Synthesis of donor-acceptor chromophores by the [2+2] cycloaddition of arylethynyl-2H-cyclohepta[b]furan-2-ones with 7,7,8,8-tetracyanoquinodimethane

Arylethynyl-2H-cyclohepta[b]furan-2-ones reacted with 7,7,8,8-tetracyanoquinodimethane (TCNQ) in a formal [2 + 2] cycloaddition reaction, followed by ring opening of the initially formed cyclobutene derivatives, to afford the corresponding dicyanoquinodimethane (DCNQ) chromophores in excellent yields. The intramolecular charge-transfer (ICT) interactions between the 2H-cyclohepta[b]furan-2-one ring and DCNQ acceptor moiety were investigated by UV/Vis spectroscopy and theoretical calculations. The redox behavior of the novel DCNQ derivatives was examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed their multistep electrochemical reduction properties depended on the number of DCNQ units in the molecule. Moreover, a significant color change was observed by visible spectroscopy under electrochemical reduction conditions.ArticleORGANIC & BIOMOLECULAR CHEMISTRY. 10(12):2431-2438 (2012)journal articl

Synthesis of 2-Aryl- and 6-Heteroaryl-1,3-di(4-pyridyl)azulenes by Katritzky’s Pyridylation of 2-Aryl- and 6-Heteroarylazulenes

Preparation of 2-aryl- and 6-heteroarylazulenes 2-6 and 8-10 was established by the palladium-catalyzed cross-coupling reaction of the corresponding haloazulenes with lithium aryl- and heteroarylmagnesium ate complexes, which were readily prepared from the corresponding aryl and heteroaryl halides. The reaction of 2-6 and 8-10, except for 3 and 8, with pyridine in the presence of Tf2O, followed by treatment with KOH in MeOH afforded the corresponding 2-aryl- and 6-heteroary1-1,3-di(4-pyridyl)azulenes 11-16 in good yields.ArticleHETEROCYCLES. 89(11):2588-2603 (2014)journal articl

Novel bronchofiberscopic catheter spray device allows effective anesthetic spray and sputum suctioning

AbstractStudy objectives: To evaluate how serum lidocaine concentrations (SLC) rise when lidocaine is administered by a Bronchofiberscopic Catheter Spray Device (BCSD), and to demonstrate the effect on the aspiration speed of a substitute for sputum when a catheter spray remains in the channel of the bronchofiberscope (BF).Methods: This is a prospective randomized clinical study. After lidocaine ultrasonic nebulizer, the BF was inserted orally. During the procedure patients received 4% lidocaine by two methods. In Group 1, 11 patients received lidocaine by bronchofiberscopic (BF) injection. In Group 2, 15 patients received lidocaine by spraying from the ∅1.06mm catheter through the BF channel. SLC were measured at 40min from onset of nebulization. Separately, we examined how effectively sputum was aspirated through the BF channel with a catheter.Results: Total lidocaine dose (TLD) is the total dose used for nebulization and for the BF injection or spray. The TLD for Groups 1 and 2 were 698.2±162.1mg (mean±sd) and 498.7±103.8mg, respectively (P=0.03). The SLC for Groups 1 and 2 were 1.28±0.72 and 1.48±0.70mg/l, respectively (P=0.49).Conclusions: Using BCSD allows easier in administration of lidocaine and is not associated with a significant increase in SLC in comparison with BF injection. Although sputum aspiration using the BF inserted with our catheter was somewhat slow, we did not feel inconvenient so much. Compared to the conventional method, using BCSD may be preferable for patients and bronchoscopists

Neuroradiological and neurofunctional examinations for the patients with 22q11.2 deletion

Since neuroradiological features of patients with 22q11.2 deletion syndrome are not well-understood, examinations using functional imaging were performed in this study. Brain magnetic resonance imaging(MRI) and 1H-magnetic resonance spectroscopy(MRS) were performed using a clinical 3-tesla MR imager in 4 patients with 22q11.2 deletion syndrome (2 boys and 2 girls; 2~6 years.) and 20 age- and sex-matched healthy control subjects. Furthermore, interictal 123I- iomazenil (IMZ) single photon emission computed tomography(SPECT) was examined in two of the four patients. Among 4 patients with 22q11.2 deletion syndrome, 2 patients showed polymicrogyria and 1 patient showed agyria. Those patients with brain malformations also showed abnormal brain artery and decreased accumulation of IMZ in 123I-IMZ SPECT. Although all 4 patients showed epileptic discharges in electroencephalogram(EEG), one patient with polymicrogyria had no seizure episode. Decreases in γ-aminobutyric acid(GABA) corresponding to the areas of polymicrogyria and/or epileptic discharges in EEG were shown in all patients except for the patient with agyria. Although consistent evidence was not seen in patients with 22q11.2 deletion syndrome in this study, brain malformations and disturbances of the GABAergic nervous system would be underlying mechanisms of the neurodevelopmental abnormalities in this syndrome

Age-related changes in a patient with Pelizaeus-Merzbacher disease by repeated 1H-MRS

Purpose: In this report, we describe a patient with Pelizaeus-Merzbacher disease (PMD) who underwent repeated evaluations by 1H-Magnetic resonance spectroscopy (MRS). Subject: The patient was given a definitive diagnosis of PMD based on genetic testing, which showed overlap of the proteolipid protein 1 (PLP1) gene. The control subjects for 1H-MRS consisted of healthy age-matched children. Methods: All measurements were performed with a clinical 3-tesla magnetic resonance imaging (MRI) system. For 1H-MRS, the center of a voxel was positioned in the right parietal lobe. 1H-MRS was performed when the patient was 2, 6, 14, and 25 months old. Results: The concentration of GABA in early childhood (2 months 1.72 mM, 6 months 2.15 mM) was increased compared with that in normal controls. However, his GABA concentration was normalized at 14 and 25 months. The concentrations of Ins were increased after 6 months. No remarkable changes were seen in the concentration of Cho at any time. Conclusion These results suggest that the changes in metabolite concentrations during growth may reflect the pathological state of PMD. Furthermore, the lack of a change in the Cho concentration may be useful for differentiating PMD from other demyelinating diseases

