{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,29]],"date-time":"2026-09-29T08:18:41Z","timestamp":1790669921846,"version":"4.1.0"},"reference-count":33,"publisher":"American Chemical Society (ACS)","issue":"10","license":[{"start":{"date-parts":[[2018,5,15]],"date-time":"2018-05-15T00:00:00Z","timestamp":1526342400000},"content-version":"vor","delay-in-days":18,"URL":"https:\/\/pubs.acs.org\/page\/policy\/authorchoice_ccby_termsofuse.html"}],"funder":[{"DOI":"10.13039\/501100000266","name":"Research Councils UK","doi-asserted-by":"publisher","award":["EP\/N006615\/1"],"award-info":[{"award-number":["EP\/N006615\/1"]}],"id":[{"id":"10.13039\/501100000266","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2018,5,15]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>A major problem limiting reproducible use of liquid extraction surface analysis (LESA) array sampling of dried surface-deposited liquid samples is the unwanted spread of extraction solvent beyond the dried sample limits, resulting in unreliable data. Here, we explore the use of the Droplet Microarray (DMA), which consists of an array of superhydrophilic spots bordered by a superhydrophobic material giving the potential to confine both the sample spot and the LESA extraction solvent in a defined area. We investigated the DMA method in comparison with a standard glass substrate using LESA analysis of a mixture of biologically relevant compounds with a wide mass range and different physicochemical properties. The optimized DMA method was subsequently applied to urine samples from a human intervention study. Relative standard deviations for the signal intensities were all reduced at least 3-fold when performing LESA-MS on the DMA surface compared with a standard glass surface. Principal component analysis revealed more tight clusters indicating improved spectral reproducibility for a human urine sample extracted from the DMA compared to glass. Lastly, in urine samples from an intervention study, more significant ions (145) were identified when using LESA-MS spectra of control and test urine extracted from the DMA. We demonstrate that DMA provides a surface-assisted LESA-MS method delivering significant improvement of the surface extraction repeatability leading to the acquisition of more robust and higher quality data. The DMA shows potential to be used for LESA-MS for controlled and reproducible surface extraction and for acquisition of high quality, qualitative data in a high-throughput manner.<\/jats:p>","DOI":"10.1021\/acs.analchem.8b00973","type":"journal-article","created":{"date-parts":[[2018,4,27]],"date-time":"2018-04-27T17:39:37Z","timestamp":1524850777000},"page":"6001-6005","source":"Crossref","is-referenced-by-count":17,"title":["Improved Extraction Repeatability and Spectral Reproducibility\nfor Liquid Extraction Surface Analysis\u2013Mass Spectrometry Using\nSuperhydrophobic\u2013Superhydrophilic Patterning"],"prefix":"10.1021","volume":"90","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-0288-0422","authenticated-orcid":true,"given":"Joris","family":"Meurs","sequence":"first","affiliation":[{"name":"University of Nottingham , , University Park, , ,","place":["Nottingham, United Kingdom, NG7 2RD"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Morgan R.","family":"Alexander","sequence":"additional","affiliation":[{"name":"University of Nottingham , , University Park, , ,","place":["Nottingham, United Kingdom, NG7 2RD"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5975-948X","authenticated-orcid":true,"given":"Pavel A.","family":"Levkin","sequence":"additional","affiliation":[{"name":"Karlsruhe Institute of Technology (KIT) , , Hermann-von-Helmholtz Platz 1 , , ,","place":["Eggenstein-Leopoldshafen, Germany, 76344"]},{"name":"Karlsruhe Institute of Technology (KIT) , , , ,","place":["Karlsruhe, Germany, 76131"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Simon","family":"Widmaier","sequence":"additional","affiliation":[{"name":"Karlsruhe Institute of Technology (KIT) , , Hermann-von-Helmholtz Platz 1 , , ,","place":["Eggenstein-Leopoldshafen, Germany, 76344"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Josephine","family":"Bunch","sequence":"additional","affiliation":[{"name":"National Physical Laboratory , , Hampton Road , , ,","place":["Teddington, Middlesex, United Kingdom, TW11 0LW"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"David A.","family":"Barrett","sequence":"additional","affiliation":[{"name":"University of Nottingham , , University Park, , ,","place":["Nottingham, United Kingdom, NG7 2RD"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Dong-Hyun","family":"Kim","sequence":"additional","affiliation":[{"name":"University of Nottingham , , University Park, , ,","place":["Nottingham, United Kingdom, NG7 2RD"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2018,4,27]]},"reference":[{"issue":"3","key":"2026090315265734400_cit1","doi-asserted-by":"publisher","first-page":"252","DOI":"10.1002\/jms.1709","article-title":"Fully Automated\nLiquid Extraction-Based Surface Sampling\nand Ionization Using a Chip-Based Robotic Nanoelectrospray Platform","volume":"45","author":"Kertesz","year":"2010","journal-title":"J. Mass Spectrom."