Pub Date : 2025-05-09DOI: 10.1007/s44211-025-00789-7
Naoki Sasaki
Microfluidic devices integrated with track-etched porous membranes are useful for cell-based bioanalysis. In this mini review, our latest achievements based on membrane-integrated microfluidic devices are reviewed. The membrane-integrated microfluidic devices in parallel configuration have been employed to develop a microfluidic model of microcirculation and for the development of nanomedicines. Co-culture of endothelial cells with tumor cells and parallel permeation assays through keratinocyte cell layer have also been demonstrated. Membrane-integrated microfluidic devices in perpendicular configuration have been employed to simulate extravasation of tumor cells and to evaluate the efficacy of anti-inflammatory drug on the function of keratinocyte cell layer formed on the membrane. These microfluidic devices have unique features and a lot of advantages, so we hope that they are utilized as a powerful tool for cell-based bioanalysis.
{"title":"Microfluidic devices integrated with track-etched porous membranes for cell-based bioanalysis","authors":"Naoki Sasaki","doi":"10.1007/s44211-025-00789-7","DOIUrl":"10.1007/s44211-025-00789-7","url":null,"abstract":"<div><p>Microfluidic devices integrated with track-etched porous membranes are useful for cell-based bioanalysis. In this mini review, our latest achievements based on membrane-integrated microfluidic devices are reviewed. The membrane-integrated microfluidic devices in parallel configuration have been employed to develop a microfluidic model of microcirculation and for the development of nanomedicines. Co-culture of endothelial cells with tumor cells and parallel permeation assays through keratinocyte cell layer have also been demonstrated. Membrane-integrated microfluidic devices in perpendicular configuration have been employed to simulate extravasation of tumor cells and to evaluate the efficacy of anti-inflammatory drug on the function of keratinocyte cell layer formed on the membrane. These microfluidic devices have unique features and a lot of advantages, so we hope that they are utilized as a powerful tool for cell-based bioanalysis.</p><h3>Graphical abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":7802,"journal":{"name":"Analytical Sciences","volume":"41 8","pages":"1107 - 1113"},"PeriodicalIF":2.0,"publicationDate":"2025-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143952769","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}
Pub Date : 2025-05-08DOI: 10.1007/s44211-025-00787-9
Deepak Kumar, Daraksha Bano, Subhash Chandra, Bharat Kumar, Vivek Kumar, Pradeep Kumar Yadav, Syed Hadi Hasan
The Pd-MnO2 nanoparticles attached to carbon quantum dots nanocomposite were synthesized using the green synthesis and hydrothermal process. Characterization of the as-prepared nanocomposite was intensively performed by FT-IR, powder XRD, XPS, and HR-TEM analysis. The synthesized nanomaterial was further examined for its selective and sensitive ascorbic acid (ASA) sensing using a Pd-MnO2@CQD modified glassy carbon electrode (GCE). The Pd-MnO2@CQD nanocomposite exhibits a distinct and improved peak current of ASA when compared to electrodes treated with Pd-MnO2 and bare GCE. The designed sensor has excellent performance, with a linear range of 10–1500 μM, a low detection limit of 0.14 μM (S/N = 3), a high sensitivity of 1.9671 μAµM−1 cm−2. Furthermore, the constructed sensor demonstrates good sensitivity for detecting ASA in a variety of real samples.
