Self-Photosensitizing Dinuclear Ruthenium Catalyst for CO2 Reduction to CO.

The promise of artificial photosynthesis to solve environmental and energy issues such as global warming and the depletion of fossil fuels has inspired intensive research into photocatalytic systems for CO2 reduction to produce value-added chemicals such as CO and CH3OH. Among the photocatalytic systems for CO2 reduction, self-photosensitizing catalysts, bearing the functions of both photosensitization and catalysis, have attracted considerable attention recently, as such catalysts do not depend on the efficiency of electron transfer from the photosensitizer to the catalyst. Here, we have synthesized and characterized a dinuclear RuII complex bearing two molecules of a tripodal hexadentate ligand as chelating and linking ligands by X-ray crystallography to establish the structure explicitly and have used various spectroscopic and electrochemical methods to elucidate the photoredox characteristics. The dinuclear complex has been revealed to act as a self-photosensitizing catalyst, which acts not only as a photosensitizer but also as a catalyst for CO2 reduction. The dinuclear RuII complex is highly durable and performs efficient and selective CO2 reduction to produce CO with a turnover number of 2400 for 26 h. The quantum yield of the CO formation is also very high─19.7%─and the catalysis is efficient, even at a low concentration (∼1.5%) of CO2.

Simulation of ultrasonically induced electrical potentials in bone.

Low-intensity pulsed ultrasound treatment is known to shorten the healing period of bone fractures by 30%-40%, but the initial mechanism of the healing process remains unknown. One possible mechanism is related to the piezoelectricity of bone. However, the complex geometry of bones results in inherent challenges to evaluating electric fields induced therein. Therefore, in this study, we investigate the piezoelectric responses of bones by using simulations to study the wave propagation and induced potentials in bone, according to the piezoelectric finite-difference time-domain (PE-FDTD) method. First, we verify the suitability of the PE-FDTD method by comparing the simulated electric field results with the experimental data obtained by an ultrasound receiver using bone as the piezoelectric element. Next, ultrasound irradiation into a real bone model (the radius of a 66-year-old woman) is simulated at different incident angles. At normal incidence and off-axis incidence (45°), the maximum electric field strength was 4.3 and 5.6 mV/cm, respectively. We also present evidence of significant shear wave contribution to the induced potential. The results of this study confirm the existence of ultrasonically induced potentials in heterogenous bones with complex shapes, equal in magnitude to potentials generated in electrically stimulated bone healing.

Piezoelectric and Opto-Acoustic Material Properties of Bone.

In this chapter, recent piezoelectric and opto-acoustic studies on bone are introduced. The former are certainly related to ultrasound since piezoelectricity is one of the electro-mechanical properties. The latter are divided into two parts: Photo Acoustics (PA) and Brillouin Scattering (BS). PA is the energy conversion from light to ultrasound while Brillouin scattering is the interaction between phonons and photons. These studies seem very different; however, they are all studies on the ultrasonic material characterization of bone. Another common aspect of these studies is that they are generally targeting the material characterization of bone extracellular matrix. These studies have started later than the conventional ultrasonic bone studies and are expected to provide different characteristics of bone in the micrometer scale area.

Isolation of dermatophytes and related species from domestic fowl (Gallus gallus domesticus).

We investigated 793 bird combs [645 chickens and 148 fighting cocks (Shamo)] to determine the prevalence of dermatophytes and their related fungal species. The targeted fungal species were recovered from 195 of the 793 examined birds (24.6 %). Prevalence ratios were compared in temperate (the mainland) and subtropical (Nansei Islands) areas, genders, strains, breeding scale (individual and farm), and housing system (in cage and free ranging). The frequency of the fungal species in the mainland, males, fighting cocks, breeding scale by individual nursing, and free-range housing system exhibited significantly higher positive ratios than that in the other groups. A total of 224 dermatophytes and related species were isolated, including 101 Arthroderma (Ar.) multifidum, 83 Aphanoascus (Ap.) terreus, five Uncinocarpus queenslandicus, two U. reesii, two Ap. pinarensis, one Amauroascus kuehnii, one Ar. simii, one Gymnoascus petalosporus, one Microsporum gallinae, and 28 Chrysosporium-like (Chrysosporium spp.) isolates, which were identified using internal transcribed spacer regions of ribosomal RNA gene sequences. The predominant fungal species in the mainland was Ap. terreus and that in the Nansei Islands was Ar. multifidum. Pathogenic fungal species to humans and animals were limited to M. gallinae and Ar. simii, which corresponded to 0.025 % of the isolates in this study.

