2-Amino-3-aroyl-4,5-alkylthiophenes: Agonist allosteric enhancers at human A1 adenosine receptors

2-Amino-3-benzoylthiophenes are allosteric enhancers (AE) of agonist activity at the A₁ adenosine receptor. The present report describes syntheses and assays of the AE activity at the human A₁AR (hA₁AR) of a panel of compounds consisting of nine 2-amino-3-aroylthiophenes (3a-i), eight 2-amino-3-benzoyl-4,5-dimethylthiophenes (12a-h), three 3-aroyl-2-carboxy-4,5- dimethylthiophenes (15a-c), 10 2-amino-3-benzoyl-5,6-dihydro 4H-cyclopenta[b]thiophenes (17a-j), 14 2-amino-3-benzoyl-4,5,6,7-tetrahydrobenzo[b]thiophenes (18a-n), and 15 2-amino- 3-benzoyl-5,6,7,8-tetrahydro-4H-cyclohepta[b]thiophenes (19a-o). An in vitro assay employing the A₁AR agonist [¹²⁵I]ABA and membranes from CHO-K1 cells stably expressing the hA¹AR measured, as an index of AE activity, the ability of a candidate AE to stabilize the agonist- A₁AR-G protein ternary complex. Compounds 3a-i had little or no AE activity, and compounds 12a-h had only modest activity, evidence that AE activity depended absolutely on the presence of at least a methyl group at C-4 and C-5. Compounds 17a-c lacked AE activity, suggesting the 2-amino group is essential. Polymethylene bridges linked thiophene C-4 and C-5 of compounds 17a-j, 18a-n, and 19a-o. AE activity increased with the size of the -(CH₂)_n- bridge, n ) 3 < n ) 4 < n ) 5. The 3-carbethoxy substituents of 17a, 18a, and 19a did not support AE activity, but a 3-aroyl group did. Bulky (or hydrophobic) substituents at the meta and para positions of the 3-benzoyl group and also 3-naphthoyl groups greatly enhanced activity. Thus, the hA₁AR contains an allosteric binding site able to accommodate 3-aroyl substituents that are bulky and/or hydrophobic but not necessarily planar. A second region in the allosteric binding site interacts constructively with alkyl substituents at thiophene C-4 and/or C-5.

Donor-п-acceptor conjugated copolymers for photovoltaic applications : tuning the open-circuit voltage by adjusting the donor/acceptor ratio

A class of new conjugated copolymers containing a donor (thiophene)−acceptor (2-pyran-4-ylidene-malononitrile) was synthesized via Stille coupling polymerization. The resulting copolymers were characterized by 1H NMR, elemental analysis, GPC, TGA, and DSC. UV−vis spectra indicated that the increase in the content of the thiophene units increased the interaction between the polymer main chains to cause a red-shift in the optical absorbance. Cyclic voltammetry was used to estimate the energy levels of the lowest unoccupied molecular orbital (LUMO) and the highest occupied molecular orbital (HOMO) and the band gap (Eg) of the copolymers. The basic electronic structures of the copolymers were also studied by DFT calculations with the GGA/B3LYP function. Both the experimental and the calculated results indicated an increase in the HOMO energy level with increasing the content of thiophene units, whereas the corresponding change in the LUMO energy level was much smaller. Polymer photovoltaic cells of a bulk heterojunction were fabricated with the structure of ITO/PEDOT/PSS (30 nm)/copolymer−PCBM blend (70 nm)/Ca (8 nm)/Al (140 nm). It was found that the open-circuit voltage (Voc) increased (up to 0.93 V) with a decrease in the content of thiophene units. Although the observed power convention efficiency is still relatively low (up to 0.9%), the corresponding low fill factor (0.29) indicates considerable room for further improvement in the device performance. These results provided a novel concept for developing high Voc photovoltaic cells based on donor-π-acceptor conjugated copolymers by adjusting the donor/acceptor ratio.

