Moving beyond empirical approaches, this work seeks to formulate a rational design principle for ion-imprinted polymers by deciphering the influence of monomer substituent volume. A systematic series—varying from H to CH3 to C2H5—was employed to probe how substituent volume modulates the binding energy toward Ru(III) and ultimately governs the adsorption-desorption efficacy of the synthesized thermo-responsive imprinted polymers. The DFT-calculated binding energies ranked as follows: DMAM (-451.7 kcal/mol) > DEAM (-378.5 kcal/mol) > AM (-341.5 kcal/mol), delineating a distinct trend in monomer-template affinity. Employing a common PDEAM-b-P(DEAM-co-AM) block copolymer as a smart scaffold, we synthesized three Ru(III)-imprinted polymers (TIIPs) differentiated solely by the functional monomer (AM, DMAM, or DEAM). By correlating a suite of characterization data (chemical, porous, morphological, surface) with adsorption performance, definitive structure-function principles were elucidated. Specifically, the structural simplicity and moderate binding affinity of the AM monomer promoted the assembly of a well-defined pre-polymerization complex. This, in turn, yielded a TIIP material with an optimal performance balance: Accessible pore channels, optimal surface charge, and robust stability. Although AM-TIIP did not exhibit the highest absolute adsorption capacity, its integrated performance profile was exceptional, featuring efficient mass transfer, excellent selectivity (evidenced by separation factors), and superior reusability (67.98% capacity retention after multiple cycles). In contrast, DMAM's exceptionally high binding energy, coupled with methyl-induced steric hindrance, and DEAM's strong hydrophobicity from ethyl groups, led to less favorable polymer morphologies—such as constricted pores or overly hydrophobic environments—which ultimately compromised practical performance parameters like desorption efficiency and adsorption kinetics. A critical finding was that an exceedingly high binding energy, while theoretically favorable for affinity, can create kinetic barriers for desorption and hinder mass transfer. Therefore, this work established that a monomer with structural simplicity and a balanced binding energy—exemplified by AM—is pivotal for designing high-performance, intelligent adsorbents that harmonize high selectivity with efficient regenerability.
{"title":"Effect of Substituent Volume on the Adsorption and Separation Performance of Thermo-Responsive Ion-Imprinted Polymers","authors":"Jiazhen Liu, Wenjie Wei, Jinjie Feng, Zhibin Lu, Fu Wang, Yuzhe Liu, Yuan Sun, Zhenbin Chen","doi":"10.1016/j.aca.2026.345388","DOIUrl":"https://doi.org/10.1016/j.aca.2026.345388","url":null,"abstract":"Moving beyond empirical approaches, this work seeks to formulate a rational design principle for ion-imprinted polymers by deciphering the influence of monomer substituent volume. A systematic series—varying from H to CH<sub>3</sub> to C<sub>2</sub>H<sub>5</sub>—was employed to probe how substituent volume modulates the binding energy toward Ru(III) and ultimately governs the adsorption-desorption efficacy of the synthesized thermo-responsive imprinted polymers. The DFT-calculated binding energies ranked as follows: DMAM (-451.7 kcal/mol) > DEAM (-378.5 kcal/mol) > AM (-341.5 kcal/mol), delineating a distinct trend in monomer-template affinity. Employing a common PDEAM-b-P(DEAM-co-AM) block copolymer as a smart scaffold, we synthesized three Ru(III)-imprinted polymers (TIIPs) differentiated solely by the functional monomer (AM, DMAM, or DEAM). By correlating a suite of characterization data (chemical, porous, morphological, surface) with adsorption performance, definitive structure-function principles were elucidated. Specifically, the structural simplicity and moderate binding affinity of the AM monomer promoted the assembly of a well-defined pre-polymerization complex. This, in turn, yielded a TIIP material with an optimal performance balance: Accessible pore channels, optimal surface charge, and robust stability. Although AM-TIIP did not exhibit the highest absolute adsorption capacity, its integrated performance profile was exceptional, featuring efficient mass transfer, excellent selectivity (evidenced by separation factors), and superior reusability (67.98% capacity retention after multiple cycles). In contrast, DMAM's exceptionally high binding energy, coupled with methyl-induced steric hindrance, and DEAM's strong hydrophobicity from ethyl groups, led to less favorable polymer morphologies—such as constricted pores or overly hydrophobic environments—which ultimately compromised practical performance parameters like desorption efficiency and adsorption kinetics. A critical finding was that an exceedingly high binding energy, while theoretically favorable for affinity, can create kinetic barriers for desorption and hinder mass transfer. Therefore, this work established that a monomer with structural simplicity and a balanced binding energy—exemplified by AM—is pivotal for designing high-performance, intelligent adsorbents that harmonize high selectivity with efficient regenerability.","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"7 1","pages":""},"PeriodicalIF":6.2,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471720","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-17DOI: 10.1016/j.aca.2026.345412
Shahin Khatiri Nejad Fard, Abbas Besharati-Seidani
Background
Lead pollution is a critical environmental problem and has significant adverse health effects. Lead continues to enter the environment from industrial processes, despite regulation. Traditional techniques for detecting and removing Pb2+, especially at trace levels, are generally ineffective and non-selective. Ion-imprinted polymers (IIPs) for Pb2+ detection and removal are promising new materials, as they are selective, adsorptive, and reusable. In this work, a novel Pb2+-imprinted polymer nanoparticle, was synthesized using quinizarin-based ion-imprinting chemistry and was introduced for effective Pb2+ detection and removal.
