Pub Date : 2025-09-15DOI: 10.1016/j.jcoa.2025.100257
Mayu Onozato, Syuntei Fu, Tomoya Takaura, Tatsuya Sakamoto, Takeshi Fukushima
1-Methyl-d-tryptophan (d-MT) is an inhibitor of the tryptophan (Trp)-catabolizing enzyme indoleamine 2,3-dioxygenase (IDO). d-MT has been used in studies on Trp metabolism inhibition and as a concomitant drug with antitumor agents. In this study, we investigated the enantiomeric separation of d-MT and its enantiomer, l-MT, via LC-MS/MS following pre-column derivatization with succinimidyl 2-(3-((benzyloxy)carbonyl)-1-methyl-5-oxoimidazolidin-4-yl) acetate ((R)-CIMa-OSu). Consequently, the use of a mixed-mode stationary phase, ScherzoⓇ SM-C18, provided a separation factor (α) of 1.44 and a resolution (Rs) of 6.14, with both values being higher than those obtained with a reversed-phase column (α: 1.29, Rs: 2.69). Using the proposed LC-MS/MS method, the time-course profiles of plasma d-MT concentrations in rats administered d-MT were investigated. Consequently, a chiral inversion of d-MT to l-MT was observed in rats administered d-MT, whereas no inversion of l-MT to d-MT was observed in rats administered l-MT. The involvement of d-amino acid oxidase (DAO) in the chiral inversion of d-MT to l-MT was suggested, as pre-administration of DAO inhibitors significantly increased the d-MT concentrations in rat plasma.
{"title":"Enantiomeric separation of 1-methyl-tryptophan on a mixed-mode stationary phase via pre-column derivatization and in vivo assessment of chiral inversion in rats","authors":"Mayu Onozato, Syuntei Fu, Tomoya Takaura, Tatsuya Sakamoto, Takeshi Fukushima","doi":"10.1016/j.jcoa.2025.100257","DOIUrl":"10.1016/j.jcoa.2025.100257","url":null,"abstract":"<div><div>1-Methyl-<span>d</span>-tryptophan (<span>d</span>-MT) is an inhibitor of the tryptophan (Trp)-catabolizing enzyme indoleamine 2,3-dioxygenase (IDO). <span>d</span>-MT has been used in studies on Trp metabolism inhibition and as a concomitant drug with antitumor agents. In this study, we investigated the enantiomeric separation of <span>d</span>-MT and its enantiomer, <span>l</span>-MT, via LC-MS/MS following pre-column derivatization with succinimidyl 2-(3-((benzyloxy)carbonyl)-1-methyl-5-oxoimidazolidin-4-yl) acetate ((<em>R</em>)-CIMa-OSu). Consequently, the use of a mixed-mode stationary phase, Scherzo<sup>Ⓡ</sup> SM-C18, provided a separation factor (<em>α</em>) of 1.44 and a resolution (<em>R</em><sub>s</sub>) of 6.14, with both values being higher than those obtained with a reversed-phase column (<em>α</em>: 1.29, <em>R</em><sub>s</sub>: 2.69). Using the proposed LC-MS/MS method, the time-course profiles of plasma <span>d</span>-MT concentrations in rats administered <span>d</span>-MT were investigated. Consequently, a chiral inversion of <span>d</span>-MT to <span>l</span>-MT was observed in rats administered <span>d</span>-MT, whereas no inversion of <span>l</span>-MT to <span>d</span>-MT was observed in rats administered <span>l</span>-MT. The involvement of <span>d</span>-amino acid oxidase (DAO) in the chiral inversion of <span>d</span>-MT to <span>l</span>-MT was suggested, as pre-administration of DAO inhibitors significantly increased the <span>d</span>-MT concentrations in rat plasma.</div></div>","PeriodicalId":93576,"journal":{"name":"Journal of chromatography open","volume":"8 ","pages":"Article 100257"},"PeriodicalIF":3.2,"publicationDate":"2025-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145157315","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-07DOI: 10.1016/j.jcoa.2025.100256
Wolfgang Thormann
Sulfated cyclodextrin based enantioselective capillary electrophoresis for the monitoring of the stereoisomers of ketamine and its metabolites norketamine, 5,6-dehydronorketamine and hydroxynorketamine in biosamples is reviewed. A survey of reported assays with their specifications is presented together with their limitations in terms of distinguishing between the various hydroxynorketamine stereoisomers formed in vitro and in vivo. Applications discussed include (i) the identification of single cytochrome P450 enzymes that are involved in the various metabolic steps in humans, equines and canines, (ii) the assessment of the metabolic patterns present after incubation of ketamine or norketamine with liver microsomes of different species, (iii) the quantitation of an in vitro metabolic step in absence and presence of an inhibitor, (iv) the monitoring of the stereoisomers of ketamine and its metabolites in urine, plasma, cerebrospinal fluid, brain and hair, and (v) the pharmacokinetics of ketamine and norketamine enantiomers after bolus application, target control infusion or low-dose, subanesthetic constant rate infusion of racemic ketamine and S-ketamine to equines and canines. The reviewed metabolic ketamine work assessed by enantioselective capillary electrophoresis provides insight into the stereoselectivity of the metabolic pathways of ketamine and improved infusion, anesthetic and antinociceptive application schemes of racemic ketamine and S-ketamine in veterinary medicine.
