Synthesis and Characterization of DOPO-Containing Poly(2,6-dimethyl-1,4-phenylene oxide)s by Oxidative Coupling Polymerization.

A set of polyphenylene oxides incorporating DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) functionality, denoted as DOPO-R-PPO, was synthesized by copolymerization of 2,6-dimethylphenol (2,6-DMP) with various DOPO-substituted tetramethyl bisphenol monomers. In the initial step, a Friedel-Crafts acylation reaction was employed to react 2,6-DMP with different acyl chlorides, leading to the formation of ketone derivatives substituted with 2,6-dimethylphenyl groups. Subsequently, the ketones, along with DOPO and 2,6-DMP, underwent a condensation reaction to yield a series of DOPO-substituted bisphenol derivatives. Finally, polymerizations of 2,6-dimethylphenol with these DOPO-substituted bisphenols were carried out in organic solvents using copper(I) bromide/N-butyldimethylamine catalysts (CuBr/DMBA) under a continuous flow of oxygen, yielding telechelic PPO oligomers with DOPO moieties incorporated into the polymer backbone. The chemical structures of the synthesized compounds were characterized using various analytical techniques, including Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance (1H NMR), phosphorus nuclear magnetic resonance (31P NMR), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). When compared to conventional poly(2,6-dimethyl-1,4-phenylene oxide)s with a similar molecular weight range, all DOPO-PPOs exhibited higher glass transition temperatures, enhanced thermal degradability, and increased char yield formation at 800 °C without compromising solubility in organic solvents.

Synthesis and Characterization of N-Substituted Polyether-Block-Amide Copolymers.

A series of N-substituted polyether-block-amide (PEBA-X%) copolymers were prepared by melt polycondensation of nylon-6 prepolymer and polytetramethylene ether glycol at an elevated temperature using titanium isopropoxide as a catalyst. The structure, thermal properties, and crystallinity of PEBA-X% were investigated using nuclear magnetic resonance spectroscopy, Fourier-transform infrared spectroscopy, differential scanning calorimetry, wide angle X-ray diffraction, and thermogravimetric analysis. In general, the crystallinity, melting point, and thermal degradation temperature of PEBA-X% decreased as the incorporation of N-methyl functionalized groups increased, owing to the disruption caused to the structural regularity of the copolymer. However, in N-acetyl functionalized analogues, the crystallinity first dropped and then increased because of a new γ form arrangement that developed in the microstructure. After the cross-linking reaction of the N-methyl-substituted derivative, which has electron-donating characteristics, with poly(4,4'-methylenebis(phenyl isocyanate), the decomposition temperature of the resulting polymer significantly increased, whereas no such improvements could be observed in the case of the electro-withdrawing N-acetyl-substituted derivative, because of the incompleteness of its cross-linking reaction.

Radical and Atom Transfer Halogenation (RATH): A Facile Route for Chemical and Polymer Functionalization.

This work demonstrates a new halogenation reaction through sequential radical and halogen transfer reactions, named as "radical and atom transfer halogenation" (RATH). Both benzoxazine compounds and poly(2,6-dimethyl-1,4-phenylene oxide) have been demonstrated as active species for RATH. Consequently, the halogenated compound becomes an active initiator of atom transfer radical polymerization. Combination of RATH and sequential ATRP provides an convenient and effective approach to prepare reactive and crosslinkable polymers. The RATH reaction opens a new window both to chemical synthesis and molecular design and preparation of polymeric materials.

Sigma-delta receive beamformer based on cascaded reconstruction for ultrasound imaging application.

A pre-delay reconstruction sigma-delta beamformer (SDBF) was recently proposed to achieve a higher level of integration in ultrasound imaging systems. Nevertheless, the high-order reconstruction filter used in each channel of SDBF makes the beamformer highly complex. The beamformer can be simplified by reconstructing the signal after the delay-and-sum process with only one filter. However, this post-delay reconstruction-based design degrades image quality when dynamic focusing is performed. This paper shows that employing a simple pre-delay filter is sufficient to achieve similar performance as conventional pre-delay reconstruction SDBF, as long as the pre-delay filter provides the required pre-delay signal to-quantization noise ratio (SQNR). Based on this finding, we proposed a cascaded reconstruction beamformer that uses a boxcar filter as the pre-delay filter in each channel. Simulations using real phantom data demonstrate that the proposed beamforming method can achieve a contrast resolution comparable to that of the pre-delay reconstruction beamforming method. In addition, the hardware can be greatly simplified compared with the pre-delay reconstruction beamformers.

