Quantum-classical rate coefficient datasets of vibrational energy transfer in carbon monoxide based on highly accurate potential energy surface.

A merged potential energy surface (PES) is introduced for CO + CO collisions by combining a recent full-dimensional ab initio PES [Chen et al. J. Chem. Phys. 153, 054310 (2020)] and analytical long-range multipolar interactions. This merged PES offers a double advantage: it retains the precision of the ab initio PES in describing the van der Waals well and repulsive short range while providing an accurate physical description of long-range interaction; it significantly reduces the computational time required for trajectory integration since the long-range portion of the ab initio PES (involving numerous neural network fitting parameters) is now replaced by the analytical model potential. Based on the present merged PES, mixed Quantum-Classical (MQC) calculations, which capture quantum effects related to vibrational motion, align with a range of experimental data, including transport properties, vibrational energy transfer between CO and its isotoplogues, as well as rate coefficients for V-V and V-T/R processes. Notably, the original ab initio PES yields V-T/R rate coefficients at low temperatures that are significantly higher than the experimental data due to the artificial contribution of its unphysical long-range potential. In addition to conducting extensive MQC calculations to obtain raw data for V-V and V-T/R rate coefficients, we employ Gaussian process regression to predict processes lacking computed MQC data, thereby completing the considered V-V and V-T/R datasets. These extensive rate coefficient datasets, particularly for V-T/R processes, are unprecedented and reveal the significant role played by V-T/R processes at high temperatures, emphasizing the necessity of incorporating both V-V and V-T/R processes in the applications.

Improved Quantum-Classical Treatment of N2-N2 Inelastic Collisions: Effect of the Potentials and Complete Rate Coefficient Data Sets.

In this study, complete (i.e., including all vibrational quantum numbers in an N2 vibrational ladder) data sets of vibration-to-vibration and vibration-to-translation rate coefficients for N2-N2 collisions are explicitly computed along with transport properties (shear and bulk viscosity, thermal conductivity, and self-diffusion) in the temperature range 100-9000 K. To reach this goal, we improved a mixed quantum-classical (MQC) dynamics approach by lifting the constraint of a Morse treatment of the vibrational wave function and intramolecular potential and permitting the use of more realistic and flexible representations. The new formulation has also allowed us to separately analyze the role of intra- and intermolecular potentials on the calculated rates and properties. Ab initio intramolecular potentials are indispensable for highly excited vibrational states, though the Morse potential still gives reasonable values up to v = 20. An accurate description of the long-range interaction and the van der Waals well is a requisite for the correct reproduction of qualitative and quantitative rate coefficients, particularly at low temperatures, making physically meaningful analytical representations still the best choice compared to currently available ab initio potential energy surfaces. These settings were used to directly compute the MQC rates corresponding to a large number of initial vibrational quantum numbers, and the missing intermediate values were predicted using a machine learning technique (i.e., the Gaussian process regression approach). The obtained values are reliable in the wide temperature range employed and are therefore valuable data for many communities dealing with nonlocal thermal equilibrium conditions in different environments.

IRMPD spectroscopy and quantum-chemical simulations of the reaction products of cisplatin with the dipeptide CysGly.

The inorganic antineoplastic drug cisplatin was made to react in solution with the dipeptide cysteinylglycine (CysGly), chosen as a functional model of glutathione, and the reaction products were analyzed using electrospray ionization mass spectrometry (ESI-MS). Selected complexes, i.e., the primary substitution product cis-[PtCl(NH3)2(CysGly)]+ and the chelate cis-[PtCl(NH3)(CysGly)]+, were submitted to IR multiple photon dissociation (IRMPD) spectroscopy obtaining their vibrational features. The experimental IR ion spectra were compared with the calculated IR absorptions of different plausible isomeric families, finding CysGly to bind preferentially platinum(II) via its deprotonated thiolic group in the monovalent complex, cis-[PtCl(NH3)2(CysGly)]+, and to evolve in the S,N-bound chelate structure cis-[PtCl(NH3)(CysGly)]+ through the SH and NH2 functionality of the cysteine residue. Moreover, our findings indicate that the platination reaction does not affect the CysGly peptide bond, which remains in its trans configuration. These results provide additional insights into the reactivity of Pt(II)-complexes with glutathione which is involved in cellular cisplatin resistance.

