{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,21]],"date-time":"2026-08-21T12:07:12Z","timestamp":1787314032221,"version":"build-2736575974"},"reference-count":47,"publisher":"Frontiers Media SA","license":[{"start":{"date-parts":[[2021,7,2]],"date-time":"2021-07-02T00:00:00Z","timestamp":1625184000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/100000001","name":"National Science Foundation","doi-asserted-by":"publisher","award":["CHE-1905312 MRI-1726897"],"award-info":[{"award-number":["CHE-1905312 MRI-1726897"]}],"id":[{"id":"10.13039\/100000001","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["frontiersin.org"],"crossmark-restriction":true},"short-container-title":["Front. Chem."],"abstract":"<jats:p>\n                    We present the analysis of formaldehyde (HCHO) in anhydrous methanol (CH\n                    <jats:sub>3<\/jats:sub>\n                    OH) as a case study to quantify HCHO in non-aqueous samples. At higher concentrations (C &amp;gt; 0.07\u00a0M), we detect a product of HCHO, methoxy methanol (MM, CH\n                    <jats:sub>3<\/jats:sub>\n                    OCH\n                    <jats:sub>2<\/jats:sub>\n                    OH), by Fourier transform infrared spectroscopy, FTIR. Formaldehyde reacts with CH\n                    <jats:sub>3<\/jats:sub>\n                    OH, CD\n                    <jats:sub>3<\/jats:sub>\n                    OH, and CD\n                    <jats:sub>3<\/jats:sub>\n                    OD as shown by FTIR with a characteristic spectral feature around 1,195\u00a0cm\n                    <jats:sup>\u22121<\/jats:sup>\n                    for CH\n                    <jats:sub>3<\/jats:sub>\n                    OH used for the qualitative detection of MM, a formaldehyde derivative in neat methanol. Ab initio calculations support this assignment. The extinction coefficient for 1,195\u00a0cm\n                    <jats:sup>\u22121<\/jats:sup>\n                    is in the order of 1.4 \u00d7 10\n                    <jats:sup>2<\/jats:sup>\n                    \u00a0M\n                    <jats:sup>\u22121<\/jats:sup>\n                    cm\n                    <jats:sup>\u22121<\/jats:sup>\n                    , which makes the detection limit by FTIR in the order of 0.07\u00a0M. For lower concentrations, we performed the quantitative analysis of non-aqueous samples by derivatization with dinitrophenylhydrazine (DNPH). The derivatization uses an aqueous H\n                    <jats:sub>2<\/jats:sub>\n                    SO\n                    <jats:sub>4<\/jats:sub>\n                    solution to yield the formaldehyde derivatized hydrazone. Ba(OH)\n                    <jats:sub>2<\/jats:sub>\n                    removes sulfate ions from the derivatized samples and a final extraction with isobutyl acetate to yield a 1:1 methanol: isobutyl acetate solvent for injection for electrospray ionization (ESI). The ESI analysis gave a linear calibration curve for concentrations from 10 to 200\u00a0\u00b5M with a time-of-flight analyzer (TOF). The detection and quantification limits are 7.8\u00a0and 26\u00a0\u03bcM, respectively, for a linear correlation with\n                    <jats:italic>R<\/jats:italic>\n                    <jats:sup>2<\/jats:sup>\n                    &amp;gt; 0.99. We propose that the formaldehyde in CH\n                    <jats:sub>3<\/jats:sub>\n                    OH is in equilibrium with the MM species, without evidence of HCHO in solution. In the presence of water, the peaks for MM become less resolved, as expected from the well-known equilibria of HCHO that favors the formation of methylene glycol and polymeric species. Our results show that HCHO, in methanol does not exist in the aldehyde form as the main chemical species. Still, HCHO is in equilibrium between the production of MM and the formation of hydrated species in the presence of water. We demonstrate the ESI-MS analysis of HCHO from a non-aqueous TiO\n                    <jats:sub>2<\/jats:sub>\n                    suspension in methanol. Detection of HCHO after illumination of the colloid indicates that methanol photooxidation yields formaldehyde in equilibrium with the solvent.