Pub Date : 2019-10-20DOI: 10.15583/JPCHROM.2019.015
Shimba Kawasue, Yohei Sakaguchi, Ena Yano, Tadashi Hayama, Reiko Koga, H. Yoshida, H. Nohta
Curcumin has been shown to be pharmacologically active in the prevention and treatment of various human diseases. In this study, we developed a fluorous derivatization method for selective analysis of curcumin with liquid chromatography (LC)tandem mass spectrometry (MS/MS). Curcumin was derivatized with the thiol-containing fluorous reagent (1H,1H,2H,2Hperfluoro-1-decanethiol) under mild conditions via Michael addition reaction, and the obtained derivative was introduced to a fluorous LC column (Fluofix-II 120E, 150 × 2.0 mm i.d., 5 μm, Wako). The selectively retained fluorous-derivatized curcumin on the column was also enabled highly sensitive detection with negative electrospray ionization MS/MS. Pretreatment of human serum sample was used protein precipitation with CH3CN. The calibration curve obtained by the present method showed good linearity (r2 = 0.9998) in the range of 7.4-442 ng/mL serum, and the limit of detection (S/N = 3) and limit of quantification (S/N = 10) were 1.8 ng/mL serum and 6.1 ng/mL serum, respectively. The present method was successfully applied to the analysis of curcumin in human serum sample.
姜黄素已被证明在预防和治疗各种人类疾病方面具有药理活性。在本研究中，我们开发了一种用液相色谱（LC）串联质谱（MS/MS）选择性分析姜黄素的荧光衍生方法。姜黄素与含硫醇的含氟试剂（1H，1H，2H，2H-全氟-1-癸硫醇）在温和条件下通过Michael加成反应进行衍生，并将获得的衍生物引入含氟LC柱（Fluofix II 120E，150×2.0mm i.d.，5μm，Wako）。柱上选择性保留的氟衍生姜黄素也能够通过负电喷雾电离MS/MS进行高灵敏度检测。人血清样品的预处理采用CH3CN蛋白沉淀法。本方法得到的校准曲线在7.4-442 ng/mL血清范围内呈良好的线性关系（r2=0.9998），检测限（S/N=3）和定量限（S/N=10）分别为1.8 ng/mL血清和6.1 ng/mL血清。本方法已成功应用于人血清样品中姜黄素的分析。
{"title":"Fluorous Derivatization Method for Selective Analysis of Curcumin with Liquid Chromatography-Tandem Mass Spectrometry","authors":"Shimba Kawasue, Yohei Sakaguchi, Ena Yano, Tadashi Hayama, Reiko Koga, H. Yoshida, H. Nohta","doi":"10.15583/JPCHROM.2019.015","DOIUrl":"https://doi.org/10.15583/JPCHROM.2019.015","url":null,"abstract":"Curcumin has been shown to be pharmacologically active in the prevention and treatment of various human diseases. In this study, we developed a fluorous derivatization method for selective analysis of curcumin with liquid chromatography (LC)tandem mass spectrometry (MS/MS). Curcumin was derivatized with the thiol-containing fluorous reagent (1H,1H,2H,2Hperfluoro-1-decanethiol) under mild conditions via Michael addition reaction, and the obtained derivative was introduced to a fluorous LC column (Fluofix-II 120E, 150 × 2.0 mm i.d., 5 μm, Wako). The selectively retained fluorous-derivatized curcumin on the column was also enabled highly sensitive detection with negative electrospray ionization MS/MS. Pretreatment of human serum sample was used protein precipitation with CH3CN. The calibration curve obtained by the present method showed good linearity (r2 = 0.9998) in the range of 7.4-442 ng/mL serum, and the limit of detection (S/N = 3) and limit of quantification (S/N = 10) were 1.8 ng/mL serum and 6.1 ng/mL serum, respectively. The present method was successfully applied to the analysis of curcumin in human serum sample.","PeriodicalId":91226,"journal":{"name":"Chromatography (Basel)","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.15583/JPCHROM.2019.015","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"43549500","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 : 2019-10-20DOI: 10.15583/JPCHROM.2019.016
T. Takayanagi, Yuto Mizuta, Yuta Becchaku, H. Mizuguchi
