Preparation and applications of novel cross‐linked fluoroalkyl end‐capped oligomeric nanocomposites possessing aromatic siloxane segments as core units

Fluoroalkyl end‐capped N,N‐dimethylacrylamide oligomer and N‐(1,1‐dimethyl‐3‐oxobutyl)acrylamide oligomer were reacted with phenylene‐ and biphenylene‐bridged ethoxysilanes under alkaline conditions to yield cross‐linked fluoroalkyl end‐capped oligomeric composites possessing aromatic siloxane segments as core units. These isolated fluorinated composite powders were found to be nanometer size‐controlled fine particles with a good dispersibility and stability in water and organic solvents. Nitrogen adsorption–desorption isotherms confirmed the presence of micropores in these nanocomposites; the micropore size estimated by the HK method was 0.7–0.8 nm. Interestingly, fluorinated nanocomposites possessing a higher micropore volume ratio were found to exhibit a selective encapsulation ability of fullerene into their composite cores. These fluorinated nanocomposites were also applied to the surface modification of poly(methyl methacrylate) film, resulting in a good oleophobicity imparted by fluorine on the surface. In addition, fluorescence emission was visibly observed only from the modified PMMA film surface treated with fluorinated nanocomposites possessing biphenylene units when irradiated by light. Copyright © 2009 John Wiley & Sons, Ltd.     

Near-ultraviolet femtosecond laser ionization of dioxins in gas chromatography/time-of-flight mass spectrometry

Gas chromatography/multiphoton ionization/time-of-flight mass spectrometry (GC/MPI/TOF-MS) was applied to the trace analysis of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs). To determine the optimum wavelength for analysis of PCDD/Fs, the wavelength of the femtosecond laser utilized for multiphoton ionization was converted to near-ultraviolet status using stimulated Raman scattering. A femtosecond laser emitting at 300 nm completely eliminated the background signal arising from the bleeding compounds generated from a stationary phase of the capillary column in GC.     

Aging Effects on the Structure Underlying Balance Abilities Tests

Balance impairment is one of the biggest risk factors for falls reducing inactivity, resulting in nursing care. Therefore, balance ability is crucial to maintain the activities of independent daily living of older adults. Many tests to assess balance ability have been developed. However, few reports reveal the structure underlying results of balance performance tests comparing young and older adults. Covariance structure analysis is a tool that is used to test statistically whether factorial structure fits data. This study examined aging effects on the factorial structure underlying balance performance tests. Participants comprised 60 healthy young women aged 22 ± 3 years (young group) and 60 community-dwelling older women aged 69 ± 5 years (older group). Six balance tests: postural sway, one-leg standing, functional reach, timed up and go (TUG), gait, and the EquiTest were employed. Exploratory factor analysis revealed that three clearly interpretable factors were extracted in the young group. The first factor had high loadings on the EquiTest, and was interpreted as ‘Reactive’. The second factor had high loadings on the postural sway test, and was interpreted as ‘Static’. The third factor had high loadings on TUG and gait test, and was interpreted as ‘Dynamic’. Similarly, three interpretable factors were extracted in the older group. The first factor had high loadings on the postural sway test and the EquiTest and therefore was interpreted as ‘Static and Reactive’. The second factor, which had high loadings on the EquiTest, was interpreted as ‘Reactive’. The third factor, which had high loadings on TUG and the gait test, was interpreted as ‘Dynamic’. A covariance structure model was applied to the test data: the second-order factor was balance ability, and the first-order factors were static, dynamic and reactive factors which were assumed to be measured based on the six balance tests. Goodness-of-fit index (GFI) of the models were acceptable (young group, GFI=0.931; older group, GFI=0.923). Static, dynamic and reactive factors relating to balance ability had loadings 0.21, 0.24, and 0.76 in the young group and 0.71, 0.28, and 0.43 in the older group, respectively. It is suggested that the common factorial structure of balance abilities were static, dynamic and reactive, and that for young people reactive balance ability was characterized and explained by balance ability, whereas for older people it was static balance ability.     

Two-dimensional imaging of atomic distribution morphology created by holographically induced mass transfer of monomer molecules and nanoparticles in a silica-nanoparticle-dispersed photopolymer film

We report an electron-probe microanalysis of a hologram recorded in a silica-nanoparticle-dispersed photopolymer film. We used S and Si atoms as label elements to identify formed polymer and nanoparticle species, respectively. It is found that the periodic density distributions of S and Si atoms are out of phase with each other, indicating that those of the formed polymer and nanoparticles are out of phase each other. This result shows decisive evidence of the mutual diffusion of monomer molecules and silica nanoparticles in the film under holographic two-beam interference exposure.     

