Antibacterial fibers impregnated with mycosynthetized AgNPs for control of Pectobacterium carotovorum.

Using biopolymers functionalized with antibacterial agents to manufacture active packaging is a clean alternative to mitigate food losses due to postharvest plant diseases. In this study, two mycosynthetized AgNPs impregnation methodologies on cotton (cationization and in situ biochemical reduction) were used to obtain the antibacterial fibers (A-AgNPs-C and A-AgNPs-IBR), which, in addition to being characterized by SEM-EDX, XRD, were evaluated as antibacterial materials. The cotton fibers showed growth inhibition of Pectobacterium carotovorum at 48 h. The reuse tests of these cotton fibers showed that the two types of fibers could have up to three successive uses without losing their effectiveness, regardless of the impregnation method used. Is important to highlight that the retention tests indicated that the AgNPs remain attached to the A-AgNPs-C and A-AgNPs-IBR fibers after several successive washes. Finally, the mycosynthesized AgNPs were also impregnated on fique fibers (Fique-AgNPs) by cationization to obtain little antibacterial sacks. Nanostructured materials that in in vivo tests on potatoes showed only 7.8 % of affectation, while the tubers stored in the traditional sacks had an affectation of 25 %. This immobilization of AgNPs in natural fibers will allow the development of a nanobiotechnological application in the storage and transport of potatoes, after performing some additional cytotoxicity tests to guarantee its safety.

Determination of changes in physicochemical and sensory characteristics of purple passion fruit with the application of different packaging systems, including an ethylene scavenger additive.

To achieve a suitable packaging configuration, it is important first to determine the physicochemical characteristics related to the packaged product. In this study, the physicochemical characterization of fresh purple passion fruits of three different ripening stages was carried out to determine key variables for the packaging, such as O2 consumption and CO2 -ethylene production rates. Subsequently, intermediate-ripe fruits were packaged for 21 days at 6 °C under three packaging conditions: Xtend® perforated bags, low-density polyethylene (LDPE) bags, and LDPE bags with a novel ethylene scavenger active additive (ESAA). It was observed that an equilibrium modified atmosphere was formed in the packages. For the Xtend® bags, the highest values of O2 (yo2  = 0.184 to 0.192) and lowest of CO2 (yco2  = 0.033 to 0.041) were reached, whereas for the LDPE bags with ESAA these values were moderate. In the case of ethylene, the LDPE bags showed the highest levels in the headspace (26 to 31 ppm), whereas the lowest levels were obtained in the LDPE bags with additive (2 to 4 ppm). These levels resulted in a delay in the ripening of the fruits during storage, which was verified through a sensory acceptability test that was carried out on the juice extracted from the fruits. In this sensory test, panelists identified similar characteristics between the fruits packaged with ESAA and the Xtend® bags, regarding the control fruits. The LDPE bags with the ethylene scavenger performed satisfactorily and can considerably delay the ripening, which may result in longer shelf life and conservation of fresh purple passion fruits. PRACTICAL APPLICATION: This work presents a novel packaging proposal that reduces oxygen and ethylene levels in contact with purple passion fruits. Our proposed active packaging can be used to increase the fruit shelf life by improving its conservation conditions throughout the chain of storage, transport, and distribution in the market. With this, it will be possible to reduce the fruit's losses due to senescence and to reduce the substrate consumption by using a more effective packaging system.

Volatile Organic Compounds, Spectral Characterization and Morphology of Ammonium Nitrate Fuel Oil (ANFO) Samples.

Ammonium nitrate fuel oil is an explosive mixture found in most antipersonnel landmines (APL) buried throughout the Colombian territory. During more than 50 years of internal conflict, the Colombian government has found that trained dogs are the most effective method to detect APL. However, the olfactive signature in ANFO is unknown and also if there are differences in detection related to the explosive manufacturing origin. Therefore, this work begins with the analytical validation of the method used to determine ammonia, in its derivatized form as carbamate, released by home-made ANFO using HS-SPME-GC-FID. Once validated, the method was used to identify ammonia and other organic volatile compounds present in ANFO, under laboratory and simulated field conditions. The validation process includes the evaluation of the optimum conditions for the derivation and extraction of butylcarbamate, the determination of the working ranges with linear response in FID, the limits of detection and quantification, the sensitivity, and the precision. The results of the validation established linearity and sensitivity in a concentration between 20 and 120 mg/L, as well as low limits of detection and quantification of 6.4 and 21.4 mg/L, respectively. Also, an intermediate precision of 11% for butylcarbamate with a repeatability of 8%. The validated method showed in real samples of home-made ANFO besides ammonia, the presence of low molecular methylamines, and also exhibited differences in volatile compositions according to the origin. The objective of this work is to offer a reliable analytical methodology for the extraction and analysis of volatile compounds from ANFO.

