Formation of Methanol via Fischer-Tropsch Catalysis by Cosmic Iron Sulphide.

Chemical reactions in the gas phase of the interstellar medium face significant challenges due to its extreme conditions (i. e., low gas densities and temperatures), necessitating the presence of dust grains to facilitate the synthesis of molecules inaccessible in the gas phase. While interstellar grains are known to enhance encounter rates and dissipate energy from exothermic reactions, their potential as chemical catalysts remain less explored. Here, we present mechanistic insights into the Fischer-Tropsch-type methanol (FTT-CH3OH) synthesis by reactivity of CO with H2 and using cosmic FeS surfaces as heterogeneous catalysts. Periodic quantum chemical calculations were employed to characterize the potential energy surface of the reactions on the (011) and (001) FeS surfaces, considering different Fe coordination environments and S vacancies. Kinetic calculations were also conducted to assess catalytic capacity and allocate reaction processes within the astrochemical framework. Our findings demonstrate the feasibility of FeS-based astrocatalysis in the FTT-CH3OH synthesis. The reactions and their energetics were elucidated from a mechanistic standpoint. Kinetic analysis demonstrates the temperature dependency of the simulated processes, underscoring the compulsory need of energy sources considering the astrophysical scenario. Our results provide insights into the presence of CH3OH in diverse regions where current models struggle to explain its observational quantity.

Binding energies of ethanol and ethylamine on interstellar water ices: synergy between theory and experiments.

Experimental and computational chemistry are two disciplines used to conduct research in astrochemistry, providing essential reference data for both astronomical observations and modeling. These approaches not only mutually support each other, but also serve as complementary tools to overcome their respective limitations. Leveraging on such synergy, we characterized the binding energies (BEs) of ethanol (CH3CH2OH) and ethylamine (CH3CH2NH2), two interstellar complex organic molecules (iCOMs), on crystalline and amorphous water ices through density functional theory (DFT) calculations and temperature-programmed desorption (TPD) experiments. Experimentally, CH3CH2OH and CH3CH2NH2 behave similarly, in which desorption temperatures are higher on the water ices than on a bare gold surface. Computed cohesive energies of pure ethanol and ethylamine bulk structures allow describing of the BEs of the pure species deposited on the gold surface, as extracted from the TPD curve analyses. The BEs of submonolayer coverages of CH3CH2OH and CH3CH2NH2 on the water ices cannot be directly extracted from TPD due to their co-desorption with water, but they are computed through DFT calculations, and found to be greater than the cohesive energy of water. The behaviour of CH3CH2OH and CH3CH2NH2 is different when depositing adsorbate multilayers on the amorphous ice, in that, according to their computed cohesive energies, ethylamine layers present weaker interactions compared to ethanol and water. Finally, from the computed BEs of ethanol, ethylamine and water, we can infer that the snow-lines of these three species in protoplanetary disks will be situated at different distances from the central star. It appears that a fraction of ethanol and ethylamine is already frozen on the grains in the water snow-lines, causing their incorporation in water-rich planetesimals.

Adsorption of HCN on cosmic silicates: a periodic quantum mechanical study.

Hydrogen cyanide (HCN) represents a small but widely distributed fraction of the interstellar molecules, and it has been observed in all the environments characterizing the formation of a new planetary system. HCN can polymerize to form biomolecules, including adenine (H5C5N5), and it has drawn attention as a possible precursor of several building blocks of life due to the presence of its polymerization products in meteorites, comets and other asteroidal bodies. To elucidate the potential catalytic role that cosmic silicates have played in these processes, we have investigated, at DFT-PBE level inclusive of a posteriori dispersion correction, the energetic and spectroscopic features of the adsorption of HCN molecules on the most relevant crystalline surfaces of the mineral forsterite (Mg2SiO4), a common silicate constituent of the interstellar core grains and planetary rocky bodies. The results reveal that HCN adsorbs both in molecular and dissociative ways, within a wide range of adsorption energies (-29.4 to -466.4 kJ mol-1). Thermodynamic and kinetic results show that dissociative adsorption is dominant already at low temperatures, a fact particularly relevant at the protoplanetary conditions (i.e., the latest stages in the star system formation process). The simulated spectroscopic features of the studied adducts show a wide range of different degrees of perturbation of C-H and CN bonds. This finding agrees with previous experimental works, and our results confirm that a complex chemistry is observed when this astrochemically-relevant molecule interacts with Mg2SiO4, which may be associated with a considerable potential reactivity towards the formation of relevant prebiotic compounds.

