Rapid DNA hybridization analysis using a PDMS microfluidic sensor and a molecular beacon.

A rapid DNA analysis has been developed based on a fluorescence intensity change of a molecular beacon in a PDMS microfluidic channel. Recently, we reported a new analytical method of DNA hybridization involving a PDMS microfluidic sensor using fluorescence energy transfer (FRET). However, there are some limitations in its application to real DNA samples because the target DNA must be labelled with a suitable fluorescent dye. To resolve this problem, we have developed a new DNA microfluidic sensor using a molecular beacon. By monitoring the change in the restored fluorescence intensity along the channel length, it is possible to rapidly detect any hybridization of the molecular beacon to the target DNA. In this case, the target DNA does not need to be labelled. Our experimental results demonstrate that this microfluidic sensor using a molecular beacon is a promising diagnostic tool for rapid DNA hybridization analysis.     

Atom transfer radical polymerization of methyl methacrylate by copper(I)‐pyridine‐2‐carboximidate catalysts

Pyridine‐2‐carboximidates [methyl ( 1a ), ethyl ( 1b ), isopropyl ( 1c ), cyclopentyl ( 1d ), cyclohexyl ( 1e ), n‐octyl ( 1f ), and benzyl ( 1g )] were prepared from the reaction of 2‐cyanopyridine with the corresponding alcohols. Cyclopentyl‐substituted 1d was found to be a highly effective ligand for copper‐catalyzed atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA). For example, the observed rate constant for a CuBr/ 1d catalytic system was found to be nearly twice as high as the cyclohexyl‐substituted CuBr/ 1e catalytic system [k_obs = (1.19 vs 0.56) × 10^?4 s^?1). The effects of the solvents, temperature, catalyst/initiator, and solvent/monomer ratio on the ATRP of MMA were studied systematically for the CuBr/ 1d catalytic system. The optimum condition for the ATRP of MMA was found to be a 1:2:1:400 [CuBr]_o/[ 1d ]_o/[ethyl 2‐bromoisobutyrate]_o/[MMA]_o ratio at 60 °C in veratrole solution, which yielded well‐defined poly(MMA) with a narrow molecular weight distribution of 1.14. The catalytically active copper complex 2d was isolated from the reaction of CuBr with 1d . Narrow molecular weight distributions as low as 1.06 were achieved for the CuBr/ 1d catalytic system by employing 10% of the deactivator CuBr₂. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2747–2755, 2004     

Synthesis and characterization of soluble polyimides containing trifluoromethyl groups in their backbone

A series of polyimides were synthesized from 2,2‐Bis(3,4‐dicarboxyphenyl)hexafluoropropane, 2,2‐bis(3‐amino‐4‐hydroxyphenyl)‐hexafluoropropane, and 4,4′‐oxydianiline by chemical imidization. The effects of the diamine ratios on the properties of the films were evaluated through the study of their thermal, electrical, and morphological properties. All the polymers exhibited better solubility in most of the organic solvents and hence were easily processable. Polyimides with more 2,2‐bis(3‐amino‐4‐hydroxyphenyl)‐hexafluoropropane exhibited better solubility and a low refractive index, which is highly desired for microelectronic applications. The dielectric constant and birefringence were strongly dependent on the fluorine content. With an increase in the fluorine substitution, both the dielectric constant and birefringence decreased. All the polymers exhibited high thermal stability (>400 °C). The absence of crystalline melting in differential scanning calorimetry and broad wide‐angle X‐ray diffraction patterns revealed the amorphous nature of the polymers, which was due to the presence of bulky CF₃ groups and hinged ether linkages of the diamine component. The residual stress values decreased with an increase in the 4,4′‐oxydianiline content, and the results were in agreement with the dielectric constant. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4303–4312, 2004     

Diffraction grating in noncrosslinked polymers

The diffraction efficiency and morphology of the transmission modes of holographic polymer dispersed liquid crystals were studied with respect to the molecular structure of poly(urethane acrylate) (PUA), the film (polymer/liquid crystal) and resin (oligomer/monomer) compositions, and the cell thickness. PUA, based on N‐vinylpyrrolidone and ethyl hexyl acrylate, with low‐molecular‐weight poly(propylene glycol) at a low oligomer content, showed high diffraction efficiency. The results were interpreted in terms of the monomer reactivity and polymer elasticity. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 613–620, 2004     

Desorption behavior of a surfactant in a linear low‐density polyethylene blend at elevated temperatures

The desorption behavior of a surfactant in a linear low‐density polyethylene (LLDPE) blend at elevated temperatures of 50, 70, and 80 °C was studied with Fourier transform infrared spectroscopy. The composition of the LLDPE blend was 70:30 LLDPE/low‐density polyethylene. Three different specimens (II, III, and IV) were prepared with various compositions of a small molecular penetrant, sorbitan palmitate (SPAN‐40), and a migration controller, poly(ethylene acrylic acid) (EAA), in the LLDPE blend. The calculated diffusion coefficient (D) of SPAN‐40 in specimens II, III, and IV, between 50 and 80 °C, varied from 1.74 × 10^?11 to 6.79 × 10^?11 cm²/s, from 1.10 × 10^?11 to 5.75 × 10^?11 cm²/s, and from 0.58 × 10^?11 to 4.75 × 10^?11 cm²/s, respectively. In addition, the calculated activation energies (E_D) of specimens II, III, and IV, from the plotting of ln D versus 1/T between 50 and 80 °C, were 42.9, 52.7, and 65.6 kJ/mol, respectively. These values were different from those obtained between 25 and 50 °C and were believed to have been influenced by the interference of Tinuvin (a UV stabilizer) at elevated temperatures higher than 50 °C. Although the desorption rate of SPAN‐40 increased with the temperature and decreased with the EAA content, the observed spectral behavior did not depend on the temperature and time. For all specimens stored over 50 °C, the peak at 1739 cm^?1 decreased in a few days and subsequently increased with a peak shift toward 1730 cm^?1. This arose from the carbonyl stretching vibration of Tinuvin, possibly because of oxidation or degradation at elevated temperatures. In addition, the incorporation of EAA into the LLDPE blend suppressed the desorption rate of SPAN‐40 and retarded the appearance of the 1730 cm^?1 peak. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1114–1126, 2004     

