Self‐assembly of Carbon Particles as a Heat Sink Coating to Promote Radiative Cooling

Novel composite carbon particles are developed that can self‐assemble as a coating on a substrate without a binder. These carbon particles were used as a coating to enhance thermal dissipation and their thermal conductivity, surface emissivity and cooling performance were measured. Carbon particles with both thiol and epoxy functional groups self‐assembled to form a coating on the surface of a heat sink without a binder, which greatly improved the thermal conductivity of the coating. Coating a heat sink with the carbon particles yielded a higher thermal conductivity and emissivity than could be obtained with the addition of binder in the conventional approach, and significantly enhanced the cooling performance. In addition, the cooling performance of the carbon nanotube outperformed all other particles when coated on a substrate, because it had the highest thermal conductivity and good radiation emissivity. We developed an equation to describe the various parameters affecting the cooling performance of the thermally dissipative coating. This equation was confirmed by the experimental data.     

Supramolecular functionalization of electron-beam generated nanostructures

Electron-beam lithography was used to pattern poly(styrene-co-(methyldiaminotriazine) styrene) (PS-Triaz). These polymer nanopatterns were utilized as molecular scaffolds for assembling complementary thymine-functionalized CdSe-ZnS quantum dots (Thy-QDs) via three-point hydrogen-bonding molecular recognition. This interaction was very specific, with N-methyl thymine-functionalized QDs (MeThy-QDs) not depositing on the surfaces. The "lock and key" specificity of the assembly is mirrored in the disassembly process, where complete removal of the QD was observed using a competing thymine guest.     

Amperometric morphine sensing using a molecularly imprinted polymer-modified electrode

This study incorporates morphine into a molecularly imprinted polymer (MIP) for the amperometric detection of morphine. The polymer, poly(3,4-ethylenedioxythiophene), PEDOT, is an electroactive film that catalyzes morphine oxidation and lowers the oxidization potential on an indium tin oxide (ITO) electrode. The MIP-PEDOT modified electrode is prepared by electropolymerizing PEDOT onto an ITO electrode in a 0.1 M LiClO₄ solution with template addition (morphine). After template molecule extraction, the oxidizing current of the MIP-PEDOT modified electrode is measured in a 0.1 M KCl solution (pH = 5.3) at 0.75 V (versus Ag/AgCl/sat’d KCl) with the morphine concentration varying in the 0.1-5 mM range. A linear range, displaying the relationship between steady-state currents and morphine concentrations, from 0.1 to 1 mM, is obtained. The proposed amperometric sensor could be used for morphine detection with a sensitivity of 91.86 μA/cm² per mM. A detection limit of 0.2 mM at a signal-to-noise ratio of 3 is achieved. Moreover, the proposed method can discriminate between morphine and its analogs, such as codeine.     

Measurement of the Binding of Adenosylcobalamin to Glutamate Mutase by Fluorescence Spectroscopy

Fluorescence spectroscopy is a fast, highly sensitive technique for investigating protein‐ligand interactions. Intrinsic protein fluorescence is usually occurred by exciting the proteins with 280‐295 nm ultraviolet light, and the light emission is observed approximately between 330‐350 nm. No emission light between 330‐350 nm can be observed when adenosylcobalamin (AdoCbl) is excited at 282 nm. The binding of AdoCbl to glutamate mutase was therefore investigated by fluorescence spectroscopy in this study. Our results show that direct measurement for determining the K_d of AdoCbl by fluorescence spectroscopy leads to significant errors. Here we report the source of error and a corrected method for measuring the binding of coenzyme B₁₂ to glutamate mutase using fluorescence spectroscopy.     

Analyses of preservatives by capillary electrochromatography using methacrylate ester-based monolithic columns

Five common food preservatives were analyzed by capillary electrochromatography, utilizing a methacrylate ester-based monolithic capillary as separation column. In order to optimize the separation of these preservatives, the effects of the pore size of the polymeric stationary phase, the pH and composition of the mobile phase on separation were examined. For all analytes, it was found that an increase in pore size caused a reduction in retention time. However, separation performances were greatly improved in monolithic columns with smaller pore sizes. The pH of the mobile phase had little influence on separation resolution, but a dramatic effect on the amount of sample that was needed to be electrokinetically injected into the monolithic column. In addition, the retention behaviors of these analytes were strongly influenced by the level of acetonitrile in the mobile phase. An optimal separation of the five preservatives was obtained within 7.0 min with a pH 3.0 mobile phase composed of phosphate buffer and acetonitrile 35:65 v/v. Finally, preservatives in real commercial products, including cold syrup, lotion, wine, and soy sauces, were successfully determined by the methacrylate ester-based polymeric monolithic column under this optimized condition.     

Intramolecular 1,3-dipolar cycloaddition of cyclo-1,3-diene-tethered nitrile oxides

Intramolecular 1,3-dipolar cycloaddition of cyclo-1,3-diene- and -1,3,5-triene-tethered nitrile oxides gave tricyclic isoxazolines as a single stereoisomer in most cases. The relative stereochemistry of tricycle-fused isoxazolines resulting from 1,3-dipolar cycloaddition of cyclo-1,3-diene-tethered nitrile oxides is cis-cis, whereas from cyclohepta-1,3,5-triene-tethered nitrile oxides the cis-trans isomer predominates.     