},{"issue":"12","key":"2026090315265734400_cit2","doi-asserted-by":"publisher","first-page":"1927","DOI":"10.1007\/s13361-013-0737-3","article-title":"Ambient DESI and LESA-MS Analysis\nof Proteins Adsorbed\nto a Biomaterial Surface Using In-Situ Surface Tryptic Digestion","volume":"24","author":"Rao","year":"2013","journal-title":"J. Am. Soc. Mass Spectrom."},{"issue":"16","key":"2026090315265734400_cit3","doi-asserted-by":"publisher","first-page":"3373","DOI":"10.1039\/C6AY00782A","article-title":"Analysis of\nUrine, Oral Fluid and Fingerprints by Liquid Extraction Surface Analysis\nCoupled to High Resolution MS and MS\/MS \u2013 Opportunities for\nForensic and Biomedical Science","volume":"8","author":"Bailey","year":"2016","journal-title":"Anal. Methods"},{"issue":"3","key":"2026090315265734400_cit4","doi-asserted-by":"publisher","first-page":"1749","DOI":"10.1021\/ac503627z","article-title":"Quantitative\nSpatial Analysis of\nthe Mouse Brain Lipidome by Pressurized Liquid Extraction Surface\nAnalysis","volume":"87","author":"Almeida","year":"2015","journal-title":"Anal. Chem."},{"issue":"7","key":"2026090315265734400_cit5","doi-asserted-by":"publisher","first-page":"3323","DOI":"10.1021\/ac4035136","article-title":"Electro-Focusing\nLiquid Extractive Surface Analysis\n(EF-LESA) Coupled to Mass Spectrometry","volume":"86","author":"Brenton","year":"2014","journal-title":"Anal.\nChem."},{"issue":"21","key":"2026090315265734400_cit6","doi-asserted-by":"publisher","first-page":"10504","DOI":"10.1021\/ac503349d","article-title":"Direct Analysis of Intact Proteins\nfrom Escherichia Coli Colonies by Liquid Extraction\nSurface Analysis Mass Spectrometry","volume":"86","author":"Randall","year":"2014","journal-title":"Anal. Chem."},{"issue":"11","key":"2026090315265734400_cit7","doi-asserted-by":"publisher","first-page":"1312","DOI":"10.1002\/rcm.6904","article-title":"Fully Automated Laser Ablation Liquid\nCapture Surface Analysis Using Nanoelectrospray Ionization Mass Spectrometry","volume":"28","author":"Lorenz","year":"2014","journal-title":"Rapid Commun. Mass Spectrom."},{"issue":"7","key":"2026090315265734400_cit8","doi-asserted-by":"publisher","first-page":"1144","DOI":"10.1002\/rcm.2428","article-title":"Evaluation\nof a Surface-Sampling Probe Electrospray Mass Spectrometry System\nfor the Analysis of Surface-Deposited and Affinity-Captured Proteins","volume":"20","author":"Van Berkel","year":"2006","journal-title":"Rapid Commun. Mass Spectrom."},{"issue":"35","key":"2026090315265734400_cit9","doi-asserted-by":"publisher","first-page":"5217","DOI":"10.1002\/adma.201502115","article-title":"Droplet-Array (DA)\nSandwich Chip: A Versatile Platform\nfor High-Throughput Cell Screening Based on Superhydrophobic-Superhydrophilic\nMicropatterning","volume":"27","author":"Popova","year":"2015","journal-title":"Adv. Mater."},{"issue":"36","key":"2026090315265734400_cit10","doi-asserted-by":"publisher","first-page":"8424","DOI":"10.1002\/anie.201102545","article-title":"Superhydrophobic-Superhydrophilic\nMicropatterning: Towards Genome-on-a-Chip Cell Microarrays","volume":"50","author":"Geyer","year":"2011","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026090315265734400_cit11","doi-asserted-by":"publisher","first-page":"93","DOI":"10.1016\/j.colsurfa.2014.02.016","article-title":"Super-Non-Wettable\nSurfaces: A Review","volume":"448","author":"Valipour","year":"2014","journal-title":"Colloids Surf., A"},{"issue":"7","key":"2026090315265734400_cit12","doi-asserted-by":"publisher","first-page":"819","DOI":"10.4155\/bio.13.42","article-title":"Automated\nLiquid Microjunction Surface Sampling-HPLC\u2013MS\/MS\nAnalysis of Drugs and Metabolites in Whole-Body Thin Tissue Sections","volume":"5","author":"Kertesz","year":"2013","journal-title":"Bioanalysis"},{"issue":"22","key":"2026090315265734400_cit13","doi-asserted-by":"publisher","first-page":"9679","DOI":"10.1021\/ac302634u","article-title":"in het Panhuis, M. Direct Lipid Profiling of Single Cells from Inkjet\nPrinted Microarrays","volume":"84","author":"Ellis","year":"2012","journal-title":"Anal. Chem."},{"issue":"2","key":"2026090315265734400_cit14","doi-asserted-by":"publisher","first-page":"340","DOI":"10.1002\/rcm.7441","article-title":"Determination of Tissue-Specific\nIon Suppression by Liquid Extraction Surface Analysis Mass Spectrometry","volume":"30","author":"Moench","year":"2016","journal-title":"Rapid Commun. Mass Spectrom."