Results
The IIP nanoparticles were prepared by complexing quinizarin with Pb2+ in dimethylformamide, followed by polymerization with ethylene glycol dimethacrylate. Characterization using ICP-AES, infrared spectroscopy, SEM, and elemental analysis indicated successful polymerization and the formation of Pb2+-selective cavities. The uptake of Pb2+ was maximized at pH 5.0, showing a rapid adsorption rate (within 5–30 min) and a maximum capacity of 146.9 μmol g-1, corresponding to a preconcentration factor of 17.8. Competitive sorption experiments demonstrated high selectivity for Pb2+. Desorption using 0.1 M hydrochloric acid yielded 98.5% recovery of the ion. The polymer exhibited high reusability over six cycles with a relative standard deviation of 1.9% and a detection limit (3.3σ) of 2.6 ng mL-1.
Significance
The synthesized Pb2+-imprinted polymer offers a highly efficient, selective, and reusable approach for Pb2+ removal and detection in complex water systems. .Its rapid sorption/desorption kinetics, high reusability, and strong selectivity present a highly applicable technique for environmental monitoring and water purification, providing a sustainable method for treating lead contamination down to trace levels.
背景：铅污染是一个严重的环境问题，对健康有重大的不利影响。尽管有监管规定，铅仍继续从工业过程中进入环境。传统的检测和去除Pb2+的技术，特别是在痕量水平，通常是无效的和非选择性的。离子印迹聚合物（IIPs）具有选择性、吸附性和可重复使用性，是一种很有前途的用于Pb2+检测和去除的新材料。本研究利用奎尼扎林离子印迹化学方法合成了一种新型的Pb2+印迹聚合物纳米颗粒，并引入了有效的Pb2+检测和去除方法。结果将喹啉与Pb2+在二甲基甲酰胺中络合，再与二甲基丙烯酸乙二醇酯聚合，制备了IIP纳米颗粒。通过ICP-AES，红外光谱，SEM和元素分析表征表明聚合成功并形成了Pb2+选择性空腔。pH为5.0时对Pb2+的吸附量最大，吸附速率在5 ~ 30 min内，最大吸附量为146.9 μmol g-1，预富集系数为17.8。竞争性吸附实验表明，Pb2+具有较高的选择性。用0.1 M盐酸解吸，离子回收率为98.5%。该聚合物在6个循环内具有较高的可重复使用性，相对标准偏差为1.9%，检出限（3.3σ）为2.6 ng mL-1。意义所合成的Pb2+印迹聚合物为复杂水系统中Pb2+的去除和检测提供了一种高效、选择性和可重复使用的方法。其快速的吸附/解吸动力学、高可重复使用性和强选择性为环境监测和水净化提供了一种高度适用的技术，为处理痕量铅污染提供了一种可持续的方法。
{"title":"Rapid and highly selective surfactant-free lead(II) ion-imprinted nanoparticles for preconcentration with negligible memory effect","authors":"Shahin Khatiri Nejad Fard, Abbas Besharati-Seidani","doi":"10.1016/j.aca.2026.345412","DOIUrl":"https://doi.org/10.1016/j.aca.2026.345412","url":null,"abstract":"<h3>Background</h3>Lead pollution is a critical environmental problem and has significant adverse health effects. Lead continues to enter the environment from industrial processes, despite regulation. Traditional techniques for detecting and removing Pb<sup>2+</sup><strong>,</strong> especially at trace levels, are generally ineffective and non-selective. Ion-imprinted polymers (IIPs) for Pb<sup>2+</sup> detection and removal are promising new materials, as they are selective, adsorptive, and reusable. In this work, a novel Pb<sup>2+</sup>-imprinted polymer nanoparticle, was synthesized using quinizarin-based ion-imprinting chemistry and was introduced for effective Pb<sup>2+</sup> detection and removal.<h3>Results</h3>The IIP nanoparticles were prepared by complexing quinizarin with Pb<sup>2+</sup> in dimethylformamide<strong>,</strong> followed by polymerization with ethylene glycol dimethacrylate. Characterization using ICP-AES, infrared spectroscopy, SEM, and elemental analysis indicated successful polymerization and the formation of Pb<sup>2+</sup>-selective cavities. The uptake of Pb<sup>2+</sup> was maximized at pH 5.0, showing a rapid adsorption rate (within 5–30 min) and a maximum capacity of 146.9 μmol g<sup>-1</sup>, corresponding to a preconcentration factor of 17.8. Competitive sorption experiments demonstrated high selectivity for Pb<sup>2+</sup>. Desorption using 0.1 M hydrochloric acid yielded 98.5% recovery of the ion. The polymer exhibited high reusability over six cycles with a relative standard deviation of 1.9% and a detection limit (3.3σ) of 2.6 ng mL<sup>-1</sup>.<h3>Significance</h3>The synthesized Pb<sup>2+</sup>-imprinted polymer offers a highly efficient, selective, and reusable approach for Pb<sup>2+</sup> removal and detection in complex water systems. .Its rapid sorption/desorption kinetics, high reusability, and strong selectivity present a highly applicable technique for environmental monitoring and water purification, providing a sustainable method for treating lead contamination down to trace levels.","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"414 1","pages":""},"PeriodicalIF":6.2,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147465208","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-16DOI: 10.1016/j.aca.2026.345386
Kayle J. Bender, Joanna E. Spurgeon, Chuo Ying Zhai, Manish Arora, Elizabeth K. Neumann
Background
Human teeth preserve a rich temporal record of biological and environmental information throughout an individual’s life. Accessing this record requires analytical techniques capable of providing both spatial and chemical resolution. Matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI MSI) offers powerful capabilities for visualizing the spatial distribution of biomolecules. However, successful analysis demands preservation of both morphology and chemical integrity. The hard and brittle nature of enamel and dentin presents a major challenge, as preparing sufficiently thin sections typically requires decalcification, which can compromise molecular content.
