Hermínio Diogo - Academia.edu (original) (raw)

Papers by Hermínio Diogo

Research paper thumbnail of Conformational and Nonconformational Polymorphism in 4′-Hydroxyvalerophenone: A Structure–Energetics–Dynamics Perspective

Crystal Growth & Design, Mar 2, 2020

Research paper thumbnail of Molecular mobility on the crystalline state of a hypolipidemic drug: simvastatin

HAL (Le Centre pour la Communication Scientifique Directe), Jul 1, 2011

Research paper thumbnail of Relations structure-dynamique dans un cristal à intérêt pharmaceutique: couplage RX, techniques de relaxation diélectrique et simulation moléculaire

HAL (Le Centre pour la Communication Scientifique Directe), Nov 1, 2017

Research paper thumbnail of Experimental and Molecular Dynamics Simulation Study of the Sublimation Energetics of Cyclopentadienyltricarbonylmanganese (Cymantrene)

Journal of Physical Chemistry A, Sep 18, 2008

The standard molar enthalpy of sublimation of monoclinic cyclopentadienyltricarbonylmanganese, Mn... more The standard molar enthalpy of sublimation of monoclinic cyclopentadienyltricarbonylmanganese, Mn(eta (5)-C 5H 5)(CO) 3, at 298.15 K, was determined as Delta sub H m (o)[Mn(eta (5)-C 5H 5)(CO) 3] = 75.97 +/- 0.37 kJ x mol (-1) from Knudsen effusion and Calvet-drop microcalorimetry measurements, thus considerably improving the very large inaccuracy (>10 kJ x mol (-1)) of the published data. The obtained value was used to assess the extension of the OPLS-based all-atom force field we previously developed for iron metallocenes to manganese organometallic compounds. The modified force field was able to reproduce the volumetric properties (density and unit-cell volume) of crystalline Mn(eta (5)-C 5H 5)(CO) 3 with a deviation of 0.6% and the experimentally determined enthalpy of sublimation with an accuracy of 1 kJ x mol (-1). The interaction (epsilon) and atomic-diameter (sigma) parameters of the Lennard-Jones (12-6) potential function used to calculate dispersion contributions within the framework of the force field were found to be transferable from iron to manganese.

Research paper thumbnail of Thermal behavior and dynamic fragility in amorphous carisoprodol. Correlation between the dynamic and thermodynamic fragilities

Thermochimica Acta, May 1, 2018

3-Results and discussion 3.1-Polymorphism in carisoprodol 3.1.1-Estimation of the enthalpy of fus... more 3-Results and discussion 3.1-Polymorphism in carisoprodol 3.1.1-Estimation of the enthalpy of fusion of polymorph B 3.1.2-Qualitative information on the kinetics of the phase transformations 3.2-Dynamic analysis of the glass transition by DSC 3.3-Molecular mobility in amorphous carisoprodol studied by TSDC 3.3.1-Estimation of the dynamic fragility from TSDC data 3.4-Dynamic and thermodynamic fragility 4-Conclusions Appendix-The calculation of the temperature dependent relaxation time, (T), from TSDC data.

[Research paper thumbnail of Phase transitions and charge transport of a novel ionic liquid with pharmacological applications [C2OHmim][Ibu)](https://a.academia-assets.com/images/blank-paper.jpg)

Research paper thumbnail of Disorder in Pharmaceuticals: Insights from Dielectric Spectroscopies and MD Simulations

Research paper thumbnail of Irreversible Magnetic Behaviour Caused by the Thermosalient Phenomenon in an Iron(III) Spin Crossover Complex

European Journal of Inorganic Chemistry, 2018

The new iron(III) complex [Fe(5‐I‐salEen)2]ClO4 exhibits both spin crossover, with hysteresis, be... more The new iron(III) complex [Fe(5‐I‐salEen)2]ClO4 exhibits both spin crossover, with hysteresis, between 304 K and 320 K (16 K hysteresis loop), and thermosalient phenomena. After a symmetry‐breaking phase transition between 120 and 130 K, confirmed by single‐crystal X‐ray diffraction, and the fragmentation of the crystals around 312 K, confirmed by differential scanning calorimetry and hot stage microscopy, the hysteresis loop disappears. This is the first example where the explicitly reported thermosalient effect modifies the magnetic properties of a given spin crossover crystal.

