Search

Dirhodium complexes bearing bulky carboxylate ligands are synthesized and characterized. The steric bulk of carboxylate ligands could affect the reaction selectivity in Rh‐catalyzed intramolecular reactions: Rh catalysts with bulky carboxylate ligands provided five‐membered ring products preferentially via the insertion into a carbon–hydrogen bond. Meanwhile, six‐membered ring products were obtained using conventional Rh catalysts via the insertion of a carbon‐carbon double bond. [ABSTRACT FROM AUTHOR]

Background: We investigated the efficacy and safety of twice‐daily bilayer sustained‐release tramadol hydrochloride tablets (35% immediate‐release; 65% sustained‐release) in patients with postherpetic neuralgia. Methods: This was a Phase III treatment‐withdrawal study with 1–4‐week dose‐escalation, 1‐week fixed‐dose, and 4‐week randomized, double‐blind, placebo‐controlled withdrawal periods performed at 43 medical institutions in Japan. Patients aged ≥20 years, ≥3 months after the onset of herpes zoster with localized, persistent pain despite fixed‐dose analgesics for ≥2 weeks before enrollment were eligible. Patients started tramadol at 100 mg/day and its dose escalated to a maximum of 400 mg/day to achieve a reduction in their Numeric Rating Scale (NRS) for pain of ≥2 points. Eligible patients were randomized to continue tramadol or switched to placebo for 4 weeks (double‐blind period). Patients were withdrawn due to inadequate analgesia (NRS deteriorated on ≥2 consecutive days) or their request. Results: Overall, 252 patients started tramadol and 173 were randomized (tramadol: 85; placebo: 88). Tramadol was superior to placebo for the primary endpoint (time from randomization to an inadequate analgesic effect) with log‐rank test p = 0.0005. The hazard ratio was 0.353 (95% confidence interval 0.190–0.657) in favor of tramadol and fewer patients in the tramadol group experienced inadequate analgesic effects (16.9% vs. 39.8%). Adverse events in ≥10% of patients in the open‐label period were constipation (43.8%), nausea (34.9%), somnolence (18.5%), and dizziness (11.6%). The frequencies of adverse events in the double‐blind period were similar in both groups. Conclusion: Sustained‐release tramadol tablets with an immediate‐release component are effective and well tolerated for managing postherpetic neuralgia. [ABSTRACT FROM AUTHOR]

BPh3 catalyzes the N‐methylation of secondary amines and the C‐methylenation (methylene‐bridge formation between aromatic rings) of N,N‐dimethylanilines or 1‐methylindoles in the presence of CO2 and PhSiH3; these reactions proceed at 30–40 °C under solvent‐free conditions. In contrast, B(C6F5)3 shows little or no activity. 11B NMR spectra suggested the generation of [HBPh3]−. The detailed mechanism of the BPh3‐catalyzed N‐methylation of N‐methylaniline (1) with CO2 and PhSiH3 was studied by using DFT calculations. BPh3 promotes the conversion of two substrates (N‐methylaniline and CO2) into a zwitterionic carbamate to give three‐component species [Ph(Me)(H)N+CO2−⋅⋅⋅BPh3]. The carbamate and BPh3 act as the nucleophile and Lewis acid, respectively, for the activation of PhSiH3 to generate [HBPh3]−, which is used to produce key CO2‐derived species, such as silyl formate and bis(silyl)acetal, essential for the N‐methylation of 1. DFT calculations also suggested other mechanisms involving water for the generation of [HBPh3]− species. [ABSTRACT FROM AUTHOR]

We report a carbon(sp2)‐carbon(sp3) bond‐forming cross‐coupling reactions by employing a nano‐size nickel catalyst supported on sulfur‐modified gold (SANi). This transformation demonstrates an efficient synthesis of functionalized aryl compounds, including heterocycles. Notably, the reactions proceeded in good yields with significantly low leaching of nickel from SANi. Moreover, SANi could be recycled several times without significant loss of catalytic activity. [ABSTRACT FROM AUTHOR]

A linear inertial electrostatic confinement fusion neutron source equipped with a cooling system for high power operation was developed and its discharge characteristics and neutron production performance were tested under a wide range of discharge conditions. Four different types of discharge anodes were prepared and the dependencies of the device performance on the anode shape were precisely investigated. A maximum neutron production rate of 3.4×106 n/s was achieved when the device was operated with single‐cylinder‐type anodes under a discharge voltage of 94 kV, a current of 20 mA, and a deuterium gas pressure of 0.5 Pa. By comparing the discharge characteristics and neutron generation rates under different anode shapes, we found that the larger inner diameter of the anode leads to longer effective gap length and lower operating pressure, which may result in relatively high fusion reaction rate observed with the single‐cylinder‐type anodes. [ABSTRACT FROM AUTHOR]

Spin‐inversion dynamics in O2 binding to a model heme complex, which consisted of Fe(II)‐porphyrin and imidazole, were studied using nonadiabatic wave packet dynamics calculations. We considered three active nuclear degrees of freedom in the dynamics, including the motions along the Fe–O distance, Fe–O–O angle, and Fe out‐of‐plane distance. Spin‐free potential energy surfaces for the singlet, triplet, quintet, and septet states were developed using density functional theory calculations, and spin–orbit coupling elements were obtained from CASSCF‐level electronic structure calculations. The spin‐inversion mainly occurred between the singlet state and one of the triplet states due to large spin–orbit couplings and the contributions of other states were extremely small. The present quantum dynamics calculations suggested that the narrow crossing region model plays a dominant role in the O2 binding dynamics. In addition, the one‐dimensional Landau–Zener model underestimated the nonadiabatic transition probability. [ABSTRACT FROM AUTHOR]

