Search

A dirhodium carbonyl complex with 1,4-bis((diphenylphosphino)methyl)phthalazine (PNNPPh), [(μ-κ2:κ2-PNNPPh){Rh(CO)}2](BF4)2, has been prepared and its reactivity studied as compared with the previously reported 3,5-bis((diphenylphosphino)methyl)pyrazolate (PNNPPy) analogue [(μ-κ2:κ2-PNNPPy){Rh(CO)2}2]BF4. The two quadridentate ligands are different in the size of the central ring and the charge; six-membered ring/neutral (PNNPPh) vs five-membered ring/mononegative (PNNPPy). The reactivities of the two systems turn out to be very similar, as can be seen from formation of the analogous, unique tetranuclear μ4-acetylide ([(μ-PNNPPh)2{Rh(CO)}4(μ4-C≡C-p-tol)]BF4) and μ4-dicarbide complexes ([(μ-PNNPPh)2{Rh(CO)}4(μ4-C2)](BF4)2). However, the PNNPPh system exhibits the following features. (1) The enlargement of the central ring causes shortening of the metal−metal distance, frequently leading to bond formation between them. For more positively charged PNNPPh species, (2) back-donation decreases to facilitate CO ...

Overweight/obesity among adult survivors of childhood SCT has been considered to be predictive of eventual development of metabolic abnormalities. Fatty liver is increasingly recognized as a major cause of liver-related morbidity and mortality in the general population. However, the real incidence of fatty liver in adult survivors of SCT has not been fully elucidated. We determined whether adult survivors are at risk for overweight/obesity, metabolic abnormalities and fatty liver and whether these risks are associated with cranial radiotherapy (CRT) before SCT. Among the 51 patients (30 males), only two male patients were overweight/obese at the last evaluation. On the other hand, 9 male (30%) and 15 female (71%) patients were underweight. Fatty liver was diagnosed in 11 male (37%) and 10 female (48%) patients during the follow-up period, although patients who had fatty liver did not tend to be overweight/obese. Significantly more patients who received CRT before SCT developed fatty liver with insulin resistance than those who did not (P

Communication between the two iron centres in (dithienylethyne)diyl complex 1 can be finely tuned by reversible addition to, ligand replacement at and removal from the C≡C moiety in 1 of dicobalt fragments Co2(CO)n(PR3)6–n. Performance analysis reveals that disparate mechanisms are in operation for the two systems. In the case of the dicobalt adducts, indirect communication via the dicobalt steppingstone can be finely tuned by controlling the electronic structure of the dicobalt unit.

Dinuclear acetylide-type complexes bridged by a photochromic dithienylethene unit (DTE), [Y-C[triple bond]C-DTE-C[triple bond]C-Y] 1 (Y={MCp*(dppe)}; Cp*=pentamethylcyclopentadienyl, M=Fe (1(Fe)), Ru (1(Ru))), have been prepared, and their wirelike and switching behavior, as well as their oxidation chemistry has been investigated. The DTE complexes 1 exhibit photochromic behavior in a manner similar to organic DTE derivatives; UV irradiation causes ring closure of the open isomer 1O to form the closed isomer 1C and visible-light irradiation of the resultant 1C causes reverse ring opening to regenerate 1O. But the performance is dependent on the metals. With respect to the interconversion rates and the 1C content at the photostationary state under UV irradiation, the ruthenium complex 1(Ru) is superior to the iron analogue 1(Fe). The wirelike performance is associated with the photochromic processes, and the efficient switching performance has been verified for 1(Fe) as characterized by the V(ab) values [V(ab) is the electronic coupling derived from intervalence charge-transfer (IVCT) bands: V(ab)(1(Fe)C; ON)=0.047 eV versus V(ab)(1(Fe)O; OFF)=0 eV], and are also supported by the large switching factor (SF=K(C)(C; ON)/K(C)(O; OFF)=39; K(C)=comproportionation constant). SF for 1(Ru) is determined to be 4.2. The remarkable switching behavior arises from the different pi-conjugated systems in the two isomeric forms, that is, cross-conjugated (1O) and fully conjugated pi-systems (1C). It was also found that, in contrast to the reversible redox behavior of the iron complex 1(Fe), the ruthenium complex 1(Ru)O undergoes oxidative ring closure to form the dicationic species of the closed isomer 1(Ru)C(2+) and, thus, the ruthenium system 1(Ru) shows dual photo- and electrochromism. The distinct oxidation behavior of 1(Fe) and 1(Ru) can be ascribed to the spin distribution on the diradical intermediates 1(Fe)O(2+) and 1(Ru)O(2+), as supported by DFT calculations.

