{"title":"Decoupling Variable Capacitance and Diffusive Components of Active Solid–Liquid Interfaces with Flex Points","authors":"Liam Deehan, Ajeet Kumar Kaushik, Ganga Ram Chaudhary, Pagona Papakonstantinou, Nikhil Bhalla","doi":"10.1021/acsmeasuresciau.4c00057","DOIUrl":"https://doi.org/10.1021/acsmeasuresciau.4c00057","url":null,"abstract":"Understanding the current transport characteristics of electrode interfaces is essential for optimizing device performance across a wide range of applications including bio-/chemical sensing and energy storage sectors. Cyclic voltammetry (CV) is a popular method for studying interfacial properties, particularly those involving redox systems. However, it remains challenging to differentiate between electron movements that contribute to capacitive and diffusive behaviors. In this study, we introduce a technique called flex point analysis, which uses a single differentiation step to separate capacitive and diffusive electron movements at the electrode interface during a redox reaction. Our results show that the variable capacitance at the electrode surface exhibited both positive and negative values on the order of 10<sup>–6</sup> (micro) Farad. This approach provides a clearer understanding of interfacial electron dynamics, enhancing the interpretation of CV data and potentially improving the design and optimization of related materials and devices.","PeriodicalId":29800,"journal":{"name":"ACS Measurement Science Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142194493","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Measurement Science AuPub Date : 2024-08-29DOI: 10.1021/acsmeasuresciau.4c0005710.1021/acsmeasuresciau.4c00057
Liam Deehan, Ajeet Kumar Kaushik, Ganga Ram Chaudhary, Pagona Papakonstantinou and Nikhil Bhalla*,
{"title":"Decoupling Variable Capacitance and Diffusive Components of Active Solid–Liquid Interfaces with Flex Points","authors":"Liam Deehan, Ajeet Kumar Kaushik, Ganga Ram Chaudhary, Pagona Papakonstantinou and Nikhil Bhalla*, ","doi":"10.1021/acsmeasuresciau.4c0005710.1021/acsmeasuresciau.4c00057","DOIUrl":"https://doi.org/10.1021/acsmeasuresciau.4c00057https://doi.org/10.1021/acsmeasuresciau.4c00057","url":null,"abstract":"<p >Understanding the current transport characteristics of electrode interfaces is essential for optimizing device performance across a wide range of applications including bio-/chemical sensing and energy storage sectors. Cyclic voltammetry (CV) is a popular method for studying interfacial properties, particularly those involving redox systems. However, it remains challenging to differentiate between electron movements that contribute to capacitive and diffusive behaviors. In this study, we introduce a technique called flex point analysis, which uses a single differentiation step to separate capacitive and diffusive electron movements at the electrode interface during a redox reaction. Our results show that the variable capacitance at the electrode surface exhibited both positive and negative values on the order of 10<sup>–6</sup> (micro) Farad. This approach provides a clearer understanding of interfacial electron dynamics, enhancing the interpretation of CV data and potentially improving the design and optimization of related materials and devices.</p>","PeriodicalId":29800,"journal":{"name":"ACS Measurement Science Au","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmeasuresciau.4c00057","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142436876","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Laíse Aparecida Fonseca Dinali, Anny Talita Maria da Silva, Keyller Bastos Borges
{"title":"Silver Core Coated with Molecularly Imprinted Polymer as Adsorbent in Pipet-Tip Solid Phase Extraction for Neonicotinoids Determination from Coconut Water","authors":"Laíse Aparecida Fonseca Dinali, Anny Talita Maria da Silva, Keyller Bastos Borges","doi":"10.1021/acsmeasuresciau.4c00036","DOIUrl":"https://doi.org/10.1021/acsmeasuresciau.4c00036","url":null,"abstract":"In this work, we report an innovative adsorbent named Ag-MPS@MIP that has a core@shell structure, i.e., silver nanoparticles modified with 3-methacryloxypropyltrimethoxysilane as the core and molecularly imprinted polymer based on methacrylic acid as its shell. Thiamethoxam, imidacloprid, and acetamiprid were extracted from coconut water samples using Ag-MPS@MIP in pipet-tip solid phase, prior to high-performance liquid chromatography analysis. The separation was carried out on isocratic mode using a mobile phase consisting of C18 column (Phenomenex, 150 mm × 4.6 mm, 5 μm), ultrapure water acidified with 0.3% phosphoric acid:acetonitrile (78:22, v/v), flow rate at 1.0 mL min<sup>–1</sup>, injection volume of 10 μL, temperature of 25 °C, and wavelength at 260 nm. The adsorbent and precursor materials were properly characterized by different instrumental techniques. The main factors affecting the recovery of analytes from coconut water samples by pipet-tip solid phase were optimized, such as sample volume (250 μL), sample pH (pH = 5.0), ionic strength (1%, m/v), washing solvent (300 μL ultrapure water), volume and type of eluent (500 μL methanol), amount of adsorbent (15 mg), cycle of percolation–dispensing (1×), and reuse (5×). Thereby, the neonicotinoids presented extraction recoveries between 82.80 and 96.36%, enrichment factor of 5, linearity ranged from 15 to 4000 ng mL<sup>–1</sup>, correlation coefficient (<i>r</i>) > 0.99, limit of detection of 5 ng mL<sup>–1</sup>, satisfactory selectivity, stability, and proper precision (RSD%: 0.52–9.64%) and accuracy (RE%: −5.19–6.45%). The method was successfully applied to real samples of coconut water.","PeriodicalId":29800,"journal":{"name":"ACS Measurement Science Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142194491","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Measurement Science AuPub Date : 2024-08-28DOI: 10.1021/acsmeasuresciau.4c0003610.1021/acsmeasuresciau.4c00036
Laíse Aparecida Fonseca Dinali, Anny Talita Maria da Silva and Keyller Bastos Borges*,
{"title":"Silver Core Coated with Molecularly Imprinted Polymer as Adsorbent in Pipet-Tip Solid Phase Extraction for Neonicotinoids Determination from Coconut Water","authors":"Laíse Aparecida Fonseca Dinali, Anny Talita Maria da Silva and Keyller Bastos Borges*, ","doi":"10.1021/acsmeasuresciau.4c0003610.1021/acsmeasuresciau.4c00036","DOIUrl":"https://doi.org/10.1021/acsmeasuresciau.4c00036https://doi.org/10.1021/acsmeasuresciau.4c00036","url":null,"abstract":"<p >In this work, we report an innovative adsorbent named Ag-MPS@MIP that has a core@shell structure, i.e., silver nanoparticles modified with 3-methacryloxypropyltrimethoxysilane as the core and molecularly imprinted polymer based on methacrylic acid as its shell. Thiamethoxam, imidacloprid, and acetamiprid were extracted from coconut water samples using Ag-MPS@MIP in pipet-tip solid phase, prior to high-performance liquid chromatography analysis. The separation was carried out on isocratic mode using a mobile phase consisting of C18 column (Phenomenex, 150 mm × 4.6 mm, 5 μm), ultrapure water acidified with 0.3% phosphoric acid:acetonitrile (78:22, v/v), flow rate at 1.0 mL min<sup>–1</sup>, injection volume of 10 μL, temperature of 25 °C, and wavelength at 260 nm. The adsorbent and precursor materials were properly characterized by different instrumental techniques. The main factors affecting the recovery of analytes from coconut water samples by pipet-tip solid phase were optimized, such as sample volume (250 μL), sample pH (pH = 5.0), ionic strength (1%, m/v), washing solvent (300 μL ultrapure water), volume and type of eluent (500 μL methanol), amount of adsorbent (15 mg), cycle of percolation–dispensing (1×), and reuse (5×). Thereby, the neonicotinoids presented extraction recoveries between 82.80 and 96.36%, enrichment factor of 5, linearity ranged from 15 to 4000 ng mL<sup>–1</sup>, correlation coefficient (<i>r</i>) > 0.99, limit of detection of 5 ng mL<sup>–1</sup>, satisfactory selectivity, stability, and proper precision (RSD%: 0.52–9.64%) and accuracy (RE%: −5.19–6.45%). The method was successfully applied to real samples of coconut water.</p>","PeriodicalId":29800,"journal":{"name":"ACS Measurement Science Au","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmeasuresciau.4c00036","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142436863","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mushfeqa Iqfath, Syeda Nazifa Wali, Sara Amer, Emerson Hernly, Julia Laskin
{"title":"Nanospray Desorption Electrospray Ionization Mass Spectrometry Imaging (nano-DESI MSI): A Tutorial Review","authors":"Mushfeqa Iqfath, Syeda Nazifa Wali, Sara Amer, Emerson Hernly, Julia Laskin","doi":"10.1021/acsmeasuresciau.4c00028","DOIUrl":"https://doi.org/10.1021/acsmeasuresciau.4c00028","url":null,"abstract":"Nanospray desorption electrospray ionization (nano-DESI) is a liquid-based ambient mass spectrometry imaging (MSI) technique that enables visualization of analyte distributions in biological samples down to cellular-level spatial resolution. Since its inception, significant advancements have been made to the nano-DESI experimental platform to facilitate molecular imaging with high throughput, deep molecular coverage, and spatial resolution better than 10 μm. The molecular selectivity of nano-DESI MSI has been enhanced using new data acquisition strategies, the development of separation and online derivatization approaches for isobar separation and isomer-selective imaging, and the optimization of the working solvent composition to improve analyte extraction and ionization efficiency. Furthermore, nano-DESI MSI research has underscored the importance of matrix effects and established normalization methods for accurately measuring concentration gradients in complex biological samples. This tutorial offers a comprehensive guide to nano-DESI experiments, detailing fundamental principles and data acquisition and processing methods and discussing essential operational parameters.","PeriodicalId":29800,"journal":{"name":"ACS Measurement Science Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142194492","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Measurement Science AuPub Date : 2024-08-21DOI: 10.1021/acsmeasuresciau.4c0002810.1021/acsmeasuresciau.4c00028
