Yi Yu, Fei Wang, Xiaorong Guo, Chaofan Chen, Yuqian Wang and Hailong Chen
Gas flooding plays a crucial role in enhanced oil recovery; however, the underlying microscopic mechanisms, especially those related to interfacial changes, remain unclear. Based on a realistic geometric model of porous media, this study employs the level-set method to simulate the oil displacement processes of N2 flooding, CO2 immiscible flooding, CO2 miscible flooding, and foam flooding at the microscale. The oil–gas interface is tracked throughout the simulations to compare and analyze the displacement behaviors of different gases. First, a dynamic simulation of the gas flooding process is conducted, analyzing the variations in pressure, velocity, and remaining oil volume fraction over time. Second, the effects of factors such as injection rate, foam gas–liquid ratio, and surface tension on oil displacement efficiency are investigated. Finally, the displacement performance of N2 flooding, CO2 flooding, and foam flooding is compared under specific conditions to examine the oil recovery mechanisms associated with different gases. The results indicate that the remaining oil volume fractions after N2 flooding and CO2 immiscible flooding are approximately 30%. Increasing the injection rate of N2 and CO2 can improve early-stage displacement performance and slightly enhance oil recovery. In contrast, the remaining oil volume fractions after CO2 miscible flooding and foam flooding are about 10%. The optimal foam flooding effect is achieved at a gas–liquid ratio of 3 : 1 and a surface tension of 0.02, which corresponds to the lowest remaining oil volume fraction. Furthermore, the inlet pressure declines rapidly during N2 and CO2 immiscible flooding, resulting in a relatively low final pressure. In comparison, the inlet pressure decreases more gradually during CO2 miscible flooding and foam flooding, maintaining a certain pressure level by the end of the process.
{"title":"Dynamic simulation study on gas flooding mechanism based on level set method at the micro–nano scale","authors":"Yi Yu, Fei Wang, Xiaorong Guo, Chaofan Chen, Yuqian Wang and Hailong Chen","doi":"10.1039/D5RA10088G","DOIUrl":"https://doi.org/10.1039/D5RA10088G","url":null,"abstract":"<p >Gas flooding plays a crucial role in enhanced oil recovery; however, the underlying microscopic mechanisms, especially those related to interfacial changes, remain unclear. Based on a realistic geometric model of porous media, this study employs the level-set method to simulate the oil displacement processes of N<small><sub>2</sub></small> flooding, CO<small><sub>2</sub></small> immiscible flooding, CO<small><sub>2</sub></small> miscible flooding, and foam flooding at the microscale. The oil–gas interface is tracked throughout the simulations to compare and analyze the displacement behaviors of different gases. First, a dynamic simulation of the gas flooding process is conducted, analyzing the variations in pressure, velocity, and remaining oil volume fraction over time. Second, the effects of factors such as injection rate, foam gas–liquid ratio, and surface tension on oil displacement efficiency are investigated. Finally, the displacement performance of N<small><sub>2</sub></small> flooding, CO<small><sub>2</sub></small> flooding, and foam flooding is compared under specific conditions to examine the oil recovery mechanisms associated with different gases. The results indicate that the remaining oil volume fractions after N<small><sub>2</sub></small> flooding and CO<small><sub>2</sub></small> immiscible flooding are approximately 30%. Increasing the injection rate of N<small><sub>2</sub></small> and CO<small><sub>2</sub></small> can improve early-stage displacement performance and slightly enhance oil recovery. In contrast, the remaining oil volume fractions after CO<small><sub>2</sub></small> miscible flooding and foam flooding are about 10%. The optimal foam flooding effect is achieved at a gas–liquid ratio of 3 : 1 and a surface tension of 0.02, which corresponds to the lowest remaining oil volume fraction. Furthermore, the inlet pressure declines rapidly during N<small><sub>2</sub></small> and CO<small><sub>2</sub></small> immiscible flooding, resulting in a relatively low final pressure. In comparison, the inlet pressure decreases more gradually during CO<small><sub>2</sub></small> miscible flooding and foam flooding, maintaining a certain pressure level by the end of the process.</p>","PeriodicalId":102,"journal":{"name":"RSC Advances","volume":" 10","pages":" 8499-8516"},"PeriodicalIF":4.6,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2026/ra/d5ra10088g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146147874","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Stefan Desimpel, Matthieu Dorbec, Kevin M Van Geem, Christian V Stevens
Bayesian optimization (BO) enables data-efficient optimization of complex chemical reactions by balancing exploration and exploitation in large, mixed-variable parameter spaces. This review provides an accessible introduction for chemists wishing to adopt BO, outlining the fundamentals of surrogate models, acquisition functions, and key mathematical concepts. Practical considerations are emphasized, including kernel design, representation of categorical variables, and strategies for multi-objective and batch optimization. Applications are comprehensively surveyed across experimental scales, from high-throughput platforms to automated flow reactors and larger-scale processes. Finally, emerging directions such as transfer learning and data reuse are discussed in the context of accelerating optimization campaigns and enabling more generalizable, data-driven strategies in chemistry.