Results
In this study, we present a sample preparation method using cryofilm, embedding, and specific cryostat blade angles to enable the analysis of non-decalcified human teeth by MALDI MSI. We further demonstrate this approach using various MALDI matrices, highlighting the potential of this technique for spatial analysis of biomolecules in teeth.
Significance
This method provides a foundation for future investigations into the spatial and temporal distribution of small molecules in human teeth.
{"title":"Non-Decalcified Human Teeth Sample Preparation Method for MALDI Mass Spectrometry Imaging","authors":"Kayle J. Bender, Joanna E. Spurgeon, Chuo Ying Zhai, Manish Arora, Elizabeth K. Neumann","doi":"10.1016/j.aca.2026.345386","DOIUrl":"https://doi.org/10.1016/j.aca.2026.345386","url":null,"abstract":"<h3>Background</h3>Human teeth preserve a rich temporal record of biological and environmental information throughout an individual’s life. Accessing this record requires analytical techniques capable of providing both spatial and chemical resolution. Matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI MSI) offers powerful capabilities for visualizing the spatial distribution of biomolecules. However, successful analysis demands preservation of both morphology and chemical integrity. The hard and brittle nature of enamel and dentin presents a major challenge, as preparing sufficiently thin sections typically requires decalcification, which can compromise molecular content.<h3>Results</h3>In this study, we present a sample preparation method using cryofilm, embedding, and specific cryostat blade angles to enable the analysis of non-decalcified human teeth by MALDI MSI. We further demonstrate this approach using various MALDI matrices, highlighting the potential of this technique for spatial analysis of biomolecules in teeth.<h3>Significance</h3>This method provides a foundation for future investigations into the spatial and temporal distribution of small molecules in human teeth.","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"78 1","pages":"345386"},"PeriodicalIF":6.2,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147465210","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-15Epub Date: 2026-01-27DOI: 10.1016/j.aca.2026.345159
Jorgelina Zaldarriaga-Heredia , Antonella E. Montemerlo , José M. Camiña , Mirta R. Alcaraz , Silvana M. Azcarate , Héctor C. Goicoechea
Background
The exploitation of multidimensional information represents a key challenge in analytical chemistry, particularly for classification tasks involving complex systems. This study systematically investigates the influence of data structure—ranging from first-to third-order—on classification performance using simulated and experimental fluorescence datasets. Chemometric models based on partial least squares–discriminant analysis (PLS-DA), multi-way PLS-DA (N-PLS-DA), and parallel factor analysis combined with discriminant analysis (PARAFAC-DA) were evaluated under varying conditions of class balance, noise, and sample size. Simulated and experimental datasets based on excitation–emission fluorescence spectroscopy were used.
Results
Simulated results demonstrated that increasing data dimensionality markedly enhanced discrimination ability, yielding higher accuracy and reduced error rates. Third-order models achieved average accuracies above 93 %, improving by up to 20 % and 10 % compared to the first- and second-order models, respectively. The methodology was further validated using excitation–emission fluorescence data from extra virgin and virgin olive oils subjected to infrared heating. Both N-PLS-DA and PARAFAC-DA provided successful discrimination, with PARAFAC-DA offering superior interpretability through chemically meaningful component profiles describing degradation and oxidation processes. Overall, the findings confirm that third-order chemometric models effectively integrate structural, spectral, and kinetic information, thereby improving classification reliability and interpretability. Even under conditions of class imbalance and limited sample availability, third-order models maintained low error rates and consistently high accuracy values, confirming their robustness and generalizability.
Significance
This study provides a comprehensive evaluation of how data structure influences multivariate classification performance. The proposed approach highlights the analytical potential of higher-order data modelling as a powerful and versatile strategy for classifying complex matrices. The findings firmly establish third-order modelling as a versatile and compelling tool for analytical applications where data complexity and real-world variability are unavoidable.
