP-iRBCs inside and outside the maternal blood vessels. Taken together, we conclude that fast deposition of particles inside blood vessels seems to be an intrinsic characteristic of placenta blood flow, but iRBCs could be internalized by trophoblast cells. Thus these results represent one of the many possible uses of our intravital imaging technique to address important questions inside the parasitological field.

Layer-by-Layer assembled cobalt ferrite nanoparticles for chemical sensing

Ultra-thin (thicknesses of 50-90 nm) nanocomposite films of cobalt ferrite nanoparticles (np-CoFe2O4, 18 nm in diameter) and polyelectrolytes (doped polyaniline-PANI, poly-3,4-ethylenedioxy thiophene: polystyrene sulfonic acid-PEDOT:PSS, and sulfonated lignin-SL) are assembled layer-by-layer onto interdigitated microelectrodes aiming at to create novel nanostructured sensoactive materials for liquid media chemical sensors. The nanocomposites display a distinctive globular morphology with nanoparticles densely-packed while surrounded by polyelectrolytes. Due to the presence of np-CoFe2O4 the nanocomposites display low electrical conductivity according to impedance data. On the other hand, this apparent shortcoming turns such nanocomposites much more sensitive to the presence of ions in solution than films made exclusively of conducting polyelectrolytes. For example, the electrical resistance of np-CoFe2O4/PEDOT:PSS and PANI/SL/np-CoFe2O4/SL architectures has a 10-fold decrease when they are immersed in 20 mmol. L-1 NaCl solution. Impedance spectra fitted with the response of an equivalent circuit model suggest that the interface created between nanoparticles and polyelectrolytes plays a major role on the nanocomposites electrical/dielectrical behavior. Since charge transport is sensitive to nanoparticle-polyelectrolyte interfaces as well as to the physicochemical conditions of the environment, the np-CoFe2O4-based nanocomposites can be used as sensing elements in chemical sensors operated under ac regime and room temperature.

Determination of degree of ionization of poly(allylamine hydrochloride) (PAH) and poly[1-[4-(3-carboxy‑4 hydroxyphenylazo)benzene sulfonamido]-1,2-ethanediyl, sodium salt] (PAZO) in layer-by-layer films using vacuum photoabsorption spectroscopy

Electrostatic and hydrophobic interactions govern most of the properties of supramolecular systems, which is the reason determining the degree of ionization of macromolecules has become crucial for many applications. In this paper, we show that highresolution ultraviolet spectroscopy (VUV) can be used to determine the degree of ionization and its effect on the electronic excitation energies of layer-by-layer (LbL) films of poly(allylamine hydrochloride) (PAH) and poly[1-[4-(3-carboxy-4 hydroxyphenylazo)- benzene sulfonamido]-1,2-ethanediyl, sodium salt] (PAZO). A full assignment of the VUV peaks of these polyelectrolytes in solution and in cast or LbL films could be made, with their pH dependence allowing us to determine the p'K IND. a' using the Henderson-Hasselbach equation. The p'K IND. a' for PAZO increased from ca. 6 in solution to ca. 7.3 in LbL films owing to the charge transfer from PAH. Significantly, even using solutions at a fixed pH for PAH, the amount adsorbed on the LbL films still varied with the pH of the PAZO solutions due to these molecular-level interactions. Therefore, the procedure based on a comparison of VUV spectra from solutions and films obtained under distinct conditions is useful to determine the degree of dissociation of macromolecules, in addition to permitting interrogation of interface effects in multilayer films.

