Hsien-Tsung Wu, Yi-Jia Tu, Yu-Xuan Huang, Kim Hoong Ng
{"title":"Monodisperse protein nanoparticles production by supercritical assisted atomization","authors":"Hsien-Tsung Wu, Yi-Jia Tu, Yu-Xuan Huang, Kim Hoong Ng","doi":"10.1016/j.supflu.2025.106517","DOIUrl":"10.1016/j.supflu.2025.106517","url":null,"abstract":"<div><div>Monodisperse nanoparticles of bovine serum albumin (BSA) and lysozyme (LYS) were generated using supercritical assisted atomization (SAA). The impact of several key factors, including the solvent effect, precipitator and saturator temperatures, concentration of protein solutions, and the flow rate ratio of carbon dioxide to protein solutions, on the morphology and size of protein particles was examined. Increasing the ethanol content in the protein solution reduced the particle size, likely due to enhanced secondary atomization by CO<sub>2</sub>-dissolved aqueous ethanol. Higher precipitator and saturator temperatures increased protein particle size. This effect was attributed to intermolecular aggregation from thermal denaturation. Under optimal conditions, the mean sizes of the BSA and LYS particles were 430 nm and 300 nm, respectively, along with an average process recovery of approximately 60 %. In addition, high-temperature processing enhanced the hydrolytic resistance of protein particles and could be used for the controlled release of drug formulations.</div></div>","PeriodicalId":17078,"journal":{"name":"Journal of Supercritical Fluids","volume":"218 ","pages":"Article 106517"},"PeriodicalIF":3.4,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968067","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}
Oxana N. Fedyaeva, Aleksander P. Grebennikov, Anatoly A. Vostrikov
{"title":"The role of water in the oxidation of lead and bismuth by high-density water-oxygen fluid","authors":"Oxana N. Fedyaeva, Aleksander P. Grebennikov, Anatoly A. Vostrikov","doi":"10.1016/j.supflu.2024.106509","DOIUrl":"10.1016/j.supflu.2024.106509","url":null,"abstract":"<div><div>The paper presents the research results on oxidation of liquid lead (Pb)<sup>l</sup> and bismuth (Bi)<sup>l</sup> by high density water-oxygen fluid (ρ<sub>H2O</sub> = 0.91–4.69 and ρ<sub>O2</sub> = 0.75–2.93 mol/dm<sup>3</sup>). Time dependences of the pressure were obtained by the method of H<sub>2</sub>O/O<sub>2</sub> fluid injection into the reactor at different temperatures (623–873 K), from which the dependences of the amount of O<sub>2</sub> in the reaction mixture were calculated and the oxidation kinetics was described. The results revealed a non-monotonic dependence of the (Pb)<sup>l</sup> oxidation rate and mechanisms on temperature and H<sub>2</sub>O/O<sub>2</sub> molar ratio, caused by the transition from kinetic to diffusion modes. The oxidation rate of (Bi)<sup>l</sup> was observed to increase with increasing temperature and is governed by diffusion. The oxidation of (Pb)<sup>l</sup> at 653–723 K and molar ratio H<sub>2</sub>O/O<sub>2</sub> = 1.45–1.70 was found to lead to the formation of a porous oxide layer consisting of polyhedral Pb<sub>3</sub>O<sub>4</sub> crystals. The oxidation of (Bi)<sup>l</sup> gives rise to the synthesis of Bi(OH)<sub>3</sub> and Bi<sub>2</sub>O<sub>3</sub> in the form of plates, ribbons, and rods exhibiting diverse crystal structures. It is shown that H<sub>2</sub>O molecules can participate in oxidation of (Pb)<sup>l</sup> as a catalyst, whereas in the oxidation of (Bi)<sup>l</sup> they act as the reagent. The results obtained may be useful in developing new approaches to the synthesis of oxide particles using supercritical water fluids, evaluating the stability of catalysts based on variable valence metal oxides, and ensuring the safety of power units.</div></div>","PeriodicalId":17078,"journal":{"name":"Journal of Supercritical Fluids","volume":"218 ","pages":"Article 106509"},"PeriodicalIF":3.4,"publicationDate":"2025-01-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968091","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}
Hamed Peyrovedin , Seyed Ali Sajadian , Sara Bahmanzade , Kamiar Zomorodian , Mohammad Khorram