Spin‐inversion mechanisms in O2 binding to a model heme complex, consisting of Fe(II)‐porphyrin and imidazole, were investigated using density‐functional theory calculations. First, we applied the recently proposed mixed‐spin Hamiltonian method to locate spin‐inversion structures between different total spin multiplicities. Nine spin‐inversion structures were successfully optimized for the singlet–triplet, singlet–quintet, triplet–quintet, and quintet–septet spin‐inversion processes. We found that the singlet–triplet spin‐inversion points are located around the potential energy surface region at short Fe–O distances, whereas the singlet–quintet and quintet–septet spin‐inversion points are located at longer Fe–O distances. This suggests that both narrow and broad crossing models play roles in O2 binding to the Fe‐porphyrin complex. To further understand spin‐inversion mechanisms, we performed on‐the‐fly Born‐Oppenheimer molecular dynamics calculations. The reaction coordinates, which are correlated to the spin‐inversion dynamics between different spin multiplicities, are also discussed. [ABSTRACT FROM AUTHOR]

Methyl‐selective α‐oxygenation of tertiary amines is a highly attractive approach for synthesizing formamides while preserving the amine substrate skeletons. Therefore, the development of efficient catalysts that can advance regioselective α‐oxygenation at the N‐methyl positions using molecular oxygen (O2) as the terminal oxidant is an important subject. In this study, we successfully developed a highly regioselective and efficient aerobic methyl‐selective α‐oxygenation of tertiary amines by employing a Cu/nitroxyl radical catalyst system. The use of moderately hindered nitroxyl radicals, such as 1,5‐dimethyl‐9‐azanoradamantane N‐oxyl (DMN‐AZADO) and 1‐methyl‐2‐azaadamanane N‐oxyl (1‐Me‐AZADO), was very important to promote the oxygenation effectively mainly because these N‐oxyls have longer life‐times than less hindered N‐oxyls. Various types of tertiary N‐methylamines were selectively converted to the corresponding formamides. A plausible reaction mechanism is also discussed on the basis of experimental evidence, together with DFT calculations. The high regioselectivity of this catalyst system stems from steric restriction of the amine‐N‐oxyl interactions. [ABSTRACT FROM AUTHOR]

Dehydrogenative aromatization is one of the attractive alternative methods for directly synthesizing primary anilines from NH3 and cyclohexanones. However, the selective synthesis of primary anilines is quite difficult because the desired primary aniline products and the cyclohexanone substrates readily undergo condensation affording the corresponding imines (i.e. N‐cyclohexylidene‐anilines), followed by hydrogenation to produce N‐cyclohexylanilines as the major products. In this study, primary anilines were selectively synthesized in the presence of supported Pd nanoparticle catalysts (e.g. Pd/HAP, HAP=hydroxyapatite, Ca10(PO4)6(OH)2) by utilizing competitive adsorption unique to heterogeneous catalysis; in other words, when styrene was used as a hydrogen acceptor, which preferentially adsorbs on the Pd nanoparticle surface in the presence of N‐cyclohexylidene‐anilines, various structurally diverse primary anilines were selectively synthesized from readily accessible NH3 and cyclohexanones. The Pd/HAP catalyst was reused several times though its catalytic performance gradually declined. [ABSTRACT FROM AUTHOR]

Aim: This study aimed to examine the relationship between blood coagulability and sense of burden among caregivers of patients with senile dementia of the Alzheimer type. Methods: A cross‐sectional study was carried out involving healthy older caregivers who lived with their patients with senile dementia of the Alzheimer type. We evaluated the Zarit Burden Interview score, levels of von Willebrand factor antigen, D‐dimer, thrombin–antithrombin III complex, tissue plasminogen activator/plasminogen activator inhibitor type 1 complex, number of chronic diseases, body mass index and number of medications. A linear regression model was used to estimate adjusted associations. Results: Thrombin–antithrombin III complex levels were higher in female caregivers than in male caregivers (P = 0.07). Headaches were significantly more frequent in female caregivers than in male caregivers, as assessed by a visual analog scale (P < 0.01). The number of chronic diseases and body mass index were positively associated with levels of tissue plasminogen activator/plasminogen activator inhibitor type 1 complex (P < 0.05). Similarly, the number of medications was positively associated with levels of D‐dimer (P < 0.05). However, the Zarit Burden Interview score was not associated with blood coagulability (P > 0.05). Conclusions: The present study found that the number of chronic diseases and body mass index were associated with blood coagulability, and that female caregivers were more prone to headaches and higher blood coagulability than male caregivers. These findings highlight the essential nature of health management during caregiving. The impact of caregiver burden on blood coagulability is likely to differ depending on the long‐term or short‐term psychological stress associated with caregiving conditions. Geriatr Gerontol Int 2019; 19: 804–808. [ABSTRACT FROM AUTHOR]

A structure optimization method with ionization energy constraint is developed to explore structures with specific ionization energy. The Levine‐Coe‐Martínez penalty function (J Phys Chem B 2008, 112, 405) was adopted, and the penalty function includes a predefined core‐ionization energy and inner‐shell ionization energy. For an SN2 reaction, isomerization of a platinum complex, a proton transfer reaction, and carbon monoxide adsorption on a palladium cluster, the present method was tested, and the targeted energy minima were obtained as designated by the input ionization energy. The shape of the objective function, the parameters in the penalty function, and structural changes during the optimization process were discussed. An automated parameter setting and possible problems are discussed for future direction. © 2018 Wiley Periodicals, Inc. A structure optimization method with ionization energy constraint is developed to explore structures with specific ionization energy. The Levine‐Coe‐Martínez penalty function was adopted, and the penalty function includes a predefined core‐ionization energy and inner‐shell ionization energy. The present method was tested for an SN2 reaction, isomerization of a platinum complex, a proton transfer reaction, and carbon monoxide adsorption on a palladium cluster. [ABSTRACT FROM AUTHOR]

