Optical Fingerprinting of Dynamic Interfacial Reaction Pathways Using Liquid Crystals
Reactions at interfaces between fluid phases are widely used to synthesize small molecules, polymers, and nanoparticles. In situ monitoring of the underlying dynamic reaction pathways remains challenging. Liquid crystals (LCs) have been used to detect simple chemical transformations at interfaces in...
Saved in:
Published in | Langmuir Vol. 39; no. 5; pp. 1793 - 1803 |
---|---|
Main Authors | , , , , |
Format | Journal Article |
Language | English |
Published |
United States
American Chemical Society
07.02.2023
|
Online Access | Get full text |
Cover
Loading…
Abstract | Reactions at interfaces between fluid phases are widely used to synthesize small molecules, polymers, and nanoparticles. In situ monitoring of the underlying dynamic reaction pathways remains challenging. Liquid crystals (LCs) have been used to detect simple chemical transformations at interfaces in situations where interface-bound reactants and products trigger distinct equilibrium orientations of LCs. However, whether or not LCs can be used to report complex reaction pathways via nonequilibrium states generated by reactions has not been explored. Here we explore this question using SN2′ nucleophilic substitution reactions that involve a synthetic amphiphile and a series of amine-based nucleophiles with one to four reaction sites. Although all reactants and products generate the same equilibrium LC orientation, we find that each nucleophile defines a distinct set of possible reaction pathways with a characteristic spatial and temporal LC optical response unique to the nucleophile. Additional experiments reveal that the nonequilibrium orientational states of the LCs arise from a combination of dynamic interfacial processes that include adsorption/desorption of reactants, the presence of reaction intermediates on the LC interface, and the generation of interfacial tension gradients (Marangoni stresses). Overall, our results reveal that the spatiotemporal optical outputs of LCs (“optical fingerprints”) can be a rich source of information regarding interfacial reactions. |
---|---|
AbstractList | Reactions at interfaces between fluid phases are widely used to synthesize small molecules, polymers, and nanoparticles. In situ monitoring of the underlying dynamic reaction pathways remains challenging. Liquid crystals (LCs) have been used to detect simple chemical transformations at interfaces in situations where interface-bound reactants and products trigger distinct equilibrium orientations of LCs. However, whether or not LCs can be used to report complex reaction pathways via nonequilibrium states generated by reactions has not been explored. Here we explore this question using SN2′ nucleophilic substitution reactions that involve a synthetic amphiphile and a series of amine-based nucleophiles with one to four reaction sites. Although all reactants and products generate the same equilibrium LC orientation, we find that each nucleophile defines a distinct set of possible reaction pathways with a characteristic spatial and temporal LC optical response unique to the nucleophile. Additional experiments reveal that the nonequilibrium orientational states of the LCs arise from a combination of dynamic interfacial processes that