Tuning cell surface charge in E. coli with conjugated oligoelectrolytes.

Cationic conjugated oligoelectrolytes (COEs) varying in length and structural features are compared with respect to their association with E. coli and their effect on cell surface charge as determined by zeta potential measurements. Regardless of structural features, at high staining concentrations COEs with longer molecular dimensions associate less, but neutralize the negative surface charge of E. coli to a greater degree than shorter COEs

Principal factors that determine the extension of detection range in molecular beacon aptamer/conjugated polyelectrolyte bioassays.

A strategy to extend the detection range of weakly-binding targets is reported that takes advantage of fluorescence resonance energy transfer (FRET)-based bioassays based on molecular beacon aptamers (MBAs) and cationic conjugated polyelectrolytes (CPEs). In comparison to other aptamer-target pairs, the aptamer-based adenosine triphosphate (ATP) detection assays are limited by the relatively weak binding between the two partners. In response, a series of MBAs were designed that have different stem stabilities while keeping the constant ATP-specific aptamer sequence in the loop part. The MBAs are labeled with a fluorophore and a quencher at both termini. In the absence of ATP, the hairpin MBAs can be opened by CPEs via a combination of electrostatic and hydrophobic interactions, showing a FRET-sensitized fluorophore signal. In the presence of ATP, the aptamer forms a G-quadruplex and the FRET signal decreases due to tighter contact between the fluorophore and quencher in the ATP/MBA/CPE triplex structure. The FRET-sensitized signal is inversely proportional to [ATP]. The extension of the detection range is determined by the competition between opening of the ATP/MBA G-quadruplex by CPEs and the composite influence by ATP/aptamer binding and the stem interactions. With increasing stem stability, the weak binding of ATP and its aptamer is successfully compensated to show the resistance to disruption by CPEs, resulting in a substantially broadened detection range (from millimolar up to nanomolar concentrations) and a remarkably improved limit of detection. From a general perspective, this strategy has the potential to be extended to other chemical- and biological-assays with low target binding affinity

Influence of molecular structure on the antimicrobial function of phenylenevinylene conjugated oligoelectrolytes.

Conjugated oligoelectrolytes (COEs) with phenylenevinylene (PV) repeat units are known to spontaneously intercalate into cell membranes. Twelve COEs, including seven structures reported here for the first time, were investigated for the relationship between their membrane disrupting properties and structural modifications, including the length of the PV backbone and the presence of either a tetraalkylammonium or a pyridinium ionic pendant group. Optical characteristics and interactions with cell membranes were determined using UV-Vis absorption and photoluminescence spectroscopies, and confocal microscopy. Toxicity tests on representative Gram-positive (Enterococcus faecalis) and Gram-negative (Escherichia coli) bacteria reveal generally greater toxicity to E. faecalis than to E. coli and indicate that shorter molecules have superior antimicrobial activity. Increased antimicrobial potency was observed in three-ring COEs appended with pyridinium ionic groups but not with COEs with four or five PV repeat units. Studies with mutants having cell envelope modifications indicate a possible charge based interaction with pyridinium-appended compounds. Fluorine substitutions on COE backbones result in structures that are less toxic to E. coli, while the addition of benzothiadiazole to COE backbones has no effect on increasing antimicrobial function. A weakly membrane-intercalating COE with only two PV repeat units allowed us to determine the synthetic limitations as a result of competition between solubility in aqueous media and association with cell membranes. We describe, for the first time, the most membrane disrupting structure achievable within two homologous series of COEs and that around a critical three-ring backbone length, structural modifications have the most effect on antimicrobial activity

Pentamethylcyclopentadienyl-dicarbollide derivatives of scandium

The reactions of [Cp*ScCl_2]_x (Cp* = (η^5-C_5Me_5)) with Na_2[C_2B_9H_(11) or [Cp*ScMe_2]_x, with C_2B_9H_(13), followed by treatment with THF yield Cp*(C_2B_9H_(11))Sc(THF)_3. Alkylation of Cp*-(C_2 B_9 H_(11)) with LiCH(SiMe_3)_2 yields Cp(C_2B_9H_(11))ScCH(SiMe_3)_2Li(THF)_3, and {[Cp*(C_2B_9H_(11))ScCH(SiMe_3)_2]_2Li}-Li(THF)_3, which is obtained by its recrystallization from pentane/toluene, has been characterized structurally. This alkyl derivative reacts slowly with H_2 to yield [Cp*(C_2B_9H_(11))SCH]_2[LiTHF)_n]_2, a surprisingly reactive scandium hydride dimer. Once again, recrystallization from toluene affords a crystalline form with less coordinated THF, [Cp*(C_2B_9H_(11))ScH]_2[Li(THF)_2•(3/2)(C_6H_5CH_)3, whose structure reveals that the two anionic [Cp*(C_2B_9H_(11))ScH]^- fragments are held together by reciprocal B-H dative bonding from the dicarbollide ligand to the electron deficient scandium. The potential of pentamethylcyclopentadienyl-dicarbollide derivatives of scandium to serve as efficient a olefin polymerization catalysts is discussed

