Rocking-Chair Proton Batteries with Conducting Redox Polymer Active Materials and Protic Ionic Liquid Electrolytes.

Rechargeable batteries that use redox-active organic compounds are currently considered an energy storage technology for the future. Functionalizing redox-active groups onto conducting polymers to make conducting redox polymers (CRPs) can effectively solve the low conductivity and dissolution problems of redox-active compounds. Here, we employ a solution-processable postdeposition polymerization (PDP) method, where the rearrangements ensured by partial dissolution of intermediated trimer during polymerization were found significant to produce high-performance CRPs. We show that quinizarin (Qz)- and naphthoquinone (NQ)-based CRPs can reach their theoretical capacity through optimization of the polymerization conditions. Combining the two CRPs, with the Qz-CRP as a cathode, the NQ-CRP as an anode, and a protic ionic liquid electrolyte, yields a 0.8 V proton rocking-chair battery. The conducting additive-free all-organic proton battery exhibits a capacity of 62 mAh/g and a capacity retention of 80% after 500 cycles using rapid potentiostatic charging and galvanostatic discharge at 4.5 C.

Formation of persistent organic diradicals from N,N'-diphenyl-3,7-diazacyclooctanes.

ABSTRACT: N,N'-Diphenyl-3,7-diazacyclooctane and structurally related N,N'-diphenylbispidine derivatives react with silver(I) ions in a high-yielding C-C coupling reaction to produce dication-diradical species, with the silver ions serving a double function both as template and as an oxidant. The resulting bis(benzidino)phane derivatives are persistent organic radicals, stable for several months in solution as well as in the solid state, at room temperature and above, as well as being exposed to the atmosphere. The molecular structure features a double-decker cyclophane motif, stabilized by intramolecular π-dimerization of two delocalized benzidinium radical segments. Intermolecular π-dimers are formed in the solid state.

Structural Control of Charge Storage Capacity to Achieve 100% Doping in Vapor Phase-Polymerized PEDOT/Tosylate.

Vapor phase polymerization (VPP) is used to fabricate a series of tosylate-doped poly(3,4-ethylenedioxythiophene) (PEDOT) electrodes on carbon paper. The series of VPP PEDOT/tosylate coatings has varying levels of crystallinity and electrical conductivity because of the use (or not) of nonionic triblock copolymers in the oxidant solution during synthesis. As a result, the impact of the structure on charge storage capacity is investigated using tetra-n-butylammonium hexafluorophosphate (0.1 M in acetonitrile). The ability to insert anions, and hence store charge, of the VPP PEDOT/tosylate is inversely related to its electrical conductivity. In the case of no nonionic triblock copolymer employed, the VPP PEDOT/tosylate achieves electrochemical doping levels of 1.0 charge per monomer or greater (≥100% doping level). Such high doping levels are demonstrated to be plausible by molecular dynamics simulations and density functional theory calculations. Experiments show that this high doping level is attainable when the PEDOT structure is weakly crystalline with (relatively) large crystallite domains.

Synthesis and characterization of poly-3-((2,5-hydroquinone)vinyl)-1H-pyrrole: investigation on backbone/pendant interactions in a conducting redox polymer.

We herein report the synthesis and electrochemical characterization of poly-3-((2,5-hydroquinone)vinyl)-1H-pyrrole, consisting of a polypyrrole backbone derivatized at the beta position by a vinyl-hydroquinone pendant group. The structure of the polymer was characterized by solid state NMR spectroscopy. The interactions between the polypyrrole backbone and the oxidized quinone or reduced hydroquinone pendant groups are probed by several in situ methods. In situ attenuated total reflectance-Fourier transform infrared spectroscopy shows a spectroscopic response from both the doping of the polymer backbone and the redox activity of the pendant groups. Using an in situ Electrochemical Quartz Crystal Microbalance we reveal that the polymer doping is unaffected by the pendant group redox chemistry, as opposed to previous reports. Despite the continuous doping the electrochemical conversion from the hydroquinone state to the quinone state results in a significant conductance drop, as observed by in situ conductivity measurements using an Interdigitated Array electrode set-up. Twisting of the conducting polymer backbone as a result of a decreased separation between pendant groups due to π-π stacking in the oxidized state is suggested as the cause of this conductance drop.

Quantifying TEMPO Redox Polymer Charge Transport toward the Organic Radical Battery.

To design new and better organic active battery materials in a rational fashion, fundamental parameters of the charge transport must be studied. Herein we report on the electronic conductivity by electron diffusion in a TEMPO-containing redox polymer, and the reorganization energy of the TEMPO self-exchange in an organic solvent is determined for the first time. The electronic conductivity was 8.5 µS/cm at E0 and corresponded to a redox hopping mechanism. The apparent electron diffusion coefficient was 1.9 × 10-9 cm2/s at room temperature, and at short times the ion diffusion was limiting with a diffusion coefficient of 6.5 × 10-10 cm2/s. The reorganization energy was determined to be 1.01 eV, indicating a rather polar chemical environment for the TEMPO groups. The implications for the usage of this type of materials in organic energy storage are discussed. As conductivity through 10 µm was demonstrated, we show that, if sufficient swellability can be ensured, charge can be transported through several micrometer thick layers in a battery electrode without any conducting additive.

In search of the severity dimension of traffic events: Extended Delta-V as a traffic conflict indicator.