\n                  <\/jats:p>","DOI":"10.3389\/fchem.2021.678112","type":"journal-article","created":{"date-parts":[[2021,7,2]],"date-time":"2021-07-02T01:49:02Z","timestamp":1625190542000},"update-policy":"https:\/\/doi.org\/10.3389\/crossmark-policy","source":"Crossref","is-referenced-by-count":11,"title":["Formaldehyde Analysis in Non-Aqueous Methanol Solutions by Infrared Spectroscopy and Electrospray Ionization"],"prefix":"10.3389","volume":"9","author":[{"given":"Krishna K.","family":"Barakoti","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Pradeep","family":"Subedi","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Farzaneh","family":"Chalyavi","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Salvador","family":"Gutierrez-Portocarrero","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Matthew J.","family":"Tucker","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mario A.","family":"Alpuche-Aviles","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1965","published-online":{"date-parts":[[2021,7,2]]},"reference":[{"key":"B1","doi-asserted-by":"crossref","first-page":"1454","DOI":"10.1039\/jr9480001454","article-title":"The Infra-red Spectra of Mixtures of Aldehydes and Alcohols","volume":"296","author":"Ashdown","year":"1948","journal-title":"J. Chem. Soc. (Resumed)"},{"key":"B2","doi-asserted-by":"publisher","first-page":"387","DOI":"10.1016\/s0021-9673(00)94256-0","article-title":"High-performance Liquid Chromatographic Determination of Free Formaldehyde in Cosmetics","volume":"464","author":"Benassi","year":"1991","journal-title":"J. Chromatogr. A"},{"key":"B3","doi-asserted-by":"publisher","first-page":"5S","DOI":"10.1177\/1091581813511831","article-title":"Amended Safety Assessment of Formaldehyde and Methylene Glycol as Used in Cosmetics","volume":"32","author":"Boyer","year":"2013","journal-title":"Int. J. Toxicol."},{"key":"B4","doi-asserted-by":"publisher","first-page":"87","DOI":"10.1016\/j.molcata.2008.03.029","article-title":"Synthesis of Precursors to Ethylene Glycol from Formaldehyde and Methyl Formate Catalyzed by Heteropoly Acids","volume":"288","author":"Celik","year":"2008","journal-title":"J. Mol. Catal. A: Chem."},{"key":"B5","doi-asserted-by":"publisher","first-page":"786","DOI":"10.1021\/la980798o","article-title":"Formaldehyde Yields from Methanol Electrochemical Oxidation on Carbon-Supported Platinum Catalysts","volume":"15","author":"Childers","year":"1999","journal-title":"Langmuir"},{"key":"B6","doi-asserted-by":"publisher","first-page":"601","DOI":"10.1021\/acs.jpca.7b12390","article-title":"Generation and Stability of the Gem-Diol Forms in Imidazole Derivatives Containing Carbonyl Groups. Solid-State NMR and Single-Crystal X-Ray Diffraction Studies","volume":"122","author":"Crespi","year":"2018","journal-title":"J. Phys. Chem. A."},{"key":"B7","doi-asserted-by":"publisher","first-page":"284","DOI":"10.1016\/0021-9673(92)85422-p","article-title":"Determination of Formaldehyde in Air by Chemisorption on Glass Filters Impregnated with 2,4-dinitrophenylhydrazine Using Gas Chromatography with Thermionic Specific Detection","volume":"626","author":"Dalene","year":"1992","journal-title":"J. Chromatogr. A"},{"key":"B8","doi-asserted-by":"publisher","first-page":"401","DOI":"10.1021\/ac60366a030","article-title":"Gas Chromatographic and Nuclear Magnetic Resonance Determination of Linear Formaldehyde Oligomers in Formalin","volume":"48","author":"Dankelman","year":"1976","journal-title":"Anal. Chem."