Graphene was dispersed in an aqueous solution with poly(sodium 4-styrenesulfonate) as a dispersant. The charge of the graphene came to be apparently negative by the adsorption of poly(4-styrenesulfonate) ion (PSS). Two kinds of PSS were examined: the average molecular masses of 70,000 and 1,000,000 (PSS 70,000 and PSS 1,000,000, respectively). Capillary electrophoresis was used to evaluate the dispersion of the apparently anionic graphene in an aqueous solution. A broad signal corresponding to the dispersed graphene was detected in the electropherograms. The effective electrophoretic mobility of the dispersed graphene was somewhat larger at higher concentrations of PSS 70,000, suggesting that the adsorbed amount of PSS 70,000 increased. Even when the separation buffer did not contain PSS, the broad signal of the anionic graphene was still detected. The peak height and/or the peak area, as well as the effective electrophoretic mobility of the graphene decreased little at the reduced applied voltages, i.e., at longer separation/detection time. Therefore, the adsorption of PSS is irreversible or the desorption of PSS from the graphene surface is very slow. Accordingly, the dispersed graphene with PSS would be separated from the matrix PSS by the electrophoretic separation.
{"title":"Dispersion of Graphene in an Aqueous Solution with Poly(sodium 4-styrenesulfonate) Monitored by Capillary Electrophoresis","authors":"T. Takayanagi, Yuto Mizuta, Yuta Becchaku, H. Mizuguchi","doi":"10.15583/JPCHROM.2019.016","DOIUrl":"https://doi.org/10.15583/JPCHROM.2019.016","url":null,"abstract":"Graphene was dispersed in an aqueous solution with poly(sodium 4-styrenesulfonate) as a dispersant. The charge of the graphene came to be apparently negative by the adsorption of poly(4-styrenesulfonate) ion (PSS). Two kinds of PSS were examined: the average molecular masses of 70,000 and 1,000,000 (PSS 70,000 and PSS 1,000,000, respectively). Capillary electrophoresis was used to evaluate the dispersion of the apparently anionic graphene in an aqueous solution. A broad signal corresponding to the dispersed graphene was detected in the electropherograms. The effective electrophoretic mobility of the dispersed graphene was somewhat larger at higher concentrations of PSS 70,000, suggesting that the adsorbed amount of PSS 70,000 increased. Even when the separation buffer did not contain PSS, the broad signal of the anionic graphene was still detected. The peak height and/or the peak area, as well as the effective electrophoretic mobility of the graphene decreased little at the reduced applied voltages, i.e., at longer separation/detection time. Therefore, the adsorption of PSS is irreversible or the desorption of PSS from the graphene surface is very slow. Accordingly, the dispersed graphene with PSS would be separated from the matrix PSS by the electrophoretic separation.","PeriodicalId":91226,"journal":{"name":"Chromatography (Basel)","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"43460160","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 : 2019-10-20DOI: 10.15583/jpchrom.2019.019
R. Nishioka, Syuji Harada, Kazuhiro Umehara
Enantiomeric separation ability on high-performance liquid chromatography (HPLC) of novel chiral stationary phase (CSP) was evaluated. A chiral selector of the CSP investigated in this study (SUMICHIRALTM OA-SHELL P1) is one of helical poly(diphenylacetylene) derivatives which is coated on core-shell silica support. OA-SHELL P1 showed excellent chiral separation ability for a wide range of aromatic chiral alcohols and it was also effective for separation of some chiral carboxylic acids, ketones and lactones. It is considered to be a new option for enantiomeric separation of these chiral compounds. OA-SHELL P1 is used in normal phase mode with a mobile phase of simple composition and one of its features is easy method development. The analysis time is relatively short even with conventional HPLC system since a core-shell support with particle size of 2.6 μm is used.
