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Synergies on the Trio Energy-Structure-Reactivity: Nitrogen- containing Heterocyclic Compounds

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A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Physical Chemistry".

Deadline for manuscript submissions: closed (31 March 2023) | Viewed by 29123

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Special Issue Editors

Dr. Vera L. S. Freitas

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Guest Editor

Universidade do Porto, Porto, Portugal
Interests: molecular energetics; thermophysics; computational thermochemistry; calorimetry; heteropolycyclic compounds

Dr. Maria Ribeiro da Silva

E-Mail Website1 Website2 Website3 Website4
Guest Editor

Universidade do Porto, Porto, Portugal
Interests: thermochemistry; molecular energetics; reactivity assessment; structure-energy-reactivity relationships; calorimetry; bond energies

Special Issue Information

Dear Colleagues,

How does structure influence the energy and the reactivity of molecules? This is a key question that comes up many times during an investigation in order to explain the chemical behavior of the species. The knowledge of the answer is a competitive advantage, often being a factor of success in different areas of research. With this Special Issue, we intend to collect a set of works that contribute to increasing the clarification of the structure–energy–reactivity trio for nitrogen heterocyclic compounds.

Nitrogen heterocyclic compounds constitute the object of numerous research studies on the synthesis, characterization, and development of new products, due to their properties providing them with a broad applicability. In fact, nitrogen heterocyclic derivatives play an important role in different fields, from environmental chemistry or geochemistry to the agricultural or pharmaceutical industries, being also relevant today in material science as valuable targets of synthesis. The extensive range of chemical and biological activities of such nitrogen heterocycles has been attracting the attention of a large number of researchers who aim to use the features determining the chemical behavior of the molecules, mainly to plan the design of synthetic strategies in order to obtain new species with the desired characteristics.

Dr. Vera L.S. Freitas
Dr. Maria D.M.C. Ribeiro Da Silva
Guest Editors

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Keywords

Thermodynamic characterization
Nitrogen functional groups
Energetic binding
Reactivity
Calorimetry
Stability

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Published Papers (10 papers)

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16 pages, 2889 KiB

Open AccessArticle

Determination and Analysis of Thermodynamic Properties of Methyl Methylanthranilate Isomers

by Carlos A. O. Silva, Vera L. S. Freitas and Maria D. M. C. Ribeiro da Silva

Molecules 2023, 28(18), 6686; https://doi.org/10.3390/molecules28186686 - 18 Sep 2023

Cited by 2 | Viewed by 1545

Abstract

The enthalpies of formation in the gaseous phase of methyl 3-methylanthranilate and methyl 5-methylanthranilate were determined from experimental measurements of the corresponding standard energies of combustion, obtained from combustion calorimetry, and the standard enthalpies of vaporization and sublimation, obtained from Calvet microcalorimetry and Knudsen mass-loss effusion. A computational study, using the G3(MP2)//B3LYP composite method, has also been performed for the calculation of the gas-phase standard enthalpies of formation of those two molecules at T = 298.15 K, as well as for the remaining isomers, methyl 4-methylanthranilate and methyl 6-methylanthranilate. The results have been used to evaluate and analyze the energetic effect of the methyl substituent in different positions of the ring. Full article

(This article belongs to the Special Issue Synergies on the Trio Energy-Structure-Reactivity: Nitrogen- containing Heterocyclic Compounds)

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9 pages, 984 KiB

Open AccessArticle

Thermochemical Study of 1-Methylhydantoin

by Juan M. Ledo, Henoc Flores, Fernando Ramos and Elsa A. Camarillo

Molecules 2022, 27(2), 556; https://doi.org/10.3390/molecules27020556 - 16 Jan 2022

Cited by 1 | Viewed by 2176

Abstract

Using static bomb combustion calorimetry, the combustion energy of 1-methylhydantoin was obtained, from which the standard molar enthalpy of formation of the crystalline phase at T = 298.15 K of the compound studied was calculated. Through thermogravimetry, mass loss rates were measured as a function of temperature, from which the enthalpy of vaporization was calculated. Additionally, some properties of fusion were determined by differential scanning calorimetry, such as enthalpy and temperature. Adding the enthalpy of fusion to the enthalpy of vaporization, the enthalpy of sublimation of the compound was obtained at T = 298.15 K. By combining the enthalpy of formation of the compound in crystalline phase with its enthalpy of sublimation, the respective standard molar enthalpy of formation in the gas phase was calculated. On the other hand, the results obtained in the present work were compared with those of other derivatives of hydantoin, with which the effect of the change of some substituents in the base heterocyclic ring was evaluated. Full article

