Amphiphilic Homopolymer as a Reaction Medium in Water: Product Selectivity within Polymeric Nanopockets
A styrene-based water-soluble polymer has been explored for its use as a host for lipophilic substrates in aqueous medium. Unimolecular reactions, namely, photo-Fries rearrangement of naphthyl esters, α-cleavage reaction of 1-phenyl-3-p-tolyl-propan-2-one, and Norrish type I and type II reactions of...
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| Veröffentlicht in: | Journal of the American Chemical Society 2005-09, Vol.127 (38), p.13200-13206 |
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| container_title | Journal of the American Chemical Society |
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| creator | Arumugam, Selvanathan Vutukuri, Dharma Rao Thayumanavan, S Ramamurthy, V |
| description | A styrene-based water-soluble polymer has been explored for its use as a host for lipophilic substrates in aqueous medium. Unimolecular reactions, namely, photo-Fries rearrangement of naphthyl esters, α-cleavage reaction of 1-phenyl-3-p-tolyl-propan-2-one, and Norrish type I and type II reactions of benzoin alkyl ethers were examined. We find that the hydrophobic domains generated by the polymer not only restrict the mobility of the radicals but also modestly incarcerate the substrate, intermediates, and products during the time scale of the reactions. Comparative studies of the same photoreactions in micelles formed from small molecule surfactants and an amphiphilic diblock copolymer demonstrate that the styrene-based water-soluble polymer aggregates in aqueous medium offer better selectivity. |
| doi_str_mv | 10.1021/ja051107v |
| format | Article |
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Unimolecular reactions, namely, photo-Fries rearrangement of naphthyl esters, α-cleavage reaction of 1-phenyl-3-p-tolyl-propan-2-one, and Norrish type I and type II reactions of benzoin alkyl ethers were examined. We find that the hydrophobic domains generated by the polymer not only restrict the mobility of the radicals but also modestly incarcerate the substrate, intermediates, and products during the time scale of the reactions. 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Am. Chem. Soc</addtitle><description>A styrene-based water-soluble polymer has been explored for its use as a host for lipophilic substrates in aqueous medium. Unimolecular reactions, namely, photo-Fries rearrangement of naphthyl esters, α-cleavage reaction of 1-phenyl-3-p-tolyl-propan-2-one, and Norrish type I and type II reactions of benzoin alkyl ethers were examined. We find that the hydrophobic domains generated by the polymer not only restrict the mobility of the radicals but also modestly incarcerate the substrate, intermediates, and products during the time scale of the reactions. Comparative studies of the same photoreactions in micelles formed from small molecule surfactants and an amphiphilic diblock copolymer demonstrate that the styrene-based water-soluble polymer aggregates in aqueous medium offer better selectivity.</description><subject>Chemistry</subject><subject>Esters - chemical synthesis</subject><subject>Esters - chemistry</subject><subject>Esters - radiation effects</subject><subject>Exact sciences and technology</subject><subject>Free Radicals - chemistry</subject><subject>General and physical chemistry</subject><subject>Light</subject><subject>Micelles</subject><subject>Molecular Weight</subject><subject>Nanostructures - chemistry</subject><subject>Photochemistry</subject><subject>Photolysis</subject><subject>Physical chemistry of induced reactions (with radiations, particles and ultrasonics)</subject><subject>Polystyrenes - chemistry</subject><subject>Polystyrenes - radiation effects</subject><subject>Surface Properties</subject><subject>Water - chemistry</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2005</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNptkEFrFDEUgINY7Fo9-AckFws9TE0yk0zqrSy2ta267Fb0Fp6ZNzTbmcmaZKp769W_6S8xskv3IgQe4X18PD5CXnF2zJngb5fAJOesvn9CJlwKVkgu1FMyYYyJotaq3CfPY1zmbyU0f0b2ueJ1WVf1hCxP-9Wty69zll743q98t-4xUIgU6BzBJucH-hEbN_bUDfQrJAzv_jz8prPgm9EmusAOM3Xv0pr-dOk2Q7ONJCs_wZCV9g5TfEH2WugivtzOA_Ll7P3N9KK4_nz-YXp6XUBV1akAwbVipWVt01qtrUSmZCNO6pMWG86FVE1l81ooUFpUUpWlVUo3KFCiZlgekMONdxX8jxFjMr2LFrsOBvRjNEqrXE2oDB5tQBt8jAFbswquh7A2nJl_Yc1j2My-3krH7z02O3JbMgNvtgBEC10bYLAu7riaV5UsdeaKDediwl-Pewh3RmWTNDezhbm8WpxPv80vzXznBRvN0o9hyO3-c-Bf6tWc3g</recordid><startdate>20050928</startdate><enddate>20050928</enddate><creator>Arumugam, Selvanathan</creator><creator>Vutukuri, Dharma Rao</creator><creator>Thayumanavan, S</creator><creator>Ramamurthy, V</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>IQODW</scope><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20050928</creationdate><title>Amphiphilic Homopolymer as a Reaction Medium in Water: Product Selectivity within Polymeric Nanopockets</title><author>Arumugam, Selvanathan ; Vutukuri, Dharma Rao ; Thayumanavan, S ; Ramamurthy, V</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a447t-a218603c0fdfc88c5e065d2979fed11256d4c3c026a68245633c668de2e5e80e3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2005</creationdate><topic>Chemistry</topic><topic>Esters - chemical synthesis</topic><topic>Esters - chemistry</topic><topic>Esters - radiation effects</topic><topic>Exact sciences and technology</topic><topic>Free Radicals - chemistry</topic><topic>General and physical chemistry</topic><topic>Light</topic><topic>Micelles</topic><topic>Molecular Weight</topic><topic>Nanostructures - chemistry</topic><topic>Photochemistry</topic><topic>Photolysis</topic><topic>Physical chemistry of induced reactions (with radiations, particles and ultrasonics)</topic><topic>Polystyrenes - chemistry</topic><topic>Polystyrenes - radiation effects</topic><topic>Surface Properties</topic><topic>Water - chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Arumugam, Selvanathan</creatorcontrib><creatorcontrib>Vutukuri, Dharma Rao</creatorcontrib><creatorcontrib>Thayumanavan, S</creatorcontrib><creatorcontrib>Ramamurthy, V</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</collection><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Arumugam, Selvanathan</au><au>Vutukuri, Dharma Rao</au><au>Thayumanavan, S</au><au>Ramamurthy, V</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Amphiphilic Homopolymer as a Reaction Medium in Water: Product Selectivity within Polymeric Nanopockets</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. 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| subjects | Chemistry Esters - chemical synthesis Esters - chemistry Esters - radiation effects Exact sciences and technology Free Radicals - chemistry General and physical chemistry Light Micelles Molecular Weight Nanostructures - chemistry Photochemistry Photolysis Physical chemistry of induced reactions (with radiations, particles and ultrasonics) Polystyrenes - chemistry Polystyrenes - radiation effects Surface Properties Water - chemistry |
| title | Amphiphilic Homopolymer as a Reaction Medium in Water: Product Selectivity within Polymeric Nanopockets |
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