Research paper thumbnail of A force field for MD simulations on rhenium organometallic compounds developed from enthalpy of sublimation and X-ray diffraction measurements

The Journal of Chemical Thermodynamics, 2019

Research paper thumbnail of Bulk dynamics of the thermoresponsive random copolymer of di(ethylene glycol) methyl ether methacrylate (MEO2MA) and oligo(ethylene glycol) methyl ether methacrylate (OEGMA)

Research paper thumbnail of The standard molar enthalpy of the base catalysed hydrolysis of methyl paraben revisited

The Journal of Chemical Thermodynamics, 2016

Research paper thumbnail of Dynamic spin interchange in a tridentate Fe(iii) Schiff-base compound

Chemical Science, 2016

Dynamic spin interchange where crystals explode with preservation of magnetic memory is observed ... more Dynamic spin interchange where crystals explode with preservation of magnetic memory is observed for a mononuclear hysteretic Fe(iii) Schiff-base compound.

Research paper thumbnail of The Enthalpy of Formation of Pyracyclene

The enthalpy of formation of pyracyclene (I) in the cryst. state, at 298.15 K, has been detd. by ... more The enthalpy of formation of pyracyclene (I) in the cryst. state, at 298.15 K, has been detd. by microcombustion calorimetry, Delta fH Degmicro (I, cr, 298 K) = 324.1 +- 3.6 kJ mol-1. An estd. value of the enthalpy of sublimation, 84.9 +- 5.0 kJ mol-1, was used to derive the enthalpy of formation of I in the gaseous state, Delta fH Degmicro (I, g, 298 K) = 409.0 +- 6.2 kJ.mol-1. This value is compared to the corresponding predictions of several theor. methods. The MM2 mol. mechanics method reproduces the Delta fH Degmicro (I, g, 298 K) value proposed in this work to within 1 kJ mol-1. Ab initio MO calcns. give larger deviations (ca. 23 kJ mol-1). The MNDO and PM3 semiempirical methods give values that are 52 and 94 kJ mol-1 too high, resp. Group additivity schemes predict values ca. 40 kJ mol-1 lower than the result obtained in this work. [on SciFinder (R)]

Research paper thumbnail of Assessment and comparison of the properties of biodiesel synthesized from three different types of wet microalgal biomass

Journal of Applied Phycology, 2015

Research paper thumbnail of Hermínio Diogo, Manuel E. Minas da Piedade, Clementina Teixeira, “A Microscopia Química Associada ao Estudo da Série Electroquímica dos Metais”, Comunicação oral CO19, XXI Encontro Nacional da Sociedade Portuguesa de Química, Faculdade de Engenharia da Universidade do Porto, 11-13 de Junho de 2008

A Microscopia Química, explorada ao nível do ensino, permite uma abordagem muito apelativa das re... more A Microscopia Química, explorada ao nível do ensino, permite uma abordagem muito apelativa das reacções de oxidação-redução, pelo menos do ponto de vista qualitativo. Com ampliações até 15 é possível, para além disso, obter informação sobre reacções paralelas e, ao mesmo tempo, registar em forma de fotomicrografia e filme, padrões susceptíveis de serem utilizados para aplicações comerciais e industriais (indústria têxtil, papel, plásticos, artes gráficas, antiguidades, ourivesaria, etc). A série electroquímica dos metais foi estudada por este método, conjugando-a com a interpretação de diagramas de Latimer e de Frost, E-pH, e com a determinação experimental das forças electromotrizes padrão de redução pela equação de Nernst, constantes de equilíbrio termodinâmica e estequiométrica, tendo em conta os desvios à idealidade (determinação de coeficientes de actividade). Foram estudadas células galvânicas de concentração, composição e precipitação, para os metais Cu, Ag, Zn e Pb. Foram a...

Research paper thumbnail of A Microscopia Química Associada Ao Estudo Da Série Electroquímica Dos Metais

A Microscopia Química, explorada ao nível do ensino, permite uma abordagem muito apelativa das re... more A Microscopia Química, explorada ao nível do ensino, permite uma abordagem muito apelativa das reacções de oxidação-redução, pelo menos do ponto de vista qualitativo. Com ampliações até 15 é possível, para além disso, obter informação sobre reacções paralelas e, ao mesmo tempo, registar em forma de fotomicrografia e filme, padrões susceptíveis de serem utilizados para aplicações comerciais e industriais (indústria têxtil, papel, plásticos, artes gráficas, antiguidades, ourivesaria, etc). A série electroquímica dos metais foi estudada por este método, conjugando-a com a interpretação de diagramas de Latimer e de Frost, E-pH, e com a determinação experimental das forças electromotrizes padrão de redução pela equação de Nernst, constantes de equilíbrio termodinâmica e estequiométrica, tendo em conta os desvios à idealidade (determinação de coeficientes de actividade). Foram estudadas células galvânicas de concentração, composição e precipitação, para os metais Cu, Ag, Zn e Pb. Foram a...

