The mechanisms of boronate ester formation and fluorescent turn-on in ortho-aminomethylphenylboronic acids
ortho -Aminomethylphenylboronic acids are used in receptors for carbohydrates and various other compounds containing vicinal diols. The presence of the o -aminomethyl group enhances the affinity towards diols at neutral pH, and the manner in which this group plays this role has been a topic of debat...
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| Veröffentlicht in: | Nature chemistry 2019-09, Vol.11 (9), p.768-778 |
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| creator | Sun, Xiaolong Chapin, Brette M. Metola, Pedro Collins, Byron Wang, Binghe James, Tony D. Anslyn, Eric V. |
| description | ortho
-Aminomethylphenylboronic acids are used in receptors for carbohydrates and various other compounds containing vicinal diols. The presence of the
o
-aminomethyl group enhances the affinity towards diols at neutral pH, and the manner in which this group plays this role has been a topic of debate. Further, the aminomethyl group is believed to be involved in the turn-on of the emission properties of appended fluorophores upon diol binding. In this treatise, a uniform picture emerges for the role of this group: it primarily acts as an electron-withdrawing group that lowers the p
K
a
of the neighbouring boronic acid thereby facilitating diol binding at neutral pH. The amine appears to play no role in the modulation of the fluorescence of appended fluorophores in the protic-solvent-inserted form of the boronic acid/boronate ester. Instead, fluorescence turn-on can be consistently tied to vibrational-coupled excited-state relaxation (a loose-bolt effect). Overall, this Review unifies and discusses the existing data as of 2019 whilst also highlighting why
o
-aminomethyl groups are so widely used, and the role they play in carbohydrate sensing using phenylboronic acids.
ortho
-Aminomethylphenylboronic acids are routinely used in sensors for carbohydrates, but the function of the
o
-aminomethyl group in enhancing binding affinity and modulating the emission of appended fluorophores has been the matter of some debate. This Review presents a unified picture of the structural features, mechanisms of sugar complexation and photophysics of these kinds of sensors. |
| doi_str_mv | 10.1038/s41557-019-0314-x |
| format | Article |
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-Aminomethylphenylboronic acids are used in receptors for carbohydrates and various other compounds containing vicinal diols. The presence of the
o
-aminomethyl group enhances the affinity towards diols at neutral pH, and the manner in which this group plays this role has been a topic of debate. Further, the aminomethyl group is believed to be involved in the turn-on of the emission properties of appended fluorophores upon diol binding. In this treatise, a uniform picture emerges for the role of this group: it primarily acts as an electron-withdrawing group that lowers the p
K
a
of the neighbouring boronic acid thereby facilitating diol binding at neutral pH. The amine appears to play no role in the modulation of the fluorescence of appended fluorophores in the protic-solvent-inserted form of the boronic acid/boronate ester. Instead, fluorescence turn-on can be consistently tied to vibrational-coupled excited-state relaxation (a loose-bolt effect). Overall, this Review unifies and discusses the existing data as of 2019 whilst also highlighting why
o
-aminomethyl groups are so widely used, and the role they play in carbohydrate sensing using phenylboronic acids.
ortho
-Aminomethylphenylboronic acids are routinely used in sensors for carbohydrates, but the function of the
o
-aminomethyl group in enhancing binding affinity and modulating the emission of appended fluorophores has been the matter of some debate. This Review presents a unified picture of the structural features, mechanisms of sugar complexation and photophysics of these kinds of sensors.