{"title":"Enantiomeric Separation of Chiral Alcohols Using Novel Core-Shell Type Chiral Stationary Phase Coated with Helical Poly(diphenylacetylene) Derivative by High-Performance Liquid Chromatography","authors":"R. Nishioka, Syuji Harada, Kazuhiro Umehara","doi":"10.15583/jpchrom.2019.019","DOIUrl":"https://doi.org/10.15583/jpchrom.2019.019","url":null,"abstract":"Enantiomeric separation ability on high-performance liquid chromatography (HPLC) of novel chiral stationary phase (CSP) was evaluated. A chiral selector of the CSP investigated in this study (SUMICHIRALTM OA-SHELL P1) is one of helical poly(diphenylacetylene) derivatives which is coated on core-shell silica support. OA-SHELL P1 showed excellent chiral separation ability for a wide range of aromatic chiral alcohols and it was also effective for separation of some chiral carboxylic acids, ketones and lactones. It is considered to be a new option for enantiomeric separation of these chiral compounds. OA-SHELL P1 is used in normal phase mode with a mobile phase of simple composition and one of its features is easy method development. The analysis time is relatively short even with conventional HPLC system since a core-shell support with particle size of 2.6 μm is used.","PeriodicalId":91226,"journal":{"name":"Chromatography (Basel)","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.15583/jpchrom.2019.019","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"42111111","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 : 2019-06-20DOI: 10.15583/jpchrom.2019.009
Masamitsu Maekawa, Taku Tsukamoto, Shinya Takasaki, M. Kikuchi, Yu Sato, Jiro Ogura, Yoshihiro Hayakawa, Hiroaki Yamaguchi, N. Mano
Therapeutic drug monitoring (TDM) is a clinical practice that designs personalized medication for patients with blood concentrations of the drug. TDM approach is used for many drugs, including immunosuppressant, antifungal, antiarrhythmic, and anti-cancer drugs. Combination therapies are often adopted in TDM. Liquid chromatography tandem mass spectrometry (LC-MS/MS) is a useful analytical method in such cases. However, the development of a simultaneous LC-MS/MS analytical method is difficult owing to the differences in MS sensitivity and the therapeutic range of each drug. In order to avoid saturation of the detector, in-source collision induced dissociation (CID) was used to reduce the ion inlet. In this study, we investigated the in-source CID behavior of 13 compounds of drugs and metabolites in TDM practice. As a result, all compounds provided a sharp reduction of ion inlet over the threshold ion guide voltage. In addition, a shift to the higher concentration of the calibration range was observed according to such changes. The intensity and linearity data in this study that all 13 drugs could be analyzed under in-source CID conditions simultaneously. These results might be useful for TDM of combination therapy in clinical practice.