Studies of Inorganic Layer and Framework Structures Using Time-, Temperature- and Pressure-Resolved Powder Diffraction Techniques

This thesis is concerned with in-situ time-, temperature- and pressure-resolved synchrotron X-ray powder diffraction investigations of a variety of inorganic compounds with twodimensional layer structures and three-dimensional framework structures. In particular, phase stability, reaction kinetics, thermal expansion and compressibility at non-ambient conditions has been studied for 1) Phosphates with composition MIV(HPO4)2·nH2O (MIV = Ti, Zr); 2) Pyrophosphates and pyrovanadates with composition MIVX2O7 (MIV = Ti, Zr and X = P, V); 3) Molybdates with composition ZrMo2O8. The results are compiled in seven published papers and two manuscripts. Reaction kinetics for the hydrothermal synthesis of α-Ti(HPO4)2·H2O and intercalation of alkane diamines in α-Zr(HPO4)2·H2O was studied using time-resolved experiments. In the high-temperature transformation of γ-Ti(PO4)(H2PO4)·2H2O to TiP2O7 three intermediate phases, γ'-Ti(PO4)(H2PO4)·(2-x)H2O, β-Ti(PO4)(H2PO4) and Ti(PO4)(H2P2O7)0.5 were found to crystallise at 323, 373 and 748 K, respectively. A new tetragonal three-dimensional phosphate phase called τ-Zr(HPO4)2 was prepared, and subsequently its structure was determined and refined using the Rietveld method. In the high-temperature transformation from τ-Zr(HPO4)2 to cubic α-ZrP2O7 two new orthorhombic intermediate phases were found. The first intermediate phase, ρ-Zr(HPO4)2, forms at 598 K, and the second phase, β-ZrP2O7, at 688 K. Their respective structures were solved using direct methods and refined using the Rietveld method. In-situ high-pressure studies of τ-Zr(HPO4)2 revealed two new phases, tetragonal ν-Zr(HPO4)2 and orthorhombic ω-Zr(HPO4)2 that crystallise at 1.1 and 8.2 GPa. The structure of ν-Zr(HPO4)2 was solved and refined using the Rietveld method. The high-pressure properties of the pyrophosphates ZrP2O7 and TiP2O7, and the pyrovanadate ZrV2O7 were studied up to 40 GPa. Both pyrophosphates display smooth compression up to the highest pressures, while ZrV2O7 has a phase transformation at 1.38 GPa from cubic to pseudo-tetragonal β-ZrV2O7 and becomes X-ray amorphous at pressures above 4 GPa. In-situ high-pressure studies of trigonal α-ZrMo2O8 revealed the existence of two new phases, monoclinic δ-ZrMo2O8 and triclinic ε-ZrMo2O8 that crystallises at 1.1 and 2.5 GPa, respectively. The structure of δ-ZrMo2O8 was solved by direct methods and refined using the Rietveld method.

Mesoscale dynamics and boundary-layer structure in topographically forced low-level jets

Two types of mesoscale wind-speed jet and their effects on boundary-layer structure were studied. The first is a coastal jet off the northern California coast, and the second is a katabatic jet over Vatnajökull, Iceland. Coastal regions are highly populated, and studies of coastal meteorology are of general interest for environmental protection, fishing industry, and for air and sea transportation. Not so many people live in direct contact with glaciers but properties of katabatic flows are important for understanding glacier response to climatic changes. Hence, the two jets can potentially influence a vast number of people. Flow response to terrain forcing, transient behavior in time and space, and adherence to simplified theoretical models were examined. The turbulence structure in these stably stratified boundary layers was also investigated. Numerical modeling is the main tool in this thesis; observations are used primarily to ensure a realistic model behavior. Simple shallow-water theory provides a useful framework for analyzing high-velocity flows along mountainous coastlines, but for an unexpected reason. Waves are trapped in the inversion by the curvature of the wind-speed profile, rather than by an infinite stability in the inversion separating two neutral layers, as assumed in the theory. In the absence of blocking terrain, observations of steady-state supercritical flows are not likely, due to the diurnal variation of flow criticality. In many simplified models, non-local processes are neglected. In the flows studied here, we showed that this is not always a valid approximation. Discrepancies between simulated katabatic flow and that predicted by an analytical model are hypothesized to be due to non-local effects, such as surface inhomogeneity and slope geometry, neglected in the theory. On a different scale, a reason for variations in the shape of local similarity scaling functions between studies is suggested to be differences in non-local contributions to the velocity variance budgets.