scholarly journals Can Aromaticity of Fused Aromatic Ring in 1,3-Pentadiene Modulate its Reactivity towards [1,5]-Halo Shift? - A DFT Study

2021 ◽  
Vol 33 (2) ◽  
pp. 447-452
Author(s):  
Padmanaban Kalpana ◽  
Lakshminarayanan Akilandeswari
Keyword(s):  
Transition State ◽  
Aromatic Ring ◽  
Driving Force ◽  
Reaction Pathway ◽  
The Other ◽  
Transition Structure ◽  
Activation Barriers ◽  
Aromaticity Index ◽  
Pericyclic Reaction

In (Z)-1,3-pentadienes, [1,5]-H migration is suprafacially allowed while fluorine shift in this system takes place by a Contra Hoffmann antarafacial pathway for which aromaticity is the driving force. If aromaticity of the transition structure (TS) can drive a reaction towards a disallowed pathway as found in the case of fluorine, the role of aromatic ring annealed to (Z)-1,3-pentadienes in determining the reaction pathway and barrier is worth noting. Hence, the combined role of aromaticity of transition state and the loss in aromaticity of the annealed ring has been explored during the [1,5]-X (X = H, F, Cl, Br) shifts in aromatic (benzene/naphthalene) annealed 1,3-pentadiene system. Notable correlations between various aromaticity index NICS(0,1) with activation barriers show that aromaticity of transition structure in pericyclic reaction can drive the stereochemical course of a reaction. The distinct effect of fluorine to other halogens is the antara migration while the other halogens (Cl & Br) prefer supramode.

scholarly journals The role of second coordination-sphere interactions in incommensurately modulated structures, using β-K5Yb(MoO4)4 as an example

2005 ◽  
Vol 61 (4) ◽  
pp. 400-406 ◽  
Author(s):  
Alla Arakcheeva ◽  
Gervais Chapuis ◽  
Vâclav Petricek ◽  
Vladimir Morozov
Keyword(s):  
Coordination Sphere ◽  
Driving Force ◽  
The Other ◽  
Structure Model ◽  
Unit Cell Parameters ◽  
Cell Parameters ◽  
The Third ◽  
Modulated Structures ◽  
Coordination Spheres

The incommensurate palmierite-like structure of β-K5Yb(MoO4)4, potassium ytterbium tetramolydate, has been refined in the (3 + 1)-dimensional monoclinic superspace group X2/m(0ρ0)00, with X = [0 0 0 0; ½ ½ 0 0; 0 0 ½ ½; ½ ½ ½ ½] and the unit-cell parameters a = 10.4054 (16), b = 6.1157 (12), c = 19.7751 (18) Å, β = 136.625 (10)°; q = 0.6354 (30)b*. The occupations of the K and Yb atomic positions are described by crenel functions. The structure model reveals a balanced interaction between the atoms of the first and second coordination spheres. It is shown that the third coordination sphere should not be neglected in studies of modulated structures. The ordering of the K and Yb atoms appears to be the driving force for the modulation of all the other atoms.

scholarly journals The effect of magnesium ions on triphosphate hydrolysis

2017 ◽  
Vol 89 (6) ◽  
pp. 715-727 ◽  
Author(s):  
Alexandre Barrozo ◽  
David Blaha-Nelson ◽  
Nicholas H. Williams ◽  
Shina C. L. Kamerlin
Keyword(s):  
Transition State ◽  
Metal Ions ◽  
Density Functional ◽  
Reaction Pathway ◽  
Enzymatic Reaction ◽  
Phosphate Ester ◽  
Mechanistic Pathway ◽  
Phosphate Hydrolysis ◽  
The Impact

AbstractThe role of metal ions in catalyzing phosphate ester hydrolysis has been the subject of much debate, both in terms of whether they change the transition state structure or mechanistic pathway. Understanding the impact of metal ions on these biologically critical reactions is central to improving our understanding of the role of metal ions in the numerous enzymes that facilitate them. In the present study, we have performed density functional theory studies of the mechanisms of methyl triphosphate and acetyl phosphate hydrolysis in aqueous solution to explore the competition between solvent- and substrate-assisted pathways, and examined the impact of Mg2+ on the energetics and transition state geometries. In both cases, we observe a clear preference for a more dissociative solvent-assisted transition state, which is not significantly changed by coordination of Mg2+. The effect of Mg2+ on the transition state geometries for the two pathways is minimal. While our calculations cannot rule out a substrate-assisted pathway as a possible solution for biological phosphate hydrolysis, they demonstrate that a significantly higher energy barrier needs to be overcome in the enzymatic reaction for this to be an energetically viable reaction pathway.

