Physical review. B./Physical review. B, Год журнала: 2025, Номер 111(24)
Опубликована: Июнь 5, 2025
Journal of the American Chemical Society, Год журнала: 2025, Номер unknown
Опубликована: Янв. 11, 2025
Nitrogen fixation is essential for the sustainable development of both human society and environment. Due to chemical inertness N≡N bond, traditional Haber–Bosch process operates under extreme conditions, making nitrogen ambient conditions highly desirable but challenging. In this study, we present an ultrasonic atomizing microdroplet method that achieves using water air in a rationally designed sealed device, without need any catalyst. The total rate achieved 6.99 μmol/h, yielding ammonium as reduction product nitrite nitrate oxidation products, with hydrogen peroxide produced byproduct at 4.29 μmol/h. Using electron paramagnetic resonance (EPR) spectroscopy, captured reactive species, including hydrogen, hydroxyl, singlet oxygen, superoxide anion, NO radicals. conjunction situ mass spectrometry (MS) isotope labeling, confirmed presence nitrogen-containing intermediates, such HN═NOH+•, H2N–N(OH)2+•, HNO+, NH2OH+•. Supported by these findings theoretical calculations, propose radical-mediated disproportionation mechanism. Simulations naturally occurring condensed microdroplets also demonstrated redox fixation. This microdroplet-based not only offers potential pathway practical applications deepens our understanding natural cycle.
Язык: Английский
Процитировано
5
Journal of the American Chemical Society, Год журнала: 2025, Номер unknown
Опубликована: Янв. 8, 2025
Our recent molecular dynamics simulations of decomposing Alzheimer's disease plaques, under oscillating- and static external electric fields (Os-EEFs St-EEFs), revealed the superiority Os-EEF for plaques consisting 7-residue peptide segment. This conclusion is now reinforced by studying dimers short peptides trimers full-length Aβ-42 peptide. Thus, dispersed obtained following St-EEF applications reformed once subsided. In contrast, originating from application remained long time scales. The present study provides insights into these results modeling decomposition modes that transpire both field types. Additionally, this frequency effects on processes within THz–MHz regions. simulation shows in lower range (≤GHz) decomposes plaque a scale ∼50 ns, whereas higher Os-EEFs (≥THz) are less effective. As such, with moderate-to-low frequencies lead to an "explosion," whereby fly distantly apart inhibit reformation. By St-EEFs form parallel pairs, which stabilized EEF due large dipole moment ensemble. sluggish reversible processes. We further conclude impact maximal pulses, prevents propensity arrange pairs. over maintained irrespective peptides' length. A model formulated predicts dependence EEF.
Язык: Английский
Процитировано
0
Environmental Science & Technology, Год журнала: 2025, Номер unknown
Опубликована: Март 25, 2025
InfoMetricsFiguresRef. Environmental Science & TechnologyASAPArticle This publication is free to access through this site. Learn More CiteCitationCitation and abstractCitation referencesMore citation options ShareShare onFacebookXWeChatLinkedInRedditEmailBlueskyJump toExpandCollapse ViewpointMarch 25, 2025Microdroplets: An Overlooked "Engine" of Chemistry in AirClick copy article linkArticle link copied!Deming Xia*Deming XiaKey Laboratory Industrial Ecology Engineering (Ministry Education), Dalian Key on Chemicals Risk Control Pollution Prevention Technology, School University 116024, China*[email protected]More by Deming XiaView Biographyhttps://orcid.org/0000-0003-4877-0058Hong-bin XieHong-bin XieKey ChinaMore Hong-bin XieView Biographyhttps://orcid.org/0000-0002-9119-9785Zhiqiang FuZhiqiang FuKey Zhiqiang Fuhttps://orcid.org/0000-0003-4199-7436Jingwen Chen*Jingwen ChenKey Jingwen Chenhttps://orcid.org/0000-0002-5756-3336Open PDFEnvironmental TechnologyCite this: Environ. Sci. Technol. 