Biomedical subjects

Masafumi Harada

Publications and source records attributed to Masafumi Harada.

At least 19 recordsLinked to original sources

PubMed2006

Diffusion of platinum ions and platinum nanoparticles during photoreduction processes using the transient grating method.

The photoreduction process of PtCl(6)2- to Pt nanoparticles in poly(N-vinyl-2-pyrrolidone) solutions upon UV light irradiation was investigated by monitoring the change in the diffusion coefficient (D). The D values of chemical species during UV irradiation was measured by the laser-induced transient grating (TG) method. The TG signal of the PtCl(6)2- solution before UV irradiation was composed of three kinds of contributions, the thermal grating, the species grating due to the creation of PtCl4(2-), and the species grating due to the depletions of PtCl6(2-). Upon UV irradiation of the solution, the species grating signal due to PtCl6(2-) diminished and then the TG signal of Pt nanoparticles gradually appeared. This result indicates that the gradual clustering of Pt0 atoms into Pt nanoparticles occurs after all PtCl(6)2- ions are photochemically reduced to PtCl(4)2- and subsequently transformed to Pt0 atoms with a short delay. With increasing time of the UV irradiation, the TG signal intensity increased, while D of the Pt nanoparticles did not change. This suggests that the number of Pt nanoparticles increases, but the size of the Pt nanoparticles with the polymer layer is unchanged, in the course of the UV irradiation.

Chlorine↗

PubMed2006

Structure and photochemical properties of (mu-alkoxo)bis(mu-carboxylato)diruthenium complexes with naphthylacetate ligands.

Two new dinuclear Ru(III) complexes containing naphthalene moieties, K[Ru2(dhpta)(mu-O2CCH2-1-naph)2] (1) and K[Ru2(dhpta)(mu-O2CCH2-2-naph)2] (2) (H5dhpta = 1,3-diamino-2-hydroxypropane-N,N,N',N'-tetraacetic acid, naph-1-CH2CO2H = 1-naphthylacetic acid, naph-2-CH2CO2H = 2-naphthylacetic acid), were synthesized. Complex 2 crystallized as an orthorhombic system having a space group of Pbca with unit cell parameters a = 10.6200(5) A, b = 20.270(1) A, c = 35.530(2) A, and Z = 8. EXAFS analysis of 1 and 2 in the solid states and in solution clarified that the dinuclear structures of 1 and 2 were kept in DMSO solutions. Variable-temperature magnetic susceptibility data indicated that the two Ru(III) centers are strongly antiferromagnetically coupled as shown by the large coupling constants, J = -581 cm(-1) (1) and -378 cm(-1) (2). In the cyclic voltammograms of 1 and 2, one oxidation peak and two reduction peaks which were assigned to the redox reaction of the ruthenium moieties were observed in DMF. The large conproportionation constants estimated from the reduction potentials of Ru(III)Ru(III) and Ru(III)Ru(II) indicated the great stability of the mixed-valent state. The mixed-valent species [Ru(III)Ru(II)(dhpta)(mu-O2CCH2-R)2](2-) (R = 1-naph (6) and R = 2-naph (7)) were prepared by controlled potential electrolysis of 1 and 2 in DMF. The electronic absorption spectra of 6 and 7 were similar to that of [Ru(III)Ru(II) (dhpta)(mu-O2CCH3)2](2-) which is a typical Class II type mixed-valent complex. The fluorescence decay of 1 and 2 indicated that there are two quenching processes which come from the excimer and monomer states. The short excimer lifetimes of 1 and 2 were ascribed to the energy transfer from the naphthyl moieties to the Ru centers. The different excimer ratio between 1 and 2 suggested that the excimer formation is affected by the conformation of the naphthyl moieties in the diruthenium(III) complexes.

Electrochemistry↗

PubMed2006

Proton magnetic resonance spectroscopy reveals an abnormality in the anterior cingulate of a subgroup of obsessive-compulsive disorder patients.