{"title":"Highly sensitive electrochemical sensing of ascorbic acid (vitamin C) using Pd-doped MnO2 supported on carbon quantum dots (Pd-MnO2@CQD) in water and fruit juices","authors":"Deepak Kumar, Daraksha Bano, Subhash Chandra, Bharat Kumar, Vivek Kumar, Pradeep Kumar Yadav, Syed Hadi Hasan","doi":"10.1007/s44211-025-00787-9","DOIUrl":"10.1007/s44211-025-00787-9","url":null,"abstract":"<div><p>The Pd-MnO<sub>2</sub> nanoparticles attached to carbon quantum dots nanocomposite were synthesized using the green synthesis and hydrothermal process. Characterization of the as-prepared nanocomposite was intensively performed by FT-IR, powder XRD, XPS, and HR-TEM analysis. The synthesized nanomaterial was further examined for its selective and sensitive ascorbic acid (ASA) sensing using a Pd-MnO<sub>2</sub>@CQD modified glassy carbon electrode (GCE). The Pd-MnO<sub>2</sub>@CQD nanocomposite exhibits a distinct and improved peak current of ASA when compared to electrodes treated with Pd-MnO<sub>2</sub> and bare GCE. The designed sensor has excellent performance, with a linear range of 10–1500 μM, a low detection limit of 0.14 μM (S/N = 3), a high sensitivity of 1.9671 μAµM<sup>−1</sup> cm<sup>−2</sup>. Furthermore, the constructed sensor demonstrates good sensitivity for detecting ASA in a variety of real samples.</p><h3>Graphical Abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":7802,"journal":{"name":"Analytical Sciences","volume":"41 7","pages":"1029 - 1040"},"PeriodicalIF":2.0,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143973224","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}
Pub Date : 2025-05-08DOI: 10.1007/s44211-025-00780-2
Peter Polyak, Paweł Chaber, Marta Musioł, Grażyna Adamus, Marek Kowalczuk, Judit E. Puskas, Miroslawa El Fray
In this paper, we present a method for calculating the average molecular weight of microbial polyesters using Fourier transform infrared spectroscopy (FTIR) data as input. FTIR spectra provide the necessary quantitative information, as the impact of chain ends on the spectra is influenced by the average molecular weight of the polymer. Since FTIR data can be collected rapidly and is available in abundance, it serves as an ideal input for machine learning algorithms, such as artificial neural networks. The robustness and reliability of the model are improved by designing the neural network to use absorbance ratios instead of absolute absorbances as input. We also propose a new feature selection method that facilitates the identification of absorbance ratio regions best suited to serve as input for the neural network. Our approach ensures that variations in sample preparation do not compromise the accuracy of the model. The proposed computational method is demonstrated using a microbial polyester [poly(3-hydroxybutyrate), PHB], which is a biopolymer natively synthesized by multiple bacterial strains. Although the computational method has been tested with PHB, the underlying concept can be extended to other polymers. To facilitate broader application, a step-by-step guide for developing similar models is also provided.
{"title":"Estimation of the average molecular weight of microbial polyesters from FTIR spectra using artificial intelligence","authors":"Peter Polyak, Paweł Chaber, Marta Musioł, Grażyna Adamus, Marek Kowalczuk, Judit E. Puskas, Miroslawa El Fray","doi":"10.1007/s44211-025-00780-2","DOIUrl":"10.1007/s44211-025-00780-2","url":null,"abstract":"<div><p>In this paper, we present a method for calculating the average molecular weight of microbial polyesters using Fourier transform infrared spectroscopy (FTIR) data as input. FTIR spectra provide the necessary quantitative information, as the impact of chain ends on the spectra is influenced by the average molecular weight of the polymer. Since FTIR data can be collected rapidly and is available in abundance, it serves as an ideal input for machine learning algorithms, such as artificial neural networks. The robustness and reliability of the model are improved by designing the neural network to use absorbance ratios instead of absolute absorbances as input. We also propose a new feature selection method that facilitates the identification of absorbance ratio regions best suited to serve as input for the neural network. Our approach ensures that variations in sample preparation do not compromise the accuracy of the model. The proposed computational method is demonstrated using a microbial polyester [poly(3-hydroxybutyrate), PHB], which is a biopolymer natively synthesized by multiple bacterial strains. Although the computational method has been tested with PHB, the underlying concept can be extended to other polymers. To facilitate broader application, a step-by-step guide for developing similar models is also provided.</p><h3>Graphical abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":7802,"journal":{"name":"Analytical Sciences","volume":"41 7","pages":"1015 - 1027"},"PeriodicalIF":2.0,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12202672/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143952227","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-05-07DOI: 10.1007/s44211-025-00784-y
