Search for: All records

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. 

Abstract Reconstructing the history of polar temperature from ice core water isotope (δ¹⁸O) calibration has remained a challenge in paleoclimate research, because of our incomplete understanding of various temperature–δ¹⁸O relationships. This paper resolves this classical problem in a new framework called the unified slope equations (USE), which illustrates the general relations among spatial and temporalδ¹⁸O–surface temperature slopes. The USE is applied to the Antarctica temperature change during the last deglaciation in model simulations and observations. It is shown that the comparable Antarctica-mean spatial slope with deglacial temporal slope inδ¹⁸O–surface temperature reconstruction is caused, accidentally, by the compensation responses between theδ¹⁸O–inversion layer temperature relation and the inversion layer temperature itself. Furthermore, in light of the USE, we propose that the present seasonal slope ofδ¹⁸O–inversion layer temperature is an optimal paleothermometer that is more accurate and robust than the spatial slope. This optimal slope suggests the possibility of reconstructing past Antarctic temperature changes using present and future instrumental observations. Significance StatementThis paper develops a new framework called the unified slope equations (USE) to provide, for the first time, a general relation among various spatial and temporal water isotope–temperature slopes. The application of the USE to Antarctic deglacial temperature change shows that the optimal paleothermometer is the seasonal slope of the inversion layer temperature.