Analytical Methods最新文献

{"title":"Integrated serum metabolomics and machine learning for classification of <i>Datura stramonium</i> L. exposure using plant part-specific metabolic signatures.","authors":"Fei Gao, Bo Zou, Peng Zhao, Ge Song, Xiaojun Wu, Jing Chang, Xinxin Ren, Ruihua Wang, Ruiqin Yang, Yunfeng Zhang","doi":"10.1039/d6ay01330a","DOIUrl":"https://doi.org/10.1039/d6ay01330a","url":null,"abstract":"<p><p><i>Datura stramonium</i> L. (DS) poisoning remains a significant toxicological concern in clinical and forensic contexts. In forensic casework, leaf ingestion is mainly associated with accidental exposure, whereas seed ingestion is more frequently linked to suspected intentional poisoning. However, conventional toxicological analysis based on tropane alkaloids cannot distinguish between these exposure sources, limiting forensic interpretation. This study developed a serum metabolomics strategy integrating machine learning to viably discriminate between seed- and leaf-derived <i>Datura</i> exposure using metabolic signatures. Serum samples from DSS (seed-derived) and DSL (leaf-derived) exposure models were analyzed using UPLC-Orbitrap-MS-based untargeted metabolomics. Multivariate analysis revealed distinct metabolic profiles between DSS and DSL groups, involving alterations in alkaloids, phenylpropanoids, lipids, and organic acids. Later, a supervised machine learning framework was developed to classify exposure sources based on metabolic signatures. The optimized model achieved an area under the curve (AUC) of 0.90. Feature interpretation further identified key metabolites contributing to classification, enabling biological interpretation of forensic decision boundaries. Meanwhile, higher metabolites in machine learning can also reflect different pathological mechanisms, providing a mechanistic basis for exposure differentiation. These results demonstrate that the integration of serum metabolomics and machine learning enables accurate and interpretable forensic source attribution of Datura poisoning. The proposed framework extends traditional toxicological analysis from exposure confirmation to data-driven forensic reconstruction, offering a novel approach to high-resolution forensic toxicology in complex plant poisoning cases.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" ","pages":""},"PeriodicalIF":3.0,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149177964","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Long-term performance monitoring of a secondary electrospray ionisation high-resolution mass spectrometry platform using a vapor generator for routine quality control.","authors":"Albin Vadakkechira, Renato Zenobi, Daniel Pohl, Kathryn J Burton-Pimentel, Stamatios Giannoukos","doi":"10.1039/d6ay01843b","DOIUrl":"10.1039/d6ay01843b","url":null,"abstract":"<p><p>Secondary electrospray ionisation high-resolution mass spectrometry (SESI-HRMS) is a powerful, non-invasive tool for real-time breath analysis. However, instrumental drift, capillary degradation and other technical variations compromise clinical applications, especially for long-term studies, which require robust quality control (QC) methodologies. In this work, we present the use of an evaporation chamber-based reference gas system to monitor SESI-MS system performance over almost two years. Targeted QC measurements with deuterated butyric acid were recorded three times on each measurement day. Analytical stability was systematically quantified across both positive and negative ion modes. In a standalone continuous characterization, the reference gas generator delivered a stable signal over several hours. A Linear Mixed-Effects Model (LMM) was constructed to evaluate the influence of time-of-day on instrument performance. This revealed significant effects: positive mode signal intensity progressively increased throughout the day, whereas for negative mode, an initial drop in signal intensity and subsequent stabilisation was observed. Furthermore, the longitudinal QC framework successfully tracked capillary performance over time, providing objective performance metrics to retrospectively evaluate the impact of targeted hardware maintenance on system performance. The implementation of a structured QC protocol provides a valid methodology for long-term SESI-HRMS performance monitoring, ensuring data integrity and supporting the translation of SESI-HRMS into large-scale clinical applications.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" ","pages":""},"PeriodicalIF":3.0,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13662781/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149177966","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Dual-plane n-DEP gating for active retention and controlled ejection of colloidal particles in nanowell arrays.","authors":"Radin Tahvildari, Bing-Yang Shih, Senne Fransen, Kruti Trivedi, Farrukh Yasin, Iuliana Rachita, Geert Van den Bosch, Willem Van Roy, Maarten Rosmeulen","doi":"10.1039/d6ay02205g","DOIUrl":"https://doi.org/10.1039/d6ay02205g","url":null,"abstract":"<p><p>We introduce a dual-plane, independently addressable electrode architecture integrated with nanowell arrays for frequency-tuned dielectrophoretic control of 200 nm particles. Unlike conventional single-plane systems, vertical field decoupling enables array-wide p-DEP capture, n-DEP refinement and stable retention, and controlled ejection without auxiliary flow-based or mechanical confinement, establishing reversible on-chip particle manipulation.