Hard nanocomposite comprising stereoregular syndiotactic polypropylene with chemically bonded gold nanoparticles

An effective method to synthesize directly a hard composite material containing uniformly dispersed nanogold particles chemically bonded with a stereospecific, crystalline polymer matrix has been developed. Syndiotactic polypropylene was synthesized and functionalized to have a hydroxyl terminal group (sPP_OH) via a metallocene catalysis with a selective chain transfer. Next, sPP_OH was activated to react with ethylene sulfide forming the thiol‐terminated polymer, sPP_SH. sPP_SH was then chemically bonded to gold nanoparticles (AuNPs) formed in situ via a reduction of HAuCl₄. The bonding between thiol and AuNP stabilized the AuNPs and led to the formation of sPP_AuNPs composite containing uniformly‐dispersed AuNPs of a 19–40 nm size without noticeable aggregation. Furthermore, the chemical bonding of AuNPs has afforded sPP_AuNPs a thermal degradation temperature (T_D) 49.4 °C higher than the pristine sPP or sPP_OH and 25.7 °C higher than sPP_SH without any adverse effect on the crystalline temperature and melting temperature. In addition, the characteristic UV‐Vis absorption wavelength of sPP_AuNPs remains the same at various temperatures, thus indicating the independence of optical property on temperature as well as the good thermal stability of the sPP_AuNPs composite. ¹H NMR, ¹³C NMR, FESEM, STEM, XPS, TGA and DSC were used to investigate the molecular structure, morphology and thermal properties of the resulting sPP_AuNPs nanocomposite. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Characterizing fracture energy of proton exchange membranes using a knife slit test

Pinhole formation in proton exchange membranes (PEM) may be caused by a process of flaw formation and crack propagation within membranes exposed to cyclic hygrothermal loading. Fracture mechanics can be used to characterize the propagation process, which is thought to occur in a slow, time‐dependent manner under cyclic loading conditions, and believed to be associated with limited plasticity. The intrinsic fracture energy has been used to characterize the fracture resistance of polymeric material with limited viscoelastic and plastic dissipation, and has been found to be associated with long‐term durability of polymeric materials. Insight into this limiting value of fracture energy may be useful in characterizing the durability of proton exchange membranes, including the formation of pinhole defects. In an effort to collect fracture data with limited plasticity, a knife slit test was adapted to measure fracture energies of PEMs, resulting in fracture energies that were two orders of magnitude smaller than those obtained with other fracture test methods. The presence of a sharp knife blade reduces crack tip plasticity, providing fracture energies that may be more representative of the intrinsic fracture energies of the thin membranes. Three commercial PEMs were tested to evaluate their fracture energies (G_c) at temperatures ranging from 40 to 90 °C and humidity levels varying from dry to 90% relative humidity (RH). Experiments were also conducted with membrane specimens immersed in water at various temperatures. The time temperature moisture superposition principle was applied to generate fracture energy master curves plotted as a function of reduced cutting rate based on the humidity and temperature conditions of the tests. The shift with respect to temperature and humidity suggests that the slitting process is viscoelastic in nature. Also such shifts were found to be consistent with those obtained from constitutive tests such as stress relaxation. The fracture energy is more sensitive to temperature than on humidity. The master curves converge at the lowest reduced cutting rates, suggesting similar intrinsic fracture energies; but diverge at higher reduced cutting rates to significantly different fracture energies. Although the relationship between G_c and ultimate mechanical durability has not been established, the test method may hold promise for investigating and comparing membrane resistance to failure in fuel cell environments. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 333–343, 2010     

Compatible and tearing properties of poly(lactic acid)/poly(ethylene glutaric‐co‐terephthalate) copolyester blends

Fourier transform infrared and nuclear magnetic resonance results suggest that the carboxylic acid groups of poly(lactic acid) (PLA) molecules react with the hydroxyl groups of FePol (FP) molecules during the melt‐blending of PLA_xFP_y specimens. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) experiments of PLA and PLA/FP specimens suggest that only small amounts of poor PLA and/or FP crystals are present in their corresponding melt crystallized specimens. In fact, the percentage crystallinity, peak melting temperature, and onset re‐crystallization temperature values of PLA/FP specimens reduce gradually as their FP contents increase. However, the glass transition temperatures of PLA molecules found by DSC and DMA reduce to a minimum value as the FP contents of PLA_xFP_y specimens reach 6 wt %. Further DMA and morphological analysis of PLA/FP specimens reveal that FP molecules are compatible with PLA molecules at FP contents equal to or less than 6 wt %, as no distinguished phase‐separated FP droplets and tan δ transitions were found on fracture surfaces and tan δ curves of PLA/FP specimens, respectively. In contrast to PLA, the FP specimen exhibits highly deformable and tearing properties. After blending proper amounts of FP in PLA, the inherent brittle deformation and poor tearing behavior of PLA were successfully improved. Possible reasons accounting for these interesting crystallization, compatible and tearing properties of PLA/FP specimens are proposed. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 913–920, 2010