Sho Kimura, Akira Yamaguchi
This study investigated the anion recognition properties of acridine–urea conjugate (AcU) in bulk DMSO and silica nanopore. The free AcU in bulk DMSO was in tautomeric equilibrium between fluorescent amino form (a-AcU) and non-fluorescent imino form (i-AcU). Owing to this tautomerization of AcU, the free AcU worked as fluorescence enhancement sensing by hydrogen bonds mediated complexation between urea unit and anion. The estimated dissociation constants were 1.4 ± 0.2 mM for CH3COO– and 3.1 ± 1.0 mM for H2PO4–, whereas those for Cl–, ClO4–, and HSO4–were quite large. The hydrogen bond between urea unit and anion was also available for the anion recognition by AcU immobilized at the pore surface of mesoporous silica when the anion concentration is above 0.2 mM. In addition, we found that fluorescence of protonated a-AcU (a-AcHU+) could also be utilized for the recognition of weak acid anions over strong acid anions when the anion concentration is below 0.1 mM. The AcU@MPS with two recognition system has potential application for the anion recognition.
{"title":"Anion recognition properties of acridine–urea conjugate in bulk and silica nanopore systems","authors":"Sho Kimura, Akira Yamaguchi","doi":"10.1007/s44211-025-00784-y","DOIUrl":"10.1007/s44211-025-00784-y","url":null,"abstract":"<div><p>This study investigated the anion recognition properties of acridine–urea conjugate (AcU) in bulk DMSO and silica nanopore. The free AcU in bulk DMSO was in tautomeric equilibrium between fluorescent amino form (a-AcU) and non-fluorescent imino form (i-AcU). Owing to this tautomerization of AcU, the free AcU worked as fluorescence enhancement sensing by hydrogen bonds mediated complexation between urea unit and anion. The estimated dissociation constants were 1.4 ± 0.2 mM for CH<sub>3</sub>COO<sup>–</sup> and 3.1 ± 1.0 mM for H<sub>2</sub>PO<sub>4</sub><sup>–</sup>, whereas those for Cl<sup>–</sup>, ClO<sub>4</sub><sup>–</sup>, and HSO<sub>4</sub><sup>–</sup>were quite large. The hydrogen bond between urea unit and anion was also available for the anion recognition by AcU immobilized at the pore surface of mesoporous silica when the anion concentration is above 0.2 mM. In addition, we found that fluorescence of protonated a-AcU (a-AcHU<sup>+</sup>) could also be utilized for the recognition of weak acid anions over strong acid anions when the anion concentration is below 0.1 mM. The AcU@MPS with two recognition system has potential application for the anion recognition.</p><h3>Graphical abstract</h3>\u0000<div><figure><div><div><picture><img></picture></div></div></figure></div></div>","PeriodicalId":7802,"journal":{"name":"Analytical Sciences","volume":"41 7","pages":"1041 - 1049"},"PeriodicalIF":2.0,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143973105","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}
We have developed a protocol for a high-throughput high-performance liquid chromatography–surface enhanced Raman spectroscopy (HPLC–SERS), whereby a 15 μL eluent droplet was captured every second and a series of SERS spectra was obtained to show a time course in the chemical composition within the eluent. To accomplish this, we prepared arrays of SERS spots based on metal film on nanosphere (MFON). Fifty of these spots 3 mm in diameter were formed in a 5 by 10 array format on a special glass slide covered by a hydrophobic coating. In a second version, the SERS spot size was reduced to 1 mm, surrounded by a superhydrophobic area with a contact angle greater than 120 degrees. Here, 2 μL of the eluent droplet was placed on each spot. Heating of the array substrate allowed complete evaporation of the droplet under 3 min, without the adverse coffee ring effect. We demonstrated the utility of such a setup by injecting 1 mM adenine into a portable HPLC instrument and capturing the time course of SERS spectra. We characterize our MFON SERS spots in terms of its dependence on the concentration and incubation time as well as a two-dimensional SERS imaging showing the uniformity in the signal intensity.