The number of long-term surviving stem cell transplant (SCT) recipients has increased steadily, and attention has now extended to the late complications of this procedure. The objective of this study was to investigate relationship among growth and endocrine functions in long-term adult survivors of childhood SCT. The inclusion criteria of this study were survival at least 5 yr after SCT and achievement of adult height. Fifty-four patients (39 males) fulfilled these criteria and were included in this study. Growth was mainly evaluated by height standard deviation score (SDS) and individual longitudinal growth curves. Among the 54 patients, those that received SCT before 10 yr of age showed significantly greater reductions in changes in height SDS (mean –1.75, range –4.80 to –0.10) compared with those that received SCT at or after 10 yr of age (mean –0.50, range –1.74 to 1.20; P

A series of 16-electron Cp*Ir amide complexes with C−N chelating ligands, Cp*Ir[κ2(N,C)-(NHCR2-2-C6H4)] (2a: R = C6H5, 2b: R = CH3), and the chiral version, Cp*Ir[κ2(N,C)-(R)-{NHCH(CH3)-2-C10H6}] (2e), were obtained in good to excellent yields from reactions of 18-electron iridium amine complexes, Cp*IrCl[κ2(N,C)-(NH2CR2-2-C6H4)] (1a: R = C6H5, 1b: R = CH3) and Cp*IrCl[κ2(N,C)-(R)-{NH2CH(CH3)-2-C10H6}] (1e), with a base. The amido complexes 2 readily reacted with 2-propanol to convert into hydrido(amine) complexes 3 in almost quantitative yields. The chiral amido complex has proven to serve as an efficient catalyst for asymmetric transfer hydrogenation of acetophenone with 2-propanol, giving 1-phenylethanol with a moderate ee. The Bronsted basicity on the metal−NH moiety in the amido complexes was evaluated by deprotonation of acetic acid, dimethyl malonate, and acetone, leading to the corresponding acetato(amine) complex 4 and alkyl(amine) complexes 5 and 6, respectively, indicating that the amido−Ir com...

A new method for measuring delayed luminescence (delayed fluorescence) employs preillumination and a dark waiting period before normal excitation. The preillumination results in a concavity and a convexity in the decay curve in delayed luminescence in the green alga Pseudokirchneriella subcapitata. Formation of the concavity and the convexity is not affected by excitation wavelength (680 nm and 700 nm). However, the concavity and the convexity progressively decrease as the dark waiting period increases after preillumination. The formation of the concavity and the convexity was inhibited by exposure to the electron transport inhibitors DBMIB (644 microg/L, 2.0 microM) and Antimycin A (55 microg/L, 0.1 microM). Samples exposed to DBMIB exhibited noticeable reduction in the concavity, whereas samples exposed to Antimycin A exhibited pronounced reduction in the convexity. There is a possibility that the formation and disappearance of the concavity and the convexity are due to the reduction-oxidation state of the plastoquinone pool and the cyclic electron transport. We expect this method being useful in evaluating the effects of chemicals (particularly toxic chemicals) on photosynthetic reactions, and the method may also help to resolve questions regarding the source of long delayed luminescence.

