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Multistimuli-Responsive Enaminitrile Molecular Switches DisplayingH+‑Induced Aggregate Emission, Metal Ion-Induced Turn-OnFluorescence, and Organogelation Properties
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemistry, Organic chemistry. KTH - Royal Institute of Technology.ORCID iD: 0000-0001-5807-8343
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemistry, Organic chemistry.
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2018 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 140, no 42, p. 13640-13643Article in journal (Refereed) Published
Abstract [en]

Multistimuli-responsive enaminitrile-based configurational switches displaying aggregation-induced emission (AIE), fluorescence turn-on effects, and supergelation properties are presented. The E-isomers dominated (>97%) in neutral/basic solution, and the structures underwent precisely controlled switching around the enamine C═C bond upon addition of acid/base. Specific fluorescence output was observed in response to different external input in the solution and solid states. In response to H+, configurational switching resulted in complete formation of the nonemissive Z-H+-isomers in solution, however displaying deep-blue to blue fluorescence (ΦF up to 0.41) in the solid state. In response to CuII in the solution state, the E-isomers exhibited intense, turn-on, blue-green fluorescence, which could be turned off by addition of competitive coordination. The acid/base-activated switching, together with the induced AIE-effects, further enabled the accomplishment of a responsive superorganogelator. In nonpolar solvents, a blue-fluorescent supramolecular gel was formed upon addition of acid to the E-isomer suspension. The gelation could be reversed by addition of base, and the overall, reversible process could be repeated at least five cycles.

Place, publisher, year, edition, pages
2018. Vol. 140, no 42, p. 13640-13643
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-237425DOI: 10.1021/jacs.8b09843ISI: 000448755200025PubMedID: 30351138Scopus ID: 2-s2.0-85055124605OAI: oai:DiVA.org:kth-237425DiVA, id: diva2:1259070
Note

QC 20181030

Available from: 2018-10-26 Created: 2018-10-26 Last updated: 2020-05-20Bibliographically approved
In thesis
1. Dynamic Chemistry for Asymmetric Synthesis, Molecular Motion and Constitutional Exchange
Open this publication in new window or tab >>Dynamic Chemistry for Asymmetric Synthesis, Molecular Motion and Constitutional Exchange
2018 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Living matter is built on complex dynamic systems consisting of numerus biotransformations. By exploiting the adaptive and evolutive behaviors ofmolecular matter, dynamic chemistry has developed as an important tool tounderstand the organization of nonliving matter into complex living systems.This thesis concerns three aspects of dynamic chemistry with a general focus onthe influence of different stimuli on the structures and functions of dynamicsystems.The first section focuses on dynamic kinetic resolution, where enzymes areutilized for asymmetric synthesis of an enantiopure (2R,5R)-1,3-oxathiolane. Byemploying surfactant-treated subtilisin Carlsberg and Candida antarcticalipase B, the absolute configuration of the resulting 1,3-oxathiolane ring couldbe efficiently controlled.The second section addresses the motional dynamics of configurational enamineswitch systems controlled by multiple stimuli. Complete forward and backwardrotation around the enamine C=C bond could be precisely regulated uponaddition of acid/base or metal ions. The enamine switches exhibited specificsensing ability for CuII ions in solution. Moreover, the enamines exhibitedswitchable aggregation-induced emission in the solid state, which could beapplied in the development of sensors as well as fluorescent organogel.Lastly, the enamine switches could readily undergo constitutional exchange withprimary amines under catalytic acidic conditions, resulting in dynamic enaminesystems. However, under basic conditions or in the presence of excessive acid,this process exhibited extremely slow kinetics, leading to an efficient regulationof the exchange process by controlling the switch status with regulation of pHin the system.

Abstract [sv]

Levande organismer är uppbyggda av komplexa dynamiska system avsammankopplade biokemiska transformationer. Dynamisk kemi har genom attutnyttja adaptiva och evolutionära effekter hos molekylära system utvecklats tillett viktigt verktyg för att förstå principerna som styr självorganisation av ickelevande materia. Denna avhandling behandlar tre aspekter av dynamisk kemi,med fokus på vilken påverkan olika stimuli kan ha på strukturer och funktionerhos dynamiska system.Den första sektionen fokuserar på dynamisk kinetisk resolvering, där enzymeranvänds för asymmetrisk syntes av enantiomeriskt rena (2R,5R)-1,3-oxatiolanstrukturer. Genom att utnyttja surfaktant-behandlad subtilisinCarlsberg och Candida antarctica lipas B kunde absolutkonfigurationen av denresulterande 1,3-oxatiolanringen effektivt kontrolleras.Det andra avsnittet behandlar utvecklingen av konfigurationella dynamiskaenamin-omkopplare vars rörelsedynamiska beteende kan påverkas genomstimuli. Rotation av enaminens C=C-binding kunde specifikt kontrolleras i bådefram- och bakåtriktning genom addition av syra/bas eller metalljoner.Enanminkopplingen visade även upp specifik molekylär igenkänningsförmågaför CuII-joner i lösning. Vidare uppvisade enaminen reversibeltaggregationsinducerad emission i det fasta tillståndet, vilket kunde tillämpasinom utveckling av sensorer samt inom materialvetenskap.Slutligen kunde enaminomkopplaren visas genomgå reversibelt utbyte medprimära aminer i närvaro av katalytiska mängder syra, vilket resulterade idynamiska enaminsystem. Under basiska förhållanden eller i närvaro av ettöverskott syra uppvisade denna process mycket långsam kinetik, vilket ledde tilleffektiv reglering av utbytesprocessen och full kontroll av riktning ochkonstitution hos omkopplaren genom systemets pH-värde.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2018. p. 76
Series
TRITA-CBH-FOU ; 2018:55
Keywords
dynamic chemistry, constitutional dynamic chemistry, motional dynamics, dynamic kinetic resolution, enzyme, subtilisin Carlsberg, Candida antarctica lipase B, anti-HIV, 1, 3-oxathiolane, dynamic exchange, enamines, E/Z-isomerization, molecular switches, aggregation, gelation, fluorescence., dynamisk kemi, konstitutionell dynamisk kemi, molekylär rörelsedynamik, dynamisk kinetisk resolvering, enzym, subtilisin Carlsberg, Candida antarctica lipase B, anti-HIV, 1, 3-oxatiolan, dynamisk utbyte, enaminer, E/Z-isomerisering, molekylära omkopplare, aggregering, gelbildning, fluorescens.
National Category
Organic Chemistry
Research subject
Chemistry
Identifiers
urn:nbn:se:kth:diva-237420 (URN)978-91-7873-000-1 (ISBN)
Public defence
2018-12-05, F3, Lindstedtsvägen 26, Stockholm, 10:00 (English)
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Note

QC 20181030

Available from: 2018-10-30 Created: 2018-10-26 Last updated: 2020-05-20Bibliographically approved

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Publisher's full textPubMedScopushttps://pubs.acs.org/doi/abs/10.1021/jacs.8b09843

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Ren, YansongXie, ShengRamström, Olof

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