Graphene as Nanocarrier for Gold(I)-Monocarbene Complexes: Strength and Nature of Physisorption.

Gold(I) metal complexes are finding increasing applications as therapeutic agents against a variety of diseases. As their potential use as effective metallodrugs is continuously confirmed, the issue of their administration, distribution and delivery to desired biological targets emerges. Graphene and its derivatives possess attractive properties in terms of high affinity and low toxicity, suggesting that they can efficaciously be used as drug nanocarriers. In the present study, we computationally address the adsorption of a gold(I) N-heterocyclic monocarbene, namely, IMeAuCl (where IMe = 1,3-dimethylimidazol-2-ylidene), on graphene. The Au(I) N-heterocyclic carbene family has indeed shown promising anticancer activity and the N-heterocyclic ring could easily interact with planar graphene nanostructures. By means of high-level electronic structure approaches, we investigated the strength and nature of the involved interaction using small graphene prototypes, which allow us to benchmark the best-performing DFT functionals as well as assess the role of the different contributions to total interaction energies. Moreover, realistic adsorption enthalpies and free energy values are obtained by exploiting the optimal DFT method to describe the drug adsorption on larger graphene models. Such values (ΔHads = -18.4 kcal/mol and ΔGads= -7.20 kcal/mol for the largest C150H30 model) indicate a very favorable adsorption, mainly arising from the dispersion component of the interaction, with the electrostatic attraction also playing a non-negligible role.

The FMO2 analysis of the ligand-receptor binding energy: the Biscarbene-Gold(I)/DNA G-Quadruplex case study.

In this work, the ab initio fragment molecular orbital (FMO) method was applied to calculate and analyze the binding energy of two biscarbene-Au(I) derivatives, [Au(9-methylcaffein-8-ylidene)2]+ and [Au(1,3-dimethylbenzimidazol-2-ylidene)2]+, to the DNA G-Quadruplex structure. The FMO2 binding energy considers the ligand-receptor complex as well as the isolated forms of energy-minimum state of ligand and receptor, providing a better description of ligand-receptor affinity compared with simple pair interaction energies (PIE). Our results highlight important features of the binding process of biscarbene-Au(I) derivatives to DNA G-Quadruplex, indicating that the total deformation-polarization energy and desolvation penalty of the ligands are the main terms destabilizing the binding. The pair interaction energy decomposition analysis (PIEDA) between ligand and nucleobases suggest that the main interaction terms are electrostatic and charge-transfer energies supporting the hypothesis that Au(I) ion can be involved in π-cation interactions further stabilizing the ligand-receptor complex. Moreover, the presence of polar groups on the carbene ring, as C = O, can improve the charge-transfer interaction with K+ ion. These findings can be employed to design new powerful biscarbene-Au(I) DNA-G quadruplex binders as promising anticancer drugs. The procedure described in this work can be applied to investigate any ligand-receptor system and is particularly useful when the binding process is strongly characterized by polarization, charge-transfer and dispersion interactions, properly evaluated by ab initio methods.

Elusive intermediates in cisplatin reaction with target amino acids: Platinum(II)-cysteine complexes assayed by IR ion spectroscopy and DFT calculations.

