Induced Anticlinic Ordering and Nanophase Segregation of Bow-Shaped Molecules in a Smectic Solvent

Recent experiments indicate that doping low concentrations of bent-core molecules into calamitic smectic solvents can induce anticlinic and biaxial smectic phases. We have carried out Monte Carlo (MC) simulations of mixtures of rodlike molecules (hard spherocylinders with length/breadth ratio $L_{\rm rod}/D = 5$) and bow- or banana-shaped molecules (hard spherocylinder dimers with length/breadth ratio $L_{ban}/D = 5$ or 2.5 and opening angle $\psi$) to probe the molecular-scale organization and phase behavior of rod/banana mixtures. We find that a low concentration (3%) of $L_{ban}/D = 5$ dimers induces anticlinic (SmC$_A$) ordering in an untilted smectic (SmA) phase for $100^\circ \le \psi < 150^\circ$. For smaller $\psi$, half of each bow-shaped molecule is nanophase segregated between smectic layers, and the smectic layers are untilted. For $L_{ban}/D = 2.5$, no tilted phases are induced. However, with decreasing $\psi$ we observe a sharp transition from {\sl intralamellar} nanophase segregation (bow-shaped molecules segregated within smectic layers) to {\sl interlamellar} nanophase segregation (bow-shaped molecules concentrated between smectic layers) near $\psi = 130^\circ$. These results demonstrate that purely entropic effects can lead to surprisingly complex behavior in rod/banana mixtures.Comment: 5 pages Revtex, 7 postscript figure

Activity of topical antimicrobial agents against multidrug-resistant bacteria recovered from burn patients

Background: Topical antimicrobials are employed for prophylaxis and treatment of burnwound infections despite no established susceptibility breakpoints, which are becoming vital in an era of multidrug-resistant (MDR) bacteria. We compared two methods of determining topical antimicrobial susceptibilities. Methods: Isolates of Pseudomonas aeruginosa, methicillin-resistant Staphylococcus aureus (MRSA), extended spectrum beta-lactamase (ESBL) producing Klebsiella pneumoniae, and Acinetobacter baumanii-calcoaceticus (ABC) from burn patients were tested using broth microdilution and agar well diffusion to determine minimum inhibitory concentrations (MICs) and zones of inhibition (ZI). Isolates had systemic antibiotic resistance and clonality determined. MDR included resistance to antibiotics in three or more classes. Results: We assessed 22 ESBL-producing K. pneumoniae, 20 ABC (75% MDR), 20 P. aeruginosa (45% MDR), and 20 MRSA isolates. The most active agents were mupirocin for MRSA and mafenide acetate for the gram-negatives with moderate MICs/ZI found with silver sulfadiazene, silver nitrate, and honey. MDR and non-MDR isolates had similar topical resistance. There was no clonality associated with resistance patterns. Conclusion: Despite several methods to test bacteria for topical susceptibility, no defined breakpoints exist and standards need to be established. We recommend continuing to use silver products for prophylaxis against gram-negatives and mafenide acetate for treatment, and mupirocin for MRSA

The Effect of Monomer Structure on Oxygen Inhibition of (Meth)acrylates Photopolymerization

Oxygen inhibition during the free-radical photopolymerization of various monomers containing ether groups was investigated using photo-DSC and real-time FTIR (RTIR). Methacrylates and acrylates containing different number and types of ether groups were selected to determine the effects of ether group concentration and structure on oxygen inhibition. Also, the oxygen sensitivity of the free-radical polymerization of methacrylate and acrylate was compared. Compared to acrylates, methacrylates are much less sensitive to oxygen. Model poly(tetramethylene oxide) and poly(propylene glycol) system were evaluated to determine the effect of ether groups on polymerization kinetics in air. The polymerizations of the (meth)acrylates containing ether groups were found to be relatively insensitive to oxygen inhibition. The reduction of oxygen inhibition occurs by a series of chain transfer/oxygen scavenging reactions. (C) 2004 Published by Elsevier Ltd

Photopolymerization Kinetics of Pigmented Systems Using a Thin-Film Calorimeter

A thin-film calorimeter was used to evaluate the polymerization rates of pigmented photopolymerizable systems. As a result of a wide linear response range, which is more than an order of magnitude greater than that of the photo-DSC, the thin-film calorimeter is capable of measuring both small and large signals accurately. It was used to measure the polymerization exotherms of thin-films of a photocurable acrylate monomer with added pigment as well as commercial UV curable pigmented ink formulations

Design and Performance of a Thin-Film Calorimeter for Quantitative Characterization of Photopolymerizable Systems

A thin-film calorimeter (TFC) was designed for the quantitative characterization of photopolymerizable systems. A detailed description of its construction indicates the ease with which a TFC can be assembled and the flexibility inherent in its design. The mechanics of operation were optimized to yield a significantly faster instrument response time than other calorimetric methods such as photodifferential scanning calorimetry (photo-DSC). The TFC has enhanced sensitivity, more than an order of magnitude greater linear response range to changes in light intensity than that of the photo-DSC, resulting in the ability to measure both smaller and larger signals more accurately. The photopolymerization exotherm curves are reproducible and can be collected over a broad range of film thicknesses. © 2005 American Institute of Physics

Influence of the Alkene Structure On the Mechanism and Kinetics of Thiol-Alkene Photopolymerizations With Real-Time Infrared Spectroscopy

The effect of the chemical structure on the reactivity of alkenes used in thiol-ene photopolymerizations has been investigated with real-time infrared spectroscopy. Model studies of thiol-ene photoreactions with various monofunctional hydrocarbon alkenes and the monofunctional thiol ethyl-3-mercaptopropionate have been performed to identify and understand structure-reactivity relationships. The results demonstrate that terminal enes react very rapidly with thiol, achieve complete conversion, and are independent of the aliphatic hydrocarbon substituent length. Disubstitution on a single carbon of a terminal ene significantly reduces the reactivity, whereas substitution on the carbon a to the terminal ene has a minimal influence on the reactivity. Internal trans enes display reduced reactivity and a lower overall conversion and deviate from the standard thiol-ene reaction mechanism because of steric strain induced by 1,3-interactions. The reactivity and conversion of internal trans enes decrease as the substituents on the ene become larger, reaching a minimum when the substituent size is greater than or equal to that of propyl groups. Internal cis enes react rapidly with thiol; however, they undergo a fast isomerization-elimination reaction sequence generating the trans ene, which proceeds to react at a reduced rate with thiol. The reactivity of cyclic enes is dictated by ring strain, stereoelectronic effects, and hydrogen abstractability. The reactivity trends in the model studies have been used to explain the photopolymerization mechanism and kinetics of a series of multifunctional thiol-ene systems. (C) 2004 Wiley Periodicals, Inc

Monoterpenes of lodgepole pine phloem as related to mountain pine beetles /

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