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...
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Veröffentlicht in: | Macromolecular rapid communications. 2021-09, Vol.42 (18), p.e2100169-n/a |
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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 |
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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> |
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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 |
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