},{"key":"B9","doi-asserted-by":"publisher","first-page":"469","DOI":"10.1016\/s0033-3506(98)80191-1","article-title":"The Prevention of Tuberculosis","volume":"11","author":"Del\u00e9pine","year":"1898","journal-title":"Public Health"},{"key":"B10","doi-asserted-by":"publisher","first-page":"581","DOI":"10.1021\/es00160a009","article-title":"Fast Fluorometric Flow Injection Analysis of Formaldehyde in Atmospheric Water","volume":"21","author":"Dong","year":"1987","journal-title":"Environ. Sci. Technol."},{"key":"B11","doi-asserted-by":"publisher","first-page":"637","DOI":"10.1021\/es00148a016","article-title":"Solubility of Gaseous Formaldehyde in Liquid Water and Generation of Trace Standard Gaseous Formaldehyde","volume":"20","author":"Dong","year":"1986","journal-title":"Environ. Sci. Technol."},{"key":"B12","first-page":"8","article-title":"Analytical Chemistry; Solubility Product Constants","volume-title":"CRC Handbook of Chemistry and Physics","author":"Lide","year":"2004"},{"key":"B13","doi-asserted-by":"publisher","first-page":"389","DOI":"10.1084\/jem.67.3.389","article-title":"The Effect of Formaldehyde on Pneumococci","volume":"67","author":"Dubos","year":"1938","journal-title":"J. Exp. Med."},{"key":"B14","doi-asserted-by":"publisher","first-page":"2887","DOI":"10.1002\/adma.201100283","article-title":"Advances in Tailoring Resorcinol-Formaldehyde Organic and Carbon Gels","volume":"23","author":"Elkhatat","year":"2011","journal-title":"Adv. Mater."},{"key":"B15","doi-asserted-by":"publisher","first-page":"551","DOI":"10.1021\/ac00076a021","article-title":"Continuous Automated Determination of Atmospheric Formaldehyde at the Parts Per Trillion Level","volume":"66","author":"Fan","year":"2002","journal-title":"Anal. Chem."},{"key":"B16","doi-asserted-by":"publisher","first-page":"2108","DOI":"10.1021\/jp205563d","article-title":"High-Pressure Photoinduced Reactivity of CH3OH and CD3OH","volume":"116","author":"Fanetti","year":"2011","journal-title":"J. Phys. Chem. C"},{"key":"B17","doi-asserted-by":"publisher","first-page":"H3025","DOI":"10.1149\/2.0041604jes","article-title":"Transient Interactions of Agglomerates of Sensitized TiO2Nanoparticles in Colloidal Suspensions","volume":"163","author":"Fernando","year":"2016","journal-title":"J. Electrochem. Soc."},{"key":"B18","doi-asserted-by":"publisher","first-page":"10894","DOI":"10.1021\/ja4007639","article-title":"Observation of Individual Semiconducting Nanoparticle Collisions by Stochastic Photoelectrochemical Currents","volume":"135","author":"Fernando","year":"2013","journal-title":"J. Am. Chem. Soc."},{"key":"B19","doi-asserted-by":"publisher","first-page":"915","DOI":"10.1021\/es60011a002","article-title":"Method for Sampling and Determination of Organic Carbonyl Compounds in Automobile Exhaust","volume":"1","author":"Fracchia","year":"1967","journal-title":"Environ. Sci. Technol."},{"key":"B20","doi-asserted-by":"publisher","first-page":"168","DOI":"10.1021\/ac00225a009","article-title":"Determination of Nanogram Amounts of Carbonyls as 2,4-dinitrophenylhydrazones by High-Performance Liquid Chromatography","volume":"53","author":"Fung","year":"1981","journal-title":"Anal. Chem."},{"key":"B21","doi-asserted-by":"publisher","first-page":"9262","DOI":"10.1021\/ie403252x","article-title":"Equilibrium Speciation in Moderately Concentrated Formaldehyde-Methanol-Water Solutions Investigated Using13C and1H Nuclear Magnetic Resonance Spectroscopy","volume":"53","author":"Gaca","year":"2014","journal-title":"Ind. Eng. Chem. Res."