© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.The development of batteries and fuel cells has brought to light a need for carbon anode materials doped homogeneously with electrocatalytic metals. In particular, combinations of electrocatalysts in carbon have shown promising activity. A method to derive functional carbon materials is from pyrolysis of metallopolymers. This work describes the synthesis of a bi-functional phosphonium-based system derived from a phosphane-ene network. The olefin functionality can be leveraged in a hydrogermylation reaction to functionalize the material with Ge. Unaffected by this radical addition, the bromide counterion of phosphonium cation can be used to subsequently incorporate a second metal in an ion complexation reaction with CuBr2. The characterization of the polymers and the derived ceramics are discussed. © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.Silver nanowires (AgNWs) have been extensively studied as a kind of promising nanomaterials in optics, next generation flexible electronics, and energy-related fields, but the stability and the properties from single nanowire level are still needed to be investigated carefully. In this contribution, single palladium@silver nanowire electrodes (Pd@AgNWEs) were successfully prepared by using laser-assisted pulling method and followed by galvanic replacement reaction (GRR). Results show that the chemical stability of AgNWs can be improved greatly through coating a small amount of Pd, and the Pd@AgNWEs exhibit superior electrocatalytic performance towards methanol oxidation reaction. This work can give us a new insight to investigate the performance of devices/catalysts at single particle/nanowire level, which will benefit the research in flexible electronics and energy-related fields. © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.OBJECTIVES The objective of the study was to determine whether exposure of pregnant women to stresses caused by World War II (WWII) negatively affected pregnancy and perinatal outcomes. METHODS Individual medical documents deposited in the Gynaecology and Obstetrics Clinic of Medical University, Poznań (1934-1943; N = 7058) were evaluated. These were divided into two birth cohorts before WWII and during it. Frequency tables were constructed for the numbers of pregnancy outcomes miscarriages, stillbirths, live births, and neonatal deaths, according to the period of birth and sex of a child. The numbers of recorded days were standardized and the numbers of cases per day were computed. https://www.selleckchem.com/products/fadraciclib.html Statistical differences in the averages (medians) between periods and years under study were tested. Birth weight, length, and body mass index (BMI) were compared according to the periods related to WWII. RESULTS Significant differences in proportions of males, females, and subjects with unknown sex were found between the periods a higher proportion of males and different structure of/within negative outcomes were found during WWII. Children born during WWII were heavier and longer than those born before it. CONCLUSIONS As an explanation, adverse conditions of WWII, related to the psychological stress and food shortages, could have influenced greater elimination of fetuses and neonates of male sex during pregnancy and shortly after delivery. Higher average body size in newborns recorded during WWI could be explained by a hidden process of increased early prenatal mortality of weaker individuals, differences in average gestation length between the periods, differences in parity, or some undocumented differences in social/ethnic composition of the sample. © 2020 Wiley Periodicals, Inc.The Cope rearrangement of selectively deuterated isotopomers of 1,5-dimethylsemibullvalene 2a and 3,7-dicyano-1,5-dimethyl-semibullvalene 2b were studied in cryogenic matrices. In both semibullvalenes the Cope rearrangement is governed by heavy atom tunneling (HAT). The driving force for the rearrangements is the small difference in the zero-point vibrational energies of the isotopomers. To evaluate the effect of the driving force on the tunneling probability in 2a and 2b, two different pairs of isotopomers were studied for each of the semibullvalenes. The reaction rates for the rearrangement of 2b in cryogenic matrices were found to be smaller than the ones of 2a under similar conditions, whereas differences in the driving force do not influence the rates. Small curvature tunneling (SCT) calculations suggest that the reduced tunneling rate of 2b compared to that of 2a results from a change in the shape of the potential energy barrier. The tunneling probability of the semibullvalenes strongly depends on the matrix environment, however, for 2a in a qualitatively different way than for 2b. © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.Liver inflammation is a common extraintestinal manifestation in inflammatory bowel disease (IBD), yet, the mechanisms driving gut-liver axis inflammation remain poorly understood. IBD leads to a breakdown in the integrity of the intestinal barrier causing an increase in portal and systemic gut-derived antigens, which challenge the liver. Here, we examined the role of platelet activating factor receptor (PAFR) in colitis-associated liver damage using dextran sulfate sodium (DSS) and anti-CD40-induced colitis models. Both DSS and anti-CD40 models exhibited liver inflammation associated with colitis. Colitis reduced global PAFR protein expression in mouse livers causing an exclusive re-localization of PAFR to the portal triad. The global decrease in liver PAFR was associated with increased sirtuin 1 while relocalized PAFR expression was limited to Kupffer cells (KCs) and co-localized with toll-like receptor 4. DSS activated the NLRP3-inflammasome and increased interleukin (IL)-1β in the liver. Antagonism of PAFR amplified the inflammasome response by increasing NLRP3, caspase-1, and IL-1β protein levels in the liver. LPS also increased NLRP3 response in human hepatocytes, however, overexpression of PAFR restored the levels of NLPR3 and caspase-1 proteins. Interestingly, KCs depletion also increased IL-1β protein in mouse liver after DSS challenge. These data suggest a protective role for PAFR-expressing KCs during colitis and that regulation of PAFR is important for gut-liver axis homeostasis. © 2020 Federation of American Societies for Experimental Biology.
© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.The development of batteries and fuel cells has brought to light a need for carbon anode materials doped homogeneously with electrocatalytic metals. In particular, combinations of electrocatalysts in carbon have shown promising activity. A method to derive functional carbon materials is from pyrolysis of metallopolymers. This work describes the synthesis of a bi-functional phosphonium-based system derived from a phosphane-ene network. The olefin functionality can be leveraged in a hydrogermylation reaction to functionalize the material with Ge. Unaffected by this radical addition, the bromide counterion of phosphonium cation can be used to subsequently incorporate a second metal in an ion complexation reaction with CuBr2. The characterization of the polymers and the derived ceramics are discussed. © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.Silver nanowires (AgNWs) have been extensively studied as a kind of promising nanomaterials in optics, next generation flexible electronics, and energy-related fields, but the stability and the properties from single nanowire level are still needed to be investigated carefully. In this contribution, single palladium@silver nanowire electrodes (Pd@AgNWEs) were successfully prepared by using laser-assisted pulling method and followed by galvanic replacement reaction (GRR). Results show that the chemical stability of AgNWs can be improved greatly through coating a small amount of Pd, and the Pd@AgNWEs exhibit superior electrocatalytic performance towards methanol oxidation reaction. This work can give us a new insight to investigate the performance of devices/catalysts at single particle/nanowire level, which will benefit the research in flexible electronics and energy-related fields. © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.OBJECTIVES The objective of the study was to determine whether exposure of pregnant women to stresses caused by World War II (WWII) negatively affected pregnancy and perinatal outcomes. METHODS Individual medical documents deposited in the Gynaecology and Obstetrics Clinic of Medical University, Poznań (1934-1943; N = 7058) were evaluated. These were divided into two birth cohorts before WWII and during it. Frequency tables were constructed for the numbers of pregnancy outcomes miscarriages, stillbirths, live births, and neonatal deaths, according to the period of birth and sex of a child. The numbers of recorded days were standardized and the numbers of cases per day were computed. https://www.selleckchem.com/products/fadraciclib.html Statistical differences in the averages (medians) between periods and years under study were tested. Birth weight, length, and body mass index (BMI) were compared according to the periods related to WWII. RESULTS Significant differences in proportions of males, females, and subjects with unknown sex were found between the periods a higher proportion of males and different structure of/within negative outcomes were found during WWII. Children born during WWII were heavier and longer than those born before it. CONCLUSIONS As an explanation, adverse conditions of WWII, related to the psychological stress and food shortages, could have influenced greater elimination of fetuses and neonates of male sex during pregnancy and shortly after delivery. Higher average body size in newborns recorded during WWI could be explained by a hidden process of increased early prenatal mortality of weaker individuals, differences in average gestation length between the periods, differences in parity, or some undocumented differences in social/ethnic composition of the sample. © 2020 Wiley Periodicals, Inc.The Cope rearrangement of selectively deuterated isotopomers of 1,5-dimethylsemibullvalene 2a and 3,7-dicyano-1,5-dimethyl-semibullvalene 2b were studied in cryogenic matrices. In both semibullvalenes the Cope rearrangement is governed by heavy atom tunneling (HAT). The driving force for the rearrangements is the small difference in the zero-point vibrational energies of the isotopomers. To evaluate the effect of the driving force on the tunneling probability in 2a and 2b, two different pairs of isotopomers were studied for each of the semibullvalenes. The reaction rates for the rearrangement of 2b in cryogenic matrices were found to be smaller than the ones of 2a under similar conditions, whereas differences in the driving force do not influence the rates. Small curvature tunneling (SCT) calculations suggest that the reduced tunneling rate of 2b compared to that of 2a results from a change in the shape of the potential energy barrier. The tunneling probability of the semibullvalenes strongly depends on the matrix environment, however, for 2a in a qualitatively different way than for 2b. © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.Liver inflammation is a common extraintestinal manifestation in inflammatory bowel disease (IBD), yet, the mechanisms driving gut-liver axis inflammation remain poorly understood. IBD leads to a breakdown in the integrity of the intestinal barrier causing an increase in portal and systemic gut-derived antigens, which challenge the liver. Here, we examined the role of platelet activating factor receptor (PAFR) in colitis-associated liver damage using dextran sulfate sodium (DSS) and anti-CD40-induced colitis models. Both DSS and anti-CD40 models exhibited liver inflammation associated with colitis. Colitis reduced global PAFR protein expression in mouse livers causing an exclusive re-localization of PAFR to the portal triad. The global decrease in liver PAFR was associated with increased sirtuin 1 while relocalized PAFR expression was limited to Kupffer cells (KCs) and co-localized with toll-like receptor 4. DSS activated the NLRP3-inflammasome and increased interleukin (IL)-1β in the liver. Antagonism of PAFR amplified the inflammasome response by increasing NLRP3, caspase-1, and IL-1β protein levels in the liver. LPS also increased NLRP3 response in human hepatocytes, however, overexpression of PAFR restored the levels of NLPR3 and caspase-1 proteins. Interestingly, KCs depletion also increased IL-1β protein in mouse liver after DSS challenge. These data suggest a protective role for PAFR-expressing KCs during colitis and that regulation of PAFR is important for gut-liver axis homeostasis. © 2020 Federation of American Societies for Experimental Biology.
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