include adsorption/desorption of reactants, the presence of reaction intermediates on the LC interface, and the generation of interfacial tension gradients (Marangoni stresses). Overall, our results reveal that the spatiotemporal optical outputs of LCs (“optical fingerprints”) can be a rich source of information regarding interfacial reactions. Reactions at interfaces between fluid phases are widely used to synthesize small molecules, polymers, and nanoparticles. monitoring of the underlying dynamic reaction pathways remains challenging. Liquid crystals (LCs) have been used to detect simple chemical transformations at interfaces in situations where interface-bound reactants and products trigger distinct equilibrium orientations of LCs. However, whether or not LCs can be used to report complex reaction pathways via nonequilibrium states generated by reactions has not been explored. Here we explore this question using S 2' nucleophilic substitution reactions that involve a synthetic amphiphile and a series of amine-based nucleophiles with one to four reaction sites. Although all reactants and products generate the same equilibrium LC orientation, we find that each nucleophile defines a distinct set of possible reaction pathways with a characteristic spatial and temporal LC optical response unique to the nucleophile. Additional experiments reveal that the nonequilibrium orientational states of the LCs arise from a combination of dynamic interfacial processes that include adsorption/desorption of reactants, the presence of reaction intermediates on the LC interface, and the generation of interfacial tension gradients (Marangoni stresses). Overall, our results reveal that the spatiotemporal optical outputs of LCs ("optical fingerprints") can be a rich source of information regarding interfacial reactions. |
Author | Abbott, Nicholas L. Krishna, Jithu Fernandez, Ann Wang, Xin Thayumanavan, S. |
AuthorAffiliation | Department of Chemistry Smith School of Chemical and Biomolecular Engineering |
AuthorAffiliation_xml | – name: Smith School of Chemical and Biomolecular Engineering – name: Department of Chemistry |
Author_xml | – sequence: 1 givenname: Xin orcidid: 0000-0002-3004-3293 surname: Wang fullname: Wang, Xin organization: Smith School of Chemical and Biomolecular Engineering – sequence: 2 givenname: Jithu surname: Krishna fullname: Krishna, Jithu organization: Department of Chemistry – sequence: 3 givenname: Ann surname: Fernandez fullname: Fernandez, Ann organization: Department of Chemistry – sequence: 4 givenname: S. orcidid: 0000-0002-6475-6726 surname: Thayumanavan fullname: Thayumanavan, S. email: thai@umass.edu organization: Department of Chemistry – sequence: 5 givenname: Nicholas L. orcidid: 0000-0002-9653-0326 surname: Abbott fullname: Abbott, Nicholas L. email: nla34@cornell.edu organization: Smith School of Chemical and Biomolecular Engineering |
BackLink | https://www.ncbi.nlm.nih.gov/pubmed/36693164$$D View this record in MEDLINE/PubMed |
BookMark | eNp9kMtOwzAQRS1URB_wBwhlySbFjzyXqFBAqlSE2nU0fqS4apzWdoTy97hqy5LVzOLcO5ozRgPTGoXQPcFTgil5AuGmOzCbptN2SgWmGaVXaERSiuO0oPkAjXCesDhPMjZEY-e2GOOSJeUNGrIsKxnJkhFaL_deC9hFc202yu6tNj5sUVtHL72BRovow3hlaxA6UF8KhNetiT7Bf_9A76K1O-ILfei0jGa2dx527hZd12Gou_OcoNX8dTV7jxfLt4_Z8yIGlhQ-5rzkpcSiAKYkCM6pLCXwIhWS00TmlAmi6jTjDFhBsOQFkyKlBXBCOGRsgh5PtXvbHjrlfNVoJ9QuaFFt5yqaZ2Va4oKygCYnVNjWOavqKrzagO0rgqujzyr4rC4-q7PPEHs4X-h4o-Rf6CIwAPgEHOPbtrMm_Pt_5y8-oIk4 |
