Role of film history and observational timescale in redox switching kinetics of electroactive films. Part 2.—Visualizing electrochemical redox switching pathways involving four or more distinct relaxation times

1993 ◽  
Vol 89 (20) ◽  
pp. 3779-3782 ◽  
Author(s):  
A. Robert Hillman ◽  
Stanley Bruckenstein

1981 ◽  
Vol 59 (13) ◽  
pp. 1944-1953 ◽  
Author(s):  
Michael J. Weaver ◽  
H. Y. Liu ◽  
Yongjoo Kim

The electroreduction rates of Cr(OH2)63+ and Cr(NH3)63+ at the mercury–aqueous interface were monitored as a function of electrode potential in electrolytes containing univalent, divalent, or trivalent cations with systematically varying atomic number in order to scrutinize the role of the supporting electrolyte cation in the kinetics of these simple one-electron outer-sphere electrode reactions. The comparison between the corresponding rate responses for Cr(OH2)63+ and Cr(NH3)63+ reduction brought about by changing the supporting electrolyte cation is expected to provide information on the influence of the cation upon the potential profile in the double layer; despite the close structural and mechanistic similarity of the reactants, the transition state for the latter reaction appears to lie significantly closer to the electrode than that for the former process. The virtues of comparing rate responses at a constant electrode charge density rather than at a constant electrode potential are pointed out. It was found that the variations in the effective average potential at constant charge [Formula: see text]ding changes in the electrode potential [Formula: see text] derived from thermodynamic double-layer measurements. These results, along with the observed variations in the transfer coefficients for the two reactions, are semiquantitatively consistent with a model involving changes in the position of the oHp as the supporting electrolyte cation is altered, but are inconsistent with a model attributing the rate variations to cation specific adsorption.







1993 ◽  
Vol 58 (5) ◽  
pp. 1001-1006 ◽  
Author(s):  
Oľga Vollárová ◽  
Ján Benko

The kinetics of oxidation of [Co(en)2SCH2COO]+ with S2O82- was studied in water-methanol and water-tert-butyl alcohol mixtures. Changes in the reaction activation parameters ∆H≠ and ∆S≠ with varying concentration of the co-solvent depend on the kind of the latter, which points to a significant role of salvation effects. The solvation effect on the reaction is discussed based on a comparison of the transfer functions ∆Ht0, ∆St0 and ∆Gt0 for the initial and transition states with the changes in the activation parameters accompanying changes in the CO-solvent concentration. The transfer enthalpies of the reactant were obtained from calorimetric measurements.



Author(s):  
Aminata Hallimat Cissé ◽  
Sandrine Lioret ◽  
Blandine de Lauzon-Guillain ◽  
Anne Forhan ◽  
Ken K. Ong ◽  
...  

Abstract Background Early adiposity rebound (AR) has been associated with increased risk of overweight or obesity in adulthood. However, little is known about early predictors of age at AR. We aimed to study the role of perinatal factors and genetic susceptibility to obesity in the kinetics of AR. Methods Body mass index (BMI) curves were modelled by using mixed-effects cubic models, and age at AR was estimated for 1415 children of the EDEN mother–child cohort study. A combined obesity risk-allele score was calculated from genotypes for 27 variants identified by genome-wide association studies of adult BMI. Perinatal factors of interest were maternal age at delivery, parental education, parental BMI, gestational weight gain, maternal smoking during pregnancy, and newborn characteristics (sex, prematurity, and birth weight). We used a hierarchical level approach with multivariable linear regression model to investigate the association between these factors, obesity risk-allele score, and age at AR. Results A higher genetic susceptibility to obesity score was associated with an earlier age at AR. At the most distal level of the hierarchical model, maternal and paternal educational levels were positively associated with age at AR. Children born to parents with higher BMI were more likely to exhibit earlier age at AR. In addition, higher gestational weight gain was related to earlier age at AR. For children born small for gestational age, the average age at AR was 88 [±39] days lower than for children born appropriate for gestational age and 91 [±56] days lower than for children born large for gestational age. Conclusion The timing of AR seems to be an early childhood manifestation of the genetic susceptibility to adult obesity. We further identified low birth weight and gestational weight gain as novel predictors of early AR, highlighting the role of the intrauterine environment in the kinetics of adiposity.



2021 ◽  
Vol 22 (7) ◽  
pp. 3787
Author(s):  
Hussam Ibrahim ◽  
Philipp Reus ◽  
Anna Katharina Mundorf ◽  
Anna-Lena Grothoff ◽  
Valerie Rudenko ◽  
...  

Repressor protein period (PER) complexes play a central role in the molecular oscillator mechanism of the mammalian circadian clock. While the main role of nuclear PER complexes is transcriptional repression, much less is known about the functions of cytoplasmic PER complexes. We found with a biochemical screen for PER2-interacting proteins that the small GTPase regulator GTPase-activating protein and VPS9 domain-containing protein 1 (GAPVD1), which has been identified previously as a component of cytoplasmic PER complexes in mice, is also a bona fide component of human PER complexes. We show that in situ GAPVD1 is closely associated with casein kinase 1 delta (CSNK1D), a kinase that regulates PER2 levels through a phosphoswitch mechanism, and that CSNK1D regulates the phosphorylation of GAPVD1. Moreover, phosphorylation determines the kinetics of GAPVD1 degradation and is controlled by PER2 and a C-terminal autoinhibitory domain in CSNK1D, indicating that the regulation of GAPVD1 phosphorylation is a novel function of cytoplasmic PER complexes and might be part of the oscillator mechanism or an output function of the circadian clock.



Author(s):  
Lorenzo Lisuzzo ◽  
Giuseppe Cavallaro ◽  
Stefana Milioto ◽  
Giuseppe Lazzara

AbstractIn this work, we investigated the effects of the vacuum pumping on both the loading efficiencies and the release kinetics of halloysite nanotubes filled with drug molecules dissolved in ethanol. As model drugs, salicylic acid and sodium diclofenac were selected. For comparison, the loading of the drug molecules was conducted on platy kaolinite to explore the key role of the hollow tubular morphology on the filling mechanism of halloysite. The effects of the pressure conditions used in the loading protocol were interpreted and discussed on the basis of the thermodynamic results provided by Knudsen thermogravimetry, which demonstrated the ethanol confinement inside the halloysite cavity. Several techniques (TEM, FTIR spectroscopy, DLS and $$\zeta$$ ζ -potential experiments) were employed to characterize the drug filled nanoclays. Besides, release kinetics of the drugs were studied and interpreted according to the loading mechanism. This work represents a further step for the development of nanotubular carriers with tunable release feature based on the loading protocol and drug localization into the carrier. Graphic abstract The filling efficiency of halloysite nanotubes is enhanced by the reduction of the pressure conditions used in the loading protocol.



1980 ◽  
Vol 255 (1) ◽  
pp. 225-229
Author(s):  
D.J. Goss ◽  
L.J. Parkhurst ◽  
A.J. Wahba


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