Photoswitching of holographic polymer-dispersed liquid crystals doped with chiral dopant

Chiral dopants were added to the formulation of holographic polymer-dispersed liquid crystals and the effects studied in terms of grating formation dynamics, morphology, diffraction efficiency, contrast ratio and electro-optical properties of the films. A gradual increase of real-time diffraction efficiency, decrease of droplet size and increase of diffraction efficiency of the composite film were obtained with the addition and increasing content of chiral dopant, due to the increased viscosity of the liquid crystal (LC) doped with the chiral dopant leading to decreased droplet coalescence. The contrast ratio decreased with increasing content of chiral dopant due to the difficult orientation of LC molecules caused by the formation of a helical structure. Addition of a small amount of the chiral dopant increased the driving voltage slightly, whereas the decay time is decreased significantly as a result of the high twisting of the helical structure.     

Synthesis and adsorption properties of gold nanoparticles within pores of surface‐functional porous polymer microspheres

Mesoporous polymer microspheres with gold (Au) nanoparticles inside their pores were prepared considering their surface functionality and porosity. The Au/polymer composite microspheres prepared were characterized by transmission electron microscope (TEM), X‐ray diffraction (XRD), and Brunauer–Emmett–Teller (BET) techniques. The results showed that the adsorption of Au nanoparticles could be increased by imparting the pore structure and surface‐functional groups into the supporting polymer microspheres (in this study, poly (ethylene glycol dimethacrylate‐co‐acrylonitrile) and poly (EGDMA‐co‐AN) system). Above all, from this study, it was established that the porosity of the polymer microspheres is the most important factor that determines the distribution and adsorption amount of face‐centered cubic (fcc) Au nanoparticles in the final products. Our study showed that the continuous adsorption of Au nanoparticles with the aid of the large surface area and surface interaction sites formed more favorably the Au/polymer composite microspheres. The BET measurements of Au/poly(EGDMA‐co‐AN) composite microspheres reveals that the adsorption of Au nanoparticles into the pores kept the pore structure intact and made it more porous. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5627–5635, 2004     

Dual effects of fullerene doped to holographic polymer dispersed liquid crystals

Doping of conductive fullerene particles to the formulation of conventional holographic polymer dispersed liquid crystal‐induced dual effects of reducing both droplet coalescence and operating voltage. Fullerene induced an induction period which otherwise does not exist, followed by a gradual increase of diffraction efficiency to a saturation value being increased with increasing fullerene content. The increased diffraction efficiency was caused by the decreased droplet coalescence which was due to the hindered migration of LC by the fullerene particles. On the other hand, doped fullerene particles augmented the conductivity of polymer phase and hence the local electrical field imposed on LC droplet, which overcome the threshold for driving and reduced operating voltage and response times. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5590–5596, 2007     

Effect of biotransformation on multispecies plume evolution and natural attenuation

Biological transformation of volatile organic compounds is one of the key factors that influence contaminant-plume evolution and thus natural attenuation. In this study we investigate the effect of biological transformation on the transport of contaminants in the aqueous and gaseous phases. The analysis includes the study of the effect of density-driven advection of contaminants in the gaseous phase on multiphase and multispecies flow, fate and transport modeling in the subsurface. Trichloroethylene (TCE) and its two byproducts, dichloroethylene and vinyl chloride, are analyzed as the target contaminants. Our results indicate that density-driven advection of the gaseous phase, which is initiated by evaporation of TCE as a nonaqueous phase liquid, increases the downward and also the lateral migration of TCE within the unsaturated zone. This process also influences the location of high-concentration zones of the byproducts of TCE in the unsaturated and the saturated zones. Biotransformation of TCE contributes to the reduction of dissolved TCE plume development as expected. The daughter byproducts, which are introduced into the subsurface system, show distinct transport patterns as they are affected by their independent degradation kinetics and density-driven advection. These observations, which are based on our simulation results for biotransformation and transport of TCE and its byproducts, are useful in evaluating the natural attenuation processes, its potential health hazards and also the evaluation of potential plume development at contaminated sites.     

Synthesis and luminescence characteristics of conjugated dendrimers with 2,4,6‐triaryl‐1,3,5‐triazine periphery

We have synthesized conjugated dendrimer with triazine peripheries, and their luminescence properties were investigated. The dendrimers consist of dendritic triazine wedges for electron transport, distyrylbenzene core as an emitting moiety, and t‐butyl peripheral groups for good processing properties. The dendrimers have LUMO values of about ?2.7 eV possibly because of the triazine moiety with high electron affinity. Photoluminescence study indicates that energy transfer occurs from the triazine wedges to the stilbene bridge, and finally to the core chromophore units due to a cascade decrease of bandgap from the peripheral wedge to core moiety. Therefore, the emission wavelength was determined by the structure of the core unit. The energy transfer efficiency of distyrylbenzene‐cored dendrimers was about 75 and 55% for Trz‐1GD‐DSB and Trz‐2GD‐DSB, respectively. A preliminary electroluminescence property also was investigated. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 254–263, 2006