Generation of Highly Vibrationally Excited CO in Sequential Photodissociation of Iron Carbonyl Complexes.

Ultraviolet photochemistry of iron pentacarbonyl, Fe(CO)5, was investigated with resonantly enhanced multiphoton ionization (REMPI) spectroscopy and ion imaging. The REMPI spectrum of CO photofragments, generated by ultraviolet irradiation of Fe(CO)5, showed the generation in the highly vibrationally excited states with v = 11-15. Analysis of the band intensities observed in the 213-235 nm region indicated that the high-v CO generation was maximized at around 220 nm. Generation yields of the coordinatively unsaturated intermediates, Fe(CO)n=1-4, were measured as a function of the photolysis wavelength using a nonresonant detection scheme. The yield spectrum of FeCO was correlated with that of the high-v CO fragments, suggesting high-v CO generation in the photodissociation of FeCO. The density functional theory calculations of the excited states of FeCO showed an intense photoabsorption to the metal-centered state near 220 nm. The theoretical results were consistent with the interpretation of FeCO + hν → Fe + high-v CO, which was experimentally indicated. The momentum distribution obtained from the velocity distributions of Fe, Fe(CO)4, and CO fragments further supported that Fe is the counter-product of the high-v CO fragment. The present results provided selective observation of the photochemistry of the unsaturated iron carbonyl complexes, which has not been well elucidated in laser-based experiments because of the uncontrollable sequential photodissociation producing mixed Fe(CO)n intermediates.

Primary and Secondary Loss of CO and NO Ligands in the Ultraviolet Photodissociation of the Heteroleptic Co(CO)3NO Complex.

The photodissociation dynamics of the heteroleptic Co(CO)3NO complex were investigated in the metal-to-carbonyl (CO) ligand charge-transfer band to compare the reactivity of the CO and nitrosyl (NO) ligands. The final state distributions of both the CO and NO fragments were measured using resonance-enhanced multiphoton ionization (REMPI) spectroscopy and velocity-map ion-imaging. The primary CO photofragment was differentiated from the secondary fragments of the subsequent unimolecular decomposition of coordinatively unsaturated intermediates by comparing the momentum distributions. The internal energy of the Co(CO)2NO intermediate was sufficiently high (≥348 kJ/mol) to be generated in the electronic excited state, indicating the occurrence of the primary CO elimination on an excited state. The NO fragments exhibited two velocity components. The analysis of the final state distributions suggested that the higher- and lower-kinetic-energy components originated from the direct primary elimination and sequential elimination, respectively. The direct photoelimination through a transiently bent ligand conformation was illustrated on the basis of a two-dimensional REMPI approach and time-dependent density functional theory calculations. The present results of both ligands demonstrate the correlation between elimination mechanisms and possible ligand conformations in the electronic excited state.

Incidence and risk factors for norovirus-related diarrhea in Japanese geriatric intermediate care facilities: A prospective cohort study.

AIM: The risk of developing infectious diarrhea among elderly residents at Japanese geriatric intermediate care facilities is unclear. We investigated the incidence rate and risk factors of norovirus-related diarrhea at such facilities. METHODS: This prospective cohort study followed 1727 residents from November 2018 to April 2020 at 10 geriatric intermediate care facilities in Osaka, Japan regarding the occurrence of diarrhea. Resident data were collected from their medical records using structured forms at two to three of the following three time points: at recruitment, if they developed diarrhea, and when they left the facility. Residents who developed diarrhea were tested using rapid diagnostic tests for norovirus. Cox proportional hazard model was employed to hazard ratios (HRs) with 95% confidence intervals (CIs) to estimate the risk factors for norovirus-related diarrhea. RESULTS: During the study period, 74 residents developed diarrhea, 13 of whom were norovirus positive. The incidence rate of norovirus-related diarrhea was 10.11 per 1000 person-years (95% CI: 4.61-15.61). In terms of risk factors, people with care-needs level 3 were at a higher risk for developing norovirus-related diarrhea (adjusted HR [aHR] = 7.35, 95% CI: 1.45-37.30). Residents with hypertension (aHR = 3.41, 95% CI: 1.05-11.04) or stroke (aHR = 8.84, 95% CI: 2.46-31.83), and those who walked with canes (aHR = 16.68, 95% CI: 1.35-206.52) also had a significantly higher risk for norovirus-related diarrhea. CONCLUSIONS: Throughout the study period, the incidence of development of diarrhea was low. Care-needs level 3, stroke, hypertension and use of a cane were identified as risk factors for norovirus-related diarrhea in Japanese geriatric intermediate care facilities. Geriatr Gerontol Int 2023; 23: 179-187.

