Pub Date : 2024-10-26DOI: 10.1016/j.supflu.2024.106431
Francisco Adrián Sánchez , Martín Cismondi Duarte
The computation of Global Phase Equilibrium Diagrams (GPED) for binary systems, including critical and three-phase equilibrium curves, is crucial for analyzing process conditions and assessing thermodynamic models. In the past two decades, algorithmic strategies and GPEC software have become essential tools. However, numerical problems can arise with the original algorithm for highly asymmetric systems, such as gases or water with heavy compounds or polymers, hindering the completion of GPED and related diagrams.
This study presents an innovative calculation methodology to address these challenges. Our approach extends existing algorithms to achieve automatic GPED generation without user intervention, focusing on nearly pure phases. We apply our methodology to systems such as methane or water with heavy alkanes, and CO2 + silicones. The proposed algorithmic strategies effectively handle asymmetric systems, different types of phase behavior, and the estimation of extremely low concentrations in nearly pure phases along the vapor-liquid-liquid equilibrium curve.
{"title":"Calculation of critical endpoints and phase diagrams of highly asymmetric binary systems","authors":"Francisco Adrián Sánchez , Martín Cismondi Duarte","doi":"10.1016/j.supflu.2024.106431","DOIUrl":"10.1016/j.supflu.2024.106431","url":null,"abstract":"<div><div>The computation of Global Phase Equilibrium Diagrams (GPED) for binary systems, including critical and three-phase equilibrium curves, is crucial for analyzing process conditions and assessing thermodynamic models. In the past two decades, algorithmic strategies and GPEC software have become essential tools. However, numerical problems can arise with the original algorithm for highly asymmetric systems, such as gases or water with heavy compounds or polymers, hindering the completion of GPED and related diagrams.</div><div>This study presents an innovative calculation methodology to address these challenges. Our approach extends existing algorithms to achieve automatic GPED generation without user intervention, focusing on nearly pure phases. We apply our methodology to systems such as methane or water with heavy alkanes, and CO2 + silicones. The proposed algorithmic strategies effectively handle asymmetric systems, different types of phase behavior, and the estimation of extremely low concentrations in nearly pure phases along the vapor-liquid-liquid equilibrium curve.</div></div>","PeriodicalId":17078,"journal":{"name":"Journal of Supercritical Fluids","volume":"216 ","pages":"Article 106431"},"PeriodicalIF":3.4,"publicationDate":"2024-10-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142571569","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-18DOI: 10.1016/j.supflu.2024.106430
Priscilla C. Veggi , Tahmasb Hatami , Leonardo F. Campos , Luciana P. Mazur , Luana E. do Carmo , Lucia H.I. Mei , Juliane Viganó
Renowned for its medicinal properties, barbatimão bark extract contains bioactive compounds susceptible to degradation, necessitating their safeguarding within a stable matrix for diverse biomedical applications. This study investigates using high-pressure liquid impregnation (HPLI) to load barbatimão extract into biopolymeric membranes at 30, 45, and 60 °C, and 11 MPa. HPLI combines the simplicity of direct immersion with improved mass transfer rates under high pressure. Biopolymeric membranes made from poly(butylene succinate) (PBS), poly(lactic acid) (PLA), and Cloisite 20 A (C20A) in a 50/45/5 (v/v) composition were created using electrospinning. Comparative analysis with conventional methods, along with evaluation of impregnated membrane properties using SEM, FTIR, and thermogravimetric analysis, demonstrated the effectiveness of HPLI. HPLI yielded markedly higher phenolic compound loadings, peaking at 43.79 mg ETA/g membrane at 11 MPa and 45 °C over 6 h, compared to 25.44 mg ETA/g membrane with conventional impregnation at ambient pressure and 45 °C over the same duration.
