Supramolecular Gel Control of Cisplatin Crystallization: Identification of a New Solvate Form Using a Cisplatin-Mimetic Gelator

Abstract

. (2015) 'Supramolecular gel control of cisplatin crystallization : identi cation of a new solvate form using a cisplatin-mimetic gelator.', Crystal growth design., 15 (9). pp. 4591-4599. Further information on publisher's website:http://dx.doi.org/10.1021/acs.cgd.5b00840Publisher's copyright statement:This document is the Accepted Manuscript version of a Published Work that appeared in nal form in Crystal Growth Design, copyright c 2015 American Chemical Society after peer review and technical editing by the publisher. To access the nal edited and published work see http://dx.doi.org/10.1021/acs.cgd.5b00840. Additional information:Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-pro t purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. ABSTRACT: A series of platinum based low molecular weight urea-based gelators C1, C2 and C3, mimicking the structure of the anticancer drug cisplatin has been synthesized, as part of the development of a targeted, supramolecular gel phase crystallization and polymorphism screening strategy. Morphological and rheological studies established that inclusion of a longer spacer between the urea and cisplatin-mimetic regions of the gelator (C3) resulted in optimal gelation performance. Interfacial crystallization of cisplatin in a gel-sol biphasic system has been employed to address the insolubility of the drug molecule in organic solvents. A new N,N-dimethylacetamide (DMA) solvate of cisplatin has been identified and a crystal habit modification of the known N,Ndimethylformamide (DMF) solvate form of cisplatin has been observed on crystallization of cisplatin in C3 gels prepared in xylenes. While both targeted and non-targeted gels resulted in the formation of the new DMA solvate, only the targeted C3 gel resulted in high quality single crystal suitable for characterization by single crystal crystallography. The high crystal quality is attributed to a close match between the core geometry of C3 with that of cisplatin together with local order in the gel fibers of C3.

Gels with sense: supramolecular materials that respond to heat, light and sound

“…Due to their large surface areas, fibrous gels can serve as supports for catalytic particles, enzymes or quantum dots, or as tuneable media for controlling crystallisation and nanofabrication processes. 39,[118][119][120][121][122][123][124] Precipitation in a gel may deliver materials with unusual crystal structures or particle Fig. 6 Structure of L-proline-based gelator 5 and reaction schemes illustrating the dominant reaction pathways in its gels and sols.…”

The Tris(pentafluoroethyl)silanide Anion

“…Them olecular structure in the solid state reveals an almost square-planar geometry with aC l-Pt-Cl angle of approximately 1768 8 and an N-Pt-Si angle of about 1798 8.I n contrast to cis-PtCl 2 (NEt 3 ) 2 ,t he chlorine atoms in [PtCl 2 (Si-(C 2 F 5 ) 3 )(NH i Pr 2 )] (7)a re trans-oriented, but there are no marked differences in the PtÀCl bond lengths (230-233 pm). [27] Theplatinum-silicon bond (223.7 pm) in complex 7 is significantly shorter than in other alkyl-or arylsilylsubstituted platinum complexes (236-239 pm;F igure 4). [28] In conclusion, we have presented the synthesis of tris(pentafluoroethyl)silane,w hich was subsequently employed in hydrosilylation as well as Benkeser-type reactions.D eprotonation of tris(pentafluoroethyl)silane with LDAr esulted in ah ighly reactive and thermally unstable silanide,w hich was isolated after complexation with crown ethers.T ot he best of our knowledge, ][Si-(C 2 F 5 ) 3 ]i st he first example of as alt of ap erfluorinated alkylsilanide that was isolated and fully characterized.…”

“…[27] Theplatinum-silicon bond (223.7 pm) in complex 7 is significantly shorter than in other alkyl-or arylsilylsubstituted platinum complexes (236-239 pm;F igure 4). [27] Theplatinum-silicon bond (223.7 pm) in complex 7 is significantly shorter than in other alkyl-or arylsilylsubstituted platinum complexes (236-239 pm;F igure 4).…”

Das Tris(pentafluorethyl)silanid‐Anion

“…Anions -e ines Schlüsselintermediats in nukleophilen Tr ifluormethylierungen -z ue rhalten, indem das Kaliumkation mithilfe von [18]Krone-6 eingefangen wurde. 19 [27] Die Platin-Silicium-Bindung (223.7 pm) in Komplex 7 ist signifikant kürzer als in anderen Alkyl-oder Arylsilyl-substituierten Platinkomplexen (236-239 pm;Abbildung 4). [26] In Anlehnung an diese Befunde sollten die Stabilisierung des Lithiumsalzes des Tr is(pentafluorethyl)silyl-Anions sowie eine anschließende Isolierung mçglich sein.…”

“…Wiei nA bbildung 3 zu sehen ist, stimmen das experimentelle sowie das simulierte und iterierte 29 Si-NMR-Spektrum von 6 perfekt überein. 19 [27] Die Platin-Silicium-Bindung (223.7 pm) in Komplex 7 ist signifikant kürzer als in anderen Alkyl-oder Arylsilyl-substituierten Platinkomplexen (236-239 pm;Abbildung 4). [28] Uns gelang die Synthese von Tr is(pentafluorethyl)silan, das anschließend in Hydrosilylierungen sowie in Benkeser- [12]Krone-4}][Si-(C 2 F 5 ) 3 ]d as erste Beispiel eines perfluorierten Alkylsilanidsalzes,d as isoliert und vollständig charakterisiert werden konnte.…”