{"title":"Enantioselective capillary electrophoresis with sulfated cyclodextrins for monitoring ketamine and its metabolites in biosamples and its application to assess metabolic steps and kinetic parameters","authors":"Wolfgang Thormann","doi":"10.1016/j.jcoa.2025.100256","DOIUrl":"10.1016/j.jcoa.2025.100256","url":null,"abstract":"<div><div>Sulfated cyclodextrin based enantioselective capillary electrophoresis for the monitoring of the stereoisomers of ketamine and its metabolites norketamine, 5,6-dehydronorketamine and hydroxynorketamine in biosamples is reviewed. A survey of reported assays with their specifications is presented together with their limitations in terms of distinguishing between the various hydroxynorketamine stereoisomers formed in vitro and in vivo. Applications discussed include (i) the identification of single cytochrome P450 enzymes that are involved in the various metabolic steps in humans, equines and canines, (ii) the assessment of the metabolic patterns present after incubation of ketamine or norketamine with liver microsomes of different species, (iii) the quantitation of an in vitro metabolic step in absence and presence of an inhibitor, (iv) the monitoring of the stereoisomers of ketamine and its metabolites in urine, plasma, cerebrospinal fluid, brain and hair, and (v) the pharmacokinetics of ketamine and norketamine enantiomers after bolus application, target control infusion or low-dose, subanesthetic constant rate infusion of racemic ketamine and S-ketamine to equines and canines. The reviewed metabolic ketamine work assessed by enantioselective capillary electrophoresis provides insight into the stereoselectivity of the metabolic pathways of ketamine and improved infusion, anesthetic and antinociceptive application schemes of racemic ketamine and S-ketamine in veterinary medicine.</div></div>","PeriodicalId":93576,"journal":{"name":"Journal of chromatography open","volume":"8 ","pages":"Article 100256"},"PeriodicalIF":3.2,"publicationDate":"2025-09-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145049343","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-04DOI: 10.1016/j.jcoa.2025.100253
Carmela Maria Montone , Nina Felli , Massimo Giuseppe De Cesaris , Lorenzo Antonelli , Tecla Gasperi , Maria Bianchi , Patrizia Papacci , Luciana Teofili , Salvatore Fanali , Alessandra Gentili
The determination of fat-soluble antioxidants represents a significant analytical challenge, particularly when dealing with biological matrices available only in limited quantities, such as those collected from preterm infants. This paper presents the development, validation, and application of a multianalyte high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method for the determination of 21 fat-soluble antioxidants (including vitamins and carotenoids) in meconium, cord plasma, and maternal plasma samples. All the analytes were separated by non-aqueous reversed phase chromatography, detected by atmospheric pressure chemical ionization, acquiring in Scheduled/Multiple Reaction Monitoring mode to improve sensitivity. Their extraction was performed with hexane, after protein precipitation with cold ethanol, followed by a “lipid freezing” clean-up. Recoveries ranged between 63 and 100 % with relative standard deviations ≤ 18 %. For all matrices, limits of detection and lower limits of quantitation were in the ppb and ppm-ppb range, respectively. The developed approach enabled the study of the distribution of 21 fat-soluble antioxidants, which play a protective role against oxidative stress at various levels within the human body. To better interpret the data obtained from an unconventional matrix such as meconium, the results were compared with those from cord plasma and maternal plasma, revealing, in most cases, a common trend across the 24 cases under study.