Enhanced properties in chemically polymerized poly(terthiophene) using vapour phase techniques

Poly(terthiophene) is an electronically conducting polymer with potential applications in solar energy devices. In the present study a series of poly(terthiophene) (PTTh) films are chemically polymerized (CP) at various temperatures and compared with a novel method of vapour phase polymerization (VPP). Utilizing the thiophene trimer (terthiophene) as the starting material, polymerization is achieved with Fe(III) tosylate. The films are characterized by their Raman and absorption spectra, in addition to differential scanning calorimetry (DSC), optical microscopy, electrochemical impedance spectroscopy (EIS) and four-point probe surface conductivity measurements. From the spectroscopy studies, increased conjugation length of the polymer chains with decreasing temperature or vapour phase polymerization is evident. More surprisingly, DSC results indicate the order of the polymer chains is dramatically enhanced by vapour phase polymerization and the D.C. conductivity is an order of magnitude higher for VPP compared with traditional CP films. Additionally, the optical micrographs reveal a significantly different morphology than the films cast from solution.

Effect of organic additives on the cycling performances of lithium metal polymer cells

Gel polymer electrolytes were prepared by immersing a porous poly(vinylidene fluoride-co-hexafluoropropylene) membrane in an electrolyte solution containing small amounts of organic additive. Three kinds of organic compounds, thiophene, 3,4-ethylenedioxythiophene and biphenyl, were used as a polymerizable monomeric additive. The organic additives were found to be electrochemically oxidized to form conductive polymer films on the electrode at high potential. By using the gel polymer electrolytes containing different organic additive, lithium metal polymer cells, composed of lithium anode and LiCoO2 cathode, were assembled and their cycling performance evaluated. Adding small amounts of a suitable polymerizable additive to the gel polymer electrolyte was found to reduce the interfacial resistance in the cell during cycling, and it thus exhibited less capacity fade and better high rate performance. Differential scanning calorimetric studies showed that the thermal stability of the fully charged LiCoO2 cathode was improved in the cell containing an organic additive.

Control of magnesium interfacial reactions in aqueous electrolytes towards a biocompatible battery

A stable magnesium battery has been developed based on a magnesium anode, a poly(dioxyethane thiophene) (PEDOT) cathode and a near-saturated aqueous solution of LiCl, MgCl₂, or mixture of these salts at pH of 11. This combination leads to a low water activity in the electrolyte, which thus suppresses the hydrogen evolution reaction on Mg, as well as producing a stable oxy-hydroxide film which protects the metal surface from freely corroding. The conducting polymer cathode is reduced somewhat during the discharge process, however, appears to be readily re-oxidised (as determined from the resistance) by the oxygen present in the cell. The cell is therefore primarily a Mg/O₂ battery, however, the PEDOT appears to enhance the performance, in particular the discharge voltage.

Influence of ionic liquids on the electrical conductivity and morphology of PEDOT:PSS films

Small-molecule nonvolatile additives based on ionic liquids (IL) as electrical conductivity enhancer in Poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) was studied. Ionic liquids were investigated in the synthesis of self-assembled, highly organized hybrid nanostructures due to their ability as supramolecular solvents. Different percentage of five ionic liquids, such as 1-butyl-3-methylimidazolium tetrafluoroborate (bmim) F 4 and 1-butyl-3-methylimidazolium bromide (bmim)Br were added to a PEDOT:PSScommercial dispersion. Films of pure PEDOT:PSS showed an average conductivity of 14 S cm-1, which corresponded to the value range given by the supplier. AFM images showed that IL induced the formation of a three-dimensional conducting network with smaller PEDOT domains. The ionic character of the films was significantly increased because of the presence of ionic liquids, which can be used effectively in optoelectronic devices.

Novel dithiolene complexes incorporating conjugated electroactive ligands

A series of new metal (M) dithiolene complexes bearing terthiophene (3, 12, M = Ni; 4, M = Pd; 5, 6, M = Au) and 2,5-bis(para-methoxyphenyl)thiophene units (14, M = Ni; 15, 16, M = Au; 17, M = Pd) have been synthesised in 38–99% yield. The electrochemical properties of the materials have been characterised by cyclic voltammetry and UV-vis spectroelectrochemistry. The nickel complexes possess low oxidation potentials (−0.12 to −0.25 V vs Ag/AgCl) due to the electron-rich dithiolene centres and all complexes display ligand-based redox activity. The terthiophene derivatives have been polymerised by electrochemical oxidation to give stable films with, in the case of poly(3), broad absorption characteristics. Charge transfer materials have been isolated from 14 and 16 with conductivities in the range 9 × 10⁻⁶ to 7 × 10⁻⁸ S cm⁻¹.