{"title":"High-pressure liquid impregnation of barbatimão bark extract into biopolymeric membrane composed of PBS/PLA and Cloisite 20 A blend","authors":"Priscilla C. Veggi , Tahmasb Hatami , Leonardo F. Campos , Luciana P. Mazur , Luana E. do Carmo , Lucia H.I. Mei , Juliane Viganó","doi":"10.1016/j.supflu.2024.106430","DOIUrl":"10.1016/j.supflu.2024.106430","url":null,"abstract":"<div><div>Renowned for its medicinal properties, barbatimão bark extract contains bioactive compounds susceptible to degradation, necessitating their safeguarding within a stable matrix for diverse biomedical applications. This study investigates using high-pressure liquid impregnation (HPLI) to load barbatimão extract into biopolymeric membranes at 30, 45, and 60 °C, and 11 MPa. HPLI combines the simplicity of direct immersion with improved mass transfer rates under high pressure. Biopolymeric membranes made from poly(butylene succinate) (PBS), poly(lactic acid) (PLA), and Cloisite 20 A (C20A) in a 50/45/5 (v/v) composition were created using electrospinning. Comparative analysis with conventional methods, along with evaluation of impregnated membrane properties using SEM, FTIR, and thermogravimetric analysis, demonstrated the effectiveness of HPLI. HPLI yielded markedly higher phenolic compound loadings, peaking at 43.79 mg ETA/g membrane at 11 MPa and 45 °C over 6 h, compared to 25.44 mg ETA/g membrane with conventional impregnation at ambient pressure and 45 °C over the same duration.</div></div>","PeriodicalId":17078,"journal":{"name":"Journal of Supercritical Fluids","volume":"216 ","pages":"Article 106430"},"PeriodicalIF":3.4,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142535466","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-16DOI: 10.1016/j.supflu.2024.106428
J.A. López-Limón , A.S. Hernández-Cázares , J.V. Hidalgo-Contreras , G. Romero - De la Vega , R.A. Mellado-Pumarino , M.A. Ríos-Corripio
C-phycocyanin (CPC) is a phycobiliprotein present in spirulina, which, due to its blue color, non-toxic nature, fluorescent and antioxidant properties, is of interest in the food and pharmaceutical industries. Different methods of extraction and stabilization are being investigated, including supercritical CO2 extraction, a method applied to obtain bioactive compounds from plant matrices. In this work, the effect of applying supercritical CO2 as pretreatment for the extraction of CPC at different parameters (pressure, temperature, use of cosolvent) was evaluated. Best pretreatment conditions to obtain the highest purity were at 17 MPa and 45 °C, considering it reagent grade. When comparing UV and FTIR spectra of the raffinates, a similarity was obtained with the analytical standard, with the presence of a band at 620 nm in UV and for FTIR a band at 1650 and 1540 cm−1 that corresponds to amide I and amide II, corroborating their presence and the structural characteristics.
{"title":"Effect of supercritical CO2 extraction as pretreatment to obtain C-phycocyanin from spirulina (Arthrospira maxima)","authors":"J.A. López-Limón , A.S. Hernández-Cázares , J.V. Hidalgo-Contreras , G. Romero - De la Vega , R.A. Mellado-Pumarino , M.A. Ríos-Corripio","doi":"10.1016/j.supflu.2024.106428","DOIUrl":"10.1016/j.supflu.2024.106428","url":null,"abstract":"<div><div>C-phycocyanin (CPC) is a phycobiliprotein present in spirulina, which, due to its blue color, non-toxic nature, fluorescent and antioxidant properties, is of interest in the food and pharmaceutical industries. Different methods of extraction and stabilization are being investigated, including supercritical CO<sub>2</sub> extraction, a method applied to obtain bioactive compounds from plant matrices. In this work, the effect of applying supercritical CO<sub>2</sub> as pretreatment for the extraction of CPC at different parameters (pressure, temperature, use of cosolvent) was evaluated. Best pretreatment conditions to obtain the highest purity were at 17 MPa and 45 °C, considering it reagent grade. When comparing UV and FTIR spectra of the raffinates, a similarity was obtained with the analytical standard, with the presence of a band at 620 nm in UV and for FTIR a band at 1650 and 1540 cm<sup>−1</sup> that corresponds to amide I and amide II, corroborating their presence and the structural characteristics.</div></div>","PeriodicalId":17078,"journal":{"name":"Journal of Supercritical Fluids","volume":"215 ","pages":"Article 106428"},"PeriodicalIF":3.4,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142525919","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-16DOI: 10.1016/j.supflu.2024.106426
