The photocatalytic water oxidation to evolve O 2 was performed by photoirradiation (l > 420 nm) of an aqueous solution containing [Ru(bpy) 3 ] 2+ (bpy ¼ 2,2 0 -bipyridine), Na 2 S 2 O 8 and water-soluble cobalt complexes with various organic ligands as precatalysts in the pH range of 6.0-10. The turnover numbers (TONs) based on the amount of Co for the photocatalytic O 2 evolution with [Co II (Me 6 tren)(OH 2 )] 2+ (1) and [Co III (Cp * )(bpy)(OH 2 )] 2+ (2) [Me 6 tren ¼ tris(N,N 0 -dimethylaminoethyl) amine, Cp * ¼ h 5 -pentamethylcyclopentadienyl] at pH 9.0 reached 420 and 320, respectively. The evolved O 2 yield increased in proportion to concentrations of precatalysts 1 and 2 up to 0.10 mM. However, the O 2 yield dramatically decreased when the concentration of precatalysts 1 and 2 exceeded 0.10 mM. When the concentration of Na 2 S 2 O 8 was increased from 10 mM to 50 mM, CO 2 evolution was observed during the photocatalytic water oxidation. These results indicate that a part of the organic ligands of 1 and 2 were oxidized to evolve CO 2 during the photocatalytic reaction. The degradation of complex 2 under photocatalytic conditions and the oxidation of Me 6 tren ligand of 1 by [Ru(bpy) 3 ] 3+ were confirmed by 1 H NMR measurements. Dynamic light scattering (DLS) experiments indicate the formation of particles with diameters of around 20 AE 10 nm and 200 AE 100 nm during the photocatalytic water oxidation with 1 and 2, respectively. The particle sizes determined by DLS agreed with those of the secondary particles observed by TEM. The XPS measurements of the formed particles suggest that the surface of the particles is covered with cobalt hydroxides, which could be converted to active species containing high-valent cobalt ions during the photocatalytic water oxidation. The recovered nanoparticles produced from 1 act as a robust catalyst for the photocatalytic water oxidation.

Oxidative C-H bond cleavage of toluene derivatives and sulfoxidation of thioanisole derivatives by a nonheme iron(IV)-oxo complex, [(N4Py)Fe(IV)(O)](2+) (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine), were remarkably enhanced by the presence of triflic acid (HOTf) and Sc(OTf)3 in acetonitrile at 298 K. All the logarithms of the observed second-order rate constants of both the oxidative C-H bond cleavage and sulfoxidation reactions exhibit remarkably unified correlations with the driving forces of proton-coupled electron transfer (PCET) and metal ion-coupled electron transfer (MCET) in light of the Marcus theory of electron transfer when the differences in the formation constants of precursor complexes between PCET and MCET were taken into account, respectively. Thus, the mechanisms of both the oxidative C-H bond cleavage of toluene derivatives and sulfoxidation of thioanisole derivatives by [(N4Py)Fe(IV)(O)](2+) in the presence of HOTf and Sc(OTf)3 have been unified as the rate-determining electron transfer, which is coupled with binding of [(N4Py)Fe(IV)(O)](2+) by proton (PCET) and Sc(OTf)3 (MCET). There was no deuterium kinetic isotope effect (KIE) on the oxidative C-H bond cleavage of toluene via the PCET pathway, whereas a large KIE value was observed with Sc(OTf)3, which exhibited no acceleration of the oxidative C-H bond cleavage of toluene. When HOTf was replaced by DOTf, an inverse KIE (0.4) was observed for PCET from both toluene and [Ru(II)(bpy)3](2+) (bpy =2,2'-bipyridine) to [(N4Py)Fe(IV)(O)](2+). The PCET and MCET reactivities of [(N4Py)Fe(IV)(O)](2+) with Brønsted acids and various metal triflates have also been unified as a single correlation with a quantitative measure of the Lewis acidity.