Antibody responses after BNT162b2 vaccination in Japanese geriatric intermediate care facilities.

Background: To evaluate antibody responses against the primary series of vaccination of severe acute respiratory syndrome coronavirus-2 [SARS-CoV-2] vaccines in the staff and residents of Japanese geriatric intermediate care facilities. Methods: All subjects (159 staff and 96 residents) received two doses of the BNT162b2 mRNA vaccine 3 weeks apart. Baseline data of subject were collected using a structured form. Serum samples were collected three times: before vaccination, 3 weeks after the first dose, and 4 weeks after the second dose, and anti-receptor binding domain of the spike protein of SARS-CoV-2 [anti-RBD] IgG was measured using two immunoassays. Results: After the second dose, geometric mean titers [GMT] of anti-RBD with both the Abbott and Roche assay were significantly lower in residents than staff (2282 AU/mL vs. 8505 AU/mL, and 258 U/mL vs. 948 U/mL, respectively). Multivariate analysis of characteristics affecting antibody responses (≥1280 AU/mL for Abbott and > 210 U/mL for Roche) showed lower odds ratios [ORs] for older age (adjusted OR per 10 year increase [aOR] = 0.62, 95 % confidence interval [95 %CI]; 0.38-1.02), steroid usage (aOR = 0.09, 95 %CI; 0.01-0.60) and regular nonsteroidal anti-inflammatory drugs [NSAIDs] usage (aOR = 0.16, 95 %CI; 0.03-0.88). Conclusions: Elderly people and steroid and NSAID users had lower antibody responses following the second vaccine dose.

Studying and Utilizing Traditional Technologies: Microstructure and Formation Mechanism of ε-Fe2O3 on Traditional Japanese Bizen Stoneware.

Traditional Japanese Bizen stoneware is produced by firing a specific type of green clay in a wood-fired kiln at approximately 1200 °C. During this process, single crystalline branched dendrite-like particles of Al-substituted ε-Fe2O3 (ε-Fe1.7Al0.3O3) with widths and lengths of approximately 15 and 30 µm, respectively, are formed on the surface of the ceramic. Composite particles consisting of ε-Fe2O3 epitaxially connected to spinel structure compounds [comprising the Fe-substituted spinel (Mg,Fe)(Al,Fe)2O4 and γ-Fe2O3)] with lengths of approximately 3 µm are also generated. The present work clarified the crystallographic relationship between ε-Fe2O3 and the spinel structure compounds. In addition, brown-colored samples similar to Bizen pottery and with surface Al-substituted ε-Fe2O3 particles were prepared by heating clay with K2CO3 under a 10 vol % CO gas and 90 vol % Ar gas mixture using an electric furnace instead of a firewood kiln. Hence, a traditional method was adapted to achieve the industrial production of ε-Fe2O3 crystals.

A Cross-sectional Survey of the Clinical Manifestations and Underlying Illness of Cough.

AIM: The aim of this study was to identify factors affecting the final diagnosis of cough. MATERIALS AND METHODS: This study recruited 463 consecutive patients who visited five Japanese general hospitals due to cough from October 2006 to September 2007. Of these, 418 patients (90%) who completed a questionnaire designed to acquire data regarding clinical manifestations of cough were included. RESULTS: Most patients with bronchial asthma had cough with seasonal variation and wheezing. Patients with gastro esophageal reflux disease suffered from heartburn and cough without daily or seasonal variation. Cough associated with sinobronchial syndrome was only observed in females and was linked to increased sputum. Patients with whooping cough were bothered by cough interrupting sleep and talking. Patients with cardiogenic cough had exertional dyspnea. CONCLUSION: The specific items on our questionnaire relating to patient characteristics, complications, and triggers of cough, represent useful tools for diagnosing the primary disease producing cough.

A large abdominal wall mass as an initial manifestation of malignant mesothelioma.

