scholarly journals A Generalized Kinetic Model for Compartmentalization of Organometallic Catalysis

2021 ◽  
Author(s):  
Brandon Jolly ◽  
Chong Liu
Keyword(s):  
Kinetic Model ◽  
Organometallic Chemistry ◽  
Catalytic Performance ◽  
Side Reactions ◽  
Turnover Frequency ◽  
Organometallic Catalysis ◽  
Optimal Values ◽  
Generalized Kinetic Model ◽  
Design Guidance ◽  
Key Parameter

Compartmentalization is an attractive approach to enhance catalytic activity by retaining reactive intermediates and mitigating deactivating pathways. Such a concept has been well explored in biochemical and more recently, organometallic catalysis to ensure high reaction turnovers with minimal side reactions. However, a scarcity of theoretical framework towards confined organometallic chemistry impedes a broader utility for the implementation of compartmentalization. Herein, we report a general kinetic model and offer design guidance for a compartmentalized organometallic catalytic cycle. In comparison to a non-compartmentalized catalysis, compartmentalization is quantitatively shown to prevent the unwanted intermediate deactivation, boost the corresponding reaction efficiency (𝛾), and subsequently increase catalytic turnover frequency (𝑇𝑂𝐹). The key parameter in the model is the volumetric diffusive conductance (𝐹 ) that describes catalysts’ diffusion propensity across a compartment’s boundary. Optimal values of 𝐹 for a specific organometallic chemistry are needed to achieve maximal values of 𝛾 and 𝑇𝑂𝐹. Our model suggests a tailored compartment design, including the use of nanomaterials, is needed to suit a specific organometallic catalysis. This work provides justification and design principles for further exploration into compartmentalizing organometallics to enhance catalytic performance.

scholarly journals A Generalized Kinetic Model for Compartmentalization of Organometallic Catalysis

2021 ◽  
Author(s):  
Brandon Jolly ◽  
Nathalie Co ◽  
Ashton Davis ◽  
Paula Diaconescu ◽  
Chong Liu
Keyword(s):  
Kinetic Model ◽  
Organometallic Chemistry ◽  
Catalytic Performance ◽  
Catalytic Cycle ◽  
Side Reactions ◽  
Catalytic Systems ◽  
Organometallic Catalysis ◽  
Proper Design ◽  
Generalized Kinetic Model ◽  
Design Guidance

Compartmentalization is an attractive approach to enhance catalytic activity by retaining reactive intermediates and mitigating deactivating pathways. Such a concept has been well explored in biochemical and more recently, organometallic catalysis to ensure high reaction turnovers with minimal side reactions. However, a scarcity of theoretical framework towards confined organometallic chemistry impedes a broader utility for the implementation of compartmentalization. Herein, we report a general kinetic model and offer design guidance for a compartmentalized organometallic catalytic cycle. In comparison to a non-compartmentalized catalysis, compartmentalization is quantitatively shown to prevent the unwanted intermediate deactivation, boost the corresponding reaction efficiency (γ), and subsequently increase catalytic turnover frequency (TOF). The key parameter in the model is the volumetric diffusive conductance (F_V) that describes catalysts’ diffusion propensity across a compartment’s boundary. Optimal values of F_V for a specific organometallic chemistry are needed to achieve maximal values of γ and TOF. As illustrated in specific reaction examples, our model suggests that a tailored compartment design, including the use of nanomaterials, is needed to suit a specific organometallic catalytic cycle. This work provides justification and design principles for further exploration into compartmentalizing organometallics to enhance catalytic performance. The conclusions from this work are generally applicable to other catalytic systems that need proper design guidance in confinement and compartmentalization.

scholarly journals A Generalized Kinetic Model for Compartmentalization of Organometallic Catalysis

2022 ◽  
Author(s):  
Brandon J Jolly ◽  
Nathalie H Co ◽  
Ashton R Davis ◽  
Paula L. Diaconescu ◽  
Chong Liu
Keyword(s):  
Catalytic Activity ◽  
Kinetic Model ◽  
Reactive Intermediates ◽  
Organometallic Catalysis ◽  
Generalized Kinetic Model

Compartmentalization is an attractive approach to enhance catalytic activity by retaining reactive intermediates and mitigating deactivating pathways. Such a concept has been well explored in biochemical and more recently, organometallic...

scholarly journals Lithium-mediated Ferration of Fluoroarenes

2020 ◽  
Vol 74 (11) ◽  
pp. 866-870
Author(s):  
Lewis C. H. Maddock ◽  
Alan Kennedy ◽  
Eva Hevia
Keyword(s):  
Hydrogen Atom ◽  
Organometallic Chemistry ◽  
Room Temperature ◽  
Structural Elucidation ◽  
Side Reactions ◽  
Metal Base ◽  
Lithium Amide ◽  
Mixed Metal ◽  
Important Challenge

