Hoctapa: synthesis, solution equilibria and complexes with useful radiopharmaceutical metal ions
H 4 octapa is an extremely versatile acyclic chelator for a wide variety of medicinally relevant metal ions, forming complexes of both high thermodynamic and kinetic stability. This work reports a significantly simplified 3 step high yield straightforward synthesis of H 4 octapa directly from EDDA....
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Veröffentlicht in: | Dalton transactions : an international journal of inorganic chemistry 2017-10, Vol.46 (42), p.14647-14658 |
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container_title | Dalton transactions : an international journal of inorganic chemistry |
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creator | Jaraquemada-Peláez, María de Guadalupe Wang, Xiaozhu Clough, Thomas J Cao, Yang Choudhary, Neha Emler, Kirsten Patrick, Brian O Orvig, Chris |
description | H
4
octapa is an extremely versatile acyclic chelator for a wide variety of medicinally relevant metal ions, forming complexes of both high thermodynamic and kinetic stability. This work reports a significantly simplified 3 step high yield straightforward synthesis of H
4
octapa directly from EDDA. Crystals of the octa-protonated form of the ligand [H
8
octapa]
4+
as its tetrachloride salt, and of the mixed lanthanum-sodium salt of [La(octapa)]
−
were isolated and characterized by X-ray diffraction. All eight protonation constants for the ligand were determined through combined potentiometric-spectrophotometric titrations and in batch experiments using UV spectrophotometry and
1
H NMR spectroscopy. Synthesis, characterisation and solution equilibria studies are presented for complexes [Ln(octapa)]
−
(Ln = lanthanide element) with Sm(
iii
), Dy(
iii
), and Yb(
iii
) (each of which have radiopharmaceutical applications). Complex formation equilibria studies provided evidence of Ln(Hoctapa), [Ln(octapa)]
−
and [Ln(octapa)(OH)]
2−
species in solution, and their stability constants were evaluated by pH-potentiometric competition titrations using [ttha]
6−
as a competing ligand, and by UV-vis spectrophotometric measurements. The high stability constants of the [Ln(octapa)]
−
complexes with Sm(
iii
), Dy(
iii
), and Yb(
iii
) (log
K
SmL
= 20.10(2), log
K
DyL
= 20.14(3) and log
K
YbL
= 19.90(1)) are similar to the published values for other lanthanides and consequently these initial investigations confirm H
4
octapa as a valuable ligand for Sm(
iii
), Dy(
iii
), Yb(
iii
) and other Ln for application in diagnostic and therapeutic nuclear medicine.
H
4
octapa is synthesized and complexed to nine metals of medicinal interest. Crystal structures of the ligand and its La complex were obtained. Solution equilibria for the ligand and several lanthanide complexes were investigated. |
doi_str_mv | 10.1039/c7dt02343j |
format | Article |
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4
octapa is an extremely versatile acyclic chelator for a wide variety of medicinally relevant metal ions, forming complexes of both high thermodynamic and kinetic stability. This work reports a significantly simplified 3 step high yield straightforward synthesis of H
4
octapa directly from EDDA. Crystals of the octa-protonated form of the ligand [H
8
octapa]
4+
as its tetrachloride salt, and of the mixed lanthanum-sodium salt of [La(octapa)]
−
were isolated and characterized by X-ray diffraction. All eight protonation constants for the ligand were determined through combined potentiometric-spectrophotometric titrations and in batch experiments using UV spectrophotometry and
1
H NMR spectroscopy. Synthesis, characterisation and solution equilibria studies are presented for complexes [Ln(octapa)]
−
(Ln = lanthanide element) with Sm(
iii
), Dy(
iii
), and Yb(
iii
) (each of which have radiopharmaceutical applications). Complex formation equilibria studies provided evidence of Ln(Hoctapa), [Ln(octapa)]
−
and [Ln(octapa)(OH)]
2−
species in solution, and their stability constants were evaluated by pH-potentiometric competition titrations using [ttha]
6−
as a competing ligand, and by UV-vis spectrophotometric measurements. The high stability constants of the [Ln(octapa)]
−
complexes with Sm(
iii
), Dy(
iii
), and Yb(
iii
) (log
K
SmL
= 20.10(2), log
K
DyL
= 20.14(3) and log
K
YbL
= 19.90(1)) are similar to the published values for other lanthanides and consequently these initial investigations confirm H
4
octapa as a valuable ligand for Sm(
iii
), Dy(
iii
), Yb(
iii
) and other Ln for application in diagnostic and therapeutic nuclear medicine.