{"title":"Fundamental Study of Behaviors of In-Source Collision Induced Dissociation and Shifting the Linear Range of Calibration Curves of Various Drugs and the Metabolites Used for Therapeutic Drug Monitoring","authors":"Masamitsu Maekawa, Taku Tsukamoto, Shinya Takasaki, M. Kikuchi, Yu Sato, Jiro Ogura, Yoshihiro Hayakawa, Hiroaki Yamaguchi, N. Mano","doi":"10.15583/jpchrom.2019.009","DOIUrl":"https://doi.org/10.15583/jpchrom.2019.009","url":null,"abstract":"Therapeutic drug monitoring (TDM) is a clinical practice that designs personalized medication for patients with blood concentrations of the drug. TDM approach is used for many drugs, including immunosuppressant, antifungal, antiarrhythmic, and anti-cancer drugs. Combination therapies are often adopted in TDM. Liquid chromatography tandem mass spectrometry (LC-MS/MS) is a useful analytical method in such cases. However, the development of a simultaneous LC-MS/MS analytical method is difficult owing to the differences in MS sensitivity and the therapeutic range of each drug. In order to avoid saturation of the detector, in-source collision induced dissociation (CID) was used to reduce the ion inlet. In this study, we investigated the in-source CID behavior of 13 compounds of drugs and metabolites in TDM practice. As a result, all compounds provided a sharp reduction of ion inlet over the threshold ion guide voltage. In addition, a shift to the higher concentration of the calibration range was observed according to such changes. The intensity and linearity data in this study that all 13 drugs could be analyzed under in-source CID conditions simultaneously. These results might be useful for TDM of combination therapy in clinical practice.","PeriodicalId":91226,"journal":{"name":"Chromatography (Basel)","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.15583/jpchrom.2019.009","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41262626","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 : 2019-06-20DOI: 10.15583/JPCHROM.2019.008
F. Kitagawa, Osamu Osanai, Isoshi Nukatsuka
To achieve highly sensitive analyses of cationic analytes with simple experimental procedures in non-aqueous capillary electrophoresis (NACE), large-volume sample stacking with an electroosmotic flow pump (LVSEP) was performed in dynamically polymer coated capillaries. As the dynamic coating polymers, cationic polybrene (PB), and neutral polymer, (hydroxypropyl)methyl cellulose (HPMC), were employed in methanolic media to reverse and suppress the electroosmotic flow. In the analysis of cationic amines, good enrichments were attained with the sensitive enhancement factor (SEF) of 70 and 687 for benzylamine and 1-(1-naphthyl)ethylamine, respectively, with a methanolic running solution containing 1.0% HPMC and 0.5% PB. In the NACE-LVSEP analysis of Ru(bpy)3 and Ru(phen)3, furthermore, the values of SEF were almost 40 with almost no-loss of the resolution.
{"title":"LVSEP Analysis of Cationic Analytes in Non-Aqueous Capillary Electrophoresis","authors":"F. Kitagawa, Osamu Osanai, Isoshi Nukatsuka","doi":"10.15583/JPCHROM.2019.008","DOIUrl":"https://doi.org/10.15583/JPCHROM.2019.008","url":null,"abstract":"To achieve highly sensitive analyses of cationic analytes with simple experimental procedures in non-aqueous capillary electrophoresis (NACE), large-volume sample stacking with an electroosmotic flow pump (LVSEP) was performed in dynamically polymer coated capillaries. As the dynamic coating polymers, cationic polybrene (PB), and neutral polymer, (hydroxypropyl)methyl cellulose (HPMC), were employed in methanolic media to reverse and suppress the electroosmotic flow. In the analysis of cationic amines, good enrichments were attained with the sensitive enhancement factor (SEF) of 70 and 687 for benzylamine and 1-(1-naphthyl)ethylamine, respectively, with a methanolic running solution containing 1.0% HPMC and 0.5% PB. In the NACE-LVSEP analysis of Ru(bpy)3 and Ru(phen)3, furthermore, the values of SEF were almost 40 with almost no-loss of the resolution.","PeriodicalId":91226,"journal":{"name":"Chromatography (Basel)","volume":"832 2","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.15583/JPCHROM.2019.008","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41279077","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 : 2019-06-20DOI: 10.15583/JPCHROM.2019.005
Chisato Takahashi, Tatsuya Yazaki, Naoyuki Sugiyama, Y. Ishihama
We developed a capillary LC/MS/MS-based approach to monitor intracellular kinase activities. Selected reaction monitoring (SRM) mode was employed to quantitate a kinase substrate-digested peptide phosphorylated by kinase or kinase-digested peptides containing phosphosites which regulate the kinase activities. Ten kinases in EGFR-MAPK signaling pathway were targeted for the SRM assay and the experimental conditions such as the selection of target phosphopeptides, SRM transitions, LC parameters and sample pre-treatment steps were optimized. The validation study on accuracy, precision, linearity, limit of detection and limit of quantitation was carried out to confirm the capability for measuring the kinase activities through the phosphopeptide quantities in the biological samples. Finally, we applied this SRM assay to kinase activation dynamics induced by pervanadate, a tyrosine phosphatase inhibitor, in HeLa cells. As a result, it was found that 6 kinases out of 10 were activated, which were consistent with those by conventional Western blotting using phosphosite-specific antibodies. Since this SRM assay can be extended to kinome-wide analysis, it will be useful to unveil the entire signaling network in cells.
