Development of reactive phosphonated methacrylates

Five novel phosphonated mono‐ and dimethacrylate monomers have been synthesized by two different routes. Monomers 1 and 2 were synthesized by reactions of methacryloyl chloride with diethyl (2‐hydroxyphenyl) phosphonate or tetraethyl (2,5‐dihydroxy‐1,4‐phenylene) bisphosphonate; monomers 3 and 4 by reactions of α‐(chloromethyl)acryloyl chloride (CMAC) first with dimethyl (2‐hydroxyethyl) phosphonate and then with benzoic or formic acids. The reaction of CMAC with two moles of dimethyl (2‐hydroxyethyl) phosphonate gave monomer 5 . Thermal homopolymerization of monomers 1 , 3 , 4 , and 5 and copolymerization of monomer 1 with methyl methacrylate (MMA) were investigated using azobisisobutyronitrile (AIBN) at 60 °C. Glass transition temperatures were observed for poly‐ 1 , poly(MMA‐co‐ 1 ) (50:50), poly(MMA‐co‐ 1 ) (90:10), PMMA, poly‐ 3 , and poly‐ 5 at 52, 90, 99, 129, 50, and 70 °C, respectively. TGA analysis of these polymers indicated formation of char on combustion. Homo‐ and/or copolymerization behavior of the synthesized monomers with 2,2‐bis[4‐(2‐hydroxy‐3‐methacryloyloxy propyloxy) phenyl] propane (Bis‐GMA) were investigated with photodifferential scanning calorimetry. The maximum rate of polymerizations decreased in the following order: Bis‐GMA～ 3 > 1 > 4 > 5 . The conversions of monomers 1 , 3 , 4 , and 5 (73.9, 85.9, 98.2, and 62.2%) were very high compared with Bis‐GMA (40.5%). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5737–5746, 2009     

A computational study on the reactivity enhancement in the free radical polymerization of alkyl α‐hydroxymethacrylate and acrylate derivatives

The free radical polimerizability behavior of alkyl α‐hydroxymethacrylate (RHMA) derivatives ( M1–M3 ) has been modeled by considering the propagation of the dimeric units of the compounds of interest. All the transition structures in this class of monomers are stabilized by long‐range C?O…H? C interactions. The RHMA monomer bearing the ester functionality ( M2 ) polymerizes slightly faster than the one with the ether functionality ( M1 ) because of stronger electrostatic interactions between the C?O and H? C groups. 2‐(Methoxycarbonyl)allyl benzoate ( M3 ) shows higher reactivity as compared to M1 and M2 due to stronger electrostatic interactions. The same type of study has been carried out for hexyl ( M4 ), benzyl ( M5 ), and phenyl ( M6 ) acrylate derivatives whose increasing reactivity has been attributed to the presence of C?O…H? C, C?O…H‐? as well as π–π stabilizing interactions, respectively. While B3LYP/6‐31+G(d) has been used to locate the stationary points along the free radical polymerization of nonaromatic species, long‐range stabilizing interactions have only been detected with M06‐2X/6‐31+G(d). The kinetics that we obtain with this latter methodology for the free radical polymerization reactions of M1 – M6 agree well qualitatively with experiment. An implicit solvent model has reproduced the kinetics of M1–M3 in benzene the best. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Experimental study of convective heat transfer under arrays of impinging air jets from slots and circular holes

 Impinging air jets are widely used in industry, for heating, cooling, drying, etc, because of the high heat transfer rates which is developed in the impingement region. To provide data for designers of industrial equipment, a large multi-nozzle rig was used to measure average heat transfer coefficients under arrays of both slot nozzles and circular holes. The aim of the present paper is to develop the relationship between heat transfer coefficient, air mass flow and fan power which is required for the optimum design of nozzle systems. The optimum free area was obtained directly from experimental results. The theory of optimum free area was analysed and good agreement was found between theoretical and experimental results. It was also possible to optimise the variables, to achieve minimum capital and running costs. Received on 21 November 2000 / Published online: 29 November 2001     