H
4
octapa is synthesized and complexed to nine metals of medicinal interest. Crystal structures of the ligand and its La complex were obtained. Solution equilibria for the ligand and several lanthanide complexes were investigated.</description><identifier>ISSN: 1477-9226</identifier><identifier>EISSN: 1477-9234</identifier><identifier>DOI: 10.1039/c7dt02343j</identifier><ispartof>Dalton transactions : an international journal of inorganic chemistry, 2017-10, Vol.46 (42), p.14647-14658</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids></links><search><creatorcontrib>Jaraquemada-Peláez, María de Guadalupe</creatorcontrib><creatorcontrib>Wang, Xiaozhu</creatorcontrib><creatorcontrib>Clough, Thomas J</creatorcontrib><creatorcontrib>Cao, Yang</creatorcontrib><creatorcontrib>Choudhary, Neha</creatorcontrib><creatorcontrib>Emler, Kirsten</creatorcontrib><creatorcontrib>Patrick, Brian O</creatorcontrib><creatorcontrib>Orvig, Chris</creatorcontrib><title>Hoctapa: synthesis, solution equilibria and complexes with useful radiopharmaceutical metal ions</title><title>Dalton transactions : an international journal of inorganic chemistry</title><description>H
4
octapa is an extremely versatile acyclic chelator for a wide variety of medicinally relevant metal ions, forming complexes of both high thermodynamic and kinetic stability. This work reports a significantly simplified 3 step high yield straightforward synthesis of H
4
octapa directly from EDDA. Crystals of the octa-protonated form of the ligand [H
8
octapa]
4+
as its tetrachloride salt, and of the mixed lanthanum-sodium salt of [La(octapa)]
−
were isolated and characterized by X-ray diffraction. All eight protonation constants for the ligand were determined through combined potentiometric-spectrophotometric titrations and in batch experiments using UV spectrophotometry and
1
H NMR spectroscopy. Synthesis, characterisation and solution equilibria studies are presented for complexes [Ln(octapa)]
−
(Ln = lanthanide element) with Sm(
iii
), Dy(
iii
), and Yb(
iii
) (each of which have radiopharmaceutical applications). Complex formation equilibria studies provided evidence of Ln(Hoctapa), [Ln(octapa)]
−
and [Ln(octapa)(OH)]
2−
species in solution, and their stability constants were evaluated by pH-potentiometric competition titrations using [ttha]
6−
as a competing ligand, and by UV-vis spectrophotometric measurements. The high stability constants of the [Ln(octapa)]
−
complexes with Sm(
iii
), Dy(
iii
), and Yb(
iii
) (log
K
SmL
= 20.10(2), log
K
DyL
= 20.14(3) and log
K
YbL
= 19.90(1)) are similar to the published values for other lanthanides and consequently these initial investigations confirm H
4
octapa as a valuable ligand for Sm(
iii
), Dy(
iii
), Yb(
iii
) and other Ln for application in diagnostic and therapeutic nuclear medicine.
