Cisplatin, (NH 3 ) 2 PtCl 2 , has been known as a successful metal-based anticancer drug for more than half a century. Its analogue, Argplatin, arginine-linked cisplatin, (Arg)PtCl 2 , is being investigated because it exhibits reactivity towards DNA and RNA that differs from that of cisplatin. In order to understand the basis for its altered reactivity, the deprotonated and sodium cationized forms of Argplatin, [(Arg-H)PtCl 2 ] − and [(Arg)PtCl 2 + Na] + , are examined by infrared multiple photon dissociation (IRMPD) action spectroscopy in the IR fingerprint and hydrogen-stretching regions. Complementary electronic structure calculations are performed using density functional theory approaches to characterize the stable structures of these complexes and to predict their infrared spectra. Comparison of the theoretical IR spectra predicted for various stable conformations of these Argplatin complexes to their measured IRMPD spectra enables determination of the binding mode(s) of Arg to the Pt metal center to be identified. Arginine is found to bind to Pt in a bidentate fashion to the backbone amino nitrogen and carboxylate oxygen atoms in both the [(Arg-H)PtCl 2 ] − and [(Arg)PtCl 2 + Na] + complexes, the NO − binding mode. The neutral side chain of Arg also interacts with the Pt center to achieve additional stabilization in the [(Arg-H)PtCl 2 ] − complex. In contrast, Na + binds to both chlorido ligands in the [(Arg)PtCl 2 + Na] + complex and the protonated side chain of Arg is stabilized via hydrogen-bonding interactions with the carboxylate moiety. These findings are consistent with condensed-phase results, indicating that the NO − binding mode of arginine to Pt is preserved in the electrospray ionization process even under variable pH and ionic strength.
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Noble Metal Ion‐Directed Assembly of 2D Materials for Heterostructured Catalysts and Metallic Micro‐Texturing
Abstract Assembling 2D‐material (2DM) nanosheets into micro‐ and macro‐architectures with augmented functionalities requires effective strategies to overcome nanosheet restacking. Conventional assembly approaches involve external binders and/or functionalization, which inevitably sacrifice 2DM's nanoscale properties. Noble metal ions (NMI) are promising ionic crosslinkers, which can simultaneously assemble 2DM nanosheets and induce synergistic properties. Herein, a collection of NMI–2DM complexes are screened and categorized into two sub‐groups. Based on the zeta potentials, two assembly approaches are developed to obtain 1) NMI‐crosslinked 2DM hydrogels/aerogels for heterostructured catalysts and 2) NMI–2DM inks for templated synthesis. First, tetraammineplatinum(II) nitrate (TPtN) serves as an efficient ionic crosslinker to agglomerate various 2DM dispersions. By utilizing micro‐textured assembly platforms, various TPtN–2DM hydrogels are fabricated in a scalable fashion. Afterward, these hydrogels are lyophilized and thermally reduced to synthesize Pt‐decorated 2DM aerogels (Pt@2DM). The Pt@2DM heterostructures demonstrate high, substrate‐dependent catalytic activities and promote different reaction pathways in the hydrogenation of 3‐nitrostyrene. Second, PtCl4can be incorporated into 2DM dispersions at high NMI molarities to prepare a series of PtCl4–2DM inks with high colloidal stability. By adopting the PtCl4–graphene oxide ink, various Pt micro‐structures with replicated topographies are synthesized with accurate control of grain sizes and porosities.
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- Award ID(s):
- 2045258
- PAR ID:
- 10411958
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Functional Materials
- Volume:
- 33
- Issue:
- 30
- ISSN:
- 1616-301X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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