Numerous neuroimaging studies have suggested that obsessive-compulsive disorder (OCD) patients had a neurobiological abnormality in the frontal-subcortical circuits. On the other hand, there are distinct differences in the responses to pharmacological treatment among OCD patients. In the present study, we measured the concentration of N-acetyl aspartate (NAA), a putative marker of neuronal viability, with proton magnetic resonance spectroscopy (MRS) in OCD patients with different pharmacological responses. Participants comprised 20 patients and 26 healthy control subjects. OCD patients were divided into three groups according to the pharmacological response; responders to a selective serotonin reuptake inhibitor (SSRI) (group A: n=7), responders to SSRI with an atypical antipsychotic (group B: n=8) and non-responders to either SSRI or SSRI with an atypical antipsychotic (group C: n=5). Short echo proton MRS was used to measure NAA concentrations in the anterior cingulate, the left basal ganglia and the left prefrontal lobe of subjects. A significantly lower NAA concentration was observed only in group B compared with control subjects in the anterior cingulate. Our results suggest that a subgroup of OCD patients who respond to an SSRI with an atypical antipsychotic have distinct biological abnormalities in the anterior cingulate.

Adult↗

PubMed2006

Formation mechanism of Pt particles by photoreduction of Pt ions in polymer solutions.

The formation mechanisms of metal particles (platinum (Pt) particles) in an aqueous ethanol solution of poly(N-vinyl-2-pyrrolidone) (PVP) by the photoreduction method have been studied by transmission electron microscopy (TEM) and in situ and ex situ X-ray absorption fine structure (XAFS) analysis. The average diameter of the dilute and concentrated Pt particles in the PVP solution is estimated from TEM to be 2.0 and 2.5 nm, respectively. XAFS analysis was performed for the reduction process of Pt4+ ions to metallic Pt particles for the Pt L3 edge of the colloidal dispersions of the concentrated Pt solutions. The photoreduction process proceeds by the following steps: (1) reduction of PtCl6(2-) to PtCl4(2-), (2) dissociation of Cl from PtCl4(2-), followed by reduction of Pt2+ ionic species to Pt0, (3) formation of a Pt0-Pt0 bond and particle growth by the association of Pt0-Pt0. The reduction of PtCl4(2-) to Pt0 is a slower process, compared with the reduction of PtCl6(2-) to PtCl4(2-). There is a delay between the disappearance of PtCl4(2-) and the formation of Pt0-Pt0 clusters.

Journal Article↗

PubMed2006

Novel oxygen chirality induced by asymmetric coordination of an ether oxygen atom to a metal center in a series of sugar-pendant dipicolylamine copperII complexes.

Six sugar-pendant 2,2'-dipicolylamine (DPA) ligands (L1-3 and L'1-3) have been prepared. OH-protected and unprotected D-glucose, D-mannose, and D-xylose were attached to a DPA moiety via an O-glycoside linkage. X-ray crystallography of the copper(II) complexes (1-5) with these ligands revealed that the anomeric oxygen atom is coordinated to the metal center in the solid state, generating a chiral center at the oxygen atom. The CD spectra of these copper complexes in methanol or aqueous solution exhibit Cotton effects in the d-d transition region, which indicates that the ether oxygen atoms remain coordinated to the metal center and the oxygen-atom chirality is preserved even in solution. For complexes 1 and 2, the inverted oxygen-atom chirality and chelate-ring conformation in the solid state are well correlated with the mirror-image CD spectra in methanol solution. The concomitant inversion of the asymmetric configuration around the copper center was also observed in a methanol solution of complex 3 and a pyridine solution of complex 2. The square-pyramidal/octahedral copper(II) centers also exhibited characteristic absorption and CD spectra.

Journal Article↗

PubMed2006

Effect of repetitive transcranial magnetic stimulation applied over the premotor cortex on somatosensory-evoked potentials and regional cerebral blood flow.