Front Cover: Paddle-Wheel Dirhodium Complexes Bearing Bulky Carboxylate Ligands: Synthesis and Catalysis in Carbene Insertion Reactions (Chem. The steric bulk of carboxylate ligands could affect the reaction selectivity in Rh-catalyzed intramolecular competitive carbene insertions: Rh catalysts with bulky carboxylates could provide five-membered ring products preferentially via the insertion into a carbon-hydrogen bond while conventional Rh catalysts gave six-membered ring products via the insertion of a carbon-carbon double bond. Keywords: Carbene; Carboxylic Acid; DFT Calculations; Rhodium; Selectivity EN Carbene Carboxylic Acid DFT Calculations Rhodium Selectivity 1 1 1 06/05/23 20230601 NES 230601 B Paddle-Wheel dirhodium complexes b bearing bulky carboxylate ligands were synthesized and characterized. [Extracted from the article]

Highly active bifunctional metalloporphyrin catalysts were developed for the coupling reaction of epoxides with CO2 to produce cyclic carbonates. The bifunctional catalysts have both quaternary ammonium halide groups and a metal center. To elucidate the roles of these catalytic groups, DFT calculations were performed. Control reactions using tetrabutylammonium halide as a catalyst were also investigated for comparison. In the present article, the results of our computational studies are overviewed. The computational results are consistent with the experimental data and are useful for elucidating the structure-activity relationship. The key features responsible for the high catalytic activity of the bifunctional catalysts are as follows: 1) the cooperative action of the halide anion (nucleophile) and the metal center (Lewis acid); 2) the near-attack conformation, leading to the efficient opening of the epoxide ring in the rate-determining step; and 3) the conformational change of the quaternary ammonium cation to stabilize various anionic species generated during catalysis, in addition to the robustness (thermostability) of the catalysts. [ABSTRACT FROM AUTHOR]

Bifunctional metalloporphyrins with quaternary ammonium bromides (nucleophiles) at the meta, para, or ortho positions of meso-phenyl groups were synthesized as catalysts for the formation of cyclic carbonates from epoxides and carbon dioxide under solvent-free conditions. The meta-substituted catalysts exhibited high catalytic performance, whereas the para- and ortho-substituted catalysts showed moderate and low activity, respectively. DFT calculations revealed the origin of the advantage of the meta-substituted catalyst, which could use the flexible quaternary ammonium cation at the meta position to stabilize various anionic species generated during catalysis. A zinc(II) porphyrin with eight nucleophiles at the meta positions showed very high catalytic activity (turnover number (TON)=240 000 at 120 °C, turnover frequency (TOF)=31 500 h−1 at 170 °C) at an initial CO2 pressure of 1.7 MPa; catalyzed the reaction even at atmospheric CO2 pressure (balloon) at ambient temperature (20 °C); and was applicable to a broad range of substrates, including terminal and internal epoxides. [ABSTRACT FROM AUTHOR]

Bis(diaryl)-1,3-butadiynes bearing two amino moieties were easily synthesized by a sequential coupling reaction by using an electrochemical method. This sequential reaction consists of electrochemical oxidative homocoupling and Suzuki-Miyaura coupling. The fluorescence of the obtained bis(diaryl)-1,3-butadiynes is solvatochromic despite their symmetric linear structure and lack of a strong acceptor moiety. [ABSTRACT FROM AUTHOR]

Background Diabetes mellitus has been recognized as the most common systemic disease associated with deep neck infection. We report the first systematic review and meta-analysis of the influence of diabetes on clinical and bacteriological characteristics of deep neck infection. Methods Articles were retrieved from PubMed, EMBASE, and the Japan Medical Abstracts Society database. A critical review of 227 studies identified 20 studies eligible for quantitative synthesis. Results Diabetes was associated with higher prevalences of multispace spread of infection, complications, and failure to identify pathogenesis, with risk ratios (RRs) of 1.96, 2.42, and 1.29, respectively. Bacteriologically, patients with diabetes showed a higher prevalence of culture identification of Klebsiella pneumoniae (RR, 3.28), and lower prevalences of Streptococcus spp. (RR, 0.57) and anaerobes (RR, 0.54). Conclusion Deep neck infection with diabetes differs from that without in several clinical aspects. Again, bacteriological differences imply that diabetic infections might be populated by different bacterial flora. © 2014 Wiley Periodicals, Inc. Head Neck 37: 1536-1546, 2015 [ABSTRACT FROM AUTHOR]

meso-Monobenzoporphycene (mMBPc) and meso-dibenzoporphycene (mDBPc), in which one or two benzene moieties are fused at ethylene-bridged positions ( meso-positions) of porphycene, were prepared in an effort to further delocalize the π-electrons within the porphycene molecule. mMBPc and mDBPc were fully characterized by mass spectrometry, 1H and 13C NMR spectroscopy, and X-ray crystallography. The longest-wavelength Q-bands of mMBPc and mDBPc are red-shifted by 92 nm and 418 nm, respectively, compared to that of the unsubstituted porphycene (Pc). Electrochemical measurements indicate that the HOMO is destabilized and the LUMO is stabilized by the fused benzene moieties at the meso positions. Furthermore, both XPS and theoretical studies support the presence of a cis tautomeric form in the ground state of mDBPc, despite the fact that essentially all known porphycene derivatives adopt the trans tautomeric form. [ABSTRACT FROM AUTHOR]

Carbon-based materials have attracted interest as high-performance catalysts for the aqueous-phase conversion of cellulose. The adsorption of β-glucans plays a crucial role in the catalytic performance of carbons, although the primary driving force and details of the adsorption process remain unclear. This study demonstrates that adsorption occurs at hydrophobic sites on the carbon surface and that hydrophilic groups are not involved. Analysis of adsorption temperature dependence also reveals that the entropy change associated with adsorption is positive. Our results indicate that adsorption occurs by entropically driven hydrophobic interactions in addition to CH-π hydrogen bonding. These same CH-π hydrogen bonds are also confirmed by DFT calculations. The adsorption of β-glucans on carbons is significantly stronger than the affinity between β-glucans. The adsorption equilibrium constants of β-glucans on carbons increase exponentially with increasing degrees of polymerization, which supports the theory of strong interactions between the carbon and the long β-glucans found in cellulose. [ABSTRACT FROM AUTHOR]

