Kinetics of Reductive N−O Bond Fragmentation:  The Role of a Conical Intersection

2002 ◽  
Vol 124 (51) ◽  
pp. 15225-15238 ◽  
Author(s):  
Edward D. Lorance ◽  
Wolfgang H. Kramer ◽  
Ian R. Gould
Keyword(s):  
Conical Intersection ◽  
Kinetics Of

Thermodynamic and Kinetic Investigation of the Solvent Effect on the Oxidation of [Co(en)2SCH2COO]+ with S2O82- In Water-Methanol and Water-tert-Butyl Alcohol Mixtures

1993 ◽  
Vol 58 (5) ◽  
pp. 1001-1006 ◽  
Author(s):  
Oľga Vollárová ◽  
Ján Benko
Keyword(s):  
Transfer Functions ◽  
Activation Parameters ◽  
Butyl Alcohol ◽  
Oxidation Of Co ◽  
Kinetics Of Oxidation ◽  
Tert Butyl ◽  
Tert Butyl Alcohol ◽  
Alcohol Mixtures ◽  
Kinetics Of

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.

scholarly journals Association between perinatal factors, genetic susceptibility to obesity and age at adiposity rebound in children of the EDEN mother–child cohort

2021 ◽  
Author(s):  
Aminata Hallimat Cissé ◽  
Sandrine Lioret ◽  
Blandine de Lauzon-Guillain ◽  
Anne Forhan ◽  
Ken K. Ong ◽  
...  
Keyword(s):  
Weight Gain ◽  
Genetic Susceptibility ◽  
Gestational Weight Gain ◽  
Gestational Age ◽  
Obesity Risk ◽  
Perinatal Factors ◽  
Gestational Weight ◽  
Adiposity Rebound ◽  
Kinetics Of

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.

scholarly journals Phosphorylation of GAPVD1 Is Regulated by the PER Complex and Linked to GAPVD1 Degradation

2021 ◽  
Vol 22 (7) ◽  
pp. 3787
Author(s):  
Hussam Ibrahim ◽  
Philipp Reus ◽  
Anna Katharina Mundorf ◽  
Anna-Lena Grothoff ◽  
Valerie Rudenko ◽  
...  
Keyword(s):  
Circadian Clock ◽  
Transcriptional Repression ◽  
Small Gtpase ◽  
Main Role ◽  
Interacting Proteins ◽  
Casein Kinase 1 ◽  
Bona Fide ◽  
Kinetics Of

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.

scholarly journals Halloysite nanotubes filled with salicylic acid and sodium diclofenac: effects of vacuum pumping on loading and release properties

2021 ◽  
Author(s):  
Lorenzo Lisuzzo ◽  
Giuseppe Cavallaro ◽  
Stefana Milioto ◽  
Giuseppe Lazzara
Keyword(s):  
Salicylic Acid ◽  
Release Kinetics ◽  
Halloysite Nanotubes ◽  
Drug Molecules ◽  
Sodium Diclofenac ◽  
Tunable Release ◽  
Feature Based ◽  
Kinetics Of ◽  
Filling Mechanism

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.

On the Role of Diffusion in the Oxidation of Fe, Ni, Co and the Fe-Sn Alloy by Calcium and Sodium Sulfates

2006 ◽  
Vol 258-260 ◽  
pp. 63-67
Author(s):  
V.M. Chumarev ◽  
V.P. Maryevich ◽  
V.A. Shashmurin
Keyword(s):  
Co Oxidation ◽  
Chemical Reaction ◽  
Diffusion Processes ◽  
Transport Processes ◽  
Diffusion Transport ◽  
Sodium Sulfates ◽  
Product Forms ◽  
Kinetics Of ◽  
Dominant Part

Diffusion processes play a dominant part in the macro kinetics of Fe, Ni and Co oxidation by calcium and sodium sulfates. Here, the reaction product forms a compact covering which spatially divides the reagents on the surface in the same way as in the oxidation and sulfidization of metals by oxygen and sulfur. Therefore, it is possible to assume in advance that interaction of metals with calcium and sodium sulfates will be determined not by the actual chemical reaction properly but by the diffusion transport processes.

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