Fluoride‐Triggered Self‐Degradation of Poly(2,4‐disubstitued 4‐hydroxybutyric acid) Derivatives

Self‐immolative polymers are a special kind of degradable polymers that depolymerize into small molecules through a cascade of reactions upon stimuli‐triggered cleavage of the polymer chain ends. This work reports the design and synthesis of a fluoride‐triggered self‐immolative polyester. A 2,4‐disu...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Veröffentlicht in:Macromolecular rapid communications. 2021-09, Vol.42 (18), p.e2100169-n/a
Hauptverfasser: Kan, Xiao‐Wei, Zhang, Li‐Jing, Li, Zhao‐Yue, Du, Fu‐Sheng, Li, Zi‐Chen
Format: Artikel
Sprache:eng
Schlagworte:
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
container_end_page n/a
container_issue 18
container_start_page e2100169
container_title Macromolecular rapid communications.
container_volume 42
creator Kan, Xiao‐Wei
Zhang, Li‐Jing
Li, Zhao‐Yue
Du, Fu‐Sheng
Li, Zi‐Chen
description Self‐immolative polymers are a special kind of degradable polymers that depolymerize into small molecules through a cascade of reactions upon stimuli‐triggered cleavage of the polymer chain ends. This work reports the design and synthesis of a fluoride‐triggered self‐immolative polyester. A 2,4‐disubstitued 4‐hydroxy butyrate is first confirmed to quickly cyclize in solution to form a γ−butyrolactone derivative. Then, the Passerini three component reaction (P‐3CR) of an AB dimer (A: aldehyde, B: carboxylic acid) with tert‐butyl isocyanide or oligo(ethylene glycol) isocyanide affords two poly(2,4‐disubstitued 4‐hydroxybutyrate) derivatives (P2 and P3). Two silyl ether end‐capped polymers (P4 and P5) are abtained from P2 and P3, and their degradation in solution is examined by NMR spectrum and size exclusion chromatography. Polymers P4 and P5 are stable in the absence of tetrabutylammonium fluoride (TBAF), while in the presence of TBAF, the molar masses of P4 and P5 gradually decrease with time together with the increase of the amount of formed 2,4‐disubstitued γ‐butyrolactone. The depolymerization mechanism is proposed. The first step is the fast removal of the silyl ether by fluoride. Then, the released hydroxyl group initiates the quick head‐to‐tail depolymerization of the polyester via intramolecular cyclization. A silyl ether end‐capped group poly(2,4‐disubstitued 4‐hydroxybutyric acid) derivative is designed and synthesized via Passerini three component reaction. This polyester is stable in solution with no random hydrolysis or other non‐specific trigger‐induced degradation. Upon triggering by fluoride, it depolymerizes via intramolecular cyclization into 2,4‐disubstitued γ‐butyrolactone derivatives.
doi_str_mv 10.1002/marc.202100169
format Article
fullrecord <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_2531534277</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2531534277</sourcerecordid><originalsourceid>FETCH-LOGICAL-c3509-17ac3163a9c563726894407ee0a789ca930cfcf541e8655f503fe0e1f77afea23</originalsourceid><addsrcrecordid>eNqFkE1LAzEQhhdR8PPqecFLBbdOks2mOUr9hIqi9bzE7KSmbJua7Kp78yf4G_0lplQUvHiamXeedxjeJNkn0CcA9HimvO5ToHEghVxLtginJGOSivXYA6UZYazYTLZDmALAIAe6lUzO69Z5W-Hn-8fY28kEPVbpPdYmCqc48apSjXXz1Jn01tVdjx7lcVPZ0D6GxjZtpJfCU1d599Y9tk3nrU6VttVheorevkT7C4bdZMOoOuDed91JHs7PxsPLbHRzcTU8GWWacZAZEUozUjAlNS-YoMVA5jkIRFBiILWSDLTRhucEBwXnhgMzCEiMEMqgomwn6a3uLrx7bjE05cwGjXWt5ujaUFLOCGc5FSKiB3_QqWv9PH4XKZEXecEkRKq_orR3IXg05cLbGHVXEiiXuZfL3Muf3KNBrgyvtsbuH7q8Prkb_nq_AAGiip4</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2574646390</pqid></control><display><type>article</type><title>Fluoride‐Triggered Self‐Degradation of Poly(2,4‐disubstitued 4‐hydroxybutyric acid) Derivatives</title><source>Wiley Online Library All Journals</source><creator>Kan, Xiao‐Wei ; Zhang, Li‐Jing ; Li, Zhao‐Yue ; Du, Fu‐Sheng ; Li, Zi‐Chen</creator><creatorcontrib>Kan, Xiao‐Wei ; Zhang, Li‐Jing ; Li, Zhao‐Yue ; Du, Fu‐Sheng ; Li, Zi‐Chen</creatorcontrib><description>Self‐immolative polymers are a special kind of degradable polymers that depolymerize into small molecules through a