TY - JOUR
T1 - Platinum(II)-glutamic acid dendrimer conjugates
T2 - Synthesis, characterization, DFT calculation, conformational analysis and catalytic properties
AU - Lataifeh, Anas
AU - Kraatz, Heinz Bernhard
AU - Awwadi, Firas F.
AU - Zaitoun, Mohammed A.
AU - Sakai, Ken
N1 - Funding Information:
A. Lataifeh wishes to thank University of Western Ontario/Chemistry Department for ASPIRE award and Dr. T. Ashboul/ Friedrich Schiller-University of Jena for running the elemental analysis. A. Lataifeh is grateful to financial support from Tafila Technical University(TTU)/Jordan (grant number: 150/2012). This work was funded by Natural Sciences and Engineering Research Council of Canada (NSERC) and the University of Western Ontario (UWO). This work was partly supported by the International Institute for Carbon Neutral Energy Research (WPI-I2CNER), sponsored by the World Premier International Research Center Initiative (WPI), MEXT, Japan. Appendix A
Publisher Copyright:
© 2018 Elsevier B.V.
PY - 2018/3/24
Y1 - 2018/3/24
N2 - A series of platinum(II)-L-glutamic acid dendrimer conjugates having the formula PtCl2(5,5′-Gn(OR)-2,2′-bipyridine); Gn (n = 0, 1, 2), have been synthesized by various amide bond formation methods. The dendrimer complexes were terminated as carboxylic acid (R = H) or methyloxy ester (R = Me). The complexes were characterized by mass spectrometry, elemental analysis, UV-vis, FTIR, 1H-, 13C NMR, 1H-TOCSY, HSQC. The G1(OH) complex aggregate in solution and solid state, giving rise to a rigid conformation for the glutmaic acid side chain. The G2(OH) exists in the “monomeric” form with several conformations for the glutamic acid side chains. Complexes terminated with carboxyl group (R = H) were active catalyst toward hydrogen gas (H2) production by photo-induced splitting of water. The turnover frequency (TOF) for the G1(OH) complex is 14.7 × 1015 s−1, and it exhibits a ∼ 2-fold enhancement in H2 production compared to the unmodified parent complex G0(OH) (TOF = 7×1015 s−1). While G2(OH) complex displayed a lower hydrogen activity (TOF = 3.8 × 1015 s−1) compared to G0(OH). The platinum-glutamic acid dendrimer conjugates showed a correlation between H2 evolution activity and their ability to form aggregates, which driven by the steric hindrance of the peptide residues in the vicinity of Pt-center.
AB - A series of platinum(II)-L-glutamic acid dendrimer conjugates having the formula PtCl2(5,5′-Gn(OR)-2,2′-bipyridine); Gn (n = 0, 1, 2), have been synthesized by various amide bond formation methods. The dendrimer complexes were terminated as carboxylic acid (R = H) or methyloxy ester (R = Me). The complexes were characterized by mass spectrometry, elemental analysis, UV-vis, FTIR, 1H-, 13C NMR, 1H-TOCSY, HSQC. The G1(OH) complex aggregate in solution and solid state, giving rise to a rigid conformation for the glutmaic acid side chain. The G2(OH) exists in the “monomeric” form with several conformations for the glutamic acid side chains. Complexes terminated with carboxyl group (R = H) were active catalyst toward hydrogen gas (H2) production by photo-induced splitting of water. The turnover frequency (TOF) for the G1(OH) complex is 14.7 × 1015 s−1, and it exhibits a ∼ 2-fold enhancement in H2 production compared to the unmodified parent complex G0(OH) (TOF = 7×1015 s−1). While G2(OH) complex displayed a lower hydrogen activity (TOF = 3.8 × 1015 s−1) compared to G0(OH). The platinum-glutamic acid dendrimer conjugates showed a correlation between H2 evolution activity and their ability to form aggregates, which driven by the steric hindrance of the peptide residues in the vicinity of Pt-center.
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U2 - 10.1016/j.ica.2017.12.022
DO - 10.1016/j.ica.2017.12.022
M3 - Article
AN - SCOPUS:85041624001
SN - 0020-1693
VL - 473
SP - 245
EP - 254
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
ER -