Dimensional Control of Block Copolymer Nanofibers with a π-Conjugated Core: Crystallization-Driven Solution Self-Assembly of Amphiphilic Poly(3-hexylthiophene)-b-poly(2-vinylpyridine)
With the aim of accessing colloidally stable, fiberlike, π‐conjugated nanostructures of controlled length, we have studied the solution self‐assembly of two asymmetric crystalline–coil, regioregular poly(3‐hexylthiophene)‐b‐poly(2‐vinylpyridine) (P3HT‐b‐P2VP) diblock copolymers, P3HT23‐b‐P2VP115 (bl...
Gespeichert in:
| Veröffentlicht in: | Chemistry : a European journal 2013-07, Vol.19 (28), p.9186-9197 |
|---|---|
| Hauptverfasser: | , , , , , , , , |
| Format: | Artikel |
| Sprache: | eng |
| Schlagworte: | |
| Online-Zugang: | Volltext |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| container_end_page | 9197 |
|---|---|
| container_issue | 28 |
| container_start_page | 9186 |
| container_title | Chemistry : a European journal |
| container_volume | 19 |
| creator | Gwyther, Jessica Gilroy, Joe B. Rupar, Paul A. Lunn, David J. Kynaston, Emily Patra, Sanjib K. Whittell, George R. Winnik, Mitchell A. Manners, Ian |
| description | With the aim of accessing colloidally stable, fiberlike, π‐conjugated nanostructures of controlled length, we have studied the solution self‐assembly of two asymmetric crystalline–coil, regioregular poly(3‐hexylthiophene)‐b‐poly(2‐vinylpyridine) (P3HT‐b‐P2VP) diblock copolymers, P3HT23‐b‐P2VP115 (block ratio=1:5) and P3HT44‐b‐P2VP115 (block ratio=ca. 1:3). The self‐assembly studies were performed under a variety of solvent conditions that were selective for the P2VP block. The block copolymers were prepared by using Cu‐catalyzed azide–alkyne cycloaddition reactions of azide‐terminated P2VP and alkyne end‐functionalized P3HT homopolymers. When the block copolymers were self‐assembled in a solution of a 50 % (v/v) mixture of THF (a good solvent for both blocks) and an alcohol (a selective solvent for the P2VP block) by means of the slow evaporation of the common solvent; fiberlike micelles with a P3HT core and a P2VP corona were observed by transmission electron microscopy (TEM). The average lengths of the micelles were found to increase as the length of the hydrocarbon chain increased in the P2VP‐selective alcoholic solvent (MeOH |
| doi_str_mv | 10.1002/chem.201300463 |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_1778049200</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>1778049200</sourcerecordid><originalsourceid>FETCH-LOGICAL-c2983-c466fa28410b4c95b3ffc907705c9678373c06c4d5da0de39df2cfbbc5aa73403</originalsourceid><addsrcrecordid>eNqFkcFu1DAQhiMEokvhyhH5uBy82HFib7ht07IFlYJUEBIXy3EmxK0TBztpm576WLwFr0SiLStuSJZGHn3_P6P5o-glJStKSPxG19CsYkIZIQlnj6IFTWOKmeDp42hBskRgnrLsIHoWwiUhJOOMPY0OYiYYY5Qvol_HpoE2GNcqi3LX9t5Z5Cp0ZJ2-mhqds2MDHp2r1lWmAB_QjelrpNDvezzxl8MP1UM5kR7eotyPoVfWmjvVT5b42JtraNGFs8P8RxdgK7wJAZrCjvOYTdPVZnrWaPR5GrVkuIbb0fa1cV0NLbzGBZ53WMb42rSj7UZvSjP1n0dPKmUDvHioh9HXdydf8lN89mn7Pt-cYR1na4Z1wnml4nVCSZHoLC1YVemMCEFSnXGxng6hCddJmZaKlMCysop1VRQ6VUqwhLDDaLnz7bz7OUDoZWOCBmtVC24IkgqxJkkWkxld7VDtXQgeKtl50yg_SkrknJac05L7tCbBqwfvoWig3ON_45mAbAfcGAvjf-xkfnry8V9zvNOa0MPtXqv8leSCiVR-O99K8p2uU7pN5Af2B0BStGU</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>1778049200</pqid></control><display><type>article</type><title>Dimensional Control of Block Copolymer Nanofibers with a π-Conjugated Core: Crystallization-Driven Solution Self-Assembly of Amphiphilic Poly(3-hexylthiophene)-b-poly(2-vinylpyridine)</title><source>Access