Highly efficient green light emitting polyfluorene incorporated with 4-diphenylamino-1,8-naphthalimide as green dopant

The dopant/host methodology, which enables efficient tuning of emission color and enhancement of the electroluminescence (EL) efficiency of organic light emitting diodes (OLEDs) based on small molecules, is applied to the design and synthesis of highly efficient green light emitting polymers. Highly efficient green light emitting polymers were obtained by covalently attaching just 0.3-1.0 mol% of a green dopant, 4-(N,N-diphenyl) amino-1,8-naphthaliniide (DPAN), to the pendant chain of polyfluorene (the host). The polymers emit green light and exhibit a high photoluminescence (PL) quantum yield of Lip to 0.96 in solid films, which is attributed to the energy transfer from the polyfluorene host to the DPAN dopant unit. Single layer devices (device configuration: ITO/PEDOT/Polymer/Ca/Al) of the polymers exhibit a turn on voltage of 4.8 V, luminance efficiency of 7.43 cd A(-1), power efficiency of 2.96 lm W-1 and CIE coordinates at (0.26, 0.58). The good device performance can be attributed to the energy transfer and charge trapping from the polyfluorene host to the DPAN dopant unit as well as the molecular dispersion of the dopant in the host.

Highly efficient red electroluminescence from stacked organic light-emitting devices based on a europium complex

Stacked organic light-emitting devices (OLEDs) based on a europium complex Eu(TTA)(3) (Tmphen) (TTA = thenoyltrifluoroacetone,Tmphen = 3,4,7,8-tetramethyl-1,10-phenanthroline) were fabricated. In this stacked OLEDs, Li:BCP/V2O5 was used the intermediate charge generation layer sandwiched between two identical emissive units consisting of TPD/CBP:DCJTB:Eu(TTA)(3)(Tmphen)/BCP. As expected, the brightness and electroluminescent (EL) current efficiency were approximately enhanced by double times that of conventional single-unit devices. The stacked OLEDs showed the maximum luminance up to 3000 cd/m(2) at a current density of 190 mA/cm(2) and a current efficiency of 14.5 cd/A at a current density of 0.08 mA/cm(2). At the brightness of 100 cd/m(2), the current efficiency reached 10 cd/A at a current density of 1.6 mA/cm2.

Novel PPV-based light-emitting copolymers containing triazole moiety

Two new light-emitting PPV-based copolymers bearing electron-withdrawing triazole unit in the main chain have been synthesized by Wittig reaction between triazole diphosphonium salt and the corresponding dialdehyde monomers, respectively. Their optical and physical properties are characterized by UV-vis, photoluminescence (PL), TGA and DSC. The resulting copolymers are highly soluble in common organic solvents and have high Tg and Td values. They show blue-greenish fluorescence in solution (lambda(max) 502 and 508 nm) and green fluorescence in the solid state (lambda(max) 520 and 526 nm), respectively.

Polymer light-emitting diodes based on a bipolar transporting luminescent polymer

A soluble electroluminescent polymer containing hole-deficient triphenylamine and electron-deficient oxadiazole units in the main chains has been designed and studied. The design is based on the consideration that the triphenylamine group possesses good hole-transporting property and the oxadiazole unit is known to be of electron-transporting character. Because of the good bipolar transporting performance, the brightness and electroluminescent efficiency are significantly improved and the turn-on voltage is reduced compared with a similar polymer without the electron-deficient oxadiazole units in the main chains. For a device with configuration ITO/PEDOT/polymer/CsF/Al, a maximum brightness of 3600 cd m(-2) and a maximum luminescent efficiency of 0.65 cd A(-1) (quantum efficiency of 0.3%) were obtained in the polymer with oxadiazole units, about 15 times brighter and 15 times more efficient than the corresponding polymer without oxadiazole units.

HOEK UNIT C (Y)

Light brown sediment with mainly small clasts. The clast shape ranges from sub-angular to sub-rounded. Lineations are abundant throughout the sample. Edge-to-edge grain crushing, as well as crushed grains, can also be seen.

HOEK UNIT C (Z) B3

Light brown sediment with clasts ranging from small to medium in size. The clast shape ranges from sub-angular to rounded. Lineations and edge-to-edge grain crushing can mainly be seen in this sample. There are also a few examples of grain stacking and crushed grains.

HOEK UNIT C 81

Light brown sediment with clast sizes ranging from small to medium. Clast shape ranges from sub-angular to sub-rounded. Lineations are common throughout the sample. Minor amounts of edge-to-edge grain crushing can also be seen.