Somatosensory-evoked potentials (SEPs) are attenuated by movement. This phenomenon of 'gating' reflects sensorimotor integration for motor control. The frontal N30 component after median nerve stimulation was shown to be reduced in amplitude prior to hand movement. To investigate the mechanism of this sensory gating, we recorded median SEPs immediately before and after application of monophasic very low-frequency (0.2 Hz) repetitive transcranial magnetic stimulation (rTMS) of 250 stimuli over motor cortex (MC), premotor cortex (PMC), or supplementary motor area (SMA) in 9 healthy volunteers. The stimulus intensity for MC or PMC was set 85% of the resting motor threshold for the hand muscle, and that for SMA was at the active motor threshold for the leg muscle. SEPs showed significant increases in amplitudes of the frontal N30 component after PMC stimulation, but not after SMA or MC stimulation. Low-frequency (1 Hz) biphasic stimulation over PMC showed no significant N30 changes in 6 out of 9 subjects tested, indicating the effect being specific for 0.2 Hz monophasic stimulation. To examine the functional anatomy of the N30 change, single photon emission computed tomography was performed immediately before and after monophasic 0.2 Hz rTMS over PMC in all the 9 subjects. Regional cerebral blood flow showed significant increases mainly in PMC and prefrontal cortex, indicating the involvement of these cortical areas in sensory input gating for motor control.

Adult↗

PubMed2006

Change of diffusion anisotropy in patients with acute cerebral infarction using statistical parametric analysis.

PURPOSE: We conducted statistical parametric comparison of fractional anisotropy (FA) images and quantified FA values to determine whether significant change occurs in the ischemic region. MATERIALS AND METHODS: The subjects were 20 patients seen within 24 h after onset of ischemia. For statistical comparison of FA images, a sample FA image was coordinated by the Talairach template, and each FA map was normalized. Statistical comparison was conducted using SPM99. Regions of interest were set in the same region on apparent diffusion coefficient (ADC) and FA maps, the region being consistent with the hyperintense region on diffusion-weighted images (DWIs). The contralateral region was also measured to obtain asymmetry ratios of ADC and FA. RESULTS: Regions with areas of statistical significance on FA images were found only in the white matter of three patients, although the regions were smaller than hyperintense regions on DWIs. The mean ADC and FA ratios were 0.64 +/- 0.16 and 0.93 +/- 0.09, respectively, and the degree of FA change was less than that of the ADC change. Significant change in diffusion anisotropy was limited to the severely infarcted core of the white matter. CONCLUSION: We believe statistical comparison of FA maps to be useful for detecting different regions of diffusion anisotropy.

Acute Disease↗

PubMed2006

New trend of MRI diagnosis based on the function and metabolism in the central nervous system.

The movement of a subject is a major problem in MRI experiments and diagnosis. At first, this review introduces a new technology named the "Propeller Technique" which can improve the motion artifact by changing the data sampling method in the K trajectory. Our experience of a case who underwent measurement by Propeller technique is reported and the effect of this technique is explained. One of the recent hot topics is the appearance of the clinical 3T MR instrument, with its characteristic differences from that at 1.5T. The advantage of 3T is that it facilitates the evaluation of functional and metabolic information using MR spectroscopy (MRS) and functional MRI. The application of proton MRS in clinical cases is shown and the standard method to use proton MRS in a clinical setting is demonstrated. Furthermore, the new techniques, which can measure important metabolites in small amount such as neurotransmitters, was developed using a high signal to noise ratio and frequency resolution, which are advantages of 3T.

Artifacts↗

PubMed2006

Hemodynamic changes with liver fibrosis measured by dynamic contrast-enhanced MRI in the rat.

PURPOSE: To evaluate the hemodynamic changes of liver cirrhosis in the rat and investigate the relationship between hemodynamic changes and properties of fibrotic change in the liver. MATERIALS AND METHODS: Three rats with cirrhosis induced by thioacetamide (TAA), three with disease induced by carbon tetrachloride (CCl4), and three with no treatment were measured on dynamic MRI using a 1.5T scanner. Compartment and moment analysis were used to quantitate hemodynamic changes. RESULTS: Compartment model analysis showed that increased transition speed from vessels to the liver correlated with grade of liver fibrosis. Moment analysis demonstrated that decrease of area under the curve (AUC), mean residence time (MRT), variance of residence time (VRT), half life (T1/2) and increased total clearance (CL) correlated with grade of liver fibrosis. CONCLUSIONS: Hemodynamic changes in injured fibrotic liver may be influenced by the grade of fibrosis. Compartment model and moment analysis may be useful for evaluating hemodynamic changes in injured liver.