The reactivity of a widely used metal based antineoplastic drug, cisplatin, cis-PtCl2(NH3)2, with L-cysteine (Cys) has been investigated using a combination of electrospray ionization mass spectrometry (ESI-MS), IRMPD gas phase ion spectroscopy and DFT calculations. The cysteine lateral chain represents one of the main platination sites in proteins, which is believed to be related to the resistance mechanisms to cisplatin. The vibrational features of the mass-selected substitution product cis-[PtCl(NH3)2(Cys)]+ and the intercepted cis-[PtCl(NH3)2(H2O)(Cys)]+ intermediate complex were compared to calculated IR spectra, enabling the assessment of the sampled ions structures. In cis-[PtCl(NH3)2(Cys)]+, cysteine was found to bind platinum through the sulfur atom as a thiolate zwitterion, highlighting the enhanced acidity of the cysteine thiol group upon metal coordination. The cis-[PtCl(NH3)2(H2O)(Cys)]+ structure complies with the non-covalent encounter complex, formed by cis-[PtCl(NH3)2(H2O)]+ and neutral cysteine. This species is able to undergo the substitution process to produce cis-[PtCl(NH3)2(Cys)]+ when activated as a mass-isolated ion suggesting its participation in the reaction mechanism of cisplatin with cysteine in solution. Finally, the DFT-calculated energy profile for the substitution reaction was correlated with the peculiar gas-phase reactivity of this non-covalent complex, resulting to be 10-fold less reactive toward substitution than the corresponding methionine complex.

IRMPD Spectroscopy of Bare Monodeprotonated Genistein, an Antioxidant Flavonoid.

Genistein is a naturally occurring polyphenol belonging to the family of flavonoids with estrogenic properties and proven antioxidant, anti-inflammatory, and hormonal effects. Genistein and its derivatives are involved in radical scavenging activity by way of mechanisms based on sequential proton-loss electron transfer. In view of this role, a detailed structural characterization of its bare deprotonated form, [geni-H]-, generated by electrospray ionization, has been performed by tandem mass spectrometry and infrared multiple photon dissociation (IRMPD) spectroscopy in the 800-1800 cm-1 spectral range. Quantum chemical calculations at the B3LYP/6-311+G(d,p) level of theory were carried out to determine geometries, thermochemical data, and anharmonic vibrational properties of low-lying isomers, enabling to interpret the experimental spectrum. Evidence is gathered that the conjugate base of genistein exists as a single isomeric form, which is deprotonated at the most acidic site (7-OH) and benefits from a strong intramolecular H-bond interaction between 5-OH and the adjacent carbonyl oxygen in the most stable arrangement.

Reactions of Arsenoplatin-1 with Protein Targets: A Combined Experimental and Theoretical Study.

Arsenoplatin-1 (AP-1) is a dual-action anticancer metallodrug with a promising pharmacological profile that features the simultaneous presence of a cisplatin-like center and an arsenite center. We investigated its interactions with proteins through a joint experimental and theoretical approach. The reactivity of AP-1 with a variety of proteins, including carbonic anhydrase (CA), superoxide dismutase (SOD), myoglobin (Mb), glyceraldehyde 3-phosphate dehydrogenase (GAPDH), and human serum albumin (HSA), was analyzed by means of electrospray ionization mass spectrometry (ESI MS) measurements. In accordance with previous observations, ESI MS experiments revealed that the obtained metallodrug-protein adducts originated from the binding of the [(AP-1)-Cl]+ fragment to accessible protein residues. Remarkably, in two cases, i.e., Mb and GAPDH, the formation of a bound metallic fragment that lacked the arsenic center was highlighted. The reactions of AP-1 with various nucleophiles side chains of neutral histidine, methionine, cysteine, and selenocysteine, in neutral form as well as cysteine and selenocysteine in anionic form, were subsequently analyzed through a computational approach. We found that the aquation of AP-1 is energetically disfavored, with a reaction free energy of +19.2 kcal/mol demonstrating that AP-1 presumably attacks its biological targets through the exchange of the chloride ligand. The theoretical analysis of thermodynamics and kinetics for the ligand-exchange processes of AP-1 with His, Met, Cys, Sec, Cys-, and Sec- side chain models unveils that only neutral histidine and deprotonated cysteine and selenocysteine are able to effectively replace the chloride ligand in AP-1.

