{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,29]],"date-time":"2026-09-29T01:22:17Z","timestamp":1790644937011,"version":"4.1.0"},"reference-count":48,"publisher":"MDPI AG","issue":"8","license":[{"start":{"date-parts":[[2023,4,12]],"date-time":"2023-04-12T00:00:00Z","timestamp":1681257600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"Russian Science Foundation","award":["22-73-10053"],"award-info":[{"award-number":["22-73-10053"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>Unsymmetrical dimethylhydrazine (UDMH) is a widely used rocket propellant. Entering the environment or being stored in uncontrolled conditions, UDMH easily forms an enormous variety (at least many dozens) of transformation products. Environmental pollution by UDMH and its transformation products is a major problem in many countries and across the Arctic region. Unfortunately, previous works often use only electron ionization mass spectrometry with a library search, or they consider only the molecular formula to propose the structures of new products. This is quite an unreliable approach. It was demonstrated that a newly proposed artificial intelligence-based workflow allows for the proposal of structures of UDMH transformation products with a greater degree of certainty. The presented free and open-source software with a convenient graphical user interface facilitates the non-target analysis of industrial samples. It has bundled machine learning models for the prediction of retention indices and mass spectra. A critical analysis of whether a combination of several methods of chromatography and mass spectrometry allows us to elucidate the structure of an unknown UDMH transformation product was provided. It was demonstrated that the use of gas chromatographic retention indices for two stationary phases (polar and non-polar) allows for the rejection of false candidates in many cases when only one retention index is not enough. The structures of five previously unknown UDMH transformation products were proposed, and four previously proposed structures were refined.<\/jats:p>","DOI":"10.3390\/molecules28083409","type":"journal-article","created":{"date-parts":[[2023,4,13]],"date-time":"2023-04-13T02:09:21Z","timestamp":1681351761000},"page":"3409","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":14,"title":["Intelligent Workflow and Software for Non-Target Analysis of Complex Samples Using a Mixture of Toxic Transformation Products of Unsymmetrical Dimethylhydrazine as an Example"],"prefix":"10.3390","volume":"28","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-4192-1677","authenticated-orcid":false,"given":"Anastasia Yu.","family":"Sholokhova","sequence":"first","affiliation":[{"name":"A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, 31 Leninsky Prospect, GSP-1, 119071 Moscow, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0978-7666","authenticated-orcid":false,"given":"Dmitriy D.","family":"Matyushin","sequence":"additional","affiliation":[{"name":"A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, 31 Leninsky Prospect, GSP-1, 119071 Moscow, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8242-5461","authenticated-orcid":false,"given":"Oksana I.","family":"Grinevich","sequence":"additional","affiliation":[{"name":"A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, 31 Leninsky Prospect, GSP-1, 119071 Moscow, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Svetlana A.","family":"Borovikova","sequence":"additional","affiliation":[{"name":"A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, 31 Leninsky Prospect, GSP-1, 119071 Moscow, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Aleksey K.","family":"Buryak","sequence":"additional","affiliation":[{"name":"A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, 31 Leninsky Prospect, GSP-1, 119071 Moscow, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2023,4,12]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"128708","DOI":"10.1016\/j.jhazmat.2022.128708","article-title":"Unsymmetrical Dimethylhydrazine and Related Compounds in the Environment: Recent Updates on Pretreatment, Analysis, and Removal Techniques","volume":"432","author":"Hu","year":"2022","journal-title":"J. Hazard. Mater."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"142","DOI":"10.1016\/j.jtice.2014.11.008","article-title":"Cavitational Decontamination of Unsymmetrical Dimethylhydrazine Waste Water","volume":"49","author":"Ghiaee","year":"2015","journal-title":"J. Taiwan Inst. Chem. Eng."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"580","DOI":"10.1017\/S0032247417000547","article-title":"Toxic Splash: Russian Rocket Stages Dropped in Arctic Waters Raise Health, Environmental and Legal Concerns","volume":"53","author":"Byers","year":"2017","journal-title":"Polar Rec."