{"title":"Bayesian optimization for chemical reactions.","authors":"Stefan Desimpel, Matthieu Dorbec, Kevin M Van Geem, Christian V Stevens","doi":"10.1039/d5cs00962f","DOIUrl":"https://doi.org/10.1039/d5cs00962f","url":null,"abstract":"<p><p>Bayesian optimization (BO) enables data-efficient optimization of complex chemical reactions by balancing exploration and exploitation in large, mixed-variable parameter spaces. This review provides an accessible introduction for chemists wishing to adopt BO, outlining the fundamentals of surrogate models, acquisition functions, and key mathematical concepts. Practical considerations are emphasized, including kernel design, representation of categorical variables, and strategies for multi-objective and batch optimization. Applications are comprehensively surveyed across experimental scales, from high-throughput platforms to automated flow reactors and larger-scale processes. Finally, emerging directions such as transfer learning and data reuse are discussed in the context of accelerating optimization campaigns and enabling more generalizable, data-driven strategies in chemistry.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":" ","pages":""},"PeriodicalIF":39.0,"publicationDate":"2026-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146148519","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Due to asphaltene's complex structure and its status as the most polar and surfactant component, it is extremely challenging to investigate the interaction between asphaltenes and wax molecules. In this study, we employ molecular dynamics methods to investigate the interaction mechanisms between asphaltenes including the isolated-island-type and the archipelago type and wax molecules with carbon numbers of 20, 25, and 30. By analyzing the aggregation rates, cluster sizes, distributions, and interaction energies of asphaltenes and wax molecules during the simulation process, we were able to elucidate that the branched structures of the isolated-island-type asphaltenes and the aromatic ring structures of the archipelago type asphaltenes play a dominant role in their interactions with wax molecules, which leads to a diffusion coefficient for island-type asphaltenes that is about 15% higher than that for archipelago-type asphaltene. In addition, as the wax molecules (C20, C25, and C30) aggregated, they tend to form elliptical structures, which exhibit affinity with the aromatic ring structure of asphaltenes. However, when wax molecules with C20, C25, and C30 are mixed and aggregated, the resulting ellipse-like structures have short chains at their ends due to varying wax molecule lengths. In this case, these short chains are attracted to the branched structures of asphaltenes, thereby enhancing the interaction between asphaltenes and waxes.