Vibrational Energy Transfer in CO+N2 Collisions: A Database for V-V and V-T/R Quantum-Classical Rate Coefficients.

Knowledge of energy exchange rate constants in inelastic collisions is critically required for accurate characterization and simulation of several processes in gaseous environments, including planetary atmospheres, plasma, combustion, etc. Determination of these rate constants requires accurate potential energy surfaces (PESs) that describe in detail the full interaction region space and the use of collision dynamics methods capable of including the most relevant quantum effects. In this work, we produce an extensive collection of vibration-to-vibration (V-V) and vibration-to-translation/rotation (V-T/R) energy transfer rate coefficients for collisions between CO and N2 molecules using a mixed quantum-classical method and a recently introduced (A. Lombardi, F. Pirani, M. Bartolomei, C. Coletti, and A. Laganà, Frontiers in chemistry, 7, 309 (2019)) analytical PES, critically revised to improve its performance against ab initio and experimental data of different sources. The present database gives a good agreement with available experimental values of V-V rate coefficients and covers an unprecedented number of transitions and a wide range of temperatures. Furthermore, this is the first database of V-T/R rate coefficients for the title collisions. These processes are shown to often be the most probable ones at high temperatures and/or for highly excited molecules, such conditions being relevant in the modeling of hypersonic flows, plasma, and aerospace applications.

Computational Studies of Au(I) and Au(III) Anticancer MetalLodrugs: A Survey.

Owing to the growing hardware capabilities and the enhancing efficacy of computational methodologies, computational chemistry approaches have constantly become more important in the development of novel anticancer metallodrugs. Besides traditional Pt-based drugs, inorganic and organometallic complexes of other transition metals are showing increasing potential in the treatment of cancer. Among them, Au(I)- and Au(III)-based compounds are promising candidates due to the strong affinity of Au(I) cations to cysteine and selenocysteine side chains of the protein residues and to Au(III) complexes being more labile and prone to the reduction to either Au(I) or Au(0) in the physiological milieu. A correct prediction of metal complexes' properties and of their bonding interactions with potential ligands requires QM computations, usually at the ab initio or DFT level. However, MM, MD, and docking approaches can also give useful information on their binding site on large biomolecular targets, such as proteins or DNA, provided a careful parametrization of the metal force field is employed. In this review, we provide an overview of the recent computational studies of Au(I) and Au(III) antitumor compounds and of their interactions with biomolecular targets, such as sulfur- and selenium-containing enzymes, like glutathione reductases, glutathione peroxidase, glutathione-S-transferase, cysteine protease, thioredoxin reductase and poly (ADP-ribose) polymerase 1.

Molecular beam scattering experiments on noble gas-propylene oxide: Total integral cross sections and potential energy surfaces of He- and Ne-C3H6O.

The interactions of He and Ne with propylene oxide have been investigated with the molecular beam technique by measuring the total (elastic + inelastic) integral cross section as a function of collision velocity. Starting from the analysis of these experimental data, potential energy surfaces, formulated as a function of the separation distance and orientation of propylene oxide with respect to the interacting partners, have been built: The average depth of potential wells (located at intermediate separation distances) has been characterized by analyzing the observed "glory" quantum effects, and the strength of long-range attractions has been obtained from the magnitude and the velocity dependence of the smooth component of measured cross sections. The surfaces, tested and improved against new ab initio calculations of minima interaction energies at the complete basis set level of theory, are defined in the full space of relative configurations. This represents a crucial condition to provide force fields useful to carry out, in general, important molecular property simulations and to evaluate, in the present case, the spectroscopic features and the dynamical selectivity of weakly bound complexes formed by propylene oxide, a prototype chiral species, during collisions in interstellar clouds and winds, in the space and planetary atmospheres. The adopted formulation of the interaction can be readily extended to similar systems, involving heavier noble gases or diatomic molecules (H2, O2, and N2) as well as to propylene oxide dimers.

