Digital image analysis of polymer blends morphology

Application of digital image analysis (DIA) to polymer blends morphology is discussed with examples. Various operations in DIA including two-dimensional Fourier transformation (2DFT), intensity distribution, recursive region extraction, etc. are applied to morphology of polymer blends due to spinodal decomposition (SD), nucleation 6 growth (NG), and eutectic solidification (ES). Merits and drawbacks of DIA to study polymer blends morphology are discussed and the possibility of future development is presented.     

Atomic and molecular spectroscopy with a continuous-wave, doubly resonant, monolithic optical parametric oscillator

Doppler-broadened atomic and molecular spectra were observed with a one octave tunable, continuous-wave, doubly resonant, monolithic optical parametric oscillator (OPO) using 5% MgO-doped LiNbO₃ as a non-linear crystal with a birefringent phase-matching configuration. By tuning the frequency of a pump laser, longitudinal mode selection over 20 successive modes, corresponding to a 60 GHz span, was possible, owing to the simple structure of the monolithic OPO. Continuous frequency tuning was achieved using an external waveguide-type electrooptic phase modulator (EOM). By changing the modulation frequency of the EOM, frequency tuning of the optical sidebands over 12 GHz was possible, which is larger than the one free spectral range of the monolithic cavity of 3 GHz. We could observe the Cs-D₁ (894 nm), Cs-D₂ (852 nm), Rb-D₁ (795 nm), acetylene R9 (1520 nm) and P9 (1530 nm) transitions with the single monolithic OPO.     

Apparent diffusion coefficient of line scan diffusion image in normal prostate and prostate cancer—comparison with single-shot echo planner image

Purpose

This retrospective study was designed to evaluate the apparent diffusion coefficient (ADC) of line scan diffusion images (LSDI) in normal prostate and prostate cancer. Single-shot echo planner images (SS-EPI) were used for comparison.

Materials and Methods

Twenty prostate tumors were examined by conventional MRI in 14 patients prior to radical prostatectomy. All patients were examined with a 1.5-T MR imager (Signa CV/i ver. 9.1 GE Medical System Milwaukee, WI, USA). Diffusion-weighted MR imaging (DWI) using LSDI was performed with a pelvic phased-array coil, with b values of 5 and 800 s/mm². DWI using SS-EPI was performed with a body coil, with b values of 0 and 800 s/mm². The ADCs of each sequence for 14 normal prostate and 20 prostate cancers were histopathologically assessed. Signal-to-noise ratio (SNR) on DWI was estimated and compared for each sequence.

Results

The mean ADCs (±S.D.) of normal peripheral zones (PZ), transition zones (TZ) and cancer (in 10⁻³ mm²/s) that used LSDI were 1.42±0.12, 1.23±0.10 and 0.79±0.19, respectively. Those that used SS-EPI were 1.76±0.26, 1.38±0.20 and 1.05±0.27, respectively. Using unpaired t test (P<.05), we found a significant difference in each sequence between normal tissue (both PZ and TZ) and the cancer. Paired t test (P<.05) also registered a significant difference between LSDI and SS-EPI. Mean SNR for DWI using LSDI was 16.49±5.03, while the DWI using SS-EPI was 18.85±9.26. The difference between the SNR of each sequence was not statistically significant by paired t test.

Conclusion

We found that ADCs using LSDI and SS-EPI showed similar tendencies in the same patients. However, in all regions, LSDI ADCs had smaller standard deviations than SS-EPI ADCs.     

Pushing exercise program to correct glottal incompetence

A voice therapy program using pushing exercises to correct glottal incompetence is described. The program utilizes various types of instrumentation to determine whether or not a given patient is likely to benefit from the treatment. The program also provides feedback of target voices. Three cases with incomplete glottal closure and subsequent vocal dysphonia characterized by an asthenic breathy quality are used to illustrate the program. Details of the program, termination criteria, and problems and precautions learned from treating 29 patients over a 3-year period are presented.     