},{"key":"B22","doi-asserted-by":"crossref","first-page":"44","DOI":"10.1016\/j.vibspec.2018.05.001","article-title":"Investigation of IR and Raman Spectra of Species Present in Formaldehyde-Water-Methanol Systems","volume":"97","author":"Gaca-Zajac","year":"2018","journal-title":"Vibrational Spectrosc."},{"key":"B23","doi-asserted-by":"publisher","first-page":"1022","DOI":"10.1021\/ie00028a033","article-title":"1H- and 13C-NMR-Spectroscopic Study of Chemical Equilibria in Solutions of Formaldehyde in Water, Deuterium Oxide, and Methanol","volume":"33","author":"Hahnenstein","year":"1994","journal-title":"Ind. Eng. Chem. Res."},{"key":"B24","doi-asserted-by":"publisher","first-page":"218","DOI":"10.1366\/0003702914337551","article-title":"GC\/MS and FT-IR Spectra of Methoxymethanol","volume":"45","author":"Johnson","year":"1991","journal-title":"Appl. Spectrosc."},{"key":"B25","doi-asserted-by":"publisher","first-page":"119","DOI":"10.1016\/0022-0728(87)80313-3","article-title":"Infrared Spectroscopic Study of the Methanol Adsorbates at a Platinum Electrode","volume":"237","author":"Juanto","year":"1987","journal-title":"J. Electroanalytical Chem. Interfacial Electrochemistry"},{"key":"B26","doi-asserted-by":"publisher","first-page":"489","DOI":"10.1021\/jp9731157","article-title":"Formaldehyde Yields from Methanol Electrochemical Oxidation on Platinum","volume":"102","author":"Korzeniewski","year":"1998","journal-title":"J. Phys. Chem. B"},{"key":"B27","doi-asserted-by":"publisher","first-page":"819","DOI":"10.1021\/es00089a007","article-title":"Determination of Formaldehyde in Clean Air","volume":"15","author":"Lowe","year":"1981","journal-title":"Environ. Sci. Technol."},{"key":"B28","doi-asserted-by":"publisher","first-page":"1705","DOI":"10.1080\/00021369.1976.10862306","article-title":"Release of Formaldehyde from Dimethylol Dimethylhydantoin, a Possible Antiseptic Agent","volume":"40","author":"Maeda","year":"2014","journal-title":"Agric. Biol. Chem."},{"key":"B29","doi-asserted-by":"publisher","first-page":"2025","DOI":"10.1021\/j100878a053","article-title":"Equilibria between Cyclic and Linear Molecules in Aqueous Formaldehyde","volume":"70","author":"Moedritzer","year":"1966","journal-title":"J. Phys. Chem."},{"key":"B30","volume-title":"Report on Carcinogens","year":"2016"},{"key":"B31","doi-asserted-by":"publisher","first-page":"744","DOI":"10.1093\/chromsci\/10.12.744","article-title":"Chromatographic Determination of Carbonyl Compounds as Their 2,4-Dinitrophenylhydrazones I. Gas Chromatography","volume":"10","author":"Papa","year":"1972","journal-title":"J. Chromatogr. Sci."},{"key":"B32","doi-asserted-by":"publisher","first-page":"763","DOI":"10.1016\/0039-9140(84)80196-4","article-title":"The Determination of Traces of Formaldehyde","volume":"31","author":"Pockard","year":"1984","journal-title":"Talanta"},{"key":"B33","first-page":"94","article-title":"Hydroxyl Group Compounds: O-H Group","volume-title":"Infrared and Raman Characteristic Group Frequencies","author":"Socrates","year":"2001"},{"key":"B35","doi-asserted-by":"publisher","first-page":"4127","DOI":"10.1021\/jp9505800","article-title":"Determination of the Quantum Yield for the Photochemical Generation of Hydroxyl Radicals in TiO2Suspensions","volume":"100","author":"Sun","year":"1996","journal-title":"J. Phys. Chem."},{"key":"B36","doi-asserted-by":"publisher","first-page":"416","DOI":"10.1021\/ja055866p","article-title":"Direct Observation of Reactive Trapped Holes in TiO2 Undergoing Photocatalytic Oxidation of Adsorbed Alcohols: Evaluation of the Reaction Rates and Yields","volume":"128","author":"Tamaki","year":"2006","journal-title":"J. Am. Chem. Soc."