Family members' perceptions of nurse caring behaviours in the intensive care unit

La présence de membres de la famille dans les milieux de soins critiques a augmentée graduellement au cours des dernières années. La présente recherche visait à décrire la perception que les membres de la famille avait eu à l’égard des comportements de caring des infirmières lors de leur visite aux soins intensifs. Plus spécifiquement, ce projet avait pour but d’explorer les différences entre les perceptions de membres de la famille dont le proche était hospitalisé pour une blessure traumatique versus une maladie grave non-traumatique. Les différences ont aussi été examinées selon certaines caractéristiques personnelles d’un membre de la famille soit leur genre, leur expérience antérieure de visites aux soins intensifs, leur âge et leur perception de la gravité du problème de santé de leur proche. Le cadre de référence de cette étude était basé sur les facteurs caratifs proposés par Watson (1985). L’importance et la satisfaction des membres de la famille à l’égard des comportements de caring de la part des infirmières ont été mesurées par les versions française et anglaise adaptées du Caring Behaviors Assessment (CBA) (Cronin & Harrison, 1988). Les données ont été analysées en utilisant les techniques d’analyse MANOVA et des tests de corrélation de Pearson. En général, les résultats indiquent que les membres de la famille rapportent des degrés d’importance et de satisfaction similaires selon que leur proche était hospitalisé pour une blessure traumatique ou une maladie grave non-traumatique. Peu de différences émergent selon les caractéristiques personnelles des membres de la famille. Un coefficient de corrélation significatif (0.36, p = 0.012) existe entre la perception des membres de la famille de la gravité du problème de santé, et l’importance de la dimension ‘réponses aux besoins’. Par ailleurs, les comportements de caring regroupés dans la dimension ‘réponses aux besoins’ ont été perçus comme étant les plus importants et les membres de familles étaient très satisfaits des comportements de caring des infirmières. Cette étude fournit des pistes pour l’enseignement, la clinique et la recherche et met en lumière la perception des membres de la famille des soins infirmiers humains chez des proches hospitalisés dans une unité de soins intensifs.

Étude de la fonction anti-apoptotique de la sous-unité R1 de la ribonucléotide réductase des virus de l’herpès simplex

L’élimination des cellules infectées par apoptose constitue un mécanisme de défense antivirale. Les virus de l’herpès simplex (HSV) de type 1 et 2 encodent des facteurs qui inhibent l’apoptose induite par la réponse antivirale. La sous-unité R1 de la ribonucléotide réductase d’HSV-2 (ICP10) possède une fonction anti-apoptotique qui protège les cellules épithéliales de l’apoptose induite par les récepteurs de mort en agissant en amont ou au niveau de l’activation de la procaspase-8. Puisqu’une infection avec un mutant HSV-1 déficient pour la R1 diminue la résistance des cellules infectées vis à vis du TNFα, il a été suggéré que la R1 d’HSV-1 (ICP6) pourrait posséder une fonction anti-apoptotique. Le but principal de cette thèse est d’étudier le mécanisme et le potentiel de la fonction anti-apoptotique de la R1 d’HSV-1 et de la R1 d'HSV-2. Dans une première étude, nous avons investigué le mécanisme de la fonction anti-apoptotique de la R1 d’HSV en utilisant le TNFα et le FasL, deux inducteurs des récepteurs de mort impliqués dans la réponse immune anti-HSV. Cette étude a permis d’obtenir trois principaux résultats concernant la fonction anti-apoptotique de la R1 d’HSV. Premièrement, la R1 d’HSV-1 inhibe l’apoptose induite par le TNFα et par le FasL aussi efficacement que la R1 d’HSV-2. Deuxièmement, la R1 d’HSV-1 est essentielle à l’inhibition de l’apoptose induite par le FasL. Troisièmement, la R1 d’HSV interagit constitutivement avec la procaspase-8 d’une manière qui inhibe la dimérisation et donc l’activation de la caspase-8. Ces résultats suggèrent qu’en plus d’inhiber l’apoptose induite par les récepteurs de mort la R1 d’HSV peut prévenir l’activation de la caspase-8 induite par d’autres stimuli pro-apoptotiques. Les ARN double-brins (ARNdb) constituant un intermédiaire de la transcription du génome des HSV et activant l’apoptose par une voie dépendante de la caspase-8, nous avons testé dans une seconde étude l’impact de la R1 d’HSV sur l’apoptose induite par l’acide polyriboinosinique : polyribocytidylique (poly(I:C)), un analogue synthétique des ARNdb. Ces travaux ont montré qu’une infection avec les HSV protège les cellules épithéliales de l’apoptose induite par le poly(I:C). La R1 d’HSV-1 joue un rôle majeur dans l’inhibition de l’activation de la caspase-8 induite par le poly(I:C). La R1 d’HSV interagit non seulement avec la procaspase-8 mais aussi avec RIP1 (receptor interacting protein 1). En interagissant avec RIP1, la R1 d’HSV-2 inhibe l’interaction entre RIP1 et TRIF (Toll/interleukine-1 receptor-domain-containing adapter-inducing interferon β), l’adaptateur du Toll-like receptor 3 qui est un détecteur d’ARNdb , laquelle est essentielle pour signaler l’apoptose induite par le poly(I:C) extracellulaire et la surexpression de TRIF. Ces travaux démontrent la capacité de la R1 d’HSV à inhiber l’apoptose induite par divers stimuli et ils ont permis de déterminer le mécanisme de l’activité anti-apoptotique de la R1 d’HSV. Très tôt durant l’infection, cFLIP, un inhibiteur cellulaire de la caspase-8, est dégradé alors que la R1 d’HSV s’accumule de manière concomitante. En interagissant avec la procapsase-8 et RIP1, la R1 d’HSV se comporte comme un inhibiteur viral de l’activation de la procaspase-8 inhibant l’apoptose induite par les récepteurs de mort et les détecteurs aux ARNdb.