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"120209","DOI":"10.1016\/j.jclepro.2020.120209","article-title":"The Environmental Impact of Emissions from Space Launches: A Comprehensive Review","volume":"255","author":"Dallas","year":"2020","journal-title":"J. Clean. Prod."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"1063","DOI":"10.1080\/00032717908059785","article-title":"Oxidation of Aqueous Unsymmetrical Dimethylhydrazine by Calcium Hypochlorite or Hydrogen Peroxide\/Copper Sulfate","volume":"12","author":"Mach","year":"1979","journal-title":"Anal. Lett."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"190263","DOI":"10.1098\/rsos.190263","article-title":"Investigation on the Compositions of Unsymmetrical Dimethylhydrazine Treatment with Different Oxidants Using Solid-Phase Micro-Extraction-Gas Chromatography\u2013Mass Spectrometer","volume":"6","author":"Huang","year":"2019","journal-title":"R. Soc. Open Sci."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"11","DOI":"10.4137\/EHI.S889","article-title":"A QSAR\/QSTR Study on the Environmental Health Impact by the Rocket Fuel 1,1-Dimethyl Hydrazine and Its Transformation Products","volume":"1","author":"Carlsen","year":"2008","journal-title":"Environ. Health Insights"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"32","DOI":"10.1016\/j.aca.2010.05.040","article-title":"Screening of Transformation Products in Soils Contaminated with Unsymmetrical Dimethylhydrazine Using Headspace SPME and GC\u2013MS","volume":"674","author":"Kenessov","year":"2010","journal-title":"Anal. Chim. Acta"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"1254","DOI":"10.1080\/03067319.2014.940342","article-title":"Simultaneous Determination of 1,1-Dimethylhydrazine and Products of Its Oxidative Transformations by Liquid Chromatography\u2013Tandem Mass Spectrometry","volume":"94","author":"Kosyakov","year":"2014","journal-title":"Int. J. Environ. Anal. Chem."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"911","DOI":"10.1134\/S003602440806006X","article-title":"Transformations of Asymmetric Dimethylhydrazine in Soils","volume":"82","author":"Rodin","year":"2008","journal-title":"Russ. J. Phys. Chem. A"},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"106821","DOI":"10.1016\/j.microc.2021.106821","article-title":"Rapid Quantification and Screening of Nitrogen-Containing Rocket Fuel Transformation Products by Vortex Assisted Liquid-Liquid Microextraction and Gas Chromatography\u2013High-Resolution Orbitrap Mass Spectrometry","volume":"171","author":"Kosyakov","year":"2021","journal-title":"Microchem. J."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"78","DOI":"10.1016\/j.scitotenv.2012.04.017","article-title":"Transformation Products of 1,1-Dimethylhydrazine and Their Distribution in Soils of Fall Places of Rocket Carriers in Central Kazakhstan","volume":"427\u2013428","author":"Kenessov","year":"2012","journal-title":"Sci. Total Environ."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"335","DOI":"10.1016\/j.chemosphere.2019.04.141","article-title":"Effects of Oxidant and Catalyst on the Transformation Products of Rocket Fuel 1,1-Dimethylhydrazine in Water and Soil","volume":"228","author":"Kosyakov","year":"2019","journal-title":"Chemosphere"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"66","DOI":"10.1016\/j.chemosphere.2017.01.118","article-title":"Characterisation of Oxidation Products of 1,1-Dimethylhydrazine by High-Resolution Orbitrap Mass Spectrometry","volume":"174","author":"Kosyakov","year":"2017","journal-title":"Chemosphere"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"550","DOI":"10.1134\/S0040579510051057","article-title":"Investigation of the Reaction Products of Unsymmetrical Dimethylhydrazine with Potassium Permanganate by Gas Chromatography-Mass Spectrometry","volume":"45","author":"Buryak","year":"2011","journal-title":"Theor. Found. Chem. Eng."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"95","DOI":"10.1016\/j.chemosphere.2018.10.155","article-title":"Isomeric Derivatives of Triazoles as New Toxic Decomposition Products of 1,1-Dimethylhydrazine","volume":"217","author":"Milyushkin","year":"2019","journal-title":"Chemosphere"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"135764","DOI":"10.1016\/j.chemosphere.2022.135764","article-title":"Machine Learning-Assisted Non-Target Analysis of a Highly Complex Mixture of Possible Toxic Unsymmetrical Dimethylhydrazine Transformation Products with Chromatography-Mass Spectrometry","volume":"307","author":"Sholokhova","year":"2022","journal-title":"Chemosphere"},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"64225","DOI":"10.1007\/s11356-022-22157-y","article-title":"1-Methyl-1H-1,2,4-Triazole as the Main Marker of 1,1-Dimethylhydrazine Exposure in Plants","volume":"29","author":"Karnaeva","year":"2022","journal-title":"Environ. Sci. Pollut. Res."