Spectroscopic studies on photoinduced reactions of the anticancer prodrug, trans,trans,trans-[Pt(N3)2(OH)2(py)2]

The photodecomposition mechanism of trans,trans,trans-[Pt(N3)2(OH)2(py)2] (1, py = pyridine), an anticancer prodrug candidate, was probed using complementary Attenuated Total Reflection Fourier Transform Infrared (ATR-FTIR), transient electronic absorption and UV-Vis spectroscopy. Data fitting using Principal Component Analysis (PCA) and multi-curve resolution alternating least squares, suggests the formation of a trans-[Pt(N3)(py)2(OH/H2O)] intermediate and trans [Pt(py)2(OH/H2O)2] as the final product upon 420 nm irradiation of 1 in water. Rapid disappearance of the hydroxido ligand stretching vibration upon irradiation is correlated with a -10 cm-1 shift to the anti-symmetric azido vibration, suggesting a possible second intermediate. Experimental proof of subsequent dissociation of azido ligands from platinum is presented, where at least one hydroxyl radical is formed in the reduction of Pt(IV) to Pt(II). Additionally, the photoinduced reaction of 1 with 5'-guanosine monophosphate was studied, and the identity of key photoproducts was assigned with the help of ATR FTIR spectroscopy, mass spectrometry and DFT calculations. The identification of marker bands for photoproducts, e.g. trans-[Pt(N3)(py)2(5'-GMP)] and trans-[Pt(py)2(5'-GMP)2], will aid elucidation of the chemical and biological mechanism of anticancer action of 1. In general, these studies demonstrate the potential of vibrational spectroscopic techniques as promising tools for studying such metal complexes

Comprehensive vibrational spectroscopic investigation of trans,trans,trans-[Pt(N3)2(OH)2(py)2], a Pt(IV) diazido anticancer prodrug candidate

We report a detailed study of a promising photoactivatable metal-based anticancer prodrug candidate, trans,trans,trans-[Pt(N3)2(OH)2(py)2] (C1; py = pyridine), using vibrational spectroscopic techniques. Attenuated total reflection Fourier transform infrared (ATR-FTIR), Raman, and synchrotron radiation far-IR (SR-FIR) spectroscopies were applied to obtain highly resolved ligand and Pt-ligand vibrations for C1 and its precursors (trans-[Pt(N3)2(py)2] (C2) and trans-[PtCl2(py)2] (C3)). Distinct IR- and Raman-active vibrational modes were assigned with the aid of density functional theory calculations, and trends in the frequency shifts as a function of changing Pt coordination environment were determined and detailed for the first time. The data provide the ligand and Pt-ligand (azide, hydroxide, pyridine) vibrational signatures for C1 in the mid- and far-IR region, which will provide a basis for the better understanding of the interaction of C1 with biomolecules

Studies of Carbon Monoxide Release from Ruthenium(II) Bipyridine Carbonyl Complexes upon UV-Light Exposure

The UV-light-induced CO release characteristics of a series of ruthenium­(II) carbonyl complexes of the form <i>trans</i>-Cl­[RuLCl₂(CO)₂] (L = 4,4′-dimethyl-2,2′-bipyridine, 4′-methyl-2,2′-bipyridine-4-carboxylic acid, or 2,2′-bipyridine-4,4′-dicarboxylic acid) have been elucidated using a combination of UV–vis absorbance and Fourier transform infrared spectroscopies, multivariate curve resolution alternating least-squares analysis, and density functional theory calculations. In acetonitrile, photolysis appears to proceed via a serial three-step mechanism involving the sequential formation of [RuL­(CO)­(CH₃CN)­Cl₂], [RuL­(CH₃CN)₂Cl₂], and [RuL­(CH₃CN)₃Cl]⁺. Release of the first CO molecule occurs quickly (<i>k</i>₁ ≫ 3 min^–1), while release of the second CO molecule proceeds at a much more modest rate (<i>k</i>₂ = 0.099–0.17 min^–1) and is slowed by the presence of electron-withdrawing carboxyl substituents on the bipyridine ligand. In aqueous media (1% dimethyl sulfoxide in H₂O), the two photodecarbonylation steps proceed much more slowly (<i>k</i>₁ = 0.46–1.3 min^–1 and <i>k</i>₂ = 0.026–0.035 min^–1, respectively) and the influence of the carboxyl groups is less pronounced. These results have implications for the design of new light-responsive CO-releasing molecules (“photoCORMs”) intended for future medical use

Data for Comprehensive vibrational spectroscopic investigation of trans,trans,trans-[Pt(N3)2(OH)2(py)2], a Pt(IV) diazido anticancer prodrug candidate

We report a detailed study of a promising photoactivatable metal-based anticancer prodrug candidate, trans,trans,trans-[Pt(N3)2(OH)2(py)2] (C1; py = pyridine), using vibrational spectroscopic techniques. Attenuated total reflection Fourier transform infrared (ATR-FTIR), Raman, and synchrotron radiation far-IR (SR-FIR) spectroscopies were applied to obtain highly resolved ligand and Pt-ligand vibrations for C1 and its precursors (trans-[Pt(N3)2(py)2] (C2) and trans-[PtCl2(py)2] (C3)). Distinct IR- and Raman-active vibrational modes were assigned with the aid of density functional theory calculations, and trends in the frequency shifts as a function of changing Pt coordination environment were determined and detailed for the first time. The data provide the ligand and Pt-ligand (azide, hydroxide, pyridine) vibrational signatures for C1 in the mid- and far-IR region, which will provide a basis for the better understanding of the interaction of C1 with biomolecules

Comprehensive Vibrational Spectroscopic Investigation of <i>trans,trans,trans</i>-[Pt(N₃)₂(OH)₂(py)₂], a Pt(IV) Diazido Anticancer Prodrug Candidate

We report a detailed study of a promising photoactivatable metal-based anticancer prodrug candidate, <i>trans</i>,<i>trans</i>,<i>trans</i>-[Pt­(N₃)₂(OH)₂(py)₂] (<b>C1</b>; py = pyridine), using vibrational spectroscopic techniques. Attenuated total reflection Fourier transform infrared (ATR-FTIR), Raman, and synchrotron radiation far-IR (SR-FIR) spectroscopies were applied to obtain highly resolved ligand and Pt-ligand vibrations for <b>C1</b> and its precursors (<i>trans</i>-[Pt­(N₃)₂(py)₂] (<b>C2</b>) and <i>trans</i>-[PtCl₂(py)₂] (<b>C3</b>)). Distinct IR- and Raman-active vibrational modes were assigned with the aid of density functional theory calculations, and trends in the frequency shifts as a function of changing Pt coordination environment were determined and detailed for the first time. The data provide the ligand and Pt-ligand (azide, hydroxide, pyridine) vibrational signatures for <b>C1</b> in the mid- and far-IR region, which will provide a basis for the better understanding of the interaction of <b>C1</b> with biomolecules