Analytical Sciences最新文献_第7页

Mid-FTIR and machine learning for predicting fig leaf macronutrients content 中傅里叶红外光谱和机器学习预测无花果叶常量营养素含量。

IF 2 4区化学 Q3 CHEMISTRY, ANALYTICAL

Analytical Sciences

Pub Date : 2025-06-29 DOI: 10.1007/s44211-025-00814-9

Lahcen Hssaini, Rachid Razouk

Predicting leaf mineral composition is critical for monitoring plant health and optimizing agricultural practices. This study combines Fourier-transform infrared spectroscopy with attenuated total reflectance (FTIR-ATR) and machine learning (ML) to specific macronutrients, namely nitrogen (N), phosphorus (P), potassium (K), calcium (Ca), and magnesium (Mg), in fig leaves (Ficus carica L.). A dataset of 90 leaves was analyzed, with FTIR spectra (450–4000 cm⁻¹) preprocessed via baseline correction and second-derivative transformations. Three ML models were evaluated using fivefold cross-validation including Random Forest (RF), Support Vector Regression (SVR), and Gradient Boosting (GB), with performance assessed via root mean square error (RMSE), coefficient of determination (R²), and ratio of performance to deviation (RPD). GB outperformed other models, achieving validation RMSE/RPD values of 0.133/1.60 (nitrogen, N), 0.0107/1.79 (phosphorus, P), 0.1328/1.65 (potassium, K), 0.0636/1.96 (magnesium, Mg), and 0.2657/1.60 (calcium, Ca). Predictions for Mg (validation R² = 0.7351) and P (validation R² = 0.6873) exhibited the highest accuracy, potentially attributed to their stronger or more distinct spectral features (e.g., Mg-O stretching around 1050– 1150 cm⁻¹; P-O vibrations around 1240 cm⁻¹). Cross-validation revealed robust generalization for GB; while mean training RMSE was very low (< 0.01 for P and Mg), validation RMSE remained relatively low, underscoring the model’s utility for screening (RPD > 1.5). Despite evidence of overfitting (training R² ≈ 0.999 vs. validation R² = 0.61–0.74), GB’s performance evaluated using both RMSE and RPD confirmed its superiority over RF and SVR, which showed higher errors (e.g., SVR for Ca: RMSE = 0.4574, RPD = 1.07). This study demonstrates that FTIR-ATR coupled with ML is a rapid, non-destructive alternative to conventional destructive chemical analysis and that GB’s reliability, as indicated by RPD values > 1.5, offers actionable insights for precision nutrient management in sustainable agriculture.

Graphical abstract

预测叶片矿物成分对监测植物健康和优化农业实践至关重要。本研究将傅里叶变换红外光谱与衰减全反射（FTIR-ATR）和机器学习（ML）相结合，研究无花果（Ficus carica L.）叶片中的特定常量营养素，即氮(N)、磷(P)、钾(K)、钙（Ca）和镁（Mg）。对90片叶子的数据集进行分析，通过基线校正和二阶导数变换对FTIR光谱（450-4000 cm - 1）进行预处理。采用随机森林（Random Forest， RF）、支持向量回归（Support Vector Regression， SVR）和梯度增强（Gradient Boosting， GB）三种ML模型进行五重交叉验证，并通过均方根误差（root mean square error， RMSE）、决定系数（coefficient of determination, R2）和性能偏差比（performance to deviation， RPD）来评估其性能。GB模型的验证RMSE/RPD值优于其他模型，分别为0.133/1.60（氮，N）、0.0107/1.79（磷，P）、0.1328/1.65（钾，K）、0.0636/1.96（镁，Mg）和0.2657/1.60（钙，Ca）。预测毫克(验证R2 = 0.7351)和P(验证R2 = 0.6873)表现出最高的准确性,可能归因于他们的更强大、更独特的光谱特性(例如,Mg-O延伸约1050 - 1150厘米⁻1;P-O振动在1240厘米左右(1)。交叉验证显示了GB的稳健泛化；而平均训练RMSE非常低（1.5）。尽管存在过拟合的证据（训练R2≈0.999 vs验证R2 = 0.61-0.74），但使用RMSE和RPD评估GB的性能证实了其优于RF和SVR，后者显示出更高的误差（例如，Ca的SVR: RMSE = 0.4574, RPD = 1.07）。本研究表明，FTIR-ATR结合ML是传统破坏性化学分析的快速、非破坏性替代方法，并且GB的可靠性（RPD值为> 1.5）为可持续农业的精确养分管理提供了可操作的见解。