Mushfeqa Iqfath, Syeda Nazifa Wali, Sara Amer, Emerson Hernly and Julia Laskin*,
{"title":"Nanospray Desorption Electrospray Ionization Mass Spectrometry Imaging (nano-DESI MSI): A Tutorial Review","authors":"Mushfeqa Iqfath, Syeda Nazifa Wali, Sara Amer, Emerson Hernly and Julia Laskin*, ","doi":"10.1021/acsmeasuresciau.4c0002810.1021/acsmeasuresciau.4c00028","DOIUrl":"https://doi.org/10.1021/acsmeasuresciau.4c00028https://doi.org/10.1021/acsmeasuresciau.4c00028","url":null,"abstract":"<p >Nanospray desorption electrospray ionization (nano-DESI) is a liquid-based ambient mass spectrometry imaging (MSI) technique that enables visualization of analyte distributions in biological samples down to cellular-level spatial resolution. Since its inception, significant advancements have been made to the nano-DESI experimental platform to facilitate molecular imaging with high throughput, deep molecular coverage, and spatial resolution better than 10 μm. The molecular selectivity of nano-DESI MSI has been enhanced using new data acquisition strategies, the development of separation and online derivatization approaches for isobar separation and isomer-selective imaging, and the optimization of the working solvent composition to improve analyte extraction and ionization efficiency. Furthermore, nano-DESI MSI research has underscored the importance of matrix effects and established normalization methods for accurately measuring concentration gradients in complex biological samples. This tutorial offers a comprehensive guide to nano-DESI experiments, detailing fundamental principles and data acquisition and processing methods and discussing essential operational parameters.</p>","PeriodicalId":29800,"journal":{"name":"ACS Measurement Science Au","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmeasuresciau.4c00028","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142436886","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Achiral Plasmonic Antennas Enhance Differential Absorption To Increase Preferential Detection of Chiral Single Molecules","authors":"Saaj Chattopadhyay, Julie S. Biteen","doi":"10.1021/acsmeasuresciau.4c00026","DOIUrl":"https://doi.org/10.1021/acsmeasuresciau.4c00026","url":null,"abstract":"Plasmonic antennas increase the photon flux in their vicinity, which can lead to plasmon-enhanced fluorescence for molecules near these nanostructures. Here, we combine plasmon-coupled fluorescence and fluorescence-detected circular dichroism to build a specific and sensitive detection strategy for chiral single molecules. Electromagnetic simulations indicate that a two-dimensional gold nanoparticle dimer antenna enhances the electric field and optical chirality of a plane wave in its near field. Furthermore, this optical chirality enhancement can be tuned based on the polarization of the incident electric field, such that enhancing the optical chirality via these antennas will increase the differential absorption of parity-inverted fields. We measured the fluorescence from single molecules of chiral absorbers─Cy5 J-dimers assembled in double-stranded DNA backbones─and achieved increased detectability of these right-handed molecules near achiral gold nanoparticle dimer antennas under right circularly polarized illumination. This strategy offers a new approach to distinguishing weakly fluorescent enantiomers.","PeriodicalId":29800,"journal":{"name":"ACS Measurement Science Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141931243","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Measurement Science AuPub Date : 2024-08-06DOI: 10.1021/acsmeasuresciau.4c0002110.1021/acsmeasuresciau.4c00021
Ahmed Choukri Abdullah, Erfan Ahmadinejad and Savas Tasoglu*,
{"title":"Optimizing Solid Microneedle Design: A Comprehensive ML-Augmented DOE Approach","authors":"Ahmed Choukri Abdullah, Erfan Ahmadinejad and Savas Tasoglu*, ","doi":"10.1021/acsmeasuresciau.4c0002110.1021/acsmeasuresciau.4c00021","DOIUrl":"https://doi.org/10.1021/acsmeasuresciau.4c00021https://doi.org/10.1021/acsmeasuresciau.4c00021","url":null,"abstract":"<p >Microneedles (MNs), that is, a matrix of micrometer-scale needles, have diverse applications in drug delivery, skincare therapy, and health monitoring. MNs offer a minimally invasive alternative to hypodermic needles, characterized by rapid and painless procedures, cost-effective fabrication methods, and reduced tissue damage. This study explores four MN designs, cone-shaped, tapered cone-shaped, pyramidal with a square base, and pyramidal with a triangular-shaped base, and their optimization based on predefined criteria. The workflow encompasses three loading conditions: compressive load during insertion, critical buckling load, and bending loading resulting from incorrect insertion. Geometric parameters such as base