Aim To clarify the association between nutritional status and the prevalence of geriatric conditions in dependent older adults. Methods A cross-sectional observational study of dependent older adults aged 65years or older who were living either in the community ( n = 511, mean age 81.2years) or in nursing homes ( n = 587, mean age 85.2years) was carried out. Data included the participants' demographic characteristics, basic activities of daily living, Charlson Comorbidity Index and the prevalence of eight geriatric conditions (visual impairment, hearing impairment, falls, bladder control problems, cognitive impairment, impaired mobility, swallowing disturbance and loss of appetite). Nutritional status was assessed by the Mini Nutritional Assessment short form ( MNA-SF). Results Of 1098 participants, 21.4% ( n = 235) were categorized as 'malnourished', according to the MNA-SF classification. Participants in the 'malnourished' group had a greater number of geriatric conditions than those in the other two groups. A higher prevalence of all the geriatric conditions except for falls was detected in the group with poorer nutritional status. Multivariate logistic regression analysis showed that malnutrition was associated with the number of geriatric conditions, but not with that of comorbidities, even after controlling for confounders. Conclusions Malnutrition was confirmed to have significant associations with geriatric conditions in dependent older adults. Geriatr Gerontol Int 2014; 14: 198-205. [ABSTRACT FROM AUTHOR]

The excitation energy transfer (EET) between a fluorescent resonance energy transfer (FRET) pair, cyan fluorescent protein chromophore (CFPc)/ green fluorescent protein chromophore (GFPc), is used for measuring molecular proximity in experimental studies. In this article, the role of the bridging protein media has been investigated using the quantum chemical calculations for the EET electronic coupling. We adopted a model peptide connecting GFPc and CFPc, a GFPc-X-CFPc model, and examined the X (amino acids) dependence. The major part of the EET coupling element arises from the direct interaction between GFPc and CFPc via the Förster mechanism. The magnitude of the through-X interactions vary for the type of residues. The contribution of the X was, however, at most 10% of the total value. Together with the contributions from through-peptide and charge-transfer types, X gives minor modifications to the total coupling via the super-exchange mechanism. © 2012 Wiley Periodicals, Inc. [ABSTRACT FROM AUTHOR]

Aims: To identify predictors of long-term care placement and to examine the effect of day-care service use on long-term care placement over a 36-month follow-up period among community-dwelling dependent elderly. Methods: This study was a prospective cohort analysis of 1739 community-dwelling elderly and 1442 caregivers registered in the Nagoya Longitudinal Study for Frail Elderly. Data included the clients' demographic characteristics, basic activities of daily living, comorbidities, and use of home care services, including the day-care, visiting nurse, and home-help services, as well as caregivers' demographic characteristics and care burden. Analysis of long-term care placement over 36 month was conducted using Kaplan-Meier curves and multivariate Cox proportional hazards models. Results: Among the 1739 participants, 217 were institutionalized at long-term care facilities during the 36-month follow-up. Multivariate Cox regression models, adjusted for potential confounders, showed that day-care service use was significantly associated with an elevated risk for long-term care placement within the 36-month follow-up period. Participants using a day-care service two or more times/week had significantly higher relative hazard ratios than participants not using such a service. Conclusion: The results highlight the need for effective measures to reduce the long-term care placement of day-care service users. Policy makers and practitioners must consider implementing multidimensional support programs to reduce the caregivers' willingness to consider long-term care placement. Geriatr Gerontol Int 2012; 12: 322-329. [ABSTRACT FROM AUTHOR]

The kinetics of carbamate formation from the reaction of carbon dioxide with α-amino acids in D2O was first investigated by means of nuclear magnetic resonance spectroscopy. Potassium carbonate was used as the CO2 source. For each amino acid, the maximum carbamate yield, the apparent rate constant for the carbamate formation kapp, and the rate constants for the formation k1 and the breakdown k−1 of the carbamate were estimated. Plots of log k1 or log k−1 versus p Ka of amino acids indicated that the formation rate k1 increased with the basicity (p Ka) of amino acid, while the decomposition rate k−1 decreased. A Brϕnsted β value of 0.39 was obtained from the former plot, being in good agreement with the previously reported ones (0.26-0.43). The observed negative p Ka dependence of log k−1 (Brϕnsted α = 0.34) is reasonable, because the carbamate decomposition is acid-catalyzed and the steady-state concentration of H+ should be higher for weaker basic amines. The charge (σ) and the lone-pair energy ( EN) at the nitrogen atom of the amino group were calculated. Although log k1 correlated with σ and EN, log k−1 was unrelated with both of these parameters. Considering that the carbamate formation ( k1) is not only base-catalyzed but should also be promoted by the nucleophilicity of the amino nitrogen, its correlation with σ and EN in addition to p Ka is rational. The irrelevance of log k−1 to σ and EN is not surprising, because σ and EN are not a direct measure of [H+] of the solution. Copyright © 2011 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Reactive power supply plays an important role in active power supply with adequate system voltages. Various pricing mechanisms for reactive power supply have been developed and some of them have been adopted in some power systems, but they are in a trial stage. The authors also focus on development of a pricing method for reactive power ancillary services. This problem involves two technical issues: rational estimation of the cost associated with reactive power supply, and fair and transparent allocation of the estimated cost among the market participants. This paper proposes methods for evaluating the contribution of generators and demands. © 2010 Wiley Periodicals, Inc. Electr Eng Jpn, 174(2): 36-45, 2011; Published online in Wiley Online Library (). DOI 10.1002/eej.21016 [ABSTRACT FROM AUTHOR]

