Substituted Cyclopentannulated Tetraazapentacenes

Brominated pentannulated dihydrotetraazapentacenes were prepared by gold- or palladium-catalyzed 5-endo-dig cyclization of TIPS-ethynylated dihydrotetraazaacenes (TIPS = triisopropylsilyl). Post-functionalization was demonstrated by Sonogashira alkynylation and Rosenmund-von Braun cyanation. Calculations predict these species to act as n-type semiconductors, which was verified for two derivates through characterization in organic field-effect transistors.     

Limit and shakedown analysis of pressurized pipelines containing defects

In this paper, the integrity assessment of pressurized pipelines containing defects is performed by direct simplified methods of limit and shakedown analysis. The defects considered are part-through slots of various geometrical configurations. The engineering situation considered here has practical importance in the pressure vessel and pipe industry. The results are compared with those obtained by a step-by-step procedure using the professional code ABAQUS and where possible, with those provided by semi-empirical formulae used in engineering. The simplified methods are found more economical and more reliable than marching solutions achieved by step-by-step evolutive elastic-plastic analysis. The effects of various part-through slots on the load-carrying capacities of pipelines are investigated. The project was supported by the National Science and Technology Commission of China and by the Department of Structural Engineering, Technical University of Milan, Italy     

On linear versus nonlinear flow rules in strain localization analysis

Summary This note contains some remarks on the analysis of bifurcation phenomena, specifically strain localization (onset of a strain rate discontinuity), in small-deformation elastoplasticity. Nonassociative flow rules are allowed for to cover constitutive models frequently adopted for frictional (and softening) materials such as concrete. The conventional derivation of the localization criterion resting on an incrementally linear comparison material is critically reviewed and compared to the criterion resulting from actual nonlinear plastic flow laws.

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Sommario Si svolgono alcune considerazioni sui fenomeni di biforcazione in solidi elastoplastici in regime di piccole deformazioni (di linearità geometrica) e precisamente sul manifestarsi di localizzazioni intese come discontinuità nel campo delle deformazioni incrementali. Si considerano leggi nonassociate. Vengono così inclusi nella trattazione modelli costitutivi frequentemente adottati per descrivere il comportamento di materiali ad attrito interno e soggetti a danneggiamento (nel senso di degrado di rigidezze elastiche in seguito a deformazioni anelastiche), oltre che soggetti a manifestazioni di instabilità per incrudimento negativo (softening). Si esamina criticamente il criterio, frequentemente adottato in letteratura, di localizzazione fondato su materiale di confronto incrementalmente lineare e si fornisce, corredato da osservazioni comparative, il criterio che risulta dall'assunzione del modello di materiale incrementale non lineare

     

Magnetic NiFe2O4 Nanoparticles Prepared via Non-Aqueous Microwave-Assisted Synthesis for Application in Electrocatalytic Water Oxidation

Phase-pure spinel-type magnetic nickel ferrite (NiFe₂O₄) nanocrystals in the size range of 4 to 11 nm were successfully synthesized by a fast and energy-saving microwave-assisted approach. Size and accessible surface areas can be tuned precisely by the reaction parameters. Our results highlight the correlation between size, degree of inversion, and magnetic characteristics of NiFe₂O₄ nanoparticles, which enables fine-tuning of these parameters for a particular application without changing the elemental composition. Moreover, the application potential of the synthesized powders for the electrocatalytic oxygen evolution reaction in alkaline media was demonstrated, showing that a low degree of inversion is beneficial for the overall performance. The most active sample reaches an overpotential of 380 mV for water oxidation at 10 mA cm⁻² and 38.8 mA cm⁻² at 1.7 V vs. RHE, combined with a low Tafel slope of 63 mV dec⁻¹.     