Evaluation of the GABAergic nervous system in autistic brain : 123I-iomazenil SPECT study

Purpose: To evaluate the GABAA receptor in the autistic brain, we performed 123I-IMZ SPECT in patients with ASD. We compared 123I-IMZ SPECT abnormalities in patients who showed intellectual disturbance or focal epileptic discharge on EEG to those in patients without such findings. Subjects and methods: The subjects consisted of 24 patients with ASD (mean age, 7.3±3.5years), including 9 with autistic disorder (mean age, 7.0±3.7years) and 15 with Asperger’s disorder (mean age, 7.5±3.2years). We used 10 non-symptomatic partial epilepsy patients (mean age, 7.8±3.6years) without intellectual delay as a control group. For an objective evaluation of the 123I-IMZ SPECT results, we performed an SEE (Stereotactic Extraction Estimation) analysis to describe the decrease in accumulation in each brain lobule numerically. Results In the comparison of the ASD group and the control group, there was a dramatic decrease in the accumulation of 123I-IMZ in the superior and medial frontal cortex. In the group with intellectual impairment and focal epileptic discharge on EEG, the decrease in accumulation in the superior and medial frontal cortex was greater than that in the group without these findings. Conclusion The present results suggest that disturbance of the GABAergic nervous system may contribute to the pathophysiology and aggravation of ASD, since the accumulation of 123I-IMZ was decreased in the superior and medial frontal cortex, which is considered to be associated with inference of the thoughts, feelings, and intentions of others (Theory of Mind)

Multi-delay arterial spin labeling brain magnetic resonance imaging study for pediatric autism

Introduction Arterial spin labeling (ASL) is a non-invasive magnetic resonance imaging (MRI) technique that can measure regional cerebral blood flow (rCBF) without radiation exposure. This study aimed to evaluate rCBF in individuals with autism and their age-matched controls, globally and regionally. Methods We performed ASL MRI (3T, pulsed-continuous ASL, 3 delayed ASL imaging sequences) for 33 patients with autism spectrum disorder (ASD) (average age: 7.3 years, range: 2-14 years). Nineteen children (average age: 8.6 years, range: 3-15 years) without ASD and intellectual delay were included as controls. Patients with morphological abnormalities detected on MRI were excluded. Objective analysis was performed with automatic region of interest analysis of the ASL results. The Mann-Whitney U test was used to compare the rCBF results between the groups. Results Compared to the controls, patients with ASD showed a statistically significant decrease in rCBF, respectively, in the insula [left, rCBF 51.8±9.5 mL/100 g/min (mean±SD) versus 59.9±9.8, p=0.0017; right, 51.2±10.1 versus 57.8±8.8, p=0.0354], superior parietal lobule (left, 44.6±8.4 versus 52.0±7.8, p=0.003), superior temporal gyrus (left, 50.0±8.6 versus 56.9±8.6, p=0.007; right, 49.5±8.4 versus 56.4±7.7, p=0.0058), and inferior frontal gyrus (left, 53.0±9.8 versus 59.3±9.9, p=0.0279), which are associated with the mirror neuron system. Conclusions We concluded that patients with ASD showed a statistically significant decline in CBF in regions associated with the mirror neuron system. The advantages of ASL MRI include low invasiveness (no radiation exposure) and short imaging time (approximately 5 min). Studies with larger sample sizes are required to establish the diagnostic value of ASL MRI for ASD

Synthesis of 2-amino- and 2-arylazoazulenes via nucleophilic aromatic substitution of 2-chloroazulenes with amines and arylhydrazines

The SNAr reaction of 2-chloroazulene derivative 1 with ethoxycarbonyl groups at the 1,3-positions of the azulene ring with several amines afforded the corresponding 2-aminoazulenes 3-9 in excellent yields. 2-Chloroazulene (2) without the electron-withdrawing groups reacted with highly nucleophilic cyclic amines (i.e., morpholine, piperidine and pyrrolidine) under the high-temperature conditions in a sealed tube to produce the corresponding 2-aminoazulenes 10-12 in good yields. 2-Aminoazulenes 10-14 without the electron-withdrawing groups were also obtained in good yields by the treatment of compounds 3-7 with 100% H3PO4, but in the cases of the reaction of 8 and 9 with a secondary amine function, the decomposition of the products resulted. The synthesis of 2-arylazoazulenes 15-18 was also established via the SNAr reaction of 1 with arylhydrazines. The optical and electrochemical properties of the 2-arylazoazulene derivatives were examined by UV/Vis spectroscopy, theoretical calculations and voltammetric experiments.ArticleORGANIC & BIOMOLECULAR CHEMISTRY. 94(10):3917-3923 (2017)journal articl

Three topics of monopole dynamics in abelian projected QCD

Three topics about monopole dynamics after abelian projection are reported. The first is the new and detailed analyses of $SU(2)$ monopole action obtained after the block-spin transformation on the dual lattice. The $b=na(\beta)$ dependence for all couplings are well fitted with a universal curve. The distance dependence of the couplings is well reproduced by a massive propagator with the mass $m=0.8$ in unit of $b$. The second is the $SU(3)$ monopole action recently obtained. The third is new interesting gauges showing abelian and monopole dominances as in the maximally abelian gauge.Comment: Talk presented at LATTICE96(topology), 4 Pages, 7 eps figure