Using only the very accurately known experimental enthalpy of hydrogenation of ethylene as a reference standard in the atomization method

Rogers, Donald W.; Zavitsas, Andreas A.

doi:10.1007/s11224-013-0250-0

Cited by 4 publications

(3 citation statements)

References 50 publications

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“…The structure of these long chain molecules can now be determined due to advances in both computational capabilities and computational molecular modeling software [10,15,16]. A body of work has been built determining the structures of short chain molecules [17,18,20,21]. Many of these PUFA compounds have potent physiological properties tied to intra-and extra-cellular messengers whose mechanisms of action are poorly understood.…”

Section: Determiningmentioning

confidence: 99%

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Helical Structure of Polyunsaturated Fatty Acids: Gaussian G4 Thermodynamic Functions

Bennett¹,

Rogers²,

Zavitsas³

2021

SDRP-JCCMM

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Molecular modeling of lipids has been hampered by the size of these complex, biologically important molecules. Yet, understanding the structure and energy (enthalpy) of large molecules is critical to identifying their function in chemical equilibrium and transition state theory. In this work, we use both experimental data and G4 computed results, to show that cis polyunsaturated lipids have helical conformers. We present linear functions for the enthalpy of formation ΔfH°298 and the Gibbs free energy of formation ΔfG°298 as a function of n, where n is the number of carbon atoms in a linear carboxylic acid chain. Taking ΔfH°298 of a saturated acid as a starting point, we add the enthalpy of hydrogenation ΔhydH°298 at appropriate locations on the carbon chain to model polyunsaturated fatty acids. For example, taking eicosanoic acid (C20) as a saturated starting point, we add four enthalpies of cis-dehydrogenation (ΔhydH°298) to obtain arachidonic acid (eicosa-5Z,8Z,11Z,14Z-tetraenoic acid). We compare Gaussian-4 computational results, to show evidence of helical structure. We conclude that fatty acids can have helical conformers facilitating a broad range of biological functions. Keywords: G4 Calculations, Helix, Lipid, Molecular Structure, Thermochemistry

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Section: Determiningmentioning

confidence: 99%

“…This helical structure is more compact and stable than a chain conformation which has important implications for biological function. Based on historical as well as theoretical grounds, many properties of a (large) molecule can be seen as the sum of its parts [20,22,23]. Using this method, we find that the PUFA may have helical conformers.…”

mentioning

confidence: 99%

Helical Structure of Polyunsaturated Fatty Acids: Gaussian G4 Thermodynamic Functions

Bennett¹,

Rogers²,

Zavitsas³

2021

SDRP-JCCMM

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“…Mixed computed (G3(MP2)) and experimental results were used by Rogers and Zavitsas [150] to calculate the enthalpies of hydrogenation of polyunsaturated compounds by referring calculated values to the very accurately known enthalpy of hydrogenation of ethylene. Given that so many of the species that the authors discussed have conjugated pbonds, we wonder if anything would be gained by using the enthalpy of hydrogenation of the conjugated 1,3-butadiene as a reference; perhaps it might be of greater utility at less rigorous calculational levels.…”

Section: Issuementioning

confidence: 99%

Interplay of thermochemistry and structural chemistry, the journal (volume 24, 2013, issues 5–6) and the discipline

2014

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Aspects of the Chemical Energetics of Species with Carbon–Boron Bonds and Related Compounds

Slayden¹,

Liebman²

2020

Patai's Chemistry of Functional Groups

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In this chapter, we discuss selected energetics and thermochemical aspects of species with carbon–boron bonds. Although they lack a carbon–boron bond, atomic boron, its anion, and binary metal borides—the hypothetical alkali metal borides MB—and structurally complex metal borides are briefly introduced. Consideration of species with carbon–boron bonds begins with binary species such as the gas‐phase diatomic BC and the solid B 4 C and proceeds to the highly reactive methyl and phenyl derivatives of univalent borylene, BH. The question of regular behavior as homologous series is addressed for the relatively stable and long‐known classes of compounds, trialkylboranes and carboranes, with their normal (threefold) and higher boron‐coordination numbers. Trivalent boron and nitrogen species are then compared, first as organoboranes and amines, then as their organoborate and ammonium ions, and also as their “dimer” anions and cations. Pyridine borane complexes are likewise discussed and compared with benzene derivatives. Species with boron in the ring, borabenzenes and their amine complexes, are much more poorly understood. However, aromatic derivatives with both boron and nitrogen in the ring have evinced considerable interest, and the derivatives of the isomeric 1,2‐, 1,3‐, and 1,4‐azaborinines are described at some length. The chapter closes with species that contain oxygen along with boron, carbon, and hydrogen. Borane carbonyl (BH 3 CO), boronic acid derivatives, and boroxines are discussed.

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Using only the very accurately known experimental enthalpy of hydrogenation of ethylene as a reference standard in the atomization method

Cited by 4 publications

References 50 publications

Helical Structure of Polyunsaturated Fatty Acids: Gaussian G4 Thermodynamic Functions

Helical Structure of Polyunsaturated Fatty Acids: Gaussian G4 Thermodynamic Functions

Interplay of thermochemistry and structural chemistry, the journal (volume 24, 2013, issues 5–6) and the discipline

Aspects of the Chemical Energetics of Species with Carbon–Boron Bonds and Related Compounds

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