{"title":"Multi-way data modelling for enhancing classification performance: Fluorescence data as a case of study","authors":"Jorgelina Zaldarriaga-Heredia , Antonella E. Montemerlo , José M. Camiña , Mirta R. Alcaraz , Silvana M. Azcarate , Héctor C. Goicoechea","doi":"10.1016/j.aca.2026.345159","DOIUrl":"10.1016/j.aca.2026.345159","url":null,"abstract":"<div><h3>Background</h3><div>The exploitation of multidimensional information represents a key challenge in analytical chemistry, particularly for classification tasks involving complex systems. This study systematically investigates the influence of data structure—ranging from first-to third-order—on classification performance using simulated and experimental fluorescence datasets. Chemometric models based on partial least squares–discriminant analysis (PLS-DA), multi-way PLS-DA (N-PLS-DA), and parallel factor analysis combined with discriminant analysis (PARAFAC-DA) were evaluated under varying conditions of class balance, noise, and sample size. Simulated and experimental datasets based on excitation–emission fluorescence spectroscopy were used.</div></div><div><h3>Results</h3><div>Simulated results demonstrated that increasing data dimensionality markedly enhanced discrimination ability, yielding higher accuracy and reduced error rates. Third-order models achieved average accuracies above 93 %, improving by up to 20 % and 10 % compared to the first- and second-order models, respectively. The methodology was further validated using excitation–emission fluorescence data from extra virgin and virgin olive oils subjected to infrared heating. Both N-PLS-DA and PARAFAC-DA provided successful discrimination, with PARAFAC-DA offering superior interpretability through chemically meaningful component profiles describing degradation and oxidation processes. Overall, the findings confirm that third-order chemometric models effectively integrate structural, spectral, and kinetic information, thereby improving classification reliability and interpretability. Even under conditions of class imbalance and limited sample availability, third-order models maintained low error rates and consistently high accuracy values, confirming their robustness and generalizability.</div></div><div><h3>Significance</h3><div>This study provides a comprehensive evaluation of how data structure influences multivariate classification performance. The proposed approach highlights the analytical potential of higher-order data modelling as a powerful and versatile strategy for classifying complex matrices. The findings firmly establish third-order modelling as a versatile and compelling tool for analytical applications where data complexity and real-world variability are unavoidable.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1391 ","pages":"Article 345159"},"PeriodicalIF":6.0,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146056528","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-15Epub Date: 2026-01-24DOI: 10.1016/j.aca.2026.345156
Karolina Ostrowska , Maria Mazurkiewicz-Bełdzińska , Jakub Szymarek , Sylwia Studzińska
Background
Antisense oligonucleotides are synthetic nucleic acid molecules capable of selectively modulating gene expression. As the number of approved antisense oligonucleotide therapies grows, reliable analytical procedures are needed to monitor their pharmacokinetics, metabolism, and safety. Current solid phase extraction strategies often suffer from limited recovery or poor reproducibility. Methods using non-polar, hydrophilic or anion-exchange sorbents, require application of ion-pair reagents, or high concentration of salts or long conditioning. On the other hand, the potential of sorbents with hydrophobic-hydrophilic properties used for mixed-mode extraction remains unexplored. Our study presents the first application of newly synthesized materials for the isolation of therapeutic antisense oligonucleotides from cerebrospinal fluid samples.
Results
Five silica-based sorbents modified with aminopropyl, aliphatic, aromatic, and dicarboxylic groups were designed, synthesized, and characterized. The functionalization of sorbents enables various interactions with oligonucleotides, namely electrostatic, hydrophobic, π … π interactions, and hydrogen bonding. A new, mixed-mode dispersive solid phase extraction procedure was developed using a central composite design, enabling a systematic evaluation of the factors governing antisense oligonucleotide desorption. The effectiveness of the procedure was assessed for oligonucleotides varying in chemical modification and length. Recoveries depended on both factors and were the highest for shortmers with 2′-O-methyl modification. This effect is advantageous for the extraction of antisense oligonucleotide metabolites. The developed method was successfully used for the extraction of antisense oligonucleotides from cerebrospinal fluid, enabling reproducible recoveries (40–93 %). The matrix effects ranged from 89 % to 100 %. The highest recoveries were obtained for an oligonucleotide modified at two structural elements, making the method advantageous for the extraction of oligonucleotides used in therapy.
Significance
The proposed mixed-mode dispersive solid-phase extraction procedure provides a simple, fast, and reproducible approach for isolating of antisense oligonucleotides from cerebrospinal fluid. The method significantly simplifies sample preparation, since the procedure may be straightforwardly applied without additional purification steps. These results for the first time demonstrate the suitability and high analytical potential of hydrophobic-hydrophilic sorbents for the extraction of antisense oligonucleotides from biological samples.