CitedBy_id | crossref_primary_10_1016_j_cej_2024_149969 crossref_primary_10_1016_j_compchemeng_2024_108723 crossref_primary_10_1021_acs_langmuir_3c03570 |
Cites_doi | 10.1002/anie.201305778 10.1021/acssensors.2c00362 10.1039/C2SM27160E 10.1021/acsami.0c11138 10.1021/acs.langmuir.9b02864 10.1093/oso/9780198520245.003.0004 10.1038/nature01331 10.1039/D0AN02220A 10.1126/science.1195639 10.1002/anie.201916473 10.1021/ja400619k 10.1021/acs.langmuir.1c00133 10.1002/adma.200702012 10.1021/ja802178s 10.1021/acs.langmuir.0c00651 10.1002/1521-4095(200108)13:15<1135::AID-ADMA1135>3.0.CO;2-S 10.1002/adma.201401226 10.1021/ja01577a030 10.1021/jacs.1c04115 10.1021/jacs.9b09216 10.1038/s41586-018-0098-y 10.1007/978-1-4899-1816-1_1 10.1002/smll.201502137 10.1021/jacs.9b13360 10.1126/science.1062293 10.1021/acs.jpcc.0c01942 10.1021/acs.chemmater.0c01107 10.1002/9783527620760 10.1039/C9SC05841A 10.1002/adma.200802289 10.1021/np9600816 10.1021/ja0706955 10.1038/s41929-017-0010-4 10.1002/3527608001 10.1021/jp201909m 10.1021/acsnano.5b07379 10.1021/ja0774055 10.1021/ja036919a 10.1017/jfm.2020.170 |
ContentType | Journal Article |
Copyright | 2023 American Chemical Society |
Copyright_xml | – notice: 2023 American Chemical Society |
DBID | NPM AAYXX CITATION 7X8 |
DOI | 10.1021/acs.langmuir.2c02622 |
DatabaseName | PubMed CrossRef MEDLINE - Academic |
DatabaseTitle | PubMed CrossRef MEDLINE - Academic |
DatabaseTitleList | PubMed |
Database_xml | – sequence: 1 dbid: NPM name: PubMed url: https://proxy.k.utb.cz/login?url=http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed sourceTypes: Index Database |
DeliveryMethod | fulltext_linktorsrc |
Discipline | Chemistry |
EISSN | 1520-5827 |
EndPage | 1803 |
ExternalDocumentID | 10_1021_acs_langmuir_2c02622 36693164 b0554232 |
Genre | Journal Article |
GroupedDBID | --- -~X .K2 4.4 55A 5GY 5VS 7~N AABXI ABFRP ABMVS ABPTK ABQRX ABUCX ACGFS ACJ ACNCT ACS ADHLV AEESW AENEX AFEFF AGXLV AHGAQ ALMA_UNASSIGNED_HOLDINGS AQSVZ BAANH CS3 DU5 EBS ED~ F5P GGK GNL IH9 IHE JG~ RNS ROL TN5 UI2 UPT VF5 VG9 W1F YQT ~02 53G AAHBH ABJNI CUPRZ NPM AAYXX CITATION 7X8 |
ID | FETCH-LOGICAL-a348t-bb9b9d0c8a3edacbb2d9dab85cdb24d723c1ef56b3a3810db83dc528ab11ba63 |
IEDL.DBID | ACS |
ISSN | 0743-7463 |
IngestDate | Sat Aug 17 02:27:53 EDT 2024 Fri Aug 23 01:06:55 EDT 2024 Sat Sep 28 08:22:39 EDT 2024 Thu Jul 06 08:30:32 EDT 2023 |
IsPeerReviewed | true |
IsScholarly | true |
Issue | 5 |
Language | English |
LinkModel | DirectLink |
MergedId | FETCHMERGED-LOGICAL-a348t-bb9b9d0c8a3edacbb2d9dab85cdb24d723c1ef56b3a3810db83dc528ab11ba63 |
Notes | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ORCID | 0000-0002-6475-6726 0000-0002-3004-3293 0000-0002-9653-0326 |
PMID | 36693164 |
PQID | 2769590823 |
PQPubID | 23479 |
PageCount | 11 |
ParticipantIDs | proquest_miscellaneous_2769590823 crossref_primary_10_1021_acs_langmuir_2c02622 pubmed_primary_36693164 acs_journals_10_1021_acs_langmuir_2c02622 |
PublicationCentury | 2000 |
PublicationDate | 20230207 2023-Feb-07 2023-02-07 |
PublicationDateYYYYMMDD | 2023-02-07 |
PublicationDate_xml | – month: 02 year: 2023 text: 20230207 day: 07 |
PublicationDecade | 2020 |
PublicationPlace | United States |
