Redox Potential and C−H Bond Cleaving Properties of a Nonheme Fe^IVO Complex in Aqueous Solution

High-valent iron−oxo intermediates have been identified as the key oxidants in the catalytic cycles of many nonheme enzymes. Among the large number of synthetic FeIVO complexes characterized to date, [FeIV(O)(N4Py)]2+ (1) exhibits the unique combination of thermodynamic stability, allowing its structural characterization by X-ray crystallography, and oxidative reactivity sufficient to cleave C−H bonds as strong as those in cyclohexane (DC−H = 99.3 kcal mol−1). However, its redox properties are not yet well understood. In this work, the effect of protons on the redox properties of 1 has been investigated electrochemically in nonaqueous and aqueous solutions. While the cyclic voltammetry of 1 in CH3CN is complicated by coupling of several chemical and redox processes, the FeIV/III couple is reversible in aqueous solution with E1/2 = +0.41 V versus SCE at pH 4 and involves the transfer of one electron and one proton to give the FeIII−OH species. This is in fact the first example of reversible electrochemistry to be observed for this family of nonheme oxoiron (IV) complexes. C−H bond oxidations by 1 have been studied in H2O and found to have reaction rates that depend on the C−H bond strength but not on the solvent. Furthermore, our electrochemical results have allowed a DO−H value of 78(2) kcal mol−1 to be calculated for the FeIII−OH unit derived from 1. Interestingly, although this DO−H value is 6−11 kcal mol−1 lower than those corresponding to oxidants such as [FeIV(O)(TMP)] (TMP = tetramesitylporphinate), [RuIV(O)(bpy)2(py)]2+ (bpy = bipyridine, py = pyridine), and the tert-butylperoxyl radical, the oxidation of dihydroanthracene by 1 occurs at a rate comparable to rates for these other oxidants. This comparison suggests that the nonheme N4Py ligand environment confers a kinetic advantage over the others that enhances the C−H bond cleavage ability of 1

Table_1_Longitudinal analysis of ovarian cancer death patterns during a rapid transition period (2005-2020) in Shanghai, China: A population-based study.xlsx

ObjectivesIt is important to assess the burden of ovarian cancer related premature death so as to develop appropriate evidence-based care and improve women’s health. This study aimed to characterize the long-term trends in mortality, survival and disease burden of ovarian cancer in Shanghai, China.Materials and MethodsCo-morbidities, crude mortality rate (CMR), age-standardised mortality rate by Segi’s world standard population (ASMRW), years of life lost (YLL), and survival rates were analysed. Temporal trends for the mortality rates and disease burden were analyzed using the Joinpoint Regression Program. Mortality rate increases by demographic and non-demographic factors were estimated by the decomposition method.ResultsA total of 1088 ovarian cancer as underlying cause of deaths were recorded. CMR and ASMRW were 4.82/105 and 2.32/105 person-years, respectively. The YLL was 16372.96 years, and the YLL rate was 72.46/105 person-years. The YLL rate increased only in the age group of 70-79 years (P = 0.017). The survival rates of ovarian cancer patients did not improve during the ten year period (2005-2015). The top co-morbidities were diseases of the respiratory system, digestive system, and circulatory system. The rates of ovarian cancer deaths caused by non-demographic and demographic factors increased by 21.29% (95%CI: 4.01% to 41.44%, P = 0.018) and 25.23% (95%CI: 14.64% to 36.81%, P ConclusionsPopulation ageing and all cause of death may affect ovarian cancer related deaths in Pudong, Shanghai. The high mortality and the stagnant survival rates suggest the need for more efforts in targeted prevention and treatment of this disease.</p

Table_6_Longitudinal analysis of ovarian cancer death patterns during a rapid transition period (2005-2020) in Shanghai, China: A population-based study.xlsx

ObjectivesIt is important to assess the burden of ovarian cancer related premature death so as to develop appropriate evidence-based care and improve women’s health. This study aimed to characterize the long-term trends in mortality, survival and disease burden of ovarian cancer in Shanghai, China.Materials and MethodsCo-morbidities, crude mortality rate (CMR), age-standardised mortality rate by Segi’s world standard population (ASMRW), years of life lost (YLL), and survival rates were analysed. Temporal trends for the mortality rates and disease burden were analyzed using the Joinpoint Regression Program. Mortality rate increases by demographic and non-demographic factors were estimated by the decomposition method.ResultsA total of 1088 ovarian cancer as underlying cause of deaths were recorded. CMR and ASMRW were 4.82/105 and 2.32/105 person-years, respectively. The YLL was 16372.96 years, and the YLL rate was 72.46/105 person-years. The YLL rate increased only in the age group of 70-79 years (P = 0.017). The survival rates of ovarian cancer patients did not improve during the ten year period (2005-2015). The top co-morbidities were diseases of the respiratory system, digestive system, and circulatory system. The rates of ovarian cancer deaths caused by non-demographic and demographic factors increased by 21.29% (95%CI: 4.01% to 41.44%, P = 0.018) and 25.23% (95%CI: 14.64% to 36.81%, P ConclusionsPopulation ageing and all cause of death may affect ovarian cancer related deaths in Pudong, Shanghai. The high mortality and the stagnant survival rates suggest the need for more efforts in targeted prevention and treatment of this disease.</p