Pericyclic Reactions in the Syntheses of Densely Functionalized Heterocylces

2018 ◽  
Vol 15 (4) ◽  
pp. 438-486 ◽  
Author(s):  
Rabia Qamar ◽  
Aamer Saeed
Keyword(s):  
Transition State ◽  
Driving Force ◽  
High Efficiency ◽  
Reaction Pathways ◽  
Pericyclic Reactions ◽  
Cyclic Transition ◽  
Cyclic Transition State ◽  
Molecular Complexity ◽  
Nitrogen Ring

Background: Pericyclic reactions characterized by a cyclic transition state, have been established as a dominant approach for the synthesis of heterocyclic scaffolds owing to their tremendous efficacy, regioselectivity, and enantioselectivity. Pericyclic chemistry is a promising and creative route to various biologically significant five and six membered oxygen or nitrogen ring systems. Recognizing the reaction's potential, synthetic organic chemists have invested significant efforts in developing and applying a seemingly endless array of useful variations of pericyclic reactions. Objective: The driving force of this review is to focus the character of perfection and beauty inherent in these powerful reaction pathways that lead to unique and densely functionalized heterocylic assemblies. Conclusion: In this review, we have presented recent strategic applications of pericyclic reactions that provide quick access to molecular complexity with high efficiency. A summary of these illustrative examples will showcase the extensive role of pericyclic chemistry in the construction of synthetically intimidating structural motifs.

On the Concerted Ring Opening of Protonated Squalene Oxide and A-Ring Formation in the Biosynthesis of Lanosterol

2003 ◽  
Vol 68 (1) ◽  
pp. 202-210 ◽  
Author(s):  
B. Andes Hess
Keyword(s):  
Ring Opening ◽  
Density Functional ◽  
Reaction Pathway ◽  
Ring Expansion ◽  
Membered Ring ◽  
Ring Formation ◽  
Ring Closure ◽  
Primary Role ◽  
Transition Structure

Density functional calculations were performed on a model system of squalene oxide to study the mechanism of the formation of ring A in the biosynthesis of lanosterol from squalene. When (2Z)-6,7-epoxy-3,7-dimethyloct-2-ene was protonated, it was calculated to undergo a very facile ring opening of the oxirane in concert with the formation of the six-membered ring of the 4-(hydroxymethyl)-1,2,3,3-tetramethy1cyclohexyl cation. A study of the reaction pathway (IRC) indicates a very early transition structure in which the carbon- carbon double bond participates anchimerically in the ring-opening of the protonated oxirane. It is suggested that the primary role of the enzyme in this first step of the biosynthesis of lanosterol is protonation of the oxirane ring along with holding the substrate in the proper conformation for the concerted ring-closure to occur. The similarity between this mechanism and that recently proposed for concerted C-ring expansion and D-ring formation in the biosynthesis of lanosterol is discussed.

Plasma Levels of Protein S, Protein C, and Factor X: Effects of Sex, Hormonal State and Age

1995 ◽  
Vol 74 (05) ◽  
pp. 1271-1275 ◽  
Author(s):  
C M A Henkens ◽  
V J J Bom ◽  
W van der Schaaf ◽  
P M Pelsma ◽  
C Th Smit Sibinga ◽  
...  
Keyword(s):  
Regression Analysis ◽  
Postmenopausal Women ◽  
Protein C ◽  
Blood Donors ◽  
Premenopausal Women ◽  
Protein S ◽  
The Other ◽  
Factor X ◽  
Normal Ranges

SummaryWe measured total and free protein S (PS), protein C (PC) and factor X (FX) in 393 healthy blood donors to assess differences in relation to sex, hormonal state and age. All measured proteins were lower in women as compared to men, as were levels in premenopausal women as compared to postmenopausal women. Multiple regression analysis showed that both age and subgroup (men, pre- and postmenopausal women) were of significance for the levels of total and free PS and PC, the subgroup effect being caused by the differences between the premenopausal women and the other groups. This indicates a role of sex-hormones, most likely estrogens, in the regulation of levels of pro- and anticoagulant factors under physiologic conditions. These differences should be taken into account in daily clinical practice and may necessitate different normal ranges for men, pre- and postmenopausal women.