(This article belongs to the Special Issue Synergies on the Trio Energy-Structure-Reactivity: Nitrogen- containing Heterocyclic Compounds)

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15 pages, 1751 KiB

Open AccessArticle

A Promising Thermodynamic Study of Hole Transport Materials to Develop Solar Cells: 1,3-Bis(N-carbazolyl)benzene and 1,4-Bis(diphenylamino)benzene

by Juan Mentado-Morales, Arturo Ximello-Hernández, Javier Salinas-Luna, Vera L. S. Freitas and Maria D. M. C. Ribeiro da Silva

Molecules 2022, 27(2), 381; https://doi.org/10.3390/molecules27020381 - 7 Jan 2022

Cited by 4 | Viewed by 3154

Abstract

The thermochemical study of the 1,3-bis(N-carbazolyl)benzene (NCB) and 1,4-bis(diphenylamino)benzene (DAB) involved the combination of combustion calorimetric (CC) and thermogravimetric techniques. The molar heat capacities over the temperature range of (274.15 to 332.15) K, as well as the melting temperatures and enthalpies of fusion were measured for both compounds by differential scanning calorimetry (DSC). The standard molar enthalpies of formation in the crystalline phase were calculated from the values of combustion energy, which in turn were measured using a semi-micro combustion calorimeter. From the thermogravimetric analysis (TGA), the rate of mass loss as a function of the temperature was measured, which was then correlated with Langmuir’s equation to derive the vaporization enthalpies for both compounds. From the combination of experimental thermodynamic parameters, it was possible to derive the enthalpy of formation in the gaseous state of each of the title compounds. This parameter was also estimated from computational studies using the G3MP2B3 composite method. To prove the identity of the compounds, the ¹H and ¹³C spectra were determined by nuclear magnetic resonance (NMR), and the Raman spectra of the study compounds of this work were obtained. Full article

(This article belongs to the Special Issue Synergies on the Trio Energy-Structure-Reactivity: Nitrogen- containing Heterocyclic Compounds)

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14 pages, 1158 KiB

Open AccessArticle

Thermodynamic Stability of Fenclorim and Clopyralid

by Ana R. R. P. Almeida, Bruno D. A. Pinheiro, Ana I. M. C. Lobo Ferreira and Manuel J. S. Monte

Molecules 2022, 27(1), 39; https://doi.org/10.3390/molecules27010039 - 22 Dec 2021

Cited by 2 | Viewed by 2586

Abstract

The present work reports an experimental thermodynamic study of two nitrogen heterocyclic organic compounds, fenclorim and clopyralid, that have been used as herbicides. The sublimation vapor pressures of fenclorim (4,6-dichloro-2-phenylpyrimidine) and of clopyralid (3,6-dichloro-2-pyridinecarboxylic acid) were measured, at different temperatures, using a Knudsen mass-loss effusion technique. The vapor pressures of both crystalline and liquid (including supercooled liquid) phases of fenclorim were also determined using a static method based on capacitance diaphragm manometers. The experimental results enabled accurate determination of the standard molar enthalpies, entropies and Gibbs energies of sublimation for both compounds and of vaporization for fenclorim, allowing a phase diagram representation of the (p,T) results, in the neighborhood of the triple point of this compound. The temperatures and molar enthalpies of fusion of the two compounds studied were determined using differential scanning calorimetry. The standard isobaric molar heat capacities of the two crystalline compounds were determined at 298.15 K, using drop calorimetry. The gas phase thermodynamic properties of the two compounds were estimated through ab initio calculations, at the G3(MP2)//B3LYP level, and their thermodynamic stability was evaluated in the gaseous and crystalline phases, considering the calculated values of the standard Gibbs energies of formation, at 298.15 K. All these data, together with other physical and chemical properties, will be useful to predict the mobility and environmental distribution of these two compounds. Full article

(This article belongs to the Special Issue Synergies on the Trio Energy-Structure-Reactivity: Nitrogen- containing Heterocyclic Compounds)

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8 pages, 2227 KiB

Open AccessArticle

Experimental and Theoretical Investigation on the Thermochemistry of 3-Methyl-2-benzoxazolinone and 6-Nitro-2-benzoxazolinone

by Ana L. R. Silva, Vânia M. S. Costa and Maria D. M. C. Ribeiro da Silva

Molecules 2022, 27(1), 24; https://doi.org/10.3390/molecules27010024 - 21 Dec 2021