via Wiley Online Library</source><creator>Gwyther, Jessica ; Gilroy, Joe B. ; Rupar, Paul A. ; Lunn, David J. ; Kynaston, Emily ; Patra, Sanjib K. ; Whittell, George R. ; Winnik, Mitchell A. ; Manners, Ian</creator><creatorcontrib>Gwyther, Jessica ; Gilroy, Joe B. ; Rupar, Paul A. ; Lunn, David J. ; Kynaston, Emily ; Patra, Sanjib K. ; Whittell, George R. ; Winnik, Mitchell A. ; Manners, Ian</creatorcontrib><description>With the aim of accessing colloidally stable, fiberlike, π‐conjugated nanostructures of controlled length, we have studied the solution self‐assembly of two asymmetric crystalline–coil, regioregular poly(3‐hexylthiophene)‐b‐poly(2‐vinylpyridine) (P3HT‐b‐P2VP) diblock copolymers, P3HT23‐b‐P2VP115 (block ratio=1:5) and P3HT44‐b‐P2VP115 (block ratio=ca. 1:3). The self‐assembly studies were performed under a variety of solvent conditions that were selective for the P2VP block. The block copolymers were prepared by using Cu‐catalyzed azide–alkyne cycloaddition reactions of azide‐terminated P2VP and alkyne end‐functionalized P3HT homopolymers. When the block copolymers were self‐assembled in a solution of a 50 % (v/v) mixture of THF (a good solvent for both blocks) and an alcohol (a selective solvent for the P2VP block) by means of the slow evaporation of the common solvent; fiberlike micelles with a P3HT core and a P2VP corona were observed by transmission electron microscopy (TEM). The average lengths of the micelles were found to increase as the length of the hydrocarbon chain increased in the P2VP‐selective alcoholic solvent (MeOH<iPrOH<nBuOH). Very long (>3 μm) fiberlike micelles were prepared by the dialysis of solutions of the block copolymers in THF against iPrOH. Furthermore the widths of the fibers were dependent on the degree of polymerization of the chain‐extended P3HT blocks. The crystallinity and π‐conjugated nature of the P3HT core in the fiberlike micelles was confirmed by a combination of UV/Vis spectroscopy, photoluminescence (PL) measurements, and wide‐angle X‐ray scattering (WAXS). Intense sonication (iPrOH, 1 h, 0 °C) of the fiberlike micelles formed by P3HT23‐b‐P2VP115 resulted in small (ca. 25 nm long) stublike fragments that were subsequently used as initiators in seeded growth experiments. Addition of P3HT23‐b‐P2VP115 unimers to the seeds allowed the preparation of fiberlike micelles with narrow length distributions (Lw/Ln <1.11) and lengths from about 100‐300 nm, that were dependent on the unimer‐to‐seed micelle ratio.
From polymers to micelles: Colloidally‐stable π‐conjugated nanowires of controlled length up to 300 nm are available through the crystallization‐driven, solution self‐assembly of poly(3‐hexylthiophene)‐b‐poly(2‐vinylpyridine) (P3HT‐b‐P2VP) diblock copolymers. Detailed studies show that the degree of polymerization of the regioregular, crystalline P3HT core‐forming block, the solvent quality, and the rate of the self‐assembly process profoundly influence the formation of well‐defined fiberlike micelle structures.