Research paper thumbnail of Metal—Carbon and Metal—Hydrogen Bond Dissociation Enthalpies from Classical and Nonclassical Calorimetric Studies

ACS Symposium Series, 1990

Research paper thumbnail of Standard enthalpy of formation and enthalpy of vaporization of di-1,1-dimethylethyl peroxide. Re-evaluation of the standard enthalpy of formation of the di-1,1-dimethylethoxy radical

The Journal of Chemical Thermodynamics, 1995

The standard molar enthalpy of formation of B = CH3C(CH3)2OOC(CH3)2CH3(1): ΔfHm°(B,1) = −(380.8 ±... more The standard molar enthalpy of formation of B = CH3C(CH3)2OOC(CH3)2CH3(1): ΔfHm°(B,1) = −(380.8 ± 2.0) kJ·mol−1, and its standard molar enthalpy of vaporization: ΔvapHm°(B) = (39.3 ± 1.0) kJ·mol−1have been determined at the temperature 298.15 K using combustion calorimetry, ebulliometry, and heat-capacity measurements by d.s.c. The obtained values were used to re-evaluate the standard molar enthalpy of formation of CH3C(CH3)2O

Research paper thumbnail of A micro-combustion calorimeter suitable for samples of mass 10 mg to 50 mg. Application to solid compounds of C, H, and O, and of C, H, O, and N

The Journal of Chemical Thermodynamics, 1995

A micro-combustion calorimeter suitable for samples of mass about 10 mg to 50 mg is described. Ca... more A micro-combustion calorimeter suitable for samples of mass about 10 mg to 50 mg is described. Calibration with benzoic acid led to the energy equivalent ε° = (1809.82 ± 0.28) J·K−1. The calorimeter was tested by determining the standard molar enthalpies of formation at the temperature 298.15 K of salicylic acid: ΔfHm°{o-C6H4(OH)(CO2H), cr} = −(587.8 ± 1.5) kJ mol−1and of urea: ΔfHm°(H2NCONH2, cr) = − (333.4 ± 0.6) kJ mol−1.

Research paper thumbnail of Enthalpies of formation of buckminsterfullerene (C60) and of the parent ions C60 +, C60 2+, C60 3+ and C60 ?

Journal of the Chemical Society, Faraday Transactions, 1993

Research paper thumbnail of Conformational and Nonconformational Polymorphism in 4′-Hydroxyvalerophenone: A Structure–Energetics–Dynamics Perspective

Crystal Growth & Design, Mar 2, 2020

Research paper thumbnail of Molecular mobility on the crystalline state of a hypolipidemic drug: simvastatin

HAL (Le Centre pour la Communication Scientifique Directe), Jul 1, 2011

Research paper thumbnail of Relations structure-dynamique dans un cristal à intérêt pharmaceutique: couplage RX, techniques de relaxation diélectrique et simulation moléculaire

HAL (Le Centre pour la Communication Scientifique Directe), Nov 1, 2017

Research paper thumbnail of Experimental and Molecular Dynamics Simulation Study of the Sublimation Energetics of Cyclopentadienyltricarbonylmanganese (Cymantrene)

Journal of Physical Chemistry A, Sep 18, 2008

The standard molar enthalpy of sublimation of monoclinic cyclopentadienyltricarbonylmanganese, Mn... more The standard molar enthalpy of sublimation of monoclinic cyclopentadienyltricarbonylmanganese, Mn(eta (5)-C 5H 5)(CO) 3, at 298.15 K, was determined as Delta sub H m (o)[Mn(eta (5)-C 5H 5)(CO) 3] = 75.97 +/- 0.37 kJ x mol (-1) from Knudsen effusion and Calvet-drop microcalorimetry measurements, thus considerably improving the very large inaccuracy (>10 kJ x mol (-1)) of the published data. The obtained value was used to assess the extension of the OPLS-based all-atom force field we previously developed for iron metallocenes to manganese organometallic compounds. The modified force field was able to reproduce the volumetric properties (density and unit-cell volume) of crystalline Mn(eta (5)-C 5H 5)(CO) 3 with a deviation of 0.6% and the experimentally determined enthalpy of sublimation with an accuracy of 1 kJ x mol (-1). The interaction (epsilon) and atomic-diameter (sigma) parameters of the Lennard-Jones (12-6) potential function used to calculate dispersion contributions within the framework of the force field were found to be transferable from iron to manganese.

