Modeling on debonding dynamics of pressure-sensitive adhesives

We propose a simple mechanical model describing viscoelasticity and cavitation during the debonding process in pressure-sensitive adhesives (PSA). Our calculation qualitatively reproduces typical stress-strain curves in the probe-tack test, such as the steep stress maxima and the following plateau region. It is shown that in the thin-film geometry the stress-strain curve is essentially determined by the cavities created by the large negative pressure. Effects of pre-existent air bubbles due to surface roughness are also discussed.     

Synthesis of conjugated allenes through copper-catalyzed γ-selective and stereospecific coupling between propargylic phosphates and aryl- or alkenylboronates

A Cu-catalyzed γ-selective coupling reaction between propargylic phosphates and aryl- or alkenylboronates afforded aryl- or alkenyl-conjugated allenes. The reaction showed excellent functional group compatibility in both the propargylic substrates and the boronates. The reaction of an enantioenriched propargylic phosphate proceeded with excellent chirality transfer with 1,3-anti stereochemistry to give axially chiral aryl- and alkenylallenes.     

One‐Handed Helical Screw Direction of Homopeptide Foldamer Exclusively Induced by Cyclic α‐Amino Acid Side‐Chain Chiral Centers

Chiral cyclic α,α‐disubstituted amino acids, (3S,4S)‐ and (3R,4R)‐1‐amino‐3,4‐(dialkoxy)cyclopentanecarboxylic acids ((S,S)‐ and (R,R)‐Ac₅c^dOR; R: methyl, methoxymethyl), were synthesized from dimethyl L ‐(+)‐ or D ‐(?)‐tartrate, and their homochiral homoligomers were prepared by solution‐phase methods. The preferred secondary structure of the (S,S)‐Ac₅c^dOMe hexapeptide was a left‐handed (M) 3₁₀ helix, whereas those of the (S,S)‐Ac₅c^dOMe octa‐ and decapeptides were left‐handed (M) α helices, both in solution and in the crystal state. The octa‐ and decapeptides can be well dissolved in pure water and are more α helical in water than in 2,2,2‐trifluoroethanol solution. The left‐handed (M) helices of the (S,S)‐Ac₅c^dOMe homochiral homopeptides were exclusively controlled by the side‐chain chiral centers, because the cyclic amino acid (S,S)‐Ac₅c^dOMe does not have an α‐carbon chiral center but has side‐chain γ‐carbon chiral centers.     

Elucidation of the Active Conformation of Vancomycin Dimers with Antibacterial Activity against Vancomycin‐Resistant Bacteria

Covalently linked vancomycin dimers have attracted a great deal of attention among researchers because of their enhanced antibacterial activity against vancomycin‐resistant strains. However, the lack of a clear insight into the mechanisms of action of these dimers hampers rational optimization of their antibacterial potency. Here, we describe the synthesis and antibacterial activity of novel vancomycin dimers with a constrained molecular conformation achieved by two tethers between vancomycin units. Conformational restriction is a useful strategy for studying the relationship between the molecular topology and biological activity of compounds. In this study, two vancomycin units were linked at three distinct positions of the glycopeptide (vancosamine residue (V), C terminus (C), and N terminus (N)) to form two types of novel vancomycin cyclic dimers. Active NC‐VV‐linked dimers with a stable conformation as indicated by molecular mechanics calculations selectively suppressed the peptidoglycan polymerization reaction of vancomycin‐resistant Staphylococcus aureus in vitro. In addition, double‐disk diffusion tests indicated that the antibacterial activity of these dimers against vancomycin‐resistant enterococci might arise from the inhibition of enzymes responsible for peptidoglycan polymerization. These findings provide a new insight into the biological targets of vancomycin dimers and the conformational requirements for efficient antibacterial activity against vancomycin‐resistant strains.     

Estimation of Color-Difference Formulae at Color Discrimination Threshold Using CRT-Generated Stimuli

The advanced color-difference formulae, CMC, CIE94, and the recently proposed CIEDE2000 formula, together with the basic CIELAB system, were estimated using the chromaticity discrimination threshold data at CIE Gray and Blue color centers. Gray is the most basic color and blue is, perceptually, in the most different region from other areas across the color space. The test stimuli, evenly distributed in the (a#x2217;, b#x2217;)-, (a#x2217;, L#x2217;)-, and (b#x2217;, L#x2217;)-plane of the CIELAB space, were generated on a CRT display, driven by a VSG system. Each direction from each color center was assessed 3 times by a panel of 9 normal color-vision observers with the psychophysical method of interleaved staircase. The experimental data were reliable and consistent with other studies according to the observer accuracy and fitted ellipse parameters. A comprehensive analysis shows the color discrimination tolerances could be well fitted by ellipses, and the CIEDE2000 and CIELAB formulae performed better than CIE94 while the CMC worst at the threshold level for the color centers studied.     

Fundamental investigation on interaction between hexafluoroisopropylalcohol‐containing styrene and photochemical acid generator for rationale design of photoresist system

This article presents the effect of some ionic photochemical acid generators (PAGs) to inhibit the dissolution of hexafluoroisopropylalcohol (HFA)‐containing polystyrene to an aqueous alkaline developer, which is a highly important effect in photoresist application to enhance resolution of patterning. The dissolution inhibiting factors and mechanisms were investigated by evaluating the solubility and the ¹H‐NMR analysis of OH proton in HFA moiety. The dissolution inhibition effect was enhanced when the structures of PAGs fulfill some requirements: (a) their anions should have higher basicity and smaller van der Waals volume; (b) their cations should be stabilized by conjugation with electron‐rich aromatics. In the dissolution inhibition, the HFA moiety interacts with the anionic part of PAGs liberated from the electrostatic interaction with the counter cation. These interactions were predicted and quantified by DFT calculations using Gaussian 09, leading to the rational designs of PAGs with higher dissolution inhibiting effect in photoresist systems. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 531–538     

Neutron spin rotation and P-violation

A new apparatus to measure the neutron spin rotation due to interaction with matter has been developed at KEK. The present apparatus enables us to measure the parity violating neutron spin rotation in the p-wave resonance in the energy region of eV.On leave from Tohoku University.     

A note on stochastic phase lockings in a relaxation oscillator forced by a sine input with additive noise

Summary Noise effects on phase lockings in a system consisting of a piecewise-linear van der Pol relaxation oscillator driven by a periodic input are studied. The problem of finding the period of the oscillator is reduced to the first-passage-time problem of the Ornstein-Uhlenbeck process with time-varying boundary. Using the probability density functions of the first-passage time, the operator which governs a transition of an input phase density after one cycle of the oscillator is defined. Phase lockings in a stochastic sense are investigated on the basis of the density evolution by the operator. Paper presented at the International Workshop ?Fluctuations in Physics and Biology: Stochastic Resonance, Signal Processing and Related Phenomena?, Elba, 5–10 June 1994.