Charge regulation mechanism in end-tethered weak polyampholytes
Weak polyampholytes, containing oppositely charged dissociable groups, are expected to be responsive to changes in ionic conditions. Here, we determine structural and thermodynamic properties, including the charged groups' degrees of dissociation, of end-tethered weak polyampholyte layers as a...
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Veröffentlicht in: | Soft matter 2020-10, Vol.16 (38), p.8832-8847 |
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description | Weak polyampholytes, containing oppositely charged dissociable groups, are expected to be responsive to changes in ionic conditions. Here, we determine structural and thermodynamic properties, including the charged groups' degrees of dissociation, of end-tethered weak polyampholyte layers as a function of salt concentration, pH, and the solvent quality. For diblock weak polyampholytes grafted by their acidic blocks, we find that the acidic monomers increase their charge while the basic monomers decrease their charge with decreasing salt concentration for pH values less than the p
K
a
value of both monomers and
vice versa
when the pH > p
K
a
. This complex charge regulation occurs because the electrostatic attraction between oppositely charged blocks is stronger than the repulsion between monomers with the same charge in both good and poor solvents when the screening by salt ions is weak. This is evidenced by the retraction of the top block into the bottom layer. In the case of poor solvent conditions to the basic block (the top block), we find lateral segregation of basic monomers into micelles, forming a two-dimensional hexagonal pattern on the surface at intermediate and high pH values for monovalent salt concentrations from 0.01 to 0.1 M. When the solvent is poor to both blocks, we find lateral segregation of the grafted acidic block into lamellae with longitudinal undulations of low and high acidic monomer density. By exploiting weak block polyampholytes, our work expands the parameter space for creating responsive surfaces stable over a wide range of pH and salt concentration.
In diblock polyampholyte brushes, the dissociation of acid and base monomers as a function of pH is simultaneously up and downregulated. |
doi_str_mv | 10.1039/d0sm01323d |
format | Article |
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K
a
value of both monomers and
vice versa
when the pH > p
K
a
. This complex charge regulation occurs because the electrostatic attraction between oppositely charged blocks is stronger than the repulsion between monomers with the same charge in both good and poor solvents when the screening by salt ions is weak. This is evidenced by the retraction of the top block into the bottom layer. In the case of poor solvent conditions to the basic block (the top block), we find lateral segregation of basic monomers into micelles, forming a two-dimensional hexagonal pattern on the surface at intermediate and high pH values for monovalent salt concentrations from 0.01 to 0.1 M. When the solvent is poor to both blocks, we find lateral segregation of the grafted acidic block into lamellae with longitudinal undulations of low and high acidic monomer density. By exploiting weak block polyampholytes, our work expands the parameter space for creating responsive surfaces stable over a wide range of pH and salt concentration.
In diblock polyampholyte brushes, the dissociation of acid and base monomers as a function of pH is simultaneously up and downregulated.</description><identifier>ISSN: 1744-683X</identifier><identifier>EISSN: 1744-6848</identifier><identifier>DOI: 10.1039/d0sm01323d</identifier><language>eng</language><publisher>Cambridge: Royal Society of Chemistry</publisher><subject>Lamellae ; Micelles ; Monomers ; pH effects ; Polyampholytes ; Salts ; Solvents ; Thermodynamic properties</subject><ispartof>Soft matter, 2020-10, Vol.16 (38), p.8832-8847</ispartof><rights>Copyright Royal Society of Chemistry 2020</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c445t-459e28e8685a86da509c2c9132bf74bb130aa4dbd851c7b2a68ab15b3b9dbf8f3</citedby><cites>FETCH-LOGICAL-c445t-459e28e8685a86da509c2c9132bf74bb130aa4dbd851c7b2a68ab15b3b9dbf8f3</cites><orcidid>0000-0002-8708-0335 ; 0000-0002-1809-0249 ; 0000-0002-9802-3627 ; 0000000287080335 ; 0000000218090249 ; 0000000298023627</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>230,314,780,784,885,27924,27925</link.rule.ids><backlink>$$Uhttps://www.osti.gov/biblio/1658978$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Prusty, D</creatorcontrib><creatorcontrib>Nap, R. J</creatorcontrib><creatorcontrib>Szleifer, I</creatorcontrib><creatorcontrib>Olvera de la Cruz, M</creatorcontrib><title>Charge regulation mechanism in end-tethered weak polyampholytes</title><title>Soft matter</title><description>Weak polyampholytes, containing oppositely charged dissociable groups, are expected to be responsive to changes in ionic conditions. Here, we determine structural and thermodynamic properties, including the charged groups' degrees of dissociation, of end-tethered weak polyampholyte layers as a function of salt concentration, pH, and the solvent quality. For diblock weak polyampholytes grafted by their acidic blocks, we find that the acidic monomers increase their charge while the basic monomers decrease their charge with decreasing salt concentration for pH values less than the p
K
a
value of both monomers and
vice versa
when the pH > p
K
a
. This complex charge regulation occurs because the electrostatic attraction between oppositely charged blocks is stronger than the repulsion between monomers with the same charge in both good and poor solvents when the screening by salt ions is weak. This is evidenced by the retraction of the top block into the bottom layer. In the case of poor solvent conditions to the basic block (the top block), we find lateral segregation of basic monomers into micelles, forming a two-dimensional hexagonal pattern on the surface at intermediate and high pH values for monovalent salt concentrations from 0.01 to 0.1 M. When the solvent is poor to both blocks, we find lateral segregation of the grafted acidic block into lamellae with longitudinal undulations of low and high acidic monomer density. By exploiting weak block polyampholytes, our work expands the parameter space for creating responsive surfaces stable over a wide range of pH and salt concentration.