2025, XXXX, XXX, XXX-XXXClick citationCitation copied!https://pubs.acs.org/doi/10.1021/acs.est.5c01041https://doi.org/10.1021/acs.est.5c01041Published March 2025 Publication History Received 21 January 2025Published online 25 2025article-commentary© American Chemical Society. available under these Terms Use. Request reuse permissionsThis licensed for personal use The ACS Publications© SocietySubjectswhat are subjects Article automatically applied from the Subject Taxonomy describe scientific concepts themes article. Atmospheric chemistry Charge transfer reactions Ions Liquids Microdroplets everywhere, both indoor outdoor air, forming an immense air–water interface Earth's system. They appear as clouds, rain, dew, or fog outdoors arise cosmetic sprays, humidifiers, shower heads indoors. At first glance, they look simple, composed primarily water molecules (Figure 1), yet tiny droplets host a range chemical so complex that challenge long-held beliefs environmental chemistry. For example, atmospheric nitrogen (N2), long considered inert due its strong triple bond, can be unexpectedly activated at microdroplet surfaces converted into nitrous oxide (N2O), potent greenhouse gas ozone-depleting substance, reduction-then-oxidation pathway. (1) Similarly, per- polyfluoroalkyl substances (PFASs), family compounds known "forever chemicals", undergo activation even defluorination microdroplets, leading mineralization once deemed highly unlikely. (2) These surprising transformations underscore previously unrecognized importance microdroplets cycles prompt us ask how achieve such magical power. (2)Figure 1Figure 1. Ubiquitous environments plausible mechanisms which become reactive.High Resolution ImageDownload MS PowerPoint SlideHow Do Become Highly Reactive?Click section linkSection copied!Although exact driving high reactivity remain somewhat unclear, some pioneers have given diverse interpretations different perspectives. (3,4) centered around important reactive species (RS), including hydroxyl radicals (•OH), hydrogen atoms (H•), cation (H2O•+), hydrated electrons (H2O•–), peroxide (H2O2). formation RS often linked electrification microdroplets. Imagine rubbing your hands table quickly; violent friction make you feel stinging sensation. In upper troposphere, between clouds air far more intense. facilitates charge resulting acquiring non-zero charge.This disrupts initial ion distribution within further amplifying separation positive negative ions surface subsurface (3−5) As result, electric field perpendicular droplet generated, absence net charge. Such substantially lowers energy barrier hydronium (H3O+) hydroxide (OH–), two essential water, producing oxidants (e.g., •OH) reductants H•) described eq 1: (3−5)H3O++OH−→H•+•OH+H2O(1)The also occur (eq 2), generating H2O•+ H2O•–: (4)H2O+H2O→H2O•−+H2O•+(2)The strongly reducing H2O•– weaken formidable N≡N bond produce HN2 radicals, thus activating "stable" N2. Meanwhile, quickly reacts with H2O form •OH–H3O+ pair, rapidly dissociates H3O+ •OH. Once produced, those RS, especially •OH H•, opportunities escape surfaces, usually only one interfacial interactions not very strong. makes behave like "engines" continuously generate reductants, their but nearby phase.What Will We Do?Click copied!As Newton remarked "... whilst great ocean truth lay all undiscovered before me ..." 18th century, we, too, uncertain about impacts droplets, mainly seemingly simple just ocean, environment 21st century. Clearly, we need take action soon possible.First, establish bridge science. Pioneering studies frequently utilized systems analogous electrospray ionization mass spectrometry. However, approaches inherently introduce external perturbations may decouple processes. contrast, vapor adiabatic expansion ultrasonic atomization better replicate observed systems, humidifier-generated droplets. Notably, method circumvents debates over energy-driven artifacts via spontaneous nucleation vapor, where originate inherent thermodynamic forces rather than extrinsic manipulation. Consequently, environmentally representative ways useful evaluating scenarios.Second, should think substances, indoors outdoors, could potentially whether lead impactful consequences potential health risks humidifier). Compounds