Presence of manubrium-sternum joint does not assure sufficient elevation of sternum in Nuss procedure for pectus excavatum patients.

BACKGROUND: The manubrium and body of the sternum are connected by the manubrium-sternum joint (MSJ). In performing the Nuss procedure for pectus excavatum patients, the body of the sternum is elevated as the operator flips correction bars upside down. Theoretically, the presence of the MSJ should allow elevation of the sternum body. However, does the MSJ secure sufficient elevation of the sternum? This study aims to elucidate this clinical question. METHODS: Seventy-four adult pectus excavatum patients with moderate to serious deformity (with Haller Index being equal to or greater than 5) were included in the study. The MSJ was open in all patients. For 29 patients, the sternum was elevated by only bar flipping (Non-Separation Group); for 45 patients, the sternum was horizontally separated after bar flipping (Separation Group). Whether or not additional elevation for Separation Group patients results from the division was observed, and the degree of the additional elevation was evaluated. Furthermore, 74 patients subjectively evaluated postoperative pain and gave scores with a Visual Analog Scale ranging from 0 (no pain) to 10 (intolerable pain). The VAS scores were compared between the two groups. RESULTS: In the Separation Group, the sternums of all patients achieved additional elevation from sternum separation. The pain scores were lower for the Separation Group than for the Non-Separation Group. CONCLUSION: Even when the MSJ is present, horizontal separation enhances the elevation of the sternum. Furthermore, horizontal separation of the sternum reduces postoperative pain.

Pure Orbital Floor Blow-In Fracture: An Extremely Rare Case.

A 57-year-old man presented with left diplopia on an upward gaze and ophthalmalgia after hitting the left side of his head. CT revealed a fracture on the left side of the orbital floor without orbital rim fractures and the protrusion of a small bone fragment into the orbit. Hess charts indicated markedly limited vertical movement of the left eye. Based on these findings, the patient was diagnosed with a pure orbital floor blow-in fracture (BIF). Symptoms persisted after a two-week monitoring period; therefore, the bone fragment was removed by a transcutaneous surgical approach with the assistance of a navigation system and an endoscope. Symptoms resolved after surgery, and CT and Hess examinations six months after surgery showed a good outcome. A pure BIF is rare, particularly on the orbital floor. Only a few similar case reports have been published to date, and we herein describe the surgical procedures performed and the treatment outcome of our case.

Isolation of Microsporum gallinae from a fighting cock (Gallus gallus domesticus) in Japan.

A case of tinea corporis caused by Microsporum gallinae was found in 2011 in Okinawa, located in the southern part of Japan. The patient was a 96-year-old, otherwise healthy, Japanese man, who had been working as a breeder of fighting cocks for more than 70 years. He was bitten on his right forearm by one of the cocks and a few weeks later, two erythematous macules appeared on the right forearm, accompanied by a slight itchy sensation. While the first isolate of this dermatophyte was recovered from the region by Miyasato et al. in 2011, it was not obtained from the same fighting cock owned by the patient. However, frequent exchanges of fighting cocks and special domestic breeds of chickens related to fighting, mating, and/or bird fairs are common among the fans and breeders. We investigated 238 chickens and 71 fighting cocks in Okinawa and in the suburbs of Tokyo (Chiba, Tokyo, Ibaraki, and Sizuoka). One isolate of M. gallinae from a fighting cock in Chiba Prefecture in the Tokyo metropolitan area exhibited a different genotype, with a single base difference from the patient isolate based on the internal transcribed spacer 1-5.8s-ITS2 regions (ITS1-5.8S-ITS2) of the ribosomal RNA gene sequence. The isolation of M. gallinae from a fighting cock on the mainland of Japan is the first such finding in animals in our country.

Biomechanical Evaluation of Additional Surgical Maneuvers to Improve Symmetry in Performing Nuss Procedure for Asymmetric Pectus Excavatum.