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" ","pages":""},"PeriodicalIF":3.0,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149177968","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Surface-engineered cationic silver nanoparticles as a selective colorimetric sensor for mercury(II) detection in environmental water.","authors":"Aseya Akbar, Mansour Alharthi, Eman Alghamdi, Abeer Beagan, Abdullah Alswieleh","doi":"10.1039/d6ay01561a","DOIUrl":"https://doi.org/10.1039/d6ay01561a","url":null,"abstract":"<p><p>Synthesis of silver (Ag) nanoparticles was done using chemical reduction of AgNO₃ in ice cold NaBH₄, and functionalization of the surface was done using cysteamine <i>via</i> Ag-S thiolate bonding at pH 9.0. Quaternization of the surface was achieved <i>via</i> exhaustive <i>N</i>-methylation of the terminal amine group at the surface using iodomethane (CH₃I). This converts the surface -NH₂ groups stepwise into permanently positively charged quaternary ammonium moieties (-N⁺(CH₃)₃). The resulting surface-modified nanoparticles (AgNPs-QCy) were comprehensively characterized using UV-visible spectroscopy, Fourier Transform Infrared (FTIR) spectroscopy, Transmission Electron Microscopy (TEM), Scanning Electron Microscopy coupled with Energy-Dispersive X-ray spectroscopy (SEM-EDX), Dynamic Light Scattering (DLS), and zeta potential measurements. Surface quaternization was confirmed by the red shift in the Localized Surface Plasmon Resonance (LSPR) band from ∼385 nm to 393 nm, attributed to changes in the local dielectric environment at the nanoparticle surface following quaternization, and accompanied by a decrease in the hydrodynamic diameter from 314.2 nm to 149.9 nm, consistent with improved colloidal uniformity upon surface charge stabilization. Zeta potential measurements confirmed the pH-independent positive surface charge, thus confirming the stability of the permanent quaternary ammonium group over a broad range of pH. AgNPs-QCy exhibited high selectivity toward Hg²⁺ ions in the presence of several competing metal ions, including Fe²⁺, Zn²⁺, Cd²⁺, Mn²⁺, Pb²⁺, Al³⁺, Co²⁺, Ni²⁺, Cu²⁺, As⁵⁺, Cr³⁺, and La³⁺. The selective response toward Hg²⁺ is attributed to its strong interaction with the functionalized AgNP surface, leading to pronounced changes in nanoparticle interfacial interactions and plasmonic properties. These changes result in aggregation and suppression of the LSPR signal, producing a distinct colorimetric response that can be visually observed. AgNPs-QCy-based sensors exhibit a limit of detection (LOD) of 50.38 nM and limit of quantification (LOQ) of 167.9 nM. The sensing platform was successfully validated in real water matrices including lake, tap, and underground water collected from the Riyadh region (Kingdom of Saudi Arabia), confirming its practical applicability for environmental Hg²⁺ monitoring, and supporting its potential as a rapid, low-cost, single-use screening tool for Hg²⁺ detection.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" ","pages":""},"PeriodicalIF":3.0,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149177962","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Immobilization of thrombin on magnetic layered double hydroxide ZIF-8 composite materials and establishment of a thrombin inhibitor screening system.","authors":"Weiqing Liu, Yiting Shen, Yuan Xue, Huifeng Xu, Zhucan Lin, Lishuang Yu","doi":"10.1039/d6ay01483f","DOIUrl":"https://doi.org/10.1039/d6ay01483f","url":null,"abstract":"<p><p>In this study, magnetic Fe₃O₄@ZnCr-LDH/ZIF-8 composites were fabricated by co-precipitation and <i>in situ</i> growth, combining the merits of LDHs and ZIF-8 to address Fe₃O₄ particle aggregation and limited enzyme loading capacity. Thrombin was efficiently immobilized within this material for rapid thrombin inhibitors screening. The composites were characterized by TEM, FTIR and other techniques, verifying successful synthesis with good paramagnetic property and hierarchical pores. Compared to free enzymes, the immobilized enzyme had better temperature and pH tolerance, retaining good activity after six cycles. Two potential inhibitors, cryptotanshinone and tanshinone I, were isolated from <i>Salvia miltiorrhiza via</i> combining immobilized enzyme with LC-MS. Molecular docking validated that both compounds bound to thrombin through hydrogen bonds and hydrophobic interactions, and cryptotanshinone exhibited a more favorable binding energy (-7.41 kcal mol^-1) than tanshinone I (-6.52 kcal mol^-1). This strategy provides a new pathway to rapidly screen bioactive natural compounds using functional magnetic nanomaterials.