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.

Synthesis and Solar Cell Application of New Alternating Donor-Acceptor Copolymers Based on Variable Units of Fluorene, Thiophene, and Phenylene

A new series of donor acceptor copolymers were synthesized via the Witting route and applied as an active layer in organic thin-films solar cells. These copolymers are composed of fluorene thiophene and phenylene thiophene units. The ratio between those was systematically varied, and copolymers containing 0%, 50%, and 75% of phenylene thiophene were characterized and evaluated when used in photovoltaic devices. The copolymers' composition, photophysical, electrical, and morphological properties are addressed and correlated with device performance. The 50% copolymer ratio was found to be the best copolymer of the series, yielding a power conversion efficiency (PCE) under air mass (AM) 1.5 conditions of 2.4% in the bilayer heterojunction with the C-60 molecule. Aiming at flexible electronics applications, solutions based on the heterojunction of this copolymer with PCBM (6,6-phenyl-C-61-butyric acid methyl ester) were also successfully deposited using an inkjet printing method and used as an active layer in solar cells.

Molecular origin of charge traps in polyfluorene-based semiconductors

The comprehensive control of morphology and structure is of extreme importance in semiconducting polymers when used as active layers in optoelectronic devices. In the work reported here, a systematic investigation of the structural and dynamical properties of poly(9,9-di-n-octyl-fluorene-alt-benzothiadiazole), known as F8BT, and their correlation with electrical properties is presented when the material is used as an active layer in optoelectronic devices. By means of X-ray diffraction, one observes that in thick layer films (thickness of about 4 μm) grown by drop-cast deposition, a solvent induced crystalline phase exists which evolves to a stable phase as the temperature is raised. This was not observed in thin films (thickness of about 250 nm) prepared by spin-coating within the investigated temperature range. By modeling the current-voltages characteristics of both thick and thin film devices, important information on the influence of crystallization on the trapping states could be drawn. Furthermore, the temperature dependence of the charge carrier mobility was found to be closely related to that of the molecular relaxation processes. The understanding of the nature of such molecular relaxations, measured by solid-state nuclear magnetic resonance methods, allows one to understand the importance of molecular relaxations and microstructure changes on the trap states of the system.

Electroluminescence and electric current response spectroscopy applied to the characterization of polymer light-emitting electrochemical cells

Frequency-dependent electroluminescence and electric current response spectroscopy were applied to polymeric light-emitting electrochemical cells in order to obtain information about the operation mechanism regimes of such devices. Three clearly distinct frequency regimes could be identified: a dielectric regime at high frequencies; an ionic transport regime, characterized by ionic drift and electronic diffusion; and an electrolytic regime, characterized by electronic injection from the electrodes and electrochemical doping of the conjugated polymer. From the analysis of the results, it was possible to evaluate parameters like the diffusion speed of electronic charge carriers in the active layer and the voltage drop necessary for operation. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4752438]

Influence of Molecular Dynamics on the Dielectric Properties of Poly(9,9-di-n-octylfluorene-alt-benzothiadiazole) -Based Devices

This paper uses Nuclear Magnetic Resonance (NMR) and Differential Scanning Calorimetry (DSC) techniques to study the molecular relaxations and phase transitions in poly(9,9-di-n-octylfluorene-alt-benzothiadiazole) (F8BT), which has been extensively studied as the active thin film in organic devices. Besides the identification of the glass transition, beta relaxation and crystal-to-crystal phase transition, we correlate such phenomena with dielectric and transport mechanisms in diodes with F8BT as the active layer. The beta relaxation has been assigned to a transition at about 210 K measured by H-1 and C-13 solid state NMR, and can be attributed to local motions in the side chains. The glass transition has been detected by DSC and H-1 NMR. Dielectric spectroscopy (DS) carried out at low frequencies on diodes made from F8BT show two peaks which are coincident with the above transitions. This allowed us to correlate the electrical changes in the film with the onset of specific molecular motions. In addition, DS indicates a third peak related with a crystal-to-crystal phase transition. Finally, these transitions were correlated with changes in the carrier mobility recorded in thin films and published recently.

Parametric Analysis of Effective Material Properties of Thickness-Shear Piezoelectric Macro-Fibre Composites

A previous study on the characterization of effective material properties of a d(15) thickness-shear piezoelectric Macro-Fibre Composite (MFC) made of seven layers (Kapton, Acrylic, Electrode, Piezoceramic Fibre and Epoxy Composite, Electrode, Acrylic, Kapton) using a finite element homogenization method has shown that the packaging reduces significantly the shear stiffness of the piezoceramic material and, thus, leads to significantly smaller effective electromechanical coupling coefficient k(15) and piezoelectric stress constant e(15) when compared to the piezoceramic fibre properties. Therefore, the main objective of this work is to perform a parametric analysis in which the effect of the variations of fibre volume fraction, Epoxy elastic modulus, electrode thickness and active layer thickness on the MFC effective material properties is evaluated. Results indicate that an effective d(15) MFC should use relatively thick fibres having relatively high shear modulus and relatively stiff epoxy filler. On the other hand, the electrode thickness does not affect significantly the MFC performance.