Animals↗

PubMed2006

[Neuroradiological study of a possible progressive multifocal leukoencephalopathy using diffusion tensor imaging and proton magnetic resonance spectroscopy].

We report a possible case of progressive multifocal leukoencephalopathy (PML) that was attempted to evaluate the pathogenesis by a novel brain MRI techniques. A 72-year-old woman had developed subacute visual disturbance, right hemiparesis and sensory disturbance. Laboratory examinations revealed liver dysfunction and pancytopenia due to liver cirrhosis (type C) and preclinical status of multiple myeloma. Thus, this patient had these two underlying diseases, while anti-HIV antibody was negative. She was suspected with PML by detection of JCV-DNA in cerebrospinal fluid using with PCR. MRI showed multifocal T2-high signals in the bilateral parieto-occipital deep white matter, basal ganglia and right cerebellar hemisphere. No gadolinium enhancement was found. On FLAIR and diffusion weighted images (DWI), the lesion showed hyperintensity. The hyperintense areas on DWI showed various pattern on apparent diffusion coefficient (ADC) and fractional anisotropy (FA). In particular white matter changes, the course of FA reflected the clinical course more than ADC. Proton magnetic resonance spectroscopy (1H-MRS) in deep brain white matter showed ratios of reduced N-acetyl aspartate (NAA) and increased choline (Cho) to creatine. 1H-MRS by chemical shift imaging were undergone three times between 4 and 6 months after the onset. The change of these chemical markers correlated with her clinical course. We conclude that the approach of diffusion tensor imaging (DTI) and 1H-MRS are useful for evaluating neuropathologic observations and clinical course.

Aged↗

PubMed2005

Synthesis of colloidal dispersions of rhodium nanoparticles under high temperatures and high pressures.

Colloidal dispersions of rhodium (Rh) nanoparticles have been synthesized by the reduction of Rh ions (III) in high-temperature and high-pressure water, ethanol, or water-ethanol mixture under the existence of the protective polymer of poly(N-vinyl-2-pyrrolidone). The possibility of the regulation of the particle size and size distribution has been tested under several solvents at various temperatures and pressures. At 473 K and 25 MPa, particularly, concentrated colloidal dispersions of Rh particles of 2.5+/-0.5 nm were synthesized from the ionic solution of ethanol ([Rh]=15 mM) within a few seconds. Dilute colloidal dispersions of Rh particles were also synthesized from the dilute ionic solution ([Rh]=1.5 mM) with a diameter of 2.0+/-0.4 nm. From the water solution, Rh particles tended to form aggregates, especially for the lower concentration solution. In the case of solutions in water and ethanol mixture, the average diameter of Rh particles tended to be larger than in ethanol solution, and their distribution became broad.

Colloids↗

PubMed2005

Photochemical preparation of poly(N-vinyl-2-pyrrolidone)-stabilized platinum colloids and their deposition on titanium dioxide.

Preparation processes for Pt-deposited TiO(2) (Pt/TiO(2)) by the synthesis of Pt nanoparticles and their deposition were pursued by transmission electron microscopy, extended X-ray absorption fine structure, UV-vis spectroscopy, and Fourier transform infrared spectroscopic studies. Colloidal dispersions of Pt particles stabilized by poly(N-vinyl-2-pyrrolidone) (PVP) were photochemically synthesized in aqueous ethanol solution. The average diameter of Pt particles was estimated to be 2.0 +/- 0.5 nm, which was almost unchanged by changing the reducing agent from ethanol to methanol and 2-propanol. The PVP-stabilized Pt particles were distributed over a TiO(2) surface only by mixing the Pt colloidal dispersions and TiO(2). CO was chemically coordinated on the Pt particles on a TiO(2) surface after heat treatment was carried out in an O(2) flow at 673 K to completely remove the residual PVP on Pt/TiO(2). Hydrogen reduction at 473 K did not increase the amount of CO adsorbed on Pt sites. The Pt/TiO(2) catalyst after the oxidation treatment showed higher activity for CO photooxidation than that obtained for pure TiO(2) catalyst. The CO photooxidation rate was not unchanged by the H(2) reduction.