反义寡核苷酸是一种能够选择性调节基因表达的合成核酸分子。随着批准的反义寡核苷酸疗法数量的增加，需要可靠的分析方法来监测它们的药代动力学、代谢和安全性。目前的固相萃取策略往往存在回收率有限或重现性差的问题。使用非极性、亲水性或阴离子交换吸附剂的方法，需要使用离子对试剂，或高浓度的盐或长时间的调理。另一方面，具有疏亲水性的吸附剂用于混合模式萃取的潜力仍未得到探索。我们的研究首次应用新合成的材料从脑脊液样品中分离治疗性反义寡核苷酸。结果设计、合成了氨基丙基、脂肪基、芳香族和二羧基改性的5种硅基吸附剂，并对其进行了表征。吸附剂的功能化可以实现与寡核苷酸的各种相互作用，即静电、疏水、π…π相互作用和氢键。采用中心复合设计，开发了一种新的混合模式分散固相萃取方法，能够系统地评估控制反义寡核苷酸解吸的因素。对不同化学修饰和长度的寡核苷酸的有效性进行了评估。回收率取决于这两个因素，并且对2 ' - o -甲基改性的短链剂的回收率最高。这一效应有利于反义寡核苷酸代谢物的提取。该方法成功地用于从脑脊液中提取反义寡核苷酸，具有可重复性（40 - 93%）。基质效应从89%到100%不等。在两个结构元素修饰的寡核苷酸中获得了最高的回收率，使该方法有利于提取用于治疗的寡核苷酸。意义所提出的混合模式色散固相萃取方法为脑脊液中反义寡核苷酸的分离提供了一种简单、快速、可重复性好的方法。该方法大大简化了样品制备，因为该程序可以直接应用，而无需额外的纯化步骤。这些结果首次证明了疏水-亲水吸附剂在生物样品中反义寡核苷酸提取中的适用性和较高的分析潜力。
{"title":"Synthesis, characterization, and application of sorbents for the mixed-mode extraction of antisense oligonucleotides from cerebrospinal fluid samples","authors":"Karolina Ostrowska , Maria Mazurkiewicz-Bełdzińska , Jakub Szymarek , Sylwia Studzińska","doi":"10.1016/j.aca.2026.345156","DOIUrl":"10.1016/j.aca.2026.345156","url":null,"abstract":"<div><h3>Background</h3><div>Antisense oligonucleotides are synthetic nucleic acid molecules capable of selectively modulating gene expression. As the number of approved antisense oligonucleotide therapies grows, reliable analytical procedures are needed to monitor their pharmacokinetics, metabolism, and safety. Current solid phase extraction strategies often suffer from limited recovery or poor reproducibility. Methods using non-polar, hydrophilic or anion-exchange sorbents, require application of ion-pair reagents, or high concentration of salts or long conditioning. On the other hand, the potential of sorbents with hydrophobic-hydrophilic properties used for mixed-mode extraction remains unexplored. Our study presents the first application of newly synthesized materials for the isolation of therapeutic antisense oligonucleotides from cerebrospinal fluid samples.</div></div><div><h3>Results</h3><div>Five silica-based sorbents modified with aminopropyl, aliphatic, aromatic, and dicarboxylic groups were designed, synthesized, and characterized. The functionalization of sorbents enables various interactions with oligonucleotides, namely electrostatic, hydrophobic, π … π interactions, and hydrogen bonding. A new, mixed-mode dispersive solid phase extraction procedure was developed using a central composite design, enabling a systematic evaluation of the factors governing antisense oligonucleotide desorption. The effectiveness of the procedure was assessed for oligonucleotides varying in chemical modification and length. Recoveries depended on both factors and were the highest for shortmers with 2′-O-methyl modification. This effect is advantageous for the extraction of antisense oligonucleotide metabolites. The developed method was successfully used for the extraction of antisense oligonucleotides from cerebrospinal fluid, enabling reproducible recoveries (40–93 %). The matrix effects ranged from 89 % to 100 %. The highest recoveries were obtained for an oligonucleotide modified at two structural elements, making the method advantageous for the extraction of oligonucleotides used in therapy.</div></div><div><h3>Significance</h3><div>The proposed mixed-mode dispersive solid-phase extraction procedure provides a simple, fast, and reproducible approach for isolating of antisense oligonucleotides from cerebrospinal fluid. The method significantly simplifies sample preparation, since the procedure may be straightforwardly applied without additional purification steps. These results for the first time demonstrate the suitability and high analytical potential of hydrophobic-hydrophilic sorbents for the extraction of antisense oligonucleotides from biological samples.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1391 ","pages":"Article 345156"},"PeriodicalIF":6.0,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146048634","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Glutathione (GSH), the most abundant cellular non-protein thiol and a central antioxidant, plays essential roles in regulating redox homeostasis, signal transduction, and detoxification processes. Altered GSH levels are closely associated with various pathological conditions, including neurodegenerative disorders, and liver injury. Notably, tumor tissues exhibit markedly elevated GSH concentrations (up to 4–10 times higher than in normal cells), where it promotes tumor proliferation, invasion, and chemoresistance by sustaining a reduced microenvironment, these characteristics make GSH an important biomarker and therapeutic target in oncology.
Results
We developed a novel “switch-on” near-infrared (NIR) fluorescence nanoprobe, Ag2S–CH@Cu-TCPP, for the highly sensitive and selective detection and imaging of GSH. The nanoprobe was constructed by conjugating histidine-rich CH peptides to carboxyl-capped Ag2S quantum dots (Ag2S QDs), which were then self-assembled onto two-dimensional Cu-TCPP metal-organic framework (MOF) nanosheets via coordination between Cu2+ and imidazole groups. In this design, Cu-TCPP acts as an efficient quencher for the Ag2S–CH fluorescence via a fluorescence resonance energy transfer (FRET) mechanism. Upon encountering GSH, the reduction of Cu2+ to Cu + disrupts the FRET process, leading to the recovery of the NIR fluorescence signal. This nanoprobe demonstrated a low detection limit of 5.33 μM and a wide linear range from 0.625 to 10 mM for GSH quantification, with excellent selectivity, high reproducibility, and favorable biocompatibility. We successfully applied the platform for monitoring intracellular GSH levels and distinguishing between cancer cells and normal cells based on their differential GSH expression.
Significance and novelty
The “switch-on” probe demonstrates excellent biocompatibility and is applicable for cellular imaging. It enables discrimination between normal and cancer cells while supporting semi-quantitative analysis of both endogenous and exogenous GSH. This work provides a novel and reliable strategy for tumor diagnosis and advanced investigations into GSH-related biological processes.
