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Full-Text Articles in Physical Sciences and Mathematics
The Confluence Of Structure And Dynamics In Lanthanide(Iii) Chelates: How Dynamics Help Define Structure In Solution, Benjamin Charles Webber, Mark Woods
The Confluence Of Structure And Dynamics In Lanthanide(Iii) Chelates: How Dynamics Help Define Structure In Solution, Benjamin Charles Webber, Mark Woods
Chemistry Faculty Publications and Presentations
Coordination exchange processes tend to dominate the solution state behaviour of lanthanide chelates and generally prohibit the study of small conformational changes. In this article we take advantage of coordinatively rigid Eu3+ chelates to examine the small conformational changes that occur in these chelates as water dissociatively exchanges in and out of the inner coordination sphere. The results show that the time-averaged conformation of the chelate alters as the water exchange rate increases. This conformational change reflects a change in the hydration state (q/rLnH6) of the chelate. The hydration state has recently come …
Towards The Rational Design Of Mri Contrast Agents: Δ-Substitution Of Lanthanide(Iii) Nb-Dota-Tetraamide Chelates Influences But Does Not Control Coordination Geometry, Christiane E. Carney, Anh D. Tran, Jing Wang, Matthias C. Schabel, A. Dean Sherry, Mark Woods
Towards The Rational Design Of Mri Contrast Agents: Δ-Substitution Of Lanthanide(Iii) Nb-Dota-Tetraamide Chelates Influences But Does Not Control Coordination Geometry, Christiane E. Carney, Anh D. Tran, Jing Wang, Matthias C. Schabel, A. Dean Sherry, Mark Woods
Chemistry Faculty Publications and Presentations
LnDOTA-tetraamide chelates (DOTA=1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid) have received considerable recent attention as a result of their potential to act as PARACEST contrast agents for magnetic resonance imaging (MRI). Although PARACEST agents afford several advantages over conventional contrast agents they suffer from substantially higher detection limits; thus, improving the effectiveness of LnDOTA-tetraamide chelates is an important goal. In this study we investigate the potential to extend conformational control of LnDOTA-type ligands to those applicable to PARACEST. Furthermore, the question of whether δ- rather than α-substitution of the pendant arms could be used to control the chelate coordination geometry is addressed. Although δ-substitution does …
Analysis Of The Conformational Behavior And Stability Of The Sap And Tsap Isomers Of Lanthanide(Iii) Nb-Dota-Type Chelates, Gyula Tircso, Benjamin Charles Webber, Benjamin E. Kucera, Victor G. Young, Mark Woods
Analysis Of The Conformational Behavior And Stability Of The Sap And Tsap Isomers Of Lanthanide(Iii) Nb-Dota-Type Chelates, Gyula Tircso, Benjamin Charles Webber, Benjamin E. Kucera, Victor G. Young, Mark Woods
Chemistry Faculty Publications and Presentations
Controlling the water exchange kinetics of macrocyclic Gd(3+) chelates, a key parameter in the design of improved magnetic resonance imaging (MRI) contrast media, may be facilitated by selecting the coordination geometry of the chelate. The water exchange kinetics of the mono- capped twisted square antiprism (TSAP) being much closer to optimal than those of the mono capped square antiprism (SAP) render the TSAP isomer more desirable for high relaxivity applications. Two systems have been developed that allow for selection of the TSAP coordination geometry in 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA)-type Gd(3+) chelates, both based upon the macrocycle nitrobenzyl cyclen. In this paper …
Investigations Into Whole Water, Prototropic And Amide Proton Exchange In Lanthanide(Iii) Dota-Tetraamide Chelates, Mark Woods, Azhar Pasha, Piyu Zhao, Gyula Tircso, Somdatta Chowdhury, Garry Kiefer, Donald E. Woessner, A. Dean Sherry
Investigations Into Whole Water, Prototropic And Amide Proton Exchange In Lanthanide(Iii) Dota-Tetraamide Chelates, Mark Woods, Azhar Pasha, Piyu Zhao, Gyula Tircso, Somdatta Chowdhury, Garry Kiefer, Donald E. Woessner, A. Dean Sherry
Chemistry Faculty Publications and Presentations
Lanthanide(III) chelates of DOTA-tetraamide ligands have been an area of particular interest since the discovery that water exchange kinetics are dramatically affected by the switch from acetate to amide side-chain donors. More recently these chelates have attracted interest as potential PARACEST agents for use in MRI. In this paper we report the results of studies using chemical exchange saturation transfer (CEST) and some more recently reported chelates to re-examine the exchange processes in this class of chelate. We find that the conclusions of Parker and Aime are, for the most part, solid; water exchange is slow and a substantial amount …
The Population Of Sap And Tsap Isomers In Cyclen-Based Lanthanide(Iii) Chelates Is Substantially Affected By Solvent, Kyle J. Miller, Ali A. Saherwala, Benjamin C. Webber, Yunkou Wu, A. Dean Sherry, Mark Woods
The Population Of Sap And Tsap Isomers In Cyclen-Based Lanthanide(Iii) Chelates Is Substantially Affected By Solvent, Kyle J. Miller, Ali A. Saherwala, Benjamin C. Webber, Yunkou Wu, A. Dean Sherry, Mark Woods
Chemistry Faculty Publications and Presentations
The square antiprism/twisted square antiprism ratio in LnDOTA-tetraamide chelates is a critical parameter in governing water-exchange kinetics and ultimately the utility of a chelate as a PARACEST MRI contrast agent. In LnDOTA-tetraamide chelates with tertiary amides, this ratio and the rate of interconversion between these two structural isomers are found to be dramatically dependent upon the solvent and possibly other local environmental factors.
Effect Of The Regiochemistry Of Butyl Amide Substituents On The Solution-State Structures Of Lanthanide(Iii) Dota-Tetraamide Complexes, Tomoyasu Mani, Gyula Tircsó, Piyu Zhao, A. Dean Sherry, Mark Woods
Effect Of The Regiochemistry Of Butyl Amide Substituents On The Solution-State Structures Of Lanthanide(Iii) Dota-Tetraamide Complexes, Tomoyasu Mani, Gyula Tircsó, Piyu Zhao, A. Dean Sherry, Mark Woods
Chemistry Faculty Publications and Presentations
The coordination geometry adopted by the lanthanide complexes of DOTA-tetraamides is a critical factor in determining their water exchange kinetics. Controlling the water exchange kinetics of DOTA-tetraamide complexes, and by extension their coordination geometry, is of particular interest because of the potential application of this class of complex as PARACEST MRI contrast agents. To facilitate the maximum CEST effect at the lowest pre-saturation powers much slower exchange kinetics are required than are commonly observed with these types of chelates. Complexes that adopt the more slowly exchanging square antiprismatic coordination geometry are therefore preferred; however, the factors that govern which coordination …