1,2,5-Triarylcycloalka[c]arsoles: Structural Effects of Fused-cycloalkanes on Stability and Photophysical Properties.

Herein, we have synthesized a variety of cycloalkane-fused arsoles. Cyclopentane and cyclohexane were incorporated into the cycloalkane-fused arsoles. Surprisingly, cyclohexane-fused arsole 2 a gradually decomposed via oxidative ring-opening under ambient conditions, while cyclopentane-fused 1 a was stable. In addition, the Stokes shift of 2 a (7766 cm-1 ) is larger than that of 1 a (5120 cm-1 ). The effects of the fused cycloalkane on the stability and photophysical properties were attributed to the distortion of the cycloalkane. Computational calculations demonstrated that the cyclohexane moiety in 2 a was frustrated upon being incorporated into the rigid arsole ring, while the cyclopentane moiety in 1 a was much less distorted.

Systematic Study of Pnictogen-Fused Heterofluorenes.

Heteroatom-fused π-conjugated molecules have attracted considerable attention, and various elements for such fusion have been investigated. Herein, we focused on pnictogen-fused heterofluorenes. The structures, reactivity with O2 and I2, coordination ability to AuCl, and photophysical properties were systematically studied to better understand the effects of pnictogen atoms on the nature of π-conjugated molecules.

Novel blood-brain barrier-permeable spin probe for in vivo electron paramagnetic resonance imaging.

A novel blood-brain barrier (BBB)-permeable compound 10 was discovered, wherein the nitroxide moiety was linked to a nicotine acetylcholine receptor ligand. It was applied as a probe for electron paramagnetic resonance (EPR) imaging of the mouse brain. The results demonstrated that the newly synthesized compound 10 exhibited BBB permeability. These findings provide an essential discovery for in vivo EPR imaging.

In vivo wear particles of remelted highly crosslinked polyethylene after total hip arthroplasty: report of four cases.

This is the first report of in vivo wear particles from four total hip arthroplasties using remelted highly crosslinked polyethylene. The number of particles was (1.51 ± 0.45) × 10(7) g(-1) (mean ± standard error); particle size (equivalent circle diameter), 0.72 ± 0.15 µm; and roundness, 1.45 ± 0.05. Remelted highly crosslinked polyethylene generates fewer, rounder, equivalently sized particles compared with corresponding reported values for particles generated from conventional polyethylene.

In vivo tumour extracellular pH monitoring using electron paramagnetic resonance: the effect of X-ray irradiation.

The in vivo quantification of extracellular pH (pHe ) in tumours may provide a useful biomarker for tumour cell metabolism. In this study, we assessed the viability of continuous-wave electron paramagnetic resonance (CW-EPR) spectroscopy with a pH-sensitive nitroxide for the measurement of extracellular tumour pH in a mouse model. CW-EPR spectroscopy (750 MHz) of C3H HeJ mice hind leg squamous cell tumour was performed after intravenous tail vein injection of pH-sensitive nitroxide (R-SG, 2-(4-((2-(4-amino-4-carboxybutanamido)-3-(carboxymethylamino)-3-oxoproylthio)methyl)phenyl)-4-pyrrolidino-2,5,5-triethyl-2,5-dihydro-1Н-imidazol-1-oxyl) during stages of normal tumour growth and in response to a single 10-Gy dose of X-ray irradiation. An inverse relationship was observed between tumour volume and pHe value, whereby, during normal tumour growth, a constant reduction in pHe was observed. This relationship was disrupted by X-ray irradiation and, from 2-3 days post-exposure, a transitory increase in pHe was observed. In this study, we demonstrated the viability of CW-EPR spectroscopy using R-SG nitroxide to obtain high-sensitivity pH measurements in a mouse tumour model with an accuracy of <0.1 pH units. In addition, the measured changes in pHe in response to X-ray irradiation suggest that this may offer a useful method for the assessment of the physiological change in response to existing and novel cancer therapies.

Mechanisms Associated with Superoxide Radical Scavenging Reactions Involving Phenolic Compounds Deduced Based on the Correlation between Oxidation Peak Potentials and Second-Order Rate Constants Determined Using Flow-Injection Spin-Trapping EPR Methods.