{"title":"Studying the rifampin solubility in supercritical CO2 with/without co-solvent: Experimental data, modeling and machine learning approach","authors":"Hamed Peyrovedin , Seyed Ali Sajadian , Sara Bahmanzade , Kamiar Zomorodian , Mohammad Khorram","doi":"10.1016/j.supflu.2024.106510","DOIUrl":"10.1016/j.supflu.2024.106510","url":null,"abstract":"<div><div>Rifampin is an effective tuberculosis drug. This study examines drug solubility in supercritical carbon dioxide at 308 K to 338 K and 12 MPa to 30 MPa. This study investigates Rifampin solubility using ethanol as a co-solvent. The experimental data is then used to develop a solute-solvent system model using semi-empirical correlations, the Peng-Robinson equation of state, and machine learning models. A study showed that the mole fraction of rifampin without a co-solvent ranges from 0.147 × 10<sup>−5</sup> to 1.972 × 10<sup>−5</sup>. Using ethanol as a co-solvent enhances Rifampin mole fraction, resulting in a range of 1.880 × 10<sup>−5</sup> to 1.403 × 10<sup>−4</sup>. This study shows that ethanol can be used in this particular system as a co-solvent. The findings demonstrate that semi-empirical, equation of state-based, and machine learning methods may accurately determine Rifampin solubility. Moreover, the results indicate that the incorporation of a co-solvent enhances solubility and may facilitate the application of SCF-based micronization techniques, particularly the rapid expansion of supercritical solution (RESS) and other SCF-based methods for nanoparticle production. However, the use of a liquid co-solvent can complicate the recovery of a dry drugs powder.</div></div>","PeriodicalId":17078,"journal":{"name":"Journal of Supercritical Fluids","volume":"218 ","pages":"Article 106510"},"PeriodicalIF":3.4,"publicationDate":"2025-01-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990553","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}
{"title":"Short-term supercritical heat transfer: In memory of Anneke Levelt Sengers","authors":"Pavel Skripov , Sergey Rutin , Lin Chen","doi":"10.1016/j.supflu.2025.106516","DOIUrl":"10.1016/j.supflu.2025.106516","url":null,"abstract":"<div><div>The paper is dedicated to the memory of Anneke Levelt Sengers (Johanna/Anneke/Maria Henrica Levelt, 1929–2024), a world-renowned scientist on liquid-vapor critical phenomena. It summarizes the results of pulse heating experiments performed under conditions of short-term (units of ms) powerful heat release in supercritical-pressure water. The pressure, being the parameter of the experiment, was varied from a near-supercritical value (22.1 MPa) to 100 MPa. Initial temperature was 25 ºC, while its rise in the course of a pulse ranged from 230 ºC up to 680 ºC. Results obtained for pulse heating along the supercritical isobars are based solely on comparison with primary data. The surprising feature of the results is that a threshold drop in the intensity of heat transfer near the critical temperature occurs and becomes deeper, as the pressure approaches the supercritical pressure. The aim of the present paper is to suggest a relatively simple approach to reconciling pulse heating results with well-known peaks of thermophysical properties derived from experiments under stationary conditions. The variant suggested of such approach is based on the hypotheses of suppression of large-scale fluctuations in fast processes and the additional thermal resistance accompanying by the appearance of structural non-uniformity in an initially homogeneous fluid.</div></div>","PeriodicalId":17078,"journal":{"name":"Journal of Supercritical Fluids","volume":"218 ","pages":"Article 106516"},"PeriodicalIF":3.4,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990545","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}
{"title":"Correlating mean particle size of pure solids in supercritical antisolvent processes using dimensional analysis with the Buckingham π-theorem","authors":"Juan C. de la Fuente , Yusuke Shimoyama","doi":"10.1016/j.supflu.2024.106512","DOIUrl":"10.1016/j.supflu.2024.106512","url":null,"abstract":"<div><div>In supercritical antisolvent processes, two correlations have been proposed to estimate the mean particle size of precipitated pure solid compounds. These easy-to-use correlations, each with six adjustable coefficients were developed by applying dimensional analysis based on the Buckingham π-theorem, relating the particle size to feeding, thermodynamic, and mechanical process parameters. These correlations can help in scaling-up microparticle production processes; however, they do not conceptually explain the influence of process parameters on particle sizes, and remain limited by the experimental available data. The two correlations are differentiated by employing either solute supersaturation data or molar volumes of CO<sub>2</sub>+solvent systems. These correlations were evaluated by testing seventeen ternary systems, with deviations from experimental values ≤ 88 %. They proved capable of correlating all solutes grouped by the same solvent. Pilot-scale data were estimated using coefficients adjusted with laboratory-scale data. Finally, the correlations successfully reproduced the particle size as a function of temperature and pressure.</div></div>","PeriodicalId":17078,"journal":{"name":"Journal of Supercritical Fluids","volume":"218 ","pages":"Article 106512"},"PeriodicalIF":3.4,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990546","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}
