Raman microspectroscopic study on polymerization and degradation processes of a diacetylene derivative at surface enhanced Raman scattering active substrates. 1. Reaction kinetics.

Raman microspectroscopy was applied to study the polymerization kinetics of the Langmuir-Blodgett (LB) films of 10,12-pentacosadiynoic acid (DA) adsorbed on surface enhanced Raman scattering (SERS) active Ag island films. A two-dimensional (2D) Raman microscopic image measured at 1520 cm(-1) exhibits bright and dim spots with the diameter of several hundred nanometers. Raman microscopic spectra, measured by defocusing the excitation laser light (532 nm, diameter of ca. 10 mum) on the samples at room temperature, proved the occurrence of the surface processes consisting of the formation of polydiacetylene (PDA) in the blue phase, its conversion to the red phase, and subsequent bleaching. These reactions were negligible under the same condition for the DA-LB films prepared on a smooth (i.e., SERS-inactive) Ag film, indicating that the 532-nm-induced polymerization and the bleaching process are enhanced by the SERS-active substrates. At low temperatures below -50 degrees C, the Raman microscopic measurements proved the formation of the blue phase and its conversion to the red phase with much lower reaction rates compared to the corresponding rates at room temperature. The bleaching, however, was much suppressed at the low temperatures. The kinetic analyses of the formation of the blue phase and its conversion to the red phase were performed by using the intensity changes of the Raman bands due to the blue (1477 cm(-1)) and red (1517 cm(-1)) phases as a function of the irradiation time. The results strongly suggested the existence of at least two processes taking place simultaneously on the SERS-active substrates; that is, one of the processes is a sequential reaction, DA-monomers --> PDA in the blue phase --> PDA in the red phase, and the other is another sequential reaction, DA-monomers --> PDA in the red phase --> degradation species (probably amorphous carbon). Thus, even at the low temperatures, there occurs the surface reaction consisting of the formation of PDA and its degradation. The reaction can be ascribed to a process taking place at the highly SERS-active site, which gives the bright spot (so-called "hot spot") on the 2D Raman image, as proved by the confocal Raman microscopic measurement in the following paper.

Raman microspectroscopic study on polymerization and degradation processes of a diacetylene derivative at surface enhanced Raman scattering active substrates. 2. Confocal Raman microscopic observation of polydiacetylene adsorbed on active sites.

Confocal Raman microscopic measurements were performed at room temperature on the Langmuir-Blodgett (LB) monolayer of 10,12-pentacosadiynoic acid (DA) prepared on surface enhanced Raman scattering (SERS) active Ag island films, two-dimensional (2D) Raman images of which exhibit bright and dim spots on a dark background. The measurements performed by focusing the excitation laser light (488 nm) on the dark background indicate the prompt appearance of the Raman bands (1515 and 2115 cm(-1)) due to polydiacetylene (PDA) in the red phase and subsequent diminution of the Raman bands. On the other hand, the spectra observed by focusing the excitation laser spot on the dim and bright spots exhibit almost random fluctuations, giving rather narrow Raman bands in the 1620-1000 cm(-1) region, which appear and disappear temporarily with varying intensities under the continuous irradiation at 488 nm. Broad Raman bands appear around 1580 and 1360 cm(-1), which are ascribable to amorphous carbon, at a later stage of the observation, the intensities from the bright spot being more than 100 times stronger than those from the dim spot. The narrow bands are ascribed to a series of carbonaceous intermediates such as polyenes, graphite sheets with various sizes, and folded or reorganized forms of the sheets including carbon nanotubes and fullerenes, which are formed during the conversion of PDA to amorphous carbon. The random spectral fluctuation was interpreted by considering that the intermediates undergo thermally activated diffusion and get temporarily in contact with the SERS-active site, resulting in the enhancement of their Raman bands and the fluctuation.

Cortical activity related to cue-invariant shape perception in humans.