Research paper thumbnail of Thermal behavior and dynamic fragility in amorphous carisoprodol. Correlation between the dynamic and thermodynamic fragilities

Thermochimica Acta, May 1, 2018

3-Results and discussion 3.1-Polymorphism in carisoprodol 3.1.1-Estimation of the enthalpy of fus... more 3-Results and discussion 3.1-Polymorphism in carisoprodol 3.1.1-Estimation of the enthalpy of fusion of polymorph B 3.1.2-Qualitative information on the kinetics of the phase transformations 3.2-Dynamic analysis of the glass transition by DSC 3.3-Molecular mobility in amorphous carisoprodol studied by TSDC 3.3.1-Estimation of the dynamic fragility from TSDC data 3.4-Dynamic and thermodynamic fragility 4-Conclusions Appendix-The calculation of the temperature dependent relaxation time, (T), from TSDC data.

[Research paper thumbnail of Phase transitions and charge transport of a novel ionic liquid with pharmacological applications [C2OHmim][Ibu)](https://a.academia-assets.com/images/blank-paper.jpg)

Research paper thumbnail of Disorder in Pharmaceuticals: Insights from Dielectric Spectroscopies and MD Simulations

Research paper thumbnail of Irreversible Magnetic Behaviour Caused by the Thermosalient Phenomenon in an Iron(III) Spin Crossover Complex

European Journal of Inorganic Chemistry, 2018

The new iron(III) complex [Fe(5‐I‐salEen)2]ClO4 exhibits both spin crossover, with hysteresis, be... more The new iron(III) complex [Fe(5‐I‐salEen)2]ClO4 exhibits both spin crossover, with hysteresis, between 304 K and 320 K (16 K hysteresis loop), and thermosalient phenomena. After a symmetry‐breaking phase transition between 120 and 130 K, confirmed by single‐crystal X‐ray diffraction, and the fragmentation of the crystals around 312 K, confirmed by differential scanning calorimetry and hot stage microscopy, the hysteresis loop disappears. This is the first example where the explicitly reported thermosalient effect modifies the magnetic properties of a given spin crossover crystal.

Research paper thumbnail of A force field for MD simulations on rhenium organometallic compounds developed from enthalpy of sublimation and X-ray diffraction measurements

The Journal of Chemical Thermodynamics, 2019

Research paper thumbnail of Bulk dynamics of the thermoresponsive random copolymer of di(ethylene glycol) methyl ether methacrylate (MEO2MA) and oligo(ethylene glycol) methyl ether methacrylate (OEGMA)

Research paper thumbnail of The standard molar enthalpy of the base catalysed hydrolysis of methyl paraben revisited

The Journal of Chemical Thermodynamics, 2016

Research paper thumbnail of Dynamic spin interchange in a tridentate Fe(iii) Schiff-base compound

Chemical Science, 2016

Dynamic spin interchange where crystals explode with preservation of magnetic memory is observed ... more Dynamic spin interchange where crystals explode with preservation of magnetic memory is observed for a mononuclear hysteretic Fe(iii) Schiff-base compound.

Research paper thumbnail of The Enthalpy of Formation of Pyracyclene

The enthalpy of formation of pyracyclene (I) in the cryst. state, at 298.15 K, has been detd. by ... more The enthalpy of formation of pyracyclene (I) in the cryst. state, at 298.15 K, has been detd. by microcombustion calorimetry, Delta fH Degmicro (I, cr, 298 K) = 324.1 +- 3.6 kJ mol-1. An estd. value of the enthalpy of sublimation, 84.9 +- 5.0 kJ mol-1, was used to derive the enthalpy of formation of I in the gaseous state, Delta fH Degmicro (I, g, 298 K) = 409.0 +- 6.2 kJ.mol-1. This value is compared to the corresponding predictions of several theor. methods. The MM2 mol. mechanics method reproduces the Delta fH Degmicro (I, g, 298 K) value proposed in this work to within 1 kJ mol-1. Ab initio MO calcns. give larger deviations (ca. 23 kJ mol-1). The MNDO and PM3 semiempirical methods give values that are 52 and 94 kJ mol-1 too high, resp. Group additivity schemes predict values ca. 40 kJ mol-1 lower than the result obtained in this work. [on SciFinder (R)]

Research paper thumbnail of Assessment and comparison of the properties of biodiesel synthesized from three different types of wet microalgal biomass

Journal of Applied Phycology, 2015

Research paper thumbnail of Hermínio Diogo, Manuel E. Minas da Piedade, Clementina Teixeira, “A Microscopia Química Associada ao Estudo da Série Electroquímica dos Metais”, Comunicação oral CO19, XXI Encontro Nacional da Sociedade Portuguesa de Química, Faculdade de Engenharia da Universidade do Porto, 11-13 de Junho de 2008