{"title":"High-throughput HPLC–SERS capable of generating a spectrum from individual eluent droplets based on a superhydrophobic SERS array","authors":"Umi Yamaguchi, Hiroaki Honda, Shusuke Kumagai, Hiroyuki Takei","doi":"10.1007/s44211-025-00761-5","DOIUrl":"10.1007/s44211-025-00761-5","url":null,"abstract":"<div><p>We have developed a protocol for a high-throughput high-performance liquid chromatography–surface enhanced Raman spectroscopy (HPLC–SERS), whereby a 15 μL eluent droplet was captured every second and a series of SERS spectra was obtained to show a time course in the chemical composition within the eluent. To accomplish this, we prepared arrays of SERS spots based on metal film on nanosphere (MFON). Fifty of these spots 3 mm in diameter were formed in a 5 by 10 array format on a special glass slide covered by a hydrophobic coating. In a second version, the SERS spot size was reduced to 1 mm, surrounded by a superhydrophobic area with a contact angle greater than 120 degrees. Here, 2 μL of the eluent droplet was placed on each spot. Heating of the array substrate allowed complete evaporation of the droplet under 3 min, without the adverse coffee ring effect. We demonstrated the utility of such a setup by injecting 1 mM adenine into a portable HPLC instrument and capturing the time course of SERS spectra. We characterize our MFON SERS spots in terms of its dependence on the concentration and incubation time as well as a two-dimensional SERS imaging showing the uniformity in the signal intensity.</p><h3>Graphical abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":7802,"journal":{"name":"Analytical Sciences","volume":"41 7","pages":"1083 - 1088"},"PeriodicalIF":2.0,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143952746","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}
A systematic analytical method for discriminating methamphetamine (MA) from its structural analogs was developed by combining a solid-phase chromogenic method with the use of a molecularly imprinted polymer (MIP) and Simon reaction. L-proline (Pro), L-hydroxyproline (HYP), N-methylbenzylamine (NMe-BA), and N-isopropylbenzylamine (NIP-BA) were selected as false positives, while tert-butoxycarbonyl derivatized MA (t-Boc-MA) was selected as a false-negative substance. MA and the structural analogs were loaded into SupelMIP™ SPE-Amphetamines cartridges and Simon's reagent was added to the cartridge, then the coloration of the solid-phase gel was observed from outside the cartridge. After elution with a basic solution, Simon's reagent was added to the eluate (first-step eluate), and a change in color tone was observed. The MIP was then heated under acidic conditions, and the analytes were eluted (second-step eluate) with water, basified at pH 10, and the Simon reaction was repeated. Pro and HYP could be discriminated from MA by the color tone of the MIP solid-phase gel, whereas NMe-BA and NIP-BA could be discriminated from MA by the color tone of the first-step eluate. In addition, the color tone of the second-step eluate confirmed the presence of t-Boc-MA.