Designing stem cell transplantation (SCT) conditioning regimens for Fanconi anemia (FA) has proved difficult because of hypersensitivity to the DNA cross-linking agents. We performed chromosome fragility tests with 56 FA patients and with 50 non-FA patients with severe aplastic anemia or myelodysplastic syndrome. We evaluated peripheral blood lymphocyte specimens cultured for 72 hours and treated with mitomycin C, diepoxybutane (DEB), cyclophosphamide (CY) metabolites, cytosine arabinoside (Ara-C), and fludarabine (Flu) metabolite (9-beta-D-arabinofuranosyl-2-fluoroadenine [2-F-Ara-A]). The DEB and CY metabolite tests were highly sensitive and specific for FA (P10(-4)) for both tests), and the number of aberrations per cell for DEB correlated with that for the CY metabolite test (P10(-4)) but did not correlate with the number of aberrations per cell for the Ara-C and 2-F-Ara-A tests. The difference in breakage frequencies between FA and non-FA patients for cultures treated with 2-F-Ara-A was not statistically significant. Most of the breakages observed in cells treated with 2-F-Ara-A-and Ara-C were chromatid breaks. It may be possible to determine the appropriate CY dose in the preconditioning regimen for SCT in FA patients on the basis of the in vitro effects on fragility, and Flu or Ara-C may be a safer drug than high-dose CY for conditioning in FA patients.

A series of 18-electron alkylruthenium complexes, RuR[κ 2 ( N , N ′)-( S , S )-R′SO 2 NCHPhCHPhNH 2 ](η 6 -arene) (Ph = C 6 H 5 , R′ = p -CH 3 C 6 H 4 and CH 3 ), bearing a N-sulfonylated diamine ligand was synthesized from the reaction of RuCl[κ 2 ( N , N ′)-( S , S )-R′SO 2 NCHPhCHPhNH 2 ](η 6 -arene) with alkylzinc reagents, in which transmetalation proceeded smoothly to give the desired alkyl complexes in good yield and selectivity. Although the isolable amine Ru complexes bearing functionalized alkyl ligands were thermally stable, the simple methyl and ethyl Ru complexes underwent intramolecular deprotonation from NH protons to give the amido Ru complexes with release of the alkanes. The reactivity of the alkyl Ru complexes is highly affected by the structures of the arene ligands.

The principles and utility of photoredox catalysis in organic synthesis are described. After a brief description of the features of the two types of catalytic photoredox processes following the reductive quenching cycle (RQC) and the oxidative quenching cycle (OQC), the discussion is focused on organic transformations based on OQC, in particular the trifluoromethylation of olefinic substrates with electrophilic trifluoromethylating reagents furnishing solvolytic addition products and substitution products. It is concluded that catalytic photoredox systems are green from the point of view of harmfulness, safety, and energy source (visible light, including sunlight). Future prospects of photoredox catalysis will be also discussed.

Here we investigated the characteristics of users of an emergency system that tracks elderly people, known as the "elderly monitoring key ring." The relevance of a spreading policy or strategy and the user characteristics were investigated to develop programs conducted by local governments to manage unidentified elderly people with dementia.A questionnaire was conducted in July 2013 in a district of the Ota Ward in Tokyo. The questionnaire was administered to residents65 years of age (N=7,608), of which 5,166 (67.9%) responded. Fully completed responses (N=4,475) were analyzed with binomial logistic regression analysis using "monitoring key rings" as the dependent variable and simultaneously inputted sex, age, living arrangement, social isolation, Instrumental Activities of Daily Living (IADL), and complaints of memory loss as independent variables. Interviews were also conducted in August 2014 of the staff members (N=12) of six community comprehensive support centers in the Ota Ward.The logistic regression analysis results indicated that women used the monitoring key rings 1.64 times more often than men, late elderly used it 4.39 times more often than early elderly, elderly living alone used it 2.14 times more often than elderly not living alone, non-isolated people used it 1.36 times more often than isolated people, IADL non-independent people used it 1.50 times more often than independent people, and people with complaints of memory loss used it 1.37 times more often than those without such complaints. On the other hand, the results of interviews indicated that elderly people living alone, those with worries, and relatively young and healthy elderly people were targets. The main targets of community comprehensive support centers were elderly individuals living alone and early elderly individuals. The utilization rate of elderly people living alone was high; however, that of early elderly people was low. They recognized that people registered with the system tended to have high anxiety, be relatively young and highly independent, and register after learning about the system from their peers or through neighborhood associations.Individuals who were female, late elderly, elderly living alone, non-isolated, IADL non-independent, or had complaints of memory loss were most likely to be registered with the key ring. The circumstance of registration which community comprehensive support centers recognize related to the low utilization rate of elderly people who are isolated. In the future, the system should be introduced to socially isolated as well as relatively young elderly people.