{"title":"Mid-FTIR and machine learning for predicting fig leaf macronutrients content","authors":"Lahcen Hssaini, Rachid Razouk","doi":"10.1007/s44211-025-00814-9","DOIUrl":"10.1007/s44211-025-00814-9","url":null,"abstract":"<div><p>Predicting leaf mineral composition is critical for monitoring plant health and optimizing agricultural practices. This study combines Fourier-transform infrared spectroscopy with attenuated total reflectance (FTIR-ATR) and machine learning (ML) to specific macronutrients, namely nitrogen (N), phosphorus (P), potassium (K), calcium (Ca), and magnesium (Mg), in fig leaves (Ficus carica L.). A dataset of 90 leaves was analyzed, with FTIR spectra (450–4000 cm⁻<sup>1</sup>) preprocessed via baseline correction and second-derivative transformations. Three ML models were evaluated using fivefold cross-validation including Random Forest (RF), Support Vector Regression (SVR), and Gradient Boosting (GB), with performance assessed via root mean square error (RMSE), coefficient of determination (R<sup>2</sup>), and ratio of performance to deviation (RPD). GB outperformed other models, achieving validation RMSE/RPD values of 0.133/1.60 (nitrogen, N), 0.0107/1.79 (phosphorus, P), 0.1328/1.65 (potassium, K), 0.0636/1.96 (magnesium, Mg), and 0.2657/1.60 (calcium, Ca). Predictions for Mg (validation R<sup>2</sup> = 0.7351) and P (validation R<sup>2</sup> = 0.6873) exhibited the highest accuracy, potentially attributed to their stronger or more distinct spectral features (e.g., Mg-O stretching around 1050– 1150 cm⁻<sup>1</sup>; P-O vibrations around 1240 cm⁻<sup>1</sup>). Cross-validation revealed robust generalization for GB; while mean training RMSE was very low (< 0.01 for P and Mg), validation RMSE remained relatively low, underscoring the model’s utility for screening (RPD > 1.5). Despite evidence of overfitting (training <i>R</i><sup>2</sup> ≈ 0.999 vs. validation <i>R</i><sup>2</sup> = 0.61–0.74), GB’s performance evaluated using both RMSE and RPD confirmed its superiority over RF and SVR, which showed higher errors (e.g., SVR for Ca: RMSE = 0.4574, RPD = 1.07). This study demonstrates that FTIR-ATR coupled with ML is a rapid, non-destructive alternative to conventional destructive chemical analysis and that GB’s reliability, as indicated by RPD values > 1.5, offers actionable insights for precision nutrient management in sustainable agriculture.</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 9","pages":"1473 - 1489"},"PeriodicalIF":2.0,"publicationDate":"2025-06-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144526105","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}

引用次数: 0

Intraparticle diffusion of proteins in diol group-functionalized porous silica particle revealed by fluorescence correlation spectroscopy 荧光相关光谱研究蛋白质在二醇基功能化多孔二氧化硅颗粒中的颗粒内扩散。

IF 2 4区化学 Q3 CHEMISTRY, ANALYTICAL

Analytical Sciences

Pub Date : 2025-06-27 DOI: 10.1007/s44211-025-00806-9

Akihisa Miyagawa, Mari Edamura, Shigenori Nagatomo, Kiyoharu Nakatani

Size exclusion chromatography (SEC) is widely employed for the purification and separation of macromolecules; however, its underlying separation mechanism remains poorly understood. In this study, we investigated the intraparticle diffusion of proteins—lysozyme (Lz), myoglobin (Mb), hemoglobin (Hb), and horseradish peroxidase (HRP)—within diol-functionalized silica particle, which serve as the stationary phase in SEC, using fluorescence correlation spectroscopy (FCS). The intraparticle diffusion coefficient (D_intra) was found to depend on protein sizes, whereas no significant pH dependence of D_intra was observed. These findings suggest that the steric hindrance between the proteins and pore walls governs intraparticle diffusion, while electrostatic interactions play a negligible role. Consequently, our results demonstrate that the intraparticle diffusion of Mb and Lz observed via FCS primarily reflects bulk-like diffusion within the pore without any interactions between the proteins and particle surface. In contrast, surface diffusion is evident for HRP and Hb.

Graphic Abstract

粒径排除色谱法（SEC）广泛应用于大分子的纯化和分离；然而，其潜在的分离机制仍然知之甚少。在这项研究中，我们利用荧光相关光谱（FCS）研究了溶菌酶（Lz）、肌红蛋白（Mb）、血红蛋白（Hb）和辣根过氧化物酶（HRP）等蛋白质在二醇功能化二氧化硅颗粒中的颗粒内扩散，二氧化硅颗粒作为SEC的固定相。颗粒内扩散系数（Dintra）与蛋白质大小有关，而Dintra对pH值没有明显的依赖性。这些发现表明，蛋白质和孔壁之间的空间位阻控制着颗粒内的扩散，而静电相互作用的作用可以忽略不计。因此，我们的研究结果表明，通过FCS观察到的Mb和Lz的颗粒内扩散主要反映了孔隙内的块状扩散，而蛋白质与颗粒表面之间没有任何相互作用。相反，HRP和Hb的表面扩散是明显的。

{"title":"Intraparticle diffusion of proteins in diol group-functionalized porous silica particle revealed by fluorescence correlation spectroscopy","authors":"Akihisa Miyagawa, Mari Edamura, Shigenori Nagatomo, Kiyoharu Nakatani","doi":"10.1007/s44211-025-00806-9","DOIUrl":"10.1007/s44211-025-00806-9","url":null,"abstract":"<div><p>Size exclusion chromatography (SEC) is widely employed for the purification and separation of macromolecules; however, its underlying separation mechanism remains poorly understood. In this study, we investigated the intraparticle diffusion of proteins—lysozyme (Lz), myoglobin (Mb), hemoglobin (Hb), and horseradish peroxidase (HRP)—within diol-functionalized silica particle, which serve as the stationary phase in SEC, using fluorescence correlation spectroscopy (FCS). The intraparticle diffusion coefficient (<i>D</i><sub>intra</sub>) was found to depend on protein sizes, whereas no significant pH dependence of <i>D</i><sub>intra</sub> was observed. These findings suggest that the steric hindrance between the proteins and pore walls governs intraparticle diffusion, while electrostatic interactions play a negligible role. Consequently, our results demonstrate that the intraparticle diffusion of Mb and Lz observed via FCS primarily reflects bulk-like diffusion within the pore without any interactions between the proteins and particle surface. In contrast, surface diffusion is evident for HRP and Hb.</p><h3>Graphic Abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":7802,"journal":{"name":"Analytical Sciences","volume":"41 9","pages":"1451 - 1459"},"PeriodicalIF":2.0,"publicationDate":"2025-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144504542","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}