Flow-injection spin-trapping electron paramagnetic resonance (FI-EPR) methods that involve the use of 5,5-dimethyl-pyrroline-N-oxide (DMPO) as a spin-trapping reagent have been developed for the kinetic study of the O2•- radical scavenging reactions occurring in the presence of various plant-derived and synthetic phenolic antioxidants (Aox), such as flavonoid, pyrogallol, catechol, hydroquinone, resorcinol, and phenol derivatives in aqueous media (pH 7.4 at 25 °C). The systematically estimated second-order rate constants (ks) of these phenolic compounds span a wide range (from 4.5 × 10 to 1.0 × 106 M-1 s-1). The semilogarithm plots presenting the relationship between ks values and oxidation peak potential (Ep) values of phenolic Aox are divided into three groups (A1, A2, and B). The ks-Ep plots of phenolic Aox bearing two or three OH moieties, such as pyrogallol, catechol, and hydroquinone derivatives, belonged to Groups A1 and A2. These molecules are potent O2•- radical scavengers with ks values above 3.8 × 104 (M-1 s-1). The ks-Ep plots of all phenol and resorcinol derivatives, and a few catechol and hydroquinone derivatives containing carboxyl groups adjacent to the OH groups, were categorized into the group poor scavengers (ks < 1.6 × 103 M-1 s-1). The ks values of each group correlated negatively with Ep values, supporting the hypothesis that the O2•- radical scavenging reaction proceeds via one-electron and two-proton processes. The processes were accompanied by the production of hydrogen peroxide at pH 7.4. Furthermore, the correlation between the plots of ks and the OH proton dissociation constant (pKa•) of the intermediate aroxyl radicals (ks-pKa• plots) revealed that the second proton transfer process could potentially be the rate-determining step of the O2•- radical scavenging reaction of phenolic compounds. The ks-Ep plots provide practical information to predict the O2•- radical scavenging activity of plant-derived phenolic compounds based on those molecular structures.

Simultaneous imaging of an enantiomer pair by electron paramagnetic resonance using isotopic nitrogen labeling.

This Article describes the simultaneous imaging of chiral nitroxyl radicals using electron paramagnetic resonance (EPR). Chiral nitroxyl radicals could be simultaneously visualized with the labeling of isotopic nitrogen. Chiral nitroxyl radicals, hydroxylmethyl-2,2,5,5-tetramethylpyrrolidine-1-oxyl, were visualized using the method of simultaneous EPR imaging, which refers to the visualization of two kinds of molecules with unpaired electrons in a single image scan. EPR spectra of a racemic mixture of chiral nitroxyl radicals and those of the respective R and S configurations confirmed labeling by isotopic nitrogen. (1)H nuclear magnetic resonance (NMR) imaging and simultaneous imaging of solutions of chiral nitroxyl radicals were performed. The advantages and limitations of simultaneous imaging using EPR are also discussed. Simultaneous imaging with chiral-labeled nitroxyl radicals is a new application of EPR imaging and may be useful for biological studies involving biologically active chiral molecules.

4-Aryldithieno[3,2-b:2',3'-d]arsoles: effects of the As-substituent on the structure, photophysical properties, and stability.

Dithieno[3,2-b:2',3'-d]arsole (DTA) is one of the representative arsenic-containing conjugated units. In this work, the effects of the As-substituent on the structure, photophysical properties, and stability were investigated. Surprisingly, the As-substituent affected the structural relaxation and stability in the photo-excited state, while there was negligible effect in the ground state. Bulky substituents resulted in red-shifted emissions due to the relaxation of steric repulsion upon photo-excitation. In addition, the crystal structure highly affected the photo-degradation behaviors.

Hydrodynamic interpretation on the rotational diffusion of peroxylamine disulfonate solute dissolved in room temperature ionic liquids as studied by electron paramagnetic resonance spectroscopy.

