Synthesis and properties of fluorene or carbazole‐based alternating copolymers containing Si and vinylene units in the main chain

Alternating copolymerization of 9,9‐dihexyl‐2,7‐dibromofluorene (HFl), N‐hexyl‐2,7‐dibromocarbazole (2,7‐HCz) or N‐hexyl‐3,6‐dibromocarbazole (3,6‐HCz) with Si‐containing divinyl or diallyl compounds, divinyldimethylsilane, divinyldiphenylsilane, 1,3‐divinyltetramethyldisiloxane, 1,4‐bis(dimethylvinylsilyl)benznene, diallyldimethylsilane, or diallyldiphenylsilane has been investigated using Mizoroki‐Heck reaction with a Pd catalyst. The corresponding alternating copolymers were obtained in good yield. The alternating copolymers from HFl or 2,7‐HCz showed good solubility in typical organic solvents. On the other hand, the copolymer with 3,6‐HCz became insoluble due to the crosslinking. Photophysical properties of the resulting copolymers were investigated with UV–vis absorption and photoluminescence spectroscopy. All the copolymers showed absorption peak derived from π–π* transition at around 340 nm, which was blue shifted in comparison with that of the corresponding homopolymer. Whereas emission peaks of the copolymers of the cast film were red shifted in comparison with that of the homopolymers. Multiple broad absorption peaks, which would be derived from intramolecular charge transfer through σ–π moiety, were also detected in the range from 390 to 450 nm in the spectra of the copolymers containing Si‐vinylene unit. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4513–4521, 2008     

Hepatocellular lesions with increased iron uptake on superparamagnetic iron oxide-enhanced magnetic resonance imaging in cirrhosis or chronic hepatitis: comparison of four magnetic resonance sequences for lesion conspicuity

Purpose

The aim of this study was to determine the adequate MR sequence for the lesion conspicuity of hepatocellular lesions with increased iron uptake on superparamagnetic iron oxide (SPIO)-enhanced MRI.

Materials and Methods

SPIO-enhanced MRI was performed using a 1.5-T system. Among 25 patients with hypovascular hepatocellular nodules on contrast-enhanced dynamic CT (no early enhancement at arterial phase and hypoattenuation at equilibrium phase), 39 lesions with increased iron uptake on SPIO-enhanced MRI were evaluated. SPIO-enhanced MRI included (1) T1-weighted in-phase gradient recalled echo (GRE) images, (2) T2-weighted fast spin echo (FSE) images, (3) T2*-weighted GRE with moderate TE (7 ms) and (4) long TE (12 ms). The lesion-to-liver contrast-to-noise ratios of the hepatocellular nodule and the signal-to-noise ratio (SNR) of the hepatic parenchyma were calculated by one radiologist for a quantitative assessment. MR images were reviewed retrospectively by two independent radiologists to compare the subjective lesion conspicuity in each image set based on a four-point rating scale.

Result

The mean lesion-to-liver contrast-to-noise ratios with T2*-weighted GRE with moderate TE (7 ms) was highest (5.79±3.71) and was significantly higher than those with T1-weighted, in-phase images (3.79±3.23, P<.01), T2-weighted images (2.72±1.52, P<.001) and T2*-weighted GRE with long TE (12 ms) (3.93±2.69, P<.05). The subjective rating of lesion conspicuity was best on the T2*-weighted GRE with moderate TE (7 ms), followed by that on the T2*-weighted GRE with moderate TE (7 ms; P<.05).

Conclusion

T2*-weighted GRE sequence with moderate TE (7 ms) showed high lesion-to-liver contrast-to-noise ratios in hepatocellular lesions with increased iron uptake on SPIO-enhanced MRI, indicating better lesion conspicuity of hypointense hepatocellular nodules in cirrhosis or chronic hepatitis.     

A New Optical Imager for Hemoglobin Distribution in Human Skin

A new four-wavelength optical imager has been developed for the evaluation of various vascular diseases. Four-wavelength optical intensity images are transformed to an oxygenation mapping, which further provide maps of rapid changes in hemoglobin distribution in human skin related with peripheral blood flow. This paper presents the configuration of the system and test measurements for foot disease. Forty-nine volunteers took part in our measurements with an occlusion test of their legs. Some differences were observed in oxygenation change between healthy volunteers and patients, and arteriosclerosis obliterate (ASO) patients and healthy volunteers were clearly distinguishable.     

Fiber-Optic Ammonia Sensors Utilizing Rectangular-Cladding Eccentric-Core Fiber

A new fiber-optic ammonia sensor utilizing rectangular-cladding eccentric-core fiber and a sensitive film containing an indicator dye is demonstrated. The sensitive film is a SiO₂-GeO₂ gel film including an indicator dye of bromocresol purple or bromocresol green, which is dip-coated by a sol-gel technique. The attenuation of this sensor changes depending on the concentration of ammonia at the wavelength range of 500–700 nm. This sensor can detect several ppm of gaseous ammonia. Various factors determining the sensitivity to detect the ammonia gas and time response of the sensor are also studied.     