In diblock polyampholyte brushes, the dissociation of acid and base monomers as a function of pH is simultaneously up and downregulated.</description><subject>Lamellae</subject><subject>Micelles</subject><subject>Monomers</subject><subject>pH effects</subject><subject>Polyampholytes</subject><subject>Salts</subject><subject>Solvents</subject><subject>Thermodynamic properties</subject><issn>1744-683X</issn><issn>1744-6848</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2020</creationdate><recordtype>article</recordtype><recordid>eNp90UtLAzEQAOBFFKzVi3dh1YsIq8km2c2eRFpfUPGggreQx2y7dV8mKdJ_b2qlggcPYQLzMcwjig4xusCIFJcGuQZhkhKzFQ1wTmmSccq3N3_ythvtOTdHiHCKs0F0NZpJO4XYwnRRS191bdyAnsm2ck1ctTG0JvHgZ2DBxJ8g3-O-q5ey6WcheHD70U4pawcHP3EYvd7evIzuk8nT3cPoepJoSplPKCsg5cAzziTPjGSo0KkuQqeqzKlSmCApqVGGM6xzlcqMS4WZIqowquQlGUYn67qd85VwuvKhS921LWgvcMZ4kfOAztaot93HApwXTeU01LVsoVs4kVKKU5YXDAV6-ofOu4VtwwgrxXkaHg3qfK207ZyzUIreVo20S4GRWC1cjNHz4_fCxwEfrbF1euN-DxLyx__lRW9K8gV_6oer</recordid><startdate>20201007</startdate><enddate>20201007</enddate><creator>Prusty, D</creator><creator>Nap, R. 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J</au><au>Szleifer, I</au><au>Olvera de la Cruz, M</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Charge regulation mechanism in end-tethered weak polyampholytes</atitle><jtitle>Soft matter</jtitle><date>2020-10-07</date><risdate>2020</risdate><volume>16</volume><issue>38</issue><spage>8832</spage><epage>8847</epage><pages>8832-8847</pages><issn>1744-683X</issn><eissn>1744-6848</eissn><abstract>Weak polyampholytes, containing oppositely charged dissociable groups, are expected to be responsive to changes in ionic conditions. Here, we determine structural and thermodynamic properties, including the charged groups' degrees of dissociation, of end-tethered weak polyampholyte layers as a function of salt concentration, pH, and the solvent quality. For diblock weak polyampholytes grafted by their acidic blocks, we find that the acidic monomers increase their charge while the basic monomers decrease their charge with decreasing salt concentration for pH values less than the p
K
a
value of both monomers and
vice versa
when the pH > p
K
a
. This complex charge regulation occurs because the electrostatic attraction between oppositely charged blocks is stronger than the repulsion between monomers with the same charge in both good and poor solvents when the screening by salt ions is weak. This is evidenced by the retraction of the top block into the bottom layer. In the case of poor solvent conditions to the basic block (the top block), we find lateral segregation of basic monomers into micelles, forming a two-dimensional hexagonal pattern on the surface at intermediate and high pH values for monovalent salt concentrations from 0.01 to 0.1 M. When the solvent is poor to both blocks, we find lateral segregation of the grafted acidic block into lamellae with longitudinal undulations of low and high acidic monomer density. By exploiting weak block polyampholytes, our work expands the parameter space for creating responsive surfaces stable over a wide range of pH and salt concentration.
In diblock polyampholyte brushes, the dissociation of acid and base monomers as a function of pH is simultaneously up and downregulated.</abstract><cop>Cambridge</cop><pub>Royal Society of Chemistry</pub><doi>10.1039/d0sm01323d</doi><tpages>16</tpages><orcidid>https://orcid.org/0000-0002-8708-0335</orcidid><orcidid>https://orcid.org/0000-0002-1809-0249</orcidid><orcidid>https://orcid.org/0000-0002-9802-3627</orcidid><orcidid>https://orcid.org/0000000287080335</orcidid><orcidid>https://orcid.org/0000000218090249</orcidid><orcidid>https://orcid.org/0000000298023627</orcidid></addata></record> |
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subjects | Lamellae Micelles Monomers pH effects Polyampholytes Salts Solvents Thermodynamic properties |
title | Charge regulation mechanism in end-tethered weak polyampholytes |
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