Eco-friendly process toward collector- and binder-free,high-energy density electrodes for lithium-ion batteries

Journal of Solid State Electrochemistry - The preparation of collector- and binder-free, high-energy density cathodes made from carbon-coated LiFePO4 (C-LFP) and single-walled carbon nanotubes...     

Selectivity and sensitivity of a reagentless electrochemical DNA sensor studied by square wave voltammetry and fluorescence

Poly(5-hydroxy-1,4-naphthoquinone-co-5-hydroxy-3-thioacetic acid-1,4-naphthoquinone)-modified electrode is used for the direct electrochemical detection of oligonucleotide hybridization. The polymer film presents well-defined electroactivity in the cathodic potential domain (between 0 and -0.8 V/SCE), due to the quinone group embedded into the polymer structure. The detection can be performed simply by square wave voltammetry. This sensor is a "signal-on" device and works with different oligonucleotide lengths, from 10 to 30 bases. Quantitative results from fluorescence are consistent with electrochemical data. It is confirmed that the signal increase in square wave voltammetry is unambiguously due to hybridization. The biosensor presents a detection limit of target of ca. 25 nM and is highly selective as it can discriminate single mismatch base.     

ϕ-Informational Measures: Some Results and Interrelations

In this paper, we focus on extended informational measures based on a convex function ϕ: entropies, extended Fisher information, and generalized moments. Both the generalization of the Fisher information and the moments rely on the definition of an escort distribution linked to the (entropic) functional ϕ. We revisit the usual maximum entropy principle—more precisely its inverse problem, starting from the distribution and constraints, which leads to the introduction of state-dependent ϕ-entropies. Then, we examine interrelations between the extended informational measures and generalize relationships such the Cramér–Rao inequality and the de Bruijn identity in this broader context. In this particular framework, the maximum entropy distributions play a central role. Of course, all the results derived in the paper include the usual ones as special cases.     

A benzophenone‐naphthalimide derivative as versatile photoinitiator of polymerization under near UV and visible lights

A benzophenone‐naphthalimide derivative (BPND) bearing tertiary amine groups has been developed as a high‐performance photoinitiator in combination with 2,4,6‐tris(trichloromethyl)‐1,3,5‐triazine or an iodonium salt for both the free radical polymerization (FRP) of acrylates and the cationic polymerization (CP) of epoxides upon exposure to near UV and visible LEDs (385–470 nm). BPND can even produce radicals without any added hydrogen donor. The photochemical mechanisms are studied by molecular orbital calculations, steady state photolysis, electron spin resonance spin trapping, fluorescence, cyclic voltammetry and laser flash photolysis techniques. These novel BPND based photoinitiating systems exhibit an efficiency higher than that of the well‐known camphorquinone‐based systems (FRP and CP) or comparable to that of bis(2,4,6‐trimethylbenzoyl)‐phenylphosphineoxide (FRP at λ ≤ 455 nm). © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 445–451     

Functionalization of single-walled carbon nanotubes for direct and selective electrochemical detection of DNA

We report here a new strategy to graft both redox and DNA probes on carbon nanotubes to make a label-free DNA sensor. Oxidized single-walled carbon nanotubes are first immobilized on a self-assembled monolayer of cysteamine; then the redox probe, a quinone derivative 3-[(2-aminoethyl)sulfanyl-5-hydroxy-1,4-naphthoquinone], is grafted on the free carboxylic groups of the nanotubes. After that, for DNA probe grafting, new carboxylic sites are generated via an aryl diazonium route. After hybridization with a complementary sequence, the conformational changes of DNA could influence the redox kinetics of quinone, leading to a current increase of the redox signal, detected by square wave voltammetry. The system is selective, as it can discriminate a single mismatched sequence from the complementary one.     

Density functional study of the charge on Aun clusters (n=1-7) supported on a partially reduced rutile TiO2(110): are all clusters negatively charged?

It is widely believed that small gold clusters supported on an oxide surface and adsorbed at the site of an oxygen vacancy are negatively charged. It has been suggested that this negative charge helps a gold cluster adsorb oxygen and weakens the O-O bond to make oxidation reactions more efficient. Given the fact that an oxygen vacancy is electron rich and that Au is a very electronegative element, the assumption that the Au cluster will take electron density from the vacancy is plausible. However, the density functional calculations presented here show that the situation is more complicated. The authors have used the Bader method to examine the charge redistribution when a Aun cluster (n=1-7) binds next to or at an oxygen vacancy on rutile TiO2(110). For the lowest energy isomers they find that Au1 and Au3 are negatively charged, Au5 and Au7 are positively charged, and Au2, Au4, and Au6 exchange practically no charge. The behavior of the Aun isomers having the second-lowest energy is also unexpected. Au2, Au3, Au5, and Au7 are negatively charged upon adsorption and very little charge is transferred when Au4 and Au6 are adsorbed. These observations can be explained in terms of the overlap between the frontier molecular orbitals of the gold cluster and the eigenstates of the support. Aun with even n becomes negatively charged when the lowest unoccupied molecular orbital has a lobe pointing in the direction of the oxygen vacancy or towards a fivefold coordinated Ti (5c-Ti) located in the surface layer; otherwise it stays neutral. Aun with odd n becomes negatively charged when the singly occupied molecular orbital has a lobe pointing in the direction of a 5c-Ti located at the vacancy site or in the surface layer, otherwise it donates electron density into the conduction band of rutile TiO2(110) becoming positively charged.     

Recent Advances and Challenges in the Design of Organic Photoacid and Photobase Generators for Polymerizations

Photopolymerization, or the use of light to trigger polymerization, is one of the most exciting technologies for advanced manufacturing of polymers. One of the key components in the photopolymerization processes is the photoactive compound that absorbs the light, generating the active species that promotes the polymerization and largely determines the final properties of the material. The field of photopolymerization has been dominated by photoradical generators to mediate radical reactions. In the last decade, to expand the number of polymers that can be prepared by photopolymerization, intensive research has been devoted to the synthesis and utilization of photoactive molecules that are able to generate a base or an acid upon irradiation. These organic compounds are known to promote not only the ring‐opening polymerization of various heterocyclic monomers such as lactones, carbonates, or epoxides but also to trigger the step‐growth synthesis of polyurethanes. This Minireview highlights the recent advances in the development of organic photobase and photoacid generators, with the aim of encouraging the wider application of these photoactive compounds in the photopolymerization area and to expand the use of these polymers in advanced manufacturing processes.     

On the plasticization of poly(2,6-dimethyl phenylene oxide) by CO2

Change in the glass transition temperature, T_g, of poly(2,6-dimethyl phenylene oxide), PPO, due to the dissolved CO₂ has been measured as a function of the gas pressure, p, using a high-pressure DSC cell. At 61.2 atm, the highest pressure studied, T_g is depressed by 31.6°C. The depression in T_g is found to be linear with pressure, with dT_g/dp of ?0.5°C atm^?1. The experimental results are in fair agreement with those calculated from a quasilattice solid-solution model for polymer-diluent systems. The present results, however, differ markedly from a recent investigation on PPO-CO₂ system which reported a depression in T_g of 226°C at 60 atm and a dT_g/dp of ?3.8°C atm^?. © 1994 John Wiley & Sons, Inc.