},{"key":"ref_19","doi-asserted-by":"crossref","unstructured":"Liao, Q., Feng, C., and Wang, L. (2016). Biodegradation of Unsymmetrical Dimethylhydrazine in Solution and Soil by Bacteria Isolated from Activated Sludge. Appl. Sci., 6.","DOI":"10.3390\/app6040095"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"33645","DOI":"10.1007\/s11356-021-17844-1","article-title":"Quantification of Trace Transformation Products of Rocket Fuel Unsymmetrical Dimethylhydrazine in Sand Using Vacuum-Assisted Headspace Solid-Phase Microextraction","volume":"29","author":"Zhakupbekova","year":"2022","journal-title":"Environ. Sci. Pollut. Res."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"459","DOI":"10.1007\/s11270-010-0398-9","article-title":"Trace Analysis of N-Nitrosamines in Water Using Solid-Phase Microextraction Coupled with Gas Chromatograph\u2013Tandem Mass Spectrometry","volume":"213","author":"Hung","year":"2010","journal-title":"Water Air Soil Pollut."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"2709","DOI":"10.1080\/09593330.2019.1710573","article-title":"Major Products and Their Formation and Transformation Mechanism through Degrading UDMH Wastewater via DBD Low Temperature Plasma","volume":"42","author":"Mu","year":"2021","journal-title":"Environ. Technol."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"8644","DOI":"10.1016\/j.ijhydene.2018.03.092","article-title":"Gasification of Unsymmetrical Dimethylhydrazine in Supercritical Water: Reaction Pathway and Kinetics","volume":"43","author":"Yi","year":"2018","journal-title":"Int. J. Hydrogen Energy"},{"key":"ref_24","unstructured":"Brubaker, K.L., Bonilla, J.V., and Boparai, A.S. (2023, April 01). Products of the Hypochlorite Oxidation of Hydrazine Fuels. Available online: https:\/\/apps.dtic.mil\/sti\/pdfs\/ADA213557.pdf."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"2567","DOI":"10.1039\/D0EW00299B","article-title":"Chlorination of N,N-Dimethylhydrazine Compounds: Reaction Kinetics, Mechanisms, and Implications for Controlling N-Nitrosodimethylamine Formation during Ozonation","volume":"6","author":"Lee","year":"2020","journal-title":"Environ. Sci. Water Res. Technol."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"363","DOI":"10.1007\/s11090-021-10220-4","article-title":"Chemical Kinetics of Unsymmetrical Dimethylhydrazine (UDMH) Degradation in Wastewater by \u00b7OH Radical","volume":"42","author":"Fu","year":"2022","journal-title":"Plasma Chem. Plasma Process"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"81","DOI":"10.1007\/s11090-022-10307-6","article-title":"Theoretical Study on the Degradation Pathways of Unsymmetrical Dimethylhydrazine by Aqueous O3","volume":"43","author":"Luo","year":"2023","journal-title":"Plasma Chem. Plasma Process"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"102970","DOI":"10.1016\/j.jwpe.2022.102970","article-title":"Comparison of VUV\/H2O2 and VUV\/PMS (Peroxymonosulfate) for the Degradation of Unsymmetrical Dimethylhydrazine in Water","volume":"49","author":"Huang","year":"2022","journal-title":"J. Water Process Eng."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"680","DOI":"10.1134\/S199079311704025X","article-title":"Surface-Assisted Laser Desorption\/Ionization Mass Spectrometry for the Detection of Low-Molecular-Weight and Oligomeric Products of 1,1-Dimethylhydrazine Transformation on the Surfaces of Construction Materials","volume":"11","author":"Iartsev","year":"2017","journal-title":"Russ. J. Phys. Chem. B"},{"key":"ref_30","doi-asserted-by":"crossref","unstructured":"Matyushin, D.D., Sholokhova, A.Y., and Buryak, A.K. (2021). Deep Learning Based Prediction of Gas Chromatographic Retention Indices for a Wide Variety of Polar and Mid-Polar Liquid Stationary Phases. Int. J. Mol. Sci., 22.","DOI":"10.3390\/ijms22179194"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"6237","DOI":"10.1007\/s00216-015-8681-7","article-title":"Non-Target Screening with High-Resolution Mass Spectrometry: Critical Review Using a Collaborative Trial on Water Analysis","volume":"407","author":"Schymanski","year":"2015","journal-title":"Anal. Bioanal. Chem."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"23","DOI":"10.1016\/j.trac.2015.09.005","article-title":"Mass Spectral Databases for LC\/MS- and GC\/MS-Based Metabolomics: State of the Field and Future Prospects","volume":"78","author":"Vinaixa","year":"2016","journal-title":"TrAC Trends Anal. Chem."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"7689","DOI":"10.1021\/acs.analchem.6b01622","article-title":"Computational Prediction of Electron Ionization Mass Spectra to Assist in GC\/MS Compound Identification","volume":"88","author":"Allen","year":"2016","journal-title":"Anal. Chem."