Hydrogen bonding : Part 17. IR and NMR study of the lower hydrates of choline chloride

Choline chloride forms two lower hydrates — a dihydrate and a monohydrate — with quite unusual properties. The dihydrate is a highly structured liquid salt; the IR spectrum is similar to that of a crystalline framework clathrate hydrate, and there are separate ¹H-NMR signals for the cation hydroxyl and water protons. The dihydrate is a crystalline solid at reduced pressure. The crystalline monohydrate only exists at reduced pressure; at atmospheric pressure it disproportionates to liquid dihydrate and anhydrous choline chloride. The anhydrous choline chloride thus formed is a previously unreported crystal modification of choline chloride.     

Comparison of antibody--antigen interactions on collagen measured by conventional immunological techniques and atomic force microscopy

We have developed a means of using atomic force microscopy (AFM) to repeatedly localize a small area of interest (4 x 4 microm(2)) within a 0.5-cm(2) area on a heterogeneous sample, to obtain and localize high-resolution images and force measurements on nonideal samples (i.e., samples that better reflect actual biological systems, not prepared on atomically flat surfaces). We demonstrate the repeated localization and measurement of unbinding forces associated with antibody--antigen (ab--ag) interactions, by applying AFM in air and in liquid to visualize and measure polyclonal ab--ag interactions, using chicken collagen as a model system. We demonstrate that molecular interactions, in the form of ab--ag complexes, can be visualized by AFM when secondary antibodies are conjugated to 20-nm colloidal gold particles. We then compare those results with established immunological techniques, to demonstrate broader application of AFM technology to other systems. Data from AFM studies are compared with results obtained using immunological methods traditionally employed to investigate ab--ag interactions, including enzyme-linked immunosorbent assay, immunoblotting, and in situ immunofluorescence. Finally, using functionalized AFM tips with a flexible tether [poly(ethylene glycol) 800] to which a derivatized antibody was attached, we analyzed force curve data to measure the unbinding force of collagen antibody from its antigen, obtaining a value of approximately 90 +/- 40 pN with a MatLab code written to automate the analyses of force curves obtained in force--volume mode. The methodology we developed for embedded collagen sections can be readily applied to the investigation of other receptor--ligand interactions.     

Synthesis and polymerization of phosphorus‐containing acrylates

Novel phosphorus‐containing acrylate monomers were synthesized by two different routes. The first involved the reaction of ethyl α‐chloromethyl acrylate and t‐butyl α‐bromomethyl acrylate with diethylphosphonoacetic acid. The monomers were bulk‐ and solution‐polymerized at 56–64 °C with 2,2′‐azobisisobutyronitrile. The ethyl ester monomer showed a high crosslinking tendency under these conditions. The selective hydrolysis of the ethyl ester phosphonic ester compound was carried out with trimethylsilyl bromide, producing a phosphonic acid monomer. In the second route, ethyl α‐hydroxymethyl acrylate and t‐butyl α‐hydroxymethyl acrylate were reacted with diethylchlorophosphate. The bulk homopolymerization and copolymerization of these monomers with methyl methacrylate and 2,2′‐azobisisobutyronitrile gave soluble polymers. The attempted hydrolysis of the monomers was unsuccessful because of the loss of the diethylphosphate group. The relative reactivities of the monomers in the photopolymerizations were also compared. The ethyl α‐hydroxymethyl acrylate/diethylphosphonic acid monomer showed higher reactivity than the other monomers, which may explain the crosslinking during the polymerization of this monomer. The reactivities of other derivatives were similar, but the rates of polymerization were slow in comparison with those of methyl methacrylate. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3221–3231, 2002     