Background: Severing part of the thorax prior to bar placement is effective to improve outcomes in performing the Nuss procedure for asymmetric pectus excavatum. This study aims to elucidate the patterns of severing to provide an ideal outcome. Methods: Three-dimensional biomechanical computer models were produced simulating the thoraxes of 10 actual patients with asymmetric pectus excavatum. Virtual surgical operation was performed on the 10 models in 4 patterns: group 1-no part of the thorax was severed (default group). Group 2-The sternum was severed (sternum-severing group). Group 3-The ribs on the affected side were severed (rib-severing group). Group 4-Both the sternum and ribs on the affected side were severed (sternum/rib-severing group). After performing this preparation, simulation of bar placement was performed. Comparing the pre- and postoperative shapes of the models, we examined whether symmetry improved for each group. Results: Symmetry of the chest wall improved for rib-severing group and sternum/rib-severing group. Asymmetry remained for default group and sternum-severing group. Conclusions: Performance of the Nuss procedure for asymmetric pectus excavatum does not greatly improve symmetry of the chest wall. Severing the ribs as an additional maneuver is effective to improve symmetry.

Endergonic addition of N-methylamines to aromatic ketones driven by photochemical offset of the entropic cost.

Intermolecular addition reactions are generally accompanied by an entropic penalty due to the decrease of molecular numbers during the reaction, which sometimes makes the reaction endergonic. Here we demonstrate that such an endergonic reaction can be promoted with light-energy as a driving force; N-methylamines were added to aromatic ketones to produce aminoalcohols under UV-light irradiation. The reaction represents an obvious example showing that the photochemical approach is effective to offset such an entropic cost, and thereby to drive thermodynamically uphill addition reactions. Moreover the present reactions are highly expedient from the synthetic view point, being transition-metal-catalyst-free, scalable, highly atom economical, and regioselective. The product amines can be converted in one step to functional multi-arylated enamines, which are potentially valuable compounds in electronic materials.

Case of chromoblastomycosis appearing in an Okinawa patient with a medical history of Hansen's disease.

Chromoblastomycosis is one of several chronic infectious skin diseases caused by various species of dematiaceous fungi. It is clinically characterized by verrucous skin eruptions and occurs most commonly in tropical and subtropical regions. In Okinawa, a subtropical area, there have been only three reported cases of chromoblastomycosis including the present one. Direct microscopic examination of crust specimens and findings of sclerotic cells in histopathology can confirm the diagnosis, and cultures of crust and/or tissue specimens can identify the causative fungi. We herein report the third case of chromoblastomycosis in Okinawa; it arose in an 87-year-old Japanese woman with a history of Hansen's disease, who lived in a leprosarium in Miyako Island. To identify the causative agent as Fonsecaea pedrosoi, we used the polymerase chain reaction and direct sequencing analysis in addition to the usual methods, which include 20% potassium hydroxide microscopy, histopathological confirmation of sclerotic cells by periodic acid-Schiff stain, culture by Sabouraud's glucose agar, slide culture method, and observation of conidia by scanning electron microscopic examination.

A case of tinea nigra palmaris in Okinawa, Japan.

We report a case of tinea nigra on the left palm of a 13-year-old girl. She had noticed a pigmented, asymptomatic macule on the left palm approximately 4-5 years prior to her first visit to our hospital. The color of the lesion tended to change before and after a bath; it became lighter after a bath and darkened some time later. Physical examination revealed that the macule was 4 cm x 5 cm in size, dark brown in color and irregularly shaped. Direct potassium hydroxide (KOH) microscopic examination from skin scrapings revealed branched brown hyphae with light brown septa. A fungal culture on Sabouraud's agar media produced wet, medium brown, yeast-like colonies, the surface of which later became black and shiny. A slide culture disclosed light brown, elliptic or peanut-shaped conidia comprised of one to two ampullaceous cells. Scanning electron microscopic examination of the conidia showed both annellation conidia with lunate bud scars and sympodial conidiogenesis. Using extracted DNA from separately cultured fungi, we performed polymerase chain reaction with the primers specific to Hortaea werneckii. The results showed positive bands. We performed direct sequencing with the DNA segments from the positive bands. The causative fungus in our case was determined to be type C of H. werneckii on the grounds of the base sequences obtained. The final diagnosis of the present case was made as tinea nigra by H. werneckii. We also report a brief survey of all the cases of tinea nigra reported in Japan to date.