Spectroscopic and Time-Dependent DFT Study of the Photophysical Properties of Substituted 1,4-Distyrylbenzenes.

In this contribution, we examine the photophysical properties of 15 totally trans-trans 1,4-distyrylbenzene derivatives (DSBs) functionalized with different electron-donating (ED) and electron-withdrawing (EW) groups by experimental and computational methodologies. We use UV-vis and fluorescence spectroscopies to determine the experimental optical properties such as the maximum absorption (λabsexp) and emission (λemexp) wavelengths, the highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) energy gaps (ΔEabsexp), the molar extinction coefficients (ε), the fluorescence quantum yields (Φf), and the fluorescence lifetimes (τ). We also calculate the experimental spontaneous emission decay rate (krexp) and correlate all of these magnitudes to the corresponding calculated properties, maximum absorption (λabscal) and emission (λemcal) wavelengths, vertical transition energies (ΔEabscal), oscillator strength (Fosc), and spontaneous emission decay rate (krcal), obtained by the time-dependent density functional theory method. We analyze the effect of the electronic nature of the substituents on the properties of the DSBs, finding that the ED and EW groups lead to bathochromic shifts. This is consistent with the decrease of ΔE values as the strength of ED and EW substituents increases. We find excellent correlations between calculated and experimental values for λabs, λem, and ΔEabs (r ∼ 0.99-0.95). Additionally, the correlations between the relative ε with Fosc values and the kr values are in good agreement (r ∼ 0.88-0.72) with the experimental properties. Overall, we find that for substituted 1,4-DSBs, computational chemistry is an excellent tool to predict structure-property relationships, which can be useful to forecast the properties of their polymeric analogues, which are usually difficult to determine experimentally.

hIAPP forms toxic oligomers in plasma.

In diabetes, hyperamylinemia contributes to cardiac dysfunction. The interplay between hIAPP, blood glucose and other plasma components is, however, not understood. We show that glucose and LDL interact with hIAPP, resulting in ß-sheet rich oligomers with increased ß-cell toxicity and hemolytic activity, providing mechanistic insights for a direct link between diabetes and cardiovascular diseases.

Synthesis, characterization, X-ray crystal structure and DFT calculations of 4-([2,2':6',2 '' -terpyridin]-4'-yl)phenol / Síntesis, caracterización, estructura cristalina y cálculos DFT para el 4-([2,2':6',2 '' -terpiridin]-4'-il)fenol / Síntese, caracterização, estrutura de cristal e cálculos DFT para o 4-([2,2':6',2 '' -terpiridina]-4'-il)fenol

Abstract The synthesis of new terpyridine (Tpy) derivatives has been subject of extensive research due to its potential as functional materials for solar energy conversion, among other applications. In this contribution, the 4-([2,2':6',2"-terpyndm]-4'-yl)phenol (TpyOH) was synthesized, characterized and studied through several methods, including X-ray crystallography and computational approaches. Single crystal X-ray structure analysis shows that TpyOH is essentially planar, with dihedral angles of about 5.03° between the central pyridinyl and the phenolic ring, and also 6.05 and 12.2° in the terpyridine moiety. In the crystal, molecules are linked by intermolecular hydrogen bonds and through П- П stacking interactions. Using a time dependent density functional theory approach and taking into account bulk solvent effects, the absorption and fluorescence spectra of TpyOH were investigated and compared. The TD-DFT S0→Sn and S1 →S0 transition energies are in good agreement with experimental results. The frontier molecular orbitals analysis showed that the low-energy absorption band has an intraligand charge transfer character (ICT), while the high-energy band is a common feature of П- П* transitions of the Tpy moiety. The S1→S0 emission transition also has an ICT character, with a 90% contribution from the HOMO→LUMO transitions.