},{"key":"2026090315265734400_cit15","doi-asserted-by":"publisher","first-page":"43","DOI":"10.1016\/j.ijms.2016.09.011","article-title":"Liquid Extraction Surface Analysis\nfor Native Mass Spectrometry: Protein Complexes and Ligand Binding","volume":"420","author":"Mikhailov","year":"2017","journal-title":"Int. J. Mass Spectrom."},{"issue":"9","key":"2026090315265734400_cit16","doi-asserted-by":"publisher","first-page":"995","DOI":"10.1002\/rcm.6869","article-title":"Using a\nSingle, High Mass Resolution\nMass Spectrometry Platform to Investigate Ion Suppression Effects\nObserved during Tissue Imaging","volume":"28","author":"Tomlinson","year":"2014","journal-title":"Rapid Commun.\nMass Spectrom."},{"issue":"11","key":"2026090315265734400_cit17","doi-asserted-by":"publisher","first-page":"1953","DOI":"10.1007\/s13361-014-0967-z","article-title":"Top-Down\nand Bottom-Up Identification of Proteins by Liquid Extraction Surface\nAnalysis Mass Spectrometry of Healthy and Diseased Human Liver Tissue","volume":"25","author":"Sarsby","year":"2014","journal-title":"J. Am. Soc. Mass Spectrom."},{"issue":"1","key":"2026090315265734400_cit18","doi-asserted-by":"publisher","first-page":"606","DOI":"10.1021\/acs.analchem.5b03993","article-title":"Direct Tissue Profiling\nof Protein Complexes: Toward\nNative Mass Spectrometry Imaging","volume":"88","author":"Griffiths","year":"2016","journal-title":"Anal. Chem."},{"issue":"23","key":"2026090315265734400_cit19","doi-asserted-by":"publisher","first-page":"3587","DOI":"10.1002\/rcm.5274","article-title":"Liquid Extraction Surface Analysis\nMass Spectrometry (LESA-MS) as a Novel Profiling Tool for Drug Distribution\nand Metabolism Analysis: The Terfenadine Example","volume":"25","author":"Eikel","year":"2011","journal-title":"Rapid Commun. 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B"},{"issue":"1","key":"2026090315265734400_cit29","doi-asserted-by":"publisher","first-page":"142","DOI":"10.1186\/1471-2164-7-142","article-title":"Centering, Scaling, and Transformations:\nImproving the Biological Information Content of Metabolomics Data","volume":"7","author":"van den Berg","year":"2006","journal-title":"BMC Genomics"},{"issue":"2","key":"2026090315265734400_cit30","doi-asserted-by":"publisher","first-page":"193","DOI":"10.1016\/S0731-7085(97)00198-2","article-title":"Validation of Bioanalytical\nChromatographic Methods","volume":"17","author":"Hartmann","year":"1998","journal-title":"J. Pharm. Biomed. Anal."},{"issue":"24","key":"2026090315265734400_cit31","doi-asserted-by":"publisher","first-page":"18621","DOI":"10.1021\/la1039893","article-title":"Superhydrophilic and Superwetting Surfaces: Definition\nand Mechanisms of Control","volume":"26","author":"Drelich","year":"2010","journal-title":"Langmuir"},{"issue":"12","key":"2026090315265734400_cit32","doi-asserted-by":"publisher","first-page":"1329","DOI":"10.1002\/rcm.6580","article-title":"Continuous-Flow Liquid Microjunction\nSurface Sampling Probe Connected on-Line with High-Performance Liquid\nChromatography\/mass Spectrometry for Spatially Resolved Analysis of\nSmall Molecules and Proteins","volume":"27","author":"Van Berkel","year":"2013","journal-title":"Rapid Commun.\nMass Spectrom."},{"issue":"8","key":"2026090315265734400_cit33","doi-asserted-by":"publisher","first-page":"2679","DOI":"10.1039\/C4AN02334J","article-title":"Desalting\nLarge Protein Complexes during Native Electrospray\nMass Spectrometry by Addition of Amino Acids to the Working Solution","volume":"140","author":"Clarke","year":"2015","journal-title":"Analyst"}],"container-title":["Analytical Chemistry"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/acs.analchem.8b00973","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/ancham\/article-pdf\/90\/10\/6001\/67367467\/acs.analchem.8b00973.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/ancham\/article-pdf\/90\/10\/6001\/67367467\/acs.analchem.8b00973.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,9,3]],"date-time":"2026-09-03T19:27:05Z","timestamp":1788463625000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/ancham\/article\/90\/10\/6001\/817794\/Improved-Extraction-Repeatability-and-Spectral"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2018,4,27]]},"references-count":33,"journal-issue":{"issue":"10","published-online":{"date-parts":[[2018,4,27]]},"published-print":{"date-parts":[[2018,5,15]]}},"URL":"https:\/\/doi.org\/10.1021\/acs.analchem.8b00973","relation":{},"ISSN":["0003-2700","1520-6882"],"issn-type":[{"value":"0003-2700","type":"print"},{"value":"1520-6882","type":"electronic"}],"subject":[],"published":{"date-parts":[[2018,4,27]]}}}