Background/purpose: For medical and dermatological researchers, it is important to realize the molecular dynamics and its control in the stratum corneum (SC) of human skin, which may be related to some skin abnormalities such as atopic dermatitis and skin pruritus. We have tried to analyze the periodic molecular dynamics of the outermost layers of SC in vivo. Methods: We measured the skin surface molecules of human face in situ non-invasively using a Fourier-transform infrared (FTIR) spectroscopy system attached with a newly designed attenuated total reflection (ATR) probe. The water-extracted components from the SC were also analyzed using mass spectrometry, an enzymatic assay and high-performance liquid chromatography characterization. Results: The infrared spectral changes of some components on the face skin at around 1000–1200 cm−1 with circa-monthly rhythms were observed when monitored for 10 months, and the components also showed a seasonal change. The analysis of different FTIR spectrum of the changeable components with circa-monthly rhythm suggested the presence of a lactate compound. The presence of magnesium lactate in a conjugated form was detected in the water extract of SC. Conclusion: We demonstrate that the periodically changed components of the human face skin contained magnesium lactate conjugate as a major component. [ABSTRACT FROM AUTHOR]

In this article, we present the multicore (mc) QM/MM method, a QM/MM method that can optimize the structure of chromophore aggregate in protein. A QM region is composed of the sum of the QM subregions that are small enough to apply practical electronic structure calculations. QM/MM energy gradient calculations are performed for each QM subregion. Several benchmark examinations were carried out to figure out availabilities and limitations. In the interregion distances of more than 3.5–4.0 Å, the mcQM/MM energy gradient is very close to that obtained by the ordinary QM/MM method in which all the QM subregions were treated together as a single QM region. In van der Waals complex, the error exponentially drops with the distance, while the error decreases slowly in a hydrogen bonding complex. On the other hand, the optimized structures were reproduced with reasonable accuracy in both cases. The computational efficiency is the best advantage in the mcQM/MM approach, especially when the QM region is significantly large and the QM method used is computationally demanding. With this approach, we could optimize the structures of a bacterial photosynthetic reaction center protein in the ground and excited states, which consists of more than 14,000 atoms. © 2008 Wiley Periodicals, Inc. J Comput Chem 2009 [ABSTRACT FROM AUTHOR]

The authors have proposed the Flexible, Reliable and Intelligent ENergy Delivery System (called “FRIENDS”), which is a new concept for future power distribution systems. Also, a “micro grid” which is a similar concept to FRIENDS has been developed. In a micro grid, an independent distribution system can be constituted by a number of distributed generators. In this paper, FRIENDS, Micro grid, and conventional distribution systems are compared quantitatively in supply reliability and system cost through time sequential Monte Carlo simulations. In addition, for cost evaluation, interruption costs are included to show risk incurred by unsupplied energy. Finally, the authors search for preferable form with install and operation of distributed generators and network composition according to social cost including interruption cost and system cost. © 2009 Wiley Periodicals, Inc. Electr Eng Jpn, 167(2): 28–37, 2009; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/eej.20659 [ABSTRACT FROM AUTHOR]

In this paper, we assume 2 models for securing reserve capacity. One is “Commitment-based Security Model” and the other is “Reserve Market-based Security Model.” In Commitment-based security model, ISO commits procurement of reserve energy to a particular generation company. Meanwhile, in Reserve market-based security model, ISO procures reserve energy through reserve market. The main object of this research is to investigate which model will be preferable for the viewpoint of consumer's cost. To compare these models, two things are considered in this paper. One is bidding behavior of agents which bids to energy market and reserve market. To consider this, Q-Learning of multi-agent model is used. Also, the Unit Commitment (UC) is considered to calculate generation cost. This is to calculate the cost for securing reserve power more precisely. © 2009 Wiley Periodicals, Inc. Electr Eng Jpn, 167(1): 18– 25, 2009; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/eej.20705 [ABSTRACT FROM AUTHOR]

OBJECTIVES: To clarify the association between unmet medication management need and 3-year mortality and hospitalization for community-dwelling older people with various levels of disabilities. DESIGN: Prospective cohort study (the Nagoya Longitudinal Study for Frail Elderly). SETTING: Community-based. PARTICIPANTS: One thousand seven hundred seventy-two community-dwelling elderly subjects (611 men, 1,161 women). MEASUREMENTS: Data included the clients' demographic characteristics, a rating for basic and instrumental activities of daily living (ADLs), number of prescribed medications and physician-diagnosed chronic diseases, medication adherence, ability to manage medication, and presence or absence of medication assistance. Cox proportional hazard models and the Kaplan-Meier method were used to assess the association between the medication management at baseline and mortality or hospitalization during a 3-year period. RESULTS: Of 1,772 participants, 681 reported no difficulty with self-medication management, and 1,091 experienced difficulty with self-medication. Of participants with difficulty with self-medication management, 929 had medication assistance, and 162 did not. During a 3-year follow up, 424 participants died, and 758 were admitted to hospitals. The baseline data demonstrated that participants not receiving medication assistance were younger and had better ADL status and fewer comorbidities. Multivariate Cox regression models adjusting for potential confounders showed that the lack of assistance in those who needed medication assistance was associated with hospitalization but not mortality during the study period. CONCLUSION: In community-dwelling disabled elderly people, lack of medication assistance in those needing medication support was associated with higher risk of hospitalization. [ABSTRACT FROM AUTHOR]