A Microscopia Química, explorada ao nível do ensino, permite uma abordagem muito apelativa das re... more A Microscopia Química, explorada ao nível do ensino, permite uma abordagem muito apelativa das reacções de oxidação-redução, pelo menos do ponto de vista qualitativo. Com ampliações até 15 é possível, para além disso, obter informação sobre reacções paralelas e, ao mesmo tempo, registar em forma de fotomicrografia e filme, padrões susceptíveis de serem utilizados para aplicações comerciais e industriais (indústria têxtil, papel, plásticos, artes gráficas, antiguidades, ourivesaria, etc). A série electroquímica dos metais foi estudada por este método, conjugando-a com a interpretação de diagramas de Latimer e de Frost, E-pH, e com a determinação experimental das forças electromotrizes padrão de redução pela equação de Nernst, constantes de equilíbrio termodinâmica e estequiométrica, tendo em conta os desvios à idealidade (determinação de coeficientes de actividade). Foram estudadas células galvânicas de concentração, composição e precipitação, para os metais Cu, Ag, Zn e Pb. Foram a...

Research paper thumbnail of A Microscopia Química Associada Ao Estudo Da Série Electroquímica Dos Metais

A Microscopia Química, explorada ao nível do ensino, permite uma abordagem muito apelativa das re... more A Microscopia Química, explorada ao nível do ensino, permite uma abordagem muito apelativa das reacções de oxidação-redução, pelo menos do ponto de vista qualitativo. Com ampliações até 15 é possível, para além disso, obter informação sobre reacções paralelas e, ao mesmo tempo, registar em forma de fotomicrografia e filme, padrões susceptíveis de serem utilizados para aplicações comerciais e industriais (indústria têxtil, papel, plásticos, artes gráficas, antiguidades, ourivesaria, etc). A série electroquímica dos metais foi estudada por este método, conjugando-a com a interpretação de diagramas de Latimer e de Frost, E-pH, e com a determinação experimental das forças electromotrizes padrão de redução pela equação de Nernst, constantes de equilíbrio termodinâmica e estequiométrica, tendo em conta os desvios à idealidade (determinação de coeficientes de actividade). Foram estudadas células galvânicas de concentração, composição e precipitação, para os metais Cu, Ag, Zn e Pb. Foram a...

Research paper thumbnail of Metal—Carbon and Metal—Hydrogen Bond Dissociation Enthalpies from Classical and Nonclassical Calorimetric Studies

ACS Symposium Series, 1990

Research paper thumbnail of Standard enthalpy of formation and enthalpy of vaporization of di-1,1-dimethylethyl peroxide. Re-evaluation of the standard enthalpy of formation of the di-1,1-dimethylethoxy radical

The Journal of Chemical Thermodynamics, 1995

The standard molar enthalpy of formation of B = CH3C(CH3)2OOC(CH3)2CH3(1): ΔfHm°(B,1) = −(380.8 ±... more The standard molar enthalpy of formation of B = CH3C(CH3)2OOC(CH3)2CH3(1): ΔfHm°(B,1) = −(380.8 ± 2.0) kJ·mol−1, and its standard molar enthalpy of vaporization: ΔvapHm°(B) = (39.3 ± 1.0) kJ·mol−1have been determined at the temperature 298.15 K using combustion calorimetry, ebulliometry, and heat-capacity measurements by d.s.c. The obtained values were used to re-evaluate the standard molar enthalpy of formation of CH3C(CH3)2O

Research paper thumbnail of A micro-combustion calorimeter suitable for samples of mass 10 mg to 50 mg. Application to solid compounds of C, H, and O, and of C, H, O, and N

The Journal of Chemical Thermodynamics, 1995

A micro-combustion calorimeter suitable for samples of mass about 10 mg to 50 mg is described. Ca... more A micro-combustion calorimeter suitable for samples of mass about 10 mg to 50 mg is described. Calibration with benzoic acid led to the energy equivalent ε° = (1809.82 ± 0.28) J·K−1. The calorimeter was tested by determining the standard molar enthalpies of formation at the temperature 298.15 K of salicylic acid: ΔfHm°{o-C6H4(OH)(CO2H), cr} = −(587.8 ± 1.5) kJ mol−1and of urea: ΔfHm°(H2NCONH2, cr) = − (333.4 ± 0.6) kJ mol−1.

Research paper thumbnail of Enthalpies of formation of buckminsterfullerene (C60) and of the parent ions C60 +, C60 2+, C60 3+ and C60 ?

Journal of the Chemical Society, Faraday Transactions, 1993