{"title":"Molecular Dynamics Simulation of the Microscopic Interaction Mechanism between Asphaltenes and Wax Molecules/Aggregates Considering the Asphaltene Structure and Wax Carbon Number.","authors":"Pengfei Yu, Hanwen Chen, Yiling Gu, Xianghe Liu, Dechen Chang, Zichen Wu, Haoping Peng, Haoran Zhu, Yun Lei","doi":"10.1021/acs.langmuir.5c05645","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c05645","url":null,"abstract":"<p><p>Due to asphaltene's complex structure and its status as the most polar and surfactant component, it is extremely challenging to investigate the interaction between asphaltenes and wax molecules. In this study, we employ molecular dynamics methods to investigate the interaction mechanisms between asphaltenes including the isolated-island-type and the archipelago type and wax molecules with carbon numbers of 20, 25, and 30. By analyzing the aggregation rates, cluster sizes, distributions, and interaction energies of asphaltenes and wax molecules during the simulation process, we were able to elucidate that the branched structures of the isolated-island-type asphaltenes and the aromatic ring structures of the archipelago type asphaltenes play a dominant role in their interactions with wax molecules, which leads to a diffusion coefficient for island-type asphaltenes that is about 15% higher than that for archipelago-type asphaltene. In addition, as the wax molecules (C20, C25, and C30) aggregated, they tend to form elliptical structures, which exhibit affinity with the aromatic ring structure of asphaltenes. However, when wax molecules with C20, C25, and C30 are mixed and aggregated, the resulting ellipse-like structures have short chains at their ends due to varying wax molecule lengths. In this case, these short chains are attracted to the branched structures of asphaltenes, thereby enhancing the interaction between asphaltenes and waxes.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":" ","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146148576","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-10DOI: 10.1007/s00216-026-06317-4
Jin-Chi Jiang, Zhi-Yuan Feng, Long-Yue Meng, Biao Jin
Per- and polyfluoroalkyl substances (PFASs) are persistent pollutants with shifting pollution characteristics toward short-chain and structurally diverse variants, posing great challenges for precise analysis. Pretreatment, as a rate-limiting step, lacks systematic guidance for technology selection. This review makes a unique contribution by constructing a "target substance characteristics-sample matrix-detection requirements" three-dimensional matching framework, systematically categorizing pretreatment technologies into solvent-based, adsorption-based, and advanced types, and dissecting their mechanisms, advantages, limitations, and applicability. Solvent-based technologies excel in long-chain PFASs analysis in simple matrices, while adsorption-based methods enable efficient enrichment of short-chain PFASs via functional materials, and advanced technologies meet green and complex matrix demands. Background contamination control strategies are also emphasized. Current challenges include inefficient short-chain enrichment, high material costs, and underdeveloped on-site devices. Critical needs involve the development of functional solvents, artificial intelligence-driven adsorbents, standardized protocols, and full-process PFASs-free systems. This review provides actionable references for PFASs analysis optimization.
{"title":"Recent advances in pretreatment technologies for the analysis of per- and polyfluoroalkyl substances.","authors":"Jin-Chi Jiang, Zhi-Yuan Feng, Long-Yue Meng, Biao Jin","doi":"10.1007/s00216-026-06317-4","DOIUrl":"https://doi.org/10.1007/s00216-026-06317-4","url":null,"abstract":"<p><p>Per- and polyfluoroalkyl substances (PFASs) are persistent pollutants with shifting pollution characteristics toward short-chain and structurally diverse variants, posing great challenges for precise analysis. Pretreatment, as a rate-limiting step, lacks systematic guidance for technology selection. This review makes a unique contribution by constructing a \"target substance characteristics-sample matrix-detection requirements\" three-dimensional matching framework, systematically categorizing pretreatment technologies into solvent-based, adsorption-based, and advanced types, and dissecting their mechanisms, advantages, limitations, and applicability. Solvent-based technologies excel in long-chain PFASs analysis in simple matrices, while adsorption-based methods enable efficient enrichment of short-chain PFASs via functional materials, and advanced technologies meet green and complex matrix demands. Background contamination control strategies are also emphasized. Current challenges include inefficient short-chain enrichment, high material costs, and underdeveloped on-site devices. Critical needs involve the development of functional solvents, artificial intelligence-driven adsorbents, standardized protocols, and full-process PFASs-free systems. This review provides actionable references for PFASs analysis optimization.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2026-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146148654","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-10DOI: 10.1007/s00216-026-06366-9