Resumen La síntesis de derivados terpiridinicos (Tpy) se ha investigado ampliamente debido a su potencial para la conversión de energía solar En este artículo se sintetizó y caracterizó el 4-([2,2':6',2"-terpiridin]-4'-il)fenol (TpyOH), a través de varias metodologías como la cristalografía de rayos X y herramientas computacionales. El análisis de rayos X de monocristal mostró que el TpyOH es plano, con ángulos diedros de 5,03° entre el piridinilo central y el anillo fenólico, con presencia de ángulos de 6,05 y 12,2° en la porción terpiridínica. En el cristal, las moléculas están unidas por enlaces de hidrógeno intermoleculares y mediante interacciones de apilamiento n-n. Utilizando cálculos DFT dependientes del tiempo (TD-DFT) y teniendo en cuenta el efecto de los disolventes, se investigaron y compararon los espectros de absorción y fluorescencia de TpyOH. Las energías de transición TD-DFT de S0→Sn y S1→S0 concuerdan con los resultados experimentales. El análisis de orbitales moleculares de frontera mostró que la banda de absorción de baja energía corresponde a transferencia de carga intraligando (ICT); mientras que la banda de alta energía es común en las transiciones П-П* del resto Tpy. La emisión debido a la transición S1→S0 corresponde a ICT, con una contribución del 90% proveniente de transiciones HOMO→LUMO.

Resumo A síntese de derivados de terpiridina (Tpy) tem sido estudada devido ao seu potencial para a conversão de energia solar. Nesta contribuição, o 4-([2,2':6',2"- terpindina]-4'-il) fenol (TpyOH) foi sintetizado, caracterizado e estudado por vários métodos A análise de estrutura de raios X de cristal único mostra que o TpyOH é plano, com Ångulos diedros de 5,03 ° entre o piridinilo central e o anel fenólico, e também 6,05 e 12,2 ° na porção de terpiridina No cristal, as moléculas são ligadas por ligações intermoleculares de hidrogênio e através de interações de empilhamento n-n. Usando uma abordagem da teoria funcional da densidade dependente do tempo e levando em consideração os efeitos do solvente em massa, foram investigados e comparados os espectros de absorção e fluorescência do TpyOH As energias de transição TD-DFT S0→Sn e S1→S0 estão de acordo com os resultados experimentais A análise de orbitários moleculares de fronteira mostrou que a banda de absorção de baixa energia possui um caráter de transferência de carga intraligando (TIC), enquanto a banda de alta energia é uma característica comum das transições П-П* da fração Tpy. A transição de emissão S1→S0 também tem um caráter TIC, com uma contribuição de 90% das transições HOMO→LUMO.

Crystal structure of ethyl (E)-2-cyano-3-(thio-phen-2-yl)acrylate: two conformers forming a discrete disorder.

In the title compound, C10H9NO2S, all the non-H atoms, except for the ethyl fragment, lie nearly in the same plane. Despite the mol-ecular planarity, the ethyl fragment presents more than one conformation, giving rise to a discrete disorder, which was modelled with two different crystallographic sites for the eth-oxy O and eth-oxy α-C atoms, with occupancy values of 0.5. In the crystal, the three-dimensional array is mainly directed by C-H⋯(O,N) inter-actions, giving rise to inversion dimers with R22(10) and R22(14) motifs and infinite chains running along the [100] direction.

Oligo p-Phenylenevinylene Derivatives as Electron Transfer Matrices for UV-MALDI.

Phenylenevinylene oligomers (PVs) have outstanding photophysical characteristics for applications in the growing field of organic electronics. Yet, PVs are also versatile molecules, the optical and physicochemical properties of which can be tuned by manipulation of their structure. We report the synthesis, photophysical, and MS characterization of eight PV derivatives with potential value as electron transfer (ET) matrices for UV-MALDI. UV-vis analysis show the presence of strong characteristic absorption bands in the UV region and molar absorptivities at 355 nm similar or higher than those of traditional proton (CHCA) and ET (DCTB) MALDI matrices. Most of the PVs exhibit non-radiative quantum yields (φ) above 0.5, indicating favorable thermal decay. Ionization potential values (IP) for PVs, calculated by the Electron Propagator Theory (EPT), range from 6.88 to 7.96 eV, making these oligomers good candidates as matrices for ET ionization. LDI analysis of PVs shows only the presence of radical cations (M+.) in positive ion mode and absence of clusters, adducts, or protonated species; in addition, M+. threshold energies for PVs are lower than for DCTB. We also tested the performance of four selected PVs as ET MALDI matrices for analytes ranging from porphyrins and phthalocyanines to polyaromatic compounds. Two of the four PVs show S/N enhancement of 1961% to 304% in comparison to LDI, and laser energy thresholds from 0.17 µJ to 0.47 µJ compared to 0.58 µJ for DCTB. The use of PV matrices also results in lower LODs (low fmol range) whereas LDI LODs range from pmol to nmol. Graphical Abstract ᅟ.