New demodulation method for efficient phase-rotation-based beamforming.

In this paper, we present a new demodulation method to reduce hardware complexity in phase-rotation-based beamforming. Due to its low sensitivity to phase delay errors, quadrature demodulation, which consists of mixing and lowpass filtering, is commonly used in ultrasound machines. However, because it requires two lowpass filters for each channel to remove harmonics after mixing, the direct use of quadrature demodulation is computationally expensive. To alleviate the high computational requirement in quadrature demodulation, we have developed a two-stage demodulation technique in which dynamic receive focusing is performed on the mixed signal instead of the complex baseband signal. Harmonics then are suppressed by using only two lowpass filters. When the number of channels is 32, the proposed two-stage demodulation reduces the necessary number of multiplications and additions for phase-rotation beamforming by 82.7% and 88.2%, respectively, compared to using quadrature demodulation. We have found from simulation and phantom studies that the proposed method does not incur any significant degradation in image quality in terms of axial and lateral resolution. These preliminary results indicate that the proposed two-stage demodulation method could contribute to significantly reducing the hardware complexity in phase-rotation-based beamforming while providing comparable image quality.

Nonlinear diffusion in Laplacian pyramid domain for ultrasonic speckle reduction.

A new speckle reduction method, i.e., Laplacian pyramid-based nonlinear diffusion (LPND), is proposed for medical ultrasound imaging. With this method, speckle is removed by nonlinear diffusion filtering of bandpass ultrasound images in Laplacian pyramid domain. For nonlinear diffusion in each pyramid layer, a gradient threshold is automatically determined by a variation of median absolute deviation (MAD) estimator. The performance of the proposed LPND method has been compared with that of other speckle reduction methods, including the recently proposed speckle reducing anisotropic diffusion (SRAD) and nonlinear coherent diffusion (NCD). In simulation and phantom studies, an average gain of 1.55 dB and 1.34 dB in contrast-to-noise ratio was obtained compared to SRAD and NCD, respectively. The visual comparison of despeckled in vivo ultrasound images from liver and carotid artery shows that the proposed LPND method could effectively preserve edges and detailed structures while thoroughly suppressing speckle. These preliminary results indicate that the proposed speckle reduction method could improve image quality and the visibility of small structures and fine details in medical ultrasound imaging.

New demodulation filter in digital phase rotation beamforming.

In this paper, we present a new quadrature demodulation filter to reduce hardware complexity in digital phase rotation beamforming. Due to its low sensitivity to phase delay errors, digital quadrature demodulation is commonly used in ultrasound machines. However, since it requires two lowpass filters for each channel to remove harmonics, the direct use of conventional finite impulse response (FIR) filters in ultrasound machines is computationally expensive and burdensome. In our new method, an efficient multi-stage uniform coefficient (MSUC) filter is utilized to remove harmonic components in phase rotation beamforming. In comparison with the directly implemented FIR (DI-FIR) and the previously-proposed signed-power-of-two FIR (SPOT-FIR) lowpass filters, the proposed MSUC filter reduces the necessary hardware resources by 93.9% and 83.9%, respectively. In simulation, the MSUC filter shows a negligible degradation in image quality. The proposed method resulted in comparable spatial and contrast resolution to the DI-FIR approach in the phantom study. These preliminary results indicate that the proposed quadrature demodulation filtering method could significantly reduce the hardware complexity in phase rotation beamforming while maintaining comparable image quality.

A simple and direct isolation of whey components from raw milk by gel filtration chromatography and structural characterization by Fourier transform Raman spectroscopy.