Marcelle Guth de Freitas Batista, Giulia Herbst, Mônica Beatriz Kolicheski, Fernando A.P. Voll, Marcos L. Corazza
In this study, the use of supercritical CO2 (scCO2), and compressed propane (CP) were applied to obtain a crude extract rich in d-limonene (DL) from Ponkan waste from the juice industry. The moisture content of the dried waste was 8.53 % and a particle size of 28 mesh was determined for the extractions. Soxhlet extraction was performed with 5 g of waste and 150 mL of n-hexane and showed an extraction yield of 1.94 % with a DL fraction of 44.83 %. The experimental design was carried out for scCO2 and CP and the condition that resulted in the highest extraction yield (1.50 %) and DL fraction (89.01 %) using scCO2 was 80 °C and 20 MPa, while when C3H8 was used, the highest extraction yield (2.35 %) and DL fraction (89.38 %) were obtained at 40 °C and 15 MPa. The results show that scCO2 and C3H8 are selective solvents for DL extraction.
{"title":"d-Limonene extraction from Citrus reticulata Blanco wastes with compressed propane and supercritical CO2","authors":"Marcelle Guth de Freitas Batista, Giulia Herbst, Mônica Beatriz Kolicheski, Fernando A.P. Voll, Marcos L. Corazza","doi":"10.1016/j.supflu.2024.106426","DOIUrl":"10.1016/j.supflu.2024.106426","url":null,"abstract":"<div><div>In this study, the use of supercritical CO<sub>2</sub> (scCO<sub>2</sub>), and compressed propane (CP) were applied to obtain a crude extract rich in <em>d</em>-limonene (DL) from Ponkan waste from the juice industry. The moisture content of the dried waste was 8.53 % and a particle size of 28 mesh was determined for the extractions. Soxhlet extraction was performed with 5 g of waste and 150 mL of <em>n</em>-hexane and showed an extraction yield of 1.94 % with a DL fraction of 44.83 %. The experimental design was carried out for scCO<sub>2</sub> and CP and the condition that resulted in the highest extraction yield (1.50 %) and DL fraction (89.01 %) using scCO<sub>2</sub> was 80 °C and 20 MPa, while when C<sub>3</sub>H<sub>8</sub> was used, the highest extraction yield (2.35 %) and DL fraction (89.38 %) were obtained at 40 °C and 15 MPa. The results show that scCO<sub>2</sub> and C<sub>3</sub>H<sub>8</sub> are selective solvents for DL extraction.</div></div>","PeriodicalId":17078,"journal":{"name":"Journal of Supercritical Fluids","volume":"215 ","pages":"Article 106426"},"PeriodicalIF":3.4,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142525916","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-16DOI: 10.1016/j.supflu.2024.106429
Nik Suhaimi Mat Hassan , Md Mokarram Badsha , Mark Harris Zuknik , Shabib Al Rashdi , Ahmad Naim Ahmad Yahaya , Venugopal Balakrishanan , Azhar Mat Easa , Md Sohrab Hossain
The experimental conditions of supercritical carbon dioxide (scCO2) extraction of virgin palm oil (VPO) from oil palm mesocarp fiber (OPMF) were optimized using the Response Surface Methodology (RSM). Results showed that a maximum of 28.68 % of VPO extraction was obtained at the optimal experimental conditions of scCO2 extraction: pressure of 31 MPa, temperature of 340 K, and extraction time of 80 min. The second-order rate equation, Arrhenius equation and Eyring theory were employed to assess the kinetics behaviour, activation energy and thermodynamics behaviour of scCO2 extraction of VPO from oil palm mesocarp fiber. The lower activation energy value (12.17 kJ/mol) of scCO2 for the extraction of VPO from OPMF indicates that the scCO2 extraction technology is less dependent on temperature during the extraction of VPO from OPMF. The physicochemical properties and fatty acids compositions analyses reveal that the scCO2 extracted VPO contains high carotenoids content (982 μg/g), low free fatty acids content (0.31 wt%), higher oxidative stability and higher unsaturated fatty acids content.