El Corredor Ferroviario Bioceánico de Integración (CFBI) en la agenda común de Bolivia, Brasil y Perú durante la segunda década del siglo XXI

La importancia de la integración física regional aumenta en el mundo académico. Se han desarrollado investigaciones a nivel mundial sobre el impacto que implementar ese tipo de infraestructura podría tener en los ámbitos político y económico. Esto ha creado una bibliografía referente a la integración de infraestructura regional que guiará esta investigación. Dentro del caso latinoamericano destaca el Corredor Ferroviario Bioceánico de Integración (CFBI) por tratarse de un corredor bioceánico y porque su importancia, dentro de la agenda internacional, fluctuó. Es importante investigar sus causas, dada la crisis del regionalismo latinoamericano, por la influencia que los proyectos comunes pueden tener en fomentar la integración regional. Esta investigación busca explicar las razones por las cuales el grado de prioridad asignado al proyecto no se mantuvo constante. Se hipotetiza que dichos cambios se explican a partir de diversos factores: la falta de un compromiso constante de parte de Brasil, la dinámica (geo-)política de exclusión entre diversos países, y la caída del gobierno boliviano, principal impulsor del proyecto. Se concluye validando, aunque con matices, la hipótesis, por ejemplo, señalando que tanto como una dinámica de exclusión el impacto de Chile pese a ser un país externo al proyecto es central, siendo un elemento disruptivo. Se cierra resaltando el impacto que tuvo la relativa consistencia de la política exterior boliviana

Surface Plasmon Enhanced Phosphorescent Organic Light Emitting Diodes

The objective of the proposed work was to develop the fundamental understanding and practical techniques for enhancement of Phosphorescent Organic Light Emitting Diodes (PhOLEDs) performance by utilizing radiative decay control technology. Briefly, the main technical goal is the acceleration of radiative recombination rate in organometallic triplet emitters by using the interaction with surface plasmon resonances in noble metal nanostructures. Increased photonic output will enable one to eliminate constraints imposed on PhOLED efficiency by triplet-triplet annihilation, triplet-polaron annihilation, and saturation of chromophores with long radiative decay times. Surface plasmon enhanced (SPE) PhOLEDs will operate more efficiently at high injection current densities and will be less prone to degradation mechanisms. Additionally, introduction of metal nanostructures into PhOLEDs may improve their performance due to the improvement of the charge transport through organic layers via multiple possible mechanisms ('electrical bridging' effects, doping-like phenomena, etc.). SPE PhOLED technology is particularly beneficial for solution-fabricated electrophosphorescent devices. Small transition moment of triplet emitters allows achieving a significant enhancement of the emission rate while keeping undesirable quenching processes introduced by the metal nanostructures at a reasonably low level. Plasmonic structures can be introduced easily into solution-fabricated PhOLEDs by blending and spin coating techniques and can be used for enhancement of performance in existing device architectures. This constitutes a significant benefit for a large scale fabrication of PhOLEDs, e.g. by roll-to-roll fabrication techniques. Besides multieexciton annihilation, the power efficacy of PhOLEDs is often limited by high operational bias voltages required for overcoming built-in potential barriers to injection and transport of electrical charges through a device. This problem is especially pronounced in solution processed OLEDs lacking the accuracy and precision of fabrication found in their small molecule counterparts. From this point of view, it seems beneficial to develop materials allowing reduction of the operation bias voltage via improvement of the charge injection. The materials sought have to be compatible with solution-based fabrication process and allow easy incorporation of metal nanostructures

Collaborative participatory research as a learning process: the case of CIP and CARE in Peru