{"title":"A peptide-functionalized quantum Dots/MOF nanosheets fluorescence biosensor for glutathione sensing and cellular imaging","authors":"Tongfang Chen , Jingjie Liang , Weiqing Liu , Fengxia Zhou , Chanci Qiu , Yuhui Peng , Xie Zhou","doi":"10.1016/j.aca.2026.345120","DOIUrl":"10.1016/j.aca.2026.345120","url":null,"abstract":"<div><h3>Background</h3><div>Glutathione (GSH), the most abundant cellular non-protein thiol and a central antioxidant, plays essential roles in regulating redox homeostasis, signal transduction, and detoxification processes. Altered GSH levels are closely associated with various pathological conditions, including neurodegenerative disorders, and liver injury. Notably, tumor tissues exhibit markedly elevated GSH concentrations (up to 4–10 times higher than in normal cells), where it promotes tumor proliferation, invasion, and chemoresistance by sustaining a reduced microenvironment, these characteristics make GSH an important biomarker and therapeutic target in oncology.</div></div><div><h3>Results</h3><div>We developed a novel “switch-on” near-infrared (NIR) fluorescence nanoprobe, Ag<sub>2</sub>S–CH@Cu-TCPP, for the highly sensitive and selective detection and imaging of GSH. The nanoprobe was constructed by conjugating histidine-rich CH peptides to carboxyl-capped Ag<sub>2</sub>S quantum dots (Ag<sub>2</sub>S QDs), which were then self-assembled onto two-dimensional Cu-TCPP metal-organic framework (MOF) nanosheets via coordination between Cu<sup>2+</sup> and imidazole groups. In this design, Cu-TCPP acts as an efficient quencher for the Ag<sub>2</sub>S–CH fluorescence via a fluorescence resonance energy transfer (FRET) mechanism. Upon encountering GSH, the reduction of Cu<sup>2+</sup> to Cu <sup>+</sup> disrupts the FRET process, leading to the recovery of the NIR fluorescence signal. This nanoprobe demonstrated a low detection limit of 5.33 μM and a wide linear range from 0.625 to 10 mM for GSH quantification, with excellent selectivity, high reproducibility, and favorable biocompatibility. We successfully applied the platform for monitoring intracellular GSH levels and distinguishing between cancer cells and normal cells based on their differential GSH expression.</div></div><div><h3>Significance and novelty</h3><div>The “switch-on” probe demonstrates excellent biocompatibility and is applicable for cellular imaging. It enables discrimination between normal and cancer cells while supporting semi-quantitative analysis of both endogenous and exogenous GSH. This work provides a novel and reliable strategy for tumor diagnosis and advanced investigations into GSH-related biological processes.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1391 ","pages":"Article 345120"},"PeriodicalIF":6.0,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146042957","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-15Epub Date: 2026-01-22DOI: 10.1016/j.aca.2026.345136
Nerea Villarino, Isela Lavilla, Francisco Pena-Pereira, Carlos Bendicho
Background
Reliable determination of inorganic chemical preservatives is essential for ensuring food safety, due to the health concerns associated to these compounds when present at excessive levels. Nitrite and sulfite, two inorganic preservatives widely used in the food industry, increasingly demand miniaturized alternatives to conventional analytical methods. In this regard, luminescent nanosensors are of particular relevance because of their superior sensitivity. However, further improvements are still needed to enhance their selectivity and multiplexing capability, while ensuring their applicability in the analysis of complex matrices.
Results
The present study reports on the development of two paper-based analytical devices (PADs) involving luminescent silver nanoclusters (AgNCs) as sensing nanoreceptors for the simultaneous smartphone-assisted detection of sulfite and nitrite. The assays rely on the highly selective recognition of nitrogen oxides and sulfur dioxide by AgNCs protected with poly(methacrylate) and polyethylenimine, respectively, separately immobilized in the detection areas of PADs. Thus, in this work, AgNCs-containing PADs have been devised for the simultaneous determination of sulfite and nitrite involving in situ formation of the volatile derivatives and their selective trapping/interaction with the corresponding AgNCs nanoreceptors, leading to luminescence quenching. Two different configurations have been evaluated for the development of PAD-based nanosensors, namely in-vial PAD-based headspace microextraction (HS-PAD) and headspace 3D origami microfluidic PAD (HS-μPAD). Under optimal conditions, the developed assays showed limits of detection as low as 0.29 μM and 0.23 μM for sulfite and nitrite, respectively, for the HS-PAD approach, and 1.9 μM and 3.2 μM for the HS-μPAD configuration, with a repeatability expressed as relative standard deviation lower than 7.3 % (N = 8) in all cases. In addition, the developed PAD-based nanosensors were applied to the analysis of food samples, the results obtained showing excellent agreement with those obtained with reference methods.
Significance
This article reports, for the first time, on the assessment of AgNCs with different responsiveness as luminescent nanoprobes for the development of multiplexed paper-based nanosensors with headspace sampling. The proposed assays enable decentralized, affordable and straightforward detection of sulfite and nitrite, being complementary in terms of sample consumption and sensitivity, and represent advantageous alternatives for quality control and safety monitoring in the food industry.