H
4
octapa is synthesized and complexed to nine metals of medicinal interest. Crystal structures of the ligand and its La complex were obtained. Solution equilibria for the ligand and several lanthanide complexes were investigated.</description><issn>1477-9226</issn><issn>1477-9234</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2017</creationdate><recordtype>article</recordtype><sourceid/><recordid>eNqFTksKwjAUDKJg_WzcC-8AVtNULboVpQdwX59ppJG0qXkp2tvbhejSzXwYZhjGZhFfRjzerWSSey7idXzvsSBaJ0m461z_q8V2yEZEd86F4BsRsEtqpcca90Bt5QtFmhZA1jRe2wrUo9FGX51GwCoHacvaqJcieGpfQEPq1hhwmGtbF-hKlKrrSTRQKt9hN0ETNrihITX98JjNT8fzIQ0dyax2ukTXZr_b8b_8DUDsSB8</recordid><startdate>20171031</startdate><enddate>20171031</enddate><creator>Jaraquemada-Peláez, María de Guadalupe</creator><creator>Wang, Xiaozhu</creator><creator>Clough, Thomas J</creator><creator>Cao, Yang</creator><creator>Choudhary, Neha</creator><creator>Emler, Kirsten</creator><creator>Patrick, Brian O</creator><creator>Orvig, Chris</creator><scope/></search><sort><creationdate>20171031</creationdate><title>Hoctapa: synthesis, solution equilibria and complexes with useful radiopharmaceutical metal ions</title><author>Jaraquemada-Peláez, María de Guadalupe ; Wang, Xiaozhu ; Clough, Thomas J ; Cao, Yang ; Choudhary, Neha ; Emler, Kirsten ; Patrick, Brian O ; Orvig, Chris</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-rsc_primary_c7dt02343j3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><creationdate>2017</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Jaraquemada-Peláez, María de Guadalupe</creatorcontrib><creatorcontrib>Wang, Xiaozhu</creatorcontrib><creatorcontrib>Clough, Thomas J</creatorcontrib><creatorcontrib>Cao, Yang</creatorcontrib><creatorcontrib>Choudhary, Neha</creatorcontrib><creatorcontrib>Emler, Kirsten</creatorcontrib><creatorcontrib>Patrick, Brian O</creatorcontrib><creatorcontrib>Orvig, Chris</creatorcontrib><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Jaraquemada-Peláez, María de Guadalupe</au><au>Wang, Xiaozhu</au><au>Clough, Thomas J</au><au>Cao, Yang</au><au>Choudhary, Neha</au><au>Emler, Kirsten</au><au>Patrick, Brian O</au><au>Orvig, Chris</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Hoctapa: synthesis, solution equilibria and complexes with useful radiopharmaceutical metal ions</atitle><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle><date>2017-10-31</date><risdate>2017</risdate><volume>46</volume><issue>42</issue><spage>14647</spage><epage>14658</epage><pages>14647-14658</pages><issn>1477-9226</issn><eissn>1477-9234</eissn><abstract>H
4
octapa is an extremely versatile acyclic chelator for a wide variety of medicinally relevant metal ions, forming complexes of both high thermodynamic and kinetic stability. This work reports a significantly simplified 3 step high yield straightforward synthesis of H
4
octapa directly from EDDA. Crystals of the octa-protonated form of the ligand [H
8
octapa]
4+
as its tetrachloride salt, and of the mixed lanthanum-sodium salt of [La(octapa)]
−
were isolated and characterized by X-ray diffraction. All eight protonation constants for the ligand were determined through combined potentiometric-spectrophotometric titrations and in batch experiments using UV spectrophotometry and
1
H NMR spectroscopy. Synthesis, characterisation and solution equilibria studies are presented for complexes [Ln(octapa)]
−
(Ln = lanthanide element) with Sm(
iii
), Dy(
iii
), and Yb(
iii
) (each of which have radiopharmaceutical applications). Complex formation equilibria studies provided evidence of Ln(Hoctapa), [Ln(octapa)]
−
and [Ln(octapa)(OH)]
2−
species in solution, and their stability constants were evaluated by pH-potentiometric competition titrations using [ttha]
6−
as a competing ligand, and by UV-vis spectrophotometric measurements. The high stability constants of the [Ln(octapa)]
−
complexes with Sm(
iii
), Dy(
iii
), and Yb(
iii
) (log
K
SmL
= 20.10(2), log
K
DyL
= 20.14(3) and log
K
YbL
= 19.90(1)) are similar to the published values for other lanthanides and consequently these initial investigations confirm H
4
octapa as a valuable ligand for Sm(
iii
), Dy(
iii
), Yb(
iii
) and other Ln for application in diagnostic and therapeutic nuclear medicine.
H
4
octapa is synthesized and complexed to nine metals of medicinal interest. Crystal structures of the ligand and its La complex were obtained. Solution equilibria for the ligand and several lanthanide complexes were investigated.</abstract><doi>10.1039/c7dt02343j</doi><tpages>12</tpages></addata></record> |
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title | Hoctapa: synthesis, solution equilibria and complexes with useful radiopharmaceutical metal ions |
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