radius/width, tip radius/width, height, and tapered angle tip influence the output criteria, namely, total deformation, critical buckling loads, factor of safety (FOS), and bending stress. The comprehensive framework employing a design of experiment approach within the ANSYS workbench toolbox establishes a mathematical model and a response surface fitting model. The resulting regression model, sensitivity chart, and response curve are used to create a multiobjective optimization problem that helps achieve an optimized MN geometrical design across the introduced four shapes, integrating machine learning (ML) techniques. This study contributes valuable insights into a potential ML-augmented optimization framework for MNs via needle designs to stay durable for various physiologically relevant conditions.</p>","PeriodicalId":29800,"journal":{"name":"ACS Measurement Science Au","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmeasuresciau.4c00021","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142436718","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Measurement Science AuPub Date : 2024-08-06DOI: 10.1021/acsmeasuresciau.4c0002610.1021/acsmeasuresciau.4c00026
Saaj Chattopadhyay, and , Julie S. Biteen*,
{"title":"Achiral Plasmonic Antennas Enhance Differential Absorption To Increase Preferential Detection of Chiral Single Molecules","authors":"Saaj Chattopadhyay, and , Julie S. Biteen*, ","doi":"10.1021/acsmeasuresciau.4c0002610.1021/acsmeasuresciau.4c00026","DOIUrl":"https://doi.org/10.1021/acsmeasuresciau.4c00026https://doi.org/10.1021/acsmeasuresciau.4c00026","url":null,"abstract":"<p >Plasmonic antennas increase the photon flux in their vicinity, which can lead to plasmon-enhanced fluorescence for molecules near these nanostructures. Here, we combine plasmon-coupled fluorescence and fluorescence-detected circular dichroism to build a specific and sensitive detection strategy for chiral single molecules. Electromagnetic simulations indicate that a two-dimensional gold nanoparticle dimer antenna enhances the electric field and optical chirality of a plane wave in its near field. Furthermore, this optical chirality enhancement can be tuned based on the polarization of the incident electric field, such that enhancing the optical chirality via these antennas will increase the differential absorption of parity-inverted fields. We measured the fluorescence from single molecules of chiral absorbers─Cy5 J-dimers assembled in double-stranded DNA backbones─and achieved increased detectability of these right-handed molecules near achiral gold nanoparticle dimer antennas under right circularly polarized illumination. This strategy offers a new approach to distinguishing weakly fluorescent enantiomers.</p>","PeriodicalId":29800,"journal":{"name":"ACS Measurement Science Au","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmeasuresciau.4c00026","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142436717","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ahmed Choukri Abdullah, Erfan Ahmadinejad, Savas Tasoglu
{"title":"Optimizing Solid Microneedle Design: A Comprehensive ML-Augmented DOE Approach","authors":"Ahmed Choukri Abdullah, Erfan Ahmadinejad, Savas Tasoglu","doi":"10.1021/acsmeasuresciau.4c00021","DOIUrl":"https://doi.org/10.1021/acsmeasuresciau.4c00021","url":null,"abstract":"Microneedles (MNs), that is, a matrix of micrometer-scale needles, have diverse applications in drug delivery, skincare therapy, and health monitoring. MNs offer a minimally invasive alternative to hypodermic needles, characterized by rapid and painless procedures, cost-effective fabrication methods, and reduced tissue damage. This study explores four MN designs, cone-shaped, tapered cone-shaped, pyramidal with a square base, and pyramidal with a triangular-shaped base, and their optimization based on predefined criteria. The workflow encompasses three loading conditions: compressive load during insertion, critical buckling load, and bending loading resulting from incorrect insertion. Geometric parameters such as base radius/width, tip radius/width, height, and tapered angle tip influence the output criteria, namely, total deformation, critical buckling loads, factor of safety (FOS), and bending stress. The comprehensive framework employing a design of experiment approach within the ANSYS workbench toolbox establishes a mathematical model and a response surface fitting model. The resulting regression model, sensitivity chart, and response curve are used to create a multiobjective optimization problem that helps achieve an optimized MN geometrical design across the introduced four shapes, integrating machine learning (ML) techniques. This study contributes valuable insights into a potential ML-augmented optimization framework for MNs via needle designs to stay durable for various physiologically relevant conditions.","PeriodicalId":29800,"journal":{"name":"ACS Measurement Science Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141931242","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}