Crystal structures of three N-(3-acetyl-phen-yl)quinoline-2-carboxamides.

In the title compounds, N-(5-acetyl-2-methyl-phen-yl)quinoline-2-carboxamide [C19H16N2O2, (I)], N-(5-acetyl-2-bromo-phen-yl)quinoline-2-carboxamide [C18H13BrN2O2, (II)] and N-(5-acetyl-2-ethynylphen-yl)quinoline-2-carboxamide [C20H14N2O2, (III)], the quinoline ring system is essentially planar and forms a dihedral angles of 3.68 (5) (I), 5.59 (7) (II) and 1.87 (6)° (III) with the acetyl-substituted ring. The mol-ecular structures of (I) and (III) each feature an intra-molecular N-H⋯N hydrogen bond, forming an S(5) ring, while in (II) an intra-molecular bifurcated N-H⋯(N,Br) hydrogen bond forms two S(5) rings. In the crystals, weak C-H⋯O hydrogen bonds link mol-ecules of (I) into C(7) chains long [010], mol-ecules of (II) into chains of R22(8) rings along [110] and mol-ecules of (III) into C(8) chains along [010]. In (I), there are no significant π-π stacking inter-actions under 4 Å, but in both (II) and (III), π-π inter-actions link the weak hydrogen-bonded chains into layers parallel to (001) [centroid-centroid disttances of 3.748 (1) Šin (II) and 3.577 (1), 3.784 (1) and 3.780 (1) Šin (III)].

Crystal structure of N-(2-benzoyl-5-ethynylphen-yl)quinoline-2-carboxamide.

In the title compound, C25H16N2O2, the quinoline ring system is essentially planar, with a maximum deviation of 0.030 (1) Å, and forms a dihedral angle of 20.9 (1)° with benzoyl benzene ring. The unsubstituted phenyl ring forms dihedral angles of 52.7 (1)° with the quinoline ring system and 54.1 (1)° with the ethynyl-substituted benzene ring. The mol-ecule contains an intra-molecular bifurcated N-H⋯(O,N) hydrogen bond, forming S(5) and S(6) rings, which may influence the conformation of the mol-ecule. In the crystal, weak C-H⋯O hydrogen bonds link the mol-ecules into a three-dimensional network. In addition, the three-dimensional structure contains π-π stacking inter-actions, with centroid-centroid distances of 3.695 (1) and 3.751 (1) Å.

Nanostructured MnO2 catalyst in E. crassipes (water hyacinth) for indigo carmine degradation / Catalizador de MnO2 nanoestructurado en E. crassipes (jacinto de agua) para la degradación de índigo carmín / Catalisador de MnO2 nanoestruturado em E. crassipes (jacinto da água) para a degradação do índigo carmim

The use of water hyacinth's dried matter (Eichhornia crasippes) as a support matrix for nano-MnO2 and its application for the removal of indigo carmine RIC) was studied. Different pretreatment processes were tested and results indicated that an acid-alkali pretreatment is an efficient method to binding nanoparticles RNPs) to cellulosic matrix. In adittion, the MnO2 NPs were synthesized by sonochemical reduction of MnO4- using different methods Rultrasonic horn system, ultrasonic bath and reaction with ethanol), where the influence of the precursor concentration was observed. The synthesized material was further characterized by ATR-IR, AAS, XRD, SEM, nitrogen isotherms adsorption, EDS, and pHpzc. The IC removal capacity of the nanostructured material, the chemical nature of the degradation products and the effect of various parameters Rtemperature, pH, initial IC concentration, among others) were explored in water samples.

Se estudió el uso de la materia seca del jacinto de agua (Eichhornia crassipes) como matriz-soporte para nano-MnO2 y su eficiencia en la eliminación de índigo carmín RIC). Se ensayaron diferentes procesos de pretratamiento y los resultados indicaron que un tratamiento previo ácido-alcalino es un método eficiente para unir las nanopartículas (NPs) a la matriz celulósica. Así mismo, las NPs de MnO2 se sintetizaron por reducción sonoquímica de MnO4- utilizando diferentes métodos Run sistema emisor de ultrasonido, baño de ultrasonido y reacción convencional con etanol como medio). El material sintetizado se caracterizó por ATR-IR, AAS, DRX, SEM, isotermas de adsorción de nitrógeno, EDS y pHpzc. Se exploró la capacidad de eliminación de IC por parte del material nanoestructurado y la naturaleza química de los productos de degradación en muestras acuosas. Se analizó el efecto de diversos parámetros tales como temperatura, pH, concentración inicial de IC, entre otros.