Parametric analysis of effective material properties of thickness-shear piezoelectric macro-fibre composites

A previous study on the characterization of effective material properties of a d15 thickness-shear piezoelectric Macro-Fibre Composite (MFC) made of seven layers (Kapton, Acrylic, Electrode, Piezoceramic Fibre and Epoxy Composite, Electrode, Acrylic, Kapton) using a finite element homogenization method has shown that the packaging reduces significantly the shear stiffness of the piezoceramic material and, thus, leads to significantly smaller effective electromechanical coupling coefficient k15 and piezoelectric stress constant e15 when compared to the piezoceramic fibre properties. Therefore, the main objective of this work is to perform a parametric analysis in which the effect of the variations of fibre volume fraction, Epoxy elastic modulus, electrode thickness and active layer thickness on the MFC effective material properties is evaluated. Results indicate that an effective d15 MFC should use relatively thick fibres having relatively high shear modulus and relatively stiff epoxy filler. On the other hand, the electrode thickness does not affect significantly the MFC performance.

Synthesis and photovoltaic performance of a fluorene-bithiophene copolymer

We present the synthesis of a copolymer structure, poly(9,9′-n-di-hexyl-2,7-fluorene-alt-2,5- bithiophene), referred to herein as LaPPS43, and its physico-chemical characterization. Thin films of this polymer mixed with phenyl-C61-butyric acid methyl ester (PCBM) were used as the active layer in photovoltaic devices using the ITO/PEDOT:PSS/LaPPS43: PCBM/Ca/Al bulk heterojunction structure. The devices of different active layer thicknesses were electrically studied using J-V curves and the Photo-Celiv technique. The obtained results show that LaPPS43 combined with PCBM is a promising system for photovoltaic devices. Device performance is discussed in terms of the mean drift distance x for charge carriers. Photophysical data showed that the excitonic species are all localized in the aggregated forms. The mechanism of exciton formation and dissociation is also discussed.

Contribution of the cashew gum (Anacardium occidentale L.) for development of layer-by-layer films with potential application in nanobiomedical devices

The search for bioactive molecules to be employed as recognition elements in biosensors has stimulated researchers to pore over the rich Brazilian biodiversity. In this sense, we introduce the use of natural cashew gum (Anacardium occidentale L) as an active biomaterial to be used in the form of layer-by-layer films, in conjunction with phthalocyanines, which were tested as electrochemical sensors for dopamine detection. We investigated the effects of chemical composition of cashew gum from two different regions of Brazil (Piaui and Ceara states) on the physico-chemical characteristics of these nanostructures. The morphology of the nanostructures containing cashew gum was studied by atomic force microscopy which indicates that smooth films punctuated by globular features were formed that showed low roughness values. The results indicate that, independent of the origin, cashew gum stands out as an excellent film forming material with potential application in nanobiomedical devices as electrochemical sensors. (c) 2012 Elsevier B.V. All rights reserved.

Influence of the deposition parameters on the morphology and electrical conductivity of PANI/PSS self-assembled films

The influence of deposition parameters, namely polymer concentration and pH of the deposition solution, cleaning, and drying steps on the morphology and electrical characteristics of polyaniline and sulfonated polystyrene (PANI/PSS) nanostructured films deposited by the self-assembly technique is evaluated by UV-Vis spectroscopy, optical and atomic force microscopy, and electrical resistance measurements. It is found that stirring the cleaning solution during the cleaning step is crucial for obtaining homogenous films. Stirring of the cleaning solution also influences the amount of PANI adsorbed in the films. In this regard, the drying process seems to be less critical since PANI amount and film thickness are similar in films dried with N-2 flow or with an absorbent tissue. It is observed, however, that drying with N-2 flow results in rougher films. As an additional point, an assessment of the influence of the deposition method (manual versus mechanical) on the film characteristics was carried out. A significant difference on the amount of PANI and film thickness between films prepared by different human operators and by a homemade mechanical device was observed. The variability in film thickness and PANI adsorbed amount is smaller in films mechanically assembled. (c) 2007 Elsevier B.V. All rights reserved.