Rotational motion of a nitroxide radical, peroxylamine disulfonate (PADS), dissolved in room temperature ionic liquids (RTILs) was studied by analyzing electron paramagnetic resonance spectra of PADS in various RTILs. We determined physical properties of PADS such as the hyperfine coupling constant (A), the temperature dependence of anisotropic rotational correlation times (τ(∥) and τ(⊥)), and rotational anisotropy (N). We observed that the A values remain unchanged for various RTILs, which indicates negligible interaction between the N-O PADS group and the cation of RTIL. Large N values suggest strong interaction of the negative sulfonyl parts of PADS with the cations of RTILs. Most of the τ(∥), τ(⊥), and (τ(∥)τ(⊥))(1/2) values are within the range calculated on the basis of a hydrodynamic theory with stick and slip boundary conditions. It was deduced that this theory could not adequately explain the measured results in some RTILs with smaller BF(4) and PF(6) anions.

Thermal Extraction of Polycyclic Aromatic Hydrocarbons from Atmospheric 2.5 µm Particulate Matter Collected on a Filter Paper Using a High-Temperature Headspace Method.

Recently, owing to the performance improvement of the headspace (HS)-sampling devices and its consumables, HS vial samples can be analyzed at temperatures up to 300°C. Some studies have attempted to analyze polycyclic aromatic hydrocarbons (PAHs) in atmospheric 2.5 µm particulate matter (PM 2.5) collected on a filter paper by gas chromatography/mass spectrometry (GC/MS) coupled with thermal desorption device. However, no studies have reported the use of an HS-sampling device to quantify PAHs in PM 2.5 filter paper. In this study, we found that the quantification of PAH analysis using HS-GC/MS can be improved by the following steps, so that the accuracy becomes almost the same as that of a solvent-extraction method: 1) replacement of the air in the HS vial with nitrogen, 2) limiting the solvent to toluene, 3) using the hydrolyzed polyimide-covered septum, and 4) optimization of the heating temperature and heating time of the HS vial. As a result, we succeeded in protecting PAHs in an HS vial at a high temperature and in creating an analysis method with a high recovery rate and high repeatability; the limit of quantitation of each PAH in this method was 5.4 pg m-3 in the case of a volume of 10080 m3 of air being collected on the filter paper.

LMX1B-associated nephropathy that showed myelin figures on electron microscopy.

The mutation of LIM homeodomain transcription factor LMX1B gene leads to nail-patella syndrome (NPS), which is characterized by dysplastic nails, hypoplastic patellae, iliac horns and nephropathy. The characteristic renal histological finding of NPS nephropathy is irregular thickening of the glomerular basement membrane with patchy lucent areas, including deposits of bundles of type III collagen fibrils revealed by electron microscopy (EM). Fabry disease is a lysosomal storage disorder caused by a deficiency of α-galactosidase A activity, and the characteristic EM finding is a lamellated membrane structure (myelin figures). We present the case of a male with LMX1B-associated nephropathy (LAN) who showed focal segmental glomerulosclerosis (FSGS) on light microscopy, and myelin figures and slight deposits of collagen fibrils on EM, without findings of glomerular basement membrane abnormality suggestive for NPS. A 21-year-old Japanese-Brazilian man was admitted to hospital for an investigation of the cause of proteinuria and decreased renal function. A renal biopsy was performed to investigate the cause of renal damage. Fabry disease was initially considered, based on the presence of myelin figures on EM, but since he had normal α-galactosidase A activity, this initial diagnosis was denied, and the patient was subsequently diagnosed with FSGS. At 22 years after that renal biopsy, the patient was incidentally diagnosed with LAN when NM_002316:3c.746G > A:p.(Arg249Gln) LMX1B variant was identified in his older brother by a pre-transplantation examination, and the same mutation was confirmed in the patient. Myelin figures revealed by EM might become one of the clues for the diagnosis of LAN.

Wound healing after applying a gelatin-based hydrogel sheet to resected rat submandibular gland.

