{"title":"用氮端溅射碳膜电极准确评价人血清样品中电活性分析物的扩散系数。","authors":"Saki Ohta, Tomonori Ozawa, Shunsuke Shiba, Tatsuhiko Yajima, Tomoyuki Kamata, Dai Kato, Osamu Niwa","doi":"10.1007/s44211-025-00718-8","DOIUrl":null,"url":null,"abstract":"<div><p>We have developed an N-terminated carbon film electrode that allows accurate determination of the diffusion coefficient of electroactive molecules dissolved in a highly concentrated serum protein solution. The carbon film electrode was formed by the unbalanced magnetron sputtering (UBM) method. Then, nitrogen functional groups were introduced by employing NH<sub>3</sub> or H<sub>2</sub>O plasma treatment. Cyclic voltammetry measurements with ferricyanide ion ([Fe(CN)<sub>6</sub>]<sup>3−</sup>) showed that the N-terminated carbon film electrode exhibited great anti-fouling property against simulated serum proteins (50 mg/mL human serum albumin and 15 mg/mL γ-globulin dissolved in 1 M KCl solution). In contrast, glassy carbon, H<sub>2</sub>O plasma-treated, and especially untreated carbon film electrodes were subject to severe electrode fouling, making it difficult to electrochemically determine the diffusion coefficient of the [Fe(CN)<sub>6</sub>]<sup>3−</sup> ion. The control experiment using less adsorptive ethylene glycol as a viscosity modifier showed that the increase in viscosity is a main factor of the decrease in diffusion coefficient for nitrogen plasma treated electrode, which is not significantly affected by the possible interaction between [Fe(CN)<sub>6</sub>]<sup>3−</sup> ions and serum proteins. Finally, we applied the electrode for the electrochemical analysis of acetaminophen dissolved in phosphate buffer (0.1 M, pH = 7.0), which suggests that NH<sub>3</sub> plasma-treated carbon film exhibits the lowest Δ<i>E</i> increase when we compare Δ<i>E</i> with and without proteins and also a more stable peak current in continuous voltametric measurements compared with other carbon electrodes.</p><h3>Graphical abstract</h3>\n<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":7802,"journal":{"name":"Analytical Sciences","volume":"41 4","pages":"439 - 446"},"PeriodicalIF":1.8000,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Accurate evaluation of diffusion coefficient for electroactive analytes in human serum samples using nitrogen-terminated sputtered carbon film electrode\",\"authors\":\"Saki Ohta, Tomonori Ozawa, Shunsuke Shiba, Tatsuhiko Yajima, Tomoyuki Kamata, Dai Kato, Osamu Niwa\",\"doi\":\"10.1007/s44211-025-00718-8\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>We have developed an N-terminated carbon film electrode that allows accurate determination of the diffusion coefficient of electroactive molecules dissolved in a highly concentrated serum protein solution. The carbon film electrode was formed by the unbalanced magnetron sputtering (UBM) method. Then, nitrogen functional groups were introduced by employing NH<sub>3</sub> or H<sub>2</sub>O plasma treatment. Cyclic voltammetry measurements with ferricyanide ion ([Fe(CN)<sub>6</sub>]<sup>3−</sup>) showed that the N-terminated carbon film electrode exhibited great anti-fouling property against simulated serum proteins (50 mg/mL human serum albumin and 15 mg/mL γ-globulin dissolved in 1 M KCl solution). In contrast, glassy carbon, H<sub>2</sub>O plasma-treated, and especially untreated carbon film electrodes were subject to severe electrode fouling, making it difficult to electrochemically determine the diffusion coefficient of the [Fe(CN)<sub>6</sub>]<sup>3−</sup> ion. The control experiment using less adsorptive ethylene glycol as a viscosity modifier showed that the increase in viscosity is a main factor of the decrease in diffusion coefficient for nitrogen plasma treated electrode, which is not significantly affected by the possible interaction between [Fe(CN)<sub>6</sub>]<sup>3−</sup> ions and serum proteins. Finally, we applied the electrode for the electrochemical analysis of acetaminophen dissolved in phosphate buffer (0.1 M, pH = 7.0), which suggests that NH<sub>3</sub> plasma-treated carbon film exhibits the lowest Δ<i>E</i> increase when we compare Δ<i>E</i> with and without proteins and also a more stable peak current in continuous voltametric measurements compared with other carbon electrodes.