PublicationPlace_xml | – name: United States |
PublicationTitle | Langmuir |
PublicationTitleAlternate | Langmuir |
PublicationYear | 2023 |
Publisher | American Chemical Society |
Publisher_xml | – name: American Chemical Society |
References | ref9/cit9 ref6/cit6 ref36/cit36 ref3/cit3 ref27/cit27 ref18/cit18 ref11/cit11 ref25/cit25 ref16/cit16 ref29/cit29 ref32/cit32 ref23/cit23 ref39/cit39 ref14/cit14 ref8/cit8 ref5/cit5 ref31/cit31 ref2/cit2 ref34/cit34 ref37/cit37 ref28/cit28 ref40/cit40 ref20/cit20 ref17/cit17 ref10/cit10 ref26/cit26 ref35/cit35 ref19/cit19 ref21/cit21 ref12/cit12 ref15/cit15 ref42/cit42 ref41/cit41 ref22/cit22 ref13/cit13 ref33/cit33 ref4/cit4 ref30/cit30 ref1/cit1 ref24/cit24 ref38/cit38 ref7/cit7 |
References_xml | – ident: ref7/cit7 doi: 10.1002/anie.201305778 – ident: ref33/cit33 doi: 10.1021/acssensors.2c00362 – ident: ref37/cit37 doi: 10.1039/C2SM27160E – ident: ref41/cit41 doi: 10.1021/acsami.0c11138 – ident: ref25/cit25 doi: 10.1021/acs.langmuir.9b02864 – ident: ref11/cit11 doi: 10.1093/oso/9780198520245.003.0004 – ident: ref35/cit35 doi: 10.1038/nature01331 – ident: ref32/cit32 doi: 10.1039/D0AN02220A – ident: ref36/cit36 doi: 10.1126/science.1195639 – ident: ref3/cit3 doi: 10.1002/anie.201916473 – ident: ref34/cit34 doi: 10.1021/ja400619k – ident: ref17/cit17 doi: 10.1021/acs.langmuir.1c00133 – ident: ref13/cit13 doi: 10.1002/adma.200702012 – ident: ref5/cit5 doi: 10.1021/ja802178s – ident: ref18/cit18 doi: 10.1021/acs.langmuir.0c00651 – ident: ref1/cit1 – ident: ref39/cit39 doi: 10.1002/1521-4095(200108)13:15<1135::AID-ADMA1135>3.0.CO;2-S – ident: ref6/cit6 doi: 10.1002/adma.201401226 – ident: ref28/cit28 doi: 10.1021/ja01577a030 – ident: ref14/cit14 doi: 10.1021/jacs.1c04115 – ident: ref38/cit38 doi: 10.1021/jacs.9b09216 – ident: ref29/cit29 – ident: ref16/cit16 doi: 10.1038/s41586-018-0098-y – ident: ref23/cit23 doi: 10.1007/978-1-4899-1816-1_1 – ident: ref21/cit21 doi: 10.1002/smll.201502137 – ident: ref19/cit19 doi: 10.1021/jacs.9b13360 – ident: ref22/cit22 doi: 10.1126/science.1062293 – ident: ref31/cit31 doi: 10.1021/acs.jpcc.0c01942 – ident: ref24/cit24 doi: 10.1021/acs.chemmater.0c01107 – ident: ref12/cit12 doi: 10.1002/9783527620760 – ident: ref26/cit26 doi: 10.1039/C9SC05841A – ident: ref2/cit2 doi: 10.1002/adma.200802289 – ident: ref9/cit9 doi: 10.1021/np9600816 – ident: ref27/cit27 doi: 10.1021/ja0706955 – ident: ref10/cit10 doi: 10.1038/s41929-017-0010-4 – ident: ref42/cit42 – ident: ref8/cit8 doi: 10.1002/3527608001 – ident: ref20/cit20 doi: 10.1021/jp201909m – ident: ref40/cit40 doi: 10.1021/acsnano.5b07379 – ident: ref15/cit15 doi: 10.1021/ja0774055 – ident: ref4/cit4 doi: 10.1021/ja036919a – ident: ref30/cit30 doi: 10.1017/jfm.2020.170 |
SSID | ssj0009349 |
Score | 2.4902837 |
Snippet | Reactions at interfaces between fluid phases are widely used to synthesize small molecules, polymers, and nanoparticles. In situ monitoring of the underlying... Reactions at interfaces between fluid phases are widely used to synthesize small molecules, polymers, and nanoparticles. monitoring of the underlying dynamic... |
SourceID | proquest crossref pubmed acs |
SourceType | Aggregation Database Index Database Publisher |
StartPage | 1793 |
Title | Optical Fingerprinting of Dynamic Interfacial Reaction Pathways Using Liquid Crystals |