{"title":"An analytical methodology for the quantitative profiling of fat-soluble antioxidants in maternal blood, umbilical cord blood and meconium","authors":"Carmela Maria Montone , Nina Felli , Massimo Giuseppe De Cesaris , Lorenzo Antonelli , Tecla Gasperi , Maria Bianchi , Patrizia Papacci , Luciana Teofili , Salvatore Fanali , Alessandra Gentili","doi":"10.1016/j.jcoa.2025.100253","DOIUrl":"10.1016/j.jcoa.2025.100253","url":null,"abstract":"<div><div>The determination of fat-soluble antioxidants represents a significant analytical challenge, particularly when dealing with biological matrices available only in limited quantities, such as those collected from preterm infants. This paper presents the development, validation, and application of a multianalyte high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method for the determination of 21 fat-soluble antioxidants (including vitamins and carotenoids) in meconium, cord plasma, and maternal plasma samples. All the analytes were separated by non-aqueous reversed phase chromatography, detected by atmospheric pressure chemical ionization, acquiring in Scheduled/Multiple Reaction Monitoring mode to improve sensitivity. Their extraction was performed with hexane, after protein precipitation with cold ethanol, followed by a “lipid freezing” clean-up. Recoveries ranged between 63 and 100 % with relative standard deviations ≤ 18 %. For all matrices, limits of detection and lower limits of quantitation were in the ppb and ppm-ppb range, respectively. The developed approach enabled the study of the distribution of 21 fat-soluble antioxidants, which play a protective role against oxidative stress at various levels within the human body. To better interpret the data obtained from an unconventional matrix such as meconium, the results were compared with those from cord plasma and maternal plasma, revealing, in most cases, a common trend across the 24 cases under study.</div></div>","PeriodicalId":93576,"journal":{"name":"Journal of chromatography open","volume":"8 ","pages":"Article 100253"},"PeriodicalIF":3.2,"publicationDate":"2025-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145010210","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-04DOI: 10.1016/j.jcoa.2025.100250
A. Temerdashev , S. Girel , S.N. Atapattu , Y.-Q. Feng , E. Gashimova , T. Malitskaya , I. Podolskiy , Q.-F. Zhu
Current work presents main aspects of the application of liquid chromatography in combination with low- and high-resolution mass spectrometry to an analysis of steroid hormones. Advantages and challenges of both targeted and untargeted analysis are shown together with the most popular approaches to the associated sample preparation. Among emerging approaches, first applications of isotope ratio mass spectrometry in combination with liquid chromatography for the analysis of steroid hormones for doping control purposes are presented and discussed.
{"title":"Liquid chromatography coupled to mass spectrometry for steroid hormones analysis: issues and solutions in sample preparation and method development","authors":"A. Temerdashev , S. Girel , S.N. Atapattu , Y.-Q. Feng , E. Gashimova , T. Malitskaya , I. Podolskiy , Q.-F. Zhu","doi":"10.1016/j.jcoa.2025.100250","DOIUrl":"10.1016/j.jcoa.2025.100250","url":null,"abstract":"<div><div>Current work presents main aspects of the application of liquid chromatography in combination with low- and high-resolution mass spectrometry to an analysis of steroid hormones. Advantages and challenges of both targeted and untargeted analysis are shown together with the most popular approaches to the associated sample preparation. Among emerging approaches, first applications of isotope ratio mass spectrometry in combination with liquid chromatography for the analysis of steroid hormones for doping control purposes are presented and discussed.</div></div>","PeriodicalId":93576,"journal":{"name":"Journal of chromatography open","volume":"8 ","pages":"Article 100250"},"PeriodicalIF":3.2,"publicationDate":"2025-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145049340","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-04DOI: 10.1016/j.jcoa.2025.100255
Özge Altıntaş , Fatma Yılmaz , Adil Denizli
Molecularly imprinted polymers (MIPs) have emerged as a promising alternative in biomedical analysis due to their specific recognition capabilities, chemical stability and applicability in biological systems. This review focuses on recent advancements in MIP systems those integrated with monolithic structures for biomedical analytical applications. Owing to their high surface area, low flow resistance and porous morphology, monolithic MIPs exhibit superior performance in applications such as separation, diagnostics and targeted drug delivery. Compared to conventional particle-based systems, these structures are more readily integrated into microfluidic platforms and yield more effective outcomes in sample preparation, sensor-based diagnostics and chromatographic separations. Moreover, novel technologies such as 3D printing and stimuli-responsive materials further enhance the functionality of these polymers, facilitating their translation into future clinical applications. This review systematically discusses the design, synthesis strategies, analytical performance and biomedical potential of MIP-monolith composites. By considering existing challenges, it also highlights their potential for developing of high-performance systems with broader application scopes in the future.
