Rapid Discrimination of Crystal Handedness by X-ray Natural Circular Dichroism (XNCD) Mapping

An original method for determining the handedness of individual non-centrosymmetric crystals in a mixture using a tightly-focused, circularly polarized X-ray beam is presented. The X-ray natural circular dichroism (XNCD) spectra recorded at the metal K-edge on selected crystals of [Δ-M(en)₃](NO₃)₂ and [Λ-M(en)₃](NO₃)₂ (M=Co^II, Ni^II) show extrema at the metal pre-edge (7712 eV for Co, 8335 eV for Ni). A mapping of a collection of some 220 crystals was performed at the respective energies by using left and right circular polarizations. The difference in absorption for the two polarizations, being either negative or positive, directly yielded the handedness of the crystal volume probed by the beam. By using this technique, it was found that the addition of l -ascorbic acid during the synthesis of [Co(en)₃](NO₃)₂ resulted in an enantiomeric enrichment of the Λ-isomer of 67±13 %, whereas the Ni analogue was similarly, but conversely, enriched in the Δ-isomer (65±22 %).     

Experimental study on age and gender differences in microscopic movement characteristics of students

Campus security has aroused many concerns from the whole society. Stampede is one of the most frequent and influential accidents in campus. Studies on pedestrian dynamics especially focusing on students are essential for campus security, which are helpful to improve facility design and emergency evacuation strategy. In this paper, primary and middle school students were recruited to participate in the single-file experiments. The microscopic movement characteristics,including walking speed, headway, gait characteristics(step length, step frequency and swaying amplitude) and their relations were investigated. Age and gender differences in the headway-speed diagram and space requirements were analyzed by statistical tests. The results indicated that the impacts of age and gender were significant. There were three stages for the influence of gender on the headway-speed diagram for both age groups. The impacts on students' space requirements were consistent for different age and gender groups. But the impacts of age and gender on free-flow speed were affected by each other. Due to the connection of walking speed and gait characteristics, the comparisons of gait characteristics between different ages and genders were performed to understand the corresponding differences in speed more deeply. The results showed that differences in step length and swaying amplitude between males and females were significant for both age groups. The effect of gender on step frequency was significant for primary students. But for middle school students,whether gender had significant impact on step frequency was not clear here because of the large P-value. Besides, the influence of age on gait characteristics changed with gender.     

Conventional vs. Microwave- or Mechanically-Assisted Synthesis of Dihomooxacalix[4]arene Phthalimides: NMR,X-ray and Photophysical Analysis §

Direct O-alkylation of p-tert-butyldihomooxacalix[4]arene (1) with N-(bromopropyl)- or N-(bromoethyl)phthalimides and K₂CO₃ in acetonitrile was conducted under conventional heating (reflux) and using microwave irradiation and ball milling methodologies. The reactions afforded mono- and mainly distal di-substituted derivatives in the cone conformation, in a total of eight compounds. They were isolated by column chromatography, and their conformations and the substitution patterns were established by NMR spectroscopy (¹H, ¹³C, COSY and NOESY experiments). The X-ray structures of four dihomooxacalix[4]arene phthalimide derivatives (2a, 3a, 3b and 5a) are reported, as well as their photophysical properties. The microwave (MW)-assisted alkylations drastically reduced the reaction times (from days to less than 45 min) and produced higher yields of both 1,3-di-substituted phthalimides (3a and 6a) with higher selectivity. Ball milling did not reveal to be a good method for this kind of reaction.     

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.     

Projective well orders and coanalytic witnesses

We further develop a forcing notion known as Coding with Perfect Trees and show that this poset preserves, in a strong sense, definable P-points, definable tight MAD families and definable selective independent families. As a result, we obtain a model in which $\mathfrak{a}=\mathfrak{u}=\mathfrak{i}={\mathrm{?}}_1<2^{{\mathrm{?}}_0}={\mathrm{?}}_2$, each of $\mathfrak{a}$, $\mathfrak{u}$, $\mathfrak{i}$ has a ${\mathrm{\Pi }}_1^1$ witness and there is a ${\mathrm{\Delta }}_3^1$ well-order of the reals. Note that both the complexity of the witnesses of the above combinatorial cardinal characteristics, as well as the complexity of the well-order are optimal. In addition, we show that the existence of a ${\mathrm{\Delta }}_3^1$ well-order of the reals is consistent with $\mathfrak{c}={\mathrm{?}}_2$ and each of the following: $\mathfrak{a}=\mathfrak{u}<\mathfrak{i}$, $\mathfrak{a}=\mathfrak{i}<\mathfrak{u}$, $\mathfrak{a}<\mathfrak{u}=\mathfrak{i}$, where the smaller cardinal characteristics have co-analytic witnesses.Our methods allow the preservation of only sufficiently definable witnesses, which significantly differs from other preservation results of this type.     