{"title":"Multiplexed headspace paper-based analytical devices modified with silver nanoclusters for smartphone-based luminescent determination of inorganic preservatives in food samples","authors":"Nerea Villarino, Isela Lavilla, Francisco Pena-Pereira, Carlos Bendicho","doi":"10.1016/j.aca.2026.345136","DOIUrl":"10.1016/j.aca.2026.345136","url":null,"abstract":"<div><h3>Background</h3><div>Reliable determination of inorganic chemical preservatives is essential for ensuring food safety, due to the health concerns associated to these compounds when present at excessive levels. Nitrite and sulfite, two inorganic preservatives widely used in the food industry, increasingly demand miniaturized alternatives to conventional analytical methods. In this regard, luminescent nanosensors are of particular relevance because of their superior sensitivity. However, further improvements are still needed to enhance their selectivity and multiplexing capability, while ensuring their applicability in the analysis of complex matrices.</div></div><div><h3>Results</h3><div>The present study reports on the development of two paper-based analytical devices (PADs) involving luminescent silver nanoclusters (AgNCs) as sensing nanoreceptors for the simultaneous smartphone-assisted detection of sulfite and nitrite. The assays rely on the highly selective recognition of nitrogen oxides and sulfur dioxide by AgNCs protected with poly(methacrylate) and polyethylenimine, respectively, separately immobilized in the detection areas of PADs. Thus, in this work, AgNCs-containing PADs have been devised for the simultaneous determination of sulfite and nitrite involving <em>in situ</em> formation of the volatile derivatives and their selective trapping/interaction with the corresponding AgNCs nanoreceptors, leading to luminescence quenching. Two different configurations have been evaluated for the development of PAD-based nanosensors, namely in-vial PAD-based headspace microextraction (HS-PAD) and headspace 3D origami microfluidic PAD (HS-μPAD). Under optimal conditions, the developed assays showed limits of detection as low as 0.29 μM and 0.23 μM for sulfite and nitrite, respectively, for the HS-PAD approach, and 1.9 μM and 3.2 μM for the HS-μPAD configuration, with a repeatability expressed as relative standard deviation lower than 7.3 % (N = 8) in all cases. In addition, the developed PAD-based nanosensors were applied to the analysis of food samples, the results obtained showing excellent agreement with those obtained with reference methods.</div></div><div><h3>Significance</h3><div>This article reports, for the first time, on the assessment of AgNCs with different responsiveness as luminescent nanoprobes for the development of multiplexed paper-based nanosensors with headspace sampling. The proposed assays enable decentralized, affordable and straightforward detection of sulfite and nitrite, being complementary in terms of sample consumption and sensitivity, and represent advantageous alternatives for quality control and safety monitoring in the food industry.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1391 ","pages":"Article 345136"},"PeriodicalIF":6.0,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146033808","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-15Epub Date: 2026-01-21DOI: 10.1016/j.aca.2026.345138
Xiaona Yin , Ziyan Zhang , Hao Luo , Xiaolin Qin , Yang Chen , Wentao Chen , Heping Zheng
RNA has become a versatile target for diagnosing a wide range of pathogens. The demand for rapid and accurate diagnostics in point-of-care (POC) or resource-limited settings is growing. However, most RNA-based assays depend on reverse transcription and complex instruments (e.g., RT-qPCR), restricting their use in these settings. Isothermal amplification methods provide a simpler alternative with reduced instrumentation requirements, but their high amplification efficiency raises concerns about nucleic acid carry-over contamination. To address these challenges, we developed RAPID (CRISPR–Cas13a with a cascade amplification circuit-driven DNAzyme), an isothermal, one-pot RNA detection biosensing platform that eliminates the need for sample pre-amplification. RAPID integrates the precise target recognition by CRISPR–Cas13a with robust signal amplification by a toehold-mediated strand-displacement DNA circuit, eliminating the need for reverse transcription and thermal cycling. This platform enables quantitative RNA detection within 30 min at 37 °C. By reprogramming RAPID crRNAs, we successfully detected both bacterial (e.g., Treponema pallidum and Neisseria gonorrhoeae) and viral (e.g., herpes simplex virus) targets. The RAPID platform is designed for versatile detection, being compatible with both fluorescence-based (RAPID-Flu) and lateral flow assay (RAPID-LFA) readouts. The RAPID-Flu and RAPID-LFA both demonstrated a sensitivity of 5 fM per reaction, exhibiting comparable detection limits. Both methods showed excellent specificity and high concordance with clinical diagnoses of Neisseria gonorrhoeae. In summary, the RAPID platform provides rapid, programmable, and visually interpretable solutions with strong potential for POC diagnostics. Its flexibility and portability make it particularly suitable for early diagnosis and on-site monitoring of diverse infectious pathogens.
{"title":"Amplification-free one-pot RNA detection by pairing CRISPR–Cas13a with cascade amplification circuit-driven DNAzyme (RAPID)","authors":"Xiaona Yin , Ziyan Zhang , Hao Luo , Xiaolin Qin , Yang Chen , Wentao Chen , Heping Zheng","doi":"10.1016/j.aca.2026.345138","DOIUrl":"10.1016/j.aca.2026.345138","url":null,"abstract":"<div><div>RNA has become a versatile target for diagnosing a wide range of pathogens. The demand for rapid and accurate diagnostics in point-of-care (POC) or resource-limited settings is growing. However, most RNA-based assays depend on reverse transcription and complex instruments (e.g., RT-qPCR), restricting their use in these settings. Isothermal amplification methods provide a simpler alternative with reduced instrumentation requirements, but their high amplification efficiency raises concerns about nucleic acid carry-over contamination. To address these challenges, we developed RAPID (C<u>R</u>ISPR–Cas13a with a c<u>a</u>scade am<u>p</u>lification c<u>i</u>rcuit-driven <u>D</u>NAzyme), an isothermal, one-pot RNA detection biosensing platform that eliminates the need for sample pre-amplification. RAPID integrates the precise target recognition by CRISPR–Cas13a with robust signal amplification by a toehold-mediated strand-displacement DNA circuit, eliminating the need for reverse transcription and thermal cycling. This platform enables quantitative RNA detection within 30 min at 37 °C. By reprogramming RAPID crRNAs, we successfully detected both bacterial (e.g., <em>Treponema pallidum</em> and <em>Neisseria gonorrhoeae</em>) and viral (e.g., herpes simplex virus) targets. The RAPID platform is designed for versatile detection, being compatible with both fluorescence-based (RAPID-Flu) and lateral flow assay (RAPID-LFA) readouts. The RAPID-Flu and RAPID-LFA both demonstrated a sensitivity of 5 fM per reaction, exhibiting comparable detection limits. Both methods showed excellent specificity and high concordance with clinical diagnoses of <em>Neisseria gonorrhoeae</em>. In summary, the RAPID platform provides rapid, programmable, and visually interpretable solutions with strong potential for POC diagnostics. Its flexibility and portability make it particularly suitable for early diagnosis and on-site monitoring of diverse infectious pathogens.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1391 ","pages":"Article 345138"},"PeriodicalIF":6.0,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146014730","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-15Epub Date: 2026-01-06DOI: 10.1016/j.aca.2025.345050
Hanyang Ning , Miao Ma , Zhiwei Shi , Liping Ding
Background:
Accurate compositional analysis of complex mixtures directly from their overlapping spectral data is critical for advancements in materials discovery, process control, and environmental monitoring. However, existing deep learning models often lack a mechanism to enforce logical consistency, leading to physically implausible predictions, such as assigning a concentration value to a component that is simultaneously classified as absent.