The reactivity of a nonheme iron(IV)-oxo complex, [(N4Py)Fe(IV)(O)](2+) (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine), was markedly enhanced by perchloric acid (70% HClO4) in the oxidation of toluene derivatives. Toluene, which has a high one-electron oxidation potential (Eox = 2.20 V vs SCE), was oxidized by [(N4Py)Fe(IV)(O)](2+) in the presence of HClO4 in acetonitrile (MeCN) to yield a stoichiometric amount of benzyl alcohol, in which [(N4Py)Fe(IV)(O)](2+) was reduced to [(N4Py)Fe(III)(OH2)](3+). The second-order rate constant (kobs) of the oxidation of toluene derivatives by [(N4Py)Fe(IV)(O)](2+) increased with increasing concentration of HClO4, showing the first-order dependence on [HClO4]. A significant kinetic isotope effect (KIE) was observed when mesitylene was replaced by mesitylene-d12 in the oxidation with [(N4Py)Fe(IV)(O)](2+) in the absence of HClO4 in MeCN at 298 K. The KIE value drastically decreased from KIE = 31 in the absence of HClO4 to KIE = 1.0 with increasing concentration of HClO4, accompanied by the large acceleration of the oxidation rate. The absence of KIE suggests that electron transfer from a toluene derivative to the protonated iron(IV)-oxo complex ([(N4Py)Fe(IV)(OH)](3+)) is the rate-determining step in the acid-promoted oxidation reaction. The detailed kinetic analysis in light of the Marcus theory of electron transfer has revealed that the acid-promoted C-H bond cleavage proceeds via the rate-determining electron transfer from toluene derivatives to [(N4Py)Fe(IV)(OH)](3+) through formation of strong precursor complexes between toluene derivatives and [(N4Py)Fe(IV)(OH)](3+).

ObjectivesIntensified competitiveness in the healthcare industry has increased the number of healthcare centers and propelled the introduction of customer relationship management (CRM) systems to meet diverse customer demands. This study aimed to develop the information system success model of the CRM system by investigating previously proposed indicators within the model.MethodsThe evaluation areas of the CRM system includes three areas: the system characteristics area (system quality, information quality, and service quality), the user area (perceived usefulness and user satisfaction), and the performance area (personal performance and organizational performance). Detailed evaluation criteria of the three areas were developed, and its validity was verified by a survey administered to CRM system users in 13 nationwide health promotion centers. The survey data were analyzed by the structural equation modeling method, and the results confirmed that the model is feasible.ResultsInformation quality and service quality showed a statistically significant relationship with perceived usefulness and user satisfaction. Consequently, the perceived usefulness and user satisfaction had significant influence on individual performance as well as an indirect influence on organizational performance.ConclusionsThis study extends the research area on information success from general information systems to CRM systems in health promotion centers applying a previous information success model. This lays a foundation for evaluating health promotion center systems and provides a useful guide for successful implementation of hospital CRM systems.

The rate of oxidation of 2,5-dimethoxybenzyl alcohol (2,5-(MeO)(2)C(6)H(3)CH(2)OH) by [Fe(IV)(O)(N4Py)](2+) (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) was enhanced significantly in the presence of Sc(OTf)(3) (OTf(-) = trifluoromethanesulfonate) in acetonitrile (e.g., 120-fold acceleration in the presence of Sc(3+)). Such a remarkable enhancement of the reactivity of [Fe(IV)(O)(N4Py)](2+) in the presence of Sc(3+) was accompanied by the disappearance of a kinetic deuterium isotope effect. The radical cation of 2,5-(MeO)(2)C(6)H(3)CH(2)OH was detected in the course of the reaction in the presence of Sc(3+). The dimerized alcohol and aldehyde were also produced in addition to the monomer aldehyde in the presence of Sc(3+). These results indicate that the reaction mechanism is changed from one-step hydrogen atom transfer (HAT) from 2,5-(MeO)(2)C(6)H(3)CH(2)OH to [Fe(IV)(O)(N4Py)](2+) in the absence of Sc(3+) to stepwise Sc(3+)-coupled electron transfer, followed by proton transfer in the presence of Sc(3+). In contrast, neither acceleration of the rate nor the disappearance of the kinetic deuterium isotope effect was observed in the oxidation of benzyl alcohol (C(6)H(5)CH(2)OH) by [Fe(IV)(O)(N4Py)](2+) in the presence of Sc(OTf)(3). Moreover, the rate constants determined in the oxidation of various benzyl alcohol derivatives by [Fe(IV)(O)(N4Py)](2+) in the presence of Sc(OTf)(3) (10 mM) were compared with those of Sc(3+)-coupled electron transfer from one-electron reductants to [Fe(IV)(O)(N4Py)](2+) at the same driving force of electron transfer. This comparison revealed that the borderline of the change in the mechanism from HAT to stepwise Sc(3+)-coupled electron transfer and proton transfer is dependent on the one-electron oxidation potential of benzyl alcohol derivatives (ca. 1.7 V vs SCE).