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" ","pages":""},"PeriodicalIF":3.0,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149177980","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Development and performance evaluation of extraction and purification procedures for halogenated DBPs in soil and lettuce.","authors":"Mathieu Dumas, Bruno Coulomb, Carine Demelas, Laurent Vassalo, Jean-Luc Boudenne","doi":"10.1039/d6ay01611a","DOIUrl":"https://doi.org/10.1039/d6ay01611a","url":null,"abstract":"<p><p>Reuse of treated wastewater in agriculture exposes soils and edible crops to halogenated disinfection byproducts (DBPs), toxic compounds formed during chlorination. While DBPs are well characterized in water, analytical methods for soil and plant matrices remain scarce, limiting risk assessment for food safety and groundwater contamination. This gap hinders the implementation of EU Regulation 2020/741 on safe wastewater reuse. We developed and evaluated two solid-liquid extraction methods for 36 DBPs across 8 families (THMs, HANs, HNMs, HKs, HALs, HAcAms, HAs, and HAAs) in artificial/natural soils and lettuce, combined with pass-through SPE clean-up (ENVI-Carb for lettuce, Florisil for soils), to reduce matrix effects and enhance system stability and sensitivity. Extraction parameters (pH, ionic strength, and agitation/sonication time) were optimized using GC-ECD. HAAs were esterified prior to clean-up to avoid retention. Recovery rates ranged from 54.3-117.4% (29/36 analytes >80% for soil, 28/36 for lettuce), with method detection limits 14 times lower than prior work on lettuce (0.06-11.69 ng g^-1 dry soil or fresh lettuce). The clean-up step was optimized using both GC-ECD (quantitative) and GC-MS (qualitative). Matrix effects were minimized, improving system robustness using the SPE approach. Stability tests revealed rapid degradation of HNMs, HALs, HANs and HKs in moist soils (<24 h) with halohydrins, HAcAms and HAAs identified as degradation products. This work provides sensitive, reliable tools for monitoring halogenated DBPs in agricultural soil/plant systems, supporting compliance with wastewater reuse regulations and addressing critical gaps in food safety risk assessment.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" ","pages":""},"PeriodicalIF":3.0,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149177997","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Combined LA-ICP-MS with empirical coefficient correction and Bi fire assay for the determination of ultra-trace Pt, Pd, and Au in geochemical samples using a ¹⁹⁴Pt isotope spike as the internal standard.","authors":"Xiaorui Guo, Yan Liu, Wenshan Ni, Tiantian Wang, Xiangju Mao, Chen Wang","doi":"10.1039/d6ay01575a","DOIUrl":"https://doi.org/10.1039/d6ay01575a","url":null,"abstract":"<p><p>In this work, a novel and environmentally friendly method based on bismuth fire assay (Bi-FA) combined with laser ablation ICP-MS (LA-ICP-MS) was established for the determination of ultra-trace Pt, Pd, and Au in geochemical samples, using a Pt isotope spike (¹⁹⁴Pt) as the internal standard. Due to the low toxicity and low, stable blank values of the Bi₂O₃ collector, Bi-FA could be directly employed for the pre-concentration of Pt, Pd, and Au prior to analysis. The Ag slices prepared by annealing and tableting were analyzed at multiple points by LA-ICP-MS. This approach offered advantages including rapid analysis, good measurement stability, and the elimination of polyatomic ion interference and dilution effects associated with solution-based analysis. As the internal standard, the Pt isotope spike was thoroughly mixed with the target elements (Pt, Pd, and Au in the sample) in each Ag prill, and its distribution was consistent with that of the target elements. This method resolved the issue of uneven distributions of Pt, Pd, and Au in the Ag slices, thereby enabling internal standard correction for LA-ICP-MS by calculating the intensity of ¹⁹⁴Pt from the Pt isotope spike. In addition, optimization experiments were conducted for key parameters, including laser frequency, energy density, ablation spot diameter, and ICP-MS dwell time. The Ag slices prepared from certified reference materials (CRMs) were used as the calibration standards. The standard samples had the same matrix as the real samples, which reduced laser ablation fractionation effects, minimized analytical errors, and improved accuracy. The standard curves were plotted by the empirical coefficient method and showed excellent linearity with correlation coefficients (<i>R</i>²) of 0.9999 (Pt), 0.9998 (Pd), and 0.9995 (Au). The limits of detection (LODs) of the method were 0.066 (Pt), 0.052 (Pd), and 0.090 (Au) ng g^-1. The proposed method was validated by determining the Pt, Pd, and Au in CRMs, showing excellent agreement with certified values. When applied to geochemical samples, the results were consistent with those obtained by lead fire assay combined with graphite furnace atomic absorption spectrometry (Pb-FA-GF-AAS). The recoveries were 2.5-107.8% (Pt), 91.4-108.0% (Pd), and 91.0-109.2% (Au), demonstrating the good accuracy of the proposed method.