surfactants, hydrophilic −COOH, −OH, −NH2) hydrophobic −CH2–, −CH3, −CH═CH−) groups, prime candidates accumulate addition, abundant species, thought N2), warrant re-examination.Finally, extend beyond atmosphere ocean's microlayer (SML), many pollutants PFASs (6) organophosphate esters (7) exhibit significant enrichment. During wave-breaking events, hydrodynamic shear generates transient microbubbles sea-spray aerosols simultaneously, creating hot spots intense fields increased levels species. unique physicochemical conditions drive contaminant transformation distinct bulk-phase reactions. SML's matrix enriched inorganic dissolved organic matter) modulate pathways. Deciphering processes critical pollutant fates ecosystems.Author InformationClick copied!Corresponding AuthorsDeming Xia - China; https://orcid.org/0000-0003-4877-0058; Email: [email protected]Jingwen Chen https://orcid.org/0000-0002-5756-3336; protected]AuthorsHong-bin Xie https://orcid.org/0000-0002-9119-9785Zhiqiang Fu https://orcid.org/0000-0003-4199-7436NotesThe authors declare no competing financial interest.BiographiesClick XiaHigh SlideDr. received his doctoral degree Technology supervision Prof. December 2021. After finishing postdoctoral research (January 2022 2024), he was promoted associate professor university. His focuses heterogeneous surfaces. He has published 28 peer-reviewed papers.Hong-bin XieHigh been since 2001. earning Ph.D. Nanjing 1997, performed German Research Center Health Alexander von Humboldtian. interests cover computational toxicology ecological risk control technology synthetic chemicals. 360 papers, reviews, book chapters, well three books (two monographs textbook). served member Teaching Steering Committee China Ministry Education, Discipline Evaluation Group Academic Degrees State Council China, Executive Editor Associated Sustainable Engineering, editorial boards several journals. recipient Award Outstanding Young Teachers Higher Education Institutions 2000, winner (Second Class, second contributor) National Natural 2011, (First (2023) China. 2013, won Fund Distinguished Scholars appointed chair "Cheung Kong Program" Education.AcknowledgmentsClick copied!This study supported Foundation (22206019, 22136001, 22276020), R&D Program (2022YFC3902100), Postdoctoral Innovative Talents (BX20220050), Fundamental Funds Central Universities (DUT24RC(3)047).ReferencesClick copied! references 7 other publications. 1Jiang, Q.; Xia, D. M.; Li, X. F.; Zhang, H.; Yin, R. J.; Xie, H. H.-b.; Jiang, Chen, J. W.; Francisco, S. Rapid N2O Formation N2 Water Droplet Surfaces. Angew. Chem., Int. Ed. 64, e202421002 DOI: 10.1002/anie.202421002 Google ScholarThere corresponding record reference.2Xia, Ju, Y.; Su, L.; Ma, Spontaneous Degradation "Forever Chemicals" Perfluoroalkyl Polyfluoroalkyl Substances (PFASs) Am. Chem. Soc. 2024, 146 (16), 11266– 11271, 10.1021/jacs.4c00435 reference.3Qiu, Cooks, G. Simultaneous Oxidation Reduction Radical Cation/Anion Pair. 2022, 61, e202210765 10.1002/anie.202210765 Scholar3Simultaneous PairQiu, Lingqi; GrahamAngewandte Chemie, International Edition (2022), 61 (41), e202210765CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH Co. KGaA) show chem., esp. intrinsic redox properties, here add case simultaneous oxidn. redn. report concurrent conversions phosphonates phosphonic acids (R-P → H-P) pentavalent phosphoric exptl. results suggest active reagent radical cation/anion pair. obsd. directly ionized dimer while anion seen indirectly though carbon dioxide formate. coexistence oxidative reductive turn supports proposal double-layer structure surface, sepd. accumulated. >> SciFinder ®https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XitlGls7nK&md5=f7f3a5f19c80e62ffbc9ff853a552d5b4Heindel, P.; LaCour, A.; Head-Gordon, T. Role Microdroplet Redox Chemistry. Nat. Commun. 15, 3670, 10.1038/s41467-024-47879-0 reference.5Cooks, G.; Holden, Breaking down 384, 958– 959, 10.1126/science.adp7627 reference.6Casas, Martínez-Varela, Roscales, Vila-Costa, Dachs, Jiménez, B. Enrichment Sea-Surface Microlayer Sea-Spray Aerosols Southern Ocean. Pollut. 