{"title":"Supercritical CO2 as a green technology for carotenoids-rich virgin palm oil production: Process optimization, kinetics and thermodynamics modeling","authors":"Nik Suhaimi Mat Hassan , Md Mokarram Badsha , Mark Harris Zuknik , Shabib Al Rashdi , Ahmad Naim Ahmad Yahaya , Venugopal Balakrishanan , Azhar Mat Easa , Md Sohrab Hossain","doi":"10.1016/j.supflu.2024.106429","DOIUrl":"10.1016/j.supflu.2024.106429","url":null,"abstract":"<div><div>The experimental conditions of supercritical carbon dioxide (scCO<sub>2</sub>) extraction of virgin palm oil (VPO) from oil palm mesocarp fiber (OPMF) were optimized using the Response Surface Methodology (RSM). Results showed that a maximum of 28.68 % of VPO extraction was obtained at the optimal experimental conditions of scCO<sub>2</sub> extraction: pressure of 31 MPa, temperature of 340 K, and extraction time of 80 min. The second-order rate equation, <em>Arrhenius</em> equation and <em>Eyring</em> theory were employed to assess the kinetics behaviour, activation energy and thermodynamics behaviour of scCO<sub>2</sub> extraction of VPO from oil palm mesocarp fiber. The lower activation energy value (12.17 kJ/mol) of scCO<sub>2</sub> for the extraction of VPO from OPMF indicates that the scCO<sub>2</sub> extraction technology is less dependent on temperature during the extraction of VPO from OPMF. The physicochemical properties and fatty acids compositions analyses reveal that the scCO<sub>2</sub> extracted VPO contains high carotenoids content (982 μg/g), low free fatty acids content (0.31 wt%), higher oxidative stability and higher unsaturated fatty acids content.</div></div>","PeriodicalId":17078,"journal":{"name":"Journal of Supercritical Fluids","volume":"215 ","pages":"Article 106429"},"PeriodicalIF":3.4,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142525918","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-15DOI: 10.1016/j.supflu.2024.106427
Giselle Cristine Melo Aires , Kelly Roberta Pinheiro Pantoja , Eduardo Gama Ortiz Menezes , Jean Maurício Leão Pinheiro , Verônica Maria Souza Bezerra , Maria Eduarda Ferraz de Carvalho , Raul Nunes de Carvalho Junior
This study investigates the effectiveness of macaúba oil extraction using supercritical carbon dioxide, focusing on determining operational parameters such as temperature and pressure that maximize the quality and yield of the extract obtained. The extraction was carried out using freeze-dried macaúba pulp, under varying conditions of pressure and temperature. The overall yield isotherms of macaúba oil obtained, the solubility of the solute, composition of fatty acids, triglycerides, phenolic compounds, in addition to the antioxidant capacity and antimicrobial activity, were evaluated, before and after extraction. The results demonstrated that, under the conditions evaluated, the extraction process achieved maximum oil yields of 24.4 %, with a predominance of unsaturated acids rich in antioxidants and high concentrations of oleic acid (64.12 %), β-carotene (80.06 mg/kg) and α-tocopherol (114.66 mg/100 g of oil). This promising method offers a sustainable alternative for the production of compounds with high nutritional value, highlighting its potential for industrial applications.