Gas-Phase vs. Grain-Surface Formation of Interstellar Complex Organic Molecules: A Comprehensive Quantum-Chemical Study.

Several organic chemical compounds (the so-called interstellar complex organic molecules, iCOMs) have been identified in the interstellar medium (ISM). Examples of iCOMs are formamide (HCONH2), acetaldehyde (CH3CHO), methyl formate (CH3OCHO), or formic acid (HCOOH). iCOMs can serve as precursors of other organic molecules of enhanced complexity, and hence they are key species in chemical evolution in the ISM. The formation of iCOMs is still a subject of a vivid debate, in which gas-phase or grain-surface syntheses have been postulated. In this study, we investigate the grain-surface-formation pathways for the four above-mentioned iCOMs by transferring their primary gas-phase synthetic routes onto water ice surfaces. Our objective is twofold: (i) to identify potential grain-surface-reaction mechanisms leading to the formation of these iCOMs, and (ii) to decipher either parallelisms or disparities between the gas-phase and the grain-surface reactions. Results obtained indicate that the presence of the icy surface modifies the energetic features of the reactions compared to the gas-phase scenario, by increasing some of the energy barriers. Therefore, the investigated gas-phase mechanisms seem unlikely to occur on the icy grains, highlighting the distinctiveness between the gas-phase and the grain-surface chemistry.

Water formation on interstellar silicates: the role of Fe2+/H2 interactions in the O + H2 → H2O reaction.

Water is the most abundant molecule in the solid state of the interstellar medium, and its presence is critically important for life in space. Interstellar water is thought to be effectively synthesised by reactions occurring on the surfaces of interstellar grains, as gas-phase reactions are not efficient enough to justify its high abundance. In the present work, DFT simulations have been performed to investigate the formation of interstellar water through the O + H2 → H2O reaction on olivinic silicate surfaces that contain Fe2+ cations. The surfaces have been modeled adopting both periodic and cluster approaches. This study focuses on: (i) the stability of the surface models as a function of the electronic states (i.e., quintuplet, triplet and singlet) arising from the presence of the Fe2+ centers, (ii) the adsorption of H2 on the silicate surfaces and its likely activation due to the Fe2+/H2 interactions, and (iii) characterising the energy profiles of the H2O formation reaction complemented with kinetics that include tunneling effects. The results indicate that quintuplet is the most stable electronic state in all the bare surface models. H2 adsorption, however, does not show a clear trend on the relative stabilities of the H2/surface complexes with the electronic states, which is in general more favourable on singlet state surfaces. Finally, reactions simulated on the periodic surfaces show elementary high energy barriers but the reaction is kinetically feasible (considering the long lifetime of interstellar clouds) due to the dominance of tunnelling. In contrast, in the nanocluster models, tunneling effects cannot contribute due to the presence of endoenergetic elementary steps. It is predicted that the reactions on the nanoclusters are only possible if the energy released during the adsorption of the O atom is used to overcome the energy barriers.

On the stability of peptide secondary structures on the TiO2 (101) anatase surface: a computational insight.

The biological activity of proteins is partly due to their secondary structures and conformational states. Peptide chains are rather flexible so that finding ways inducing protein folding in a well-defined state is of great importance. Among the different constraint techniques, the interaction of proteins with inorganic surfaces is a fruitful strategy to stabilize selected folded states. Surface-induced peptide folding can have potential applications in different biomedicine areas, but it can also be of fundamental interest in prebiotic chemistry since the biological activity of a peptide can turn-on when folded in a given state. In this work, periodic quantum mechanical simulations (including implicit solvation effects) at the PBE-D2* level have been carried out to study the adsorption and the stability of the secondary structures (α-helix and ß-sheet) of polypeptides with different chemical composition (i.e., polyglycine, polyalanine, polyglutamic acid, polylysine, and polyarginine) on the TiO2 (101) anatase surface. The computational cost is reduced by applying periodic boundary conditions to both the surface and the peptides, thus obtaining full periodic polypeptide/TiO2 surface systems. At variance with polyglycine, the interaction of the other polypeptides with the surface takes place with the lateral chain functionalities, leaving the secondary structures almost undistorted. Results indicate that the preferred conformation upon adsorption is the α-helix over the ß-sheet, with the exception of the polyglutamic acid. According to the calculated adsorption energies, the affinity trend of the polypeptides with the (101) anatase surface is: polyarginine ≈ polylysine > polyglutamic acid > polyglycine ≈ polyalanine, both when adsorbed in gas phase and in presence of the implicit water solvent, which is very similar to the trend for the single amino acids. A set of implications related to the areas of surface-induced peptide folding, biomedicine and prebiotic chemistry are finally discussed.