Table_3_Longitudinal analysis of ovarian cancer death patterns during a rapid transition period (2005-2020) in Shanghai, China: A population-based study.xlsx

ObjectivesIt is important to assess the burden of ovarian cancer related premature death so as to develop appropriate evidence-based care and improve women’s health. This study aimed to characterize the long-term trends in mortality, survival and disease burden of ovarian cancer in Shanghai, China.Materials and MethodsCo-morbidities, crude mortality rate (CMR), age-standardised mortality rate by Segi’s world standard population (ASMRW), years of life lost (YLL), and survival rates were analysed. Temporal trends for the mortality rates and disease burden were analyzed using the Joinpoint Regression Program. Mortality rate increases by demographic and non-demographic factors were estimated by the decomposition method.ResultsA total of 1088 ovarian cancer as underlying cause of deaths were recorded. CMR and ASMRW were 4.82/105 and 2.32/105 person-years, respectively. The YLL was 16372.96 years, and the YLL rate was 72.46/105 person-years. The YLL rate increased only in the age group of 70-79 years (P = 0.017). The survival rates of ovarian cancer patients did not improve during the ten year period (2005-2015). The top co-morbidities were diseases of the respiratory system, digestive system, and circulatory system. The rates of ovarian cancer deaths caused by non-demographic and demographic factors increased by 21.29% (95%CI: 4.01% to 41.44%, P = 0.018) and 25.23% (95%CI: 14.64% to 36.81%, P ConclusionsPopulation ageing and all cause of death may affect ovarian cancer related deaths in Pudong, Shanghai. The high mortality and the stagnant survival rates suggest the need for more efforts in targeted prevention and treatment of this disease.</p

Table_4_Longitudinal analysis of ovarian cancer death patterns during a rapid transition period (2005-2020) in Shanghai, China: A population-based study.xlsx

ObjectivesIt is important to assess the burden of ovarian cancer related premature death so as to develop appropriate evidence-based care and improve women’s health. This study aimed to characterize the long-term trends in mortality, survival and disease burden of ovarian cancer in Shanghai, China.Materials and MethodsCo-morbidities, crude mortality rate (CMR), age-standardised mortality rate by Segi’s world standard population (ASMRW), years of life lost (YLL), and survival rates were analysed. Temporal trends for the mortality rates and disease burden were analyzed using the Joinpoint Regression Program. Mortality rate increases by demographic and non-demographic factors were estimated by the decomposition method.ResultsA total of 1088 ovarian cancer as underlying cause of deaths were recorded. CMR and ASMRW were 4.82/105 and 2.32/105 person-years, respectively. The YLL was 16372.96 years, and the YLL rate was 72.46/105 person-years. The YLL rate increased only in the age group of 70-79 years (P = 0.017). The survival rates of ovarian cancer patients did not improve during the ten year period (2005-2015). The top co-morbidities were diseases of the respiratory system, digestive system, and circulatory system. The rates of ovarian cancer deaths caused by non-demographic and demographic factors increased by 21.29% (95%CI: 4.01% to 41.44%, P = 0.018) and 25.23% (95%CI: 14.64% to 36.81%, P ConclusionsPopulation ageing and all cause of death may affect ovarian cancer related deaths in Pudong, Shanghai. The high mortality and the stagnant survival rates suggest the need for more efforts in targeted prevention and treatment of this disease.</p

Table_2_Longitudinal analysis of ovarian cancer death patterns during a rapid transition period (2005-2020) in Shanghai, China: A population-based study.xlsx

ObjectivesIt is important to assess the burden of ovarian cancer related premature death so as to develop appropriate evidence-based care and improve women’s health. This study aimed to characterize the long-term trends in mortality, survival and disease burden of ovarian cancer in Shanghai, China.Materials and MethodsCo-morbidities, crude mortality rate (CMR), age-standardised mortality rate by Segi’s world standard population (ASMRW), years of life lost (YLL), and survival rates were analysed. Temporal trends for the mortality rates and disease burden were analyzed using the Joinpoint Regression Program. Mortality rate increases by demographic and non-demographic factors were estimated by the decomposition method.ResultsA total of 1088 ovarian cancer as underlying cause of deaths were recorded. CMR and ASMRW were 4.82/105 and 2.32/105 person-years, respectively. The YLL was 16372.96 years, and the YLL rate was 72.46/105 person-years. The YLL rate increased only in the age group of 70-79 years (P = 0.017). The survival rates of ovarian cancer patients did not improve during the ten year period (2005-2015). The top co-morbidities were diseases of the respiratory system, digestive system, and circulatory system. The rates of ovarian cancer deaths caused by non-demographic and demographic factors increased by 21.29% (95%CI: 4.01% to 41.44%, P = 0.018) and 25.23% (95%CI: 14.64% to 36.81%, P ConclusionsPopulation ageing and all cause of death may affect ovarian cancer related deaths in Pudong, Shanghai. The high mortality and the stagnant survival rates suggest the need for more efforts in targeted prevention and treatment of this disease.</p