{"title":"Determination of global yield isotherms of macaúba (Acrocomia aculeata) extract using supercritical CO2 and its biological potential","authors":"Giselle Cristine Melo Aires , Kelly Roberta Pinheiro Pantoja , Eduardo Gama Ortiz Menezes , Jean Maurício Leão Pinheiro , Verônica Maria Souza Bezerra , Maria Eduarda Ferraz de Carvalho , Raul Nunes de Carvalho Junior","doi":"10.1016/j.supflu.2024.106427","DOIUrl":"10.1016/j.supflu.2024.106427","url":null,"abstract":"<div><div>This study investigates the effectiveness of macaúba oil extraction using supercritical carbon dioxide, focusing on determining operational parameters such as temperature and pressure that maximize the quality and yield of the extract obtained. The extraction was carried out using freeze-dried macaúba pulp, under varying conditions of pressure and temperature. The overall yield isotherms of macaúba oil obtained, the solubility of the solute, composition of fatty acids, triglycerides, phenolic compounds, in addition to the antioxidant capacity and antimicrobial activity, were evaluated, before and after extraction. The results demonstrated that, under the conditions evaluated, the extraction process achieved maximum oil yields of 24.4 %, with a predominance of unsaturated acids rich in antioxidants and high concentrations of oleic acid (64.12 %), β-carotene (80.06 mg/kg) and α-tocopherol (114.66 mg/100 g of oil). This promising method offers a sustainable alternative for the production of compounds with high nutritional value, highlighting its potential for industrial applications.</div></div>","PeriodicalId":17078,"journal":{"name":"Journal of Supercritical Fluids","volume":"215 ","pages":"Article 106427"},"PeriodicalIF":3.4,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142525915","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-15DOI: 10.1016/j.supflu.2024.106425
Gyudong Kim , Sooin Kim , Hanseob Jeong , Jaewon Chung
This study investigates the mixing behavior in a Y-junction mixer for supercritical water hydrolysis using large eddy simulation with a discrete phase model. Yield changes were simulated using a two-step reaction model with first-order kinetics, based on particles’ temporal temperature data. Effective mixing produced closely matched mass and particle flow temperature distributions, both exhibiting bell-shaped profiles near the mixed temperature. Although variations in flow rate within ±25 % and changes in the inlet temperatures of supercritical water from 350 °C to 430 °C and subcritical water from 100 °C to 170 °C did not significantly affect the overall mixing performance, they did alter the mixed temperature and, subsequently, yield changes. Additionally, backflow occurred when Richardson number for the subcritical inlet reached approximately 7. In effective mixing, simulated yields were approximately 15 % lower than the ideal theoretical yields, calculated using the reaction rate constant at the mixed temperature.
{"title":"Numerical analysis of mixing performance in Y-junction mixers and its impact on yields from supercritical water hydrolysis","authors":"Gyudong Kim , Sooin Kim , Hanseob Jeong , Jaewon Chung","doi":"10.1016/j.supflu.2024.106425","DOIUrl":"10.1016/j.supflu.2024.106425","url":null,"abstract":"<div><div>This study investigates the mixing behavior in a Y-junction mixer for supercritical water hydrolysis using large eddy simulation with a discrete phase model. Yield changes were simulated using a two-step reaction model with first-order kinetics, based on particles’ temporal temperature data. Effective mixing produced closely matched mass and particle flow temperature distributions, both exhibiting bell-shaped profiles near the mixed temperature. Although variations in flow rate within ±25 % and changes in the inlet temperatures of supercritical water from 350 °C to 430 °C and subcritical water from 100 °C to 170 °C did not significantly affect the overall mixing performance, they did alter the mixed temperature and, subsequently, yield changes. Additionally, backflow occurred when Richardson number for the subcritical inlet reached approximately 7. In effective mixing, simulated yields were approximately 15 % lower than the ideal theoretical yields, calculated using the reaction rate constant at the mixed temperature.</div></div>","PeriodicalId":17078,"journal":{"name":"Journal of Supercritical Fluids","volume":"215 ","pages":"Article 106425"},"PeriodicalIF":3.4,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142525917","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-09DOI: 10.1016/j.supflu.2024.106424
Adolfo L. Figueredo , Carolina S. Costa , Maitê L. Gothe , Reinaldo C. Bazito , Pedro Vidinha , Camila G. Pereira
The catalytic hydrogenation of fumaric acid, a prominent bioplatform molecule, was evaluated over PdRe/SiO2 within a variety of reaction media compositions comprising methanol, water, supercritical CO2, and their assorted combinations with H2, across a range of temperature and pressure regimes. Meticulous manipulation of the reaction media composition facilitated the precise modulation of catalytic activity to favor specific hydrogenation products. For instance, within a water-saturated supercritical CO2 medium, γ-butyrolactone exhibited a noteworthy 89 % selectivity at 188°C under 250 bar total pressure, whereas in the methanol-containing supercritical CO2 system, hydrogenation displayed a remarkable 91 % selectivity towards tetrahydrofuran at 175°C and 250 bar. This investigation underscores the multifaceted influence of CO2, extending beyond its pressure-derived effects - it functions as a solvent, selectively favoring catalytic pathways and enhancing product selectivity.