{"title":"Advancements in molecularly imprinted polymers-based monolithic structures for biomedical analysis","authors":"Özge Altıntaş , Fatma Yılmaz , Adil Denizli","doi":"10.1016/j.jcoa.2025.100255","DOIUrl":"10.1016/j.jcoa.2025.100255","url":null,"abstract":"<div><div>Molecularly imprinted polymers (MIPs) have emerged as a promising alternative in biomedical analysis due to their specific recognition capabilities, chemical stability and applicability in biological systems. This review focuses on recent advancements in MIP systems those integrated with monolithic structures for biomedical analytical applications. Owing to their high surface area, low flow resistance and porous morphology, monolithic MIPs exhibit superior performance in applications such as separation, diagnostics and targeted drug delivery. Compared to conventional particle-based systems, these structures are more readily integrated into microfluidic platforms and yield more effective outcomes in sample preparation, sensor-based diagnostics and chromatographic separations. Moreover, novel technologies such as 3D printing and stimuli-responsive materials further enhance the functionality of these polymers, facilitating their translation into future clinical applications. This review systematically discusses the design, synthesis strategies, analytical performance and biomedical potential of MIP-monolith composites. By considering existing challenges, it also highlights their potential for developing of high-performance systems with broader application scopes in the future.</div></div>","PeriodicalId":93576,"journal":{"name":"Journal of chromatography open","volume":"8 ","pages":"Article 100255"},"PeriodicalIF":3.2,"publicationDate":"2025-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145018626","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nanotechnology has evolved into an interdisciplinary trend spanning nearly all scientific domains and has had a profound impact on the global community over the last decade. On the surface, miniaturisation offers mechanical, chemical, and biological components that operate more quickly and affordably. Through the development of new nanoparticles (NPs), nanodevices, nanosensors, and nanosorbents for analytical procedures, the inclusion of nanotechnology has additionally had an impact on bioanalytical sciences. In recent years, numerous studies have been done on the integration of nanomaterials and their analysis in various biological samples. Given the scope of the NPs integrated bioanalysis, the purpose of this review is to provide an overview of multiple types of extraction techniques, sample preparation, and nanomaterials like magnetic NPs, carbon-based NPs, molecularly implanted polymers (MIPs) used in the determination of different drugs in biological specimens, and also to critically evaluate the tools used to examine Green Analytical Chemistry (GAC), such as Green Analytical Procedure Index (GAPI), ComplexGAPI (CoGAPI), Click Analytical Chemistry Index (CACI).