</p><h3>Graphical abstract</h3>\\n<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>\",\"PeriodicalId\":7802,\"journal\":{\"name\":\"Analytical Sciences\",\"volume\":\"41 4\",\"pages\":\"439 - 446\"},\"PeriodicalIF\":1.8000,\"publicationDate\":\"2025-02-07\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Analytical Sciences\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s44211-025-00718-8\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, ANALYTICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Analytical Sciences","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1007/s44211-025-00718-8","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, ANALYTICAL","Score":null,"Total":0}
引用次数: 0
摘要
我们开发了一种n端碳膜电极,可以准确测定溶解在高浓度血清蛋白溶液中的电活性分子的扩散系数。采用不平衡磁控溅射(UBM)法制备了碳膜电极。然后通过NH3或H2O等离子体处理引入氮官能团。铁氰化离子([Fe(CN)6]3-)循环伏安测定表明,n端碳膜电极对模拟血清蛋白(溶解在1 M KCl溶液中的50 mg/mL人血清白蛋白和15 mg/mL γ-球蛋白)具有良好的抗污染性能。相比之下,玻璃碳、水等离子体处理,特别是未经处理的碳膜电极受到严重的电极污染,使得电化学测定[Fe(CN)6]3-离子的扩散系数变得困难。采用吸附性较差的乙二醇作为黏度调节剂进行对照实验,结果表明黏度的增加是氮等离子体处理电极扩散系数降低的主要原因,而[Fe(CN)6]3-离子与血清蛋白可能的相互作用对扩散系数的影响不显著。最后,我们应用该电极对溶解在磷酸盐缓冲液(0.1 M, pH = 7.0)中的对乙酰氨基酚进行了电化学分析,结果表明,当我们比较ΔE与不含蛋白质时,NH3等离子体处理的碳膜表现出最低的ΔE增加,并且在连续伏安测量中,与其他碳电极相比,NH3等离子体处理的碳膜具有更稳定的峰值电流。
Accurate evaluation of diffusion coefficient for electroactive analytes in human serum samples using nitrogen-terminated sputtered carbon film electrode
We have developed an N-terminated carbon film electrode that allows accurate determination of the diffusion coefficient of electroactive molecules dissolved in a highly concentrated serum protein solution. The carbon film electrode was formed by the unbalanced magnetron sputtering (UBM) method. Then, nitrogen functional groups were introduced by employing NH3 or H2O plasma treatment. Cyclic voltammetry measurements with ferricyanide ion ([Fe(CN)6]3−) showed that the N-terminated carbon film electrode exhibited great anti-fouling property against simulated serum proteins (50 mg/mL human serum albumin and 15 mg/mL γ-globulin dissolved in 1 M KCl solution). In contrast, glassy carbon, H2O plasma-treated, and especially untreated carbon film electrodes were subject to severe electrode fouling, making it difficult to electrochemically determine the diffusion coefficient of the [Fe(CN)6]3− ion. The control experiment using less adsorptive ethylene glycol as a viscosity modifier showed that the increase in viscosity is a main factor of the decrease in diffusion coefficient for nitrogen plasma treated electrode, which is not significantly affected by the possible interaction between [Fe(CN)6]3− ions and serum proteins. Finally, we applied the electrode for the electrochemical analysis of acetaminophen dissolved in phosphate buffer (0.1 M, pH = 7.0), which suggests that NH3 plasma-treated carbon film exhibits the lowest ΔE increase when we compare ΔE with and without proteins and also a more stable peak current in continuous voltametric measurements compared with other carbon electrodes.
期刊介绍:
Analytical Sciences is an international journal published monthly by The Japan Society for Analytical Chemistry. The journal publishes papers on all aspects of the theory and practice of analytical sciences, including fundamental and applied, inorganic and organic, wet chemical and instrumental methods.
This publication is supported in part by the Grant-in-Aid for Publication of Scientific Research Result of the Japanese Ministry of Education, Culture, Sports, Science and Technology.