Suppression of vortex-induced vibration using moving surface boundary-layer control

Experimental results of flow around a circular cylinder with moving surface boundary-layer control (MSBC) are presented. Two small rotating cylinders strategically located inject momentum in the boundary layer of the cylinder, which delays the separation of the boundary layer. As a consequence, the wake becomes narrower and the fluctuating transverse velocity is reduced, resulting in a recirculation free region that prevents the vortex formation. The control parameter is the ratio between the tangential velocity of the moving surface and the flow velocity (U-c/U). The main advantage of the MSBC is the possibility of combining the suppression of vortex-induced vibration (VIV) and drag reduction. The experimental tests are preformed at a circulating water channel facility and the circular cylinders are mounted on a low-damping air bearing base with one degree-of-freedom in the transverse direction of the channel flow. The mass ratio is 1.8. The Reynolds number ranges from 1600 to 7500, the reduced velocity varies up to 17, and the control parameter interval is U-c/U = 5-10. A significant decreasing in the maximum amplitude of oscillation for the cylinder with MSBC is observed. Drag measurements are obtained for statically mounted cylinders with and without MSBC. The use of the flow control results in a mean drag reduction at U-c/U = 5 of almost 60% compared to the plain cylinder. PIV velocity fields of the wake of static cylinders are measured at Re = 3000. The results show that the wake is highly organized and narrower compared to the one observed in cylinders without control. The calculation of the total variance of the fluctuating transverse velocity in the wake region allows the introduction of an active closed-loop control. The experimental results are in good agreement with the numerical simulation studies conducted by other researchers for cylinders with MSBC. (C) 2012 Elsevier Ltd. All rights reserved.

Morphology and Anatomy of Stem Mines in Cipocereus minensis (Wender.) Ritter (Cactaceae), an Endemic Species to Eastern Brazil

Plant mines are structures with the form of a cavity caused by consumption of host plant tissue by the insect's miner larvae. Plant mines are more common in leaves, but in Cipocereus minensis, a species in which the leaves are modified spines, the miner activity is restricted to the stem. The aim of this paper was to document the morphological and anatomical differences in the infected and uninfected stems of C. minensis due to the feeding habit of the mining agent. Fresh tissue samples of non-mined and mined young stem of C minensis were collected and examined in transverse sections. We hypothesize that the infection begins following mating when the females scratch the surface of the stem or while they feed on fruits and lay eggs, which subsequently develop into larvae, invading the cactus stem. The insect's miner larvae had mostly consumed the parenchyma tissue towards the center of the stem, and periderm formed along the entire path of the insect. This meristematic tissue or "wound periderm" is a common response for compartmentalization to isolate the damaged tissue, in this case the incubating chamber, in which the eggs will be placed. There were no signs of consumption of vascular tissue in the infested samples, further suggesting a compartmentalized infestation. The nest chamber was found in the stem pith region, with periderm surrounding an insect's miner pupa inside identified as a member of the Cerambycidae. The mining insect depends on a host plant to complete the life cycle; however, the nature of this partnership and the long-term effects of the insect on the plant tissue are unknown. The complex mechanisms by which herbivorous insects control the morphogenesis of the plant host are discussed. We propose that C. minensis has a recognition system to identify insect attack and evaluate the effectiveness of early response triggering compartmentalized defense mechanisms by protecting the injured area with a new layer of periderm.

Morphology and Involution of the Yolk Sac during Early Gestation Bovine (Bos indicus)