{"title":"Nanotechnology in bioanalysis: Current trends and applications","authors":"Arshdeep Chopra , Yogindra Kumari , Samarth Kumar , Renuka Sharma , Rohit Bhatia","doi":"10.1016/j.jcoa.2025.100254","DOIUrl":"10.1016/j.jcoa.2025.100254","url":null,"abstract":"<div><div>Nanotechnology has evolved into an interdisciplinary trend spanning nearly all scientific domains and has had a profound impact on the global community over the last decade. On the surface, miniaturisation offers mechanical, chemical, and biological components that operate more quickly and affordably. Through the development of new nanoparticles (NPs), nanodevices, nanosensors, and nanosorbents for analytical procedures, the inclusion of nanotechnology has additionally had an impact on bioanalytical sciences. In recent years, numerous studies have been done on the integration of nanomaterials and their analysis in various biological samples. Given the scope of the NPs integrated bioanalysis, the purpose of this review is to provide an overview of multiple types of extraction techniques, sample preparation, and nanomaterials like magnetic NPs, carbon-based NPs, molecularly implanted polymers (MIPs) used in the determination of different drugs in biological specimens, and also to critically evaluate the tools used to examine Green Analytical Chemistry (GAC), such as Green Analytical Procedure Index (GAPI), ComplexGAPI (CoGAPI), Click Analytical Chemistry Index (CACI).</div></div>","PeriodicalId":93576,"journal":{"name":"Journal of chromatography open","volume":"8 ","pages":"Article 100254"},"PeriodicalIF":3.2,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145049342","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-02DOI: 10.1016/j.jcoa.2025.100252
Abdul Haseeb , Yosief Wondmagegne , Miguel X. Fernandes , Jörgen Samuelsson
In liquid chromatography (LC), adsorption heterogeneity arises from the distribution of adsorption sites on stationary phases with varying interaction energies, affecting retention and separation performance. This heterogeneity can cause peak tailing, reduced resolution, and unpredictable retention times in analytical chromatography, as well as broad, asymmetric elution profiles in preparative systems. Adsorption heterogeneity depends on the combined effects of the stationary phase, the mobile phase composition, the analyte properties, and the chromatographic conditions. Traditional adsorption isotherms often fail to fully describe these complex interactions because they assume uniform adsorption energies.
The Adsorption Energy Distribution (AED) framework offers a powerful alternative by modelling adsorption as a sum of independent homogeneous sites, each with a specific energy, offering a realistic representation of heterogeneous adsorption. This review introduces the theoretical foundations of AED, including its mathematical formulation and computational approaches, and discusses its application in interpreting retention mechanisms in LC. AED analysis is illustrated through its use in both chiral and achiral separations, as well as its ability to explain peak tailing and surface heterogeneity. Practical considerations, such as the range of concentration data in the adsorption isotherm, the selection of a suitable kernel function, and the number of iterations and grid points in AED analysis, are discussed. Special emphasis is given on how to visualize and interpret the AED. This review aims to provide chromatographers with a comprehensive understanding of AED, emphasizing its practical value in characterizing the chromatographic system and elucidating retention mechanisms in liquid chromatography.
{"title":"Adsorption energy distributions: Theory and applications in liquid chromatography","authors":"Abdul Haseeb , Yosief Wondmagegne , Miguel X. Fernandes , Jörgen Samuelsson","doi":"10.1016/j.jcoa.2025.100252","DOIUrl":"10.1016/j.jcoa.2025.100252","url":null,"abstract":"<div><div>In liquid chromatography (LC), adsorption heterogeneity arises from the distribution of adsorption sites on stationary phases with varying interaction energies, affecting retention and separation performance. This heterogeneity can cause peak tailing, reduced resolution, and unpredictable retention times in analytical chromatography, as well as broad, asymmetric elution profiles in preparative systems. Adsorption heterogeneity depends on the combined effects of the stationary phase, the mobile phase composition, the analyte properties, and the chromatographic conditions. Traditional adsorption isotherms often fail to fully describe these complex interactions because they assume uniform adsorption energies.</div><div>The Adsorption Energy Distribution (AED) framework offers a powerful alternative by modelling adsorption as a sum of independent homogeneous sites, each with a specific energy, offering a realistic representation of heterogeneous adsorption. This review introduces the theoretical foundations of AED, including its mathematical formulation and computational approaches, and discusses its application in interpreting retention mechanisms in LC. AED analysis is illustrated through its use in both chiral and achiral separations, as well as its ability to explain peak tailing and surface heterogeneity. Practical considerations, such as the range of concentration data in the adsorption isotherm, the selection of a suitable kernel function, and the number of iterations and grid points in AED analysis, are discussed. Special emphasis is given on how to visualize and interpret the AED. This review aims to provide chromatographers with a comprehensive understanding of AED, emphasizing its practical value in characterizing the chromatographic system and elucidating retention mechanisms in liquid chromatography.</div></div>","PeriodicalId":93576,"journal":{"name":"Journal of chromatography open","volume":"8 ","pages":"Article 100252"},"PeriodicalIF":3.2,"publicationDate":"2025-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145004271","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-02DOI: 10.1016/j.jcoa.2025.100251