引用次数: 0

Immobilized enzyme microreactors used for capillary electrophoresis 固定化酶微反应器用于毛细管电泳。

IF 2 4区化学 Q3 CHEMISTRY, ANALYTICAL

Analytical Sciences

Pub Date : 2025-06-26 DOI: 10.1007/s44211-025-00762-4

Toshio Takayanagi

引用次数: 0

Electrochemiluminescence of titanium dioxide nanomaterials for sensing applications 二氧化钛纳米材料的电化学发光传感应用。

IF 2 4区化学 Q3 CHEMISTRY, ANALYTICAL

Analytical Sciences

Pub Date : 2025-06-25 DOI: 10.1007/s44211-025-00808-7

Abdul Basit, Muhammad I. Syauqi, Afiten R. Sanjaya, Isnaini Rahmawati, Jarnuzi Gunlazuardi, Tribidasari A. Ivandini

This study systematically reviews the electrochemiluminescence (ECL) properties of titanium dioxide (TiO₂) synthesized via hydrothermal, sol–gel, and anodic oxidation method. TiO₂ has emerged as a highly promising candidate for ECL-based sensing applications owing to its exceptional catalytic activity, high surface area, efficient electron transport, and biocompatibility. These properties of TiO₂ allow it to function effectively as a luminophore, co-reactant, and electrode immobilization matrix for bio-organic molecules. The performance of TiO₂ in ECL is mainly determined by its efficiency in electron transfer and its surface adsorption characteristics, which affect its interactions with ECL-active species. Moreover, the doping and functionalization of conductive nanomaterials, metal ions, metal oxides, and organic modifiers greatly improves charge-transfer kinetics and surface adsorption properties, leading to enhance ECL signal intensity and stability. The recent advancements highlight the promise of TiO₂-based materials in the creation of highly sensitive and selective ECL sensor and biosensors, applicable in biomedical, environmental, and analytical fields.

Graphical abstract

本文系统地综述了水热法、溶胶-凝胶法和阳极氧化法合成二氧化钛（tio_2）的电化学发光（ECL）性能。由于其优异的催化活性、高表面积、高效的电子传递和生物相容性，TiO 2已成为基于ecl的传感应用的非常有前途的候选者。二氧化钛的这些特性使其能够有效地作为发光团，共反应物和生物有机分子的电极固定化基质。tio2在ECL中的性能主要取决于其电子转移效率和表面吸附特性，而表面吸附特性影响其与ECL活性物质的相互作用。此外，导电纳米材料、金属离子、金属氧化物和有机改性剂的掺杂和功能化极大地改善了电荷转移动力学和表面吸附性能，从而增强了ECL信号强度和稳定性。最近的进展突出了二氧化钛基材料在创建高灵敏度和选择性ECL传感器和生物传感器方面的前景，适用于生物医学，环境和分析领域。

{"title":"Electrochemiluminescence of titanium dioxide nanomaterials for sensing applications","authors":"Abdul Basit, Muhammad I. Syauqi, Afiten R. Sanjaya, Isnaini Rahmawati, Jarnuzi Gunlazuardi, Tribidasari A. Ivandini","doi":"10.1007/s44211-025-00808-7","DOIUrl":"10.1007/s44211-025-00808-7","url":null,"abstract":"<div><p>This study systematically reviews the electrochemiluminescence (ECL) properties of titanium dioxide (TiO₂) synthesized via hydrothermal, sol–gel, and anodic oxidation method. TiO₂ has emerged as a highly promising candidate for ECL-based sensing applications owing to its exceptional catalytic activity, high surface area, efficient electron transport, and biocompatibility. These properties of TiO₂ allow it to function effectively as a luminophore, co-reactant, and electrode immobilization matrix for bio-organic molecules. The performance of TiO₂ in ECL is mainly determined by its efficiency in electron transfer and its surface adsorption characteristics, which affect its interactions with ECL-active species. Moreover, the doping and functionalization of conductive nanomaterials, metal ions, metal oxides, and organic modifiers greatly improves charge-transfer kinetics and surface adsorption properties, leading to enhance ECL signal intensity and stability. The recent advancements highlight the promise of TiO₂-based materials in the creation of highly sensitive and selective ECL sensor and biosensors, applicable in biomedical, environmental, and analytical fields.</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 9","pages":"1427 - 1449"},"PeriodicalIF":2.0,"publicationDate":"2025-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144482894","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}

引用次数: 0

A dexterous fluorescence sensor for diversified-biomarker detection using cyclic EDC–CHA (EDCHA) system 采用环EDC-CHA （EDCHA）系统的灵敏荧光传感器检测多种生物标志物。