Tracing the Primordial Chemical Life of Glycine: A Review from Quantum Chemical Simulations.

Glycine (Gly), NH2CH2COOH, is the simplest amino acid. Although it has not been directly detected in the interstellar gas-phase medium, it has been identified in comets and meteorites, and its synthesis in these environments has been simulated in terrestrial laboratory experiments. Likewise, condensation of Gly to form peptides in scenarios resembling those present in a primordial Earth has been demonstrated experimentally. Thus, Gly is a paradigmatic system for biomolecular building blocks to investigate how they can be synthesized in astrophysical environments, transported and delivered by fragments of asteroids (meteorites, once they land on Earth) and comets (interplanetary dust particles that land on Earth) to the primitive Earth, and there react to form biopolymers as a step towards the emergence of life. Quantum chemical investigations addressing these Gly-related events have been performed, providing fundamental atomic-scale information and quantitative energetic data. However, they are spread in the literature and difficult to harmonize in a consistent way due to different computational chemistry methodologies and model systems. This review aims to collect the work done so far to characterize, at a quantum mechanical level, the chemical life of Gly, i.e., from its synthesis in the interstellar medium up to its polymerization on Earth.

First-Principles Modeling of Protein/Surface Interactions. Polyglycine Secondary Structure Adsorption on the TiO2 (101) Anatase Surface Adopting a Full Periodic Approach.

Computational modeling of protein/surface systems is challenging since the conformational variations of the protein and its interactions with the surface need to be considered at once. Adoption of first-principles methods to this purpose is overwhelming and computationally extremely expensive so that, in many cases, dramatically simplified systems (e.g., small peptides or amino acids) are used at the expenses of modeling nonrealistic systems. In this work, we propose a cost-effective strategy for the modeling of peptide/surface interactions at a full quantum mechanical level, taking the adsorption of polyglycine on the TiO2 (101) anatase surface as a test case. Our approach is based on applying the periodic boundary conditions for both the surface model and the polyglycine peptide, giving rise to full periodic polyglycine/TiO2 surface systems. By proceeding this way, the considered complexes are modeled with a drastically reduced number of atoms compared with the finite-analogous systems, modeling the polypeptide structures at the same time in a realistic way. Within our modeling approach, full periodic density functional theory calculations (including implicit solvation effects) and ab initio molecular dynamics (AIMD) simulations at the PBE-D2* theory level have been carried out to investigate the adsorption and relative stability of the different polyglycine structures (i.e., extended primary, ß-sheet, and α-helix) on the TiO2 surface. It has been found that, upon adsorption, secondary structures become partially denatured because the peptide C═O groups form Ti-O═C dative bonds. AIMD simulations have been fundamental to identify these phenomena because thermal and entropic effects are of paramount importance. Irrespective of the simulated environments (gas phase and implicit solvent), adsorption of the α-helix is more favorable than that of the ß-sheet because in the former, more Ti-O═C bonds are formed and the adsorbed secondary structure results less distorted with respect to the isolated state. Under the implicit water solvent, additionally, adsorbed ß-sheet structures weaken with respect to their isolated states as the H-bonds between the strands are longer due to solvation effects. Accordingly, the results indicate that the preferred conformation upon adsorption is the α-helix over the ß-sheet.

When the Surface Matters: Prebiotic Peptide-Bond Formation on the TiO2 (101) Anatase Surface through Periodic DFT-D2 Simulations.