{"title":"Selected Reaction Monitoring of Kinase Activity-Targeted Phosphopeptides","authors":"Chisato Takahashi, Tatsuya Yazaki, Naoyuki Sugiyama, Y. Ishihama","doi":"10.15583/JPCHROM.2019.005","DOIUrl":"https://doi.org/10.15583/JPCHROM.2019.005","url":null,"abstract":"We developed a capillary LC/MS/MS-based approach to monitor intracellular kinase activities. Selected reaction monitoring (SRM) mode was employed to quantitate a kinase substrate-digested peptide phosphorylated by kinase or kinase-digested peptides containing phosphosites which regulate the kinase activities. Ten kinases in EGFR-MAPK signaling pathway were targeted for the SRM assay and the experimental conditions such as the selection of target phosphopeptides, SRM transitions, LC parameters and sample pre-treatment steps were optimized. The validation study on accuracy, precision, linearity, limit of detection and limit of quantitation was carried out to confirm the capability for measuring the kinase activities through the phosphopeptide quantities in the biological samples. Finally, we applied this SRM assay to kinase activation dynamics induced by pervanadate, a tyrosine phosphatase inhibitor, in HeLa cells. As a result, it was found that 6 kinases out of 10 were activated, which were consistent with those by conventional Western blotting using phosphosite-specific antibodies. Since this SRM assay can be extended to kinome-wide analysis, it will be useful to unveil the entire signaling network in cells.","PeriodicalId":91226,"journal":{"name":"Chromatography (Basel)","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"44230758","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 : 2019-06-20DOI: 10.15583/JPCHROM.2018.022
T. Torii, K. Kanemitsu, A. Hagiwara
We simultaneously quantified fecal bile acids (BAs) and short-chain fatty acids (SCFAs) florescence labeled with 9chloromethylanthracene using high-performance liquid chromatography-fluorescence (HPLC-FL) and developed an inexpensive and highly accurate method for determining the ratio of BAs and SCFAs in colorectal cancer patients and healthy controls. Samples were extracted with hexane/ether, and extractants were measured using HPLC-FL. The healthy subject group included 17 men and 21 women, whereas the colorectal cancer group included patients with cancer in the rectum (3 men, 2 women), sigmoid colon (3 men, 2 women), and ascending colon (2 men, 3 women). The contribution rate of determination for calibration curves was >0.99, and the additional recovery rate was 67.2%–107% for the simultaneous quantification of fecal BAs and SCFAs using HPLC-FL. Intra-day and inter-day variations in the control feces ranged 2.4%–5.1% and 3.1%–9.2%, respectively. The proportion of primary BAs to total BAs was higher in the colorectal cancer group (87.3%) than in the healthy subject group (67.9%). A significant difference was observed in the ratio of BAs to butyric acid between healthy subject and colorectal cancer groups. BA levels were higher in the colorectal cancer group. Thus, the ratio of total BAs to butyric acid may be a better predictor of colon cancer than BAs or SCFAs alone.
