Rubbery wound closure adhesives. II. initiators for and initiation of 2‐octyl cyanoacrylate polymerization

The polymerization of 2‐octyl cyanoacrylate (OctCA) initiated by five N‐bases [N,N‐dimethyl‐p‐toluidine (DMT), pyridine (Pyr), triethyl amine (Et₃N), azobicyclo[2.2.2]octane (ABCO), and diazobicylo[2.2.2]octane (DABCO)] was investigated. Our main objective was to assess the suitability and relative reactivity of these initiators for neat OctCA polymerization as wound closure adhesives. Methodologies were developed to determine stir‐stop and set times of OctCA polymerization and to use these quantities to assess initiation reactivity. According to these studies Et₃N, ABCO, DABCO, and Pyr are most reactive initiators, while DMT is much less reactive. Polymerizations were much faster in the presence of small amounts of tetrahydrofuran than toluene, indicating solvent polarity effects. Initiator reactivity is discussed in terms of structural parameters. NMR and MALDI‐TOF analyses of low molecular weight P(OctCA) prepared with DMT did not show evidence for the expected aromatic head group proposed by earlier investigators, which suggests complex initiation mechanism. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1652–1659     

Breathable rubbery skin protectors: Design,synthesis, characterization,and properties of cyanoacrylated silicone rubber networks

We extended our investigations of rubbery wound closure adhesives and created novel flexible networks by crosslinking cyanoacrylated silicone rubbers (i.e., commercial methylhydrosiloxane‐dimethylsiloxane copolymers, PMHS‐co‐PDMS) with N,N‐dimethyl‐p‐toluidine in tetrahydrofuran and hexamethyldisiloxane solvents at room temperature. Cyanoacrylation was achieved by hydrosilating (anthracene‐protected) allyl cyanoacrylate with PMHS‐co‐PDMS. Steric hindrance and the molecular weight of the copolymer strongly affect the extent of hydrosilation. The rate of crosslinking is proportional with the number of cyanoacrylate groups in the copolymer and networks form in seconds with appropriate amounts of initiator. Networks on porcine skin yield well‐adhering flexible optically‐transparent colorless conformal coatings of good “feel” appropriate for clinically useful non‐occlusive “breathable” skin or wound protectors. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1367‐1372     

Structural Chemistry author wins Nobel Prize

The 2016 Nobel Prize in Chemistry highlighted another spectacular achievement in structural chemistry and supramolecular chemistry. The three awardees built molecular machines based on their intimate knowledge of molecular properties and behavior. One of the three laureates, J. Fraser Stoddart, with two co-authors, published an invited paper in 1999 in our journal in which they surveyed the interplay between the synthesis of functioning supramolecular systems and their X-ray crystallographic investigation. Structural Chemistry congratulates Stoddart and his co-laureates on this momentous occasion.     

Synthesis and Anti-HIV Activity of Further Examples of 1-[3-Deoxy-3-(N-hydroxyamino)-β-d-threo-(and β-d-erythro)-pentofuranosyl]thymine Derivatives1

Abstract

Upon sodium cyanoborohydride reduction followed by de-O-silylation, the O-methyloxime and N-benzylnitrone of 5′-TBDMS-3′-ketothymidine gave resolvable epimeric mixtures of 1-[2,3-dideoxy-3-(N-methoxyamino)-β-d-threo-and β-d-erythro-pentofuranosyl]thymine and 1-[3-(N-benzyl-N-hydroxyamino)-2,3-dideoxy-β-d-threo- and β-d-erythro-pentofuranosyl]thymine respectively. These compounds were inactive against HIV. On the other hand, 1-[2,3-dideoxy-3-(N-hydroxyamino)-5-O-TBDMS-β-d-threo-pentofuranosyl]thymine, upon treatment with acetone, then de-O-silylation, gave the bicyclonucleoside analogue 15, slightly more active against HIV in vitro than DDI.     

Testing for parameter constancy in GARCH() models

We propose a test for a change in the parameters of a GARCH(p,q) model. The test is based on approximate likelihood scores and does not require the observations to have finite variance. We show that the test has asymptotically correct size under weak assumptions on model errors.     

Fluorescence evidence for cholesterol regular distribution in phosphatidylcholine and in sphingomyelin lipid bilayers

Our previous studies indicated that sterols (including cholesterol and dehydroergosterol) can be regularly distributed into hexagonal superlattices in the plane of liquid-crystalline phosphatidylcholine bilayers. It was suggested that regular and irregular regions coexist in the membrane. In the present study, we report supporting evidence for our sterol regular distribution model. We have examined the fractional concentration dependencies of dehydroergosterol (a naturally occurring cholesterol analogue) fluorescence intensity and lifetime in various phosphatidylcholine and sphingomyelin bilayers. Fluorescence intensity and lifetime dips have been observed at specific sterol mole fractions. At those mole fractions, the acrylamide quenching rate constant of dehydroergosterol fluorescence reaches a local maximum. Those mole fractions match the critical sterol mole fractions at which sterol molecules are expected to be regularly distributed into hexagonal superlattices. The results support the idea that the sterols in the regular region are embedded in the bilayer less deep than those in the irregular regions. We have also examined the fractional cholesterol concentration dependencies of diphenylhexatriene (DPH) fluorescence intensity, lifetime, and polarization in DMPC vesicles. DPH fluorescence intensity and polarization also exhibit distinct dips and peaks, respectively, at critical sterol mole fractions for hexagonal superlattices. However, DPH lifetime changes little with sterol mole fraction. As a comparison, the fluorescence properties of DHE and DPH behave differently in response to the formation of sterol regular distribution. Furthermore, finding evidence for sterol regular distribution in both phosphatidylcholine and sphingomyelin membranes raises the possibility that sterol regular distribution may occur within phospholipid/cholesterol enriched domains of real biological membranes.     

Rate of Convergence of Wong–Zakai Approximations for Stochastic Partial Differential Equations

We investigate the rate of convergence of the Wong-Zakai approximations for second-order stochastic PDEs of parabolic type driven by a multi-dimensional Wiener process W. The title of this article in the online version was published incorrectly. The correct title appears above. Springer regrets the error. The online version of the original article can be found at