The mechanism of the peptide-bond formation between two glycine (Gly) molecules has been investigated by means of PBE-D2* and PBE0-D2* periodic simulations on the TiO2 (101) anatase surface. This is a process of great relevance both in fundamental prebiotic chemistry, as the reaction univocally belongs to one of the different organizational events that ultimately led to the emergence of life on Earth, as well as from an industrial perspective, since formation of amides is a key reaction for pharmaceutical companies. The efficiency of the surface catalytic sites is demonstrated by comparing the reactions in the gas phase and on the surface. At variance with the uncatalyzed gas-phase reaction, which involves a concerted nucleophilic attack and dehydration step, on the surface these two steps occur along a stepwise mechanism. The presence of surface Lewis and Brönsted sites exerts some catalytic effect by lowering the free energy barrier for the peptide-bond formation by about 6 kcal mol-1 compared to the gas-phase reaction. Moreover, the co-presence of molecules acting as proton-transfer assistants (i.e., H2 O and Gly) provide a more significant kinetic energy barrier decrease. The reaction on the surface is also favorable from a thermodynamic standpoint, involving very large and negative reaction energies. This is due to the fact that the anatase surface also acts as a dehydration agent during the condensation reaction, since the outermost coordinatively unsaturated Ti atoms strongly anchor the released water molecules. Our theoretical results provide a comprehensive atomistic interpretation of the experimental results of Martra et al. (Angew. Chem. Int. Ed. 2014, 53, 4671), in which polyglycine formation was obtained by successive feedings of Gly vapor on TiO2 surfaces in dry conditions and are, therefore, relevant in a prebiotic context envisaging dry and wet cycles occurring, at mineral surfaces, in a small pool.

Interaction of organic compounds with chondritic silicate surfaces. Atomistic insights from quantum chemical periodic simulations.

The interaction of 14 different probe organic molecules with the crystalline (010) forsterite Mg2SiO4 surface has been studied at quantum chemical level by means of B3LYP-D2* periodic simulations. The probe molecules are representatives of the class of soluble organic compounds found in carbonaceous meteorites, namely: aliphatic and aromatic hydrocarbons, alcohols, carbonyl compounds, amines, amides, nitrogen heterocycles, carboxylic and hydroxycarboxylic acids, sulfonic and phosphonic acids, amino acids, and carbohydrates. With the exception of the aliphatic and aromatic hydrocarbons, the interaction takes place mainly between the O and N electron donor atoms of the molecules and the outermost Mg surface cations, and/or by hydrogen bonds of H atoms of the molecules with O surface atoms. Dispersion also contributes to the final interaction energies. Each surface/molecule complex has also been characterized by computing its harmonic vibrational spectrum, in which the most significant frequency perturbations caused by the surface interaction are described. With the calculated interaction energies, a trend of the intrinsic affinity of the probe molecules with the silicate surface has been obtained. However, this affinity scale does not correlate with the experimental abundances of the class of compounds found in the Murchison meteorite. A brief discussion of this lack of correlation and the factors that can help us to understand the abundances is provided.

Radical recombination in interstellar ices, a not so simple mechanism.

Many complex organic molecules (hereafter COMs) have been detected in different regions of the interstellar medium (ISM). In each region, different energetic processes - UV irradiation, atom bombardments, etc. - that could be linked to the formation of detected COMs may occur depending on the environment. Several formation mechanisms were proposed but increasing attention is paid to radical recombination reactions. Previous studies showed that glycolaldehyde (HC(O)CH2OH) and ethylene glycol (HOCH2CH2OH) are formed by radical recombination between HC˙O and ˙CH2OH, and by ˙CH2OH dimerisation, respectively. Formyl (HC˙O), one of the most famous astrophysically-relevant radical species, has been detected as a gaseous component of the ISM. Its reactivity was already attributed to the formation of several COMs. This work aims to study the dimerisation of formyl radical HC˙O using a cryogenic matrix technique. The evolution of the chemical sample composition is monitored by infrared spectroscopy and by mass spectrometry during temperature programmed desorption (TPD) monitoring. Results indicate that the reaction of one HC˙O with another does not lead to the direct formation of glyoxal (HC(O)C(O)H) but yields H2CO and CO. Results are also compared with those for the reaction between two ˙CH2OH radicals and the recombination between HC˙O and ˙CH2OH. Also, glyceraldehyde was tentatively detected in our experiment using different spectroscopic techniques. A radical mechanism is proposed to explain its formation in our experiments. Complementary quantum chemical calculations provide an atomistic interpretation of the experimental findings.

Interstellar H adsorption and H2 formation on the crystalline (010) forsterite surface: a B3LYP-D2* periodic study.