Background: The bovine yolk sac derives from visceral endoderm and its development occurs between days 18-23 of gestation. The study of this membrane is important for comparative data and has already been performed in rodents, sheep and in cattle, especially Bos taunts. In species Bos indicus the yolk sac has not quite been studied and is believed that there are morphological differences between these species. The yolk sac undergoes a process of involution and degeneration during embryonic development and none vestige of it is found in late gestation. The period in which occurs the involution of the yolk sac coincides with the period of increased pregnancy loss in cattle, and changes in the morphology of this membrane may indicate the reasons for such high loss rates. Thus, considering that the yolk sac is important for embryonic circulation and metabolic transmission, besides participating actively in the process of cattle placentation, this study aimed characterize morphologically the involution of the bovine yolk sac. Materials, Methods & Results: The early gestational period was determined between days 20 and 70 post-insemination (p.i), according to the exterior characteristics of embryo/fetus. For macroscopic analyzes the uterus was dissected to expose the fetal membranes and subsequently the embryo/fetus was photographed. The samples were fixed for light microscopy and transmission electron microscopy. The yolk sac that emerges from the ventral part of the embryo was prominent and composed by a central part with two thin peripheral projections of different lengths. The bovine yolk sac with about 9 cm on day 25 p. i. of pregnancy permanently decreased its total length during this study. Histologically, the yolk sac is composed of three cell layers: the mesothelium, the mesenchyme and the endoderm. In mesenchyme are found blood islets. In the endoderm are formed cells invaginations toward the mesenchyme originating small canaliculi. The ultrastructure of yolk cells presented many mitochondria, rough endoplasmic reticulum, vesicles, euchromatin and the presence of two nucleoli, Discussion: The real first blood circulation in the bovine is attached with the development of yolk sac, differently from other membranes, such as the corium, that does not present evidence of vascularization by the age of 20-30 days. The erythroblasts found in the yolk sac are related to vasculogenesis and the process of differentiation of blood cells during the erythropoiesis. It could be observed on the histology of the yolk sac, in embryos of 30-50 days old, the presence of canaliculi and small folds of the epithelium. The canaliculi collapse is associated with the degeneration of the endoderm wall of the yolk sac. The organelles present in the endoderm cells of the yolk sac are associated with the function of protein metabolism and in the exchange of substances between the mesenchyme and the mesothelium, For these findings, could be observed that the yolk sac epithelium is found active until the 50th day of gestation, and thereafter regresses. However, remnants of this membrane may be present until the 70th day, These features may represent a presence of an active chorionvitelline placenta in this period responsible for the maintenance of pregnancy whereas the chorioallantoic placenta is not definitively established.

Debris and smear removal in flattened root canals after use of different irrigant agitation protocols

Scanning electron microscopy (SEM) can be used to analyze the presence of debris and smear layer on the internal walls of root canal. This study evaluated the debris and smear removal in flattened root canals using SEM after use of different irrigant agitation protocols. Fifty mandibular incisors were distributed into five groups (n = 10) according to the irrigant agitation protocol used during chemomechanical preparation: conventional syringe irrigation with NaviTip needle (no activation), active scrubbing of irrigant with brush-covered NaviTip FX needle, manual dynamic irrigation, continuous passive ultrasonic irrigation, and apical negative pressure irrigation (EndoVac system). Canals were irrigated with 5 mL of 2.5% NaOCl at each change of instrument and received a final flush with 17% EDTA for 1 min. After instrumentation, the roots were split longitudinally and SEM micrographs at x 100 and x 1,000 were taken to evaluate the amount of debris and smear layer, respectively, in each third. Data were analyzed by KruskalWallis and Dunn's post-hoc tests (a = 5%). Manual dynamic activation left significantly (p < 0.05) more debris inside the canals than the other protocols, while ultrasonic irrigation and EndoVac were the most effective (p < 0.05) for debris removal. Regarding the removal of smear layer, there was no statistically significant difference (p > 0.05) either among the irrigant agitation protocols or between the protocolcanal third interactions. Although none of the irrigant agitation protocols completely removed debris and smear layer from flattened root canals, the machine-assisted agitation systems (ultrasound and EndoVac) removed more debris than the manual techniques. Microsc. Res. Tech. 75:781790, 2012. (C) 2011 Wiley Periodicals, Inc.

Effects of Natural Radiation, Photosynthetically Active Radiation and Artificial Ultraviolet Radiation-B on the Chloroplast Organization and Metabolism of Porphyra acanthophora var. brasiliensis (Rhodophyta, Bangiales)

We undertook a study of Porphyra acanthophora var. brasiliensis to determine its responses under ambient conditions, photosynthetically active radiation (PAR), and PAR+UVBR (ultraviolet radiation-B) treatment, focusing on changes in ultrastructure, and cytochemistry. Accordingly, control ambient samples were collected in the field, and two different treatments were performed in the laboratory. Plants were exposed to PAR at 60 mu mol photons m(-2) s(-1) and PAR+UVBR at 0.35 W m(-2) for 3 h per day during 21 days of in vitro cultivation. Confocal laser scanning microscopy analysis of the vegetative cells showed single stellate chloroplast in ambient and PAR samples, but in PAR+UVBR-exposed plants, the chloroplast showed alterations in the number and form of arms. Under PAR+UVBR treatment, the thylakoids of the chloroplasts were disrupted, and an increase in the number of plastoglobuli was observed, in addition to mitochondria, which appeared with irregular, disrupted morphology compared to ambient and PAR samples. After UVBR exposure, the formation of carpospores was also observed. Plants under ambient conditions, as well as those treated with PAR and PAR+UVBR, all showed different concentrations of enzymatic response, including glutathione peroxidase and reductase activity. In summary, the present study demonstrates that P. acanthophora var. brasiliensis shows the activation of distinct mechanisms against natural radiation, PAR and PAR+UVBR.