Purpose We examined how chewing rate and the extent of reactive hyperemia affect the blood flow in denture-supporting mucosa during chewing. Methods The left palatal mucosa was loaded under conditions of simulated chewing or simulated clenching for 30s, and the blood flow during loading was recorded. We compared the relative blood flow during loading under conditions that recreated different chewing rates by combining duration of chewing cycle (DCC) and occlusal time (OT): fast chewing group, typical chewing group, slow chewing group and clenching group. The relationship between relative blood flow during simulated chewing and the extent of reactive hyperemia was also analyzed. Results When comparing the different chewing rate, the relative blood flow was highest in fast chewing rate, followed by typical chewing rate and slow chewing rate. Accordingly, we suggest that fast chewing increases the blood flow more than typical chewing or slow chewing. There was a significant correlation between the amount of blood flow during simulated chewing and the extent of reactive hyperemia. Conclusions Within the limitations of this study, we concluded that slow chewing induced less blood flow than typical or fast chewing in denture-supporting mucosa and that people with less reactive hyperemia had less blood flow in denture-supporting mucosa during chewing.

Implanted medical devices require wireless power transmission. The wireless system proposed here uses a transmitting coil that could be worn around the waist to send power to a thin, flexible receiving coil located deep in a liquid NaCl solution of 0.25% mass concentration, simulating conditions in the human body. To determine optimal transmission efficiency, we examined receiving coils mounted with varying numbers of magnetic sheets. A maximum transmission efficiency of 19.2% was obtained at 1.8 MHz with no magnetic sheet. The maximum transmission efficiencies of receiving coils mounted with one sheet and two sheets were 12.5% at 1.3 MHz and 4.68% at 0.8 MHz, respectively. Our investigation confirmed that our wireless power transmission system is able to supply power to the microcontroller in the liquid solution.

The title reaction allows the introduction of a primary aminomethyl group onto electron-deficient C=C bonds.

Trifluoromethylated ketones are useful building blocks for organic compounds with a trifluoromethyl group. A new and facile synthesis of ketones with a trifluoromethyl substituent in the α-position proceeds through a one-pot photoredox-catalyzed trifluoromethylation-oxidation sequence of aromatic alkenes. Dimethyl sulfoxide (DMSO) serves as a key and mild oxidant under these photocatalytic conditions. Furthermore, an iridium photocatalyst, fac[Ir(ppy)3 ] (ppy=2-phenylpyridine), turned out to be crucial for the present photoredox process.

The 16-electron transition metal amide complexes, Cp*M[κ2(N,N‘)-(S,S)-TsNCHPhCHPhNH] (M = Ir, Rh, Cp* = pentamethylcyclopentadienyl, Ts = p-toluenesulfonyl, Ph = C6H5) and Ru[κ2(N,N‘)-(S,S)-TsNCHPh...

L-asparaginase (L-asp) is a well-known anticancer agent used in the treatment of acute lymphoblastic leukemia (ALL) in children. However, it is also known to induce several acute complications, such as acute pancreatitis. This is a presentation of two pediatric acute lymphoblastic leukemia (ALL) cases of asparaginase-associated pancreatitis (AAP) diagnosed at an early stage based on elevated serum elastase-1 levels, in the presence of normal serum amylase levels. Early diagnosis and treatment of AAP, although imperative, is occasionally difficult if only standard diagnostic procedures are followed. Elastase-1 is a potentially useful marker for the early diagnosis of AAP. Therefore, the measurement of elastase-1 levels, in addition to amylase and lipase levels, is recommended in L-asp-treated patients.

A facile synthesis of trifluoromethylated alkenes by the radical-mediated trifluoromethylation of vinyltrifluoroborates has been developed. Togni's reagent serves as a CF(3) radical precursor in the presence of the photoredox catalyst [Ru(bpy)(3)](PF(6))(2) under visible light irradiation. This new photocatalytic protocol can be applicable to a wide variety of vinylborates containing electronically diverse substituents and hetero-aromatics.