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"W94","DOI":"10.1093\/nar\/gku436","article-title":"CFM-ID: A Web Server for Annotation, Spectrum Prediction and Metabolite Identification from Tandem Mass Spectra","volume":"42","author":"Allen","year":"2014","journal-title":"Nucleic Acids Res."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"11692","DOI":"10.1021\/acs.analchem.1c01465","article-title":"CFM-ID 4.0: More Accurate ESI-MS\/MS Spectral Prediction and Compound Identification","volume":"93","author":"Wang","year":"2021","journal-title":"Anal. Chem."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"223140","DOI":"10.1109\/ACCESS.2020.3045047","article-title":"Gas Chromatographic Retention Index Prediction Using Multimodal Machine Learning","volume":"8","author":"Matyushin","year":"2020","journal-title":"IEEE Access"},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"11818","DOI":"10.1021\/acs.analchem.0c02082","article-title":"Deep Learning Driven GC-MS Library Search and Its Application for Metabolomics","volume":"92","author":"Matyushin","year":"2020","journal-title":"Anal. Chem."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"10","DOI":"10.1186\/s13321-018-0263-1","article-title":"OPERA Models for Predicting Physicochemical Properties and Environmental Fate Endpoints","volume":"10","author":"Mansouri","year":"2018","journal-title":"J. Cheminform."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"047013","DOI":"10.1289\/EHP8495","article-title":"CATMoS: Collaborative Acute Toxicity Modeling Suite","volume":"129","author":"Mansouri","year":"2021","journal-title":"Environ. Health Perspect."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"462792","DOI":"10.1016\/j.chroma.2021.462792","article-title":"Deep Learning for Retention Time Prediction in Reversed-Phase Liquid Chromatography","volume":"1664","author":"Fedorova","year":"2022","journal-title":"J. Chromatogr. A"},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"2200","DOI":"10.1021\/acs.analchem.0c04071","article-title":"Prediction of Liquid Chromatographic Retention Time with Graph Neural Networks to Assist in Small Molecule Identification","volume":"93","author":"Yang","year":"2021","journal-title":"Anal. Chem."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"15651","DOI":"10.1021\/acs.analchem.1c03250","article-title":"Deep Neural Network Pretrained by Weighted Autoencoders and Transfer Learning for Retention Time Prediction of Small Molecules","volume":"93","author":"Ju","year":"2021","journal-title":"Anal. Chem."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"6571","DOI":"10.1021\/acs.analchem.0c00233","article-title":"Generalized Calibration Across Liquid Chromatography Setups for Generic Prediction of Small-Molecule Retention Times","volume":"92","author":"Bouwmeester","year":"2020","journal-title":"Anal. Chem."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"43","DOI":"10.1002\/mas.21349","article-title":"Ion Mobility Spectrometry-Mass Spectrometry (IMS-MS) of Small Molecules: Separating and Assigning Structures to Ions","volume":"32","author":"Lapthorn","year":"2013","journal-title":"Mass Spectrom. Rev."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"5191","DOI":"10.1021\/acs.analchem.8b05821","article-title":"Predicting Ion Mobility Collision Cross-Sections Using a Deep Neural Network: DeepCCS","volume":"91","author":"Plante","year":"2019","journal-title":"Anal. Chem."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"4334","DOI":"10.1038\/s41467-020-18171-8","article-title":"Ion Mobility Collision Cross-Section Atlas for Known and Unknown Metabolite Annotation in Untargeted Metabolomics","volume":"11","author":"Zhou","year":"2020","journal-title":"Nat. Commun."},{"key":"ref_47","doi-asserted-by":"crossref","unstructured":"Samukhina, Y.V., Matyushin, D.D., Grinevich, O.I., and Buryak, A.K. (2021). A Deep Convolutional Neural Network for Prediction of Peptide Collision Cross Sections in Ion Mobility Spectrometry. Biomolecules, 11.","DOI":"10.3390\/biom11121904"},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"6583","DOI":"10.1021\/acs.analchem.7b00741","article-title":"Prediction of Collision Cross-Section Values for Small Molecules: Application to Pesticide Residue Analysis","volume":"89","author":"Bijlsma","year":"2017","journal-title":"Anal. Chem."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/28\/8\/3409\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T19:14:55Z","timestamp":1760123695000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/28\/8\/3409"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,4,12]]},"references-count":48,"journal-issue":{"issue":"8","published-online":{"date-parts":[[2023,4]]}},"alternative-id":["molecules28083409"],"URL":"https:\/\/doi.org\/10.3390\/molecules28083409","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,4,12]]}}}