From Preassociation to Chelation: A Survey of Cisplatin Interaction with Methionine at Molecular Level by IR Ion Spectroscopy and Computations.

Methionine (Met) plays an important role in the metabolism of cisplatin anticancer drug. Yet, methionine platination in aqueous solution presents a highly complex pattern of interconnected paths and intermediates. This study reports on the reaction of methionine with the active aqua form of cisplatin, cis-[PtCl(NH3)2(H2O)]+, isolating the encounter complex of the reactant pair, {cis-[PtCl(NH3)2(H2O)]+·Met}, by electrospray ionization. In the unsolvated state, charged intermediates are characterized for their structure and photofragmentation behavior by IR ion spectroscopy combined with quantum-chemical calculations, obtaining an outline of the cisplatin-methionine reaction at a molecular level. To summarize the major findings: (i) the {cis-[PtCl(NH3)2(H2O)]+·Met} encounter complex, lying on the reaction coordinate of the Eigen-Wilkins preassociation mechanism for ligand substitution, is delivered in the gas phase and characterized by IR ion spectroscopy; (ii) upon vibrational excitation, ligand exchange occurs within {cis-[PtCl(NH3)2(H2O)]+·Met}, releasing water and cis-[PtCl(NH3)2(Met)]+, along the calculated energy profile; (iii) activated cis-[PtCl(NH3)2(Met)]+ ions undergo NH3 departure, forming a chelate complex, [PtCl(NH3)(Met)]+, whose structure is congruent with overwhelming S-Met ligation as the primary coordination step. The latter process involving ammonia loss marks a difference with the prevailing chloride replacement in protic solvent, pointing to the effect of a low-polarity environment.

Reactivity of antitumor coinage metal-based N-heterocyclic carbene complexes with cysteine and selenocysteine protein sites.

The reaction of the antitumor M(I)-bis-N-heterocyclic carbene (M(I)-NHC) complexes, M = Cu, Ag, and Au, with their potential protein binding sites, i.e. cysteine and selenocysteine, was investigated by means of density functional theory approaches. Capped cysteine and selenocysteine were employed to better model the corresponding residues environment within peptide structures. By assuming the neutral or deprotonated form of the side chains of these amino acids and by considering the possible assistance of an external proton donor such as an adjacent acidic residue or the acidic component of the surrounding buffer environment, we devised five possible routes leading to the binding of the investigated M(I)-NHC scaffolds to these protein sites, reflecting their different location in the protein structure and exposure to the bulk. The targeting of either cysteine or selenocysteine in their neutral forms is a kinetically unfavored process, expected to be quite slow if observable at all at physiological temperature. On the other hand, the reaction with the deprotonated forms is much more favored, even though an external proton source is required to assist the protonation of the leaving carbene. Our calculations also show that all coinage metals are characterized by a similar reactivity toward the binding of cysteine and selenocysteine sites, although the Au(I) complex has significantly higher reaction and activation free energies compared to Cu(I) and Ag(I).

Reconciling experimental and theoretical vibrational deactivation in low-energy O + N2 collisions.

Molecular dynamics calculations of inelastic collisions of atomic oxygen with molecular nitrogen are known to show orders of magnitude discrepancies with experimental results in the range from room temperature to many thousands of degrees Kelvin. In this work, we have achieved an unprecedented quantitative agreement with experiments even at low temperature, by including a non-adiabatic treatment involving vibronic states on newly developed potential energy surfaces. This result paves the way for the calculation of accurate and detailed databases of vibrational energy exchange rates for this collisional system. This is bound to have an impact on air plasma simulations under a wide range of conditions and on the development of Very Low Earth Orbit (VLEO) satellites, operating in the low thermosphere, objects of great technological interest due to their potential at a competitive cost.

Energy exchange rate coefficients from vibrational inelastic O2(Σg-3) + O2(Σg-3) collisions on a new spin-averaged potential energy surface.