2020, 267, 115512, 10.1016/j.envpol.2020.115512 Scholar6Enrichment perfluoroalkyl sea-surface OceanCasas, Gemma; Martinez-Varela, Alicia; Jose Maria; Jordi; Jimenez, BegonaEnvironmental (Oxford, United Kingdom) (2020), 267 (), 115512CODEN: ENPOEK; ISSN:0269-7491. (Elsevier Ltd.) Sea-spray (or sea-salt) aerosol (SSA) subsequent atm. transport deposition suggested play prominent role occurrence ionizable (PFAS) maritime Antarctica remote regions. SSA's vector PFAS lacking. Following multiphase approach, seawater (SW), (SML) SSA were sampled simultaneously South Bay (Livingston Island, Antarctica). Av. concns. 313 pg L-1, 447 0.67 m-3 SW, SML SSA, resp. enrichment factors ranged 1.2 5, 522 4690, amplification consistent surfactant properties PFAS, large facilitated area sorption org. matter. work assessing SSA. measured marine relevant long-range PFAS. ®https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhvVeqs7rJ&md5=bc5c9e2a93a7cfc4a72bb6e2a29060d77Trilla-Prieto, N.; Iriarte, Berrojalbiz, Casas, Sobrino, C.; B.; Organophosphate Esters Sea Surface Atlantic Oceans. Lett. 11 (9), 1008– 1015, 10.1021/acs.estlett.4c00636 reference.Cited By Click cited publications.Download PDFFiguresReferences Get e-AlertsGet e-AlertsEnvironmental copied!https://doi.org/10.1021/acs.est.5c01041Published 2025© permissionsArticle Views-Altmetric-Citations-Learn metrics closeArticle Views COUNTER-compliant sum full text downloads November 2008 (both PDF HTML) across institutions individuals. regularly updated reflect usage up last few days.Citations number articles citing article, calculated Crossref daily. Find information counts.The Altmetric Attention Score quantitative measure attention online. Clicking donut icon will load page altmetric.com additional details score social media presence calculated.Recommended Articles FiguresReferencesAbstractHigh SlideFigure SlideDeming Education.References There 3Simultaneous 6Enrichment reference.
Язык: Английский
Процитировано
0
The Journal of Physical Chemistry A, Год журнала: 2025, Номер unknown
Опубликована: Май 8, 2025
The chemistry underlying biological homochirality remains challenging. We propose that noncovalent clusters may have served as the means by which an enantiomeric excess of one amino acid could direct other racemic acids toward homochiral biochemistry. Serine has long been known to exhibit a chiral preference when clustering form octamer; here, we extend this finding reporting effects nonzero e.e. serine on formation with well peptides, their covalent condensation products. show (i) enantiopure directs leucine and proline enantioselective dipeptide in water microdroplets (ii) likely intermediates are seen substituted octamer clusters. This work indicates relevance microdroplet sprays, e.g., natural aerosols, molecular homochirality.
Язык: Английский
Процитировано
0
Journal of the American Chemical Society, Год журнала: 2025, Номер unknown
Опубликована: Май 9, 2025
This study engineered a superacidic interface with pronounced polar electric field within the amine-water system by inducing hydrogen bond charge transfer in interfacial water via inverted microdroplets (microbubbles), thereby stabilizing protons layer. mechanism enabled continuous alkaline release of hindered amines (AMP-MIS), enhancing CO2 absorption load capacity and reducing regeneration energy consumption. Nuclear magnetic resonance potentiometric titration elucidated product distribution, while Raman spectroscopy, pH analysis, conductivity measurements confirmed proton stabilization. Theoretical calculations provided insights into reaction mechanism. Pilot-scale testing revealed AMP-MIS achieved 74.2% increase cyclic capacity, surpassing conventional 30 wt % MEA system, reduced from 3.667 GJ/t to 1.885 CO2. innovative strategy offers valuable guidance for advancing amine-based decarbonization technologies carbon emissions power industry, representing pivotal step toward neutrality.
Язык: Английский
Процитировано
0
Physical review. B./Physical review. B, Год журнала: 2025, Номер 111(24)
Опубликована: Июнь 5, 2025
Процитировано
0