</description><identifier>ISSN: 1755-4330</identifier><identifier>EISSN: 1755-4349</identifier><identifier>DOI: 10.1038/s41557-019-0314-x</identifier><identifier>PMID: 31444486</identifier><language>eng</language><publisher>London: Nature Publishing Group UK</publisher><subject>631/92 ; 631/92/613 ; 639/638 ; 639/638/11 ; 639/638/92 ; Acids ; Analytical Chemistry ; Binding ; Biochemistry ; Carbohydrates ; Chemical compounds ; Chemistry ; Chemistry and Materials Science ; Chemistry/Food Science ; Diols ; Fluorescence ; Fluorophores ; Inorganic Chemistry ; Organic Chemistry ; pH effects ; Physical Chemistry ; Receptors ; Review Article</subject><ispartof>Nature chemistry, 2019-09, Vol.11 (9), p.768-778</ispartof><rights>The Author(s), under exclusive licence to Springer Nature Limited 2019</rights><rights>Copyright Nature Publishing Group Sep 2019</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c573t-b6219f6ff1c9bce50918da1a08ca54d825cfb1ae982ebb2ae12523f14b82356e3</citedby><cites>FETCH-LOGICAL-c573t-b6219f6ff1c9bce50918da1a08ca54d825cfb1ae982ebb2ae12523f14b82356e3</cites><orcidid>0000-0003-4003-6924 ; 0000-0002-5137-8797 ; 0000-0002-2200-5270 ; 0000-0002-4095-2191</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.ncbi.nlm.nih.gov/pubmed/31444486$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Sun, Xiaolong</creatorcontrib><creatorcontrib>Chapin, Brette M.</creatorcontrib><creatorcontrib>Metola, Pedro</creatorcontrib><creatorcontrib>Collins, Byron</creatorcontrib><creatorcontrib>Wang, Binghe</creatorcontrib><creatorcontrib>James, Tony D.</creatorcontrib><creatorcontrib>Anslyn, Eric V.</creatorcontrib><title>The mechanisms of boronate ester formation and fluorescent turn-on in ortho-aminomethylphenylboronic acids</title><title>Nature chemistry</title><addtitle>Nat. Chem</addtitle><addtitle>Nat Chem</addtitle><description>ortho
-Aminomethylphenylboronic acids are used in receptors for carbohydrates and various other compounds containing vicinal diols. The presence of the
o
-aminomethyl group enhances the affinity towards diols at neutral pH, and the manner in which this group plays this role has been a topic of debate. Further, the aminomethyl group is believed to be involved in the turn-on of the emission properties of appended fluorophores upon diol binding. In this treatise, a uniform picture emerges for the role of this group: it primarily acts as an electron-withdrawing group that lowers the p
K
a
of the neighbouring boronic acid thereby facilitating diol binding at neutral pH. The amine appears to play no role in the modulation of the fluorescence of appended fluorophores in the protic-solvent-inserted form of the boronic acid/boronate ester. Instead, fluorescence turn-on can be consistently tied to vibrational-coupled excited-state relaxation (a loose-bolt effect). Overall, this Review unifies and discusses the existing data as of 2019 whilst also highlighting why
o
-aminomethyl groups are so widely used, and the role they play in carbohydrate sensing using phenylboronic acids.
ortho
-Aminomethylphenylboronic acids are routinely used in sensors for carbohydrates, but the function of the
o
-aminomethyl group in enhancing binding affinity and modulating the emission of appended fluorophores has been the matter of some debate. This Review presents a unified picture of the structural features, mechanisms of sugar complexation and photophysics of these kinds of sensors.</description><subject>631/92</subject><subject>631/92/613</subject><subject>639/638</subject><subject>639/638/11</subject><subject>639/638/92</subject><subject>Acids</subject><subject>Analytical Chemistry</subject><subject>Binding</subject><subject>Biochemistry</subject><subject>Carbohydrates</subject><subject>Chemical compounds</subject><subject>Chemistry</subject><subject>Chemistry and Materials Science</subject><subject>Chemistry/Food Science</subject><subject>Diols</subject><subject>Fluorescence</subject><subject>Fluorophores</subject><subject>Inorganic Chemistry</subject><subject>Organic Chemistry</subject><subject>pH effects</subject><subject>Physical Chemistry</subject><subject>Receptors</subject><subject>Review Article</subject><issn>1755-4330</issn><issn>1755-4349</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2019</creationdate><recordtype>article</recordtype><sourceid>ABUWG</sourceid><sourceid>AFKRA</sourceid><sourceid>AZQEC</sourceid><sourceid>BENPR</sourceid><sourceid>CCPQU</sourceid><sourceid>DWQXO</sourceid><sourceid>GNUQQ</sourceid><recordid>eNp1kctq3DAUhkVpaZJpH6CbIuimGzW6WLa8CZTQNoFANulayPJRrMGWJpJdMm8fTSadJoVoI6Hznf9cfoQ-MfqNUaFOc8WkbAhlLaGCVeT-DTpmjZSkElX79vAW9Aid5LymtJaC1e_RUYHLUfUxWt8MgCewgwk-TxlHh7uYYjAzYMgzJOximszsY8Am9NiNS0yQLYQZz0sKpPz7gGOah0jM5EOcYB6242aAsB0fpbzFxvo-f0DvnBkzfHy6V-j3zx835xfk6vrX5fn3K2JlI2bS1Zy1rnaO2bazIGnLVG-YocoaWfWKS-s6ZqBVHLqOG2BccuFY1SkuZA1ihc72upulm6DftZrMqDfJTyZtdTRev4wEP-jb-EerUr8Rsgh8fRJI8W4pW9CTLxOPowkQl6y5EHXb0qbgK_TlP3Qdy1bKeJrzRtVCVpwWiu0pm2LOCdyhGUb1zkm9d1IXJ_XOSX1fcj4_n-KQ8de6AvA9kEso3EL6V_p11QfQQa1C</recordid><startdate>20190901</startdate><enddate>20190901</enddate><creator>Sun, Xiaolong</creator><creator>Chapin, Brette M.