Numerical Analysis of Ultrasound Backscattered Waves in Cancellous Bone Using a Finite-Difference Time-Domain Method: Isolation of the Backscattered Waves From Various Ranges of Bone Depths.

Using a finite-difference time-domain method, ultrasound backscattered waves inside cancellous bone were numerically analyzed to investigate the backscatter mechanism. Two bone models with different thicknesses were modeled with artificial absorbing layers positioned at the back surfaces of the model, and an ultrasound pulse wave was transmitted toward the front surface. By calculating the difference between the simulated waveforms obtained using the two bone models, the backscattered waves from a limited range of depths in cancellous bone could be isolated. The results showed that the fast and slow longitudinal waves, which have previously been observed only in the ultrasound waveform transmitted through the bone, could be distinguished in the backscattered waveform from a deeper bone depth when transmitting the ultrasound wave parallel to the main orientation of the trabecular network. The amplitudes of the fast and slow backscattered waves were more closely correlated with the bone porosity [R2 = 0.84 and 0.66 (p < 0.001), respectively] than the amplitude of the whole (nonisolated) backscattered waves [R2 = 0.48 (p < 0.001)]. In conclusion, the nonisolated backscattered waves could be regarded as the superposition of the fast and slow waves reflected from various bone depths, returning at different times.

Inhibition of intracellular proliferation of Leishmania parasites in vitro and suppression of skin lesion development in BALB/c mice by a novel lipid A analog (ONO-4007).

A synthetic lipid A analog (ONO-4007) exhibits antileishmanial activity by activating Leishmania-infected macrophages in experimental leishmaniasis. In the present in vitro study, ONO-4007 at concentrations between 0.01 and 1.00 mg/mL markedly inhibited the proliferation of Leishmania major and L. amazonensis promastigotes. Ultrastructurally, L. major-infected macrophages showed degenerated intracellular amastigotes after exposure to ONO-4007. Leishmania-infected macrophages treated with ONO-4007 showed poorly developed parasitophorous vacuoles. High levels of tumor necrosis factor-alpha were induced by ONO-4007 in Leishmania-infected macrophages. In this in vivo study, L. amazonensis-infected BALB/c mice were treated with a dose of 30 mg/kg of ONO-4007 by perilesional and peritoneal injections. The skin lesion size was assessed before treatment with ONO-4007 and at eight weeks after injection. The lesion size was significantly suppressed in mice perilesionally injected with ONO-4007 (P < 0.01) compared with the controls. The data from our present in vitro and in vivo studies indicate that ONO-4007 has an antileishmanial effect.

[Clinical cure of leprosy--a criteria in Japan(2002)].

In Japan, a cautious definition of clinical cure of leprosy has been used since 1988. This report presents a new definition of clinical cure for leprosy patients after multi-drug treatment is completed. When the patients complete the standard treatment published in 2000, they are defined as "clinically cured". The doctor in charge should inform the patient of the cure of the disease clearly. On the release from the treatment, it is important to explain necessary cares for protection against injuries and prevention from deformities. The patient should be careful about signs of relapse and reactions.

[Survey of newly diagnosed leprosy patients in Japan (1993-2000)].

We analyzed the medical and social problems of newly registered leprosy patients in the past 8 years from 1993 to 2000 in a low endemic country, Japan. There were 56 registered Japanese patients (males, 32; females, 24), and 76 registered foreign patients (males, 56; females, 20). The number of Japanese patients in each year was between 5 and 9, and 2/3 of them were from Okinawa Prefecture, located in subtropical zone. But the number of foreign patients in each year was between 5 and 18, and 2/5 of them were from Brazil. The number of foreign patients was greater than that of Japanese patients. Male/female ratio has decreased among the Japanese.

Numerical investigation of ultrasound reflection and backscatter measurements in cancellous bone on various receiving areas.