An analysis of viscosity effects on the fluorescence quenching of 9,10-dicyanoanthracene (DCA) by the title hydroxylamines ( 1 ) and oxygen in protic polar solvents revealed the occurrence of a diffusion-limited emission quenching for both the quenchers. It was found that the viscosity dependence of the former quenching rate constant is a major factor that controls the magnitude of dependence of the sensitized oxidation efficiency at a given hydroxylamine concentration on the solvent viscosity. The interesting finding that an increase in solvent viscosity exerts only a minor effect on the limiting quantum yield for the reaction led us to conclude that the increased viscosity lowers the rates for both processes of the return electron transfer and the diffusive separation of radical ions to almost the same extent. This finding substantiates the intervention of a solvent-separated radical ion pair as a key intermediate. Based on molecular size effects on the limiting quantum yield in methanol, it was suggested that an unpaired electron generated on the hydroxylamino nitrogen is not appreciably delocalized into the aromatic rings, thus permitting strong electrostatic and hydrogen bonding interactions between the caged 1 cation radical–DCA anion radical pair and protic polar solvent molecules.

The 16-electron amide complex, Ru[(R,R)-TsNCHPhCHPhNH](η6-p-cymene) (Ts=p-toluenesulfonyl, Ph=C6H5) readily reacts with formic acid to give the corresponding formate complex, which subsequently undergoes decarboxylation leading to the hydride complex with release of CO2. The reaction of this hydride complex with CO2 under mild reaction conditions, a pressure of 10 atm and even at −78 °C, proceeds rapidly to give the corresponding formate complex almost quantitatively. Thus, the reversible decarboxylation and carboxylation takes place with or without the aid of a metal-NH bifunctional effect of the Ru complexes.

雄イセエビの摂餌行動および摂餌量を284日間連続測定した。これらの値の変化はイセエビの脱皮や水温変化によって著しく制約された。イセエビは,夏と秋の脱皮約1ヶ月前より摂餌量が減少し始め,脱皮直前には5～17日間摂餌せず,脱皮後には2～26日間以上摂餌しなかった。夏の脱皮後は摂餌量が急激に増加した。イセエビが摂餌した最低水温は11.8℃であった。イセエビの摂餌量は水温の上昇とともに顕著な増加傾向がみられたが,水温が28℃以上となると減少傾向に転じた。

TIG arc welding and laser welding are used widely in the world. However, these welding processes have some advantages and problems respectively. In order to improve problems and make use of advantages of the arc welding and the laser welding processes, hybrid welding process combined the TIG arc with the YAG laser was studied. Especially, the suitable welding conditions for thin steel plate welding were investigated to obtain sound weld with beautiful surface and back beads but without weld defects. As a result, it was confirmed that the shot position of the laser beam is very important to obtain sound welds in hybrid welding. Therefore, a new intelligent system to monitor the welding area using vision sensor is constructed. Furthermore, control system to shot the laser beam to a selected position in molten pool, which is formed by TIG arc, is constructed. As a result of welding experiments using these systems, it is confirmed that the hybrid welding process and the control system are effective on the stable welding of thin stainless steel plates.

Visible light irradiation of a mixture of 1,3-dicarbonyls and 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) in the presence of photoredox catalysts, [Ru(bpy)3]2+ and [Ir(ppy)2(dtbbpy)]+ (bpy: 2,2′-b...

The proportion of people who are never-married and separated/widowed is rapidly increasing in Japan, and it will increase to 42% of the total population by 2030. The purpose of this study is to examine whether there are any differences in the probability of decline in IADL among married, never-married, and separated/widowed elderly, in relations with demographic characteristics, physical and cognitive health status, and social networks.

The trifluoromethyl group widely prevails in pharmaceutical and agrochemical compounds, while accompanying by the development of new methodologies for trifluoromethylation. Recently, the radical trifluoromethylation by photoredox catalysis has emerged. This Article describes several pioneering works and their representative mechanisms via generation of the trifluoromethyl radical based on photoredox processes.

Trifluoromethylative lactonization of both terminal and internal alkenoic acids by photoredox catalysis is developed.