},{"key":"B37","doi-asserted-by":"publisher","first-page":"249","DOI":"10.1016\/j.cplett.2009.07.058","article-title":"5-Cyanotryptophan as an Infrared Probe of Local Hydration Status of Proteins","volume":"478","author":"Waegele","year":"2009","journal-title":"Chem. Phys. Lett."},{"key":"B38","doi-asserted-by":"publisher","first-page":"2821","DOI":"10.1021\/ja01334a030","article-title":"Some Properties of Anhydrous Formaldehyde","volume":"55","author":"Walker","year":"1933","journal-title":"J. Am. Chem. Soc."},{"key":"B39","first-page":"1","volume-title":"Formaldehyde1. Formaldehyde Production","author":"Walker","year":""},{"key":"B40","first-page":"52","volume-title":"3. State of Dissolved formaldehydeFormaldehyde","author":"Walker","year":""},{"key":"B41","doi-asserted-by":"publisher","first-page":"169","DOI":"10.1016\/s1010-6030(02)00087-4","article-title":"Photonic Efficiency and Quantum Yield of Formaldehyde Formation from Methanol in the Presence of Various TiO2 Photocatalysts","volume":"148","author":"Wang","year":"2002","journal-title":"J. Photochem. Photobiol. A: Chem."},{"key":"B42","doi-asserted-by":"publisher","first-page":"1143","DOI":"10.1021\/bi101555y","article-title":"Optimal Salt Bridge for Trp-Cage Stabilization","volume":"50","author":"Williams","year":"2011","journal-title":"Biochemistry"},{"key":"B43","doi-asserted-by":"publisher","first-page":"4067","DOI":"10.1016\/s0009-2509(02)00358-5","article-title":"Kinetics and Chemical Equilibrium of the Hydration of Formaldehyde","volume":"57","author":"Winkelman","year":"2002","journal-title":"Chem. Eng. Sci."},{"key":"B44","doi-asserted-by":"publisher","first-page":"3693","DOI":"10.1021\/jp984631f","article-title":"Reactions of Dimethyl Ether with Atomic Oxygen: A Matrix Isolation and a Quantum Chemical Study","volume":"103","author":"Wrobel","year":"1999","journal-title":"J. Phys. Chem. A."},{"key":"B45","doi-asserted-by":"publisher","first-page":"5479","DOI":"10.1021\/ac203276f","article-title":"Complete Quantitative Online Analysis of Methanol Electrooxidation Products via Electron Impact and Electrospray Ionization Mass Spectrometry","volume":"84","author":"Zhao","year":"2012","journal-title":"Anal. Chem."},{"key":"B46","doi-asserted-by":"publisher","first-page":"2472","DOI":"10.1021\/ac902847a","article-title":"Quantitative Online Analysis of Liquid-phase Products of Methanol Oxidation in Aqueous Sulfuric Acid Solutions Using Electrospray Ionization Mass Spectrometry","volume":"82","author":"Zhao","year":"2010","journal-title":"Anal. Chem."},{"key":"B47","doi-asserted-by":"publisher","first-page":"12764","DOI":"10.1039\/c2cp40907k","article-title":"Quantification of Photoelectrogenerated Hydroxyl Radical on TiO2 by Surface Interrogation Scanning Electrochemical Microscopy","volume":"14","author":"Zigah","year":"2012","journal-title":"Phys. Chem. Chem. Phys."},{"key":"B48","first-page":"206","volume-title":"8. Chemical properties of formaldehydeformaldehyde","author":"Walker","year":""}],"container-title":["Frontiers in Chemistry"],"original-title":[],"link":[{"URL":"https:\/\/www.frontiersin.org\/articles\/10.3389\/fchem.2021.678112\/full","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2021,7,2]],"date-time":"2021-07-02T01:49:09Z","timestamp":1625190549000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.frontiersin.org\/articles\/10.3389\/fchem.2021.678112\/full"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2021,7,2]]},"references-count":47,"alternative-id":["10.3389\/fchem.2021.678112"],"URL":"https:\/\/doi.org\/10.3389\/fchem.2021.678112","relation":{},"ISSN":["2296-2646"],"issn-type":[{"value":"2296-2646","type":"electronic"}],"subject":[],"published":{"date-parts":[[2021,7,2]]},"article-number":"678112"}}