We used magnetoencephalography to search spatio-temporally for cortical activity related to the perception of shape defined by various visual cues in humans. The visual stimuli were three kinds of two-dimensional figures: two had fixed shapes (Diamond and Cross), the other did not (Noise). These figures were defined by three visual cues: difference of flicker, texture or luminance between the foreground and the background in the random dot pattern. Using this stimulus, we recorded the magnetic responses from the temporo-occipital regions of nine healthy subjects. Additionally, we measured the reaction time for the subjects to detect the figure by button-pressing. A magnetic component was identified in the responses. The properties of the first magnetic component differed for stimulus condition. The peak latency of the first magnetic component was different for the cues (270 ms for flicker, 360 ms for texture and 250 ms for luminance), but not for the figures. In contrast, the peak amplitude of the first magnetic component was different for the figures (96-144 fT for Diamond or Cross and 52-80 fT for Noise), but not for the cues. The signal source of the first magnetic component was estimated to lie on the ventral side of the extrastriate cortex: In the posterior part of the inferior temporal cortex, probably in the fusiform gyrus in four subjects, and in the lateral part of the occipital cortex which was outside of the primary visual cortex (visual area 1) in one subject. The signal source location was different inter-individually, but almost the same within each subject. Reaction time was 471 ms for flicker, 569 ms for texture and 426 ms for luminance, but the interval between the reaction time and the peak latency was constant (about 200 ms) for each cue. The first magnetic component was more clearly recorded from the right hemisphere than from the left.We found that the shape defined by the different visual cues activates the same localized site in the lateral extrastriate cortex. This spatial convergence suggests that there is a restricted locus that processes the visual shape regardless of the difference of the visual cue. The correspondence between the peak latency and the reaction time suggests that the activity of the area is responsible for the perception of visual shape. The inter-hemispheric difference suggests a dominance of the right hemisphere in visual shape processing.

Individual differences in working memory and the peak alpha frequency shift on magnetoencephalography.

The effect of the working memory demands on the peak alpha frequency of the power spectrum of magnetoencephalography (MEG) was investigated. There were one control condition and four listening span test (LST) conditions demanding the use of working memory. The results showed that the peak alpha frequency of the averaged MEG power shifted to the higher frequency region in the LST condition dominantly in the fronto-temporal region. Individual differences in working memory capacities were observed in the shift of peak alpha frequency of MEG.

Asymmetry of the human visual field in magnetic response to apparent motion.

Predominance of the lower visual field has been shown in various visual tasks, but whether the upper visual field is involved in a specific neural process is unknown. We used magnetoencephalography to study the effect of orientation and direction on the responses of five subjects to apparent motion from the human extrastriate cortex. The first magnetic response always was the largest, and the peak latency of about 200 ms did not change with the stimulus conditions. Amplitudes of the first responses were highest when motions were oriented at the horizontal meridian, decreasing with the degree of the angle between motion orientation and the horizontal meridian. There was no difference in amplitude between the two directions in the lower visual field, whereas the value of the response to downward motion in the upper visual field was significantly larger than that to upward motion. These amplitude changes are not due to differences in the anatomical distribution of neural activities because the estimated origins for the first responses always were in the same cortical area (around the occipito-parieto-temporal region) and the directions of the current vectors did not change with the stimulus conditions, and the estimated current strength changed with the stimulus conditions as did the response amplitude. These findings suggest that the human extrastriate cortex has a directional preference for downward versus upward motion in the upper visual field.

Motion aftereffect with flickering test stimuli depends on adapting velocity.

Temporal tuning property of motion aftereffect (MAE) with flickering test stimuli (flicker MAE) was examined. Using sinusoidal gratings of several spatial frequencies (SF), MAE strength was measured for various adapting temporal frequencies (TF). Unlike the traditional MAE with static test field, the results indicated that flicker MAE did not depend on TF. Rather, when plotted as a function of velocity, the peaks had approximately the same adapting velocity of 5-8 deg/sec for all SF conditions tested, suggesting velocity dependence. This is further support of the idea that the two kinds of MAE are of different origin and suggests a higher origin of flicker MAE, perhaps in the area MT or MST.