Tereza Hofmanova, Rudolf Andrys, Miroslav Lisa
The analysis of amino acids in biological samples is challenged by their high polarity, low ionization efficiency, and lack of chromophores, which limit detection by LC-UV or LC-MS. Derivatization is widely used to improve retention, sensitivity, and detection. In this study, derivatization agents based on pyridine, quinoline, and isoquinoline positional isomers scaffolds with COCl, SO₂Cl, and NHS ester reactive groups were systematically evaluated using deuterium-labeled amino acids to assess stability, derivatization efficiency, chromatographic behavior, and MS response. NHS ester-based agents were found to exhibit superior stability, maintaining activity for over 1 year, whereas carbonyl chlorides and sulfonyl chloride-based agents were highly reactive but less stable. NHS ester of isoquinoline-6-carboxylic acid (6-CiQ-NHS) was identified as the most effective agent, combining rapid derivatization, strong MS signal, and stability. LC-MS analysis demonstrated excellent linearity (R2 ≥ 0.995), low nanomolar detection limits (0.23-6.33 nM), and separation of isomeric amino acids (e.g., isoleucine/leucine). 6-CiQ-NHS is proposed as a practical derivatization approach for amino acid quantification and provides a framework for the rational design of future agents.
{"title":"Derivatization agents for LC-MS analysis of amino acids: effects of core structure and functional groups.","authors":"Tereza Hofmanova, Rudolf Andrys, Miroslav Lisa","doi":"10.1007/s00216-026-06366-9","DOIUrl":"https://doi.org/10.1007/s00216-026-06366-9","url":null,"abstract":"<p><p>The analysis of amino acids in biological samples is challenged by their high polarity, low ionization efficiency, and lack of chromophores, which limit detection by LC-UV or LC-MS. Derivatization is widely used to improve retention, sensitivity, and detection. In this study, derivatization agents based on pyridine, quinoline, and isoquinoline positional isomers scaffolds with COCl, SO₂Cl, and NHS ester reactive groups were systematically evaluated using deuterium-labeled amino acids to assess stability, derivatization efficiency, chromatographic behavior, and MS response. NHS ester-based agents were found to exhibit superior stability, maintaining activity for over 1 year, whereas carbonyl chlorides and sulfonyl chloride-based agents were highly reactive but less stable. NHS ester of isoquinoline-6-carboxylic acid (6-CiQ-NHS) was identified as the most effective agent, combining rapid derivatization, strong MS signal, and stability. LC-MS analysis demonstrated excellent linearity (R<sup>2</sup> ≥ 0.995), low nanomolar detection limits (0.23-6.33 nM), and separation of isomeric amino acids (e.g., isoleucine/leucine). 6-CiQ-NHS is proposed as a practical derivatization approach for amino acid quantification and provides a framework for the rational design of future agents.</p>","PeriodicalId":462,"journal":{"name":"Analytical and Bioanalytical Chemistry","volume":" ","pages":""},"PeriodicalIF":3.8,"publicationDate":"2026-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146148691","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Carnosic acid (CA), a diterpene abundant in rosemary, is well known for its antioxidant activity but is chemically unstable in plasma. During sample handling it rapidly undergoes autoxidation, which often makes its quantification unreliable. We developed an LC-MS/MS method that combines a simple acetonitrile-NaCl salting-out extraction with the use of antioxidant additives. Extraction conditions-solvent composition, salt ratio, and aqueous pH-were optimized using design of experiments and response surface methodology. In parallel, several antioxidants were tested for their ability to stabilize CA during preparation. The final protocol, using 100% acetonitrile, 100% NaCl, and acidic aqueous phase (pH < 1.5), together with pyrogallol as an additive, provided consistent recoveries above 80% and matrix effects within 15%. Linearity was excellent (r > 0.99) across the calibration range, and the method showed low quantification limits (5 nmol/L for CA; 1 nmol/L for its metabolites). Accuracy and precision met regulatory criteria, and reproducibility was achieved using podocarpic acid as an internal standard. In a small mouse study, the approach was able to follow CA in plasma after oral administration, with a peak observed at 0.25 h. By combining stabilization with a straightforward extraction, this work offers a practical way to quantify CA and related compounds in plasma. The strategy may also be useful for other polyphenols that share similar instability issues and could support future pharmacokinetic or bioavailability studies.