Surface analysis of particulates from laboratory hood exhaust manifold

Particulate samples collected from a laboratory ventilation manifold during routine maintenance were analyzed to determine if particulate composition had changed as a result of changes in the laboratory's atmosphere. This ventilation manifold exhausts more than 100 fume hoods. The particulate samples were analyzed using static secondary ion mass spectrometry (SIMS). The negative SIMS spectra showed abundant Cl^?, NO₃^?, and HSO₄^?, consistent with the use of mineral acids in the laboratory. Cluster anions containing primarily Zn (but also other transition metals) were detected, which signaled corrosion of the manifold's galvanized steel by the volatilized acids. The most abundant ions in the cation SIMS spectra were derived from cyclohexylamine (CHA), which had been used as an antiscaling agent in the facility's boiler. Steam from the boiler, which contained CHA, was used to humidify the building air; this practice stopped in 1997. The abundances of the CHA‐derived ions were significantly lower in the samples collected in 2004 and 2006 than in the 1992 samples, indicating that the CHA is being slowly depleted. Changes in the relative abundances suggest exponential depletion from the manifold with rate constants that are on the order of 0.01 to 0.04 month^?1. Published in 2007 John Wiley & Sons, Ltd.     

Synthesis and photopolymerizations of new phosphonated monomers for dental applications

Three novel phosphonated methacrylate monomers have been synthesized and studied for use in dental applications. Two of the monomers were synthesized from the reactions of glycidyl methacrylate (GMA) with (diethoxy‐phosphoryl)‐acetic acid (monomer 1 ) and (2‐hydroxy‐ethyl)‐phosphonic acid dimethyl ester (monomer 2 ). These monomers showed high crosslinking tendencies during thermal bulk and solution polymerizations. The third monomer (monomer 3 ) was prepared by the reaction of bisphenol A diglycidylether (DER) with (diethoxy‐phosphoryl)‐acetic acid and subsequent conversion of the resulting diol to the methacrylate with methacryloyl chloride. The homopolymerization and copolymerization behaviors of the synthesized monomers were also investigated with glycerol dimethacrylate (GDMA), triethylene glycol dimethacrylate (TEGDMA), and 2,2‐bis[4‐(2‐hydroxy‐3‐methacryloyloxy propyloxy) phenyl] propane (bis‐GMA) using photodifferential scanning calorimetry at 40 °C using 2,2′‐dimethoxy‐2‐phenyl acetophenone (DMPA) as photoinitiator. Monomer 1 showed polymerization rate similar or greater than dimethacrylates studied here but with higher conversion. The maximum rate of polymerizations decreased in the following order: 1 ～TEGDMA>GDMA～bis‐GMA～ 3 > 2 . A synergistic effect in the rate of polymerization was observed during copolymerizations. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2290–2299, 2008     

Simple and accurate model for voltage-dependent resistance of metallic carbon nanotube interconnects: An ab initio study

In this work, development of a voltage dependent resistance model for metallic carbon nanotubes is aimed. Firstly, the resistance of metallic carbon nanotube interconnects are obtained from ab initio simulations and then the voltage dependence of the resistance is modeled through regression. Self-consistent non-equilibrium Green's function formalism combined with density functional theory is used for calculating the voltage dependent resistance of metallic carbon nanotubes. It is shown that voltage dependent resistances of carbon nanotubes can be accurately modeled as a polynomial function which enables rapid integration of carbon nanotube interconnect models into electronic design automation tools.     

Investigation of the effect of different carbon film thickness on the exhaust valve

Valves working under different loads and temperatures are the mostly forced engine elements. In an internal combustion engine, pressures and temperatures affecting on the valves vary with fuel type and the combustion characteristics of the fuel. Consequently, valves are exposed to different dynamic and thermal stress. In this study, stress distributions and temperature profiles on exhaust valve are obtained depending on different carbon film thickness. It is concluded that heat losses and valve temperatures decrease and valve surfaces are exposed to less thermal shocks with increasing carbon film thickness.