{"title":"Solid-phase chromogenic method combining molecularly imprinted polymer and Simon reaction for discriminating between methamphetamine and structural analogs","authors":"Koichi Saito, Musashi Abe, Rie Ito, Hiroshi Akiyama","doi":"10.1007/s44211-025-00782-0","DOIUrl":"10.1007/s44211-025-00782-0","url":null,"abstract":"<div><p>A systematic analytical method for discriminating methamphetamine (MA) from its structural analogs was developed by combining a solid-phase chromogenic method with the use of a molecularly imprinted polymer (MIP) and Simon reaction. L-proline (Pro), L-hydroxyproline (HYP), <i>N</i>-methylbenzylamine (NMe-BA), and <i>N</i>-isopropylbenzylamine (NIP-BA) were selected as false positives, while <i>tert</i>-butoxycarbonyl derivatized MA (<i>t</i>-Boc-MA) was selected as a false-negative substance. MA and the structural analogs were loaded into SupelMIP™ SPE-Amphetamines cartridges and Simon's reagent was added to the cartridge, then the coloration of the solid-phase gel was observed from outside the cartridge. After elution with a basic solution, Simon's reagent was added to the eluate (first-step eluate), and a change in color tone was observed. The MIP was then heated under acidic conditions, and the analytes were eluted (second-step eluate) with water, basified at pH 10, and the Simon reaction was repeated. Pro and HYP could be discriminated from MA by the color tone of the MIP solid-phase gel, whereas NMe-BA and NIP-BA could be discriminated from MA by the color tone of the first-step eluate. In addition, the color tone of the second-step eluate confirmed the presence of <i>t</i>-Boc-MA.</p><h3>Graphical abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":7802,"journal":{"name":"Analytical Sciences","volume":"41 7","pages":"1089 - 1095"},"PeriodicalIF":2.0,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143959590","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}
This study presents the development of a cobalt oxide-modified screen-printed carbon electrode (CoO/SPCE) for the electrochemical detection of reserpine (RES), a drug used to treat high blood pressure. The CoO/SPCE was fabricated using an optimized electrodeposition method, resulting in a sensitive and reproducible platform for RES detection. Electrochemical characterization demonstrated that the CoO/SPCE exhibited superior electrocatalytic activity, as evidenced by a notable increase in oxidation peak current compared to bare and activated SPCEs. The electrode showed a linear response to RES concentrations ranging from 2 to 100 μM with a detection limit of 1.08 μM. Additionally, the sensor demonstrated good stability and reproducibility with relative standard deviations (RSDs) of 5.11% and 2.72%, respectively. This work highlights the CoO/SPCE’s potential for practical pharmaceutical analysis, offering a novel approach to enhancing the sensitivity and reliability of electrochemical sensors for drug monitoring.
{"title":"Cobalt oxide modified screen-printed carbon electrode for electrochemical detection of high blood pressure treating drug: reserpine","authors":"Chenxi Wu, Shengzhou Qiu, Sima Akter, Shaoli Hong, Huihong Liu, Sakil Mahmud","doi":"10.1007/s44211-025-00781-1","DOIUrl":"10.1007/s44211-025-00781-1","url":null,"abstract":"<div><p>This study presents the development of a cobalt oxide-modified screen-printed carbon electrode (CoO/SPCE) for the electrochemical detection of reserpine (RES), a drug used to treat high blood pressure. The CoO/SPCE was fabricated using an optimized electrodeposition method, resulting in a sensitive and reproducible platform for RES detection. Electrochemical characterization demonstrated that the CoO/SPCE exhibited superior electrocatalytic activity, as evidenced by a notable increase in oxidation peak current compared to bare and activated SPCEs. The electrode showed a linear response to RES concentrations ranging from 2 to 100 μM with a detection limit of 1.08 μM. Additionally, the sensor demonstrated good stability and reproducibility with relative standard deviations (RSDs) of 5.11% and 2.72%, respectively. This work highlights the CoO/SPCE’s potential for practical pharmaceutical analysis, offering a novel approach to enhancing the sensitivity and reliability of electrochemical sensors for drug monitoring.</p><h3>Graphical abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":7802,"journal":{"name":"Analytical Sciences","volume":"41 7","pages":"953 - 964"},"PeriodicalIF":2.0,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143965759","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}
Pub Date : 2025-05-02DOI: 10.1007/s44211-025-00775-z
Yuiko Tasaki-Handa