The physisorption/chemisorption of atomic hydrogen on a slab model of the Mg2SiO4 forsterite (010) surface mimicking the interstellar dust particle surface has been modeled using a quantum mechanical approach based on periodic B3LYP-D2* density functional calculations (DFT) combined with flexible polarized Gaussian type basis sets, which allows a balanced description of the hydrogen/surface interactions for both minima and activated complexes. Physisorption of hydrogen is barrierless, very weak and occurs either close to surface oxygen atoms or on Mg surface ions. The contribution of dispersion interactions accounts for almost half of the adsorption energy. Both the hydrogen adsorption energy and barrier to hydrogen jump between equivalent surface sites are overestimated compared to experimental results meant to simulate the interstellar conditions in the laboratory. The hydrogen atom exclusively chemisorbs at the oxygen site of the forsterite (010) surface, forming a SiOH surface group and its spin density being entirely transferred to the neighboring Mg ion. Barrier for chemisorption allows rapid attachment of H at the surface at 100 K, but prevents the same process from occurring at 10 K. From this H-chemisorbed state, the second hydrogen chemisorption mainly occurs on the neighboring Mg ion, thus forming a Mg-H surface group, giving rise to a surface species stabilized by favorable electrostatic interactions between the OHH-Mg pair. The formation of molecular hydrogen at the (010) forsterite surface adopting a Langmuir-Hinshelwood mechanism takes place either starting from two physisorbed H atoms with an almost negligible kinetic barrier through a spin-spin coupling driven reaction or from two chemisorbed H atoms with a barrier surmountable even at T higher than 10 K. We also suggest that a nanosized model of the interstellar dust built from a replica of the forsterite unit cell is able to adsorb half the energy released by the H2 formation by increasing its temperature by about 50 K which could then radiate in about 0.02 s.

Formation of hydroxyacetonitrile (HOCH2CN) and polyoxymethylene (POM)-derivatives in comets from formaldehyde (CH2O) and hydrogen cyanide (HCN) activated by water.

Studying chemical reactivity is an important way to improve our understanding of the origin of organic matter in astrophysical environments such as molecular clouds, protoplanetary disks, and possibly, as a final destination, in our solar system bodies such as in comets. Laboratory simulations on the reactivity of ice analogs can provide important insights into this complex reactivity. Here, the role of water as a catalytic agent is investigated under the conditions of simulated interstellar and cometary grains in the formation of complex organic molecules: the hydroxyacetonitrile (HOCH2CN) and formaldehyde polymers (polyoxymethylene POM). Using infrared spectroscopy and mass spectrometry, we show that HCN reacts with CH2O only in the presence of H2O, whereas in the absence of H2O, HCN is not sufficiently reactive to promote this reaction. Furthermore, depending on the dilution of CH2O and HCN in the water matrix, 1-cyanopolyoxymethylene polymers can also be formed (H-(O-CH2)n-CN, POM-CN), as confirmed by mass spectrometry using the HC(15)N isotopologue. Moreover, quantum chemical calculations allowed us to suggest mechanistic proposals for these reactions, the first step being the activation of HCN by water forming H3O(+) and CN(-), which subsequently condense on a neighbouring CH2O promoting the formation of (-)OCH2CN. Once (-)OCH2CN is formed, it can either recover a proton by reacting with H3O(+) or condense on CH2O molecules leading to POM-CN structures. Implications of this work for the forthcoming Rosetta mission are also addressed.

B3LYP periodic study of the physicochemical properties of the nonpolar (010) Mg-pure and fe-containing olivine surfaces.

B3LYP periodic simulations have been carried out to study some physicochemical properties of the bulk structures and the corresponding nonpolar (010) surfaces of Mg-pure and Fe-containing olivine systems; i.e., Mg2SiO4 (Fo) and Mg1.5Fe0.5SiO4 (Fo75). A detailed structural analysis of the (010) Fo and Fo75 surface models shows the presence of coordinatively unsaturated metal cations (Mg(2+) and Fe(2+), respectively) with shorter metal-O distances compared to the bulk ones. Energetic analysis devoted to the Fe(2+) electronic spin configuration and to the ion position in the surfaces reveals that Fe(2+) in its quintet state and placed at the outermost positions of the slab constitutes the most stable Fe-containing surface, which is related to the higher stability of high spin states when Fe(2+) is coordinatively unsaturated. Comparison of the simulated IR and the corresponding reflectance spectra indicates that Fe(2+) substitution induces an overall bathochromic shift of the spectra due to the larger mass of Fe compared to Mg cation. In contrast, the IR spectra of the surfaces are shifted to upper values and exhibit more bands compared to the corresponding bulk systems due to the shorter metal-O distances given in the coordinatively unsaturated metals and to symmetry reduction which brings nonequivalent motions between the outermost and the internal modes, respectively.