A new spin-averaged potential energy surface (PES) for non-reactive O2(Σg-3) + O2(Σg-3) collisions is presented. The potential is formulated analytically according to the nature of the principal interaction components, with the main van der Waals contribution described through the improved Lennard-Jones model. All the parameters involved in the formulation, having a physical meaning, have been modulated in restricted variation ranges, exploiting a combined analysis of experimental and ab initio reference data. The new PES is shown to be able to reproduce a wealth of different physical properties, ranging from the second virial coefficients to transport properties (shear viscosity and thermal conductivity) and rate coefficients for inelastic scattering collisions. Rate coefficients for the vibrational inelastic processes of O2, including both vibration-to-vibration (V-V) and vibration-to-translation/rotation (V-T/R) energy exchanges, were then calculated on this PES using a mixed quantum-classical method. The effective formulation of the potential and its combination with an efficient, yet accurate, nuclear dynamics treatment allowed for the determination of a large database of V-V and V-T/R energy transfer rate coefficients in a wide temperature range.

Dual Carbonic Anhydrase IX/XII Inhibitors and Carbon Monoxide Releasing Molecules Modulate LPS-Mediated Inflammation in Mouse Macrophages.

Low concentrations of carbon monoxide (CO) were reported to exhibit anti-inflammatory effects when administered in cells by suitable chemotypes such as CO releasing molecules (CO-RMs). In addition, the pH-modulating abilities of specific carbonic anhydrase isoforms played a crucial role in different models of inflammation and neuropathic pain. Herein, we report a series of chemical hybrids consisting of a Carbonic Anhydrase (CA) inhibitor linked to a CO-RM tail (CAI/CO-RMs). All compounds and their precursors were first tested in vitro for their inhibition activity against the human CA I, II, IX, and XII isoforms as well their CO releasing properties, aiming at corroborating the data by means of molecular modelling techniques. Then, their impact on metabolic activity modulation of RAW 264.7 mouse macrophages for 24 and 48 h was assessed with or without lipopolysaccharide (LPS) stimulation. The compounds were shown to counteract the inflammatory stimulus as also indicated by the reduced tumor necrosis factor alpha (TNF-α) release after treatment. All the biological results were compared to those of N-acetylcysteine (NAC) as a reference antioxidant compound. Within the series, two CAI/CO-RM hybrids (1 and 2), bearing both the well-known scaffold able to inhibit CAs (acesulfame) and the cobalt-based CO releasing portion, induced a higher anti-inflammatory effect up to 48 h at concentrations lower than NAC.

Mechanistic Insights Into the Anticancer Properties of the Auranofin Analog Au(PEt3)I: A Theoretical and Experimental Study.

Au(PEt3)I (AF-I hereafter), the iodide analog of the FDA-approved drug auranofin (AF hereafter), is a promising anticancer agent that produces its pharmacological effects through interaction with non-genomic targets such as the thioredoxin reductase system. AF-I is endowed with a very favorable biochemical profile showing potent in vitro cytotoxic activity against several cancer types including ovarian and colorectal cancer. Remarkably, in a recent publication, some of us reported that AF-I induces an almost complete and rapid remission in an orthotopic in vivo mouse model of ovarian cancer. The cytotoxic potency does not bring about highly severe side effects, making AF-I very well-tolerated even for higher doses, even more so than the pharmacologically active ones. All these promising features led us to expand our studies on the mechanistic aspects underlying the antitumor activity of AF-I. We report here on an integrated experimental and theoretical study on the reactivity of AF-I, in comparison with auranofin, toward relevant aminoacidic residues or their molecular models. Results point out that the replacement of the thiosugar moiety with iodide significantly affects the overall reactivity toward the amino acid residues histidine, cysteine, methionine, and selenocysteine. Altogether, the obtained results contribute to shed light into the enhanced antitumoral activity of AF-I compared with AF.

Reactions of cisplatin and cis-[PtI2(NH3)2] with molecular models of relevant protein sidechains: A comparative analysis.