cascade of reactions upon stimuli‐triggered cleavage of the polymer chain ends. This work reports the design and synthesis of a fluoride‐triggered self‐immolative polyester. A 2,4‐disubstitued 4‐hydroxy butyrate is first confirmed to quickly cyclize in solution to form a γ−butyrolactone derivative. Then, the Passerini three component reaction (P‐3CR) of an AB dimer (A: aldehyde, B: carboxylic acid) with tert‐butyl isocyanide or oligo(ethylene glycol) isocyanide affords two poly(2,4‐disubstitued 4‐hydroxybutyrate) derivatives (P2 and P3). Two silyl ether end‐capped polymers (P4 and P5) are abtained from P2 and P3, and their degradation in solution is examined by NMR spectrum and size exclusion chromatography. Polymers P4 and P5 are stable in the absence of tetrabutylammonium fluoride (TBAF), while in the presence of TBAF, the molar masses of P4 and P5 gradually decrease with time together with the increase of the amount of formed 2,4‐disubstitued γ‐butyrolactone. The depolymerization mechanism is proposed. The first step is the fast removal of the silyl ether by fluoride. Then, the released hydroxyl group initiates the quick head‐to‐tail depolymerization of the polyester via intramolecular cyclization. A silyl ether end‐capped group poly(2,4‐disubstitued 4‐hydroxybutyric acid) derivative is designed and synthesized via Passerini three component reaction. This polyester is stable in solution with no random hydrolysis or other non‐specific trigger‐induced degradation. Upon triggering by fluoride, it depolymerizes via intramolecular cyclization into 2,4‐disubstitued γ‐butyrolactone derivatives.</description><identifier>ISSN: 1022-1336</identifier><identifier>EISSN: 1521-3927</identifier><identifier>DOI: 10.1002/marc.202100169</identifier><language>eng</language><publisher>Weinheim: Wiley Subscription Services, Inc</publisher><subject>Aldehydes ; Butyrolactone ; Carboxylic acids ; Cascade chemical reactions ; Degradation ; Depolymerization ; Dimers ; Ethylene glycol ; fluoride ; Fluorides ; Hydroxyl groups ; Ions ; NMR ; Nuclear magnetic resonance ; Passerini reaction ; poly(4‐hydroxybutyric acid) ; polyesters ; Polyethylene glycol ; Polymers ; self‐immolative ; Size exclusion chromatography</subject><ispartof>Macromolecular rapid communications., 2021-09, Vol.42 (18), p.e2100169-n/a</ispartof><rights>2021 Wiley‐VCH GmbH</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c3509-17ac3163a9c563726894407ee0a789ca930cfcf541e8655f503fe0e1f77afea23</citedby><cites>FETCH-LOGICAL-c3509-17ac3163a9c563726894407ee0a789ca930cfcf541e8655f503fe0e1f77afea23</cites><orcidid>0000-0002-0746-9050</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fmarc.202100169$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fmarc.202100169$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,780,784,1417,27924,27925,45574,45575</link.rule.ids></links><search><creatorcontrib>Kan, Xiao‐Wei</creatorcontrib><creatorcontrib>Zhang, Li‐Jing</creatorcontrib><creatorcontrib>Li, Zhao‐Yue</creatorcontrib><creatorcontrib>Du, Fu‐Sheng</creatorcontrib><creatorcontrib>Li, Zi‐Chen</creatorcontrib><title>Fluoride‐Triggered Self‐Degradation of Poly(2,4‐disubstitued 4‐hydroxybutyric acid) Derivatives</title><title>Macromolecular rapid communications.</title><description>Self‐immolative polymers are a special kind of degradable polymers that depolymerize into small molecules through a cascade of reactions upon stimuli‐triggered cleavage of the polymer chain ends. This work reports the design and synthesis of a fluoride‐triggered self‐immolative polyester. A 2,4‐disubstitued 4‐hydroxy butyrate is first confirmed to quickly cyclize in solution to form a γ−butyrolactone derivative. Then, the Passerini three component reaction (P‐3CR) of an AB dimer (A: aldehyde, B: carboxylic acid) with tert‐butyl isocyanide or oligo(ethylene glycol) isocyanide affords two poly(2,4‐disubstitued 4‐hydroxybutyrate) derivatives (P2 and P3). Two silyl ether end‐capped polymers (P4 and P5) are abtained from P2 and P3, and their degradation in solution is examined by NMR spectrum and size