Perception of relation of stimuli locations successively flashed before saccade.

Based on localization error for a single perisaccadic flash, eye position signal is supposed to change more slowly than physical eye position. Nevertheless, a flicker is not perceived as moving in accordance with localization error for a single flash. We carried out two experiments to investigate this problem. Experiment 1 examined how a single flash or a flicker presented before saccade was perceived. The results showed that the flicker was not perceived as moving, although mislocalization for the single flash increases gradually before saccade. Experiment 2 was a vernier test of two stimuli successively flashed before the saccade. The results showed that the point of subjective equality shifted in accordance with the mislocalization for a single perisaccadic flash when the interstimulus interval (ISI) was about 2 s; however, it did not shift when the ISI was 78 ms. Comparison between these results and previous studies suggests that the relation of the locations of successive flashes before saccade is perceived exocentrically when the ISI and stimulus onset asynchrony between flashes was short.

Eye movement control in reading unspaced text: the case of the Japanese script.

The present study examines the landing-site distributions of the eyes during natural reading of Japanese script: a script that mixes three different writing systems (Kanji, Hiragana, and Katakana) and that misses regular spacing between words. The results show a clear preference of the eyes to land at the beginning rather than the center of the word. In addition, it was found that the eyes land on Kanji characters more frequently than on Hiragana or Katakana characters. Further analysis for two- and three-character words indicated that the eye's landing-site distribution differs depending on type of the characters in the word: the eyes prefer to land at the word beginning only when the initial character of the word is a Kanji character. For pure Hiragana words, the proportion of initial fixations did not differ between character positions. Thus, as already indicated by Kambe (National Institute of Japanese Language Report 85 (1986) 29), the visual distinctiveness of the three Japanese scripts plays a role in guiding eye movements in reading Japanese.

Low calcium (1.25 mmol/L) dialysate can normalize relative hypoparathyroidism in CAPD patients with low bone turnover.

Recently, several reports have suggested that there is a higher incidence of low turnover bone in the absence of aluminium exposure in peritoneal dialysis patients than in hemodialysis patients. Relative hypoparathyroidism with mild hypercalcemia, induced by a positive calcium balance, is considered to be one of the major causes of this disorder. Thus, we recruited 9 continuous ambulatory peritoneal dialysis (CAPD) patients with relative hypoparathyroidism and low bone turnover [intact parathyroid hormone (iPTH) < 50 pg/mL, intact osteocalcin < 10.0 ng/mL] who had been prescribed 1.75 mmol/L calcium (Ca) dialysate for 5.0 +/- 0.3 years. They were then treated by low Ca (1.25 mmol/L) dialysate for nine months without vitamin D and aluminum administration. Intact PTH and bone metabolic markers [intact osteocalcin, alkaline phosphatase (ALP)] were measured every three months. Intact PTH levels increased from 21.1 +/- 3.8 to 159.2 +/- 32.8 pg/mL after the first three months; thereafter, those levels were maintained at around 150 pg/mL. On the other hand, intact osteocalcin levels rose consecutively from 6.7 +/- 1.2 to reach 22.0 +/- 3.8 ng/mL after nine months. Interestingly, the pattern of time course changes between PTH and intact osteocalcin was different. ALP activity did not change during the nine-month period. Corrected serum calcium was significantly decreased (p < 0.001) to approximately 0.25 mmol/L within one month, and the level remained almost the same thereafter. The serum phosphate level did not change without adjusting the original dose of calcium carbonate as a phosphate binder. We concluded that low Ca dialysate (1.25 mmol/L) is effective for the treatment of CAPD-related hypoparathyroidism with low bone turnover.

Circulatory arrest with profound hypothermia during the surgical treatment of large internal carotid artery aneurysm--case report.