In this study, new ultrasound reflection and backscatter measurements in cancellous bone using a membrane-type hydrophone are proposed. A membrane hydrophone made of a piezoelectric polymer film mounted on an annular frame allows an incident ultrasound wave to pass through its aperture because it has no backing material. Therefore, in measurements using the membrane hydrophone, the receiving area could be located independently from the transmitting area. In addition, the size and shape of the receiving area, which corresponded to those of the electrode deposited on the piezoelectric film, could be arranged in various ways. To investigate the validity of the proposed measurements, before bench-top experiments, the reflected and backscattered waves from cancellous bone were numerically simulated using a finite-difference time-domain method. The reflection and backscatter parameters were measured on various receiving areas, and their correlation coefficients with the structural parameters in the cancellous bone were derived. The simulated results suggested that appropriate receiving areas for the reflection and backscatter measurements could exist and that the proposed measurements could be more effective for evaluating bone properties than conventional measurements.

[Challenges and development of a nutritional management service system home page that targets personal computer novices 65 years of age or older].

OBJECTIVES: We intended to develop contents for nutritional management for elderly people using the Internet, and to consider factors relatied to the promotion of Information and Communication Technology (ICT) use. METHODS: A questionnaire survey was carried out consisting of items on diet support conditions and promoting the use of ICT by the elderly. Then, we developed a nutritional management system using a home page on a trial basis, after which n we studied the need, operability and environmental support of this system. RESULTS: Regarding the state of ICT use more than one- half of the respondents were daily users of the Internet 62.4%, and mobile phones 65.2%. On the four items on diet, such as "buy the same food, forget to buy food", 22.7%responded that "forget to buy food", which was the highest, and interest in "lunch home delivery" showed a low percentage. Among the respondents 19.6% answer "yes" to the question that memory, "have trouble remembering where you put things" and 13.4% responded that they forget to take medicine". There was a positive correlation of what with five items on operability, "What is simple and easy to use is good" and the effectiveness of personal computers and mobile phones has been shown. In addition, 32.3% responded "When the operation is difficult, the use becomes inconvenient". CONCLUSIONS: It was suggested that by setting up an opportunity to experience the effectiveness and the satisfaction of using a system that addresses elderly people's concerns, we can modify attitudes and provide motivation, reducing the sense of weakness or irrelevance that can hinder the use of a nutritional management system. It was suggested that along with the sense of effectiveness of screen displays with color instructions and simple design that match the physical characteristics of the elderly, the sense of being able to operate the system afterwards will affect the need for ICT use and utilization rate.

Considering the effects purchase food balance guide utilizing cable television has on the user.

OBJECTIVES: The aim of this study was to empirically investigate the needfulness of the Purchased Foodstuffs Balance Guide as designed for its users and also consider its influence on better dietary habits. METHODS: The participants included 89 students who attended City A's Senior Citizens' College, and the reality of their ICT and dietary habits were surveyed. Next, 27 cable television subscribers were asked to be monitors for testing the Guide. The study took place during a period of September 2013 to March 2014. RESULTS: The results indicated that, for the senior citizens, ICT use was centred on communication with their families and that their awareness or desire was a low in terms of the functions of information transmission, entertainment and receipt of services. Next, after using the Purchased Foodstuffs Balance Guide, its needfulness and its influence on better food habits were examined. As a result, the most frequent response by the participants was that they 'understood [their own] purchasing tendencies' (36.0%), followed by the three items: 'The Guide is useful for managing my nutrition', 'The Guide enabled me to know what foodstuffs are required to supplement my diet' and 'I became more careful about purchasing foodstuffs in a balanced way.' CONCLUSIONS: The study showed that 70% of the participants felt that the Purchased Foodstuffs Balance Guide was useful and make decisions when purchasing food using the Guide. This indicates the possibility that the Guide exerts a positive influence on users' awareness of nutritional balance, foodstuff purchasing choices and dietary habits.

Numerical investigation of reflection properties of fast and slow longitudinal waves in cancellous bone.

The basic reflection properties of fast and slow waves propagating in cancellous bone were numerically investigated using finite-difference time-domain (FDTD) simulations with 18 microcomputed tomographic (µCT) models of bovine cancellous bone. The simulated results showed that both reflection coefficients of the fast and slow waves linearly increased with porosity.