{"title":"Stabilization and quantification of carnosic acid and metabolites in plasma using antioxidant-assisted salting-out extraction coupled with LC-MS/MS.","authors":"Yusuke Iwasaki, Hitomi Matsumoto, Shunpei Kanba, Ayumi Watanabe, Rena Nakazato, Kanako Yabuki, Rie Ito, Junzo Kamei, Hiroshi Akiyama","doi":"10.1007/s44211-026-00874-5","DOIUrl":"https://doi.org/10.1007/s44211-026-00874-5","url":null,"abstract":"<p><p>Carnosic acid (CA), a diterpene abundant in rosemary, is well known for its antioxidant activity but is chemically unstable in plasma. During sample handling it rapidly undergoes autoxidation, which often makes its quantification unreliable. We developed an LC-MS/MS method that combines a simple acetonitrile-NaCl salting-out extraction with the use of antioxidant additives. Extraction conditions-solvent composition, salt ratio, and aqueous pH-were optimized using design of experiments and response surface methodology. In parallel, several antioxidants were tested for their ability to stabilize CA during preparation. The final protocol, using 100% acetonitrile, 100% NaCl, and acidic aqueous phase (pH < 1.5), together with pyrogallol as an additive, provided consistent recoveries above 80% and matrix effects within 15%. Linearity was excellent (r > 0.99) across the calibration range, and the method showed low quantification limits (5 nmol/L for CA; 1 nmol/L for its metabolites). Accuracy and precision met regulatory criteria, and reproducibility was achieved using podocarpic acid as an internal standard. In a small mouse study, the approach was able to follow CA in plasma after oral administration, with a peak observed at 0.25 h. By combining stabilization with a straightforward extraction, this work offers a practical way to quantify CA and related compounds in plasma. The strategy may also be useful for other polyphenols that share similar instability issues and could support future pharmacokinetic or bioavailability studies.</p>","PeriodicalId":7802,"journal":{"name":"Analytical Sciences","volume":" ","pages":""},"PeriodicalIF":2.0,"publicationDate":"2026-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146148725","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The construction of C-C bonds is a pivotal transformation in organic synthesis. Traditional Ullmann type and Hurtley reactions for constructing C(sp3)-C(sp2) bonds rely on organometallic reagents or substrates with active methylene units. These requirements significantly limit their practical applicability. Herein, employing two readily available organic halides, we report a ligand-enabled, electrochemical copper-catalyzed cross-electrophile coupling. Although Cu is the first metal reported for C-C bond construction, cross-electrophile coupling nowadays is dominated by Ni. This work demonstrates that efficient cross-electrophile coupling can be realized by electrochemical Cu catalysis. Our protocol is applicable to a wide range of propargyl bromides and (hetero)aryl iodides or bromides, delivering the desired products in good yields with high cross-selectivity. The use of an orthodimethylamine-substituted diamine ligand is crucial for promoting the reaction and suppressing cathodic Cu deposition. We attribute this effect to an intramolecular H···N H-bonding, which facilitates hyperconjugation between the NMe2 moiety and the nitrogen atom coordinated to the Cu center. Mechanistic studies indicate that the reaction follows a radical pathway, contrasting with the SN2 pathway reported previously. This work establishes a foundation for electrochemical Cu-catalyzed cross-electrophile coupling and provides a new paradigm for Cu-catalyzed C-C bond formation via radical intermediates.