A 43-year-old male presented with a cerebral aneurysm manifesting as right facial paresthesia, without neurological deficit. Angiography revealed a large aneurysm (22 mm) of the left internal carotid artery. Intravascular treatment using placement of a detachable coil was attempted, but the coil did not stay in the aneurysmal cavity and the procedure was abandoned. The patient did not tolerate the transient balloon occlusion test of the left internal carotid artery. Therefore, the aneurysm was clipped through an open craniotomy with profound hypothermia (20 degrees C) with cardiac arrest (24 minutes). The aneurysmal dome was collapsed, allowing easy dissection of the posterior communicating artery. The closed chest method was used during the extracorporeal cardiopulmonary bypass. Postoperative angiography revealed complete neck clipping with preservation of carotid blood flow. The patient recovered well and resumed his employment. Circulatory arrest with hypothermia provides several benefits for the surgical treatment of large and giant aneurysms.

Exponent of the latency of brightness power functions in the fovea and periphery of the visual field.

RT and perceived brightness against log luminance, covering the range between 3.4 and - 1.6 log cd/m2 in steps of 1 log unit, were measured at the fovea, 20 degrees, and 40 degrees in the periphery. The RT and brightness data were fitted to the RT and brightness power function, respectively. It was found that (a) asymptotic RT increased as eccentricity increased and that (b) the RT exponent decreased as retinal eccentricity increased: Estimated mean RT exponent was found to be approximately - .31 in the fovea, but - .25 and - .17 in the 20 degrees, and 40 degrees periphery, respectively. Further, (c) the brightness exponent tended to increase as eccentricity increased. The RT exponent in the fovea was in agreement with the exponent for perceived brightness (.36); however, the RT exponent in the periphery was about 1/2 to 2/3 as small as that in the fovea. This implies that as luminance changes equal RT contour changes as a function of eccentricity. That is, RT in the periphery does not primarily depend on the target's brightness but its luminance.

Luminance range effect on brightness exponent in the fovea and periphery.

Using a method of magnitude estimation, the exponent of the brightness power function has been determined for functions describing the brightness of stimuli presented at the fovea and the following peripheral retinal locations: 10, 20, 30, 40, and 50 degrees nasally eccentric to the fovea along the horizontal meridian of the right eye. The exponent for a 1-sec. flash was significantly increased as a function of increasing eccentricity at the lower luminance ranges whereas slightly increased at the higher luminance ranges.

Two-pulse temporal resolution threshold in the peripheral visual field.

Using a 700-nm light-emitting diode, the minimum inter-pulse interval between two successively flashing pulses presented to 21 retinal loci along horizontal and vertical meridian were measured. The results showed inter-pulse interval changed as a W-shaped function of eccentricity on both meridians.

Reaction time as a function of peripheral retinal locus around fovea: effect of stimulus size.

Using targets of four sizes between 18' and 116' at a fixed luminance of 5.8 cd/m2, human visual reaction times (RT) were measured on a circle at 30 degrees eccentric to the fovea. A foveal and 12 peripheral retinal loci were explored, covering the range between 0 degrees and 330 degrees in steps of 30 degrees units on a circle about the fovea. RT decreased significantly by the stimulation to the quadrant retinal loci between nasal and superior side. RT decreased as a function of increasing target size and the amount of decrement was relatively larger in the periphery than in the fovea.

Target size and luminance in apparent brightness of the peripheral visual field.

Four target sizes between 15 and 120 min. of arc with six luminance levels covering the range between 398.1 and 1.26 cd/m2 in steps of .5 log units were presented to 0, 20, 40, 60, and 80 degrees nasal retinal loci. In both peripheral and foveal viewing, magnitude estimates to apparent brightness judged by 12 Ss changed as a function of target size and luminance. The exponent of the power function was not dependent on retinal loci but on target size. However, when target size increased, the apparent brightness was slightly greater with peripheral viewing than with foveal viewing.

Human intelligence and power spectral analysis of visual evoked potentials.