Most existing traffic conflict indicators do not sufficiently take into account the severity of the injuries resulting from a collision had it occurred. Thus far, most of the indicators that have been developed express the severity of a traffic encounter as their proximity to a collision in terms of time or space. This paper presents the theoretical framework and the first implementation of Extended Delta-V as a measure of traffic conflict severity in site-based observations. It is derived from the concept of Delta-V as it is applied in crash reconstructions, which refers to the change of velocity experienced by a road user during a crash. The concept of Delta-V is recognised as an important predictor of crash outcome severity. The paper explains how the measure is operationalised within the context of traffic conflict observations. The Extended Delta-V traffic conflict measure integrates the proximity to a crash as well as the outcome severity in the event a crash would have taken place, which are both important dimensions in defining the severity of a traffic event. The results from a case study are presented in which a number of traffic conflict indicators are calculated for interactions between left turning vehicles and vehicles driving straight through a signalised intersection. The results suggest that the Extended Delta-V indicator seems to perform well at selecting the most severe traffic events. The paper discusses how the indicator overcomes a number of limitations of traditional measures of conflict severity. While this is a promising first step towards operationalising an improved measure of traffic conflict severity, additional research is needed to further develop and validate the indicator.

Stable Deep Doping of Vapor-Phase Polymerized Poly(3,4-ethylenedioxythiophene)/Ionic Liquid Supercapacitors.

Liquid-solution polymerization and vapor-phase polymerization (VPP) have been used to manufacture a series of chloride- and tosylate-doped poly(3,4-ethylenedioxythiophene) (PEDOT) carbon paper electrodes. The electrochemistry, specific capacitance, and specific charge were determined for single electrodes in 1-ethyl-3-methylimidazolium dicyanamide (emim dca) ionic liquid electrolyte. VPP-PEDOT exhibits outstanding properties with a specific capacitance higher than 300 F g(-1) , the highest value reported for a PEDOT-based conducting polymer, and doping levels as high as 0.7 charges per monomer were achieved. Furthermore, symmetric PEDOT supercapacitor cells with the emim dca electrolyte exhibited a high specific capacitance (76.4 F g(-1) ) and high specific energy (19.8 Wh kg(-1) ). A Ragone plot shows that the VPP-PEDOT cells combine the high specific power of conventional ("pure") capacitors with the high specific energy of batteries, a highly sought-after target for energy storage.

Hydroquinone-pyrrole dyads with varied linkers.

A series of pyrroles functionalized in the 3-position with p-dimethoxybenzene via various linkers (CH2, CH2CH2, CH=CH, C≡C) has been synthesized. Their electronic properties have been deduced from (1)H NMR, (13)C NMR, and UV-vis spectra to detect possible interactions between the two aromatic subunits. The extent of conjugation between the subunits is largely controlled by the nature of the linker, with the largest conjugation found with the trans-ethene linker and the weakest with the aliphatic linkers. DFT calculations revealed substantial changes in the HOMO-LUMO gap that correlated with the extent of conjugation found experimentally. The results of this work are expected to open up for use of the investigated compounds as components of redox-active materials in sustainable, organic electrical energy storage devices.

Phototriggerable peptidomimetics for the inhibition of Mycobacterium tuberculosis ribonucleotide reductase by targeting protein-protein binding.

Incorporation of an artificial amino acid 2 with a stilbene chromophore into peptidomimetics with three to nine amino acids yields phototriggerable candidates for inhibition of the binding between the R1 and R2 subunits of the M. tuberculosis ribonucleotide reductase (RNR). Interstrand hydrogen bond probability was used as a guideline for predicting conformational preferences of the photoisomers. Binding of these inhibitors has been rationalized by docking studies with the R1 unit. Significant differences in binding of the photoisomers were observed. For the shorter peptidomimetics, stronger binding of the Z isomer might indicate hydrophobic interactions between the stilbene chromophore and the binding site.

Selection of a multidrug resistance plasmid by sublethal levels of antibiotics and heavy metals.

How sublethal levels of antibiotics and heavy metals select for clinically important multidrug resistance plasmids is largely unknown. Carriage of plasmids generally confers substantial fitness costs, implying that for the plasmid-carrying bacteria to be maintained in the population, the plasmid cost needs to be balanced by a selective pressure conferred by, for example, antibiotics or heavy metals. We studied the effects of low levels of antibiotics and heavy metals on the selective maintenance of a 220-kbp extended-spectrum ß-lactamase (ESBL) plasmid identified in a hospital outbreak of Klebsiella pneumoniae and Escherichia coli. The concentrations of antibiotics and heavy metals required to maintain plasmid-carrying bacteria, the minimal selective concentrations (MSCs), were in all cases below (almost up to 140-fold) the MIC of the plasmid-free susceptible bacteria. This finding indicates that the very low antibiotic and heavy metal levels found in polluted environments and in treated humans and animals might be sufficiently high to maintain multiresistance plasmids. When resistance genes were moved from the plasmid to the chromosome, the MSC decreased, showing that MSC for a specific resistance conditionally depends on genetic context. This finding suggests that a cost-free resistance could be maintained in a population by an infinitesimally low concentration of antibiotic. By studying the effect of combinations of several compounds, it was observed that for certain combinations of drugs each new compound added lowered the minimal selective concentration of the others. This combination effect could be a significant factor in the selection of multidrug resistance plasmids/bacterial clones in complex multidrug environments. Importance: Antibiotic resistance is in many pathogenic bacteria caused by genes that are carried on large conjugative plasmids. These plasmids typically contain multiple antibiotic resistance genes as well as genes that confer resistance to biocides and heavy metals. In this report, we show that very low concentrations of single antibiotics and heavy metals or combinations of compounds can select for a large plasmid that carries resistance to aminoglycosides, ß-lactams, tetracycline, macrolides, trimethoprim, sulfonamide, silver, copper, and arsenic. Our findings suggest that the low levels of antibiotics and heavy metals present in polluted external environments and in treated animals and humans could allow for selection and enrichment of bacteria with multiresistance plasmids and thereby contribute to the emergence, maintenance, and transmission of antibiotic-resistant disease-causing bacteria.