Journal Article↗

PubMed2005

Aggregated structure analysis of polymer-protected platinum/ruthenium colloidal dispersions using EXAFS, HRTEM, and electron diffraction measurements.

Polymer-protected platinum/ruthenium colloidal dispersions were prepared by refluxing mixed solutions of hexachloroplatinic(IV) acid and ruthenium(III) chloride in a mixture of ethanol/water (1/1 v/v) in the presence of poly(N-vinyl-2-pyrrolidone). The electronic spectra and transmission electron micrographs suggested that the colloidal dispersions are almost composed of the mixture of the small monometallic Pt and Ru clusters over all the ratio of Pt/Ru compositions. Extended X-ray absorption fine structure analyses and high resolution electron microprobe analyses indicated that no Pt/Ru alloy clusters exist in the dispersions, and the aggregation occurs between small monometallic Pt clusters (diameter ca. 15 A) and partially oxidized Ru microclusters (diameter less than 10 A). Electron diffraction measurements also suggested that the diffraction pattern of aggregated Pt/Ru cluster particles prepared by the simultaneous reduction of Pt and Ru ions is the same as that of the physical mixture of the small monometallic Pt and Ru clusters separately prepared. Therefore, it can be concluded that the aggregated Pt/Ru cluster particles, with 10 to 60 A in diameter, are built up by small monometallic Pt clusters and partially oxidized Ru microclusters, and that Pt/Ru alloy clusters are not formed.

Journal Article↗

PubMed2005

Regional changes of fractional anisotropy with normal aging using statistical parametric mapping (SPM).

OBJECTIVE: There has been reports on the usefulness of diffusion tensor imaging (DTI) about age-or disease-related degradation. DTI is generally evaluated by the region of interest (ROI) methodology. In this study, we applied a statistical way using Statistical Parametric Mapping (SPM) to assess normal aging by DTI and compared results of these two methods. METHODS: Ten young and ten senior normal volunteers were examined. On SPM, tensor images were changed into normalized tensor images. They were compared between the two groups by t-test. RESULTS: In the senior group, fractional anisotropy (FA) values were higher on the basal ganglia, cingulated gyrus and other cortical gray matter, lower in the corona radiata, internal capsule, centrum semiovale and corpus callosum by using SPM. In the ROI method, the results were almost compatible except in the brain periphery. CONCLUSIONS: Aging changes on water diffusion anisotropy was clearly shown by SPM method which would be useful to evaluate change of water diffusion anisotropy without operator bias even in clinical setting instead of ROI measurement.

Adult↗

PubMed2005

Cerebral hyperperfusion in a patient with eclampsia with perfusion-weighted magnetic resonance imaging.

The patient was a 25-year-old Japanese woman with postpartum eclampsia, in whom magnetic resonance imaging (MRI) was performed ten hours after convulsion. The patient improved within three days. Diffusion-weighted images showed a high apparent diffusion coefficient (ADC), and perfusion-weighted images obtained by the multi-slice flow-sensitive alternating inversion recovery (FAIR) method showed hyperperfusion, which was suggestive of vasogenic edema, on the parietal and occipital subcortical white matter, corresponding with transient hyperintensities on T2-weighted images. MR angiography (MRA) revealed no signs of vasospasm. These findings suggested hyperperfusion-induced vasogenic edema without cerebrovascular spastic change in the early stage of eclampsia. The FAIR method is considered a useful technique for perfusion-weighted MRI, especially useful to evaluate the cerebral perfusion of emergency patients such as those with eclampsia.

Adult↗

PubMed2004

Electro- and photochemical properties of a (mu-alkoxo)bis(mu-carboxylato)diruthenium complex having two tetraphenylporphinato zinc(II) moieties.