</creator><creator>Metola, Pedro</creator><creator>Collins, Byron</creator><creator>Wang, Binghe</creator><creator>James, Tony D.</creator><creator>Anslyn, Eric V.</creator><general>Nature Publishing Group UK</general><general>Nature Publishing Group</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>3V.</scope><scope>7QR</scope><scope>7X7</scope><scope>7XB</scope><scope>88E</scope><scope>8AO</scope><scope>8FD</scope><scope>8FE</scope><scope>8FG</scope><scope>8FH</scope><scope>8FI</scope><scope>8FJ</scope><scope>8FK</scope><scope>ABJCF</scope><scope>ABUWG</scope><scope>AFKRA</scope><scope>AZQEC</scope><scope>BBNVY</scope><scope>BENPR</scope><scope>BGLVJ</scope><scope>BHPHI</scope><scope>CCPQU</scope><scope>D1I</scope><scope>DWQXO</scope><scope>FR3</scope><scope>FYUFA</scope><scope>GHDGH</scope><scope>GNUQQ</scope><scope>HCIFZ</scope><scope>K9.</scope><scope>KB.</scope><scope>LK8</scope><scope>M0S</scope><scope>M1P</scope><scope>M7P</scope><scope>P64</scope><scope>PDBOC</scope><scope>PQEST</scope><scope>PQQKQ</scope><scope>PQUKI</scope><scope>7X8</scope><scope>5PM</scope><orcidid>https://orcid.org/0000-0003-4003-6924</orcidid><orcidid>https://orcid.org/0000-0002-5137-8797</orcidid><orcidid>https://orcid.org/0000-0002-2200-5270</orcidid><orcidid>https://orcid.org/0000-0002-4095-2191</orcidid></search><sort><creationdate>20190901</creationdate><title>The mechanisms of boronate ester formation and fluorescent turn-on in ortho-aminomethylphenylboronic acids</title><author>Sun, Xiaolong ; Chapin, Brette M. ; Metola, Pedro ; Collins, Byron ; Wang, Binghe ; James, Tony D. ; Anslyn, Eric V.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c573t-b6219f6ff1c9bce50918da1a08ca54d825cfb1ae982ebb2ae12523f14b82356e3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2019</creationdate><topic>631/92</topic><topic>631/92/613</topic><topic>639/638</topic><topic>639/638/11</topic><topic>639/638/92</topic><topic>Acids</topic><topic>Analytical Chemistry</topic><topic>Binding</topic><topic>Biochemistry</topic><topic>Carbohydrates</topic><topic>Chemical compounds</topic><topic>Chemistry</topic><topic>Chemistry and Materials Science</topic><topic>Chemistry/Food Science</topic><topic>Diols</topic><topic>Fluorescence</topic><topic>Fluorophores</topic><topic>Inorganic Chemistry</topic><topic>Organic Chemistry</topic><topic>pH effects</topic><topic>Physical Chemistry</topic><topic>Receptors</topic><topic>Review Article</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Sun, Xiaolong</creatorcontrib><creatorcontrib>Chapin, Brette M.</creatorcontrib><creatorcontrib>Metola, Pedro</creatorcontrib><creatorcontrib>Collins, Byron</creatorcontrib><creatorcontrib>Wang, Binghe</creatorcontrib><creatorcontrib>James, Tony D.</creatorcontrib><creatorcontrib>Anslyn, Eric V.</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>ProQuest Central (Corporate)</collection><collection>Chemoreception Abstracts</collection><collection>Health & Medical Collection</collection><collection>ProQuest Central (purchase pre-March 2016)</collection><collection>Medical Database (Alumni Edition)</collection><collection>ProQuest Pharma Collection</collection><collection>Technology Research Database</collection><collection>ProQuest SciTech Collection</collection><collection>ProQuest Technology Collection</collection><collection>ProQuest Natural Science Collection</collection><collection>Hospital Premium Collection</collection><collection>Hospital Premium Collection (Alumni Edition)</collection><collection>ProQuest Central (Alumni) (purchase pre-March 2016)</collection><collection>Materials Science & Engineering Collection</collection><collection>ProQuest Central (Alumni Edition)</collection><collection>ProQuest Central UK/Ireland</collection><collection>ProQuest Central Essentials</collection><collection>Biological Science Collection</collection><collection>ProQuest Central</collection><collection>Technology Collection</collection><collection>Natural