Foi estudada a utilização de matéria seca de jacinto de água (Eichhornia crassipes) como matriz de suporte para nano-MnO2 e sua aplicação para a remoção de índigo carmine RIC). Diferentes processos de prétratamento foram testados e os resultados indicaram que o prétratamento ácido-álcali é um método eficiente para ligar os NPs à matriz celulósica. Além disso, as NPs de MnO2 foram sintetizados por redução sonoquímica de MnO4- utilizando diferentes métodos (um sistema emissor de ultrassom, banho de ultrassom e a reacção com o etanol). O material sintetizado foi caracterizado por ATR-IR, AAS, DRX, SEM, isotermas de adsorção de nitrogênio, EDS e pHpzc. A facilidade de remoção de IC por o material nanoestruturado e a natureza química da degradação dos produtos foram explorados em amostras aquosas, assim mesmo foi estudado o efeito de vários parâmetros Rtemperatura, pH, concentração inicial de IC e a quantidade de nanocompósito, entre outros).

Aqueous citric acid as green reaction media for the synthesis of octahydroxanthenes / Ácido citrico acuoso como medio de reacción "verde" en la síntesis de octahidroxantenos / Ácido cítrico aquoso como meio de reação verde para a síntese de octaidroxantenos

A simple, convenient and environmentally friendly one-pot procedure for the synthesis of 1,8-dioxo-octahydroxanthenes by the reaction of dimedone and aromatic aldehydes in aqueous citric acid is described. In this green synthetic protocol promoted by the reaction media, the use of any other catalysts and hazardous organic solvents are avoided, making the work up procedure greener and easier. The isolation of the products, obtained in good yields, is readily performed by filtration and crystallization from ethanol when required and the aqueous acidic media can be easily recycled and reused several times without significant loss of catalytic activity.

En esta contribución se describe un procedimiento one-pot simple, conveniente y medioambientalmente amigable para la síntesis de 1,8-dioxo-octahidroxantenos por la reacción de dimedona y aldehídos aromáticos en ácido cítrico acuoso. En este protocolo de síntesis "verde" promovido por el medio de reacción, el uso de otros catalizadores y solventes orgánicos peligrosos es eliminado, haciendo el tratamiento final de la reacción más fácil y "verde". El aislamiento de los productos, obtenidos en buenos rendimientos, se lleva a cabo mediante filtración y recristalización en etanol cuando es necesario, y el medio acuoso ácido puede ser reciclado y reutilizado varias veces sin pérdida significativa de la actividad catalítica.

É descrito um procedimento simples, conveniente, e ambientalmente amigável para a síntese de 1,8-dioxo-octaidroxantenes pela reação de dimedona e aldeídos aromáticos em ácido cítrico aquoso em uma só etapa. Em este protocolo de síntese verde, promovido pelo meio de reação, a utilização de algum outro catalisador e solvente orgânico perigoso é evitada, fazendo o procedimento mais fácil e mais "verde". O isolamento dos produtos, obtidos em grande rendimento, é feito por meio de filtração e cristalização a partir de etanol quando é requerido e o meio aquoso ácido pode ser facilmente recuperado e reutilizado várias vezes sem perder significativamente sua atividade catalítica.

Síntesis de teriiridinas 4-fenil sustituídas y u potencial uso en la determinaación de mercurio / Synthesis of 4-phenyl-substituted-terpyridines and their potentil use for the ddetermination of mercryy / Síntese d substiituídas 4-fenil-terpyridines e sua posterior utilização na determinação de mercúrio

En este trabajo se reporta la síntesis de terpiridinas bajo la metodología de Kröhnke. Las terpiridinas obtenidas por este método, se analizaron por espectroscopia UV-Vis y de fluorescencia, y su respuesta a la presencia de varios metales en diferentes concentraciones fue evaluada para sistemas en solución acuosa. Los resultados muestran que la terpiridina TpyOH es altamente promisoria en la detección de mercurio bajo las condiciones experimentales reportadas.