IF 2 4区化学 Q3 CHEMISTRY, ANALYTICAL

Analytical Sciences

Pub Date : 2025-06-25 DOI: 10.1007/s44211-025-00791-z

Jie Du, Jinjuan Liu, Hongyan Li

Monitoring the levels of various biomarkers, such as nucleic acids and proteins, is crucial for early disease diagnosis, evaluating treatment efficacy, and predicting patient prognosis, thereby aiding clinical decision-making. Herein_, a robust double-circuit fluorescence assay combining the advantages of EDC and CHA called EDCHA is proposed. The EDCHA includes two cycles, EDC system identifies the target miRNA, realizes first signal amplification and releases an initiator chain to trigger the CHA system. CHA system realizes second signal amplification by opened hairpin structures and different fluorophore groups. In addition, by replacing the waste chain in the EDC system with fluorescent-labeled aptamer, the EDCHA can simultaneously detect both miRNA and protein. The EDCHA was verified with the specific detection of miRNA-21 with a low detection limit (LOD) of 77.18 pM. Furthermore, our method enables the simultaneous detection of two types of biomarkers—nucleic acids and proteins—with a low detection limit (LOD) of 0.94 nM for the AD-related protein AβO. These results demonstrate the enormous potential of EDCHA in diverse biomarkers analysis and cancer diagnosis.

Graphical abstract

监测各种生物标志物的水平，如核酸和蛋白质，对于疾病的早期诊断，评估治疗效果，预测患者预后，从而帮助临床决策至关重要。本文提出了一种结合EDC和CHA优点的强大的双回路荧光检测方法，称为EDCHA。EDCHA包括两个周期，EDC系统识别目标miRNA，实现第一信号放大，释放启动链触发CHA系统。CHA系统通过开口发夹结构和不同的荧光基团实现二次信号放大。此外，通过用荧光标记的适体取代EDC系统中的废物链，EDCHA可以同时检测miRNA和蛋白质。特异性检测miRNA-21验证了EDCHA，低检出限（LOD）为77.18 pM。此外，我们的方法能够同时检测两种类型的生物标志物-核酸和蛋白质- ad相关蛋白a β o的低检测限（LOD）为0.94 nM。这些结果证明了EDCHA在多种生物标志物分析和癌症诊断中的巨大潜力。

{"title":"A dexterous fluorescence sensor for diversified-biomarker detection using cyclic EDC–CHA (EDCHA) system","authors":"Jie Du, Jinjuan Liu, Hongyan Li","doi":"10.1007/s44211-025-00791-z","DOIUrl":"10.1007/s44211-025-00791-z","url":null,"abstract":"<div><p>Monitoring the levels of various biomarkers, such as nucleic acids and proteins, is crucial for early disease diagnosis, evaluating treatment efficacy, and predicting patient prognosis, thereby aiding clinical decision-making. Herein<sub><b>,</b></sub> a robust double-circuit fluorescence assay combining the advantages of EDC and CHA called EDCHA is proposed. The EDCHA includes two cycles, EDC system identifies the target miRNA, realizes first signal amplification and releases an initiator chain to trigger the CHA system. CHA system realizes second signal amplification by opened hairpin structures and different fluorophore groups. In addition, by replacing the waste chain in the EDC system with fluorescent-labeled aptamer, the EDCHA can simultaneously detect both miRNA and protein. The EDCHA was verified with the specific detection of miRNA-21 with a low detection limit (LOD) of 77.18 pM. Furthermore, our method enables the simultaneous detection of two types of biomarkers—nucleic acids and proteins—with a low detection limit (LOD) of 0.94 nM for the AD-related protein AβO. These results demonstrate the enormous potential of EDCHA in diverse biomarkers analysis and cancer diagnosis.</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":"1325 - 1334"},"PeriodicalIF":2.0,"publicationDate":"2025-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12307502/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144493471","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}

引用次数: 0

New complex iron with various functionalized 2,2ʹ-bipyridine derivatives in evaluation of total lipophilic and hydrophilic antioxidant capacity by the potentiometry 新型配合铁与各种功能化的2,2'-联吡啶衍生物在总亲脂和亲水抗氧化能力评价中的应用。

IF 2 4区化学 Q3 CHEMISTRY, ANALYTICAL

Analytical Sciences

Pub Date : 2025-06-20 DOI: 10.1007/s44211-025-00804-x

Elena Gerasimova, Elena Salimgareeva, Evgeniya Yanybaeva, Yaroslav Shtaitz, Viktoriya Kirillova, Alexey Krinochkin, Dmitry Kopchuk, Grigory Zyryanov, Alla Ivanova