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" ","pages":""},"PeriodicalIF":3.0,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149177999","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nanomaterial-assisted recycling and upcycling of polyurethane: present status, challenges, and future perspectives.","authors":"Sakshi Shukla, Darshan Sharma, Rakesh Mani Mishra","doi":"10.1039/d6ay00977h","DOIUrl":"https://doi.org/10.1039/d6ay00977h","url":null,"abstract":"<p><p>Polyurethane (PU) is one of the most versatile polymers used in everyday life. But PU waste management is a major concern for the scientific community and regulatory authorities. The thermoset architecture of PUs makes degradation and recycling/upcycling difficult. This review provides insights into PU, emphasizing its structural chemistry and wide industrial applicability. The global situation highlights the industrial importance of PUs. Using nanomaterial-based catalysts could improve depolymerization and resource recovery. The paper points out future research areas in PU degradation and suggests ways to encourage innovation and deepen knowledge in the PU waste field.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" ","pages":""},"PeriodicalIF":3.0,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149177946","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"One-pot synthesized CoFe-PBA nanocubes with intrinsic oxidase-like activity enabling colorimetric detection of alkaline phosphatase.","authors":"Chenying Liu, Wei Huang, Keke Song, Yuxiang Ma, Jitao Yang, Qian Zhou","doi":"10.1039/d6ay01607c","DOIUrl":"https://doi.org/10.1039/d6ay01607c","url":null,"abstract":"<p><p>Alkaline phosphatase (ALP) is an essential biomarker for clinical diagnosis and food safety monitoring, and the development of facile, low-cost, and sensitive ALP detection strategies is of great significance. Herein, uniform cobalt-based Prussian blue analogue (CoFe-PBA) nanocubes were successfully synthesized <i>via</i> a simple one-pot coprecipitation method. The prepared CoFe-PBA possesses intrinsic oxidase-like catalytic activity originating from mixed-valence Co²⁺/Co³⁺ and Fe²⁺/Fe³⁺ active sites, which can activate dissolved oxygen to generate superoxide anion radicals (O₂˙^-) for substrate oxidation. Based on this catalytic characteristic, a straightforward colorimetric sensing platform was constructed for ALP detection. The sensing strategy relies on the ALP-triggered hydrolysis of L-ascorbic acid 2-phosphate trisodium salt (AAP) to produce ascorbic acid (AA), which inhibits the 3,3',5,5'-tetramethylbenzidine (TMB) chromogenic reaction and induces dose-dependent absorbance attenuation. Under optimized conditions, the proposed sensor exhibits good linear correlation, high sensitivity, acceptable selectivity and anti-interference capability. Furthermore, spike-and-recovery assays in 50-fold diluted fetal bovine serum demonstrate the potential of the platform for ALP analysis in complex biological matrices. This work provides a simple, low-cost and efficient colorimetric strategy for ALP bioassay, which holds promising potential for clinical biochemical analysis and food safety monitoring.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" ","pages":""},"PeriodicalIF":3.0,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149178017","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"An AuNPs/CNT electrochemical aptasensor for accurate cortisol level discrimination assisted by machine learning.","authors":"Tianyang Guo, Huxin Lei, Jiaxin Chen, Jinyu Bai, Xin Peng, Lu Zhang, Junrui Zhang","doi":"10.1039/d6ay01856d","DOIUrl":"https://doi.org/10.1039/d6ay01856d","url":null,"abstract":"<p><p>Cortisol levels provide valuable information regarding physiological stress and abnormalities associated with endocrine and mental health disorders. In this study, an AuNPs/CNT-modified electrochemical aptasensor integrated with machine learning was developed for sensitive cortisol detection and accurate discrimination of cortisol levels. A porous CNT network supported a large specific surface area with high conductivity, and density functional theory (DFT) calculations revealed the AuNPs modified the electronic structures of CNTs and further accelerated the charge transfer efficiency. Once cortisol specifically binds to the aptamer, target-triggered conformational rearrangement could destabilize the aptamer/cDNA duplex and release the aptamer from the electrode surface. The reduced surface nucleic acid density alleviated steric and electrostatic hindrance for the diffusion of the [Fe(CN)₆]^3-/4- probe, which resulted in an accelerated interfacial electron transfer and yielded an enhanced electrochemical signal. The proposed cortisol aptasensor exhibited a good linear relationship between the current variation and the logarithm of cortisol concentration in the range of 10-5000 nM, with a limit of detection of 1.61 nM. Simultaneously, supervised machine learning was applied to classify cortisol concentrations with low, normal, and high levels, thus providing a promising strategy for intelligent stress assessment.</p>","PeriodicalId":64,"journal":{"name":"Analytical Methods","volume":" ","pages":""},"PeriodicalIF":3.0,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149177930","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}