</description><identifier>ISSN: 0947-6539</identifier><identifier>EISSN: 1521-3765</identifier><identifier>DOI: 10.1002/chem.201300463</identifier><identifier>PMID: 23733316</identifier><language>eng</language><publisher>Weinheim: WILEY-VCH Verlag</publisher><subject>Block copolymers ; Blocking ; Crystal structure ; Crystallization ; Degree of polymerization ; Micelles ; nanowires ; Self assembly ; Solvents</subject><ispartof>Chemistry : a European journal, 2013-07, Vol.19 (28), p.9186-9197</ispartof><rights>Copyright © 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><rights>Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c2983-c466fa28410b4c95b3ffc907705c9678373c06c4d5da0de39df2cfbbc5aa73403</citedby><cites>FETCH-LOGICAL-c2983-c466fa28410b4c95b3ffc907705c9678373c06c4d5da0de39df2cfbbc5aa73403</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fchem.201300463$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fchem.201300463$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,780,784,1417,27924,27925,45574,45575</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/23733316$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Gwyther, Jessica</creatorcontrib><creatorcontrib>Gilroy, Joe B.</creatorcontrib><creatorcontrib>Rupar, Paul A.</creatorcontrib><creatorcontrib>Lunn, David J.</creatorcontrib><creatorcontrib>Kynaston, Emily</creatorcontrib><creatorcontrib>Patra, Sanjib K.</creatorcontrib><creatorcontrib>Whittell, George R.</creatorcontrib><creatorcontrib>Winnik, Mitchell A.</creatorcontrib><creatorcontrib>Manners, Ian</creatorcontrib><title>Dimensional Control of Block Copolymer Nanofibers with a π-Conjugated Core: Crystallization-Driven Solution Self-Assembly of Amphiphilic Poly(3-hexylthiophene)-b-poly(2-vinylpyridine)</title><title>Chemistry : a European journal</title><addtitle>Chem. Eur. J</addtitle><description>With the aim of accessing colloidally stable, fiberlike, π‐conjugated nanostructures of controlled length, we have studied the solution self‐assembly of two asymmetric crystalline–coil, regioregular poly(3‐hexylthiophene)‐b‐poly(2‐vinylpyridine) (P3HT‐b‐P2VP) diblock copolymers, P3HT23‐b‐P2VP115 (block ratio=1:5) and P3HT44‐b‐P2VP115 (block ratio=ca. 1:3). The self‐assembly studies were performed under a variety of solvent conditions that were selective for the P2VP block. The block copolymers were prepared by using Cu‐catalyzed azide–alkyne cycloaddition reactions of azide‐terminated P2VP and alkyne end‐functionalized P3HT homopolymers. When the block copolymers were self‐assembled in a solution of a 50 % (v/v) mixture of THF (a good solvent for both blocks) and an alcohol (a selective solvent for the P2VP block) by means of the slow evaporation of the common solvent; fiberlike micelles with a P3HT core and a P2VP corona were observed by transmission electron microscopy (TEM). The average lengths of the micelles were found to increase as the length of the hydrocarbon chain increased in the P2VP‐selective alcoholic solvent (MeOH<iPrOH<nBuOH). Very long (>3 μm) fiberlike micelles were prepared by the dialysis of solutions of the block copolymers in THF against iPrOH. Furthermore the widths of the fibers were dependent on the degree of polymerization of the chain‐extended P3HT blocks. The crystallinity and π‐conjugated nature of the P3HT core in the fiberlike micelles was confirmed by a combination of UV/Vis spectroscopy, photoluminescence (PL) measurements, and wide‐angle X‐ray scattering (WAXS). Intense sonication (iPrOH, 1 h, 0 °C) of the fiberlike micelles formed by P3HT23‐b‐P2VP115 resulted in small (ca. 25 nm long) stublike fragments that were subsequently used as initiators in seeded growth experiments. Addition of P3HT23‐b‐P2VP115 unimers to the seeds allowed the preparation of fiberlike micelles with narrow length distributions (Lw/Ln <1.11) and lengths from about 100‐300 nm, that were dependent on the unimer‐to‐seed micelle ratio.