The present study was done to develop a useful experimental model for analysis of the effects of physiologically active substances on atrophy and regeneration of salivary gland acinar cells. Resection wounds (diameter, 3 mm) were made in the submandibular glands of 8-week-old Wistar rats (n = 24) for histochemical examination on Days 3, 5, 7, 10, 14, and 21 after implantation of a gelatin-based hydrogel sheet. The results showed that the sheet had nearly disappeared by Day 10. Regions around the resection wounds were classified as normal, atrophic, or necrotic. In atrophic regions, acinar cells atrophied after resection, and few acinar cells were observed on Day 7. On Days 5-7, striated and granular ducts resembled duct-like structures. On Day 10, newly formed acinar cells were confirmed by increased periodic acid-Schiff staining, and a greater number of mature cells was present thereafter. In necrotic regions, acinar and ductal cells were destroyed, and scattered enucleated acinar cells and duct-like structures were present, on Day 3; newly formed acinar cells were observed on Day 10. Thus, the experimental model demonstrated atrophy and regeneration of the submandibular gland and enabled analysis of the effects of sustained release of physiologically active substances contained within an implanted sheet.

Distribution of aquaporin-5, transforming growth factor-ß1 and laminin during regeneration of atrophic rat submandibular glands after duct ligation.

The aim of this study was to determine the localization of aquaporin-5 (AQP5), transforming growth factor-ß1 (TGF-ß1) and laminin during regeneration of the rat submandibular gland. After duct ligation for 7 days, the regenerating glands were collected on days 0, 1, 3, 7, and 14 after ligation release to study the process of regeneration. Immunohistochemical staining revealed apical expression of AQP5 in many acinar cells, strong expression in intercalated ducts (ICDs) of the normal submandibular gland at Day 14, and strong expression in duct-like structures (DLSs) during regeneration from Day 0 to 7. However, a few AQP5-negative acinar cells were detected during regeneration. At Day 0, immunopositivity for TGF-ß1 was detected in connective tissue. At Days 3 and 7 during regeneration, TGF-ß1 immunostaining was observed in DLSs, which were surrounded by α-smooth muscle actin-positive thickened myoepithelial cells. Laminin staining was strong in the thickened basement membrane of DLSs at Day 3 during regeneration, but weak around acinar cells at Day 14. These findings suggest that TGF-ß1 is involved in the environment around DLSs, myoepithelial cells and laminin, that DLSs have the same functional properties as ICDs, and that AQP5-negative acinar cells may be mucous cells.

Retrospective clinical study of 296 patients with mass lesions of the tongue.

To better understand the clinical features of mass lesions of the tongue, we retrospectively evaluated frequency, recurrence rate, and complications in 296 patients who had undergone surgery for such lesions. The diagnoses were fibroma (43.6%), mucous cyst (14.2%), papilloma (11.8%), hemangioma (7.8%), granuloma (6.4%), lipoma (1.4%), schwannoma (1.0%), ectopic tonsil (0.7%), and other (13.2%). Recurrence was noted in two patients (0.7%). Twenty-two patients (7.4%) developed surgical complications, including lingual nerve paralysis (6.4%), glossodynia (0.6%), and postoperative infection (0.3%). Lingual nerve paralysis was observed in the ventral portion (42.1%) of the tongue, apex (36.8%), lateral border (10.5%), and dorsum (10.5%). When all sites were considered together, there was no significant difference in the number of patients presenting with lingual nerve paralysis (P = 0.075). However, there were significant differences in lingual nerve paralysis at the lateral border (P < 0.05), apex (P < 0.05), and dorsum (P < 0.001) but not at the ventral portion (P > 0.05) in the size of the patients with versus without it which suggests that the risk of lingual nerve paralysis is higher at the ventral tongue, regardless of tumor size. These results shed light on the clinical features of mass lesions of the tongue.

Lipoma arborescens arising in the extra-articular bursa of the knee joint.

Lipoma arborescens arising in the extra-articular bursa of the knee joint is extremely rare. We describe an 11-year-old boy who complained of a gradual swelling mass of the lateral knee joint. Magnetic resonance imaging (MRI) showed a high signal intensity tumor on T1- and T2-weighted images with a thickened septa and nodular lesion that showed low signal intensity. The radiologist suggested the possible differential diagnosis of well-differentiated liposarcoma. At operation, the tumor was found under the iliotibial tract and was not in contact with the knee joint. Histopathologically, this lesion was diagnosed as lipoma arborescens arising in the extra-articular bursa of the knee joint. On MRI, the appearance of lipoma arborescens arising in the extra-articular bursa of the knee joint differed from that of conventional intra-articular lipoma arborescens. In this report, we describe a case of extra-articular lipoma arborescens of the knee joint bursa and discuss the diagnosis and etiology.