Leandro Oka-Duarte , Giovanni S. Baviera , Weston J. Umstead , Quezia B. Cass , Anderson R.M. de Oliveira
The widespread presence of chiral organic UV filters in the environment raises critical concerns due to their potential enantioselective toxicity and persistence. This study provides the first comprehensive enantioseparation screening of five such compounds – enzacamene, homosalate, octinoxate, octisalate, and octocrylene – using multimodal liquid chromatography (LC), as well as supercritical fluid chromatography (SFC) with 20 polysaccharide-based chiral stationary phases (CSPs). Enzacamene and homosalate were baseline-resolved across all tested conditions, including SFC, while octisalate showed separation in normal and reversed-phase modes. Octinoxate was resolved only in normal-phase mode, and octocrylene was not fully resolved, though near-baseline separation was achieved in polar organic and normal-phase modes. SFC, particularly with non-conventional CO₂/hexane–ethanol eluent, proved complementary to LC, achieving comparable or superior enantioresolution. Coated amylose columns demonstrated superior performance in reversed-phase mode, whereas immobilized CSPs, particularly chloromethylphenylcarbamate-based selectors, displayed broader applicability across multiple mobile phase systems. These findings emphasize the necessity of multimodal approaches to optimize the enantioseparation of highly lipophilic environmental contaminants and establish a robust analytical foundation for future ecotoxicological and regulatory studies.
{"title":"From multimodal liquid chromatography to supercritical fluid chromatography: Mapping chiral separation of the major organic ultraviolet filters","authors":"Leandro Oka-Duarte , Giovanni S. Baviera , Weston J. Umstead , Quezia B. Cass , Anderson R.M. de Oliveira","doi":"10.1016/j.jcoa.2025.100251","DOIUrl":"10.1016/j.jcoa.2025.100251","url":null,"abstract":"<div><div>The widespread presence of chiral organic UV filters in the environment raises critical concerns due to their potential enantioselective toxicity and persistence. This study provides the first comprehensive enantioseparation screening of five such compounds – enzacamene, homosalate, octinoxate, octisalate, and octocrylene – using multimodal liquid chromatography (LC), as well as supercritical fluid chromatography (SFC) with 20 polysaccharide-based chiral stationary phases (CSPs). Enzacamene and homosalate were baseline-resolved across all tested conditions, including SFC, while octisalate showed separation in normal and reversed-phase modes. Octinoxate was resolved only in normal-phase mode, and octocrylene was not fully resolved, though near-baseline separation was achieved in polar organic and normal-phase modes. SFC, particularly with non-conventional CO₂/hexane–ethanol eluent, proved complementary to LC, achieving comparable or superior enantioresolution. Coated amylose columns demonstrated superior performance in reversed-phase mode, whereas immobilized CSPs, particularly chloromethylphenylcarbamate-based selectors, displayed broader applicability across multiple mobile phase systems. These findings emphasize the necessity of multimodal approaches to optimize the enantioseparation of highly lipophilic environmental contaminants and establish a robust analytical foundation for future ecotoxicological and regulatory studies.</div></div>","PeriodicalId":93576,"journal":{"name":"Journal of chromatography open","volume":"8 ","pages":"Article 100251"},"PeriodicalIF":3.2,"publicationDate":"2025-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145010209","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-08-31DOI: 10.1016/j.jcoa.2025.100249
Rachel C. Halvorsen , Wenjing Ma , Caitlin N. Cain , Hep Ingham , Rachel E. Mohler , Robert E. Synovec
Historically, tile-based Fisher ratio (F-ratio) analysis of comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GC × GC-TOFMS) data was developed for analysts to use a supervised experimental design with defined sample classes to obtain a hit list to discover analytes that most significantly distinguish the sample classes at the top of the hit list. In this traditional application, a user-specified F-ratio threshold is used to discard most hits in order to focus on the top hits. To broaden the scope of tile-based F-ratio analysis, in the present study we explore the ability of the software to discover all analyte components that are detected in a set of samples, essentially taking full advantage of the tiling aspect of the software which uncovers all analytes that exhibit sufficient signal relative to the baseline noise across all samples to be deemed detectable and hence to produce an F-ratio. For this study a set of nine petroleum samples, i.e., two hydrobates (light naphthas), two reformates, four naphthas, and a “heavy” gasoline, are simultaneously analyzed and statistically compared via p-testing to blank chromatograms to produce one comprehensive hit list. The pin locations and signal areas at the top m/z F-ratio are used together with replicate blanks to generate a master peak table (MPT) that in turn is used to generate sample-specific peak tables (SSPT), one SSPT for each injection replicate of each petroleum sample (class), that are naturally retention-time aligned via the F-ratio software. The nine petroleum samples vary to a large extent in the identity and number of analytes present. Indeed, while a total of ∼715 analytes were found across all nine samples, only ∼260 of these analytes are fully shared across all sample classes. The number of analytes in the nine petroleum samples ranged from an average of 335 analytes for one of the hydrobates to 669 analytes for two of the naphthas. This workflow also facilitated generating simulated distillation curves for the nine petroleum samples to provide further insight.