Oxidative dimerization of N,N-dimethylaniline (DMA) occurs with a nonheme iron(IV)-oxo complex, [Fe(IV)(O)(N4Py)](2+) (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine), to yield the corresponding dimer, tetramethylbenzidine (TMB), in acetonitrile. The rate of the oxidative dimerization of DMA by [Fe(IV)(O)(N4Py)](2+) is markedly enhanced by the presence of scandium triflate, Sc(OTf)(3) (OTf = CF(3)SO(3)(-)), when TMB is further oxidized to the radical cation (TMB(•+)). In contrast, we have observed the oxidative N-demethylation with para-substituted DMA substrates, since the position of the C-C bond formation to yield the dimer is blocked. The rate of the oxidative N-demethylation of para-substituted DMA by [Fe(IV)(O)(N4Py)](2+) is also markedly enhanced by the presence of Sc(OTf)(3). In the case of para-substituted DMA derivatives with electron-donating substituents, radical cations of DMA derivatives are initially formed by Sc(3+) ion-coupled electron transfer from DMA derivatives to [Fe(IV)(O)(N4Py)](2+), giving demethylated products. Binding of Sc(3+) to [Fe(IV)(O)(N4Py)](2+) enhances the Sc(3+) ion-coupled electron transfer from DMA derivatives to [Fe(IV)(O)(N4Py)](2+), whereas binding of Sc(3+) to DMA derivatives retards the electron-transfer reaction. The complicated kinetics of the Sc(3+) ion-coupled electron transfer from DMA derivatives to [Fe(IV)(O)(N4Py)](2+) are analyzed by competition between binding of Sc(3+) to DMA derivatives and to [Fe(IV)(O)(N4Py)](2+). The binding constants of Sc(3+) to DMA derivatives increase with the increase of the electron-donating ability of the para-substituent. The rate constants of Sc(3+) ion-coupled electron transfer from DMA derivatives to [Fe(IV)(O)(N4Py)](2+), which are estimated from the binding constants of Sc(3+) to DMA derivatives, agree well with those predicted from the driving force dependence of the rate constants of Sc(3+) ion-coupled electron transfer from one-electron reductants to [Fe(IV)(O)(N4Py)](2+). Thus, oxidative dimerization of DMA and N-demethylation of para-substituted DMA derivatives proceed via Sc(3+) ion-coupled electron transfer from DMA derivatives to [Fe(IV)(O)(N4Py)](2+).

Background Nonalcoholic fatty liver disease (NAFLD) is a hepatic manifestation of metabolic disease and independently affects the development of cardiovascular (CV) disease. We investigated whether hepatic steatosis and/or fibrosis are associated with the development of incident heart failure (iHF), hospitalized HF (hHF), mortality, and CV death in both the general population and HF patients. Methods We analyzed 778,739 individuals without HF and 7445 patients with pre-existing HF aged 40 to 80 years who underwent a national health check-up from January 2009 to December 2012. The presence of hepatic steatosis and advanced hepatic fibrosis was determined using cutoff values for fatty liver index (FLI) and BARD score. We evaluated the association of FLI or BARD score with the development of iHF, hHF, mortality and CV death using multivariable-adjusted Cox regression models. Results A total of 28,524 (3.7%) individuals in the general population and 1422 (19.1%) pre-existing HF patients developed iHF and hHF respectively. In the multivariable-adjusted model, participants with an FLI ≥ 60 were at increased risk for iHF (hazard ratio [HR], 95% confidence interval [CI], 1.30, 1.24–1.36), hHF (HR 1.54, 95% CI 1.44–1.66), all-cause mortality (HR 1.62, 95% CI 1.54–1.70), and CV mortality (HR 1.41 95% CI 1.22–1.63) in the general population and hHF (HR 1.26, 95% CI 1.21–1.54) and all-cause mortality (HR 1.54 95% CI 1.24–1.92) in the HF patient group compared with an FLI < 20. Among participants with NAFLD, advanced liver fibrosis was associated with increased risk for iHF, hHF, and all-cause mortality in the general population and all-cause mortality and CV mortality in the HF patient group (all p < 0.05). Conclusion Hepatic steatosis and/or advanced fibrosis as assessed by FLI and BARD score was significantly associated with the risk of HF and mortality.

In order to detect microRNAs (miRNAs), we developed a colorimetric sensing method on the basis of the plasmonic coupling effect. Gold nanoplasmonic particles (GNPs) are assembled in a core-satellite configuration in the presence of target miRNA, inducing remarkable changes in the scattering color and spectra at the picomolar level with selectivity.