Recently, the basic framework of electric power systems has been changed significantly by deregulation of electric power industry. Also, distributed generators (DGs) such as renewable energy generations, co-generations, and energy storage systems have been introduced into the demand sides not only for saving energy and the global environment, but also for compensating voltage drops and supply interruption. In the future power systems, a lot of small-sized DGs will supply the electricity with existing large-scale generators under a competitive environment. In this context, it is desirable that DGs contribute to stable, reliable and economic operations by coordinating with existing large-scale generators. For example, power from large-scale generators could be leveled if DGs are operated during the peak period. Also, ancillary services such as frequency control, voltage control, and supply of reserve capacity could be executed by controlling DGs directly or indirectly. Under these circumstances, the authors have proposed a new power distribution system: Flexible, Reliable and Intelligent ENergy Delivery System (FRIENDS). This paper investigates some kinds of power supply systems which coordinate DGs with existing large-scale generators including the concept of FRIENDS and considering how DGs are managed. The effects of DGs which contribute to supply the energy and/or the reserve in every power system are evaluated. © 2008 Wiley Periodicals, Inc. Electr Eng Jpn, 163(1): 48–56, 2008; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/eej.20358 [ABSTRACT FROM AUTHOR]

As deregulation in the electric power industry has advanced in many countries, a spot market and a futures market for electric energy have already been formulated. In Japan, the foundation of a day-ahead spot market is scheduled for the 2005 fiscal year. This paper presents a method to evaluate the expected profit and risk for an electric power supplier considering both spot market and bilateral market. In this paper, the Vasicek model is used to represent the fluctuations in spot price and demand in a bilateral market, and additionally, Value at Risk (VaR) is used as a risk index. © 2007 Wiley Periodicals, Inc. Electr Eng Jpn, 161(4): 1–11, 2007; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/eej.20515 [ABSTRACT FROM AUTHOR]

Excited states of fluorescent proteins were studied using symmetry-adapted cluster-configuration interaction (SAC-CI) method. Protein-environmental effect on the excitation and fluorescence energies was investigated. In green fluorescent protein (GFP), the overall protein-environmental effect on the first excitation energy is not significant. However, glutamine (Glu) 94 and arginine (Arg96) have the red-shift contribution as reported in a previous study (Laino et al., Chem Phys 2004, 298, 17). The excited states of GFP active site (GFP-W22-Ser205-Glu222-Ser65) were also calculated. Such large-scale SAC-CI calculations were performed with an improved code containing a new algorithm for the perturbation selection. The SAC-CI results indicate that a charge-transfer state locates at 4.19 eV, which could be related to the channel of the photochemistry as indicated in a previous experimental study. We also studied the excitation and fluorescence energies of blue fluorescent protein, cyan fluorescent protein, and Y66F. The SAC-CI results are very close to the experimental ones. The protonation state of blue fluorescent protein was determined. Conformation of cyan fluorescent protein indicated by the present calculation agrees to the experimentally observed structure. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2007 [ABSTRACT FROM AUTHOR]

Based on our previous study for the O2 binding of the Fe–Por complex, this study investigates the O2 binding mechanism in the Fe–porphyrin isomers, Fe–porphycene (FePc), and Fe–corrphycene (FeCor) complexes. By calculating the potential energy surface of the O2 binding, the present study explains the reason for the dramatic increase of O2 affinities observed in the FePc complex. In the case of FeCor–O2, the O2 binding process includes the intersystem crossing from a triplet to singlet state, as in the FePor–O2 complex. However, FePc–O2 uses only a singlet surface. This is because the ground state of the FePc complex in the deoxy state is a triplet state, while those of FePor and FeCor are a quintet state. Such difference originates from character of the SOMO. We estimated an equilibrium constant for the O2 binding that reasonably reproduced the trend observed in the experiments. © 2006 Wiley Periodicals, Inc. J Comput Chem 27: 1363–1372, 2006 [ABSTRACT FROM AUTHOR]

OBJECTIVES: To clarify the association between day care service use and 21-month mortality in community-dwelling frail older people. DESIGN: Prospective cohort study (the Nagoya Longitudinal Study for Frail Elderly). SETTING: Community-based. PARTICIPANTS: One thousand six hundred seventy-three community-dwelling older people (540 men, 1,133 women). MEASUREMENTS: Data included the clients' demographic characteristics; depression as assessed using the short version of the Geriatric Depression Scale; a rating for basic activities of daily living (ADLs); comorbidity; number of prescribed medications and physician-diagnosed chronic diseases; use of home-care services, including day care, visiting nurse, and home-help services; and number of regular medical checkups. Survival analysis of 21-month mortality was conducted using Kaplan-Meier curves and multivariate Cox proportional hazards models. RESULTS: Of the 1,673 participants, 726 were day care service users at baseline, and 268 (94 day care service users, 174 nonusers) died during the 21-month follow-up. Multivariate Cox regression models adjusting for potential confounders showed that day care service use was associated with reduction in mortality. Subgroup analysis demonstrated that day care service use was associated with less risk of mortality in subjects who were female; were in the youngest age group (65–74); had higher ADL scores, lower comorbidity, depression, no dementia; and used a visiting nurse service. Participants using day care service two and three times or more a week had 63% or 44% lower relative hazard ratios, respectively, than participants not using the service. CONCLUSION: Among community-dwelling frail older people, day care service use two or more times per week was associated with 44% to 63% lower 21-month mortality. [ABSTRACT FROM AUTHOR]

