Optimizing the monomer structure of polyhedral oligomeric silsesquioxane for ion transport in hybrid organic–inorganic block copolymers

Poly(ethylene oxide)-b-polyhedral oligomeric silsesquioxane (PEO–POSS) mixed with lithium bis(trifluoromethanesulfonyl)imide salt is a nanostructured hybrid organic–inorganic block copolymer electrolyte that may enable lithium metal batteries. The synthesis and characteristics of three PEO–POSS block copolymer electrolytes which only differ by their POSS silica cage substituents (ethyl, isobutyl, and isooctyl) is reported. Changing the POSS monomer structure results in differences in both thermodynamics and ion transport. All three neat polymers exhibit lamellar morphologies. Adding salt results in the formation of a disordered window which closes and gives way to lamellae at higher salt concentrations. The width of disordered window decreases with increasing length of the POSS alkyl chain substituent from ethyl to isobutyl and is absent in the isooctyl sample. Rheological measurements demonstrate good mechanical rigidity when compared with similar all-organic block copolymers. While salt diffusion coefficient and current ratio are unaffected by substituent length, ionic conductivity increases as the length of the alkyl chain substituent decreases: the ethyl substituent is optimal for ion transport. This is surprising because conventional wisdom suggests that ion transport occurs primarily in the PEO-rich domains, that is, ion transport should be unaffected by substituent length after accounting for the minor change in conducting phase volume fraction. © 2020 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2020 © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 363–371     

Reduced magnetic disorder at low temperature in Ca3Co2O6 via zinc substitution

ABSTRACT

The compound Ca₃Co₂O₆ undergoes a transition into a spin-density wave (SDW) state near 24?K. Below ～10?K, this unstable SDW state coexists with a nearly- degenerate commensurate antiferromagnetic state as well as short-range magnetic order. Clear signatures of this strong magnetic disorder have been observed in the response of entropy to changing magnetic field and temperature. We performed a calorimetry study of Ca₃Co₂O₆ and Ca₃Co_1.9Zn_0.1O₆ in order to compare their entropic responses at low temperature. Our results for Ca₃Co₂O₆ reveal that ΔS(T, H)?≡?S(T, H)?S(T, H?=?0) increases as either temperature or magnetic field increase. In contrast, ΔS data for Ca₃Co_1.9Zn_0.1O₆ were relatively unresponsive to changes in temperature or field, suggesting that Zn substitution may reduce the low-temperature magnetic disorder observed in Ca₃Co₂O₆. These results are discussed within the context of two cases (Ca₃Co₂O₆ under applied pressure and Ca_2.75R_0.25Co₂O₆ (R?=?Dy, Lu)) in which a single magnetic ground state is stabilised.     

通过宽线固体核磁共振氢谱研究半晶高分子的相结构

宽线固体核磁共振氢谱（¹H NMR）是一种研究半晶高分子相结构的经典方法.本文以半晶聚乙烯的宽线固体¹H NMR谱为例，探讨了通过Gaussian/Sinc、Gaussian和Lorentzian函数组合对宽线固体¹H NMR谱图进行拟合的方案，并根据半晶聚乙烯的相结构成分对拟合得到的各信号成分进行归属.并在此基础上探讨了各个相结构中分子链运动与信号线型的相关性，以及利用宽线固体¹H NMR谱测量半晶高分子结晶度存在的困难.     

Critical Assessment of the DFT + U Approach for the Prediction of Vanadium Dioxide Properties

In a previous study (Stahl and Bredow, Chem. Phys. Lett. 2018, 695, 28–33), we have studied structural, energetic, and electronic properties of two vanadium dioxide VO₂ polymorphs with modified global and range-separated hybrid functionals. Since hybrid methods are computationally demanding, we evaluate the computationally more efficient DFT + U method in the present study. We assessed the widely used Dudarev PBE + U approach with a literature value of the effective Hubbard parameter U_eff = 3.4 eV. We compared the PBE + U results for the two VO₂ polymorphs with our previous results, a self-consistent hybrid functional sc-PBE0, and the meta-GGA functional SCAN. It was found that the PBE + U method yields a strongly distorted monoclinic phase and does not reproduce the metal-to-insulator transition of VO₂ correctly, even with modified values of U_eff. On the other hand, sc-PBE0 and SCAN describe the relative stability and the electronic structure of both polymorphs correctly and also provide reasonable lattice parameters. The functional SCAN yields the optimal balance between computational efficiency and accuracy. © 2019 The Authors. Journal of Computational Chemistry published by Wiley Periodicals, Inc.     