The potentiometric approach for determining the integral antioxidant capacity was developed. The reaction of antioxidants with new complexes of the iron with target functionalized 2,2ʹ-bipyridine derivatives was used as a signal-forming reaction. The approach allows the joint determination of hydrophilic and lipophilic antioxidants, which is especially important in the analysis of plant samples with a complex composition. A number of new 2,2ʹ-bipyridine derivatives have been synthesized. It has been shown that the complexing ability, especially with Fe(III), is increased by introducing halogens into the structure of 2,2ʹ-bipyridine. The solubility of the complexes in polar solutions is increased by introducing the triethylene glycol fragment into the 2,2ʹ-bipyridine at the aryl substituent in the C5 position. The electrochemical behavior of the complexes with Fe(II) and Fe(III) was studied. The metal – ligand ratios and stability constants of the complexes were estimated by the voltammetric method (the values of the conditional stability constants ranged from 1∙10⁸ to 5∙10¹⁰). Individual antioxidants with different solubilities and cereal extracts, containing antioxidants of different hydrophilicity, were studied by the potentiometric method using promising synthesized complexes. Recovery is about 100%. Relative standard deviation for promising complexes does not exceed 9%. Since the synthesized complexes have a color, they were used in the spectrophotometric method for correlation studies. In addition, the spectrophotometric method using the stable 2,2ʹ-diphenyl-1-picrylhydrazyl radical was chosen as a comparison method. It has been shown that spectrometry using both new complex compounds and the 2,2ʹ-diphenyl-1-picrylhydrazyl radical has limitations in the analysis of colored samples. Since food products are colored, this complicates the analysis by optical methods. Correlations between methods were established in cases of uncolored extracts. Thus, the developed potentiometric approach is not only simple and informative, but can also be used for a wider range of objects.

Graphical abstract

建立了测定整体抗氧化能力的电位法。抗氧化剂与铁与目标功能化2,2'-联吡啶衍生物的新配合物的反应被用作信号形成反应。该方法允许联合测定亲水性和亲脂性抗氧化剂，这在分析具有复杂成分的植物样品中尤为重要。合成了许多新的2,2'-联吡啶衍生物。研究表明，在2,2′-联吡啶结构中引入卤素可以提高其络合能力，特别是与Fe（III）的络合能力。通过在C5位置的芳基取代基的2,2′-联吡啶上引入三甘醇片段，提高了配合物在极性溶液中的溶解度。研究了Fe（II）和Fe（III）配合物的电化学行为。用伏安法测定了配合物的金属配体比和稳定性常数（条件稳定性常数取值范围为1∙108 ~ 5∙1010）。用电位法对不同溶解度的抗氧化剂和含不同亲水性抗氧化剂的谷物提取物进行了研究。回收率约为100%。有希望的配合物的相对标准偏差不超过9%。由于所合成的配合物具有颜色，因此用分光光度法进行相关性研究。此外，还选择了稳定的2,2'-二苯基-1-吡啶肼基自由基的分光光度法作为比较方法。研究表明，使用新的配合物和2,2'-二苯基-1-吡啶肼基自由基进行光谱分析在有色样品分析中存在局限性。由于食品是有色的，这使光学方法的分析变得复杂。在有色提取物的情况下，建立了方法之间的相关性。因此，所开发的电位法不仅简单且信息丰富，而且可用于更广泛的对象。

{"title":"New complex iron with various functionalized 2,2ʹ-bipyridine derivatives in evaluation of total lipophilic and hydrophilic antioxidant capacity by the potentiometry","authors":"Elena Gerasimova, Elena Salimgareeva, Evgeniya Yanybaeva, Yaroslav Shtaitz, Viktoriya Kirillova, Alexey Krinochkin, Dmitry Kopchuk, Grigory Zyryanov, Alla Ivanova","doi":"10.1007/s44211-025-00804-x","DOIUrl":"10.1007/s44211-025-00804-x","url":null,"abstract":"<div><p>The potentiometric approach for determining the integral antioxidant capacity was developed. The reaction of antioxidants with new complexes of the iron with target functionalized 2,2ʹ-bipyridine derivatives was used as a signal-forming reaction. The approach allows the joint determination of hydrophilic and lipophilic antioxidants, which is especially important in the analysis of plant samples with a complex composition. A number of new 2,2ʹ-bipyridine derivatives have been synthesized. It has been shown that the complexing ability, especially with Fe(III), is increased by introducing halogens into the structure of 2,2ʹ-bipyridine. The solubility of the complexes in polar solutions is increased by introducing the triethylene glycol fragment into the 2,2ʹ-bipyridine at the aryl substituent in the C5 position. The electrochemical behavior of the complexes with Fe(II) and Fe(III) was studied. The metal – ligand ratios and stability constants of the complexes were estimated by the voltammetric method (the values of the conditional stability constants ranged from 1∙10<sup>8</sup> to 5∙10<sup>10</sup>). Individual antioxidants with different solubilities and cereal extracts, containing antioxidants of different hydrophilicity, were studied by the potentiometric method using promising synthesized complexes. Recovery is about 100%. Relative standard deviation for promising complexes does not exceed 9%. Since the synthesized complexes have a color, they were used in the spectrophotometric method for correlation studies. In addition, the spectrophotometric method using the stable 2,2ʹ-diphenyl-1-picrylhydrazyl radical was chosen as a comparison method. It has been shown that spectrometry using both new complex compounds and the 2,2ʹ-diphenyl-1-picrylhydrazyl radical has limitations in the analysis of colored samples. Since food products are colored, this complicates the analysis by optical methods. Correlations between methods were established in cases of uncolored extracts. Thus, the developed potentiometric approach is not only simple and informative, but can also be used for a wider range of objects.</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":"1393 - 1405"},"PeriodicalIF":2.0,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144336246","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}

引用次数: 0

An immunoassay based on polyHRP signal amplification for HPV16/18 E6 RNA detection with anti-DNA-RNA hybrid antibody 基于多hrp信号扩增的抗dna -RNA杂交抗体检测HPV16/18 E6 RNA的免疫分析。