Science Collection</collection><collection>ProQuest One Community College</collection><collection>ProQuest Materials Science Collection</collection><collection>ProQuest Central Korea</collection><collection>Engineering Research Database</collection><collection>Health Research Premium Collection</collection><collection>Health Research Premium Collection (Alumni)</collection><collection>ProQuest Central Student</collection><collection>SciTech Premium Collection</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>Materials Science Database</collection><collection>ProQuest Biological Science Collection</collection><collection>Health & Medical Collection (Alumni Edition)</collection><collection>Medical Database</collection><collection>Biological Science Database</collection><collection>Biotechnology and BioEngineering Abstracts</collection><collection>Materials Science Collection</collection><collection>ProQuest One Academic Eastern Edition (DO NOT USE)</collection><collection>ProQuest One Academic</collection><collection>ProQuest One Academic UKI Edition</collection><collection>MEDLINE - Academic</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>Nature chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Sun, Xiaolong</au><au>Chapin, Brette M.</au><au>Metola, Pedro</au><au>Collins, Byron</au><au>Wang, Binghe</au><au>James, Tony D.</au><au>Anslyn, Eric V.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>The mechanisms of boronate ester formation and fluorescent turn-on in ortho-aminomethylphenylboronic acids</atitle><jtitle>Nature chemistry</jtitle><stitle>Nat. Chem</stitle><addtitle>Nat Chem</addtitle><date>2019-09-01</date><risdate>2019</risdate><volume>11</volume><issue>9</issue><spage>768</spage><epage>778</epage><pages>768-778</pages><issn>1755-4330</issn><eissn>1755-4349</eissn><abstract>ortho
-Aminomethylphenylboronic acids are used in receptors for carbohydrates and various other compounds containing vicinal diols. The presence of the
o
-aminomethyl group enhances the affinity towards diols at neutral pH, and the manner in which this group plays this role has been a topic of debate. Further, the aminomethyl group is believed to be involved in the turn-on of the emission properties of appended fluorophores upon diol binding. In this treatise, a uniform picture emerges for the role of this group: it primarily acts as an electron-withdrawing group that lowers the p
K
a
of the neighbouring boronic acid thereby facilitating diol binding at neutral pH. The amine appears to play no role in the modulation of the fluorescence of appended fluorophores in the protic-solvent-inserted form of the boronic acid/boronate ester. Instead, fluorescence turn-on can be consistently tied to vibrational-coupled excited-state relaxation (a loose-bolt effect). Overall, this Review unifies and discusses the existing data as of 2019 whilst also highlighting why
o
-aminomethyl groups are so widely used, and the role they play in carbohydrate sensing using phenylboronic acids.
ortho
-Aminomethylphenylboronic acids are routinely used in sensors for carbohydrates, but the function of the
o
-aminomethyl group in enhancing binding affinity and modulating the emission of appended fluorophores has been the matter of some debate. This Review presents a unified picture of the structural features, mechanisms of sugar complexation and photophysics of these kinds of sensors.</abstract><cop>London</cop><pub>Nature Publishing Group UK</pub><pmid>31444486</pmid><doi>10.1038/s41557-019-0314-x</doi><tpages>11</tpages><orcidid>https://orcid.org/0000-0003-4003-6924</orcidid><orcidid>https://orcid.org/0000-0002-5137-8797</orcidid><orcidid>https://orcid.org/0000-0002-2200-5270</orcidid><orcidid>https://orcid.org/0000-0002-4095-2191</orcidid><oa>free_for_read</oa></addata></record> |
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| subjects | 631/92 631/92/613 639/638 639/638/11 639/638/92 Acids Analytical Chemistry Binding Biochemistry Carbohydrates Chemical compounds Chemistry Chemistry and Materials Science Chemistry/Food Science Diols Fluorescence Fluorophores Inorganic Chemistry Organic Chemistry pH effects Physical Chemistry Receptors Review Article |
| title | The mechanisms of boronate ester formation and fluorescent turn-on in ortho-aminomethylphenylboronic acids |
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