Cited by 1 | Viewed by 2822

Abstract

The determination of the reliable thermodynamic properties of 2-benzoxazolinone derivatives is the main goal of this work. Some correlations are established between the energetic properties determined and the structural characteristics of the title compounds, and the reactivity of this class of compounds is also evaluated. Static-bomb combustion calorimetry and high-temperature Calvet microcalorimetry were used to determine, respectively, the standard molar enthalpies of formation in the solid state and the standard molar enthalpies of sublimation, both at T = 298.15 K. Using the results obtained for each compound, the respective gas-phase standard molar enthalpy of formation was derived. High-level quantum chemical calculations were performed to estimate the same property and the results evidence good accordance. Moreover, the gas-phase relative thermodynamic stability of 2-benzoxazolinone derivatives was also evaluated using the respective gas-phase standard molar Gibbs energy of formation. In addition, the relationship between the energetic and structural characteristics of the benzoxazolinones is presented, evidencing the enthalpic increments associated with the presence of a methyl and a nitro groups in the molecule, and this effect is compared with similar ones in other structurally related compounds. Full article

(This article belongs to the Special Issue Synergies on the Trio Energy-Structure-Reactivity: Nitrogen- containing Heterocyclic Compounds)

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21 pages, 3753 KiB

Open AccessArticle

Isavuconazole: Thermodynamic Evaluation of Processes Sublimation, Dissolution and Partition in Pharmaceutically Relevant Media

by Marina Ol’khovich, Angelica Sharapova, Svetlana Blokhina and German Perlovich

Molecules 2021, 26(16), 4759; https://doi.org/10.3390/molecules26164759 - 6 Aug 2021

Cited by 7 | Viewed by 2897

Abstract

A temperature dependence of saturated vapor pressure of isavuconazole (IVZ), an antimycotic drug, was found by using the method of inert gas-carrier transfer and the thermodynamic functions of sublimation were calculated at a temperature of 298.15 K. The value of the compound standard molar enthalpy of sublimation was found to be 138.1 ± 0.5 kJ·mol⁻¹. The IVZ thermophysical properties—melting point and enthalpy—equaled 302.7 K and 29.9 kJ mol⁻¹, respectively. The isothermal saturation method was used to determine the drug solubility in seven pharmaceutically relevant solvents within the temperature range from 293.15 to 313.15 K. The IVZ solubility in the studied solvents increased in the following order: buffer pH 7.4, buffer pH 2.0, buffer pH 1.2, hexane, 1-octanol, 1-propanol, ethanol. Depending on the solvent chemical nature, the compound solubility varied from 6.7 × 10⁻⁶ to 0.3 mol·L⁻¹. The Hansen s approach was used for evaluating and analyzing the solubility data of drug. The results show that this model well-described intermolecular interactions in the solutions studied. It was established that in comparison with the van’t Hoff model, the modified Apelblat one ensured the best correlation with the experimental solubility data of the studied drug. The activity coefficients at infinite dilution and dissolution excess thermodynamic functions of IVZ were calculated in each of the solvents. Temperature dependences of the compound partition coefficients were obtained in a binary 1-octanol/buffer pH 7.4 system and the transfer thermodynamic functions were calculated. The drug distribution from the aqueous solution to the organic medium was found to be spontaneous and entropy-driven. Full article

(This article belongs to the Special Issue Synergies on the Trio Energy-Structure-Reactivity: Nitrogen- containing Heterocyclic Compounds)

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12 pages, 971 KiB

Open AccessArticle

Heat Capacities of l-Histidine, l-Phenylalanine, l-Proline, l-Tryptophan and l-Tyrosine

by Václav Pokorný, Vojtěch Štejfa, Jakub Havlín, Květoslav Růžička and Michal Fulem

Molecules 2021, 26(14), 4298; https://doi.org/10.3390/molecules26144298 - 15 Jul 2021

Cited by 14 | Viewed by 4032

Abstract

In an effort to establish reliable thermodynamic data for proteinogenic amino acids, heat capacities for l-histidine (CAS RN: 71-00-1), l-phenylalanine (CAS RN: 63-91-2), l-proline (CAS RN: 147-85-3), l-tryptophan (CAS RN: 73-22-3), and l-tyrosine (CAS RN: 60-18-4) were measured over a wide temperature range. Prior to heat capacity measurements, thermogravimetric analysis was performed to determine the decomposition temperatures while X-ray powder diffraction (XRPD) and heat-flux differential scanning calorimetry (DSC) were used to identify the initial crystal structures and their possible transformations. Crystal heat capacities of all five amino acids were measured by Tian–Calvet calorimetry in the temperature interval from 262 to 358 K and by power compensation DSC in the temperature interval from 307 to 437 K. Experimental values determined in this work were then combined with the literature data obtained by adiabatic calorimetry. Low temperature heat capacities of l-histidine, for which no literature data were available, were determined in this work using the relaxation (heat pulse) calorimetry from 2 K. As a result, isobaric crystal heat capacities and standard thermodynamic functions up to 430 K for all five crystalline amino acids were developed. Full article