Background: Japan is presently experiencing a growth in the number of male caregivers and this situation has given rise to some concerns over gender differences. Previous studies have suggested that there are gender differences in caregiver burden in home care, however, it is still unclear whether or not gender differences exist. We therefore conducted this study to attain a better understanding of the Japanese male caregiver burden in home care, using data from the Nagoya Longitudinal Study of Frail Elderly (NLS-FE). Methods: NLS-FE is a large prospective study of community-dwelling elderly persons eligible for public long-term care insurance who live in Nagoya city and use the services of the Nagoya City Health Care Service Foundation for Older People, which comprises 17 visiting nursing stations and corresponding care-managing centers, from November to December 2003. Data used in this study included the Japanese version of the Zarit Caregiver Burden Interview, caregivers’ and dependents’ characteristics, and the caregiving situation. The differences in dependent and caregiver characteristics between male and female caregiver groups were assessed using the χ2-test for categorical variables or the unpaired t-test for continuous variables. Multiple logistic regression was used to examine the association between dependent and caregiver characteristics and caregiver burden. Results: A total of 399 male caregivers and 1193 female caregivers were included in our analysis. Before and after controlling baseline variables, we did not detect a difference between male and female caregivers with respect to caregiver burden. Conclusion: Our study suggests that differences in caregiver burden may not necessarily exist between male and female caregivers in Japan. [ABSTRACT FROM AUTHOR]

Background Little attention has been paid to the impact on caregivers who provide care to a family member who has falls. The purpose of the current study was to determine whether falls of care recipients are associated with caregivers' burden. Methods A cross-sectional study of 1874 community-dwelling care recipients and 1478 caregivers was conducted. We examined the characteristics of care recipients and caregivers, including demographic characteristics, depressive mood as assessed by the Geriatric Depression Scale (GDS-15), the basic activities of daily living (bADL), fall history in the past 6 months, and physician-diagnosed chronic diseases to determine whether there was an association with caregivers' burden as assessed by the Zarit Burden Interview (ZBI). Results A total of 567 care recipients (30.3%) had a history of falls in the past 6 months. The mean ZBI score of caregivers with falls was significantly higher than that of caregivers without falls. There were negative correlations between the ZBI score and recipient bADL score and positive correlations between the ZBI score and GDS-15 scores of the recipient and caregiver, the level of severity of dementia, and the Charlson comorbidity index. Male recipient, fall history, behavioral disturbance, and dementia had significantly higher ZBI scores than those of controls. The stepwise multiple regression analyses found that the GDS-15 score of caregivers and recipients, level of severity of dementia, bADL score, and fall history were independently associated with the ZBI score. Conclusion Among the community-dwelling frail elderly, falls are associated with caregiver burden even when controlling for various possible confounding factors. Copyright © 2006 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

OBJECTIVES: To test the following hypotheses: (1) the rate of polypharmacy, defined as six or more prescribing medications, is lower in the oldest old (≥85) than in younger older people (65–84); (2) beneficial medication use is lower in the oldest old; (3) the underuse of these medications in the oldest old is associated with physical or cognitive impairment or comorbid conditions. DESIGN: A cross-sectional study of the baseline data from the Nagoya Longitudinal Study for Frail Elderly. SETTING: Community-based. PARTICIPANTS: One thousand eight hundred seventy-five community-dwelling older people (632 men, 1,243 women). MEASUREMENTS: The data, which were collected at the patients' homes or from care-managing center records, included the clients' demographic characteristics, depression status as assessed using the short version of the Geriatric Depression Scale, a rating for basic activities of daily living (ADLs), prescribed medications, and physician-diagnosed chronic diseases. RESULTS: The oldest old had less polypharmacy even after controlling for ADLs and comorbid conditions. The underuse of beneficial medications for the oldest old was observed after adjusting for ADLs, cognitive impairment, comorbid conditions, antithrombotic agents for subjects with a history of cardiovascular diseases, acetylcholinesterase inhibitors for those with dementia, and antidepressants for those with depression. However, being aged 85 and older was not associated with the underuse of hypoglycemic and antihypertensive agents by those with diabetes mellitus and hypertension, respectively. CONCLUSION: Among community-dwelling frail older people, the rate of polypharmacy is lower in the oldest members than in the younger ones. The underuse of prescribed medications for chronic diseases/conditions of frail older people is common but not for all conditions. [ABSTRACT FROM AUTHOR]

Electronic mechanism of the reversible O2 binding by heme was studied by using Density Functional Theory calculations. The ground state of oxyheme was calculated to be open singlet state [Fe(S =1/2) + O2(S = 1/2)]. The potential energy surface for singlet state is associative, while that for triplet state is dissociative. Because the ground state of the O2+ deoxyheme system is triplet in the dissociation limit [Fe(S = 2) + O2(S = 1)], the O2 binding process requires relativistic spin-orbit interaction to accomplish the intersystem crossing from triplet to singlet states. Owing to the singlet-triplet crossing, the activation energies for both O2 binding and dissociation become moderate, and hence reversible. We also found that the deviation of the Fe atom from the porphyrin plane is also important reaction coordinate for O2 binding. The potential surface is associative/dissociative when the Fe atom locates in-plane/out-of-plane. © 2006 Wiley Periodicals, Inc. J Comput Chem 4: 426–433, 2006 [ABSTRACT FROM AUTHOR]

This paper discusses the virtual prostate needle biopsy system and the construction of the virtual prostate model, considering the actual distribution of prostate abnormalities. A needle biopsy simulation is performed for the constructed virtual prostate, and the actual biopsy procedure in the clinical situation is evaluated. The prostate needle biopsy is a histologic diagnosis procedure in which a sample is acquired from the prostate tissue by needle biopsy and is inspected under a microscope. In order to achieve reliable prostate needle biopsy, it is necessary to consider systematically and numerically the number of needles required, and their locations and insertion angles. For such a purpose, a system is developed in which a virtual prostate is constructed on a computer and the biopsy procedure is evaluated quantitatively by performing virtually the prostate needle biopsy. Furthermore, two different models are constructed, for the prostate with and without hypertrophy, based on the actual statistical distribution data for prostate abnormalities. Each model is partitioned into the peripheral zone and the transition zone. The constructed virtual prostate is input into the virtual needle biopsy simulation system, and three different systematic biopsy procedures actually used at clinical sites, and four different needle biopsy procedures, are experimentally evaluated. The experiments show that the insertion angle that maximizes the hit probability is not always the same as the insertion angle that maximizes cancer sample acquisition. It is evident that the proposed method can indicate a biopsy procedure which realizes a high hit probability with a small number of needles. © 2005 Wiley Periodicals, Inc. Syst Comp Jpn, 37(1): 93–104, 2006; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/scj.20181 [ABSTRACT FROM AUTHOR]

