A low molecular weight hydrogel which exhibits electroosmotic flow and its use as a bioreactor and for electrochromatography of neutral species

A low molecular weight hydrogel which exhibits electroosmotic flow is described, and its use for separation and biocatalytic applications that require passage of a solvent stream through the gel is demonstrated.     

Coding for locality in reconstructing permutations

The problem of storing permutations in a distributed manner arises in several common scenarios, such as efficient updates of a large, encrypted, or compressed data set. This problem may be addressed in either a combinatorial or a coding approach. The former approach boils down to presenting large sets of permutations with locality, that is, any symbol of the permutation can be computed from a small set of other symbols. In the latter approach, a permutation may be coded in order to achieve locality. Both approaches must present low query complexity to allow the user to find an element efficiently. We discuss both approaches, and give a particular focus to the combinatorial one. In the combinatorial approach, we provide upper and lower bounds for the maximal size of a set of permutations with locality, and provide several simple constructions which attain the upper bound. In cases where the upper bound is not attained, we provide alternative constructions using a variety of tools, such as Reed-Solomon codes, permutation polynomials, and multi-permutations. In addition, several low-rate constructions of particular interest are discussed. In the coding approach we discuss an alternative representation of permutations, present a paradigm for supporting arbitrary powers of the stored permutation, and conclude with a proof of concept that permutations may be stored more efficiently than ordinary strings over the same alphabet.     

In quest of reversibility of Friedel-Crafts acyl rearrangements in the pyrene series

Friedel-Crafts acyl rearrangements in PPA of diacetylpyrenes (80–120 °C), dibenzoylpyrenes (80–200 °C), and bis(4-flurobenzoyl)pyrenes (80–120 °C) and Scholl reactions in AlCl₃/NaCl of dibenzoylpyrenes (140–200 °C) have been studied. The substrates were 1-AcPY, 2-AcPY, 1,3-Ac₂PY, 1,6-Ac₂PY, 1,8-Ac₂PY, 2,7-Ac₂PY, 1-BzPY, 1,6-Bz₂PY, 1,8-Bz₂PY, 1-4FBzPY, 1,6-4FBz₂PY, 1,8-4FBz₂PY. The mixtures of pyrene, 1-AcPY, 2-AcPY, 1,3-Ac₂PY, 1,6-Ac₂PY, 1,8-Ac₂PY, and 2,7-Ac₂PY were separated by HPLC. The following reversible intermolecular isomerizations were established: 1,6-Ac₂PY ? 1,8-Ac₂PY, 1,6-Bz₂PY ? 1,8-Bz₂PY, and 1,6-4'FBz₂PY ? 1,8-4'FBz₂PY, albeit not in high yields. The results substantiate Gore’s 1955 proposition that “The Friedel–Crafts acylation reaction of reactive aromatic hydrocarbons is a reversible process.” The isomerizations reported here differ from the few previously reported completely reversible intramolecular Friedel-Crafts acyl rearrangements. At ≥ 140 °C, in PPA and in AlCl₃/NaCl, 1,6-Bz₂PY and 1,8-Bz₂PY underwent a highly regioselective double Scholl reaction to give pyranthrone (3) and deacylations to 1-BzPy (and pyrene), followed by mono-Scholl reactions to give 8H-dibenzo[def,qr]chrysen-8-one (1), and 11H-indeno[2,1-a]pyren-11-one (2). The formation of 3 and not the expected tribenzo[a,ghi,o]perylene-7,16-dione (4) from 1,8-Bz₂PY indicates that 1,8-Bz₂PY has first undergone isomerization to 1,6-Bz₂PY. The present study confirms the linkage between Friedel-Crafts acyl rearrangements and the Scholl reaction.

     

Stable aromatic dianion in water

Perylene diimide (PDI) bearing polyethylene glycol substituents at the imide positions was reduced in water with sodium dithionite to produce an aromatic dianion. The latter is stable for months in deoxygenated aqueous solutions, in contrast to all known aromatic dianions which readily react with water. Such stability is due to extensive electron delocalization and the aromatic character of the dianion, as evidenced by spectroscopic and theoretical studies. The dianion reacts with oxygen to restore the parent neutral compound, which can be reduced again in an inert atmosphere with sodium dithionite to give the dianion. Such reversible charging renders PDIs useful for controlled electron storage and release in aqueous media. Simple preparation of the dianion, reversible charging, high photoredox power, and stability in water can lead to development of new photofunctional and electron transfer systems in the aqueous phase.     

A characterization of the disc via a Hessian equality

LetM be a bounded open plane domain. Let f be a continuous function on the closure of M, 3-times continuously differentiable in M, which vanishes on the boundary. Polterovich and Sodin proved that the values of f cannot exceed the norm of the Hessian of f, averaged over the entire domain M. In this work we study the equality case for this inequality. We show that equality holds if and only if M is an open disc and f belongs to a special class of radial functions. We also give an upper bound for f.     

MXenes in aqueous electrochemical energy systems

Journal of Solid State Electrochemistry - Since their discovery in 2011, MXenes are extensively studied as materials for electrochemical energy storage systems. The high electric conductivity, 2D...     

The linkage between reversible Friedel–Crafts acyl rearrangements and the Scholl reaction

Structural Chemistry - Friedel–Crafts acyl rearrangements in PPA (at 80–240 °C) and Scholl reactions in AlCl3/NaCl (at 140–220 °C) of...     

Control over self-assembly through reversible charging of the aromatic building blocks in photofunctional supramolecular fibers

Self-assembling systems, whose structure and function can be reversibly controlled in situ are of primary importance for creating multifunctional supramolecular arrays and mimicking the complexity of natural systems. Herein we report on photofunctional fibers self-assembled from perylene diimide cromophores, in which interactions between aromatic monomers can be attenuated through their reduction to anionic species that causes fiber fission. Oxidation with air restores the fibers. The sequence represents reversible supramolecular depolymerization-polymerization in situ and is accompanied by a reversible switching of photofunction.     

Is “Water in Salt” Electrolytes the Ultimate Solution? Achieving High Stability of Organic Anodes in Diluted Electrolyte Solutions Via a Wise Anions Selection

The introduction of the water-in-salt (WIS) electrolytes concept to prevent water splitting and widen the electrochemical stability window, has spurred extensive research efforts toward development of improved aqueous batteries. The successful implementation of these electrolyte solutions in many electrochemical systems shifts the focus from diluted to WIS electrolyte solutions. Considering the high costs and the tendency of these nearly saturated solutions to crystallize, this trend can be carefully re-evaluated. Herein we show that the stability of organic electrodes comprising the active material perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA), is strongly influenced by the solvation character of the anions rather than the concentration of the electrolyte solution. Even though the charging process of PTCDA involves solely insertion of cations (i.e., principal counter-ions), surprisingly, the dominant factor influencing its electrochemical performance, including long-term electrode stability, is the type of the co-ions (i.e., electrolytic anions). Using systematic electrochemical analysis combined with theoretical simulations, we show that the selection of kosmotropic anions results in fast fading of the PTCDA anodes, while a selection of chaotropic anions leads to excellent stability, even at electrolytes concentrations as low as 0.2 M. These findings provide a new conceptual approach for designing advanced electrolyte solutions for aqueous batteries.