{"title":"Simultaneous Assay of Fecal Short-Chain Fatty and Bile Acids and Ratio of Total Bile Acids to Butyrate in Colon Cancer","authors":"T. Torii, K. Kanemitsu, A. Hagiwara","doi":"10.15583/JPCHROM.2018.022","DOIUrl":"https://doi.org/10.15583/JPCHROM.2018.022","url":null,"abstract":"We simultaneously quantified fecal bile acids (BAs) and short-chain fatty acids (SCFAs) florescence labeled with 9chloromethylanthracene using high-performance liquid chromatography-fluorescence (HPLC-FL) and developed an inexpensive and highly accurate method for determining the ratio of BAs and SCFAs in colorectal cancer patients and healthy controls. Samples were extracted with hexane/ether, and extractants were measured using HPLC-FL. The healthy subject group included 17 men and 21 women, whereas the colorectal cancer group included patients with cancer in the rectum (3 men, 2 women), sigmoid colon (3 men, 2 women), and ascending colon (2 men, 3 women). The contribution rate of determination for calibration curves was >0.99, and the additional recovery rate was 67.2%–107% for the simultaneous quantification of fecal BAs and SCFAs using HPLC-FL. Intra-day and inter-day variations in the control feces ranged 2.4%–5.1% and 3.1%–9.2%, respectively. The proportion of primary BAs to total BAs was higher in the colorectal cancer group (87.3%) than in the healthy subject group (67.9%). A significant difference was observed in the ratio of BAs to butyric acid between healthy subject and colorectal cancer groups. BA levels were higher in the colorectal cancer group. Thus, the ratio of total BAs to butyric acid may be a better predictor of colon cancer than BAs or SCFAs alone.","PeriodicalId":91226,"journal":{"name":"Chromatography (Basel)","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.15583/JPCHROM.2018.022","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"42757769","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 : 2019-06-20DOI: 10.15583/JPCHROM.2019.007
Nana Tanaka, S. Kitagawa, H. Ohtani, Y. Iwama, K. Kondo, Yuzo Ishigaki, N. Shibata, T. Kinoshita, Y. Kamimoto, R. Ichino
Continuous counter-current foam separation (CCFS) is a method for the recovery of valuable metals with high selectivity. It was developed as an organic solvent-free method, and the interaction of surfactants and metal ions in aqueous solution is a key precondition for the successful recovery. In this study, the interactions between the anionic complex of palladium(II) chloride and N , N ’-dimethyl- N , N ’-di- n -hexyl-thiodiglycolamide (MHTDA), which is an extraction agent for palladium(II), were investigated by capillary electrophoresis, in the presence of surfactants (sodium dodecyl sulfate (SDS) or polyoxyethylene mono-4-octylphenyl ether (POOPE)). The addition of MHTDA to an electrophoretic media containing SDS, resulted in electropherograms composed of two or three peaks. On the other hand, in the case of an electrophoretic media containing POOPE, the elimination of palladium (II) peak was observed due to MHTDA addition. This behavior suggested that the palladium-MHTDA neutral complex is rapidly captured in the POOPE micelles compared with the SDS micelles, and the use of POOPE is effective for the successful recovery of palladium(II) in CCFS.
