Solid state water motions revealed by deuterium relaxation in 2H2O-synthesized kanemite and 2H2O-hydrated Na+-zeolite A

Deuterium NMR relaxation experiments, low temperature deuterium NMR lineshape analysis, and FTIR spectra are consistent with a new model for solid state jump dynamics of water in (2)H(2)O-synthesized kanemite and (2)H(2)O-hydrated Na(+)-Zeolite A. Exchange occurs between two populations of water: one in which water molecules are directly coordinated to sodium ions and experience C(2) symmetry jumps of their OH bonds, and a population of interstitial water molecules outside the sodium ion coordination sphere that experience tetrahedral jumps of their OH bonds. For both samples the C(2) jump rate is much faster than the tetrahedral jump rate. (2)H NMR relaxation experiments match well with the fast exchange regime of the model over a wide range of temperatures, including room temperature and above. For hydrated Zeolite A, the kinetic activation parameters for the tetrahedral and C(2) symmetry jumps are Delta H tet++=+17 kJ/mol, Delta S tet++=-109 J/(mol K), Delta H C2++=+19 kJ/mol, and Delta S C2++=-20 J/(mol K). For kanemite, Delta H tet++ =+23 kJ/mol, Delta S tet++=-69 J/(mol K), Delta H C2++ =+23 kJ/mol, and Delta S C2++ =-11 J/(mol K).     

Nanoconfined heliconical structure of twist-bend nematic liquid crystal phase

We produced controlled heliconical structures of a twist-bend nematic (N_TB) liquid-crystal (LC) phase in nanoconfinement in a porous anodic aluminium oxide (AAO) film. The structural parameters of the N_TB phase such as conical angle and helical pitch can be modulated by varying the surface energy of the inner surface of the porous AAO film, done by using different self-assembled monolayers (SAMs). The LC molecules tend to be more freely packed, thus forming a larger conical angle, when placed on the tri-deca-fluoro-1,1,2,2-tetrahydrooctyl-trichlorosilane (FOTS)-treated substrate, which has a relatively low surface energy. In contrast, the molecules form a more tightly packed structure, and thus a smaller conical angle, when placed on the 2-(methoxy(polyethyleneoxy)-propyl)trimethoxysilane (PEG 6/9)-treated substrate, which has higher surface energy. This work improves our collective understanding of self-assembled heliconical structures in the N_TB phase.     

Artificial nano‐pin as a temporal molecular glue for the targeting of acidic tumor cells

Highly precise control of molecular structure for developing efficient anticancer drug delivery is challenging. Our method reported herein can satisfy the need for building novel hybrid molecule; this molecule serves as a built‐in transformer that changes its molecular configuration from a pin‐shaped arrangement to a dog bone‐shaped arrangement. This approach led to a significant increase in the efficiency of tumor inhibition. Copyright © 2014 John Wiley & Sons, Ltd.     

Environmental effects on initiation and propagation of surface defects on silicate glasses: scratch and fracture toughness study

The glass composition and surrounding environment can play an important role in the initiation and propagation of surface defects, which affect the practical strength of glass. We have studied how the environment and glass composition affect the tribological and indentation properties of multicomponent silicate glasses. Soda lime silica and aluminosilicate glasses were studied to compare the effects of the alkali ion and glass network type on surface defect formation. Although both glasses contained leachable sodium ions, the surface wear of soda lime glass decreased with increasing humidity while sodium aluminosilicate glass had an observable increase in surface wear. This indicated that sodium ion and water activity on/in glass surfaces vary depending on the glass network structure. The exchange of Na⁺ with K⁺ in aluminosilicate glass increased the elastic modulus, hardness, and resistance to fracture substantially; however, it did not improve the surface scratch resistance in humid environments. This suggested that the improved fracture toughness for the K-exchanged aluminosilicate glass is mainly due to the improved bulk properties; surface wear can readily take place regardless of Na/K-exchange.     

Synthesis and properties of mono‐ and di‐fluoro‐substituted 2,3‐didodecylquinoxaline‐based polymers for polymer solar cells

We synthesized two new alternating polymers, namely P(Tt‐FQx) and P(Tt‐DFQx) , incorporating electron rich tri‐thiophene and electron deficient 6‐fluoroquinoxaline or 6,7‐difluoroquinoxaline derivatives. Both polymers P(Tt‐FQx) and P(Tt‐DFQx) exhibited high thermal stabilities and the estimated 5% weight loss temperatures are 425 and 460 °C, respectively. Polymers P(Tt‐FQx) and P(Tt‐DFQx) displayed intense absorption band between 450 and 700 nm with an optical band gap (E_g) of 1.78 and 1.80 eV, respectively. The determined highest occupied/lowest unoccupied molecular orbital's (HOMO/LUMO) of P(Tt‐DFQx) (?5.48 eV/?3.68 eV) are slightly deeper than those of P(Tt‐FQx) ( ?5.32 eV/?3.54 eV). The polymer solar cells fabricated with a device structure of ITO/PEDOT:PSS/ P(Tt‐FQx) or P(Tt‐DFQx) :PC₇₀BM (1:1.5 wt %) + 3 vol % DIO/Al offered a maximum power conversion efficiency (PCE) of 3.65% with an open‐circuit voltage (V_oc) of 0.59 V, a short‐circuit current (J_sc) of 10.65 mA/cm² and fill factor (FF) of 59% for P(Tt‐FQx) ‐based device and a PCE of 4.36% with an V_oc of 0.69 V, a J_sc of 9.92 mA/cm², and FF of 63% for P(Tt‐DFQx) ‐based device. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 545–552     

Mechanism for CuPt-type ordering in mixed III–V epitaxial layers

A model is proposed to rationalize the occurence of CuPt-type ordering in mixed III–V epitaxial layers grown on (001) substrates. It is invoked that 2× surface reconstruction occuring on group V terminated (001) surfaces produces dilated and compressed regions in sub-surface layers. The presence of these regions biases the occupation of certain sites during the growth of a layer consisting of atoms differing in their tetrahedral radii. By assuming that the reconstruction always occurs at the growing surface, it is possible to explain the evolution of CuPt-type ordering in epitaxial layers. Also, based on the model, experimental observations pertaining to the influence of growth conditions, surface misorientation and steps on ordering can be rationalized.     

Introducing Fe2+ into Nickel–Iron Layered Double Hydroxide: Local Structure Modulated Water Oxidation Activity

Exploring materials with regulated local structures and understanding how the atomic motifs govern the reactivity and durability of catalysts are a critical challenge for designing advanced catalysts. Herein we report the tuning of the local atomic structure of nickel–iron layered double hydroxides (NiFe‐LDHs) by partially substituting Ni²⁺ with Fe²⁺ to introduce Fe‐O‐Fe moieties. These Fe²⁺‐containing NiFe‐LDHs exhibit enhanced oxygen evolution reaction (OER) activity with an ultralow overpotential of 195 mV at the current density of 10 mA cm^?2, which is among the best OER catalytic performance to date. In‐situ X‐ray absorption, Raman, and electrochemical analysis jointly reveal that the Fe‐O‐Fe motifs could stabilize high‐valent metal sites at low overpotentials, thereby enhancing the OER activity. These results reveal the importance of tuning the local atomic structure for designing high efficiency electrocatalysts.