exclusion chromatography. Polymers P4 and P5 are stable in the absence of tetrabutylammonium fluoride (TBAF), while in the presence of TBAF, the molar masses of P4 and P5 gradually decrease with time together with the increase of the amount of formed 2,4‐disubstitued γ‐butyrolactone. The depolymerization mechanism is proposed. The first step is the fast removal of the silyl ether by fluoride. Then, the released hydroxyl group initiates the quick head‐to‐tail depolymerization of the polyester via intramolecular cyclization. A silyl ether end‐capped group poly(2,4‐disubstitued 4‐hydroxybutyric acid) derivative is designed and synthesized via Passerini three component reaction. This polyester is stable in solution with no random hydrolysis or other non‐specific trigger‐induced degradation. Upon triggering by fluoride, it depolymerizes via intramolecular cyclization into 2,4‐disubstitued γ‐butyrolactone derivatives.</description><subject>Aldehydes</subject><subject>Butyrolactone</subject><subject>Carboxylic acids</subject><subject>Cascade chemical reactions</subject><subject>Degradation</subject><subject>Depolymerization</subject><subject>Dimers</subject><subject>Ethylene glycol</subject><subject>fluoride</subject><subject>Fluorides</subject><subject>Hydroxyl groups</subject><subject>Ions</subject><subject>NMR</subject><subject>Nuclear magnetic resonance</subject><subject>Passerini reaction</subject><subject>poly(4‐hydroxybutyric acid)</subject><subject>polyesters</subject><subject>Polyethylene glycol</subject><subject>Polymers</subject><subject>self‐immolative</subject><subject>Size exclusion chromatography</subject><issn>1022-1336</issn><issn>1521-3927</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2021</creationdate><recordtype>article</recordtype><recordid>eNqFkE1LAzEQhhdR8PPqecFLBbdOks2mOUr9hIqi9bzE7KSmbJua7Kp78yf4G_0lplQUvHiamXeedxjeJNkn0CcA9HimvO5ToHEghVxLtginJGOSivXYA6UZYazYTLZDmALAIAe6lUzO69Z5W-Hn-8fY28kEPVbpPdYmCqc48apSjXXz1Jn01tVdjx7lcVPZ0D6GxjZtpJfCU1d599Y9tk3nrU6VttVheorevkT7C4bdZMOoOuDed91JHs7PxsPLbHRzcTU8GWWacZAZEUozUjAlNS-YoMVA5jkIRFBiILWSDLTRhucEBwXnhgMzCEiMEMqgomwn6a3uLrx7bjE05cwGjXWt5ujaUFLOCGc5FSKiB3_QqWv9PH4XKZEXecEkRKq_orR3IXg05cLbGHVXEiiXuZfL3Muf3KNBrgyvtsbuH7q8Prkb_nq_AAGiip4</recordid><startdate>202109</startdate><enddate>202109</enddate><creator>Kan, Xiao‐Wei</creator><creator>Zhang, Li‐Jing</creator><creator>Li, Zhao‐Yue</creator><creator>Du, Fu‐Sheng</creator><creator>Li, Zi‐Chen</creator><general>Wiley Subscription Services, Inc</general><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>7U5</scope><scope>8FD</scope><scope>JG9</scope><scope>JQ2</scope><scope>L7M</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0002-0746-9050</orcidid></search><sort><creationdate>202109</creationdate><title>Fluoride‐Triggered Self‐Degradation of Poly(2,4‐disubstitued 4‐hydroxybutyric acid) Derivatives</title><author>Kan, Xiao‐Wei ; Zhang, Li‐Jing ; Li, Zhao‐Yue ; Du, Fu‐Sheng ; Li, Zi‐Chen</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c3509-17ac3163a9c563726894407ee0a789ca930cfcf541e8655f503fe0e1f77afea23</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2021</creationdate><topic>Aldehydes</topic><topic>Butyrolactone</topic><topic>Carboxylic acids</topic><topic>Cascade chemical reactions</topic><topic>Degradation</topic><topic>Depolymerization</topic><topic>Dimers</topic><topic>Ethylene glycol</topic><topic>fluoride</topic><topic>Fluorides</topic><topic>Hydroxyl groups</topic><topic>Ions</topic><topic>NMR</topic><topic>Nuclear magnetic resonance</topic><topic>Passerini reaction</topic><topic>poly(4‐hydroxybutyric acid)</topic><topic>polyesters</topic><topic>Polyethylene glycol</topic><topic>Polymers</topic><topic>self‐immolative</topic><topic>Size exclusion chromatography</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Kan, Xiao‐Wei</creatorcontrib><creatorcontrib>Zhang, Li‐Jing</creatorcontrib><creatorcontrib>Li, Zhao‐Yue</creatorcontrib><creatorcontrib>Du, Fu‐Sheng</creatorcontrib><creatorcontrib>Li, Zi‐Chen</creatorcontrib><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>ProQuest Computer Science Collection</collection><collection>Advanced Technologies Database with Aerospace</collection><collection>MEDLINE - Academic</collection><jtitle>Macromolecular rapid communications.