Síntese e caracterização de catalisadores nanométricos de LaSrNiO4 para aplicação em dessulfurização de tiofeno

The mixed metal oxides constitute an important class of catalytic materials widely investigated in different fields of applications. Studies of rare earth nickelates have been carried by several researchers in order to investigate the structural stability afforded by oxide formed and the existence of catalytic properties at room temperature. So, this study aims synthesize the nanosized catalyst of nickelate of lanthanum doped with strontium (La(1-x)SrxNiO4-d; x = 0,2 and 0,3), through the Pechini method and your characterization for subsequent application in the desulfurization of thiophene reaction. The precursor solutions were calcined at 300ºC/2h for pyrolysis of polyester and later calcinations occurred at temperatures of 500 - 1000°C. The resulting powders were characterized by thermogravimetric analysis (TG / DTG), surface area for adsorption of N2 by BET method, X-ray diffraction (XRD), scanning electron microscopy (HR_SEM) and spectrometry dispersive energy (EDS). The results of XRD had show that the perovskites obtained consist of two phases (LSN and NiO) and from 700ºC have crystalline structure. The results of SEM evidenced the obtainment of nanometric powders. The results of BET show that the powders have surface area within the range used in catalysis (5-50m2/g). The characterization of active sites was performed by reaction of desulfurization of thiophene at room temperature and 200ºC, the relation F/W equal to 0,7 mol h-1mcat -1. The products of the reaction were separated by gas chromatography and identified by the selective detection PFPD sulfur. All samples had presented conversion above 95%

Síntese e caracterização de aluminofosfato impregnado com molibdênio/zinco visando a dessulfurização por adsorção

Discussions about pollution caused by vehicles emission are old and have been developed along the years. The search for cleaner technologies and frequent weather alterations have been inducing industries and government organizations to impose limits much more rigorous to the contaminant content in fuels, which have an direct impact in atmospheric emissions. Nowadays, the quality of fuels, in relation to the sulfur content, is carried out through the process of hydrodesulfurization. Adsorption processes also represent an interesting alternative route to the removal of sulfur content. Both processes are simpler and operate to atmospheric temperatures and pressures. This work studies the synthesis and characterization of aluminophosphate impregnate with zinc, molybdenum or both, and its application in the sulfur removal from the gasoline through the adsorption process, using a pattern gasoline containing isooctane and thiophene. The adsorbents were characterized by x-ray diffraction, differential thermal analysis (DTG), x-ray fluorescence and scanning electron microscopy (SEM). The specific area, volume and pore diameter were determined by BET (Brunauer- Emmet-Teller) and the t-plot method. The sulfur was quantified by elementary analysis using ANTEK 9000 NS. The adsorption process was evaluated as function of the temperature variation and initial sulfur content through the adsorption isotherm and its thermodynamic parameters. The parameters of entropy (ΔS), enthalpy variation (ΔH) and free Gibbs energy (ΔG) were calculated through the graph ln(Kd) versus 1/T. Langmuir, Freundlich and Langmuir-Freundlich models were adjusted to the experimental data, and the last one had presented better results. The thermodynamic tests were accomplished in different temperatures, such as 30, 40 and 50ºC, where it was concluded the adsorption process is spontaneous and exothermic. The kinetic of adsorption was studied by 24 h and it showed that the capability adsorption to the adsorbents studied respect the following order: MoZnPO > MoPO > ZnPO > AlPO. The maximum adsorption capacity was 4.91 mg/g for MoZnPO with an adsorption efficiency of 49%.