{"title":"Tuning the selectivity of catalytic hydrogenation of fumaric acid with supercritical CO2","authors":"Adolfo L. Figueredo , Carolina S. Costa , Maitê L. Gothe , Reinaldo C. Bazito , Pedro Vidinha , Camila G. Pereira","doi":"10.1016/j.supflu.2024.106424","DOIUrl":"10.1016/j.supflu.2024.106424","url":null,"abstract":"<div><div>The catalytic hydrogenation of fumaric acid, a prominent bioplatform molecule, was evaluated over PdRe/SiO<sub>2</sub> within a variety of reaction media compositions comprising methanol, water, supercritical CO<sub>2</sub>, and their assorted combinations with H<sub>2</sub>, across a range of temperature and pressure regimes. Meticulous manipulation of the reaction media composition facilitated the precise modulation of catalytic activity to favor specific hydrogenation products. For instance, within a water-saturated supercritical CO<sub>2</sub> medium, γ-butyrolactone exhibited a noteworthy 89 % selectivity at 188°C under 250 bar total pressure, whereas in the methanol-containing supercritical CO<sub>2</sub> system, hydrogenation displayed a remarkable 91 % selectivity towards tetrahydrofuran at 175°C and 250 bar. This investigation underscores the multifaceted influence of CO<sub>2</sub>, extending beyond its pressure-derived effects - it functions as a solvent, selectively favoring catalytic pathways and enhancing product selectivity.</div></div>","PeriodicalId":17078,"journal":{"name":"Journal of Supercritical Fluids","volume":"215 ","pages":"Article 106424"},"PeriodicalIF":3.4,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142446094","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-03DOI: 10.1016/j.supflu.2024.106422
Luis José López-Méndez , Rubria Marlen Martínez-Cásares , Alberto López-Luna , Héctor Luna , Patricia Guadarrama , Rosa Estrada-Reyes , Raúl G. Enríquez , Julia Cassani
Hesperidin is a rutinoside of flavanone type with relevant therapeutic properties but poor water solubility which limits its therapeutic applicability. However, cyclodextrins (CDs) have been successfully used as drug carriers to enhance the solubility of several drugs, to improve their bioavailability, and therapeutic efficacy. We report herein the formation of inclusion complexes of β-cyclodextrin and hesperidin through the green approaches mechanochemistry and supercritical fluid and compare these results versus the classical lyophilization method. The resulting stoichiometries and the specific interactions of the complexes were analyzed by NMR, UV, and mass spectrometry. The β-cyclodextrin and hesperidin inclusion complex (IC) successfully obtained through green methodologies demonstrated superior levels of flavonoid content. In terms of solubility, the mechanochemistry inclusion complex showed the best improvement in solubility. We demonstrate herein that the use of green methodologies such as supercritical fluids and mechanochemistry are useful alternatives to the conventional method of lyophilization, to improve the solubility of β-cyclodextrin IC.