Unlocking the surface chemistry of ionic minerals: a high-throughput pipeline for modeling realistic interfaces.

A systematic procedure is introduced for modeling charge-neutral non-polar surfaces of ionic minerals containing polyatomic anions. By integrating distance- and charge-based clustering to identify chemical species within the mineral bulk, our pipeline, PolyCleaver, renders a variety of theoretically viable surface terminations. As a demonstrative example, this approach was applied to forsterite (Mg2SiO4), unveiling a rich interface landscape based on interactions with formaldehyde, a relevant multifaceted molecule, and more particularly in prebiotic chemistry. This high-throughput method, going beyond techniques traditionally applied in the modeling of minerals, offers new insights into the potential catalytic properties of diverse surfaces, enabling a broader exploration of synthetic pathways in complex mineral systems.

Physisorption vs. chemisorption of probe molecules on boron nitride nanomaterials: the effect of surface curvature.

The adsorption of H2O, NH3 and HCOOH as polar probe molecules and C6H6 and CH4 as non-polar ones on a series of zig-zag (n,0) single-walled boron nitride nanotubes (BNNTs) and on a boron-nitride mono-layer (BNML) has been studied by means of B3LYP-D* periodic calculations. Computed electrostatic potential maps for the pristine BN nanomaterials indicate that the smaller the radius, the larger the polar character. Polar molecules are found to be strongly chemisorbed on small radius BNNTs by means of dative interactions between electron donor atoms of the molecules and B atoms of the BNNTs, H-bonding, as well as dispersive forces. Remarkably, for HCOOH interacting with the (4,0) BNNT, this dative interaction is accompanied by a proton transfer to the nanotube. The corresponding computed adsorption energies decrease sharply with increasing tube radius, gradually approaching the values for physisorption on the BNML. Adsorption of non-polar molecules, mainly dictated by π-stacking (C6H6) and CH-π (CH4) dispersion interactions, is found to be energetically more favorable when physisorbed on large radius BNNTs, the most stable adducts being formed on the BNML.

Computational Study on the Water Corrosion Process at Schreibersite (Fe2NiP) Surfaces: from Phosphide to Phosphates.

Phosphorus (P) is a fundamental element for whatever form of life, in the same way as the other biogenic macroelements (SONCH). The prebiotic origin of P is still a matter of debate, as the phosphates present on earth are trapped in almost insoluble solid matrixes (apatites) and, therefore, hardly available for inclusion in living systems in the prebiotic era. The most accepted theories regard a possible exogenous origin during the Archean Era, through the meteoritic bombardment, when tons of reactive P in the form of phosphide ((Fe,Ni)3P, schreibersite mineral) reached the primordial earth, reacting with water and providing oxygenated phosphorus compounds (including phosphates). In the last 20 years, laboratory experiments demonstrated that the corrosion process of schreibersite by water indeed leads to reactive phosphates that, in turn, react with other biological building blocks (nucleosides and simple sugars) to form more complex molecules (nucleotides and complex sugars). In the present paper, we study the water corrosion of different crystalline surfaces of schreibersite by means of periodic DFT (density functional theory) simulations. Our results show that water adsorbs molecularly on the most stable (110) surface but dissociates on the less stable (001) one, giving rise to further reactivity. Indeed, subsequent water adsorptions, up to the water monolayer coverage, show that, on the (001) surface, iron and nickel atoms are the first species undergoing the corrosion process and, in a second stage, the phosphorus atoms also get involved. When adsorbing up to three and four water molecules per unit cell, the most stable structures found are the phosphite and phosphate forms of phosphorus, respectively. Simulation of the vibrational spectra of the considered reaction products revealed that the experimental band at 2423 cm-1 attributed to the P-H stretching frequency is indeed predicted for a phosphite moiety attached to the schreibersite (001) surface upon chemisorption of up to three water molecules.

Ligand-Aided Glycolysis of PET Using Functionalized Silica-Supported Fe2O3 Nanoparticles.