Photoredox catalysis by well-known ruthenium(II) polypyridine complexes and appropriate cyclometalated iridium(III) derivatives is a useful tool for redox reactions in synthetic chemistry, because these materials can effectively catalyze single-electron-transfer (SET) processes by irradiation with visible light. This provides a new strategy for efficient and selective radical reactions. We have developed several photocatalytic reactions in which organic radicals are generated by photoredox catalysis and which have remarkable merits in terms of green and sustainable chemistry. 1 Introduction 2 Photoredox Cycles of [Ru(bpy)3]2+ and Cyclometalated Iridium Complexes 3 Radical Reactions that Occur Through a Reductive Quenching Cycle 3.1 Oxyamination of Enamines 3.2 Tin-Free Giese-Type Reactions Through Oxidation of Organoborates 4 Radical Reactions Through an Oxidative Quenching Cycle 4.1 Two-Electron Transfer Process Mediated by Duroquinone: Oxidative Coupling of an Enamine with a Silyl Enol Ether 4.2 Radical Trifluoromethylation of Alkenes 5 Conclusions and Outlook

Photoredox catalysis by well-known ruthenium(II) polypyridine complexes is a versatile tool for redox reactions in synthetic organic chemistry, because they can effectively catalyze single-electron-transfer (SET) processes by irradiation with visible light. These favorable properties of the catalysts provide a new strategy for efficient and selective radical reactions. Salts of tris(2,2′-bipyridine)ruthenium(II), [Ru(bpy)3]2+, were first reported in 1936. Since then, a number of works related to artificial photosynthesis and photofunctional materials have been reported, but only limited efforts had been devoted to synthetic organic chemistry. Remarkably, since 2008, this photocatalytic system has gained importance in redox reactions. In this chapter, we will present a concise review of seminal works on ruthenium photoredox catalysis around 2008, which will be followed by our recent research topics on trifluoromethylation of alkenes by photoredox catalysis.

Therapy-related myelodysplastic syndrome of recipient origin in a juvenile myelomonocytic leukemia patient 17 years after allogeneic BMT

Hydroalkoxymethylation of electron-deficient alkenes using alkoxymethyltrifluoroborates by photoredox catalysis has been developed. Highly reactive alkoxymethyl radicals can be easily generated from oxidation of alkoxymethyltrifluoroborates via a visible-light-induced SET process.

Photoredox catalysis by well-known ruthenium(II) polypyridine complexes and appropriate cyclometalated iridium(III) derivatives is a useful tool for redox reactions in synthetic chemistry, because these materials can effectively catalyze single-electron-transfer (SET) processes by irradiation with visible light. This provides a new strategy for efficient and selective radical reactions. We have developed several photocatalytic reactions in which organic radicals are generated by photoredox catalysis and which have remarkable merits in terms of green and sustainable chemistry. 1 Introduction 2 Photoredox Cycles of [Ru(bpy)3]2+ and Cyclometalated Iridium Complexes 3 Radical Reactions that Occur Through a Reductive Quenching Cycle 3.1 Oxyamination of Enamines 3.2 Tin-Free Giese-Type Reactions Through Oxidation of Organoborates 4 Radical Reactions Through an Oxidative Quenching Cycle 4.1 Two-Electron Transfer Process Mediated by Duroquinone: Oxidative Coupling of an Enamine with a Silyl Enol Ether 4.2 Radical Trifluoromethylation of Alkenes 5 Conclusions and Outlook

加温水槽(22.1±1.1℃)でイセエビの摂餌行動の日周性を確認し, 水温が23.6℃から7.9℃へ徐々に低下する自然水温水槽で摂餌行動と水温の関係を調べた。餌のムラサキイガイを吊り下げた糸を電子天秤に結び, イセエビの摂餌にともなう糸の張力変化を計測した。15秒毎の計測値に0.5g以上の差が生ずる回数を数え, 摂餌頻度として摂餌行動の指標とした。明暗周期12L : 12Dのもとで, 摂餌頻度は明期に低く, 暗期に高まる日周性が認められた。摂餌頻度は水温13.7℃以下でゼロの日が現れ, それ以上では95%信頼区間において1℃の水温上昇に対し10a12回の割合で増加した。