The novel (mu-alkoxo)bis(mu-carboxylato)diruthenium complex K[Ru(2)(dhpta)(mu-O(2)C-p-ZnTPP)(2)] 3 was prepared by simple ligand substitution reaction. Strong antiferromagnetic interaction between two Ru(III) ions of 3 was observed with a coupling constant of -425 approximately -404 cm(-1). The cyclic voltammogram of 3 can be explained in terms of superposition of those of ZnTPP-p-CO(2)H and K[Ru(2)(dhpta)(mu-O(2)CPh)(2)] 2, indicating no significant electrochemical interaction. The large conproportionation constant estimated from the reduction potentials for Ru(III)Ru(III) and Ru(II)Ru(III) indicates great stability of the mixed-valence state. The mixed-valence species [Ru(II)Ru(III)(dhpta)(mu-O(2)C-p-ZnTPP)(2)](2-) 4 was prepared by controlled potential electrolysis. The electronic absorption spectrum of 4 was quite similar to that of [Ru(II)Ru(III)(dhpta)(mu-O(2)CCH(3))(2)](2-) which is a typical Class II complex. The fluorescence from the S(2) state of the ZnTPP unit of 3 was significantly (78%) quenched. The electron transfer from the ZnTPP unit to Ru(III) ions in 3 is a plausible mechanism, even though energy transfer could not be ruled out completely. The free energy change for electron transfer, Delta G(CS), was estimated to be ca.-1.1 eV, which is similar to typical values for the reorganization energy lambda in polar solvents. Hence, the electron transfer scheme is situated almost at the top of the Marcus parabola, enabling ultrafast electron transfer.

Journal Article↗

PubMed2004

Correlation between flow-sensitive alternating inversion recovery perfusion imaging with different inversion times and cerebral flow reserve evaluated by single-photon-emission computed tomography.

The purpose of this study was to evaluate the effect of different inversion times (TIs) on flow-sensitive alternating inversion recovery (FAIR) perfusion imaging and compare them with the cerebral blood flow reserve evaluated by acetazolamide challenge using single-photon-emission computed tomography (SPECT). The subjects were nine patients with unilateral obstruction of the internal carotid artery. The signal ratio (SR16/8) of two images with different TIs (1,600 ms and 800 ms) was calculated, and the cerebral blood flow reserve (CFR) was evaluated by the increase in the ratio of cerebral perfusion after administration of acetazolamide in the SPECT study. A reversed linear correlation ( r=0.75) was found between SR and CFR, indicating that differences of FAIR images with changes of TI will be affected by cerebral flow reserve.

Acetazolamide↗

PubMed2004

Detection of coronary arterial microvascular disorders using (99m)Tc-tetrofosmin uptake increase during exercise and coronary blood flow velocity patterns obtained by magnetic resonance imaging.

This study reports an evaluation of coronary arterial blood flow patterns in patients with diabetes mellitus and healthy subjects using magnetic resonance coronary angiography (MRCA). Twenty patients with diabetes mellitus (DM group) and 20 healthy subjects (N group) were studied using MRCA and myocardial SPECT images using (99m)Tc-tetrofosmin (TF). The rate of change in myocardial TF uptake was measured during a 1-day protocol of exercise and rest. Initial and delayed exercise single photon emission computed tomography (SPECT) images were acquired 30 min and 3 h after injection (370 MBq of TF) (TF1 and TF2, respectively). Thereafter, 740 MBq of TF was administered intravenously, again, and resting SPECT images (TF3) were acquired 30 min later. The myocardial counts of these three points of acquisition were defined, and the rate of change of myocardial TF uptake between exercise and rest was determined. The % increase in uptake was significantly lower in the DM group than in the N group in all myocardial segments. The average coronary arterial diastolic velocity determined using MRCA was slightly lower in the DM group than in the N group, and the average systolic peak velocity (ASPV) was slightly greater in the DM group than in the N group, although these values were not statistically significant. The diastolic/systolic velocity ratio (DSVR) in the DM group was significantly lower than that in the N group ( P < 0.05). There was a significant correlation between DSVR and % uptake increase ( r = 0.605, P < 0.05). These results indicate that the measurements made using MRCA and the % uptake increase measured using TF myocardial scintigraphy represent a potentially useful noninvasive method for diagnosing microvascular dysfunction in diabetic patients.

Blood Flow Velocity↗