IF 2 4区化学 Q3 CHEMISTRY, ANALYTICAL

Analytical Sciences

Pub Date : 2025-06-18 DOI: 10.1007/s44211-025-00807-8

Mingxia Lin, Yikui Zou, Lian Yu, Huanxin Xiao, Weiguang Chen, Qianchen Xuan, Xiping Cui, Suqing Zhao

Human papillomavirus (HPV) types 16 and 18 are major causes of cervical cancer, with their E6 oncogenes serving as key biomarkers for early diagnosis. Traditional molecular detection methods, such as PCR, are commonly used but still have limitations, including false positives and complex procedures. To address these challenges, we developed an amplification-free sandwich direct enzyme-linked immunoassay (sELISA). This assay combined the S9.6 antibody’s specificity for DNA-RNA hybrids with streptavidin-polymeric horseradish peroxidase (SA-polyHRP) for signal enhancement. The SA-polyHRP direct sELISA achieved a detection limit of 1.03 pM (0.012 pg/µL), demonstrating 59.6-fold higher sensitivity than the indirect sELISA using SA-coated plates with HRP-labeled secondary antibody (monomeric HRP) for tracer. The integral evaluation of immunoassays containing specificity, affinity, and robustness was accomplished by assessing selectivity for nucleic acid structure, length, GC content variations, and subtypes, respectively. Additionally, the assay was successfully applied to artificial plasma samples, showing acceptable recovery rates (76–108%) at various dilutions and further validating its potential for clinical diagnostics. Overall, this assay using the SA-polyHRP-based direct sELISA provided a rapid, highly specific, and sensitive diagnostic tool for the detection of HPV-related cancers, which will offer significant improvements in diagnostic accuracy, screening, and monitoring.

Graphical abstract

人乳头瘤病毒（HPV） 16型和18型是宫颈癌的主要病因，其E6致癌基因是早期诊断的关键生物标志物。传统的分子检测方法，如PCR，是常用的，但仍然有局限性，包括假阳性和复杂的程序。为了解决这些挑战，我们开发了一种无扩增的三明治直接酶联免疫分析法（sELISA）。该检测将S9.6抗体对DNA-RNA杂交体的特异性与链亲和素聚合辣根过氧化物酶（SA-polyHRP）结合起来，以增强信号。SA-polyHRP直接sELISA的检出限为1.03 pM (0.012 pg/µL)，比采用HRP标记二抗（HRP单体）的sa包被板间接sELISA的灵敏度高59.6倍。通过分别评估核酸结构、长度、GC含量变化和亚型的选择性，对免疫测定法的特异性、亲和力和稳健性进行了综合评价。此外，该方法成功应用于人造血浆样品，在各种稀释度下显示出可接受的回收率（76-108%），并进一步验证了其临床诊断的潜力。总的来说，这项基于sa - polyhrp的直接sELISA检测为hpv相关癌症的检测提供了一种快速、高度特异性和敏感的诊断工具，将在诊断准确性、筛查和监测方面提供显著提高。

{"title":"An immunoassay based on polyHRP signal amplification for HPV16/18 E6 RNA detection with anti-DNA-RNA hybrid antibody","authors":"Mingxia Lin, Yikui Zou, Lian Yu, Huanxin Xiao, Weiguang Chen, Qianchen Xuan, Xiping Cui, Suqing Zhao","doi":"10.1007/s44211-025-00807-8","DOIUrl":"10.1007/s44211-025-00807-8","url":null,"abstract":"<div><p>Human papillomavirus (HPV) types 16 and 18 are major causes of cervical cancer, with their E6 oncogenes serving as key biomarkers for early diagnosis. Traditional molecular detection methods, such as PCR, are commonly used but still have limitations, including false positives and complex procedures. To address these challenges, we developed an amplification-free sandwich direct enzyme-linked immunoassay (sELISA). This assay combined the S9.6 antibody’s specificity for DNA-RNA hybrids with streptavidin-polymeric horseradish peroxidase (SA-polyHRP) for signal enhancement. The SA-polyHRP direct sELISA achieved a detection limit of 1.03 pM (0.012 pg/µL), demonstrating 59.6-fold higher sensitivity than the indirect sELISA using SA-coated plates with HRP-labeled secondary antibody (monomeric HRP) for tracer. The integral evaluation of immunoassays containing specificity, affinity, and robustness was accomplished by assessing selectivity for nucleic acid structure, length, GC content variations, and subtypes, respectively. Additionally, the assay was successfully applied to artificial plasma samples, showing acceptable recovery rates (76–108%) at various dilutions and further validating its potential for clinical diagnostics. Overall, this assay using the SA-polyHRP-based direct sELISA provided a rapid, highly specific, and sensitive diagnostic tool for the detection of HPV-related cancers, which will offer significant improvements in diagnostic accuracy, screening, and monitoring.</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 9","pages":"1461 - 1471"},"PeriodicalIF":2.0,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144324313","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}

引用次数: 0

Mechanism of interaction between gaseous atoms and graphite determined from the back edge of atomic absorption signal with graphite furnace atomic absorption spectrometry 用石墨炉原子吸收光谱法从原子吸收信号后缘测定气体原子与石墨相互作用机理。