Chin Seng Liew , Ken Furuta , Mohammed Ahmed Mohammed Ali , Yukihiko Matsumura
{"title":"Continuous biodiesel production using canola oil and supercritical methanol with the aid of CaO/carbon nanotube catalyst","authors":"Chin Seng Liew , Ken Furuta , Mohammed Ahmed Mohammed Ali , Yukihiko Matsumura","doi":"10.1016/j.supflu.2025.106515","DOIUrl":"10.1016/j.supflu.2025.106515","url":null,"abstract":"<div><div>A catalyst can improve the rate of supercritical transesterification, thereby reducing the construction costs of the reactor. Although calcium oxide (CaO) is an effective catalyst, it has low stability and requires a support structure. Multiwall carbon nanotubes (MWCNTs) have high porosity, large specific surface area, and high tensile strength, and could serve as support structures. Therefore, this study elucidated the effectiveness of a CaO-impregnated MWCNT catalyst in accelerating the supercritical transesterification process. A 40 wt% of CaO was the optimal concentration for impregnation onto CNTs for transesterification in supercritical methanol under the following conditions: 300 °C, 20 MPa, methanol to oil molar ratio of 40:1, WHSV of 100 h<sup>−1</sup>. The fatty acid methyl esters yield of the supercritical methanol transesterification process reached 1.0 under these conditions; additionally, the yield was maintained for 6 h. The reaction was well described by the first-order reaction rate of the homogeneous and heterogeneous reactions.</div></div>","PeriodicalId":17078,"journal":{"name":"Journal of Supercritical Fluids","volume":"218 ","pages":"Article 106515"},"PeriodicalIF":3.4,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968069","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}
Diego Fernando García-Ramón , Jaime Valdiviezo-Marcelo , Christianne Elisabete da Costa Rodrigues , Juliane Viganó , Alessandra Lopes de Oliveira
{"title":"Advances and trends in compressed fluid extraction to recovering bioactive compounds from avocado: Effect of extraction parameters, biological properties, and applications","authors":"Diego Fernando García-Ramón , Jaime Valdiviezo-Marcelo , Christianne Elisabete da Costa Rodrigues , Juliane Viganó , Alessandra Lopes de Oliveira","doi":"10.1016/j.supflu.2024.106505","DOIUrl":"10.1016/j.supflu.2024.106505","url":null,"abstract":"<div><div>Avocado is widely recognized for its rich nutritional profile and as a valuable source of bioactive compounds with well-established health benefits. Traditional extraction methods, however, often involve the use of harmful solvents, extended processing times, and high temperatures, which can degrade heat-sensitive compounds. To overcome these challenges, advanced extraction techniques such as pressurized liquid extraction (PLE) and supercritical fluid extraction (SFE) have been employed to efficiently recover bioactive compounds from avocado. This review evaluates the performance of these techniques and examines key process variables, including temperature, pressure, solvent flow rate, solvent-to-feed mass ratio (S/F), the use of co-solvents, particle size, and moisture content. Additionally, it explores the biological properties of the extracts and their potential applications. The findings highlight that PLE and SFE are highly effective in extracting a diverse range of bioactive compounds, including polyphenols, unsaturated fatty acids, tocopherols, and carotenoids. These extracts exhibit notable anticancer, antidiabetic, antioxidant, and antimicrobial activities. The advantages of these methods include reduced extraction times, lower solvent consumption, and improved preservation of thermolabile compounds. However, the high cost of equipment remains a significant drawback for industrial-scale implementation. In conclusion, PLE and SFE represent sustainable and efficient strategies for the comprehensive valorization of avocado, with significant potential for the development of high-value natural ingredients. Future research should focus on multiparametric process optimization, assessment of industrial scalability, extensive in vivo studies, the creation of specific applications across various industries, and comparative sustainability analyses against conventional methods.</div></div>","PeriodicalId":17078,"journal":{"name":"Journal of Supercritical Fluids","volume":"218 ","pages":"Article 106505"},"PeriodicalIF":3.4,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990551","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}