{"title":"The mechanochemical and supercritical fluid synthesis of β-cyclodextrin-hesperidin inclusion complex: A comparison green chemistry versus lyophilization","authors":"Luis José López-Méndez , Rubria Marlen Martínez-Cásares , Alberto López-Luna , Héctor Luna , Patricia Guadarrama , Rosa Estrada-Reyes , Raúl G. Enríquez , Julia Cassani","doi":"10.1016/j.supflu.2024.106422","DOIUrl":"10.1016/j.supflu.2024.106422","url":null,"abstract":"<div><div>Hesperidin is a rutinoside of flavanone type with relevant therapeutic properties but poor water solubility which limits its therapeutic applicability. However, cyclodextrins (CDs) have been successfully used as drug carriers to enhance the solubility of several drugs, to improve their bioavailability, and therapeutic efficacy. We report herein the formation of inclusion complexes of β-cyclodextrin and hesperidin through the green approaches mechanochemistry and supercritical fluid and compare these results versus the classical lyophilization method. The resulting stoichiometries and the specific interactions of the complexes were analyzed by NMR, UV, and mass spectrometry. The β-cyclodextrin and hesperidin inclusion complex (IC) successfully obtained through green methodologies demonstrated superior levels of flavonoid content. In terms of solubility, the mechanochemistry inclusion complex showed the best improvement in solubility. We demonstrate herein that the use of green methodologies such as supercritical fluids and mechanochemistry are useful alternatives to the conventional method of lyophilization, to improve the solubility of β-cyclodextrin IC.</div></div>","PeriodicalId":17078,"journal":{"name":"Journal of Supercritical Fluids","volume":"215 ","pages":"Article 106422"},"PeriodicalIF":3.4,"publicationDate":"2024-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142424625","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-02DOI: 10.1016/j.supflu.2024.106408
Ylenia F. Rodríguez , Cristina Benito , Santiago Aparicio , Jose L. Trenzado
this study considers the high-pressure behavior of thymol + carvone Natural Deep Eutectic Solvent using a combined experimental and computational approach. Experimentally, PVT (pressure – volume/density - temperature) measurements were conducted to characterize the fluid volumetric behavior as well as compressibility and internal pressure, which are directly related with hydrogen bonding and nanoscopic structuring. Likewise, these measurements provide crucial insights into the thermodynamic properties of the considered fluid under high pressure, which is pivotal for scaling up and process design for high pressure operations. Computationally, the PC-SAFT equation of state was employed to predict phase equilibria and PVT behavior, Machine Learning for density predictions, while Density Functional Theory and Classical Molecular Dynamics simulations were considered for the structural and dynamic characterization. These simulations provides insights into the electronic structure, intermolecular interactions (hydrogen bonding), liquid structuring and they unveil the pressure's impact on microscopic interactions, structural organization, and transport properties. This comprehensive investigation aims to shed light on the behavior under high pressure, facilitating their optimization for applications in chemical processing, energy storage, and materials science.
{"title":"Unveiling the high-pressure behavior of thymol+carvone NADES: A combined experimental-computational approach","authors":"Ylenia F. Rodríguez , Cristina Benito , Santiago Aparicio , Jose L. Trenzado","doi":"10.1016/j.supflu.2024.106408","DOIUrl":"10.1016/j.supflu.2024.106408","url":null,"abstract":"<div><div>this study considers the high-pressure behavior of thymol + carvone Natural Deep Eutectic Solvent using a combined experimental and computational approach. Experimentally, PVT (pressure – volume/density - temperature) measurements were conducted to characterize the fluid volumetric behavior as well as compressibility and internal pressure, which are directly related with hydrogen bonding and nanoscopic structuring. Likewise, these measurements provide crucial insights into the thermodynamic properties of the considered fluid under high pressure, which is pivotal for scaling up and process design for high pressure operations. Computationally, the PC-SAFT equation of state was employed to predict phase equilibria and PVT behavior, Machine Learning for density predictions, while Density Functional Theory and Classical Molecular Dynamics simulations were considered for the structural and dynamic characterization. These simulations provides insights into the electronic structure, intermolecular interactions (hydrogen bonding), liquid structuring and they unveil the pressure's impact on microscopic interactions, structural organization, and transport properties. This comprehensive investigation aims to shed light on the behavior under high pressure, facilitating their optimization for applications in chemical processing, energy storage, and materials science.</div></div>","PeriodicalId":17078,"journal":{"name":"Journal of Supercritical Fluids","volume":"215 ","pages":"Article 106408"},"PeriodicalIF":3.4,"publicationDate":"2024-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142440968","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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