From polymers to micelles: Colloidally‐stable π‐conjugated nanowires of controlled length up to 300 nm are available through the crystallization‐driven, solution self‐assembly of poly(3‐hexylthiophene)‐b‐poly(2‐vinylpyridine) (P3HT‐b‐P2VP) diblock copolymers. Detailed studies show that the degree of polymerization of the regioregular, crystalline P3HT core‐forming block, the solvent quality, and the rate of the self‐assembly process profoundly influence the formation of well‐defined fiberlike micelle structures.</description><subject>Block copolymers</subject><subject>Blocking</subject><subject>Crystal structure</subject><subject>Crystallization</subject><subject>Degree of polymerization</subject><subject>Micelles</subject><subject>nanowires</subject><subject>Self assembly</subject><subject>Solvents</subject><issn>0947-6539</issn><issn>1521-3765</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2013</creationdate><recordtype>article</recordtype><recordid>eNqFkcFu1DAQhiMEokvhyhH5uBy82HFib7ht07IFlYJUEBIXy3EmxK0TBztpm576WLwFr0SiLStuSJZGHn3_P6P5o-glJStKSPxG19CsYkIZIQlnj6IFTWOKmeDp42hBskRgnrLsIHoWwiUhJOOMPY0OYiYYY5Qvol_HpoE2GNcqi3LX9t5Z5Cp0ZJ2-mhqds2MDHp2r1lWmAB_QjelrpNDvezzxl8MP1UM5kR7eotyPoVfWmjvVT5b42JtraNGFs8P8RxdgK7wJAZrCjvOYTdPVZnrWaPR5GrVkuIbb0fa1cV0NLbzGBZ53WMb42rSj7UZvSjP1n0dPKmUDvHioh9HXdydf8lN89mn7Pt-cYR1na4Z1wnml4nVCSZHoLC1YVemMCEFSnXGxng6hCddJmZaKlMCysop1VRQ6VUqwhLDDaLnz7bz7OUDoZWOCBmtVC24IkgqxJkkWkxld7VDtXQgeKtl50yg_SkrknJac05L7tCbBqwfvoWig3ON_45mAbAfcGAvjf-xkfnry8V9zvNOa0MPtXqv8leSCiVR-O99K8p2uU7pN5Af2B0BStGU</recordid><startdate>20130708</startdate><enddate>20130708</enddate><creator>Gwyther, Jessica</creator><creator>Gilroy, Joe B.</creator><creator>Rupar, Paul A.</creator><creator>Lunn, David J.</creator><creator>Kynaston, Emily</creator><creator>Patra, Sanjib K.</creator><creator>Whittell, George R.</creator><creator>Winnik, Mitchell A.</creator><creator>Manners, Ian</creator><general>WILEY-VCH Verlag</general><general>WILEY‐VCH Verlag</general><scope>BSCLL</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope></search><sort><creationdate>20130708</creationdate><title>Dimensional Control of Block Copolymer Nanofibers with a π-Conjugated Core: Crystallization-Driven Solution Self-Assembly of Amphiphilic Poly(3-hexylthiophene)-b-poly(2-vinylpyridine)</title><author>Gwyther, Jessica ; Gilroy, Joe B. ; Rupar, Paul A. ; Lunn, David J. ; Kynaston, Emily ; Patra, Sanjib K. ; Whittell, George R. ; Winnik, Mitchell A. ; Manners, Ian</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c2983-c466fa28410b4c95b3ffc907705c9678373c06c4d5da0de39df2cfbbc5aa73403</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2013</creationdate><topic>Block copolymers</topic><topic>Blocking</topic><topic>Crystal structure</topic><topic>Crystallization</topic><topic>Degree of polymerization</topic><topic>Micelles</topic><topic>nanowires</topic><topic>Self assembly</topic><topic>Solvents</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Gwyther, Jessica</creatorcontrib><creatorcontrib>Gilroy, Joe B.</creatorcontrib><creatorcontrib>Rupar, Paul A.</creatorcontrib><creatorcontrib>Lunn, David J.</creatorcontrib><creatorcontrib>Kynaston, Emily</creatorcontrib><creatorcontrib>Patra, Sanjib K.</creatorcontrib><creatorcontrib>Whittell, George R.</creatorcontrib><creatorcontrib>Winnik, Mitchell A.</creatorcontrib><creatorcontrib>Manners, Ian</creatorcontrib><collection>Istex</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><jtitle>Chemistry : a European journal</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Gwyther, Jessica</au><au>Gilroy, Joe B.</au><au>Rupar, Paul A.</au><au>Lunn, David J.</au><au>Kynaston, Emily</au><au>Patra, Sanjib K.</au><au>Whittell, George R.</au><au>Winnik, Mitchell A.