The Kii Bifurcation Current is often found along the southwest coast of the Kii Peninsula, and its frequency of occurrence reaches about 70% in the period from 1988 to 1996 (Takeuchi et al., 1998a). In order to clarify the structure and short-period variability of the Kii Bifurcation Current, detailed observations were made four times on board the R/V Seisui-maru of Mie University on October 29–31, 1996, on June 24–26, 1997, October 14–16, 1997, and December 3–4, 1997. The measured horizontal structure of the Kii Bifurcation Current indicates that the eastern portion of the Current (eastward flow near Cape Shionomisaki) consists of a part of the current zone of the Kuroshio. It is shown that the current structure, including the Kii Bifurcation Current in the vicinity of Cape Shionomisaki, is stable when the Kuroshio is flowing in a stationary straight path, but that the current structure is considerably changed when small-scale eddies pass by the cape. Such short-period variation can be monitored by using the daily variation of the sea level difference between Kushimoto and Uragami. In particular, in the case of October 29–31, 1996, when an eminent small-scale eddy passed by Cape Shionomisaki, and when the Kuroshio axis tentatively moved southwards about 50 km apart from the coast, the Kii Bifurcation Current seems to have disappeared.

The Kuroshio flows very close to Cape Shionomisaki when it takes a straight path. The detailed observations of the Kuroshio were made both on board the R/V Seisui-maru of Mie University and on board the R/V Wakayama of the Wakayama Prefectural Fisheries Experimental Station on June 11–14, 1996. It was confirmed that the current zone of the Kuroshio touches the coast and bottom slope just off Cape Shionomiaki, and that the coastal water to the east of the cape was completely separated from that to the west. The relatively high sea level difference between Kushimoto and Uragami could be caused by this separation of the coastal waters when the Kuroshio takes a straight path. This flow is rather curious, as the geostrophic flow, which has a barotropic nature and touches the bottom, would be constrained to follow bottom contours due to the vorticity conservation law. The reason why the Kuroshio leaves the bottom slope to the east of Cape Shionomisaki is attributed to the high curvature of the bottom contours there: if the current were to follow the contours, the centrifugal term in the equation of motion would become large and comparablee to the Coriolis (or pressure gradient) term, and the geostrophic balance would be destroyed. This creates a current-shadow zone just to the east of the cape. As the reason why the current zone of the Kuroshio intrudes into the coastal region to the west of the cape, it is suggested that the Kii Bifurcation Current off the southwest coast of the Kii Peninsula, which is usually found when the Kuroshio takes the straight path, has the effect of drawing the Kuroshio water into the coastal region. The sea level difference between Kushimoto and Uragami is often used to monitor the flow pattern of the Kuroshio near the Kii Peninsula. It should be noted that Uragami is located in the current shadow zone, while Kushimoto lies in the region where the offshore Kuroshio water intrudes into the coastal region. The resulting large sea level difference indicates that the Kuroshio is flowing along the straight path.

Along the southwest coast of the Kii Peninsula, a bifurcation current is regularly observed. By using ADCP data taken on board the R/V Wakayama of the Wakayama Prefectural Fisheries Experimental Station, characteristics of this bifurcation current are analyzed. The occurrence frequency of the bifurcation current reaches about 70% in the period from 1988 to 1996. The bifurcation point appears to be changeable and occurs almost evenly between Cape Ichie and Cape Shionomisaki. The current divergence in the alongshore direction was also investigated. Positive divergence values dominated in the whole analyzed area, and an onshore current appears to be dominant along the southwest coast of the Kii Peninsula, except in 1990 when the Kuroshio flowed in a large meandering path.

Anthracenebisresorcinol derivative 1 as an organic network material shows a novel catalysis in the solid state for the acrolein−cyclohexadiene Diels−Alder reaction. The suggested mechanism involves a catalytic cycle composed of sorption of the reactants in the cavities of polycrystalline host 1, preorganized intracavity reaction, and desorption of the product. The host also promotes stereoselective intracavity reactions for alkyl acrylates and cyclohexadiene but, in this case, not in a catalytic manner. Relevance of the present system as a functional organic analog of zeolites is discussed in light of the kinetics of respective elementary processes and the effects of pulverization of the catalyst thereupon as well as X-ray crystal structures.