A simple and economical method to isolate whey protein from fresh raw milk is developed by serial defatting, casein eliminating, lactose removing, and separating by gel filtration chromatography. Four major whey components, including immunoglobulin (Ig), bovine serum albumin (BSA), beta-lactoglobulin (beta-Lg) and alpha-lactalbumin (alpha-Lac), and a non-protein of low molecular mass ( approximately 1.7 kDa) but strong absorbance at 280 nm, are detected simultaneously. The small non-protein molecule is rich in aromatic amino acids and thiol groups as supported by the structural characterization with near infrared Fourier transform Raman spectroscopy (FT-Raman). FT-Raman results show that the secondary structure of Ig is dominated by anti-parallel beta-pleated sheet; BSA is mainly in alpha-helix; both beta-form and unordered structure are important in beta-Lg; while alpha-Lac is mostly in alpha-helix coupling with random coil. Differences in the Raman profile for each whey component reflect their intrinsic compositional differences and distinct spatial arrangement. The S-S linkages diverging around 510-540 cm(-1) indicate that the conformation of disulfide bonds in each whey components is different, which may be responsible for their diversified behaviors in solubility, rheological and functional properties.

Regioselective Substitution Reactions of Sulfur(VI)-Nitrogen-Phosphorus Rings: Reactions of the Halogenated Cyclic Thionylphosphazenes [NSOX(NPCl(2))(2)] (X = Cl or F) with Oxygen-Based Nucleophiles.

The reactions of the cyclic thionylphosphazenes [NSOX(NPCl(2))(2)] (1, X = Cl; 2, X = F) with three oxygen-based nucleophiles of increasing basicity, sodium phenoxide (NaOPh), sodium trifluoroethoxide (NaOCH(2)CF(3)), and sodium butoxide (NaOBu) have been studied. The reaction of 1 and 2 with 4 equiv of NaOPh at 25 degrees C yielded the regioselectively tetrasubstituted species [NSOX{NP(OPh)(2)}(2)] (5d, X = Cl; 6d, X = F). Further reaction of 5d with an additional 2 equiv of NaOPh over several days or at elevated temperatures gave the fully substituted compound [NSO(OPh){NP(OPh)(2)}(2)] (5e), whereas 6d did not react further. The reaction of 1 and 2 with 5 equiv of NaOCH(2)CF(3) yielded in both cases [NSO(OCH(2)CF(3)){NP(OCH(2)CF(3))(2)}(2)] (7e), and similarly reaction with 5 equiv of NaOBu yielded [NSO(OBu){NP(OBu)(2)}(2)] (9e). In all cases, the reactions were monitored by (31)P NMR and (where applicable) (19)F NMR and were found to involve complete substitution at phosphorus via a predominantly vicinal pathway, followed by substitution at sulfur. Substitutional control of the reactions of NaOPh, NaOBu, with 1 and 2 was found to conform to the following general order of reactivity, PCl(2) > PCl(OR) > SOX (X = Cl, F). Although the reaction with NaOCH(2)CF(3) followed the same order of reactivity, a significant enhancement of reaction rate was detected with each equivalent of trifluoroethoxide added. Reaction of 7e with excess NaOCH(2)CF(3) led to elimination of (CF(3)CH(2))(2)O and the formation of the salts Na[NSO(OCH(2)CF(3))NP(OCH(2)CF(3))(2)NP(OCH(2)CF(3))O] (11) and Na[NS(O)O{NP(OCH(2)CF(3))(2)}(2)] (12). Crystals of 6d are triclinic, space group P&onemacr;, with a = 9.789(3) Å, b = 11.393(4) Å, c = 12.079(5) Å, alpha = 107.40(3) degrees, beta = 91.23(3) degrees, gamma = 93.18(3), V = 1283.6(8) Å(3), and Z = 2. Crystals of 5e are monoclinic, space group C2/c, with a = 32.457(3) Å, b = 10.747(1) Å, c = 18.294(2) Å, beta = 110.37(1) degrees, V = 5982.4(9) Å(3), and Z = 8.