This paper reports the synthesis of terpyridines using the Kröhnke methodology. The terpyridines obtained by this method were analyzed by UV-Vis spectroscopy and fluorescence, and its response to the presence of various metals at different concentrations was evaluated in aqueous systems. The results show that the terpyridine TpyOH is highly promising for the detection of mercury under the experimental conditions reported.

Este trabalho relata a síntese de terpyridines baixo a metodologia de Kröhnke. Os terpyridines obtidos por este método foram analisadas por espectroscopia UV- Vis e de fluorescência, e a sua resposta à presença de vários metais em diferentes concentrações foi avaliada em sistemas aquosos. Os resultados mostram que o terpyridine TpyOH é altamente promissor para a detecção de mercúrio sob as condições experimentais relatados.

Photoinduced energy transfer in bichromophoric pyrene-PPV oligomer systems: the role of flexible donor-acceptor bridges.

In this contribution, we report on the electronic energy transfer dynamics of bichromophoric systems incorporating two pyrene chromophores tethered by variable-length flexible alkyloxy chains to p-phenylenevinylene oligomers. These were studied using UV-vis absorption and both steady state and time-resolved fluorescence spectroscopy. Time-resolved emission measurements showed an efficient photoinduced energy transfer process in all the multichromophoric systems, which occurs on the time scale of tens of picoseconds after excitation at 265 nm. The energy transfer process is especially efficient in systems where the linker is formed by eight atoms (up to k(ET) ≈ 2.7 × 10(10) s(-1)), which, despite not being the shortest bridge studied, allows the approach of the donor and acceptor chromophores due to an appropriate number of flexible single bonds. Using Förster theory, we calculated the donor-acceptor distance in each triad from the experimental energy transfer rate, finding them to be in the range 8.8-10 Å.

Desarrollo de uaa película polimèrica con propiedades antiempañantes / Developmentof a polymeric film with anti-foggfng properties / Desenvolvimentodde uma película polimérica com propriedades de antiembaciamento

En la búsqueda de una película polimérica con óptimas propiedades antiempañantes se seleccionó como matriz polimérica polietileno de baja densidad (LDPE), a la cual se incorporaron por extrusión uno de los siguientes aditivos: polisorbato 80, oleato de sorbitán, monooleato de glicerol y mezcla de glicéridos, cada uno a 3 concentraciones. Para evaluar la eficiencia antiempañante de los empaques se realizaron medidas de tensión superficial, ángulos de contacto, medidas de transmisión de luz y pruebas cualitativas de empañamiento en frío. Los resultados sugieren que la película con mejores propiedades antiempañantes es la que contiene oleato de sorbitán al 1%.

In search of a film with optimal antifogging properties, low density polyethylene (LDPE) was selected as polymeric matrix, and one of the following four additives were incorporated into the film by an extrusion process: polysorbate 80, sorbitan oleate, glycerol monooleate and glyceride mixture, each of them in 3 different concentrations. Measures of surface tension, light transmission, contact angles, and qualitative cold fogging test were made to assess the efficiency of fog resistant in all packages. The results suggest that the film with sorbitan oleate (1%) presents the best antifogging properties.

Na procura de uma película polimèrica com ótimas propriedades antiembaciamento, selecionou-se como matriz polimèrica polietileno de baixa densidade (LDPE) e, através de uma extrusão, incorporou-se um dos seguintes os aditivos polisorbarto 80, oleato de sorbitan, mono-oleato de glicerol e mistura de glicerídeos cada um em três concentrações diferentes. Para avaliar a eficiência antiembaciamento das películas se realizaram as medidas de tensão superficial, ângulos de contato, medidas de transmissão de luz e provas qualitativas de antiembaciamento em frio. Os resultados sugerem que a película que contèm o oleato de sorbitan 1% tem as melhores propriedades antiembaciamento.

Rendimiento cuáttico de fluorescencia en sistemas fenilvinilideno / Fluorescence qanntum yieldin phenylenevinylene systmms / Rendimieto quanttico de fluorescencia em sistemas fenilvinilidenos

En el presente trabajo se reporta la síntesis y caracterización optoelectrónica de tres sistemas fenilvinilideno con sustituyentes electrodonores tipo alcoxilo (-OR). Los sistemas fueron obtenidos por medio de la reacción de acoplamiento de Heck, con rendimientos superiores a 95%, una conjugación de configuración totalmente trans y con altos rendimientos cuánticos de fluorescencia de color verde-azul. La gran estereoselectividad de la metodología de síntesis utilizada se ve reflejada en la obtención de rendimientos cuánticos superiores a los reportados para sistemas fenilvinilideno de estructuras químicas similares, lo cual hace de estos sistemas fenilvinilideno estereoselectivos, materiales de alto atractivo comercial dentro de las nacientes tecnologías de la electrónica de polímeros.