Entropic effect implication for change in polymer coils swelling state in the demixing enthalpy recovery of aqueous poly(vinyl methyl ether) solutions

Time‐dependent demixing enthalpy recovery behavior of aqueous poly(vinyl methyl ether) (PVME) solutions exhibits distinct recovery characteristics in three concentration regions. The absence of recovery behavior below a water concentration of 38.3 wt % indicates that the PVME coil is in a globular state. The typically sigmoidal recovery behavior of demixing enthalpy above 38.3 wt % is ascribed to the reswelling of the collapsed polymer coils induced by the entropic effect. The increase in difference between the upper and lower limits indicates the continued swelling of the PVME coils. Above 65 wt %, a dominant diluting effect can be observed, and a much longer phase separation time is needed to reach the expected lower limit. In contrast, the recovery of demixing enthalpy in a wide range of water concentration (from 38.3 to 90 wt %) exhibits the same feature. The infrared spectroscopy results are in agreement with the above macroscopic differential scanning calorimetry results. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 142–151     

High-energy x-ray diffraction study on phase transition asymmetry of plastic crystal neopentylglycol

As a prototype material of colossal barocaloric effects, neopentylglycol is investigated by combining high-precision differential scanning calorimetric measurement and high-energy x-ray diffraction measurement. The diffraction data at constant temperatures indicate a first-order phase transition with thermal hysteresis as well as the phase transition asymmetry, specifically, the phase transition is completed faster at cooling than at heating. The analysis of resulting pair distribution function confirms the intermolecular disorder in the high-temperature phase. The phase transition asymmetry is quantitatively characterized by time-resolved x-ray diffraction, which is in agreement with the thermal measurement. Also, such an asymmetry is observed to be suppressed at high pressures.     

Preparation of Chiral Amino Esters by Asymmetric Phase‐Transfer Catalyzed Alkylations of Schiff Bases in a Ball Mill

The asymmetric alkylation of Schiff bases under basic conditions in a ball mill was performed. The starting Schiff bases of glycine were prepared beforehand by milling protected glycine hydrochloride and benzophenone imine, in the absence of solvent. The Schiff base was then reacted with a halogenated derivative in a ball mill in the presence of KOH. By adding a chiral ammonium salt derived from cinchonidine, the reaction proceeded asymmetrically under phase‐transfer catalysis conditions, giving excellent yields and enantiomeric excesses up to 75 %. Because an equimolar amount of starting material was used, purification was greatly simplified.     

High‐TC Ferromagnetic Semiconductor‐Like Behavior and Unusual Electrical Properties in Compounds with a 2×2×2 Superstructure of the Half‐Heusler Phase

Heusler phases, including the full‐ and half‐Heusler families, represent an outstanding class of multifunctional materials on account of their great tunability in compositions, valence electron counts (VEC), and properties. Here we demonstrate a systematic design of a series of new compounds with a 2×2×2 superstructure of the half‐Heusler unit cell in X–Y–Z (X=Fe, Ru, Co, Rh, Ir; Y=Zn, Mn; Z=Sn, Sb) systems. Their structures were solved by using both powder and single‐crystal X‐ray diffraction, and also directly observed by using high‐angle annular dark‐field imaging in a scanning transmission electron microscope (HAADF‐STEM). The VEC values of these new compounds span a wide and continuous range comparable to those for the full‐ and half‐Heusler families, thereby implying tunability in compositions and physical properties in the superstructure. In fact, we observed abnormal electrical properties and a ferromagnetic semiconductor‐like behavior with a high and tunable Curie temperature in these superstructures.     

On The Cut-off Parameters in the Bosonization Technique

Jordan's boson representation and cut-off repolarization for the one-dimensional two-fermion model (TFT) is used to get the equivalence of the model with the two-dimensional Coulomb gas and sine-Gordon model. The scaling equations for the coupling constants are thereby obtained up to the third order.     

A novel molecularly imprinted method with computational simulation for the affinity isolation and knockout of baicalein from Scutellaria baicalensis

A novel molecularly imprinted polymer (MIP) was synthesized by precipitation polymerization with baicalein (BAI) as the template and used as solid‐phase extraction (SPE) adsorbent, aiming at the affinity isolation and selective knockout of BAI from Scutellaria baicalensis Georgi (SB). We used computational simulation to predict the optimal functional monomer, polymerization solvent and molar ratio of template to functional monomer. Characterization and performance tests revealed that MIP exhibited uniform spherical morphology, rapid binding kinetics, and higher adsorption capacity for BAI compared with nonimprinted polymer (NIP). The application of MIP in SPE coupled with high‐performance liquid chromatography to extract BAI from SB showed excellent recovery (94.3%) and purity (97.0%). Not only the single BAI compound, but also the BAI‐removed SB extract was obtained by one‐step process. This new method is useful for isolation and knockout of key bioactive compounds from herbal medicines. Copyright © 2015 John Wiley & Sons, Ltd.