To examine the usage conditions and intentions to use monitoring services for independent living by the elderly living alone.A cross-sectional survey was conducted using a mail-in, self-administered questionnaire in September 2011. The target population comprised 2,569 elderly people living in Ota Ward, Tokyo. The data of individuals living alone were extracted from the data of all respondents. The response rate was 67.8%. The sample consisted of 1,095 elderly people living alone. Logistic regression analyses were conducted with the usage conditions and intention to use monitoring services set as dependent variables. The factors related to the usage conditions and the intention to use monitoring services were examined. Gender, age, medical histories, existence of children living in the neighborhood, advanced activities of daily living, frequency of going outdoors, social relations, economic status, education, and mental factors were set as independent variables.The monitoring services used to facilitate independent living included the following: emergency communication service = 124 (11.3%), information registration service = 197 (18.0%), monitoring by people = 113 (10.3%), and monitoring by sensor = 51 (4.7%). The number of respondents who indicated their intention to use monitoring services included the following: emergency communication service = 525 (47.9% of the entire sample, 81.4% of non-users), information registration service = 396 (36.2% of the entire sample, 75.1% of non-users), monitoring by people = 357 (32.6% of the entire sample, 60.0% of non-users), monitoring by sensor = 335 (30.6% of the entire sample, 53.1% of non-users). The respondents' ages and medical histories were related to the usage of monitoring services. Their level of anxiety was related to the intention to use monitoring services.Usage and intention to use services was greater in conditions in which the elderly needed help to cope with emergent situations than usage and intention to use services that monitored daily life. The elderly who were aware of their need tended to use monitoring services. A future challenge is to expand the use of monitoring services to foster independent living of the elderly living alone.

The authors present a highly efficient and regioselective difunctionalization method of C=C double bonds, also applicable to steroid and amino acid scaffolds at “late stage”.

Hydroalkoxymethylation of electron-deficient alkenes using alkoxymethyltrifluoroborates by photoredox catalysis has been developed. Highly reactive alkoxymethyl radicals can be easily generated from oxidation of alkoxymethyltrifluoroborates via a visible-light-induced SET process.

As feature size shr inkage in semiconductor device progress, process fluctuation, especially focus strongly a ffects device performance. Because focus control is an ongoing challenge in optical lithography , various studies have sought for improving focus monitor ing and control . Focus errors are due to wafer s, exposure tools, reticles, QCs, and so on. F ew studies a re performed to minimize the measurement error s of auto focus (AF) sensor s of exposure tool, especially when processed wafers are exposed. With current focus measurement techniques, the phase shift grating (PSG) focus monitor 1) ha s been already proposed and its basic principle is that the intensity of the diffraction light of the mask pattern is made asymmetric by arranging a Œ SKDVHVKLIWDUHDRQ a reticle. The resist pattern exposed at the defocus position is shifted on the wafer and shifted pattern can be easily measured using an overlay inspection tool. However, it is difficult to measure shifted pattern for the pattern on the processed wafer because of interruption s caused by other patterns in the underlayer. In this paper, we ther HIRUHSURSRVHµµ6(0 -36*¶¶ technique , where the shift of the P SG resist mark is measured by employing critical dimension -scanning electron microscope (CD -SEM) to measure the focus error on the processed wafer. First, we evaluate the accuracy of SEM -PSG tech nique . Second , by applying the SEM -PSG technique and feeding the results back to the exposure, we evaluate the focus accuracy on processed wafers. By applying SEM -PSG feedback, the focus accuracy on the processed wafer was improved from 40 to 29 nm in 3 1 . Keywords : processed wafer, auto focus sensor , SEM -PSG, feedback correction

The simple radical transformation, which uses a broad range of O-nucleophiles, proceeds under mild conditions.

Visible light irradiation of a mixture of 1,3-dicarbonyls and TEMPO in the presence of a photoredox catalyst affords two types of oxidized products.