Results:
We propose a novel multi-task learning framework to explicitly link component identification and quantification. It introduces a prediction masking mechanism where the probabilistic outputs from a multi-label classification branch directly guide the predictions of a parallel regression branch, ensuring concentrations are only predicted for components identified as present. With ResNet1D as the feature extractor, experimental results on the MetalOxides benchmark dataset show that our framework substantially outperforms common machine learning methods.
Significance:
This framework enforces physical plausibility in spectral predictions, providing a more logically consistent and accurate tool for complex mixture analysis. This work is significant for advancing critical applications in materials discovery, process control, and environmental monitoring that rely on dependable quantitative analysis.
{"title":"Accurate compositional analysis on complex mixtures via multi-task spectral data learning","authors":"Hanyang Ning , Miao Ma , Zhiwei Shi , Liping Ding","doi":"10.1016/j.aca.2025.345050","DOIUrl":"10.1016/j.aca.2025.345050","url":null,"abstract":"<div><h3>Background:</h3><div>Accurate compositional analysis of complex mixtures directly from their overlapping spectral data is critical for advancements in materials discovery, process control, and environmental monitoring. However, existing deep learning models often lack a mechanism to enforce logical consistency, leading to physically implausible predictions, such as assigning a concentration value to a component that is simultaneously classified as absent.</div></div><div><h3>Results:</h3><div>We propose a novel multi-task learning framework to explicitly link component identification and quantification. It introduces a prediction masking mechanism where the probabilistic outputs from a multi-label classification branch directly guide the predictions of a parallel regression branch, ensuring concentrations are only predicted for components identified as present. With ResNet1D as the feature extractor, experimental results on the MetalOxides benchmark dataset show that our framework substantially outperforms common machine learning methods.</div></div><div><h3>Significance:</h3><div>This framework enforces physical plausibility in spectral predictions, providing a more logically consistent and accurate tool for complex mixture analysis. This work is significant for advancing critical applications in materials discovery, process control, and environmental monitoring that rely on dependable quantitative analysis.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1391 ","pages":"Article 345050"},"PeriodicalIF":6.0,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146148655","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The BRAF V600E mutant protein is a valuable biomarker for the diagnosis and prognosis of colorectal cancer. Quantitative detection by mass spectrometry (MS) requires purification from complex cell extracts and digestion into surrogate peptides, a process that traditionally takes at least ∼12 h, which is time-consuming and labor-intensive, limiting clinical applicability.
Results
We present an automated microfluidic sample-preparation chip that integrates immunoprecipitation, multistep washing, and on-bead tryptic digestion by integrating pneumatically driven micromixers, microvalves, and magnetically guided beads. On-bead digestion was employed to eliminate multiple buffer-exchange steps, simplifying fluidic control and producing more BRAF peptides than the conventional elution–digestion workflow, in which only ∼50 % of captured proteins are recovered. Starting from clarified cell lysate, the device produces peptide samples within approximately 2.5–3 h.
Significance and novelty
Although individual components of the workflow have been reported previously, the present platform uniquely achieves end-to-end integration and automation of immuno–MS sample preparation. This work emphasizes operational simplicity and rapid turnaround time, providing a practical solution for MS-based mutant protein analysis in translational and precision medicine applications.
{"title":"Rapid microfluidic sample preparation for mass spectrometric analysis of wild-type and mutant BRAF protein","authors":"Yen-Heng Lin , Heng-Yun Chang , Chia-Chun Wu , Yung-Chin Hsiao , Ying-Hao Wen , Jau-Song Yu","doi":"10.1016/j.aca.2026.345146","DOIUrl":"10.1016/j.aca.2026.345146","url":null,"abstract":"<div><h3>Background</h3><div>The BRAF V600E mutant protein is a valuable biomarker for the diagnosis and prognosis of colorectal cancer. Quantitative detection by mass spectrometry (MS) requires purification from complex cell extracts and digestion into surrogate peptides, a process that traditionally takes at least ∼12 h, which is time-consuming and labor-intensive, limiting clinical applicability.</div></div><div><h3>Results</h3><div>We present an automated microfluidic sample-preparation chip that integrates immunoprecipitation, multistep washing, and on-bead tryptic digestion by integrating pneumatically driven micromixers, microvalves, and magnetically guided beads. On-bead digestion was employed to eliminate multiple buffer-exchange steps, simplifying fluidic control and producing more BRAF peptides than the conventional elution–digestion workflow, in which only ∼50 % of captured proteins are recovered. Starting from clarified cell lysate, the device produces peptide samples within approximately 2.5–3 h.</div></div><div><h3>Significance and novelty</h3><div>Although individual components of the workflow have been reported previously, the present platform uniquely achieves end-to-end integration and automation of immuno–MS sample preparation. This work emphasizes operational simplicity and rapid turnaround time, providing a practical solution for MS-based mutant protein analysis in translational and precision medicine applications.</div></div>","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"1391 ","pages":"Article 345146"},"PeriodicalIF":6.0,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146033802","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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