scholarly journals Target bounds on reaction selectivity via Feinberg's CFSTR equivalence principle

AIChE Journal ◽  
2017 ◽  
Vol 64 (3) ◽  
pp. 926-939 ◽  
Author(s):  
Jeffrey A. Frumkin ◽  
Michael F. Doherty
1996 ◽  
Vol 166 (1) ◽  
pp. 81-88 ◽  
Author(s):  
Anatolii A. Logunov ◽  
Mirian A. Mestvirishvili ◽  
Yu.V. Chugreev

2019 ◽  
Author(s):  
Łukasz Ciszewski ◽  
Jakub Durka ◽  
Dorota Gryko

This article describes direct photoalkylation of electron-rich aromatic compounds with diazo compoiunds. C-2 alkylated indoles and pyrroles are obtained with good yields even though the photocatalyst (Ru(bpy)3Cl2) loading is as low as 0.075 mol %. For substrates bearing electron-withdrawing substituents the addition of a catalytic amount of N,N-dimethyl-4-methoxyaniline is required. Both EWG-EWG and EWG-EDG substituted diazo esters are suitable as alkylating agents. The reaction selectivity and mechanistic experiments suggest that carbenes/carbenoid intermediates are not involved in the reaction pathway, instead radical formation is proposed.


2019 ◽  
Author(s):  
Elena Prigorchenko ◽  
Sandra Kaabel ◽  
Triin Narva ◽  
Anastassia Baškir ◽  
Maria Fomitšenko ◽  
...  

Amplification of a thermodynamically unfavoured macrocyclic product through the directed shift of the equilibrium between dynamic covalent chemistry library members is difficult to achieve. We show for the first time that during condensation of formaldehyde and <i>cis</i>-<i>N,N'</i>-cyclohexa-1,2-diylurea formation of <i>inverted-cis</i>-cyclohexanohemicucurbit[6]uril (<i>i-cis</i>-cycHC[6]) can be induced at the expense of thermodynamically favoured <i>cis</i>-cyclohexanohemicucurbit[6]uril (<i>cis</i>-cycHC[6]). The formation of <i>i-cis-</i>cycHC[6] is enhanced in low concentration of the templating chloride anion and suppressed in excess of this template. We found that reaction selectivity is governed by the solution-based template-aided dynamic combinatorial chemistry and continuous removal of the formed cycHC[6] macrocycles from the equilibrating solution by precipitation. Notably, the <i>i-cis</i>-cycHC[6] was isolated with 33% yield. Different binding affinities of three diastereomeric <i>i-cis</i>-, <i>cis</i>-cycHC[6] and their chiral isomer (<i>R,R</i>)-cycHC[6] for trifluoroacetic acid demonstrate the influence of macrocycle geometry on complex formation.


Author(s):  
David M. Wittman

The equivalence principle is an important thinking tool to bootstrap our thinking from the inertial coordinate systems of special relativity to the more complex coordinate systems that must be used in the presence of gravity (general relativity). The equivalence principle posits that at a given event gravity accelerates everything equally, so gravity is equivalent to an accelerating coordinate system.This conjecture is well supported by precise experiments, so we explore the consequences in depth: gravity curves the trajectory of light as it does other projectiles; the effects of gravity disappear in a freely falling laboratory; and gravitymakes time runmore slowly in the basement than in the attic—a gravitational form of time dilation. We show how this is observable via gravitational redshift. Subsequent chapters will build on this to show how the spacetime metric varies with location.


2020 ◽  
Vol 2020 ◽  
pp. 1-13 ◽  
Author(s):  
Jiangbin Wang ◽  
Ling Liu ◽  
Chongxin Liu ◽  
Xiaoteng Li

The main purpose of the paper is to control chaotic oscillation in a complex seven-dimensional power system model. Firstly, in view that there are many assumptions in the design process of existing adaptive controllers, an adaptive sliding mode control scheme is proposed for the controlled system based on equivalence principle by combining fixed-time control and adaptive control with sliding mode control. The prominent advantage of the proposed adaptive sliding mode control scheme lies in that its design process breaks through many existing assumption conditions. Then, chaotic oscillation behavior of a seven-dimensional power system is analyzed by using bifurcation and phase diagrams, and the proposed strategy is adopted to control chaotic oscillation in the power system. Finally, the effectiveness and robustness of the designed adaptive sliding mode chaos controllers are verified by simulation.


2021 ◽  
pp. 136471
Author(s):  
ChengGang Qin ◽  
YuJie Tan ◽  
ChengGang Shao

2021 ◽  
Vol 2021 (1) ◽  
Author(s):  
Pilar Coloma ◽  
M. C. Gonzalez-Garcia ◽  
Michele Maltoni

Abstract We quantify the effect of gauge bosons from a weakly coupled lepton flavor dependent U(1)′ interaction on the matter background in the evolution of solar, atmospheric, reactor and long-baseline accelerator neutrinos in the global analysis of oscillation data. The analysis is performed for interaction lengths ranging from the Sun-Earth distance to effective contact neutrino interactions. We survey ∼ 10000 set of models characterized by the six relevant fermion U(1)′ charges and find that in all cases, constraints on the coupling and mass of the Z′ can be derived. We also find that about 5% of the U(1)′ model charges lead to a viable LMA-D solution but this is only possible in the contact interaction limit. We explicitly quantify the constraints for a variety of models including $$ \mathrm{U}{(1)}_{B-3{L}_e} $$ U 1 B − 3 L e , $$ \mathrm{U}{(1)}_{B-3{L}_{\mu }} $$ U 1 B − 3 L μ , $$ \mathrm{U}{(1)}_{B-3{L}_{\tau }} $$ U 1 B − 3 L τ , $$ \mathrm{U}{(1)}_{B-\frac{3}{2}\left({L}_{\mu }+{L}_{\tau}\right)} $$ U 1 B − 3 2 L μ + L τ , $$ \mathrm{U}{(1)}_{L_e-{L}_{\mu }} $$ U 1 L e − L μ , $$ \mathrm{U}{(1)}_{L_e-{L}_{\tau }} $$ U 1 L e − L τ , $$ \mathrm{U}{(1)}_{L_e-\frac{1}{2}\left({L}_{\mu }+{L}_{\tau}\right)} $$ U 1 L e − 1 2 L μ + L τ . We compare the constraints imposed by our oscillation analysis with the strongest bounds from fifth force searches, violation of equivalence principle as well as bounds from scattering experiments and white dwarf cooling. Our results show that generically, the oscillation analysis improves over the existing bounds from gravity tests for Z′ lighter than ∼ 10−8→ 10−11 eV depending on the specific couplings. In the contact interaction limit, we find that for most models listed above there are values of g′ and MZ′ for which the oscillation analysis provides constraints beyond those imposed by laboratory experiments. Finally we illustrate the range of Z′ and couplings leading to a viable LMA-D solution for two sets of models.


Author(s):  
Daria S. Timofeeva ◽  
David M Lindsay ◽  
W. J. Kerr ◽  
David James Nelson

Herein we examine the relationship between reaction rate and reaction selectivity in iridium-catalysed hydrogen isotope exchange (HIE) reactions directed by Lewis basic functional groups. We have recently develped a directing...


2020 ◽  
Vol 2 (2) ◽  
Author(s):  
Sheng-Feng Yan ◽  
Chunlong Li ◽  
Lingqin Xue ◽  
Xin Ren ◽  
Yi-Fu Cai ◽  
...  

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