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

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

Improved electron injection in polymer light-emitting diodes using anionic conjugated polyelectrolyte

We report improved performance in polymer light-emitting diodes incorporating conjugated polyelectrolytes as an electron injection layer (EIL). When we introduce water soluble conjugated polymers, poly[9,9'-bis(4-sulfonatobutyl)fluorene-co-alt-1,4-phenylene] (anionic PFP), between the aluminum (Al) cathode and emissive layer, the devices show an increased electroluminescence efficiency with a lowered turn-on voltage. We believe the mobile Na(+) ions in the EIL layer directly influences the device efficiency by forming a low work function layer at the interface between the EIL and Al cathode, thereby facilitating the electron injection into the emissive layer.open141

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

Present and future of surface-enhanced Raman scattering

The discovery of the enhancement of Raman scattering by molecules adsorbed on nanostructured metal surfaces is a landmark in the history of spectroscopic and analytical techniques. Significant experimental and theoretical effort has been directed toward understanding the surface-enhanced Raman scattering (SERS) effect and demonstrating its potential in various types of ultrasensitive sensing applications in a wide variety of fields. In the 45 years since its discovery, SERS has blossomed into a rich area of research and technology, but additional efforts are still needed before it can be routinely used analytically and in commercial products. In this Review, prominent authors from around the world joined together to summarize the state of the art in understanding and using SERS and to predict what can be expected in the near future in terms of research, applications, and technological development. This Review is dedicated to SERS pioneer and our coauthor, the late Prof. Richard Van Duyne, whom we lost during the preparation of this article