Insights into MWCNTs/polyimide nanocomposites: from synthesis to application as free-standing flexible electrodes in low-cost micro-supercapacitors

In the pursuit to enlarge the library of polyimide materials for energy applications, new polyimide/MWCNTs composite films have been developed by MWCNTs-assisted polycondensation reaction of a hydroxyl and triphenylmethane-containing diamine with benzophenone tetracarboxylic dianhydride targeting to highlight their electrical storage capability as flexible electrodes in micro-supercapacitors (mSCs). The Fourier-transform infrared spectroscopy, proton nuclear magnetic resonance, UV–vis, fluorescence, and Raman spectroscopies were used to demonstrate the evolution of interfacial interactions between MWCNTs and the precursors (diamine monomer and intermediate polyamidic acid) and polyimide matrix that proved to be the origin of MWCNTs homogeneous dispersion. Thus, composite films incorporating 1, 3, 5, and 10 w.t.% MWCNTs were obtained and thoroughly investigated with regard to their morphology, mechanical behavior, thermal stability, and electrical conductivity. The electrochemical performance of these composites was first analyzed in a classical three-electrode cell by cyclic voltammetry and galvanostatic charge-discharge in both aqueous and organic electrolyte systems. By far, the best electrical storage capacity was obtained with the composite polyimide film containing 10% MWCNTs that was further used as both active material and current collector in a flexible symmetric mSC realized by a straightforward and low-cost procedure. In the attempt to better exploit the advantages of this composite film, it was layered with a graphite-containing paint and tested as an electrode in a flexible mSC, which provided satisfactory results. To our knowledge, this is the first report on the electrical charge storage capability of a polyimide/MWCNTs free-standing film as a flexible electrode in mSCs, which do not require time- and resource-consuming processing steps.     

Functionalized Silver-Ion-Mediated α-dC/β-dC Hybrid Base Pairs with Exceptional Stability: α-d-5-Iodo-2′-Deoxycytidine and Its Octadiynyl Derivative in Metal DNA

Silver-mediated α-dC–Ag⁺–β-dC hybrid base pairs decorated with 5-iodo- or 5-octadiynyl residues are well accommodated in duplex DNA. A strong T_m increase and favorable thermodynamic data for duplex DNA were observed after addition of silver ions. The phenomenon is particularly obvious when both nucleobases of the base pairs are functionalized. Neither the position of the base pair, nor the type of 5-substituent had a negative influence. On the contrary, functionalization of conventional silver-mediated β-dC–Ag⁺–β-dC homo base pairs showed a negative impact induced by the bulky substituents. To this end, cytosine modified 12-mer oligodeoxynucleotides were prepared by solid-phase synthesis employing new α-anomeric 2′-deoxycytidine phosphoramidites. A multigram scale synthesis was developed for 5-iodo-α-d -2′-deoxycytidine ( 1 ) employing the direct glycosylation of cytosine with Hoffer's α-d -halogenose followed by separation of anomeric DMT nucleosides. Regarding base-pair stability and functionalization silver-mediated α/β-dC hybrid base pairs were found to be superior to β/β-dC homo pairs. According to their extraordinary properties, they might find applications in DNA diagnostics, material science, or nanotechnology.     

The Landscape of the Spiked Tensor Model

We consider the problem of estimating a large rank-one tensor u ^⊗k ∈ (ℝⁿ)^⊗k , k ≥ 3 , in Gaussian noise. Earlier work characterized a critical signal-to-noise ratio λ  _Bayes = O(1) above which an ideal estimator achieves strictly positive correlation with the unknown vector of interest. Remarkably, no polynomial-time algorithm is known that achieved this goal unless λ ≥ Cn^{(k − 2)/4} , and even powerful semidefinite programming relaxations appear to fail for 1 ≪ λ ≪ n^{(k − 2)/4} . In order to elucidate this behavior, we consider the maximum likelihood estimator, which requires maximizing a degree-k homogeneous polynomial over the unit sphere in n dimensions. We compute the expected number of critical points and local maxima of this objective function and show that it is exponential in the dimensions n , and give exact formulas for the exponential growth rate. We show that (for λ larger than a constant) critical points are either very close to the unknown vector u or are confined in a band of width Θ(λ^{−1/(k − 1)}) around the maximum circle that is orthogonal to u . For local maxima, this band shrinks to be of size Θ(λ^{−1/(k − 2)}) . These “uninformative” local maxima are likely to cause the failure of optimization algorithms. © 2019 Wiley Periodicals, Inc.     

Finsler vector bundles -- Metrizable connections

Periodica Mathematica Hungarica -     

Mathematical modeling of two-photon thermal fields in laser–solid interaction

In this paper, we have developed an analytical model to study the temperature distributions in IR optical materials heated by laser pulses. Our model takes into account the two-photon absorption (TPA). The calculations are based on a three-dimensional model of heat diffusion in solids using the integral transform method. We find out the rigorous analytical expression of the thermal field when one considers both one- and two-photon absorption. The model is valid for any laser–solid system whose interaction can be described by the generalized Beer–Lambert law. Specific results are presented for an application of the model to ZnSe sample. We find out that TPA can produce detectable temperature variation.     

Systematic formulations for electronegativity and hardness and their atomic scales within density functional softness theory

A unified Mulliken valence with Parr ground‐state electronegativity picture is presented. It provides a useful analytical tool on which the absolute hardness as well ionization potential and electron affinity functionals are based. For all these chemical reactivity indices, systematic approximate density functionals are formulated within density functional softness theory and are applied to atomic systems. For the absolute hardness, a special relationship with the new electronegativity ansatz and a particular atomic trend paralleling the absolute electron affinity are established that should complement and augment the earlier finite‐difference energetic approach. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006     

Chelate polymers: II. Some novel transition metals complexes with azomethine‐containing siloxanes and their polyesters

New Schiff bases of 2,4‐dihydroxybenzaldehyde with siloxane‐α,ω‐diamines having different numbers of siloxane units in the chain have been synthesized and characterized by spectroscopy, elemental and thermal analyses. These azomethines were found to form complexes readily with copper(II), nickel(II), cobalt(II), cadmium(II) and zinc(II). From IR and UV–Vis studies, the phenolic oxygen and imine nitrogen of the ligand were found to be the coordination sites. Thermogravimetric analysis (TGA) data indicate the chelates to be more stable than the corresponding ligands. The melting points increase with shortening of the siloxane segment from azomethine, as well as the result of complexation. The chelates obtained were covalently inserted in polymeric linear structures by polycondensation through the OH‐difunctionalized ligand with 1,3‐bis(carboxypropyl)tetramethyldisiloxane. Direct polycondensation, assisted either by acetic anhydride or N,N′‐dicyclohexylcarbodiimide as dehydrating agent and the complex 4‐(dimethylamino)pyridinium 4‐toluenesulfonate as catalyst, was used for the synthesis of these compound types. The structures of the polymers obtained were confirmed by IR, UV and ¹H NMR. Characterization was undertaken by TGA, solubility tests and viscosity measurements. Copyright © 2003 John Wiley & Sons, Ltd.     

Limits of tangents and minimality of complex links

We show that the complex link of a large class of space germs (X,x₀) is characterized by its “simplicity”, among the Milnor fibres of functions with isolated singularity on X. This amounts to the minimality of the Milnor number, whenever this number is defined. Such a phenomenon has been first pointed out in case (X,x₀) is an isolated hypersurface singularity, by Teissier (Cycles évanescents, sections planes et conditions de Whitney, in: Singularités à Cargèse 1972, Asterisque, Nos. 7 et 8, Soc. Math. France, Paris, 1973, pp. 285-362).