</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Kan, Xiao‐Wei</au><au>Zhang, Li‐Jing</au><au>Li, Zhao‐Yue</au><au>Du, Fu‐Sheng</au><au>Li, Zi‐Chen</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Fluoride‐Triggered Self‐Degradation of Poly(2,4‐disubstitued 4‐hydroxybutyric acid) Derivatives</atitle><jtitle>Macromolecular rapid communications.</jtitle><date>2021-09</date><risdate>2021</risdate><volume>42</volume><issue>18</issue><spage>e2100169</spage><epage>n/a</epage><pages>e2100169-n/a</pages><issn>1022-1336</issn><eissn>1521-3927</eissn><abstract>Self‐immolative polymers are a special kind of degradable polymers that depolymerize into small molecules through a cascade of reactions upon stimuli‐triggered cleavage of the polymer chain ends. This work reports the design and synthesis of a fluoride‐triggered self‐immolative polyester. A 2,4‐disubstitued 4‐hydroxy butyrate is first confirmed to quickly cyclize in solution to form a γ−butyrolactone derivative. Then, the Passerini three component reaction (P‐3CR) of an AB dimer (A: aldehyde, B: carboxylic acid) with tert‐butyl isocyanide or oligo(ethylene glycol) isocyanide affords two poly(2,4‐disubstitued 4‐hydroxybutyrate) derivatives (P2 and P3). Two silyl ether end‐capped polymers (P4 and P5) are abtained from P2 and P3, and their degradation in solution is examined by NMR spectrum and size exclusion chromatography. Polymers P4 and P5 are stable in the absence of tetrabutylammonium fluoride (TBAF), while in the presence of TBAF, the molar masses of P4 and P5 gradually decrease with time together with the increase of the amount of formed 2,4‐disubstitued γ‐butyrolactone. The depolymerization mechanism is proposed. The first step is the fast removal of the silyl ether by fluoride. Then, the released hydroxyl group initiates the quick head‐to‐tail depolymerization of the polyester via intramolecular cyclization. A silyl ether end‐capped group poly(2,4‐disubstitued 4‐hydroxybutyric acid) derivative is designed and synthesized via Passerini three component reaction. This polyester is stable in solution with no random hydrolysis or other non‐specific trigger‐induced degradation. Upon triggering by fluoride, it depolymerizes via intramolecular cyclization into 2,4‐disubstitued γ‐butyrolactone derivatives.</abstract><cop>Weinheim</cop><pub>Wiley Subscription Services, Inc</pub><doi>10.1002/marc.202100169</doi><tpages>7</tpages><orcidid>https://orcid.org/0000-0002-0746-9050</orcidid></addata></record>
fulltext fulltext
identifier ISSN: 1022-1336
ispartof Macromolecular rapid communications., 2021-09, Vol.42 (18), p.e2100169-n/a
issn 1022-1336
1521-3927
language eng
recordid cdi_proquest_miscellaneous_2531534277
source Wiley Online Library All Journals
subjects Aldehydes
Butyrolactone
Carboxylic acids
Cascade chemical reactions
Degradation
Depolymerization
Dimers
Ethylene glycol
fluoride
Fluorides
Hydroxyl groups
Ions
NMR
Nuclear magnetic resonance
Passerini reaction
poly(4‐hydroxybutyric acid)
polyesters
Polyethylene glycol
Polymers
self‐immolative
Size exclusion chromatography
title Fluoride‐Triggered Self‐Degradation of Poly(2,4‐disubstitued 4‐hydroxybutyric acid) Derivatives
url https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-08T06%3A15%3A29IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Fluoride%E2%80%90Triggered%20Self%E2%80%90Degradation%20of%20Poly(2,4%E2%80%90disubstitued%204%E2%80%90hydroxybutyric%20acid)%20Derivatives&rft.jtitle=Macromolecular%20rapid%20communications.&rft.au=Kan,%20Xiao%E2%80%90Wei&rft.date=2021-09&rft.volume=42&rft.issue=18&rft.spage=e2100169&rft.epage=n/a&rft.pages=e2100169-n/a&rft.issn=1022-1336&rft.eissn=1521-3927&rft_id=info:doi/10.1002/marc.202100169&rft_dat=%3Cproquest_cross%3E2531534277%3C/proquest_cross%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=2574646390&rft_id=info:pmid/&rfr_iscdi=true