Investigation of Relationships between Grain Structure and Inhomogeneous Deformation by Means of Laboratory-Based Multimodal X-Ray Tomography: Strain Accuracy Analysis

Experimental Mechanics - The internal strain distribution developing during plastic deformation is important for understanding the mechanical properties of polycrystalline materials. Such...     

Synthesis of Organosilyl-Functionalized Cage-Type Germanoxanes Containing Fluoride Ions

Eight corners of a double-four ring cage-type germanoxane, containing a fluoride ion, were successfully silylated by the combination of chlorosilanes and silazanes. Three different silyl groups, trimethylsilyl, dimethylsilyl, and dimethylvinylsilyl, were attached on the corners of germanoxane cage. The solubility and reactivity of the cage modified with dimethylvinylsilyl groups were significantly increased, allowing for further reaction. Hydrosilylation reaction between dimethylvinylsilylated cage geramanoxanes and dimethylsilylated cage siloxanes afforded porous solids. Functionalization of the corners of germanoxanes with silyl groups should provide valuable building blocks in various functional materials.     

Modeling and design of a tuned liquid damper using triangular-bottom tank by a concentrated mass model

Nonlinear Dynamics - Rectangular flat-bottom liquid tanks known as tuned liquid dampers (TLDs) are often used as passive mechanical dampers. Sloped- and triangular-bottom TLDs have been reported to...     

Dual Chemical Modification of a Polytheonamide Mimic: Rational Design and Synthesis of Ion‐Channel‐Forming 48‐mer Peptides with Potent Cytotoxicity

Polytheonamide B ( 1 ) is a natural peptide that displays potent cytotoxicity against P388 mouse leukemia cells (IC₅₀=0.098 nm ). Linear 48‐mer 1 is known to form monovalent cation channels on binding to lipid bilayers. We previously developed a fully synthetic route to 1 , and then achieved the design and synthesis of a structurally simplified analogue of 1 , namely, dansylated polytheonamide mimic 2 . Although the synthetically more accessible 2 was found to emulate the channel function of 1 , its cytotoxicity was decreased 120‐fold. Herein, the chemical preparation and biological evaluation of seven analogues 3 – 9 of 2 are reported. Compounds 3 – 9 were modified at their N terminus and/or the side chain of residue 44 of 2 to alter their physicochemical properties. The total synthesis of 3 – 9 was accomplished in a unified fashion by a combination of solid‐phase and solution‐phase chemistry. Systematic evaluation of the hydrophobicities, single‐channel currents, ion‐exchange activities, and cytotoxicities of 3 – 9 revealed that their hydrophobicities are correlated with the total magnitude of ion exchange and determine their cytotoxic potency. Consequently, the most hydrophobic analogue 9 exhibited the lowest IC₅₀ value, which is comparable to that of 1 . Therefore, these results clarified that the bioactivity of the polytheonamide‐based peptides can be rationally controlled by changing their hydrophobicity at the N and C termini of the 48‐amino‐acid sequence.     

A new periodic pattern with five‐neighbored domain packing from ABC triblock terpolymer/B homopolymer blend

Self‐assembled structures from poly(isoprene‐b‐styrene‐b‐2‐vinylpyridine)(ISP)/styrene homopolymer blend were investigated. Five terpolymers whose total molecular weight, M, is in the narrow range of 121k < M < 214k, and volume fractions of the center block polystyrenes, ?_S, are similar at around 0.55, were prepared as parent block terpolymers. Their ?_P/?_I ratios, used as an indicator of asymmetry, are varied in the range 0.32 < ?_P/?_I < 2.46. Three low‐molecular weight styrene homopolymers with molecular weights of 3k, 9k, and 12k, respectively, were mixed with those block terpolymers to produce blends with almost constant styrene content within the range 0.65 < ?_S < 0.68. Both ISP/S(3k) and ISP/S(12k) blend series show a morphological transition from tetragonally packed cylinders (TPC) to double hexagonal structure (DHS) with hexagonally arrayed polyisoprene cylinders, each surrounded by six thin cylinders as satellites. If one focuses on ISP‐III(150k)/S blends whose ?_P/?_I is 0.88, TPC for ISP‐III/S(3k) was transformed to DHS for ISP‐III/S(12k), evidently due to the molecular weight effect of the added homopolymer. Finally a new periodic pattern, having P cylinders surrounded by five I cylinders each, has been discovered from ISP‐III/S(9k) at overall composition of ?_I/?_S/?_P = 0.17/0.68/0.15 and polystyrene block/styrene homopolymer ratio of w_S(b)/w_S(h) = 1.4. This structure was confirmed to possess hexagonal symmetry with larger unit cell than regular patterns ever known by X‐ray diffraction experiment. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 907–911     

A highly rigid diamine monomer derived from naturally occurring myo‐inositol and its use for polyamide synthesis

A rigid diamine was synthesized from myo‐inositol, a naturally occurring cyclic hexaol, and used as a monomer to synthesize polyamides. myo‐Inositol was treated with 1,1‐dimethoxycyclohexane to yield a bisketal bearing two hydroxyl groups, and from this bisketal, the target diamine was synthesized in three steps: (1) derivation of the diol into the corresponding bistriflate, (2) nucleophilic substitution of the bistriflate with sodium azide yielding a diazide, and (3) reduction of the diazide to the target diamine. The target diamine readily underwent polycondensation with dicarboxylic acid chloride in solution. The resulting polyamides, whose main chain inherited the rigid 5‐6‐5 system from the diamine monomers, have high glass transition temperatures. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3436–3443     

Synthesis of a Pentacene‐Type Silaborin via Double Dehydrogenative Cyclization of 1,4‐Diboryl‐2,5‐disilylbenzene

A new pentacene‐type silaborin, in which three benzene rings are bridged by silicon and boron atoms, has been synthesized and characterized by using NMR spectroscopy and X‐ray crystallographic analysis. The precursor, 1,4‐bis(dimesitylboryl)‐2,5‐bis(phenylsilyl)benzene ( 4 ), was prepared by stepwise introduction of a silyl group and a boryl group to a benzene ring starting from 1,4‐dibromobenzene. Double cyclization of 4 proceeds by a H‐Mes exchange and a B‐H/C‐H dehydrogenative condensation to afford pentacene‐type silaborin 5 . X‐ray crystal structure analysis reveals that 5 adopts a bent structure rather than a planar one. UV/Vis spectra and DFT calculations for 5 reveal a lowering of the LUMO energy level compared with corresponding anthracene‐type 3 .