The development of efficient catalysts for the chemical recycling of poly(ethylene terephthalate) (PET) is essential to tackling the global issue of plastic waste. There has been intense interest in heterogeneous catalysts as a sustainable catalyst system for PET depolymerization, having the advantage of easy separation and reuse after the reaction. In this work, we explore heterogeneous catalyst design by comparing metal-ion (Fe3+) and metal-oxide nanoparticle (Fe2O3 NP) catalysts immobilized on mesoporous silica (SiO2) functionalized with different N-containing amine ligands. Quantitative solid-state nuclear magnetic resonance (NMR) spectroscopy confirms successful grafting and elucidates the bonding mode of the organic ligands on the SiO2 surface. The surface amine ligands act as organocatalysts, enhancing the catalytic activity of the active metal species. The Fe2O3 NP catalysts in the presence of organic ligands outperform bare Fe2O3 NPs, Fe3+-ion-immobilized catalysts and homogeneous FeCl3 salts, with equivalent Fe loading. X-ray photoelectron spectroscopy analysis indicates charge transfer between the amine ligands and Fe2O3 NPs and the electron-donating ability of the N groups and hydrogen bonding may also play a role in the higher performance of the amine-ligand-assisted Fe2O3 NP catalysts. Density functional theory (DFT) calculations also reveal that the reactivity of the ion-immobilized catalysts is strongly correlated to the ligand-metal binding energy and that the products in the glycolysis reaction catalyzed by the NP catalysts are stabilized, showing a significant exergonic character compared to single ion-immobilized Fe3+ ions.

Does adsorption at hydroxyapatite surfaces induce peptide folding? Insights from large-scale B3LYP calculations.

Large-scale periodic quantum mechanical calculations (509 atoms, 7852 atomic orbitals) based on the hybrid B3LYP functional focused on the peptide folding induced by the adsorption on the (001) and (010) hydroxyapatite (HA) surfaces give interesting insights on the role of specific interactions between surface sites and the peptide, which stabilize the helix conformation over the "native" random coil ones for in silico designed model peptides. The two peptides were derived from the 12-Gly oligomer, with one (P1, C-tGGKGGGGGGEGGN-t) and two (P2, C-tGGKGGKEGGEGGN-t) glutamic acid (E) and lysine (K) residue mutations. The most stable gas-phase "native" conformation for both peptides resulted in a random coil (RC) structure, with the helix (H) conformation being ≈100 kJ mol(-1) higher in free energy. The two peptide conformations interact with the HA (001) and (010) surfaces by C═O groups via Ca(2+) ions, by hydrogen bond between NH(2) groups and the basic PO(4)(3-) groups and by a relevant fraction due to dispersion forces. Peptide adsorption was studied on the dry (001) surface, the wet one envisaging 2 H(2)O per surface Ca(2+) and, on the latter, also considering the adsorption of microsolvated peptides with 4 H(2)O molecules located at sites responsible of the interaction with the surface. The P1 mutant does prefer to be adsorbed as a random coil by ≈160 kJ/mol, whereas the reverse is computed for P2, preferring the helix conformation by ≈50 kJ/mol. Adsorption as helix of both P1 and P2 mutants brings about proton transfer toward the HA surfaces with a large charge transfer component to the interaction energy.

The mechanism of hexamethylenetetramine (HMT) formation in the solid state at low temperature.

There is convincing evidence that the formation of complex organic molecules occurred in a variety of environments. One possible scenario highlights the universe as a giant reactor for the synthesis of organic complex molecules, which is confirmed by numerous identifications of interstellar molecules. Among them, precursors of biomolecules are of particular significance due to their exobiological implications, and some current targets concern their search in the interstellar medium as well as understanding the mechanisms of their formation. Hexamethylenetetramine (HMT, C(6)H(12)N(4)) is one of these complex organic molecules and is of prime interest since its acid hydrolysis seems to form amino acids. In the present work, the mechanism for HMT formation at low temperature and pressure (i.e. resembling interstellar conditions) has been determined by combining experimental techniques and DFT calculations. Fourier transform infra-red spectroscopy and mass spectrometry techniques have been used to follow experimentally the formation of HMT as well as its precursors from thermal reaction of NH(3):H(2)CO:HCOOH and CH(2)NH:HCOOH ice mixtures, from 20 K to 330 K. DFT calculations have been used to compute the mechanistic steps through which HMT can be formed starting from the experimental reactants observed in solid phase. The fruitful interplay between theory and experiment has allowed establishing that the mechanism in the solid state at low temperature is different from the one proposed in liquid phase, in which a new intermediate (1,3,5-triazinane, C(3)H(9)N(3)) has been identified. In the meantime, aminomethanol has been unambiguously confirmed as the first intermediate whereas the hypothesis of methylenimine as the second is further strengthened.