The separation of lanthanides is critical for ensuring supply security of lanthanide elements, and modulating separation selectivity is a significant approach to control this process. The author's research has explored modulating lanthanide ion (Ln3+) exchange selectivity through crystallographic transitions in phosphate ligand-based crystalline coordination polymers (CCPs). This review reports Ln3+ ion exchange in two systems: LnL1, a CCP formed by bis(2-ethylhexyl) phosphate (L1) with Ce3+, Nd3+, and Sm3+, and LnL2, a CCP formed by bis(4-nitrophenyl) phosphoric acid (L2) with Ce3+. In these systems, Ln3+ selectivity deviated from the conventional pattern corresponding to the atomic number in the lanthanide series. This phenomenon can be attributed to spatial constraints of ion exchange sites within the CCP framework: the ion exchange reaction is influenced by both electrostatic interactions and steric effect. When Ln3+ is incorporated into the CCP surface, structural distortion due to the coexistence of two Ln3+ types induces a change in crystal morphology. This change acts as a gate-opening mechanism, facilitating subsequent ion exchange reactions toward the inside of CCP. The combination of two Ln3+ species likely determines the occurrence of a structural transition, finally influencing Ln3+ ion exchange selectivity. While it is challenging to directly apply the systems in this study to a practical separation system, this CCP-specific mechanism involving distortion and transition of the crystal's higher-order structure is expected to contribute to developing a new Ln separation method in the future.
{"title":"Unusual lanthanide ion exchange selectivity modulated via crystalline morphology change of a mixed-metal coordination polymer","authors":"Yuiko Tasaki-Handa","doi":"10.1007/s44211-025-00775-z","DOIUrl":"10.1007/s44211-025-00775-z","url":null,"abstract":"<div><p>The separation of lanthanides is critical for ensuring supply security of lanthanide elements, and modulating separation selectivity is a significant approach to control this process. The author's research has explored modulating lanthanide ion (Ln<sup>3+</sup>) exchange selectivity through crystallographic transitions in phosphate ligand-based crystalline coordination polymers (CCPs). This review reports Ln<sup>3+</sup> ion exchange in two systems: LnL1, a CCP formed by bis(2-ethylhexyl) phosphate (L1) with Ce<sup>3+</sup>, Nd<sup>3+</sup>, and Sm<sup>3+</sup>, and LnL2, a CCP formed by bis(4-nitrophenyl) phosphoric acid (L2) with Ce<sup>3+</sup>. In these systems, Ln<sup>3+</sup> selectivity deviated from the conventional pattern corresponding to the atomic number in the lanthanide series. This phenomenon can be attributed to spatial constraints of ion exchange sites within the CCP framework: the ion exchange reaction is influenced by both electrostatic interactions and steric effect. When Ln<sup>3+</sup> is incorporated into the CCP surface, structural distortion due to the coexistence of two Ln<sup>3+</sup> types induces a change in crystal morphology. This change acts as a gate-opening mechanism, facilitating subsequent ion exchange reactions toward the inside of CCP. The combination of two Ln<sup>3+</sup> species likely determines the occurrence of a structural transition, finally influencing Ln<sup>3+</sup> ion exchange selectivity. While it is challenging to directly apply the systems in this study to a practical separation system, this CCP-specific mechanism involving distortion and transition of the crystal's higher-order structure is expected to contribute to developing a new Ln separation method in the future.</p><h3>Graphical Abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":7802,"journal":{"name":"Analytical Sciences","volume":"41 8","pages":"1129 - 1138"},"PeriodicalIF":2.0,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143956980","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}
Pub Date : 2025-05-02DOI: 10.1007/s44211-025-00776-y
Sota Goto, Taiyo Iwasaki, Kikuo Komori
Cup-stacked carbon nanofibers (CSCNFs), the surface of which provides highly ordered graphene edges and electroactive oxygen-containing functional groups, were investigated as electrode materials for oxidation of β–Nicotinamide adenine dinucleotide (NADH) at low overpotential. The NADH oxidation was facilitated at the CSCNF-modified glassy carbon (CSCNF/GC) electrode, the surface of which was electrochemically activated at –0.40 V (vs. Ag|AgCl) to generate electrochemically reduced electroactive oxygen-containing functional groups. The anodic peak current of NADH oxidation was observed at about + 0.065 V by cyclic voltammetry measurements. The obtained value was negatively shifted by ~ 0.33 and ~ 0.63 V compared with the CSCNF/GC electrode without the electrochemical reductive pretreatment and the GC electrode, respectively. In addition, NADH-dependent glucose dehydrogenase (GDH) molecule-modified CSCNF/GC electrodes enabled the detection of glucose at the low overpotential effectively in the presence of NAD+, which accepts electrons from GDH and then reduces to NADH, after the electrochemical reductive pretreatment. Thus, the electrochemical reductive pretreatment of CSCNF electrodes would be useful for the development of highly sensitive NADH-dependent enzymatic biosensors.