从历史上看，综合二维气相色谱飞行时间质谱（GC × GC- tofms）数据的基于瓦片的Fisher ratio （F-ratio）分析是为分析人员开发的，用于使用具有定义样品类别的监督实验设计来获得命中列表，以发现在命中列表顶部最显著区分样品类别的分析物。在这个传统的应用程序中，使用用户指定的F-ratio阈值来丢弃大多数命中，以便专注于命中最多的命中。为了扩大基于瓦片的f比分析的范围，在本研究中，我们探索了软件发现在一组样品中检测到的所有分析物成分的能力，基本上充分利用了软件的瓦片方面，该软件发现了所有分析物，这些分析物相对于所有样品的基线噪声表现出足够的信号，被认为是可检测的，因此产生了f比。本研究同时分析了9种石油样品，即两种加氢产物（轻石脑油）、两种重整产物、四种石脑油和一种“重”汽油，并通过空白色谱的p检验进行统计比较，得出一个综合的攻击清单。最高m/z f比的pin位置和信号区域与重复空白一起用于生成主峰表（MPT），该主峰表反过来用于生成样品特异性峰表（SSPT），每个石油样品（类别）的每个注入重复都有一个SSPT，通过f比软件自然地保持时间对齐。这9个石油样品在特征和分析物数量上有很大的不同。事实上，虽然在所有9个样本中共发现了~ 715种分析物，但这些分析物中只有~ 260种在所有样本类别中完全共享。9个石油样品中分析物的数量从一种氢化物的平均335个分析物到两种石脑油的平均669个分析物不等。该工作流程还有助于生成9个石油样品的模拟蒸馏曲线，以提供进一步的见解。
{"title":"Implementing tile-based fisher ratio analysis of two-dimensional gas chromatography time-of-flight mass spectrometry data to obtain a master peak table of all detected analyte compounds in many petroleum-based samples","authors":"Rachel C. Halvorsen , Wenjing Ma , Caitlin N. Cain , Hep Ingham , Rachel E. Mohler , Robert E. Synovec","doi":"10.1016/j.jcoa.2025.100249","DOIUrl":"10.1016/j.jcoa.2025.100249","url":null,"abstract":"<div><div>Historically, tile-based Fisher ratio (F-ratio) analysis of comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GC × GC-TOFMS) data was developed for analysts to use a supervised experimental design with defined sample classes to obtain a hit list to discover analytes that most significantly distinguish the sample classes at the top of the hit list. In this traditional application, a user-specified F-ratio threshold is used to discard most hits in order to focus on the top hits. To broaden the scope of tile-based F-ratio analysis, in the present study we explore the ability of the software to discover all analyte components that are detected in a set of samples, essentially taking full advantage of the tiling aspect of the software which uncovers all analytes that exhibit sufficient signal relative to the baseline noise across all samples to be deemed detectable and hence to produce an F-ratio. For this study a set of nine petroleum samples, i.e., two hydrobates (light naphthas), two reformates, four naphthas, and a “heavy” gasoline, are simultaneously analyzed and statistically compared via p-testing to blank chromatograms to produce one comprehensive hit list. The pin locations and signal areas at the top <em>m/z</em> F-ratio are used together with replicate blanks to generate a master peak table (MPT) that in turn is used to generate sample-specific peak tables (SSPT), one SSPT for each injection replicate of each petroleum sample (class), that are naturally retention-time aligned via the F-ratio software. The nine petroleum samples vary to a large extent in the identity and number of analytes present. Indeed, while a total of ∼715 analytes were found across all nine samples, only ∼260 of these analytes are fully shared across all sample classes. The number of analytes in the nine petroleum samples ranged from an average of 335 analytes for one of the hydrobates to 669 analytes for two of the naphthas. This workflow also facilitated generating simulated distillation curves for the nine petroleum samples to provide further insight.</div></div>","PeriodicalId":93576,"journal":{"name":"Journal of chromatography open","volume":"8 ","pages":"Article 100249"},"PeriodicalIF":3.2,"publicationDate":"2025-08-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145004276","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-08-21DOI: 10.1016/j.jcoa.2025.100248
Janik D. Seidel , Clifford Young , Manuela Klingler-Hoffmann , Mark R. Condina , Alok Shah , Sri Ramarathinam , Woan Mei Kok , Craig Kyngdon , Peter Hoffmann