</au><au>Manners, Ian</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Dimensional Control of Block Copolymer Nanofibers with a π-Conjugated Core: Crystallization-Driven Solution Self-Assembly of Amphiphilic Poly(3-hexylthiophene)-b-poly(2-vinylpyridine)</atitle><jtitle>Chemistry : a European journal</jtitle><addtitle>Chem. Eur. J</addtitle><date>2013-07-08</date><risdate>2013</risdate><volume>19</volume><issue>28</issue><spage>9186</spage><epage>9197</epage><pages>9186-9197</pages><issn>0947-6539</issn><eissn>1521-3765</eissn><abstract>With the aim of accessing colloidally stable, fiberlike, π‐conjugated nanostructures of controlled length, we have studied the solution self‐assembly of two asymmetric crystalline–coil, regioregular poly(3‐hexylthiophene)‐b‐poly(2‐vinylpyridine) (P3HT‐b‐P2VP) diblock copolymers, P3HT23‐b‐P2VP115 (block ratio=1:5) and P3HT44‐b‐P2VP115 (block ratio=ca. 1:3). The self‐assembly studies were performed under a variety of solvent conditions that were selective for the P2VP block. The block copolymers were prepared by using Cu‐catalyzed azide–alkyne cycloaddition reactions of azide‐terminated P2VP and alkyne end‐functionalized P3HT homopolymers. When the block copolymers were self‐assembled in a solution of a 50 % (v/v) mixture of THF (a good solvent for both blocks) and an alcohol (a selective solvent for the P2VP block) by means of the slow evaporation of the common solvent; fiberlike micelles with a P3HT core and a P2VP corona were observed by transmission electron microscopy (TEM). The average lengths of the micelles were found to increase as the length of the hydrocarbon chain increased in the P2VP‐selective alcoholic solvent (MeOH<iPrOH<nBuOH). Very long (>3 μm) fiberlike micelles were prepared by the dialysis of solutions of the block copolymers in THF against iPrOH. Furthermore the widths of the fibers were dependent on the degree of polymerization of the chain‐extended P3HT blocks. The crystallinity and π‐conjugated nature of the P3HT core in the fiberlike micelles was confirmed by a combination of UV/Vis spectroscopy, photoluminescence (PL) measurements, and wide‐angle X‐ray scattering (WAXS). Intense sonication (iPrOH, 1 h, 0 °C) of the fiberlike micelles formed by P3HT23‐b‐P2VP115 resulted in small (ca. 25 nm long) stublike fragments that were subsequently used as initiators in seeded growth experiments. Addition of P3HT23‐b‐P2VP115 unimers to the seeds allowed the preparation of fiberlike micelles with narrow length distributions (Lw/Ln <1.11) and lengths from about 100‐300 nm, that were dependent on the unimer‐to‐seed micelle ratio.
From polymers to micelles: Colloidally‐stable π‐conjugated nanowires of controlled length up to 300 nm are available through the crystallization‐driven, solution self‐assembly of poly(3‐hexylthiophene)‐b‐poly(2‐vinylpyridine) (P3HT‐b‐P2VP) diblock copolymers. Detailed studies show that the degree of polymerization of the regioregular, crystalline P3HT core‐forming block, the solvent quality, and the rate of the self‐assembly process profoundly influence the formation of well‐defined fiberlike micelle structures.</abstract><cop>Weinheim</cop><pub>WILEY-VCH Verlag</pub><pmid>23733316</pmid><doi>10.1002/chem.201300463</doi><tpages>12</tpages></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 0947-6539 |
| ispartof | Chemistry : a European journal, 2013-07, Vol.19 (28), p.9186-9197 |
| issn | 0947-6539 1521-3765 |
| language | eng |
| recordid | cdi_proquest_miscellaneous_1778049200 |
| source | Access via Wiley Online Library |
| subjects | Block copolymers Blocking Crystal structure Crystallization Degree of polymerization Micelles nanowires Self assembly Solvents |
| title | Dimensional Control of Block Copolymer Nanofibers with a π-Conjugated Core: Crystallization-Driven Solution Self-Assembly of Amphiphilic Poly(3-hexylthiophene)-b-poly(2-vinylpyridine) |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-02T12%3A02%3A40IST&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=Dimensional%20Control%20of%20Block%20Copolymer%20Nanofibers%20with%20a%20%CF%80-Conjugated%20Core:%20Crystallization-Driven%20Solution%20Self-Assembly%20of%20Amphiphilic%20Poly(3-hexylthiophene)-b-poly(2-vinylpyridine)&rft.jtitle=Chemistry%20:%20a%20European%20journal&rft.au=Gwyther,%20Jessica&rft.date=2013-07-08&rft.volume=19&rft.issue=28&rft.spage=9186&rft.epage=9197&rft.pages=9186-9197&rft.issn=0947-6539&rft.eissn=1521-3765&rft_id=info:doi/10.1002/chem.201300463&rft_dat=%3Cproquest_cross%3E1778049200%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=1778049200&rft_id=info:pmid/23733316&rfr_iscdi=true |