IF 2 4区化学 Q3 CHEMISTRY, ANALYTICAL

Analytical Sciences

Pub Date : 2025-06-18 DOI: 10.1007/s44211-025-00809-6

Shoji Imai, Chisato Sasada, Yuhei Yamamoto

The energetics of interactions between gaseous atoms and pyorolytic graphite (PG) were investigated by the Gibbs free energy change (ΔG) determined from the back edge of atomic absorption (AA) signa. The Gibbs free energy was estimated by assuming an equilibrium state among the interactions between an analyte atom (M) and a PG surface. Because of its poor reactivity, lead was used as a standard to define a ΔG value of Zero to calculate the loss rate of a hypothetical M_(g) without interactions. The kinetic parameters for M were calculated using a diffusion loss model. The ratio of the experimental loss rate to the hypothetical loss rate was used to determine the equilibrium constant (K) for the interaction between M and the PG surface, from which ΔG was calculated. The slope of a linear relationship of ΔG vs. the activation energy (E_a) of atomization for individual atoms on the PG surface was consistent with that of ΔG vs. the binding energy of adatoms with graphene. It was proposed that the interaction between M_(g) and the PG surface was caused by the binding to sites of top-C for Au, C–C bridge for Ag and Pb, a hexagonal hole of sixfold sites within C-ring for Co, Fe and Ni, a pair of terminal-C on zigzag edge for Cr, top-subedge for Mn, and active sites in adjacent graphite layers controlling intercalation for Cu.

Graphical abstract

利用原子吸收（AA）信号后缘测定的吉布斯自由能变化（ΔG）研究了气态原子与热解石墨（PG）相互作用的能量学。通过假设分析物原子(M)与PG表面相互作用的平衡态来估计吉布斯自由能。由于铅的反应性较差，因此铅被用作定义ΔG值为零的标准，以计算假设的M(g)在没有相互作用的情况下的损失率。用扩散损失模型计算了M的动力学参数。利用实验损失率与假设损失率之比确定M与PG表面相互作用的平衡常数K，并由此计算ΔG。ΔG与PG表面单个原子的原子化活化能（Ea）的线性关系斜率与ΔG与石墨烯的结合能的线性关系斜率一致。提出了M(g)与PG表面的相互作用是由以下因素引起的：Au的顶部c位结合，Ag和Pb的C-C桥结合，Co、Fe和Ni的c环内六重位的六角形孔结合，Cr的锯齿状边缘的一对终端c结合，Mn的顶部亚壁结合，以及相邻石墨层中控制Cu嵌入的活性位点。

{"title":"Mechanism of interaction between gaseous atoms and graphite determined from the back edge of atomic absorption signal with graphite furnace atomic absorption spectrometry","authors":"Shoji Imai, Chisato Sasada, Yuhei Yamamoto","doi":"10.1007/s44211-025-00809-6","DOIUrl":"10.1007/s44211-025-00809-6","url":null,"abstract":"<div><p>The energetics of interactions between gaseous atoms and pyorolytic graphite (PG) were investigated by the Gibbs free energy change (<i>ΔG</i>) determined from the back edge of atomic absorption (AA) signa. The Gibbs free energy was estimated by assuming an equilibrium state among the interactions between an analyte atom (M) and a PG surface. Because of its poor reactivity, lead was used as a standard to define a <i>ΔG</i> value of Zero to calculate the loss rate of a hypothetical M<sub>(g)</sub> without interactions. The kinetic parameters for M were calculated using a diffusion loss model. The ratio of the experimental loss rate to the hypothetical loss rate was used to determine the equilibrium constant (<i>K</i>) for the interaction between M and the PG surface, from which <i>ΔG</i> was calculated. The slope of a linear relationship of <i>ΔG</i> vs. the activation energy (<i>E</i><sub>a</sub>) of atomization for individual atoms on the PG surface was consistent with that of <i>ΔG</i> vs. the binding energy of adatoms with graphene. It was proposed that the interaction between M<sub>(g)</sub> and the PG surface was caused by the binding to sites of top-C for Au, C–C bridge for Ag and Pb, a hexagonal hole of sixfold sites within C-ring for Co, Fe and Ni, a pair of terminal-C on zigzag edge for Cr, top-subedge for Mn, and active sites in adjacent graphite layers controlling intercalation for Cu.</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 9","pages":"1491 - 1499"},"PeriodicalIF":2.0,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144324314","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}

引用次数: 0

Analysis and quantification of tritium and other low-level radionuclides present in ALPS-treated water alps处理水中氚和其他低水平放射性核素的分析和定量。

IF 2 4区化学 Q3 CHEMISTRY, ANALYTICAL

Analytical Sciences

Pub Date : 2025-06-13 DOI: 10.1007/s44211-025-00803-y

Asako Shimada, Ko Hemmi, Saki Ohira, Yoshihisa Iida

Advanced liquid processing system (ALPS)-treated water was sampled from the K4-B tank group on March 24, 2022, in the presence of staff from the International Atomic Energy Agency (IAEA) and Tokyo Electric Power Company (TEPCO) Holdings, Inc. The Nuclear Safety Research Center (NSRC) of the Japan Atomic Energy Agency analyzed ten key radionuclides (³H, ¹⁴C, ⁶⁰Co, ⁹⁰Sr, ⁹⁹Tc, ¹⁰⁶Ru, ¹²⁵Sb, ¹²⁹I, ¹³⁴Cs, and ¹³⁷Cs) and three additional nuclides (³⁶Cl, ⁵⁵Fe, and ⁷⁹Se) in the ALPS-treated water as part of independent monitoring for the regulatory body. According to the obtained results, all radionuclide concentrations, except that for the ³H concentration, were ultralow and less than the standard values permitted for discharge. TEPCO’s analytical results were evaluated using the En number, which indicated satisfactory performance. In addition, reference values and ζ scores obtained via the IAEA’s interlaboratory comparisons were recalculated incorporating the NSRC’s results. All ζ scores for NSRC, IAEA, and TEPCO fell between − 2 and 2, demonstrating that the results are acceptable at a 95.4% confidence level.