While fluoroaryl fragments are ubiquitous in many pharmaceuticals, the deprotonation of fluoroarenes using organolithium bases constitutes an important challenge in polar organometallic chemistry. This has been widely attributed to the low stability of the in situ generated aryl lithium intermediates that even at –78 °C can undergo unwanted side reactions. Herein, pairing lithium amide LiHMDS (HMDS = N{SiMe3}2) with FeII(HMDS)2 enables the selective deprotonation at room temperature of pentafluorobenzene and 1,3,5-trifluorobenzene via the mixed-metal base [(dioxane)LiFe(HMDS)3] (1) (dioxane = 1,4-dioxane). Structural elucidation of the organometallic intermediates [(dioxane)Li(HMDS)2Fe(ArF)] (ArF = C6F5, 2; 1,3,5-F3-C6H2, 3) prior electrophilic interception demonstrates that these deprotonations are actually ferrations, with Fe occupying the position previously filled by a hydrogen atom. Notwithstanding, the presence of lithium is essential for the reactions to take place as Fe II (HMDS)2 on its own is completely inert towards the metallation of these substrates. Interestingly 2 and 3 are thermally stable and they do not undergo benzyne formation via LiF elimination.

Monodispersed palladium–cobalt alloy nanoparticles assembled on poly(N-vinyl-pyrrolidone) (PVP) as a highly effective catalyst for dimethylamine borane (DMAB) dehydrocoupling

RSC Advances ◽  
2016 ◽  
Vol 6 (29) ◽  
pp. 24097-24102 ◽  
Author(s):  
Betül Çelik ◽  
Yunus Yıldız ◽  
Hakan Sert ◽  
Esma Erken ◽  
Yagmur Koşkun ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Catalytic Performance ◽  
Vinyl Pyrrolidone ◽  
Alloy Nanoparticles ◽  
Turnover Frequency ◽  
Cobalt Alloy ◽  
High Turnover ◽  
Effective Catalyst ◽  
Dimethylamine Borane ◽  
Very High

Monodispersed PdCo@PVP NPs showed record catalytic activity, giving the best catalytic performance yet with a very high turnover frequency.

scholarly journals A generalized kinetic model for amine modification of proteins with application to phage display

BioTechniques ◽  
2009 ◽  
Vol 46 (3) ◽  
pp. 175-182 ◽  
Author(s):  
Xiaofang Jin ◽  
Jessica Rose Newton ◽  
Stephen Montgomery-Smith ◽  
George P. Smith
Keyword(s):  
Kinetic Model ◽  
Phage Display ◽  
Amine Modification ◽  
Generalized Kinetic Model

scholarly journals Improved catalytic effect and metal nanoparticle stability using graphene oxide surface coating and reduced graphene oxide for hydrogen generation from ammonia–borane dehydrogenation

2020 ◽  
Vol 1 (6) ◽  
pp. 1952-1962
Author(s):  
Samikannu Prabu ◽  
Kung-Yuh Chiang
Keyword(s):  
Graphene Oxide ◽  
Catalytic Effect ◽  
Hydrogen Generation ◽  
Catalytic Performance ◽  
Metal Nanoparticle ◽  
Oxide Surface ◽  
Turnover Frequency ◽  
High Turnover ◽  
Nanoparticle Stability ◽  
Reduced Graphene

GO and rGO supported metal NPs exhibited excellent catalytic performance for AB hydrolysis. It also provided a high turnover frequency (TOF) at 25 °C.

A generalized kinetic model for radical-initiated template polymerizations in dilute template systems

1991 ◽  
Vol 24 (7) ◽  
pp. 1641-1647 ◽  
Author(s):  
Y. Yong Tan ◽  
Gert O. R. Alberda van Ekenstein
Keyword(s):  
Kinetic Model ◽  
Generalized Kinetic Model

scholarly journals A Generalized Kinetic Model for Coupling between Stepping and ATP Hydrolysis of Kinesin Molecular Motors

2019 ◽  
Vol 20 (19) ◽  
pp. 4911 ◽  
Author(s):  
Xie ◽  
Guo ◽  
Chen
Keyword(s):  
Kinetic Model ◽  
Atpase Activity ◽  
Single Molecule ◽  
Rate Constants ◽  
Molecular Motors ◽  
Atp Hydrolysis ◽  
Power Production ◽  
Wild Type ◽  
Chemomechanical Coupling ◽  
Generalized Kinetic Model

A general kinetic model is presented for the chemomechanical coupling of dimeric kinesin molecular motors with and without extension of their neck linkers (NLs). A peculiar feature of the model is that the rate constants of ATPase activity of a kinesin head are independent of the strain on its NL, implying that the heads of the wild-type kinesin dimer and the mutant with extension of its NLs have the same force-independent rate constants of the ATPase activity. Based on the model, an analytical theory is presented on the force dependence of the dynamics of kinesin dimers with and without extension of their NLs at saturating ATP. With only a few adjustable parameters, diverse available single molecule data on the dynamics of various kinesin dimers, such as wild-type kinesin-1, kinesin-1 with mutated residues in the NLs, kinesin-1 with extension of the NLs and wild-type kinesin-2, under varying force and ATP concentration, can be reproduced very well. Additionally, we compare the power production among different kinesin dimers, showing that the mutation in the NLs reduces the power production and the extension of the NLs further reduces the power production.

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