Participatory research (PR) has been analyzed and documented from different points of view, but particularly taking into consideration the benefits that this process generates for farmers. Studies of the benefits of PR for other actors such as field staff, researchers and organizations have been limited, with organizational learning receiving the least attention. This paper analyzes the interaction between the International Potato Center (CIP) and CARE in Peru and makes the case that PR can also contribute to creating a collaborative learning environment that generates important lessons for the individuals and organizations involved. The paper describes the evolution of the collaborative environment of these two institutions for more than a decade. Three interactive learning periods are presented, namely the “information transfer period” (1993 –1996) the “action-learning period” (1997-2002), and the “social learning period” (on-going). Several lessons from each period, as well as changes in institutional contexts and perceptions, are described. The CIP-CARE case shows that research and developmentoriented organizations can interact fruitfully using PR as a mechanism to promote learning, as well as flexibility in interaction and innovativeness, and that a process of osmosis of information occurs between groups that use PR in a specific case to other groups within the organizations, influencing behavior. However, the paper also indicates that institutional learning should be promoted more specifically in order to extract guidelines from the lessons, which can influence the way organizations plan and implement their projects in a constantly changing environment

α,ω-Dithiol Oligo(phenylene vinylene)s for the Preparation of High-Quality π-Conjugated Self-Assembled Monolayers and Nanoparticle-Functionalized Electrodes

While thioacetate-terminated oligo(phenylene vinylene)s (OPVs) have been synthesized and employed in applications involving the formation of metal–molecule–metal junctions, the synthesis and application of potentially more versatile α,ω-dithiol OPVs have not previously been described. Here, a thiomethyl-precursor route to the synthesis of α,ω-dithiol OPVs is reported and their ability to form well-ordered self-assembled monolayers (SAMs) without the addition of exogenous deprotection reagents is described. α,ω-Dithiol OPV monolayers exhibit thicknesses consistent with molecular length and are nearly defect-free, as assayed by electrochemical measurements. To demonstrate the ease with which SAMs containing these bifunctional OPVs can, in contrast to thioacetate functionalized OPVs, be further functionalized with materials other than gold, we have modified them in a single step with a sub-monolayer of cadmium selenide nanocrystals (NCs). Scanning electron microscopy (SEM) and atomic force microscopy (AFM) confirm that these NC-modified films are both smooth and uniform over the largest areas investigated (\u3e 10 μm2) and no evidence of NC aggregation is observed. To evaluate the electrochemical response of these metal–molecule– semiconductor assemblies we have fabricated NC-modified OPV SAMs with ferrocene-coated NCs. Variable-frequency alternating current voltammetry indicates that electron transfer in these assemblies is much more rapid than in analogous structures formed using simple alkane dithiols. It thus appears that α,ω-dithiol OPVs are well suited for the formation of high-quality conducting SAMs for the functionalization of gold and other surfaces

α,ω-Dithiol Oligo(phenylene vinylene)s for the Preparation of High-Quality π-Conjugated Self-Assembled Monolayers and Nanoparticle-Functionalized Electrodes

While thioacetate-terminated oligo(phenylene vinylene)s (OPVs) have been synthesized and employed in applications involving the formation of metal–molecule–metal junctions, the synthesis and application of potentially more versatile α,ω-dithiol OPVs have not previously been described. Here, a thiomethyl-precursor route to the synthesis of α,ω-dithiol OPVs is reported and their ability to form well-ordered self-assembled monolayers (SAMs) without the addition of exogenous deprotection reagents is described. α,ω-Dithiol OPV monolayers exhibit thicknesses consistent with molecular length and are nearly defect-free, as assayed by electrochemical measurements. To demonstrate the ease with which SAMs containing these bifunctional OPVs can, in contrast to thioacetate functionalized OPVs, be further functionalized with materials other than gold, we have modified them in a single step with a sub-monolayer of cadmium selenide nanocrystals (NCs). Scanning electron microscopy (SEM) and atomic force microscopy (AFM) confirm that these NC-modified films are both smooth and uniform over the largest areas investigated (\u3e 10 μm2) and no evidence of NC aggregation is observed. To evaluate the electrochemical response of these metal–molecule– semiconductor assemblies we have fabricated NC-modified OPV SAMs with ferrocene-coated NCs. Variable-frequency alternating current voltammetry indicates that electron transfer in these assemblies is much more rapid than in analogous structures formed using simple alkane dithiols. It thus appears that α,ω-dithiol OPVs are well suited for the formation of high-quality conducting SAMs for the functionalization of gold and other surfaces