连续逆流泡沫分离(CCFS)是一种高选择性回收有价金属的方法。该方法是一种有机无溶剂方法，而表面活性剂与水溶液中金属离子的相互作用是成功回收的关键前提。在表面活性剂(十二烷基硫酸钠(SDS)或聚氧乙烯单-4-辛基苯基醚(POOPE))存在的情况下，采用毛细管电泳法研究了钯(II)氯离子配合物与钯(II)萃取剂N, N ' -二甲基- N, N ' -二- N -己基硫代二醇酰胺(MHTDA)的相互作用。将MHTDA加入到含有SDS的电泳介质中，得到由两个或三个峰组成的电泳图。另一方面，在含有POOPE的电泳介质中，由于添加了MHTDA，可以观察到钯(II)峰的消除。这一行为表明，与SDS胶束相比，POOPE胶束能快速捕获钯- mhtda中性络合物，并且使用POOPE对CCFS中钯(II)的成功回收是有效的。
{"title":"Evaluation of the Interactions Between Palladium(II) and N,N’-Dimethyl-N,N’-di-n-hexyl-thiodiglycolamide in the Presence of Surfactants Using Capillary Electrophoresis","authors":"Nana Tanaka, S. Kitagawa, H. Ohtani, Y. Iwama, K. Kondo, Yuzo Ishigaki, N. Shibata, T. Kinoshita, Y. Kamimoto, R. Ichino","doi":"10.15583/JPCHROM.2019.007","DOIUrl":"https://doi.org/10.15583/JPCHROM.2019.007","url":null,"abstract":"Continuous counter-current foam separation (CCFS) is a method for the recovery of valuable metals with high selectivity. It was developed as an organic solvent-free method, and the interaction of surfactants and metal ions in aqueous solution is a key precondition for the successful recovery. In this study, the interactions between the anionic complex of palladium(II) chloride and N , N ’-dimethyl- N , N ’-di- n -hexyl-thiodiglycolamide (MHTDA), which is an extraction agent for palladium(II), were investigated by capillary electrophoresis, in the presence of surfactants (sodium dodecyl sulfate (SDS) or polyoxyethylene mono-4-octylphenyl ether (POOPE)). The addition of MHTDA to an electrophoretic media containing SDS, resulted in electropherograms composed of two or three peaks. On the other hand, in the case of an electrophoretic media containing POOPE, the elimination of palladium (II) peak was observed due to MHTDA addition. This behavior suggested that the palladium-MHTDA neutral complex is rapidly captured in the POOPE micelles compared with the SDS micelles, and the use of POOPE is effective for the successful recovery of palladium(II) in CCFS.","PeriodicalId":91226,"journal":{"name":"Chromatography (Basel)","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"42802091","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 : 2019-06-20DOI: 10.15583/JPCHROM.2019.006
Sachio Yamamoto, Yuki Hayashi, H. Matsunaga, Fuka Okada, M. Kinoshita, Shigeo Suzuki
Quantitative analysis of monosaccharides or glycoprotein glycans by high-performance liquid chromatography (HPLC) often involves labeling of the saccharide aldehyde groups with fluorescent tags to enhance sensitivity and selectivity. However, the methods required to remove the large excess of labeling reagents from the reaction mixture are time-consuming. Furthermore, these methods often hinder the quantitative analysis of the labeled samples. Here, we developed an online sample cleanup procedure for HPLC analysis of 2-aminobenzoic acid (2-AA)-labeled monosaccharides or oligosaccharides using a ten-port valve and mini columns. An online purification system using a combination of short HLB columns with the valve was proposed for the analysis of 2-AA-labeled monosaccharides utilizing reversed-phase modes. In the analysis of 2-AA-labeled glycans derived from glycoproteins, a short CN column with the valve was proposed utilizing hydrophilic interaction liquid chromatography (HILIC) modes. Optimized conditions enabled the direct injection of the diluted labeling reaction mixture into the chromatographic system without any prior removal of the excess labeling reagents. These methods were successfully applied to the analysis of various monosaccharides and N -linked glycans released from specific glycoproteins.