In this paper, we report the synthesis and optoelectronic characterization of three phenylene vinylene systems with electron-donor substituents (alcoxide type, -OR). The systems were obtained by Heck cross-coupling reaction, with yields over 95%, pure trans configuration conjugation, and high fluorescent quantum yields of blue-green color. The high stereoselectivity of the synthesis used is shown by obtaining fluorescence quantum yields higher than similar phenylene vinylene systems reported in literature, which makes these systems very attractive materials for the emerging polymer electronic technology.

Neste trabalho, reporta-se a síntese e a ca-raterizaçâo optoeletrônica de très sistemas fenil vinilideno com substituintes eletrodoadores do tipo alcoxil (-OR). Os sistemas foram obtidos pela reacào de acoplamento de Heck, com rendimentos acima de 95%, com uma conjugacào de configuracào totalmente trans e com altos rendimentos quànticos de fluorescencia de cor verde-azul. A grande esteroseletividade da síntese utilizada se ve refletida na obtencào de rendimentos quànticos superiores aos reportados para os sistemas fenil vinilideno de estruturas químicas similares, o qual faz de estes sistemas fenil vinilideno materiais atraentes comercial-mente dentro das nascentes tecnologias da eletrònica de polímeros.

Síntesis esteresselectiva de un nitro derivado e fenilvinilideno mediante la rreacción de heck usando fosfitos / Synthesis of a stereoselective nitro phenylenevinlene derivative by the heck reaaction using phosphites / Síntese eséreoseelectiva de um nitro derivado de fenilvfniideno mediante a reacção de heck usando fosofitos

En este trabajo se describen tanto la síntesis como la caracterización de E,E-1,4-dimetoxi-2,5-bis[2-(4-nitrofenil)etenil] benceno, mediante la reacción de acoplamiento cruzado de Heck usando trifenil-fosfito como ligante, lo cual -y teniendo en cuenta la literatura científica consultada- es el primer reporte de un doble acoplamiento de Heck empleando fosfitos como ligante en la formación del complejo catalítico con paladio. La caracterización del sistema fenilvinilideno obtenido muestra que el mecanismo es altamente estereoselectivo hacia la formación de enlaces trans, y su altísimo rendimiento (98%) indica que el sistema catalítico es bastante promisorio para realizar multiacoplamientos cruzados necesarios para obtener polímeros fenilvinilideno con altos pesos moleculares y altas eficiencias en las propiedades optoelectrónicas, necesarios para la tecnología de la electrónica de polímeros.

The synthesis and characterization of E,E-1,4-dimethoxy-2,5-bis[2-(4-nitrop-henyl)ethenyl]benzene by cross coupling Heck reaction using phosphites as ligands is described. This, to the best of our knowledge, is the first report involving a double Heck coupling using phosphites as ligand in the palladium catalyst formation. The characterization for the phenylenevinylene system obtained showed that the mechanism is highly stereoselective towards trans bond formation and its quantitative yield showed that this catalytic system is very promising for the multicoupling needed to obtain phenylenevinylene polymers with high molecular weights and high efficiency optoelectronic properties, in order to be used in polymer electronic technologies.

Neste trabalho descreve-se a síntese e caracterização de E,E-1,4-dimetoxi-2,5-bis [2-(4-nitrofenil)etenil]benceno, mediante a reação de acoplamentos cruzado ao Heck com trifenilfosfito como ligante. O qual, e tendo em conta a literatura científica pesquisada, é o primeiro reporte de um duplo acoplamento de Heck empregando fosfitos como ligante na formação do complexo catalítico com paladio. A caracterização do sistema fenilvinilideno obtido mostra que o mecanismo é altamente estereoselectivo para a formação de enlaces trans e que o sistema catalítico é bastante promisorio para fazer os acoplamentos cruzados necessários para obter polímeros de fenilvinilideno com alta massa molecular e altas eficiências nas propriedades optoelectronicas, necessários para a tecnologia da eletrônica de polímeros.