Redox control of light-induced charge separation in a transition metal cluster: photochemistry of a methyl viologen-substituted [Os-3(CO)10(a-diimine)] cluster

Sub)picosecond transient absorption (TA) and time-resolved infrared (TRIR) spectra of the cluster [OS3(CO)(10-) (AcPy-MV)](2+) (the clication AcPy-MV = Acpy-MV2+ = [2-pyridylacetimine-N-(2-(1'-methyl-4,4'-bipyridine-1,1'-diium-1-yl) ethyl)] (PF6)(2)) (1(2+)) reveal that photoinduced electron transfer to the electron-accepting 4,4'-bipyridine-1,1'diium (MV2+) moiety competes with the fast relaxation of the initially populated sigmapi* excited state of the cluster to the ground state and/or cleavage of an Os-Os bond. The TA spectra of cluster 12 in acetone, obtained by irradiation into its lowest-energy absorption band, show the characteristic absorptions of the one-electron-reduced MV*(+) unit at 400 and 615 nm, in accordance with population of a charge-separated (CS) state in which a cluster-core electron has been transferred to the lowest pi* orbital of the remote MV2+ unit. This assignment is confirmed by picosecond TRIR spectra that show a large shift of the pilot highest-frequency nu(CO) band of 1(2+) by ca. +40 cm(-1), reflecting the photooxidation of the cluster core. The CS state is populated via fast (4.2 x 10(11) s(-1)) and efficient (88%) oxidative quenching of the optically populated sigmapi* excited state and decays biexponentially with lifetimes of 38 and 166 ps (1:2:1 ratio) with a complete regeneration of the parent cluster. About 12% of the cluster molecules in the sigmapi* excited state form long-lived open-core biradicals. In strongly coordinating acetonitrile, however, the cluster core-to-MV2+ electron transfer in cluster 12+ results in the irreversible formation of secondary photoproducts with a photooxidized cluster core. The photochemical behavior of the [Os-3(CO)(10)(alpha-diimine-MV)](2+) (donor-acceptor) dyad can be controlled by an externally applied electronic bias. Electrochemical one-electron reduction of the MV2+ moiety prior to the irradiation reduces its electron-accepting character to such an extent that the photoinduced electron transfer to MV*+ is no longer feasible. Instead, the irradiation of reduced cluster 1(.)+ results in the reversible formation of an open-core zwitterion, the ultimate photoproduct also observed upon irradiation of related nonsubstituted clusters [Os-3(CO)(10)(alpha-diimine)] in strongly coordinating solvents such as acetonitrile.