URI | http://dx.doi.org/10.1021/acs.langmuir.2c02622 https://www.ncbi.nlm.nih.gov/pubmed/36693164 https://search.proquest.com/docview/2769590823 |
Volume | 39 |
hasFullText | 1 |
inHoldings | 1 |
isFullTextHit | |
isPrint | |
link | http://utb.summon.serialssolutions.com/2.0.0/link/0/eLvHCXMwlV1bS8MwFA6iD_ri_TJvRPDFh841adPmUapjiDrRDfZWcisMtZtri8xfb9K0DpWhvpYQ2pOTnu985wbAaZJ4HlX6pmnbS7SDgonDtBfhhFwS5TGplcjUDt_ekU7fux74g5mj-D2Cj9xzJrKm4e5eiuGkiYT2GZD-5S4hk0RooFD0OGuyiy3cNW03A4_gulRuzi7GIInsq0GagzJLa9NeA926ZscmmTw1i5w3xfvPFo5__JB1sFoBT3hhNWUDLKh0EyxH9by3LdDvjkteG7ZLps8QfiYlGo4SeGnH1sOSPkyYYdnhg7IlEfBeY8g3Ns1gmX0Ab4avxVDCaDLVuPM52wa99lUv6jjV0AWHYS_MHc4pp7IlQoaVZIJzJKlkPPSF5MiTAcLCVYlPOGamOZjkIZbCRyHjrssZwTtgMR2lag9ALnGopDKYjWlYqJFQ4PqStmig1wcCNcCZFklc3ZksLsPhyI3Nw1pOcSWnBnDqQ4rHtg3HL-tP6pOMtRhNEISlalRkMQoItXPeG2DXHvHnjpgQirX_uP-PNzsAK2YCfZnIHRyCxXxSqCONU3J-XCrnB9ju5W4 |
link.rule.ids | 315,786,790,2782,27109,27957,27958,57093,57143 |
linkProvider | American Chemical Society |
linkToHtml | http://utb.summon.serialssolutions.com/2.0.0/link/0/eLvHCXMwlV1LT8MwDLYQHODC-zGeQeLCoYMmbdoe0WAaMB6CgbhVeVWagG2sqxD8epx0BYGEENcoslLbqT87fgDsZVkQJAZvGtpejg4K455AL8KLpeYmEBqVyNYOX1zy1l1w9hA-TEBY1cLgIXKklLtH_K_uAv6BXbMhvOeiO6xTha4DxT_vVBihS24RUeP2q9cuK1Gv7b4ZBZxVFXO_ULF2SeXf7dIvYNMZneYc3H8e1-WaPNaLkayr9x-dHP_9PfMwO4ah5KjUmwWYML1FmG5U09-W4O5q4KLcpOnifjb8ZxOkST8jx-UQe-KCiZmwMXdyY8oCCXKNiPJVvOXE5SKQdvel6GrSGL4hCn3Kl6HTPOk0Wt54BIMnWBCPPCkTmehDFQtmtFBSUp1oIeNQaUkDHVGmfJOFXDJhW4VpGTOtQhoL6ftScLYCk71-z6wBkZrFRhuL4ASCRMRFkR_q5DCJcH-kaA32kSXp-AblqXscp35qFys-pWM-1cCrZJUOyqYcf-zfrQSaIhvtk4jomX6RpzTiSTn1vQarpaQ_KTLOE4be5Po_TrYD063ORTttn16eb8CMnU3vUryjTZgcDQuzhQhmJLedvn4AzPbt2Q |
linkToPdf | http://utb.summon.serialssolutions.com/2.0.0/link/0/eLvHCXMwnV1ZS8NAEF5EQX3xPuq5gi8-pJrdZJM8SmvxqFq0BfEl7BUoalubBtFf7-wm8YIi-rosw2ZmN_PN7Ox8CO0niedFGk4a-F4GAQplDocowgmFYtrjCjaReTt8ecVOO975nX_3heoLFpGCpNRe4ptTPVBJ0WHAPTTjJo33lHWHVSIhfCDw953yDYe3QUW1289-uzRHvqYDZ-AxWr6aGyPF-CaZfvdNYwCndTyNeXT_sWRbb_JQzUaiKt9-dHP81zctoLkCjuLjfP8sogndW0IztZIFbhl1rgc2240bNv9n0oCmUBr3E1zPyeyxTSom3OTe8Y3OH0rgFiDLF_6aYluTgJvd56yrcG34Cmj0MV1B7cZJu3bqFFQMDqdeOHKEiESkjmTIqVZcCkFUpLgIfakE8VRAqHR14jNBuWkZpkRIlfRJyIXrCs7oKprs9Xt6HWGhaKiVNkiOA1gEfBS4voqOogDmB5JU0AGoJC5OUhrbS3Lixmaw1FNc6KmCnNJe8SBvzvHL_L3SqDGo0VyN8J7uZ2lMAhbl7O8VtJZb-0MiZSyiEFVu_GFlu2i6VW_EzbOri000ayjqbaV3sIUmR8NMbwOQGYkdu2XfAV8G8FM |
openUrl | ctx_ver=Z39.88-2004&ctx_enc=info%3Aofi%2Fenc%3AUTF-8&rfr_id=info%3Asid%2Fsummon.serialssolutions.com&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx%3Ajournal&rft.genre=article&rft.atitle=Optical+Fingerprinting+of+Dynamic+Interfacial+Reaction+Pathways+Using+Liquid+Crystals&rft.jtitle=Langmuir&rft.au=Wang%2C+Xin&rft.au=Krishna%2C+Jithu&rft.au=Fernandez%2C+Ann&rft.au=Thayumanavan%2C+S.&rft.date=2023-02-07&rft.issn=0743-7463&rft.eissn=1520-5827&rft.volume=39&rft.issue=5&rft.spage=1793&rft.epage=1803&rft_id=info:doi/10.1021%2Facs.langmuir.2c02622&rft.externalDBID=n%2Fa&rft.externalDocID=10_1021_acs_langmuir_2c02622 |
thumbnail_l | http://covers-cdn.summon.serialssolutions.com/index.aspx?isbn=/lc.gif&issn=0743-7463&client=summon |
thumbnail_m | http://covers-cdn.summon.serialssolutions.com/index.aspx?isbn=/mc.gif&issn=0743-7463&client=summon |
thumbnail_s | http://covers-cdn.summon.serialssolutions.com/index.aspx?isbn=/sc.gif&issn=0743-7463&client=summon |