Return map analysis of chaotic phase synchronization

We investigate chaotic phase synchronization (CPS) observed in a mutually coupled map system and a forced map oscillator by using return maps (RM) of phase difference. RM visualizes the presence or absence of the channel for phase slip which characterizes the onset of CPS. It is found that CPS occurs when the channel starts to be completely closed, and that the saddle node point is approximately equal to the point at which the channel is closed on the average. Furthermore, the proposed RM describes the critical characteristics of the phase difference and reveals the existence of the quasi-synchronized state below the synchronization point.     

Small hepatocellular carcinomas in cirrhosis: differences in contrast enhancement effects between helical CT and MR imaging during multiphasic dynamic imaging

PURPOSE: The purpose of this study was to evaluate differences in the degrees of contrast enhancement effects of small hepatocellular carcinomas (HCCs) in patients with cirrhosis between helical computed tomography (CT) and magnetic resonance (MR) imaging during multiphasic contrast-enhanced dynamic imaging and to determine the diagnostic value of MR imaging especially in assessing hypovascular HCCs detected as hypoattenuating nodules on late-phase CT. SUBJECTS AND METHODS: This study included 64 small HCCs (<3 cm in diameter) in 40 patients with chronic hepatitis or cirrhosis who underwent multiphasic (arterial, portal and late phases) contrast-enhanced dynamic helical CT and MR imaging. The contrast enhancement patterns of each lesion in the arterial and late phases were evaluated by two radiologists experienced in liver MR imaging and categorized as one of five grades (1=hypoattenuated/hypointense; 2=slightly hypoattenuated/hypointense; 3=isoattenuated/isointense; 4=slightly hyperattenuated/hyperintense; 5=hyperattenuated/hyperintense), compared with the surrounding liver parenchyma. RESULT: Forty-three (67%) of 64 lesions showed Grade 4 (n=24) or Grade 5 (n=19) enhancement on arterial-phase CT, while 51 (80%) of 64 lesions showed Grade 4 (n=20) or Grade 5 (n=31) enhancement on arterial-phase MR imaging, indicating hypervascular HCCs. The grading score of hypervascular HCCs on arterial-phase MR imaging (mean: 4.61) was significantly (P<.01) higher than that for hypervascular HCCs on arterial-phase CT (mean: 4.20), showing better detection of the hypervascularity (arterial enhancement) of the lesion on arterial-phase MR imaging. Regarding hypovascular HCCs, all (100%) of 21 hypovascular HCCs on CT showed Grade 1 (n=10) or Grade 2 (n=11) enhancement on late-phase CT, seen as hypoattenuation. In contrast, 8 (62%) of 13 hypovascular HCCs on MR imaging showed Grade 1 (n=1) or Grade 2 (n=7) enhancement on late-phase MR imaging, seen as hypointensity. Grading scores of hypovascular HCCs on late-phase images were significantly (P<.001) lower on CT than on MR imaging (mean score: 1.52 vs. 2.31), indicating better washout effects for hypovascular HCCs on late-phase CT. CONCLUSION: The washout effects for small HCCs on late-phase MR imaging were inferior to those for small HCCs on late-phase CT. Especially, hypovascular HCCs demonstrated as hypoattenuating nodules on late-phase CT were often not seen on late-phase MR imaging, requiring careful evaluation of other sequences, including unenhanced T(1)-weighted and T(2)-weighted MR images.     

Synthesis of polyolefins with unique properties by using metallocene-type catalysts

Copolymerization of ethylene and 1,5-hexadiene (HD) by zirconocene catalysts proceeded via cyclization-addition mechanism to form 1,3-didsubstituted cyclopentane structure in the polyethylene chain. The 1,3-cyclopentane structure was found to be taken in the crystalline structure of polyethylene (isomorphism) by partially chainging the trans zigzag chain into gauche conformation, thereby, inducing a transformation of orthorhombic crystal to pseudohexagonal crystal. Copolymerization of ethylene and cyclopentene (CPE) by zirconocene catalysts yielded copolymers having 1,2-disubstituted cyclopentane structure in the polyethylene chain. The 1,2-cyclopentane structure was not taken into the crystalline structure of polyethylene. The melting point (T_m) and the crystallinity (X_c) of polyethylene decreased by copolymerization of HD or CPE, and the T_m- and X_c-decreasing effect of CPE was stronger than HD. For copolymers of propylene and HD or CPE obtained with isospecific zirconocene catalyst, the isomorphism was not ovserved.