On the role of the dispute between "non-possessors" and "Josephites" in the culture of Moscow's prediction

1998 ◽  
pp. 61-62
Author(s):  
N. S. Jurtueva
Keyword(s):  
The Other ◽  
Moral Transformation ◽  
15Th Century ◽  
The Future ◽  
Secular Power

In the XIV century. centripetal tendencies began to appear in the Moscow principality. Inside the Russian church, several areas were distinguished. Part of the clergy supported the specificobar form. The other understood the need for transformations in society. As a result, this led to a split in the Russian church in the 15th century for "non-possessors" and "Josephites". The former linked the fate of the future with the ideology of hesychasm and its moral transformation, while the latter sought support in alliance with a strong secular power.

Economic Growth: New Problems and New Risks

2006 ◽  
pp. 20-37 ◽  
Author(s):  
M. Ershov
Keyword(s):  
Economic Growth ◽  
Foreign Exchange ◽  
Driving Force ◽  
Structural Changes ◽  
Rate Of Growth

The economic growth, which is underway in Russia, raises new questions to be addressed. How to improve the quality of growth, increasing the role of new competitive sectors and transforming them into the driving force of growth? How can progressive structural changes be implemented without hampering the rate of growth in general? What are the main external and internal risks, which may undermine positive trends of development? The author looks upon financial, monetary and foreign exchange aspects of the problem and comes up with some suggestions on how to make growth more competitive and sustainable.

From Container to Claustrum: Projective Identification in Couples

2014 ◽  
Vol 4 (2) ◽  
Author(s):  
Tamara Feldman
Keyword(s):  
Psychological Health ◽  
Projective Identification ◽  
The Self ◽  
The Other ◽  
Intimate Partners ◽  
And Control ◽  
The Relationship ◽  
As If

This paper is a contribution to the growing literature on the role of projective identification in understanding couples' dynamics. Projective identification as a defence is well suited to couples, as intimate partners provide an ideal location to deposit unwanted parts of the self. This paper illustrates how projective identification functions differently depending on the psychological health of the couple. It elucidates how healthier couples use projective identification more as a form of communication, whereas disturbed couples are inclined to employ it to invade and control the other, as captured by Meltzer's concept of "intrusive identification". These different uses of projective identification affect couples' capacities to provide what Bion called "containment". In disturbed couples, partners serve as what Meltzer termed "claustrums" whereby projections are not contained, but imprisoned or entombed in the other. Applying the concept of claustrum helps illuminate common feelings these couples express, such as feeling suffocated, stifled, trapped, held hostage, or feeling as if the relationship is killing them. Finally, this paper presents treatment challenges in working with more disturbed couples.

Thomas More's “rule” of pleasure before, after, and inUtopia

Moreana ◽  
2017 ◽  
Vol 54 (Number 207) (1) ◽  
pp. 36-56
Author(s):  
Gerard Wegemer
Keyword(s):  
Human Nature ◽  
The Other ◽  
Biblical Allusions ◽  
De Officiis

After establishing a context of More's lifelong engagement with the “calculus” of pleasure, this essay shows how the section devoted to the Utopians' pleasure philosophy is structured around five formulations of a “rule” to calculate “true and honest [honesta]” pleasure in ways that playfully imitate and echo the “rule” Cicero formulates several times in De officiis to discern one's duty when there seems to be a conflict between honestas et utilitas. When followed, the Utopian pleasure calculus shows the necessary role of societas, officii, iustitia, caritas, and the other aspects of human nature, most importantly friendship, that Cicero stresses in his rule and that he argued Epicurus ignored. Much of the irony and humor of this section depends on seeing the predominance of Ciceronian vocabulary in Raphael's unusual defense [patrocinium] of pleasure, rather than a Ciceronian defense of duty rooted in honestas. Throughout, however, this essay also shows how More goes beyond Cicero by including Augustinian and biblical allusions to suggest ways that our final end is not as Epicurus or the Stoics or Cicero claim; the language and allusions of this section point to a level of good cheer and care for neighbors and for God in ways quite different from any classical thinker.

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