Efecto del sustttuyente sobre el anillo porfiríico y el agente oxidante en la funcionalización de compuestos alifáticos / Effect f porphyrrin substituents and oxdizing agent on the functionaliization of aliphatic compounds / Estdo de substittuintes sobre a porfirina e o agent oxidante na fuuncionalização de oligômeros alifáticos

En este trabajo se estudió la funcionalización de escualano y tetradecano al variar el efecto electrónico del sustituyente sobre los anillos aromáticos del núcleo porfirínico y el agente oxidante (KIO4,2KHSO5 ⋅KHSO4K2SO4,NaClO yH2O2). Se sintetizaron y caracterizaron tres metaloporfirinas: cloruro de meso-tetrakis-4-nitrofenil-porfirinato manganeso(III), cloruro de meso-tetrakis-2,4,6-trirnetoxifenirporfirinato manganeso(III) y cloruro de meso-tetrafenilporfirinato manganeso(III), con rendimientos del 40, 52 y 43%, respectivamente. Posteriormente se probaron 24 sistemas de funcionalización, que se cuantificaron empleando cromatografía de gases usando el método del patrón interno, y sus productos se identificaron por cromatografía de gases acoplada a espectrometría de masas e infrarrojo. Los resultados muestran que la adecuada selección del par porfirina-agente oxidante puede llevar a funcionalizaciones hasta del 42% para el tetradecano y del 80% para el escualano.

In this work was studied the functionalizations of squalane and tetradecane varying the electronic nature of the substituents over the porphyrinic ring and the oxidizing agent (KiO4,2KHSO5-KHS(VK2SO4, NaClO and H2O2). Three metallo-porphyrins (Mn(TTP)Cl, Mn ρ-NO2TPP) Cl and Mn(triMeOTPP)Cl) were synthesized and characterized with yields of 40, 52 and 43% respectively. Twenty four different functionalisation systems were carried out and quantified by gas chromatography using internal standard method and the products were identified by gas chromatography-mass spectroscopy. The functionalisations were quantified by CG and the products identified by GC-MS and FT-IR. The results showed that a good choice porphyirin-oxidizing agent pair can produce functionalization yields up to 42% for tetradecane and 80% for squalane.

O estudo da funcionalização de oligôme-ros orgânicos mediado por metalporfirinas como uma primeira aproximação em procura da post-funcionalização de polímeros como o polietileno e polipropileno tem despertado maior interesse nos últimos anos. Dentro deste contexto, no presente trabalho foi proposto o estudo da funcionalização de escualano e tetradecano para alterar a natureza química dos substituintes dos anéis aromáticos do núcleo porfirínico e do agente oxidante (KIO4, 2KHSO5KHSO4K2SO4, NaClO eH2O²). Foram sintetizados e purificados três diferentes metaloporfirinas, cloreto de meso-tetrakis-4-nitrofenirporfirinato manganês (III), cloreto de meso-tetrakis-2,4,6-trimetoxifenilporfirinato manganês (III) e cloreto de meso-tetrafenil-porfirinato manganês (III), com rendimentos do 40, 52 e 43%, respectivamente. Posteriormente, realizaram-se 24 funcionalizações, que foram quantificadas por cromatografia gasosa de alta resolução acoplada à espectrometria de massas (CGAR-EM), usando um oxidante, e levando em consideração as características químicas de cada composto, na qual obteve-se funcionalizações de até o 42% para o tetradecano e o 80% para o escualano.

A simple multichromophore design for energy transfer in distyrylbenzenes with pyrene pendants.

A set of Don --> Acc <-- Don multichromophores was synthesized based on a simple design with two pyrene donors (absorbing antennae) connected to a bis-1,4-(3,4,5-trimethoxystyryl)benzene core acceptor using various flexible, nonconjugated tethers. Excitation of the pyrene donors at 276 nm in solution yields near exclusive emission from the core chromophore at 445-450 nm, with energy transfer efficiencies up to 92%, far better than achieved with simple mixtures. The simple tethering design imposes a high "local" concentration of the pyrene near the acceptor core unit that is maintained even at very low multichromophore concentrations. Solvent effects on absorption and emission spectra are very small, except in cases where a pi-conjugating O-C=O moiety of the tethering group is directly attached to the core chromophore, rather than being placed in the middle of the tether. Energy transfer in the systems is effective due to good donor-acceptor energy matching. The optimal energy transfer efficiency was achieved using an eight-atom flexible linker.