{"title":"Expanding Ullmann Homocoupling to Cross-Coupling: Electrochemical Copper-Catalyzed Cross-Electrophile Coupling of Alkyl and Aryl Halides.","authors":"Kailun Liang, Yuhongxu Bai, Hang Li, Yingjie Li, Chengbiao Zhu, Zhenwei Wei, Caiyou Chen","doi":"10.1021/jacs.5c20694","DOIUrl":"https://doi.org/10.1021/jacs.5c20694","url":null,"abstract":"<p><p>The construction of C-C bonds is a pivotal transformation in organic synthesis. Traditional Ullmann type and Hurtley reactions for constructing C(sp<sup>3</sup>)-C(sp<sup>2</sup>) bonds rely on organometallic reagents or substrates with active methylene units. These requirements significantly limit their practical applicability. Herein, employing two readily available organic halides, we report a ligand-enabled, electrochemical copper-catalyzed cross-electrophile coupling. Although Cu is the first metal reported for C-C bond construction, cross-electrophile coupling nowadays is dominated by Ni. This work demonstrates that efficient cross-electrophile coupling can be realized by electrochemical Cu catalysis. Our protocol is applicable to a wide range of propargyl bromides and (hetero)aryl iodides or bromides, delivering the desired products in good yields with high cross-selectivity. The use of an orthodimethylamine-substituted diamine ligand is crucial for promoting the reaction and suppressing cathodic Cu deposition. We attribute this effect to an intramolecular H···N H-bonding, which facilitates hyperconjugation between the NMe<sub>2</sub> moiety and the nitrogen atom coordinated to the Cu center. Mechanistic studies indicate that the reaction follows a radical pathway, contrasting with the S<sub>N</sub>2 pathway reported previously. This work establishes a foundation for electrochemical Cu-catalyzed cross-electrophile coupling and provides a new paradigm for Cu-catalyzed C-C bond formation via radical intermediates.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":15.6,"publicationDate":"2026-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146148428","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
2-O-α-d-glucopyranosyl-l-ascorbic acid (AA-2G) is a highly stable glycosylated derivative of vitamin C with broad applications in the food, pharmaceutical, and cosmetic industries. Sucrose phosphorylase (SPase) serves as a promising biocatalyst for the efficient synthesis of AA-2G from sucrose and L-AA. However, its industrial application is often limited by insufficient thermostability. In this study, the thermostability of SPase from Bifidobacterium longum (BlSPase) was significantly improved through an integrated computational semirational design strategy. Using PROSS, DeepDDG, and FireProt, a smart mutant library was constructed, leading to the identification of a positive mutant, G197A, with a half-life extended by 24.75 min and a melting temperature increased by 2.1 °C compared to the wild-type enzyme. Under optimized high-cell-density fermentation in a 10-L bioreactor and whole-cell catalytic conditions, G197A achieved an AA-2G titer of 383.13 g/L and a conversion rate of 80.97%. Furthermore, an anion exchange-based purification process was developed, affording high-purity AA-2G, as confirmed by HPLC and NMR analyses. This work paves the way for the industrial application of SPase by providing a robust computational framework for stability engineering, enabling sustainable and high-yield AA-2G production.