Cation‐Dependent Stabilization of Electrogenerated Naphthalene Diimide Dianions in Porous Polymer Thin Films and Their Application to Electrical Energy Storage

Porous polymer networks (PPNs) are attractive materials for capacitive energy storage because they offer high surface areas for increased double‐layer capacitance, open structures for rapid ion transport, and redox‐active moieties that enable faradaic (pseudocapacitive) energy storage. Here we demonstrate a new attractive feature of PPNs—the ability of their reduced forms (radical anions and dianions) to interact with small radii cations through synergistic interactions arising from densely packed redox‐active groups, only when prepared as thin films. When naphthalene diimides (NDIs) are incorporated into PPN films, the carbonyl groups of adjacent, electrochemically generated, NDI radical anions and dianions bind strongly to K⁺, Li⁺, and Mg²⁺, shifting the formal potentials of NDI’s second reduction by 120 and 460 mV for K⁺ and Li⁺‐based electrolytes, respectively. In the case of Mg²⁺, NDI’s two redox waves coalesce into a single two‐electron process with shifts of 240 and 710 mV, for the first and second reductions, respectively, increasing the energy density by over 20 % without changing the polymer backbone. In contrast, the formal reduction potentials of NDI derivatives in solution are identical for each electrolyte, and this effect has not been reported for NDI previously. This study illustrates the profound influence of the solid‐state structure of a polymer on its electrochemical response, which does not simply reflect the solution‐phase redox behavior of its monomers.     

The 192 solutions of the Heun equation

A machine-generated list of local solutions of the Heun equation is given. They are analogous to Kummer's  solutions of the Gauss hypergeometric equation, since the two equations are canonical Fuchsian differential equations on the Riemann sphere with four and three singular points, respectively. Tabulation is facilitated by the identification of the automorphism group of the equation with  singular points as the Coxeter group  . Each of the expressions is labeled by an element of  . Of the ,  are equivalent expressions for the local Heun function  , and it is shown that the resulting order- group of transformations of  is isomorphic to the symmetric group . The isomorphism encodes each transformation as a permutation of an abstract four-element set, not identical to the set of singular points.

     

Electronic absorption spectra of the protonated polyacetylenes HC2nH2+ (n=3,4) in the gas phase

A new approach has been developed for the purpose of measuring the electronic transitions to bound exited states for cations that have been collisionally relaxed to low vibrational and rotational temperatures. This has been used to obtain the first gas phase electronic spectra of the protonated polyacetylenes using a two-color ion-photodissociation approach. Specifically, the origin bands in the B (1)A(1)<-- X(1)A(1) transitions of HC(6)H(2) (+) and HC(8)H(2) (+) (C(2v) geometry) were observed at 26,403.3 and 21,399.8 cm(-1). Data on such cooled systems allow a direct comparison between laboratory and astrophysical measurements.     

Capillary electrophoretic method for nucleotide analysis in cells: application on inherited metabolic disorders

Purine and pyrimidine nucleotides influence many metabolic pathways and their analogs have been widely used in medicine. A capillary electrophoretic method was developed for measuring intracellular nucleotides. The final BGE consisted of 40 mM citric acid with addition of 0.8 mM CTAB titrated by gamma-aminobutyric acid to pH 4.4. The electrophoretic separations were carried out in an uncoated silica capillary (id/od - 75/375 microm; effective/total length - 90/97 cm). The method allows a complete separation of 21 nucleotides and deoxynucleotides within 15 min with separation efficiencies up to 400,000 theoretical plates per meter. Due to the use of an acidic separation medium, the method offers a high selectivity toward the studied analytes versus possible interferences from matrices. Sample preparation was optimized in order to shorten work-time and prevent analyte degradation. The method was applied for analyzing nucleotides in human erythrocytes and Chinese hamster ovary cells. Diagnostic potential for inherited metabolic disorders of nucleotide metabolism is presented.     

Gas phase electronic spectrum of linear AlCCH

The electronic spectrum of the aluminium containing species AlCCH has been detected in the gas phase in the region 315-355 nm. The experiment used a mass selective resonant two-color two-photon ionization technique coupled to a laser ablation source. Structures of the AlCCH isomers have been optimized using density functional theory (DFT) and the excitation energies to the low-lying electronic excited states calculated. Based on the analysis of the observed rotational structure and the theoretical data, the spectrum is assigned to the A (1)Pi<-- X (1)Sigma(+) electronic transition of linear AlCCH. The vibronic band system is complicated by the Renner-Teller effect in the excited state. The assignment yields nu(4)' = 516.4 cm(-1) for the stretching mode in the ground X (1)Sigma(+) state and nu(4)' = 654.5 cm(-1) for A (1)Pi excited state. Molecular constants determined from the rotational analysis are B(0)' = 0.16487(14), B(0)' = 0.17845(13) and T(0) = 28 755.04 cm(-1). The experimental and theoretical data indicate a shorter Al-C bond in the A (1)Pi excited than the X (1)Sigma(+) ground state.