Síntese e caracterização da peneira molecular MCM-41 contendo terras raras na dessulfurização, utilizando tiofeno como molécula sonda

Mesoporous molecular sieves of MCM-41 type are considered as promising support for metal in the refining processes of petroleum-based materials as catalysts and adsorbents for environmental protection. In this work, mesoporous molecular sieves MCM-41 were modified with different rare earth ions (La, Eu e Yb) for the obtaining nanostrutured materials with catalytic properties. The catalysts were synthesized by the hydrothermal method at 100oC for 120 h, presenting, all the samples, in the gel of synthesis molar ratio Si/Ln = 50. The obtained materials after calcination at 500oC for 2 h were characterized by XRD, surface area BET, TG/DTG, FTIR, and hydrothermal stability at 700ºC. The XRD analysis of the catalysts indicated that the materials containing rare earth presented characteristic hexagonal structure of the mesoporous materials of the type MCM-41. The TG curves showed that the decomposition of the structural template occurs in the materials at temperatures lower than 500oC. The samples presented variations as the specific superficial area, average diameter of pores and thickness of the silica wall, as a function of the nature of the rare earth impregnated in the mesoporous material. Hydrotermal stability was evaluated through the exposition of the materials to water vapour at 700°C. The thiophene adsorptions reach a maximum at 80% of conversion and incorporation of the rare earths showed influence in the process. Adsorption capacity followed the sequence: Yb-MCM-41 < La-MCM-41 < Eu-MCM-41 < MCM-41

Sol-gel synthesis of titania-alumina catalyst supports

Titanium oxide is a good candidate as new support for hydrotreating (HDT) catalysts, but has the inconvenience of presenting small surface area and poor thermal stability. To overcome these handicaps TiO2-Al2O3 mixed oxides were proposed as catalyst support. Here, the results concerning the preparation, characterization and testing of molybdenum catalyst supported on titania-alumina are presented. The support was prepared by sol-gel route using titanium and aluminum isopropoxides, chelated with acetylacetone (acac) to promote similar hydrolysis ratio for both the alcoxides. The effect of nominal complexing ratios [acac]/[Ti] and of sol aging temperature on the structural features of nanometric particles was analyzed by quasi-elastic light scattering (QELS) and N-2 adsorption isotherm measurements. These characterizations have shown that the addition of acac and the increase of aging temperature favor the full dispersion of primary nanoparticles in mother acid solution. The dried powder presents a monomodal distribution of slit-shaped micropores, formed by irregular packing of platelet primary particles, surface area superior to 200 m(2) g(-1) and mean pore size of about 1 nm. These characteristics of porous texture are preserved after firing at 673 K. The diffraction patterns of sample fired above 973 K show only the presence of anatase crystalline phase. The crystalline structure of the support remained unaltered after molybdenum adsorption, but the surface area and the micropore volume were drastically reduced. (C) 2002 Published by Elsevier B.V. B.V.

Electron transfer between adjacent layers in self-assembled films

A simple model of electron transfer is adapted to explain fluorescence quenching in self-assembled films of poly( p-phenylene vinylene) (PPV) alternating with poly(thiophene acetic acid) (PTAA). Quenching is caused by a photo-induced electron transfer between the excited PPV (donor, D) and the PTAA (acceptor, A). The electron-transfer process can be mediated by insertion of electronically inert spacing bilayers between the D and A layers, As the number of bilayers is increased, the fluorescence is gradually recovered which is explained theoretically by assuming that the electron-transfer rate can be described as k = Z exp(- beta r) where r is the distance between D and A. (C) 2000 Elsevier B.V. B.V. All rights reserved.

INSULATOR-TO-METAL TRANSITION IN POLYTHIOPHENE

In the present work, the electronic structure of polythiophene at several doping levels is investigated by the use of the Huckel Hamiltonian with sigma-bond compressibility. Excess charges are assumed to be stored in conformational defects of the bipolaron type. The Hamiltonian matrix elements representative of a bipolaron are obtained from a previous thiophene oligomer calculation, and then transferred to very long chains. Negative factor counting and inverse iteration techniques have been used to evaluate densities of states and wave functions, respectively. Several types of defect distributions were analyzed. Our results are consistent with the following: (i) the bipolaron lattice does not present a finite density of states at the Fermi energy at any doping level; (ii) bipolaron clusters show an insulator-to-metal transition at 8 mol% doping level; (iii) segregation disorder shows an insulator-to-metal transition for doping levels in the range 20-30 mor %.