Changes on degree of conversion of dual-cure luting light-cured with blue LED

The indirect adhesive procedures constitute recently a substantial portion of contemporary esthetic restorative treatments. The resin cements have been used to bond tooth substrate and restorative materials. Due to recently introduction of the self-bonding resin luting cement based on a new monomer, filler and initiation technology has become important to study the degree of conversion of these new materials. In the present work the polymerization reaction and the filler content of dual-cured dental resin cements were studied by means of infra-red spectroscopy (FT-IR) and thermogravimetry (TG). Twenty specimens were made in a metallic mold (8 mm diameter x 1 mm thick) from each of 2 cements, PanaviaA (R) F2.0 (Kuraray) and RelyX (TM) Unicem Applicap (3M/ESPE). Each specimen was cured with blue LED with power density of 500 mW/cm(2) for 30 s. Immediately after curing, 24 and 48 h, and 7 days DC was determined. For each time interval 5 specimens were pulverized, pressed with KBr and analyzed with FT-IR. The TG measurements were performed in Netzsch TG 209 under oxygen atmosphere and heating rate of 10A degrees C/min from 25 to 700A degrees C. A two-way ANOVA showed DC (%) mean values statistically significance differences between two cements (p < 0.05). The Tukey`s test showed no significant difference only for the 24 and 48 h after light irradiation for both resin cements (p > 0.05). The Relx-Y (TM) Unicem mean values were significantly higher than PanaviaA (R) F 2.0. The degree of conversion means values increasing with the storage time and the filler content showed similar for both resin cements.

Influence of light guide tip used in the photo-activation on degree of conversion and hardness of one nanofilled dental composite

The aim of this study was to evaluate the degree of conversion and hardness of a dental composite resin Filtek (TM) Z-350 (3M ESPE, Dental Products St. Paul, MN) photo-activated for 20 s of irradiation time with two different light guide tips, metal and polymer, coupled on blue LED Ultraled LCU (Dabi Atlante, SP, Brazil). With the metal light tip, power density was of 352 and with the polymer was of 456 mW/cm(2), respectively. Five samples (4 mm in diameter and 2mm in thickness-ISO 4049), were made for each Group evaluated. The measurements for DC (%) were made in a Nexus-470 FT-IR, Thermo Nicolet, E.U.A. Spectroscopy (FTIR). Spectra for both uncured and cured samples were analyzed using an accessory of reflectance diffuse. The measurements were recorded in absorbance operating under the following conditions: 32 scans, 4 cm(-1) resolution, 300-4000 cm(-1) wavelength. The percentage of unreacted carbon double bonds (% C=C) was determined from the ratio of absorbance intensities of aliphatic C=C (peak at 1637 cm(-1)) against internal standard before and after curing of the sample: aromatic C-C (peak at 1610 cm(-1)). The Vickers hardness measurements (top and bottom surfaces) were performed in a universal testing machine (Buehler MMT-3 digital microhardness tester Lake Bluff, Illinois USA). A 50 gf load was used and the indenter with a dwell time of 30 s. The data were submitted to the test t Student at significance level of 5%. The mean values of degree of conversion for the polymer and metal light guide tip no were statistically different (p = 0.8389). The hardness mean values were no statistically significant different among the light guide tips (p = 0.6244), however, there was difference between top and bottom surfaces (p < 0.001). The results show that so much the polymer light tip as the metal light tip can be used for the photo-activation, probably for the low quality of the light guide tip metal.

Composite resin color stability: influence of light sources and immersion media

Objective: This study evaluated the influence of light sources and immersion media on the color stability of a nanofilled composite resin. Material and Methods: Conventional halogen, high-power-density halogen and high-power-density light-emitting diode (LED) units were used. There were 4 immersion media: coffee, tea, Coke (R) and artificial saliva. A total of 180 specimens (10 mm x 2 mm) were prepared, immersed in artificial saliva for 24 h at 37 +/- 1 degrees C, and had their initial color measured with a spectrophotometer according to the CIELab system. Then, the specimens were immersed in the 4 media during 60 days. Data from the color change and luminosity were collected and subjected to statistical analysis by the Kruskall-Wallis test (p<0.05). For immersion time, the data were subjected to two-way ANOVA test and Fisher's test (p<0.05). Results: High-power-density LED (Delta E=1.91) promoted similar color stability of the composite resin to that of the tested halogen curing units (Jet Lite 4000 plus - Delta E=2.05; XL 3000 - Delta E=2.28). Coffee (Delta E=8.40; Delta L=-5.21) showed the highest influence on color stability of the studied composite resin. Conclusion: There was no significant difference in color stability regardless of the light sources, and coffee was the immersion medium that promoted the highest color changes on the tested composite resin.

Influence of light guide tip used in the photo-activation on degree of conversion and hardness of one nanofilled dental composite

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

First principles calculations on the origin of violet-blue and green light photoluminescence emission in SrZrO3 and SrTiO3 perovskites

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)