Stability analysis of thermally induced spontaneous gas oscillations in straight and looped tubes

A gas in a tube spontaneously oscillates when the temperature gradient applied along the wall of the tube is higher than the critical value. This spontaneous gas oscillation is caused by the thermal interaction between the gas and the tube wall. The stability limit of the thermally induced gas oscillation is numerically investigated by using the linear stability theory and a transfer matrix method. It is well known that an acoustic wave excited by the spontaneous gas oscillation occurring in a looped tube is different from that in a straight tube with two ends; a traveling acoustic wave is induced in a looped tube, whereas a standing acoustic wave is caused in a straight tube. The conditions for the stability limits in both tube types were calculated. The calculated and measured conditions were compared and were found to be in good agreement. Calculations performed by varying the value of the Prandtl number of the gas were used to determine the reasons for the existence of the stability limits of the looped and straight tubes.     

Superfluid 4He quantum interference grating

We report the first observation of quantum interference from a grating structure consisting of four weak link junctions in superfluid 4He. We find that an interference grating can be implemented successfully in a superfluid matter wave interferometer to enhance its sensitivity while trading away some of its dynamic range. We also show that this type of device can be used to measure absolute quantum mechanical phase differences. The results demonstrate the robust nature of superfluid phase coherence arising from quantum mechanics on a macroscopic scale.     

Bifurcations to diversify geometrical patterns of shear bands on granular material

The mechanism to diversify geometrical patterns on granular material was elucidated using a group-theoretic image analysis of patterned shear bands, with associated numerical bifurcation analysis. Pattern formation of granular materials took the course of the evolution of a diamondlike diffuse bifurcation breaking uniformity, followed by further bifurcation, mode jumping, and the formation and disappearance of shear bands through localization. A chaotic explosive increase of possible postbifurcation states was emphasized as a mechanism to diversify geometrical patterns.     

Microcrystalline germanium thin films prepared by the reactive RF sputtering method

We focus on thin film microcrystalline germanium (μc-Ge) as narrow gap semiconductor materials for high infrared sensitivity and consider applying it to thermo-photo-voltaic (TPV). The μc-Ge films were prepared on glass substrates by the reactive RF sputtering method with Ar and H₂ gas mixtures. We could successfully produce photosensitive μc-Ge films. Higher crystallinity structures do not always result in better carrier properties. Probably, the amorphous portions between crystalline grains have important roles to suppress the grain boundary defects. We applied the μc-Ge to i-layers of pin structure devices, and observed the photovoltaic effect for the first time.     

Direct Observation of Primary C−H Bond Oxidation by an Oxido‐Iron(IV) Porphyrin π‐Radical Cation Complex in a Fluorinated Carbon Solvent

Oxido‐iron(IV) porphyrin π‐radical cation species are involved in a variety of heme‐containing enzymes and have characteristic oxidation states consisting of a high‐valent iron center and a π‐conjugated macrocyclic ligand. However, the short lifetime of the complex has hampered detailed reactivity studies. Reported herein is a remarkable increase in the lifetime (80 s at 10 °C) of Fe^IV(TMP^+.)(O)(Cl) ( 2 ; TMP=5,10,15,20‐tetramesitylporphyrin dianion), produced by the oxidation of Fe^III(TMP)(Cl) ( 1 ) by ozone in α,α,α‐trifluorotoluene (TFT). The lifetime is 720 times longer compared to that of the currently most stable species reported to date. The increase in the lifetime improves the reaction efficiency of 2 toward inert alkane substrates, and allowed observation of the reaction of 2 with a primary C?H bond (BDE_C‐H=ca. 100 kcal mol^?1) directly. Activation parameters for cyclohexane hydroxylation were also obtained.     

Photo‐Modification of Melanin by a Mid‐infrared Free‐electron Laser

Melanin is rigidly constructed by several nitrogen‐containing aromatic rings, and its excess accumulation in skin tissue is closely associated with melanosis. Although visible lasers (wavelength: 600–1000 nm) are conventionally used for the photo‐thermolysis of melanocyte, several pigmented nevi are difficult to be treated. Here, we propose an alternate method for targeting the molecular structure of melanin using an infrared free‐electron laser (FEL) tuned to 5.8 μm that corresponds to the stretching vibrational mode of carboxylate group. A drastic morphological change on the black‐colored surface of melanin powder was observed after the pulse irradiation with power energy of 500 mJ cm^?2, and the minimum irradiation time for damage to the morphology was 1.4 s. Analyses by mass spectroscopy, infrared spectroscopy, and ¹³C‐nuclear magnetic resonance implied that a pyrrole group was removed by the FEL irradiation. In addition, the FEL irradiation dispersed almost all of the melanoma cells from a culture solution without any influence on other ingredients in the medium, and one‐cell analysis by infrared microscopy showed that the structure of melanoma could be substantially damaged by the irradiation. This study proposes the potency of intense mid‐infrared laser as novel alternative way to reduce melanin.