Near-IR Luminescent YbIII Coordination Polymers Composed of Pyrene Derivatives for Thermostable Oxygen Sensors

Oxygen-sensitive and near-infrared (NIR) luminescent Yb^III coordination polymers incorporating ligands based on pyrene derivatives were synthesized: Yb^III–TBAPy and Yb^III–TIAPy (TBAPy: 1,3,6,8-tetrakis(p-benzoate)pyrene; TIAPy: 1,3,6,8-tetrakis(3,5-isophthalic acid)pyrene). The coordination structures of these materials have been characterized by means of electrospray ionization mass spectrometry, X-ray diffraction analysis, and thermogravimetric analysis. Moreover, the porous structure of Yb^III–TIAPy has been evaluated by measuring its N₂ adsorption isotherm. The NIR luminescence properties of Yb^III–TBAPy and Yb^III–TIAPy have been examined by acquiring emission spectra and determining emission lifetimes under air or argon and in vacuo. Yb^III–TIAPy exhibited high thermal stability (with a decomposition temperature of 400 °C), intense luminescence (with an emission quantum yield under argon of 6.6 %), and effective oxygen-sensing characteristics. These results suggest that NIR luminescent Yb^III coordination polymers prepared using pyrene derivatives could have applications in novel thermo-stable oxygen sensors.     

Extremely Photostable Electron-Deficient Phthalocyanines that Generate High Levels of Singlet Oxygen

A robust lead-mediated synthetic procedure for the generation of phthalocyanines substituted with electron-withdrawing groups has been developed. The free-base phthalocyanine and various metal complexes were prepared without discernible degradation of the peripheral electron-withdrawing substituents. Upon irradiation with red light, some of the thus-obtained metal complexes generated high levels of singlet oxygen. In particular, a palladium complex exhibited attractive photostability upon exposure to singlet oxygen as a bleaching agent. The photostability of such complexes that may manifest concomitantly to the generation of high levels of singlet oxygen was attributed to the presence of the electron-withdrawing groups, which results in energetically low-lying highest occupied molecular orbitals.     

Shimalactone Biosynthesis Involves Spontaneous Double Bicyclo-Ring Formation with 8π-6π Electrocyclization

Shimalactones A and B are neuritogenic polyketides possessing characteristic oxabicyclo[2.2.1]heptane and bicyclo[4.2.0]octadiene ring systems that are produced by the marine fungus Emericella variecolor GF10. We identified a candidate biosynthetic gene cluster and conducted heterologous expression analysis. Expression of ShmA polyketide synthase in Aspergillus oryzae resulted in the production of preshimalactone. Aspergillus oryzae and Saccharomyces cerevisiae transformants expressing ShmA and ShmB produced shimalactones A and B, thus suggesting that the double bicyclo-ring formation reactions proceed non-enzymatically from preshimalactone epoxide. DFT calculations strongly support the idea that oxabicyclo-ring formation and 8π-6π electrocyclization proceed spontaneously after opening of the preshimalactone epoxide ring through protonation. We confirmed the formation of preshimalactone epoxide in vitro, followed by its non-enzymatic conversion to shimalactones in the dark.     

Biosynthesis of Indole Diterpene Lolitrems: Radical-Induced Cyclization of an Epoxyalcohol Affording a Characteristic Lolitremane Skeleton

Lolitrems are tremorgenic indole diterpenes that exhibit a unique 5/6 bicyclic system of the indole moiety. Although genetic analysis has indicated that the prenyltransferase LtmE and the cytochrome P450 LtmJ are involved in the construction of this unique structure, the detailed mechanism remains to be elucidated. Herein, we report the reconstitution of the biosynthetic pathway for lolitrems employing a recently established genome-editing technique for the expression host Aspergillus oryzae. Heterologous expression and bioconversion of the various intermediates revealed that LtmJ catalyzes multistep oxidation to furnish the lolitrem core. We also isolated the key reaction intermediate with an epoxyalcohol moiety. This observation allowed us to establish the mechanism of radical-induced cyclization, which was firmly supported by density functional theory calculations and a model experiment with a synthetic analogue.