Malignant mesothelioma is relatively rare and usually presents with pleural thickening and effusion at onset. In this report, we describe a 67-year-old male patient whose initial manifestation of mesothelioma was a large mass in the left flank. Mesothelioma was diagnosed from needle biopsy specimens, and, after radiotherapy, the tumor did not recur in this area. However, pleural effusion developed, which was controlled by pleurodesis, and tumors appeared around the descending aorta. Despite further radiotherapy, the patient died of cardiac tamponade due to tumor invasion 38 months after the initial diagnosis. To the best of our knowledge, this is the first description of malignant mesothelioma presenting via initial invasion of the abdominal wall without changes in the thoracic space.

Cough sensitivity in pure cough variant asthma elicited using continuous capsaicin inhalation.

BACKGROUND: Cough variant asthma has recently been described, mainly as airway inflammation in relation to bronchial asthma, but the relationship between the two types of asthma remains unclear. Further studies of cough receptor sensitivity are necessary to fully characterize cough variant asthma. METHODS: We assessed the relevance of testing cough sensitivity using an Astograph with continuous capsaicin inhalation, and compared the results with those obtained using intermittent inhalation. We showed the clinical applicability of testing cough sensitivity (0.156-80 microM capsaicin; five or more coughs, 1 minute of continuous inhalation at each concentration) using this method. We compared cough sensitivity among patients with pure cough variant asthma who did not develop bronchial asthma after an observation period of at least 1 year, patients with bronchial asthma and healthy individuals. RESULTS: The continuous cough sensitivity test using the Astograph was reproducible and reliable. Cough sensitivity in patients with pure cough variant asthma was significantly higher than that in healthy individuals. CONCLUSIONS: The cough sensitivity of patients with cough variant asthma is not necessarily identical to that of healthy individuals.

Modulated drug release from the stem-and-loop structured oligodeoxynucleotide upon UV-A irradiation in the presence of target DNA.

o-Nitrobenzyl photochemistry as induced by UV-A irradiation was applied to a photoactivated drug releasing system based on a molecular beacon strategy. A stem-and-loop structured oligodeoxynucleotide (ODN) possessing a photoreactive o-nitrobenzyl chromophore at the 3'-end and 1-aminonaphthalene quencher at the 5'-end underwent conformational change into a conventional double strand structure by hybridization with a specified target DNA. The intrinsic stem-and-loop structure suppressed photoactivated release of benzoic acid as a phantom drug from the o-nitrobenzyl chromophore because of intramolecular quenching by the 1-aminonaphthalene unit in close proximity to the chromophore. Formation of the double strand structure in the presence of perfectly matched target DNA minimized occurrence of intramolecular quenching and thereby enhanced the photoactivated drug release.

Characteristics of patients with chronic cough who developed classic asthma during the course of cough variant asthma: a longitudinal study.

BACKGROUND: Some patients develop asthmatic symptoms such as wheezing and dyspnea during the course of cough variant asthma (CVA), which are considered precursors of classical asthma. OBJECTIVES: To identify the characteristics of such patients, we investigated the nature of CVA patients with or without developing bronchial asthma in the longitudinal study. METHODS: In 28 CVA patients whom we could observe over 5 years, duration of coughing, physical examination findings, pulmonary function and bronchial hyperresponsiveness to inhaled methacholine were retrospectively assessed. RESULTS: Of these patients with CVA, 10 developed the asthmatic symptoms of wheezing and dyspnea (precursors of classical asthma) over 5 years. All these 10 patients showed marked bronchial hyperresponsiveness; however, there were no significant differences in the bronchial responsiveness to methacholine between patients with precursors of classical asthma and pure CVA patients who did not wheeze. The duration of coughing had a significant relationship with precursors of classical asthma. Seven patients with precursors of classical asthma developed wheezing in the first year and 1 patient each in the second, third and fourth year. CONCLUSIONS: These findings of a 5-year observation suggest that longer duration of coughing may be an important factor that develops precursors of classical asthma in patients with CVA.

Headache associated with postpartum cerebral angiopathy: monitoring with transcranial color-coded sonography.

We report a case of postpartum cerebral angiopathy with headache; a rare entity that affects women within the early postpartum period. Cerebral angiography revealed multiple segmental narrowings of major cerebral arteries. The patient was monitored with transcranial color-coded sonography of the middle cerebral artery. Abnormally increased flow velocity within the middle cerebral artery decreased following initiation of steroid therapy, and the patient's headache improved dramatically.