Modified Burgers-Reimschuessel model for moisture-sensitive polymers

Viscoelastic properties of moisture-sensitive polymers can be significantly affected by moisture in the ambient environment, resulting in drastic changes in the properties as the absorbed moisture content increases. In this article, a simple yet important modification to the Reimschuessel model is introduced by considering both plasticization and anti-plasticization induced by water molecules. The proposed model is validated against the results of four different polymers obtained by Onogi et al., which demonstrates its capability of describing the available data. This model can be used to estimate the performance and service life of products produced using moisture-sensitive polymers. It also reveals that small amounts of diffused moisture might have a stiffening effect on the mechanical properties of hydrophilic polymers.     

Indeno[1,2,3,4-pqra]Perylene: A Medium-Sized Aromatic Hydrocarbon Exhibiting Full-Range Visible-Light Absorption

We report the synthesis and properties of indeno[1,2,3,4-pqra]perylene, which was prepared by the fusion of one anthracene unit with one naphthalene unit via three carbon-carbon bonds. The synthetic route through two-fold C−H arylation enabled not only the synthesis of unsubstituted indenoperylene, but also rapid access to its arylated derivatives on the gram scale. Indenoperylene is a medium-sized aromatic hydrocarbon with the composition C₂₄H₁₂ that is isomeric to coronene. Nevertheless, its absorption covers the entire visible region owing to its small HOMO-LUMO gap. Furthermore, indenoperylene exhibits high stability despite the absence of peripheral substituents. We propose that the unique electronic structure of indenoperylene originates from the coexistence of an electron-withdrawing subunit (benzoaceanthrylene) and an electron-donating subunit (perylene). The electronic properties of indenoperylene were modulated via post-functionalization through regioselective bromination. The current research demonstrates that indenoperylene is a promising candidate as a main skeleton for near-infrared-responsive and redox-active materials.     

A simple and rapid route for synthesizing the nanosized g-C3N4 materials with narrow bandgap and their photocatalytic activity

The graphitic carbon nitride (g-C₃N₄) materials with many intriguing properties have attracted much attention in photocatalysis. The photocatalytic activity of g-C₃N₄ is hindered by serious aggregation and limited exposed active sites. Herein is shown that nanosized g-C₃N₄ can be simply obtained by a superfast high-pressure homogenization approach. The high-pressure homogenization treatment can provide strong force to cut and/or to exfoliate the bulk g-C₃N₄ into nanosized g-C₃N₄ with good dispersion. Moreover, choosing different solvents during treatment can cause a different surface structure of as-prepared nanosized g-C₃N₄. In addition, the narrow bandgap properties, the high photogenerated charge carrier separation, and the transport abilities are achieved in as-prepared nanosized g-C₃N₄ because of the retaining conjugated C₃N₄ system. Specifically, the photocatalytic activities of as-prepared nanosized g-C₃N₄ have been significantly enhanced in terms of degradation of organic dye Rhodamine B (RhB) under visible light irradiation (10 times higher than that of bulk g-C₃N₄). These findings can provide a promising and simple approach to the exfoliation, nanonization, and surface functionalization of 2D layered materials.     

Effect of synthesis parameters on the structural,morphological characteristics,and photocatalytic activity of La2O3 nanoparticles

This study investigates the influence of synthesis processes such as sonication, sol-gel, and microwave on the production of highly crystalline Lanthanum oxide nanoparticles (La₂O₃) employing Lanthanum nitrate and Ammonium hydroxide (NH₄OH) as precursors. X-ray diffraction (XRD), particle size analysis (DLS), Field emission scanning electron microscopy (FESEM), Fourier-transform infrared spectroscopy (FTIR), ultraviolet–visible absorption spectroscopy (UV–Vis), and electrochemical impedance spectroscopy (EIS) were used to examine the most effective processing method and its effects on the nanoparticle characteristics, such as structure, morphology, and optical and electrical behavior. Sonication produces La₂O₃ NPs with a smaller crystalline size, an agglomerated nanorod structure, a higher bandgap, and better electrical responsiveness than sol-gel and microwave techniques. Structural and optical characterization tests discovered this. The photocatalytic degradation activity of cationic Safranin and anionic Congo red dye exhibits degradation efficiency of around 90.13% and 89.66%, respectively.     

Exposing the Oxygen-Centered Radical Character of the Tetraoxido Ruthenium(VIII) Cation [RuO4]+

The tetraoxido ruthenium(VIII) radical cation, [RuO₄]⁺, should be a strong oxidizing agent, but has been difficult to produce and investigate so far. In our X-ray absorption spectroscopy study, in combination with quantum-chemical calculations, we show that [RuO₄]⁺, produced via oxidation of ruthenium cations by ozone in the gas phase, forms the oxygen-centered radical ground state. The oxygen-centered radical character of [RuO₄]⁺ is identified by the chemical shift at the ruthenium M₃ edge, indicative of ruthenium(VIII), and by the presence of a characteristic low-energy transition at the oxygen K edge, involving an oxygen-centered singly-occupied molecular orbital, which is suppressed when the oxygen-centered radical is quenched by hydrogenation of [RuO₄]⁺ to the closed-shell [RuO₄H]⁺ ion. Hydrogen-atom abstraction from methane is calculated to be only slightly less exothermic for [RuO₄]⁺ than for [OsO₄]⁺.