The relationship between intelligence and power spectra of visual evoked potential was investigated using 8 normal and 8 mentally retarded children as subjects. The results showed the power spectrum of mentally retarded has a peak at 4 to 6 Hz, whereas that of normal has two apparent peaks at 4 and 12 Hz. It appears the peak at 12 Hz reflects the difference of intelligence.

Effect of refraction on perceived locus of a target in the peripheral visual field.

A target of 44 min of arc with luminance of 1.03 log cd/m2 of 50 msec duration was presented to the loci along each of nasal, temporal, superior, and inferior half retinal meridians covering the eccentricity between 10 degrees and 50 degrees in steps of 10 degrees units. Two graduate students, serving as Ss, were instructed to point out the perceived locus where the target had appeared. The visual angles between the perceived and physical locus of the target were increased as a function of retinal eccentricity due to refraction.

[A study of association between lean body mass and serum insulin-like growth factor-1 in continuous ambulatory peritoneal dialysis patients].

Malnutrition is one of the major issues associated with high mortality and morbidity in chronic dialysis patients. Several methods to evaluate the nutritional status of these patients have been attempted for example anthropometric measurement and biochemical parameters. Recently, it was reported that insulin-like growth factor-1 (IGF-1) has been valuable for estimating nutritional status. In this study, we measured lean body mass (LBM) by dual energy X-ray absorptiometry (DXA), IGF-1 and other biochemical parameters in 35 patients on CAPD. Two years later, the second measurement of LBM was performed, and we assessed the percent changes of LBM and biochemical parameters. There was negative correlation between the percent changes of LBM and the duration of CAPD. In patients treated with CAPD for less than 36 months (group I) LBM increased, however, it decreased significantly in those treated for more than 36 months (group II). On the other hand, in group I there was a positive correlation between the percent changes of LBM and IGF-1. In group II there was no correlation between the percent changes of LBM and any other biochemical parameters. It could be concluded that IGF-1 is one of the predisposing factors for improving LBM of patients on CAPD for a limited duration.

[Evaluation of nutritional status of patients on continuous ambulatory peritoneal dialysis (CAPD) by dual photon energy X-ray absorptiometry (DEXA)].

Malnutrition is a serious complication in patients on long-term CAPD treatment. Accordingly, quantitative evaluation of nutritional status is a critical issue. This study aimed to assess nutritional status by dual photon energy x-ray absorptiometry (DEXA) in CAPD patients. Total lean body mass (D-TBM), right arm lean mass (D-RAM) and body fat percent (D-% FAT) measured by DEXA were compared with mid-arm muscle circumference (MAMC) and body fat percent (AP-% FAT) measured by anthropometrics (AP) in 51 CAPD patients. The subjects were stratified into groups by gender, age, duration on CAPD, and diabetes mellitus or non-diabetes. There was significant correlation between D-TBM, D-RAM and MAMC (r = 0.519, p = 0.001, r = 0.545, p = 0.001) or D-% FAT and AP-% FAT (r = 0.763, p = 0.0001). However, in the groups of females with over 50 years and over 48 months of dialysis duration, there was no correlation between D-TBM, D-RAM and MAMC. The DEXA method is useful in the quantitative evaluation of nutritional status of dialysis patients serially.

[Brightness power function and equal brightness contour for dark- and light-adapted eye in the peripheral visual field (author's transl)].

To test whether the equal brightness contour at supra-threshold runs parallel with the contour at threshold, magnitude estimation and the staircase procedure were employed for estimating brightness power function under dark- and light-adaptation. The luminance was changed from 43 to 83 dB re 10(-6) cd/m2 with the light adapting luminance at 53 dB. The retinal loci tested were 0 degrees to 70 degrees periphery in steps of 10 degrees. The exponent of the power function gradually increased from .37 to .73 as eccentricity and adapting luminance increased. The equal brightness contour decreased for dark-adaptation and increased for light-adaptation as eccentricity increased at supra-threshold but at threshold did not follow the parallel hypothesis for both adapting conditions.