{"title":"Computational Design and Process Intensification for High-Level Production of AA-2G by a Robust Sucrose Phosphorylase","authors":"Jiajing Guo, Lukasz Peplowski, Wei Shen, Haiquan Yang, Li Zhou, Yuanyuan Xia, Xianzhong Chen","doi":"10.1021/acssuschemeng.5c12586","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c12586","url":null,"abstract":"2-<i>O</i>-α-<span>d</span>-glucopyranosyl-l-ascorbic acid (AA-2G) is a highly stable glycosylated derivative of vitamin C with broad applications in the food, pharmaceutical, and cosmetic industries. Sucrose phosphorylase (SPase) serves as a promising biocatalyst for the efficient synthesis of AA-2G from sucrose and L-AA. However, its industrial application is often limited by insufficient thermostability. In this study, the thermostability of SPase from <i>Bifidobacterium longum</i> (BlSPase) was significantly improved through an integrated computational semirational design strategy. Using PROSS, DeepDDG, and FireProt, a smart mutant library was constructed, leading to the identification of a positive mutant, G197A, with a half-life extended by 24.75 min and a melting temperature increased by 2.1 °C compared to the wild-type enzyme. Under optimized high-cell-density fermentation in a 10-L bioreactor and whole-cell catalytic conditions, G197A achieved an AA-2G titer of 383.13 g/L and a conversion rate of 80.97%. Furthermore, an anion exchange-based purification process was developed, affording high-purity AA-2G, as confirmed by HPLC and NMR analyses. This work paves the way for the industrial application of SPase by providing a robust computational framework for stability engineering, enabling sustainable and high-yield AA-2G production.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"3 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146268","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-10DOI: 10.1021/acs.orglett.6c00041
Chang Gao, Nana Shen, Qianting Zhou, Xinying Zhang, Xuesen Fan
Presented herein is a condition-controlled selective synthesis of isochromene fused indenone (3) or Indane fused indanone derivatives (4) via the cascade reactions of 3-phenyl[1,2,3]triazolo[1,5-a]pyridine (1) with diazo indanedione (2). The formation of products is initiated by Rh(III)-catalyzed aryl C–H alkylation of 1 with 2 followed by denitrogenation of the pyridotriazole moiety to form a Rh-carbene species as the key intermediate. When the reaction is carried out in DCM, the Rh-carbene species undergoes an intramolecular O–H bond insertion with the enol moiety followed by proto-demetalation to give product 3. When the reaction is carried out in HFIP, on the other hand, the Rh-carbene species chooses to take part in an intermolecular O–H bond insertion with HFIP, followed by an intramolecular carbonyl insertion and proto-demetalation to give product 4. To our knowledge, such a solvent-dependent selective O–H bond carbene insertion leading to the formation of distinct polycyclic compounds from the same starting materials has not been reported previously. In general, the protocols developed herein feature high efficiency, good atom/step-economy, broad substrate scope and ready scalability. Moreover, the products could be readily transformed into other valuable products.
{"title":"Selective Synthesis of Isochromene Fused Indenone or Indane Fused Indanone Derivatives Featuring with Solvent-Dependent Intra- or Intermolecular O–H Bond Carbene Insertion","authors":"Chang Gao, Nana Shen, Qianting Zhou, Xinying Zhang, Xuesen Fan","doi":"10.1021/acs.orglett.6c00041","DOIUrl":"https://doi.org/10.1021/acs.orglett.6c00041","url":null,"abstract":"Presented herein is a condition-controlled selective synthesis of isochromene fused indenone (<b>3</b>) or Indane fused indanone derivatives (<b>4</b>) via the cascade reactions of 3-phenyl[1,2,3]triazolo[1,5-<i>a</i>]pyridine (<b>1</b>) with diazo indanedione (<b>2</b>). The formation of products is initiated by Rh(III)-catalyzed aryl C–H alkylation of <b>1</b> with <b>2</b> followed by denitrogenation of the pyridotriazole moiety to form a Rh-carbene species as the key intermediate. When the reaction is carried out in DCM, the Rh-carbene species undergoes an intramolecular O–H bond insertion with the enol moiety followed by proto-demetalation to give product <b>3</b>. When the reaction is carried out in HFIP, on the other hand, the Rh-carbene species chooses to take part in an intermolecular O–H bond insertion with HFIP, followed by an intramolecular carbonyl insertion and proto-demetalation to give product <b>4</b>. To our knowledge, such a solvent-dependent selective O–H bond carbene insertion leading to the formation of distinct polycyclic compounds from the same starting materials has not been reported previously. In general, the protocols developed herein feature high efficiency, good atom/step-economy, broad substrate scope and ready scalability. Moreover, the products could be readily transformed into other valuable products.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"1 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146339","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}