Table_7_Longitudinal analysis of ovarian cancer death patterns during a rapid transition period (2005-2020) in Shanghai, China: A population-based study.xlsx

ObjectivesIt is important to assess the burden of ovarian cancer related premature death so as to develop appropriate evidence-based care and improve women’s health. This study aimed to characterize the long-term trends in mortality, survival and disease burden of ovarian cancer in Shanghai, China.Materials and MethodsCo-morbidities, crude mortality rate (CMR), age-standardised mortality rate by Segi’s world standard population (ASMRW), years of life lost (YLL), and survival rates were analysed. Temporal trends for the mortality rates and disease burden were analyzed using the Joinpoint Regression Program. Mortality rate increases by demographic and non-demographic factors were estimated by the decomposition method.ResultsA total of 1088 ovarian cancer as underlying cause of deaths were recorded. CMR and ASMRW were 4.82/105 and 2.32/105 person-years, respectively. The YLL was 16372.96 years, and the YLL rate was 72.46/105 person-years. The YLL rate increased only in the age group of 70-79 years (P = 0.017). The survival rates of ovarian cancer patients did not improve during the ten year period (2005-2015). The top co-morbidities were diseases of the respiratory system, digestive system, and circulatory system. The rates of ovarian cancer deaths caused by non-demographic and demographic factors increased by 21.29% (95%CI: 4.01% to 41.44%, P = 0.018) and 25.23% (95%CI: 14.64% to 36.81%, P ConclusionsPopulation ageing and all cause of death may affect ovarian cancer related deaths in Pudong, Shanghai. The high mortality and the stagnant survival rates suggest the need for more efforts in targeted prevention and treatment of this disease.</p

<i>GRMZM2G143588</i>, <i>GRMZM2G361659</i> and <i>GRMZM2G400784</i> qRT-PCR expression levels in the biparental mapping population.

GRMZM2G143588, GRMZM2G361659 and GRMZM2G400784 qRT-PCR expression levels in the biparental mapping population.</p

Recyclable Copper Indium Sulfide Quantum Dots for Photocatalytic Homocoupling of Arenediazonium Tetrafluoroborates

Copper indium sulfide quantum dots (QDs) were prepared by a solvothermal method and characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and energy-dispersive X-ray techniques. The as-prepared CuInS2 QDs display excellent photocatalytic activity in the visible-light-driven homocoupling of arenediazonium tetrafluoroborates at room temperature. Various symmetrical biaryls were obtained in γ-valerolactone (GVL) in good to excellent yields under mild reaction conditions. In addition, the photocatalyst, CuInS2 QDs, is stable in the catalytic process and can be recycled at least five times without significant losing of its catalytic efficiency

Table_5_Longitudinal analysis of ovarian cancer death patterns during a rapid transition period (2005-2020) in Shanghai, China: A population-based study.xlsx

ObjectivesIt is important to assess the burden of ovarian cancer related premature death so as to develop appropriate evidence-based care and improve women’s health. This study aimed to characterize the long-term trends in mortality, survival and disease burden of ovarian cancer in Shanghai, China.Materials and MethodsCo-morbidities, crude mortality rate (CMR), age-standardised mortality rate by Segi’s world standard population (ASMRW), years of life lost (YLL), and survival rates were analysed. Temporal trends for the mortality rates and disease burden were analyzed using the Joinpoint Regression Program. Mortality rate increases by demographic and non-demographic factors were estimated by the decomposition method.ResultsA total of 1088 ovarian cancer as underlying cause of deaths were recorded. CMR and ASMRW were 4.82/105 and 2.32/105 person-years, respectively. The YLL was 16372.96 years, and the YLL rate was 72.46/105 person-years. The YLL rate increased only in the age group of 70-79 years (P = 0.017). The survival rates of ovarian cancer patients did not improve during the ten year period (2005-2015). The top co-morbidities were diseases of the respiratory system, digestive system, and circulatory system. The rates of ovarian cancer deaths caused by non-demographic and demographic factors increased by 21.29% (95%CI: 4.01% to 41.44%, P = 0.018) and 25.23% (95%CI: 14.64% to 36.81%, P ConclusionsPopulation ageing and all cause of death may affect ovarian cancer related deaths in Pudong, Shanghai. The high mortality and the stagnant survival rates suggest the need for more efforts in targeted prevention and treatment of this disease.</p