(This article belongs to the Special Issue Synergies on the Trio Energy-Structure-Reactivity: Nitrogen- containing Heterocyclic Compounds)

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9 pages, 712 KiB

Open AccessArticle

The Vaporization Enthalpy and Vapor Pressure of (±) N-Ethyl Amphetamine by Correlation Gas Chromatography

by James S. Chickos

Molecules 2021, 26(13), 3809; https://doi.org/10.3390/molecules26133809 - 22 Jun 2021

Cited by 3 | Viewed by 2280

Abstract

The vaporization enthalpy, and vapor pressure as a function of temperature of N-ethylamphetamine, a substance used in the 1950s as an appetite suppressant and more currently abused as a designer drug, is reported. Its physical properties are compared to those of S (+)-N-methamphetamine, a substance whose physiological properties it mimics. A vaporization enthalpy of (62.4 ± 4.4) kJ·mol⁻¹ and vapor pressure of (19 ± 11) Pa at T = 298.15 K has been evaluated by correlation gas chromatography. Results are compared to estimated values and to the limited amount of experimental property data available. Full article

(This article belongs to the Special Issue Synergies on the Trio Energy-Structure-Reactivity: Nitrogen- containing Heterocyclic Compounds)

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20 pages, 3079 KiB

Open AccessFeature PaperArticle

A Combined Experimental and Theoretical Study of Nitrofuran Antibiotics: Crystal Structures, DFT Computations, Sublimation and Solution Thermodynamics

by Alex N. Manin, Ksenia V. Drozd, Alexander P. Voronin, Andrei V. Churakov and German L. Perlovich

Molecules 2021, 26(11), 3444; https://doi.org/10.3390/molecules26113444 - 5 Jun 2021

Cited by 11 | Viewed by 3502

Abstract

Single crystal of furazolidone (FZL) has been successfully obtained, and its crystal structure has been determined. Common and distinctive features of furazolidone and nitrofurantoin (NFT) crystal packing have been discussed. Combined use of QTAIMC and Hirshfeld surface analysis allowed characterizing the non-covalent interactions in both crystals. Thermophysical characteristics and decomposition of NFT and FZL have been studied by differential scanning calorimetry (DSC), thermogravimetric analysis (TG) and mass-spectrometry. The saturated vapor pressures of the compounds have been measured using the transpiration method, and the standard thermodynamic functions of sublimation were calculated. It was revealed that the sublimation enthalpy and Gibbs energy of NFT are both higher than those for FZL, but a gain in the crystal lattice energy of NFT is leveled by an entropy increase. The solubility processes of the studied compounds in buffer solutions with pH 2.0, 7.4 and in 1-octanol was investigated at four temperatures from 298.15 to 313.15 K by the saturation shake-flask method. The thermodynamic functions of the dissolution and solvation processes of the studied compounds have been calculated based on the experimental data. Due to the fact that NFT is unstable in buffer solutions and undergoes a solution-mediated transformation from an anhydrate form to monohydrate in the solid state, the thermophysical characteristics and dissolution thermodynamics of the monohydrate were also investigated. It was demonstrated that a combination of experimental and theoretical methods allows performing an in-depth study of the relationships between the molecular and crystal structure and pharmaceutically relevant properties of nitrofuran antibiotics. Full article

(This article belongs to the Special Issue Synergies on the Trio Energy-Structure-Reactivity: Nitrogen- containing Heterocyclic Compounds)

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Review

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13 pages, 3888 KiB

Open AccessReview

Alkaloids and Selected Topics in Their Thermochemistry

by Maja Ponikvar-Svet, Diana N. Zeiger and Joel F. Liebman

Molecules 2021, 26(21), 6715; https://doi.org/10.3390/molecules26216715 - 6 Nov 2021

Cited by 9 | Viewed by 2260

Abstract

Alkaloid chemistry is varied and complex. Many alkaloids attract a great deal of interest because of their physiological activity, yet surprisingly little is known about the thermochemistry of these compounds, especially in the gas phase. In this paper, we investigate the thermochemical characteristics, specifically demethoxylation enthalpies rather than those derived from trans-methoxylation reactions, of a series of biologically relevant alkaloids in their condensed phase. Full article

(This article belongs to the Special Issue Synergies on the Trio Energy-Structure-Reactivity: Nitrogen- containing Heterocyclic Compounds)

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