Graphical abstract

2022年3月24日，在国际原子能机构（IAEA）和东京电力公司（TEPCO）控股公司的工作人员在场的情况下，从K4-B罐组取样了先进液体处理系统（ALPS）处理过的水。作为监管机构独立监测的一部分，日本原子能机构的核安全研究中心（NSRC）分析了alps处理水中的10种主要放射性核素（3H、14C、60Co、90Sr、99Tc、106Ru、125Sb、129I、134Cs和137Cs）和另外3种核素（36Cl、55Fe和79Se）。根据所得结果，除3H浓度外，所有放射性核素浓度均为超低，低于允许排放的标准值。对东京电力公司的分析结果进行了En数评价，结果令人满意。此外，通过原子能机构的实验室间比较获得的参考值和ζ分数被重新计算纳入NSRC的结果。NSRC， IAEA和TEPCO的所有ζ分数都在- 2到2之间，表明结果在95.4%的置信水平上是可以接受的。

{"title":"Analysis and quantification of tritium and other low-level radionuclides present in ALPS-treated water","authors":"Asako Shimada, Ko Hemmi, Saki Ohira, Yoshihisa Iida","doi":"10.1007/s44211-025-00803-y","DOIUrl":"10.1007/s44211-025-00803-y","url":null,"abstract":"<div><p>Advanced liquid processing system (ALPS)-treated water was sampled from the K4-B tank group on March 24, 2022, in the presence of staff from the International Atomic Energy Agency (IAEA) and Tokyo Electric Power Company (TEPCO) Holdings, Inc. The Nuclear Safety Research Center (NSRC) of the Japan Atomic Energy Agency analyzed ten key radionuclides (<sup>3</sup>H, <sup>14</sup>C, <sup>60</sup>Co, <sup>90</sup>Sr, <sup>99</sup>Tc, <sup>106</sup>Ru, <sup>125</sup>Sb, <sup>129</sup>I, <sup>134</sup>Cs, and <sup>137</sup>Cs) and three additional nuclides (<sup>36</sup>Cl, <sup>55</sup>Fe, and <sup>79</sup>Se) in the ALPS-treated water as part of independent monitoring for the regulatory body. According to the obtained results, all radionuclide concentrations, except that for the <sup>3</sup>H concentration, were ultralow and less than the standard values permitted for discharge. TEPCO’s analytical results were evaluated using the <i>En</i> number, which indicated satisfactory performance. In addition, reference values and ζ scores obtained via the IAEA’s interlaboratory comparisons were recalculated incorporating the NSRC’s results. All ζ scores for NSRC, IAEA, and TEPCO fell between − 2 and 2, demonstrating that the results are acceptable at a 95.4% confidence level.</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":"1383 - 1391"},"PeriodicalIF":2.0,"publicationDate":"2025-06-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144282017","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}

引用次数: 0

Nanofluidic devices for single-molecule analytical chemistry 用于单分子分析化学的纳米流体装置。

IF 2 4区化学 Q3 CHEMISTRY, ANALYTICAL

Analytical Sciences

Pub Date : 2025-06-12 DOI: 10.1007/s44211-025-00801-0

Qun Ma, Yan Xu

Single-molecule studies are increasingly critical across diverse scientific disciplines. While nanofluidics research has significantly advanced in the past decade, translating nanofluidic device fabrication into practical single-molecule analytical applications remains a significant challenge. This review explores the burgeoning field of single-molecule analytical chemistry utilizing nanofluidic devices. We delve into the fundamental mechanisms and technologies enabling single-molecule sampling, isolation, manipulation, detection as well as single-molecule analysis within well-defined nanofluidic channels, highlighting the unique advantages of ultrasmall confined spaces and resulting unusual effects of nanofluidic devices. Despite remarkable progress, critical challenges and promising opportunities abound in this emerging field. This review also discusses future directions for this promising area of single-molecule analytical chemistry based on nanofluidic devices.

Graphical abstract

单分子研究在不同的科学学科中越来越重要。虽然纳米流体研究在过去十年中取得了显著进展，但将纳米流体器件制造转化为实际的单分子分析应用仍然是一个重大挑战。本文综述了利用纳米流体器件的新兴单分子分析化学领域。我们深入研究了在定义良好的纳米流体通道内实现单分子采样、分离、操作、检测以及单分子分析的基本机制和技术，强调了超小密闭空间的独特优势以及纳米流体器件的不同寻常效果。尽管取得了显著进展，但在这一新兴领域，严峻的挑战和充满希望的机会比比皆是。本文还讨论了基于纳米流体器件的单分子分析化学的未来发展方向。

引用次数: 0