Biopharmaceuticals and especially antibodies represent an expanding segment of pharmaceutical drug products. Production processes for this group of complex molecules use biological expression systems such as Chinese hamster ovary (CHO) cells, that are instrumental in their assembly, folding, and post-translational modification. Process development and optimization is challenging due to the complexity of cell culture systems and interdependency of process parameters on product quality attributes. This case study presents newly applied and developed analytical technologies able to monitor the cell culture process to increase the understanding of the interconnection of process parameters and quality attribute relationships in biopharmaceutical production processes. Specifically, a high-performance liquid chromatography (HPLC) -based workflow routinely measures amino acids and other cell culture media component profiles, while a mass spectrometry-based workflow monitors and quantifies changes in expressions of host cell proteins (HCPs) both globally and for individual HCP during the culture duration. These methods were applied to an industrial process with variations in seeding density, glucose and media feeding strategy, and media composition. Observations on product titre, global HCP and individual high-risk HCPs, throughout the culture progress, as well as in the end of the culture, provide insight for potential further optimization.
{"title":"Analytical methods for in-depth characterisation of cell culture bioreactors: A case study","authors":"Janik D. Seidel , Clifford Young , Manuela Klingler-Hoffmann , Mark R. Condina , Alok Shah , Sri Ramarathinam , Woan Mei Kok , Craig Kyngdon , Peter Hoffmann","doi":"10.1016/j.jcoa.2025.100248","DOIUrl":"10.1016/j.jcoa.2025.100248","url":null,"abstract":"<div><div>Biopharmaceuticals and especially antibodies represent an expanding segment of pharmaceutical drug products. Production processes for this group of complex molecules use biological expression systems such as Chinese hamster ovary (CHO) cells, that are instrumental in their assembly, folding, and post-translational modification. Process development and optimization is challenging due to the complexity of cell culture systems and interdependency of process parameters on product quality attributes. This case study presents newly applied and developed analytical technologies able to monitor the cell culture process to increase the understanding of the interconnection of process parameters and quality attribute relationships in biopharmaceutical production processes. Specifically, a high-performance liquid chromatography (HPLC) -based workflow routinely measures amino acids and other cell culture media component profiles, while a mass spectrometry-based workflow monitors and quantifies changes in expressions of host cell proteins (HCPs) both globally and for individual HCP during the culture duration. These methods were applied to an industrial process with variations in seeding density, glucose and media feeding strategy, and media composition. Observations on product titre, global HCP and individual high-risk HCPs, throughout the culture progress, as well as in the end of the culture, provide insight for potential further optimization.</div></div>","PeriodicalId":93576,"journal":{"name":"Journal of chromatography open","volume":"8 ","pages":"Article 100248"},"PeriodicalIF":3.2,"publicationDate":"2025-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144892109","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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