{"title":"Analysis of 2-Aminobenzoic Acid-Labeled Monosaccharides and Glycoprotein-Derived Oligosaccharides by Online Cleanup Liquid Chromatography in the Reversed-Phase and Hydrophilic Interaction Liquid Chromatography Modes","authors":"Sachio Yamamoto, Yuki Hayashi, H. Matsunaga, Fuka Okada, M. Kinoshita, Shigeo Suzuki","doi":"10.15583/JPCHROM.2019.006","DOIUrl":"https://doi.org/10.15583/JPCHROM.2019.006","url":null,"abstract":"Quantitative analysis of monosaccharides or glycoprotein glycans by high-performance liquid chromatography (HPLC) often involves labeling of the saccharide aldehyde groups with fluorescent tags to enhance sensitivity and selectivity. However, the methods required to remove the large excess of labeling reagents from the reaction mixture are time-consuming. Furthermore, these methods often hinder the quantitative analysis of the labeled samples. Here, we developed an online sample cleanup procedure for HPLC analysis of 2-aminobenzoic acid (2-AA)-labeled monosaccharides or oligosaccharides using a ten-port valve and mini columns. An online purification system using a combination of short HLB columns with the valve was proposed for the analysis of 2-AA-labeled monosaccharides utilizing reversed-phase modes. In the analysis of 2-AA-labeled glycans derived from glycoproteins, a short CN column with the valve was proposed utilizing hydrophilic interaction liquid chromatography (HILIC) modes. Optimized conditions enabled the direct injection of the diluted labeling reaction mixture into the chromatographic system without any prior removal of the excess labeling reagents. These methods were successfully applied to the analysis of various monosaccharides and N -linked glycans released from specific glycoproteins.","PeriodicalId":91226,"journal":{"name":"Chromatography (Basel)","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.15583/JPCHROM.2019.006","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"44171981","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 : 2019-06-20DOI: 10.15583/JPCHROM.2019.011
Chiharu Ishii, T. Akita, M. Nagano, M. Mita, K. Hamase
Chiral amino acids in fermented products including Japanese traditional black vinegar, a processed cheese and nam pla were determined using an on-line two-dimensional (2D) HPLC-MS/MS system. As the target amino acids, Ala, Asp, Glu, Leu, Pro and Ser were selected. Prior to the HPLC separation, the fermented products were appropriately homogenized and deproteinized, then amino acids were derivatized with 4-fluoro-7-nitro-2,1,3-benzoxadiazole (NBD-F). Using the 2D-HPLC system, the target NBD-amino acids were individually purified by a microbore reversed-phase column in the first dimension and further separated by a narrowbore enantioselective column in the second dimension. The detection was performed by a fluorescence detector and also by a tandem mass spectrometer. Compared to the 2D-HPLC with fluorescence detection, the target chiral amino acids in complicated real world matrices were successfully determined using the 2D HPLC-MS/MS system without interference by the co-elution of unknown intrinsic compounds. In all the tested fermented products, various D-amino acids were observed, and the obtained values were 0.02-6.21 mmol/L (%D=0.7-29.2%) in the black vinegar, 0.02-0.73 μmol/g (0.2-24.8%) in the processed cheese and 0.07-2.30 mmol/L (0.5-23.5%) in the nam pla.
{"title":"Determination of Chiral Amino Acids in Various Fermented Products Using a Two-Dimensional HPLC-MS/MS System","authors":"Chiharu Ishii, T. Akita, M. Nagano, M. Mita, K. Hamase","doi":"10.15583/JPCHROM.2019.011","DOIUrl":"https://doi.org/10.15583/JPCHROM.2019.011","url":null,"abstract":"Chiral amino acids in fermented products including Japanese traditional black vinegar, a processed cheese and nam pla were determined using an on-line two-dimensional (2D) HPLC-MS/MS system. As the target amino acids, Ala, Asp, Glu, Leu, Pro and Ser were selected. Prior to the HPLC separation, the fermented products were appropriately homogenized and deproteinized, then amino acids were derivatized with 4-fluoro-7-nitro-2,1,3-benzoxadiazole (NBD-F). Using the 2D-HPLC system, the target NBD-amino acids were individually purified by a microbore reversed-phase column in the first dimension and further separated by a narrowbore enantioselective column in the second dimension. The detection was performed by a fluorescence detector and also by a tandem mass spectrometer. Compared to the 2D-HPLC with fluorescence detection, the target chiral amino acids in complicated real world matrices were successfully determined using the 2D HPLC-MS/MS system without interference by the co-elution of unknown intrinsic compounds. In all the tested fermented products, various D-amino acids were observed, and the obtained values were 0.02-6.21 mmol/L (%D=0.7-29.2%) in the black vinegar, 0.02-0.73 μmol/g (0.2-24.8%) in the processed cheese and 0.07-2.30 mmol/L (0.5-23.5%) in the nam pla.","PeriodicalId":91226,"journal":{"name":"Chromatography (Basel)","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.15583/JPCHROM.2019.011","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49344896","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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