Quite surprisingly, cisplatin and cis-[PtI2(NH3)2] were found to manifest significant differences in their reactions with the model protein lysozyme. We decided to explore whether these differences recur when reacting these two Pt compounds with other proteins. Notably, ESI-MS measurements carried out on cytochrome c nicely confirmed the reaction pattern observed for lysozyme. This prompted us to exploit a computational DFT approach to disclose the molecular basis of such behavior. We analyzed comparatively the reactions of cis-[PtCl2(NH3)2] and cis-[PtI2(NH3)2] with appropriate molecular models (Ls) of the sidechains of relevant aminoacids. We found that when Pt(II) complexes are reacted with sulfur ligands both quickly lose their halide ligands and then the resulting cis-[Pt(L)2(NH3)2] species loses ammonia upon reaction with a ligand excess. In the case of imidazole, again cis-[PtCl2(NH3)2] and cis-[PtI2(NH3)2] quickly lose their halide ligands but the resulting cis-[Pt(L)2(NH3)2] species does not lose ammonia by reaction with excess imidazole. These results imply that the two platinum complexes manifest a significantly different behavior in their reaction with representative small molecules in agreement with what observed in the case of model proteins. It follows that the protein itself must play a crucial role in triggering the peculiar reactivity of cis-[PtI2(NH3)2] and in governing the nature of the formed protein adducts. The probable reasons for the observed behavior are critically commented and discussed.

Interaction and Reactivity of Cisplatin Physisorbed on Graphene Oxide Nano-Prototypes.

The physical adsorption of cisplatin (CP) on graphene oxide (GO) and reduced graphene oxide (rGO) is investigated at the DFT level of theory by exploiting suitable molecular prototypes representing the most probable adsorbing regions of GO and rGO nano-structures. The results show that the CP binding energy is enhanced with respect to that for the interaction with pristine graphene. This is due to the preferential adsorption of the drug in correspondence of the epoxy and hydroxy groups located on GO basal plane: an energy decomposition analysis of the corresponding binding energy reveals that the most attractive contribution comes from the electrostatic attraction between the -NH 3 ends of CP and the oxygen groups on (r)GO, which can be associated with hydrogen bonding effects. Moreover, it is found that the reactivity of the physically adsorbed CP is practically unaltered being the free energy variation of the first hydrolysis reaction almost matching that of its free (unadsorbed drug) counterpart. The reported results suggest that the CP physical adsorption on GO and rGO carriers is overall feasible being an exergonic process in aqueous solution. The CP adsorption could facilitate its solubility and transport in water solutions, exploiting the high hydrophilicity of the peripheral carboxylic groups located on the edge of the GO and rGO nano-structures. Moreover, the the higher affinity of CP with respect to the oxidized sites suggests a possible dependence of drug loading and release on pH conditions, which would highly facilitate its specific delivery.

Inelastic rate coefficients based on an improved potential energy surface for N2 + N2 collisions in a wide temperature range.

A modification in the potential energy surface (PES) for N2-N2 interactions, reported in the literature [D. Cappelletti et al., Phys. Chem. Chem. Phys., 2008, 10, 4281], has been presented to improve its description of, particularly, the short range behavior for specific configurations, with the aim of producing a large database of vibration to vibration (V-V) and vibration to translation/rotation (V-T/R) energy transfer rate coefficients, with an increased accuracy extended to large temperature ranges relevant to the modeling of hypersonic gas flows. The modifications were introduced in a physically meaningful fashion and they are shown to improve the performance of the PES in a wide temperature range, not only for calculating rate coefficients, but also for determining a variety of physical properties. This new PES was then used to calculate V-V and V-T/R rate coefficients for inelastic N2-N2 collisions through a mixed quantum-classical method, based on the quantum treatment of molecular vibrations, for vibrationally excited states up to v = 40. Such a large V-T/R coefficient database is quite unprecedented, and the comparison of the efficiency of the related processes with the corresponding V-V coefficients shows that vibrational relaxation plays a very relevant role in high temperature regimes.