{"title":"Measurements and prediction of dynamic viscosity of binary mixtures of carbon dioxide and methanol, ethanol and 1-propanol at 313–343 K and 15–30 MPa","authors":"Norihiro Onodera, Ryuichi Oguro, Toshitaka Funazukuri","doi":"10.1016/j.supflu.2024.106514","DOIUrl":"10.1016/j.supflu.2024.106514","url":null,"abstract":"<div><div>The dynamic viscosity <em>η</em><sub>m</sub> of binary mixtures of carbon dioxide and methanol/1-propanol was measured on the basis of the pressure drop in a packed bed, which was calculated using the Ergun equation, at temperatures from 313.2 K to 343.2 K and pressures from 15 MPa to 30 MPa over the entire range of methanol/1-propanol composition. The accuracy of the rough-hard-sphere (RHS) model with various combining rules was tested and compared with that of the Eyring theory with the perturbed-chain SAFT (PC-SAFT) equation of state (EoS) model the authors proposed previously. The average relative deviations (ARD) of the RHS model with the Fender-Halsey combining rule and the interaction parameter value adjusted were 5.0 % (max.RD: 23 %), for 240 sets of conditions over the entire range of methanol/ethanol/1-propanol compositions, as compared with 6.3 % (max.RD: 26 %) of the Eyring theory with PC-SAFT EoS model with the optimized <em>k</em><sub>Eyring</sub> value.</div></div>","PeriodicalId":17078,"journal":{"name":"Journal of Supercritical Fluids","volume":"218 ","pages":"Article 106514"},"PeriodicalIF":3.4,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990560","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}
{"title":"Asymptotic Widom line of supercritical fluid within the scaling theory","authors":"M.Yu. Belyakov, V.D. Kulikov","doi":"10.1016/j.supflu.2024.106513","DOIUrl":"10.1016/j.supflu.2024.106513","url":null,"abstract":"<div><div>The work is devoted to a theoretical study of fluid thermodynamic features in the supercritical region. The analysis is carried out within the framework of the scaling theory based on the general equation of state of a near-critical fluid. Analytical expressions for fluid characteristics lines on the pressure–temperature plane are obtained. It is shown that close to the critical point the characteristic lines come closer forming the so-called single Widom line. An analytical expression is formulated for the asymptotic Widom line, as a common part of fluid characteristics. These line tracks are found to depend on the initial scaling concept. Widom line turns out to be closest to the critical isochore and is directly related to the coexistence curve of the near-critical fluid. To illustrate the results, asymptotic lines of methane, n-pentane, carbon dioxide, and water are constructed based on the NIST simulator numerical data.</div></div>","PeriodicalId":17078,"journal":{"name":"Journal of Supercritical Fluids","volume":"218 ","pages":"Article 106513"},"PeriodicalIF":3.4,"publicationDate":"2024-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968070","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}
Ulisses Silva do Nascimento , Carolina Kafka Neves , Erik Felix dos Santos , Chekwube Andrew Ezegbe , Laurent Rodrigues Rezende , Juliana Marchi , Christiane Bertachini Lombello , Lígia Passos Maia-Obi
{"title":"Ibuprofen loaded gelatin-siloxane gels prepared by supercritical CO2-assisted impregnation/deposition for controlled drug release and tissue engineering","authors":"Ulisses Silva do Nascimento , Carolina Kafka Neves , Erik Felix dos Santos , Chekwube Andrew Ezegbe , Laurent Rodrigues Rezende , Juliana Marchi , Christiane Bertachini Lombello , Lígia Passos Maia-Obi","doi":"10.1016/j.supflu.2024.106511","DOIUrl":"10.1016/j.supflu.2024.106511","url":null,"abstract":"<div><div>Gelatin-based gels are suitable for biomedical applications and have potential to be impregnated using scCO<sub>2</sub> thanks mainly to their morphology. Aiming to obtain ibuprofen loaded gelatin-siloxane cryogels suitable for controlled drug release and tissue engineering, the impregnation/deposition of the drug was studied in both cryogels and xerogels in scCO<sub>2</sub> at 25 MPa and 35 °C, by varying its concentrations and the amount of co-solvent. The obtained samples were evaluated by FTIR, SEM, drug release and cytotoxicity studies. For the xerogels, the ibuprofen dispersed in the matrix, while for cryogels, additionally, it was deposited as flake-like particles inside their pores, thus presenting a higher drug load. Increasing the ibuprofen concentration and using 3 %v/v of co-solvent, increases the drug load. An extended release was observed for gels with sufficient drug load and no significative cytotoxicity was observed, showing that these gels can be applied as multifunctional scaffolds.</div></div>","PeriodicalId":17078,"journal":{"name":"Journal of Supercritical Fluids","volume":"218 ","pages":"Article 106511"},"PeriodicalIF":3.4,"publicationDate":"2024-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968071","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}