Graphical abstract
研究了杯状叠碳纳米纤维（CSCNFs）作为低过电位氧化β-烟酰胺腺嘌呤二核苷酸（NADH）的电极材料，其表面具有高度有序的石墨烯边缘和电活性含氧官能团。NADH在CSCNF修饰的玻璃碳（CSCNF/GC）电极上氧化，CSCNF/GC电极表面在-0.40 V （vs. Ag|AgCl）下进行电化学活化，生成电化学还原的电活性含氧官能团。循环伏安法测得NADH氧化的阳极峰值电流约为+ 0.065 V。与未经电化学还原预处理的CSCNF/GC电极和GC电极相比，所得值分别负移了~ 0.33和~ 0.63 V。此外，NADH依赖性葡萄糖脱氢酶（GDH）分子修饰的CSCNF/GC电极可以在NAD+存在的情况下有效检测低过电位下的葡萄糖，NAD+接受来自GDH的电子，经过电化学还原预处理后还原为NADH。因此，CSCNF电极的电化学还原预处理将有助于开发高灵敏度的nadh依赖性酶生物传感器。
{"title":"Low-overpotential and highly sensitive detection of NADH with electrochemically pretreated cup-stacked carbon nanofiber electrodes","authors":"Sota Goto, Taiyo Iwasaki, Kikuo Komori","doi":"10.1007/s44211-025-00776-y","DOIUrl":"10.1007/s44211-025-00776-y","url":null,"abstract":"<div><p>Cup-stacked carbon nanofibers (CSCNFs), the surface of which provides highly ordered graphene edges and electroactive oxygen-containing functional groups, were investigated as electrode materials for oxidation of β–Nicotinamide adenine dinucleotide (NADH) at low overpotential. The NADH oxidation was facilitated at the CSCNF-modified glassy carbon (CSCNF/GC) electrode, the surface of which was electrochemically activated at –0.40 V (vs. Ag|AgCl) to generate electrochemically reduced electroactive oxygen-containing functional groups. The anodic peak current of NADH oxidation was observed at about + 0.065 V by cyclic voltammetry measurements. The obtained value was negatively shifted by ~ 0.33 and ~ 0.63 V compared with the CSCNF/GC electrode without the electrochemical reductive pretreatment and the GC electrode, respectively. In addition, NADH-dependent glucose dehydrogenase (GDH) molecule-modified CSCNF/GC electrodes enabled the detection of glucose at the low overpotential effectively in the presence of NAD<sup>+</sup>, which accepts electrons from GDH and then reduces to NADH, after the electrochemical reductive pretreatment. Thus, the electrochemical reductive pretreatment of CSCNF electrodes would be useful for the development of highly sensitive NADH-dependent enzymatic biosensors.</p><h3>Graphical abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":7802,"journal":{"name":"Analytical Sciences","volume":"41 7","pages":"989 - 996"},"PeriodicalIF":2.0,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12202553/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143965760","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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