Recently, consumers have shown concern about the reliability of electricity to be served. For example, some consumers need electricity with a higher reliability via automation of manufacturing processes. On the other hand, some consumers need electricity at a cheaper price even if the reliability becomes a little worse. Under such circumstances, it is necessary that power suppliers evaluate the needs of every consumer precisely and propose the most desirable measures for meeting their requirements. This paper develops a tool to analyze the reliability for high-voltage supplied consumers quantitatively. Further, this paper presents a method for evaluating the outage cost of consumers to help them choose the most appropriate measures for maintaining reliability. The proposed method applies the fuzzy reasoning approach. The validity of the proposed method is ascertained through some numerical simulations. © 2005 Wiley Periodicals, Inc. Electr Eng Jpn, 153(3): 41–51, 2005; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/eej.20137 [ABSTRACT FROM AUTHOR]

This paper discusses evaluation of the concentration of stomach wall fold patterns by using abdominal X-ray CT images. It has been noted that most stomach cancers are accompanied by concentration of folds at the pathological site. Consequently, if the extent of concentration can be represented quantitatively on the basis of an image, it will help with quantitative diagnosis of stomach cancer and make it possible to reduce the labor of image reading. Evaluation of the concentration of stomach wall folds reduces to the problem of evaluating the concentration in a line figure on a curved surface. The paper proposes, as the first step, a new method of calculation of the concentration by combining the local projection of the curved surface figure and the conventional two-dimensional concentration index calculation. Then, using this method, a procedure for stomach cancer site detection from abdominal CT images is developed. The method is applied to two real cases of cancer accompanied by fold concentration, and it is verified that a high concentration index is obtained at the cancer site. The result is significant because it demonstrates for the first time the possibility of quantitative diagnosis of stomach cancer from three-dimensional CT images. © 2005 Wiley Periodicals, Inc. Electron Comm Jpn Pt 2, 88(9): 48–57, 2005; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/ecjb.20207 [ABSTRACT FROM AUTHOR]

This paper describes a method for detecting small nodules from 3D X-ray CT images, considering small nodules with CT values of at least -600 H.U. and diameters of at least 2 mm. The proposed method is largely composed of two stages. In the first stage, for the region obtained by the threshold processing, the shape feature parameters of the figure calculated from the distance values in the connected component are applied, and the initial nodule candidate regions are extracted by discriminating the nodule region and the vessel/bronchus region. In the second stage, a minimum directional difference filter in which the filter radius is adaptively adjusted according to the size of the initial nodule candidate region is applied in order to reduce the overextracted regions. The proposed method is applied to seven actual chest CT images (six pathological cases, including multiple nodules, and one normal case), and the result for 361 nodules with a CT value not less than -600 H.U. and diameter not less than 2 mm is that the number of overextracted regions per case is 7.4 on the average, when the detection rate is set as 71%. © 2005 Wiley Periodicals, Inc. Syst Comp Jpn, 36(9): 55–64, 2005; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/scj.20175 [ABSTRACT FROM AUTHOR]

The authors have proposed a Flexible, Reliable and Intelligent ENergy Delivery System (called “FRIENDS”), which is a new concept for a future power distribution system. One of the most important feature of FRIENDS is to be able to manage the reliability of power supply. In this paper, FRIENDS and a conventional distribution system are compared quantitatively as to supply reliability and cost through time sequential Monte Carlo simulation. © 2005 Wiley Periodicals, Inc. Electr Eng Jpn, 151(4): 25–35, 2005; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/eej.20053 [ABSTRACT FROM AUTHOR]

The amino-acid sequence of cytochrome c552 (PH c552) from a moderately thermophilic bacterium, Hydrogenophilus thermoluteolus, was more than 50% identical to that of cytochrome c from an extreme thermophile, Hydrogeno-bacter thermophilus (HT c552), and from a mesophile, Pseudomonas aeruginosa (PA c551). The PH c552 gene was overexpressed as a correctly processed holoprotein in the Escherichia coil periplasm. The overexpressed PH c552 has been crystallized by vapour diffusion from polyethylene glycol 4000 pH 6.5. The crystals belong to space group C2221, with unit-cell parameters a = 48.98, b = 57.99, c = 56.20 Å. The crystals diffract X-rays to around 2.1 Å resolution. [ABSTRACT FROM AUTHOR]

IMPRESS is an image processing expert system in which the objective of processing is presented in the form of a figure (called the sample figure), and the image processing procedure to extract the corresponding figure from the original image is automatically generated. The authors have already considered the case in which multiple pairs of the original image and the sample figure are input, and have developed a procedure consolidating function whereby a procedure that works effectively in common for all pairs is generated. However, when the procedure is consolidated from a small number of learning samples, there is a problem with the effectiveness of the procedure. Specifically, when the consolidated function is applied to the ensemble of samples, the performance is sometimes greatly degraded compared to that for the learning samples. Consequently, we propose the following method. The deviation of the average score for the learning samples from the average score for the ensemble is estimated in the probabilistic sense. Then, by specifying the range of procedure search, a procedure with high versatility is derived from a small number of samples. In this study, the method under consideration is applied to the problem of automatic procedure construction for a procedure for defect extraction from real LSI package surfaces. The effectiveness of the method is investigated by comparing the result to the conventional consolidation procedure. © 2004 Wiley Periodicals, Inc. Electron Comm Jpn Pt 2, 87(11): 49–62, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/ecjb.20128 [ABSTRACT FROM AUTHOR]