Artifact suppression in electron paramagnetic resonance imaging of (14)N- and (15)N-labeled nitroxyl radicals with asymmetric absorption spectra.

This article describes an improved method for suppressing image artifacts in the visualization of (14)N- and (15)N-labeled nitroxyl radicals in a single image scan using electron paramagnetic resonance (EPR). The purpose of this work was to solve the problem of asymmetric EPR absorption spectra in spectral processing. A hybrid function of Gaussian and Lorentzian lineshapes was used to perform spectral line-fitting to successfully separate the two kinds of nitroxyl radicals. This approach can process the asymmetric EPR absorption spectra of the nitroxyl radicals being measured, and can suppress image artifacts due to spectral asymmetry. With this improved visualization method and a 750-MHz continuous-wave EPR imager, a temporal change in the distributions of a two-phase paraffin oil and water/glycerin solution system was visualized using lipophilic and hydrophilic nitroxyl radicals, i.e., 2-(14-carboxytetradecyl)-2-ethyl-4,4-dimethyl-3-oxazolidinyloxy (16-DOXYL stearic acid) and 4-hydroxyl-2,2,6,6-tetramethylpiperidine-d17-1-(15)N-1-oxyl (TEMPOL-d17-(15)N). The results of the two-phase separation experiment verified that reasonable artifact suppression could be achieved by the present method that deals with asymmetric absorption spectra in the EPR imaging of (14)N- and (15)N-labeled nitroxyl radicals.

Entropy-controlled 2D supramolecular structures of N,N'-bis(n-alkyl)naphthalenediimides on a HOPG surface.

The two-dimensional supramolecular structures of a series of N,N'-bis(n-alkyl)naphthalenediimides (NDIs), whose chain lengths span from C3 to C18, at a liquid-HOPG surface interface, studied by STM and FM-AFM, are assigned with the help of molecular dynamics/molecular mechanics calculations to demonstrate that the C3- and C4-NDIs show lamellar structures, the C4- to C12-NDIs show honeycomb (KAGOME) structures, and the C14- to C18-NDIs show lamellar structures again. The change in supramolecular structure depending on chain length can be explained semiquantitatively by the balance of entropy and enthalpy terms to show the importance of "self-avoiding walk" of the alkyl chain in entropy terms.

STM-induced light emission from thin films of perylene derivatives on the HOPG and Au substrates.

We have investigated the emission properties of N,N'-diheptyl-3,4,9,10-perylenetetracarboxylic diimide thin films by the tunneling-electron-induced light emission technique. A fluorescence peak with vibronic progressions with large Stokes shifts was observed on both highly ordered pyrolytic graphite (HOPG) and Au substrates, indicating that the emission was derived from the isolated-molecule-like film condition with sufficient π-π interaction of the perylene rings of perylenetetracarboxylic diimide molecules. The upconversion emission mechanism of the tunneling-electron-induced emission was discussed in terms of inelastic tunneling including multiexcitation processes. The wavelength-selective enhanced emission due to a localized tip-induced surface plasmon on the Au substrate was also obtained.

Examination of (e,2e) scattering models by comparison of momentum profiles of noble gases between experiment and theory.

Momentum profiles have been measured for the two outermost atomic orbitals of noble gases, Ar, Kr and Xe, at incident electron energy of about 2 keV using a newly developed multichannel (e,2e) spectrometer. The experimental results exhibit significantly improved statistics compared with those achieved in previous studies while covering a wide range of momenta up to 3.6 a.u. The results are compared with theoretical calculations using four (e,2e) scattering models, the plane-wave impulse and Born approximations (PWIA and PWBA), and the distorted-wave impulse and Born approximations (DWIA and DWBA). The DWIA and DWBA scattering models have been found to satisfactorily reproduce the experimental momentum profiles in terms of both shape and intensity over the entire momentum range covered, indicating the importance of distorted wave effects for quantitatively describing (e,2e) reaction.