Unsaturated Carbon Research Articles

Production of linear alkanes via the solid-state hydrogenation of interstellar polyynes

Highly unsaturated carbon chains, including polyynes, have been detected in many astronomical regions and planetary systems. With the success of the QUIJOTE survey of the Taurus Molecular Cloud-1 (TMC-1), the community has seen a "boom" in the number of detected carbon chains. On the other hand, the Rosetta mission revealed the release of fully saturated hydrocarbons, C_3H_8, C_4H_10, C_5H_12, and (under specific conditions) C_6H_14 with C_7H_16, from the comet 67P/Churyumov-Gerasimenko. The detection of the latter two is attributed to dust-rich events. Similarly, the analysis of samples returned from asteroid Ryugu by Hayabusa2 mission indicates the presence of long saturated aliphatic chains in Ryugu's organic matter. The surface chemistry of unsaturated carbon chains under conditions resembling those of molecular clouds can provide a possible link among these independent observations. However, laboratory-based investigations to validate such a chemistry is still lacking. In the present study, we aim to experimentally verify the formation of fully saturated hydrocarbons by the surface hydrogenation of C_2nH_2 (n>1) polyynes under ultra-high vacuum conditions at 10 K. We undertook a two-step experimental technique. First, a thin layer of C_2H_2 ice was irradiated by UV-photons (≥ 121 nm) to achieve a partial conversion of C_2H_2 into larger polyynes: C_4H_2 and C_6H_2. Afterwards, the obtained photoprocessed ice was exposed to H atoms to verify the formation of various saturated hydrocarbons. In addition to C_2H_6, which was investigated previously, the formation of larger alkanes, including C_4H_10 and (tentatively) C_6H_14, is confirmed by our study. A qualitative analysis of the obtained kinetic data indicates that hydrogenation of HCCH and HCCCCH triple bonds proceeds at comparable rates, given a surface temperature of 10 K. This can occur on the timescales typical for the dark cloud stage. A general pathway resulting in formation of other various aliphatic organic compounds by surface hydrogenation of N- and O-bearing polyynes is also proposed. We also discuss the astrobiological implications and the possibility of identifying alkanes with JWST.

Reductive Dissolution Mechanisms of Manganese Oxide Mediated by Algal Extracellular Organic Matter and the Effects on 17α-Ethinylestradiol Removal.

Reductive dissolution of manganese oxide (MnOx) is a major process that improves the availability of manganese in natural aquatic environments. The extracellular organic matter (EOM) secreted by algae omnipresent in eutrophic waters may affect MnOx dissolution thus the fate of organic micropollutants. This study investigates the mechanisms of MnOx reductive dissolution mediated by EOM and examines the effects of this process on 17α-ethinylestradiol degradation. The influences of EOM concentration (1.0-20.0 mgC/L) and pH (6.0-9.0) in both dark and irradiated conditions were assessed. In the dark, EOM was found to facilitate MnOx reductive dissolution via the ligand-to-metal charge transfer (LMCT). The dissolution was further enhanced under irradiation, with the participation of superoxide ions (O2•-). Higher EOM concentrations increased the contents of available reducing substances and O2•-, accelerating the reductive dissolution. Higher pH slowed the photoreductive dissolution rates, while O2•--mediated reduction became more important. Polyphenols and highly unsaturated carbon and phenolic formulas in EOM were found to drive the reductive dissolution. Soluble reactive Mn(III) formed through reductive dissolution of MnOx effectively removed 17α-ethinylestradiol in solution. Overall, the findings regarding the mechanisms behind reductive dissolution of MnOx have broad implications for Mn geochemical cycles and organic micropollutant fate.

Elucidating the Mechanism of Electrooxidative Allene Dioxygenation: Dual Role of Tetramethylpiperidine N-Oxyl (TEMPO).

The cumulated π system of a nonsymmetric allene contains three distinct unsaturated carbons that imbue it with unique reactivity toward radicals as compared to its alkene and alkyne counterparts. Despite the synthetic potential of these versatile building blocks, electrochemical transformations of allenes have been historically underexplored. Myriad strategies for easy access to allenes, coupled with the resurgence of interest in sustainable oxidative transformations of hydrocarbons, prompted our efforts to conduct an in-depth investigation of a rare example of an electrochemical TEMPO-mediated allene dioxygenation. The resultant vinyl-TEMPO motif is readily postfunctionalized to install a heteroatom at each allene carbon. Mechanistic investigations, including cyclic voltammetry (CV) studies, computations, and monitoring by operando NMR (ReactNMR) were performed to lay the groundwork for future electrochemical allene functionalizations that deliver unique synthetic building blocks.

Solid-State NMR Validation of OPLS4: Structure of PC-Lipid Bilayers and Its Modulation by Dehydration.

Atomistic molecular dynamics (MD) simulations are a much-used tool for investigating the structure and dynamics of biomembranes with atomic resolution. The validity of the representations obtained is determined by the accuracy and realism of the MD model (force field). Here, we evaluated the proprietary OPLS4 force field of Schrödinger, Inc. against atomic-resolution experimental data, and compared its performance to CHARMM36, one of the best-performing openly available force fields. As a benchmark, we used high-resolution nuclear magnetic resonance (NMR) order parameters for C-H bonds─directly and reliably calculable from MD simulations─measured in phosphatidylcholine (PC) lipid bilayers under varying hydration conditions. Comparisons were made with two dehydration data sets: for saturated (1,2-dimyristoylphosphatidylcholine, DMPC) lipid bilayers from the literature and for unsaturated (1-palmitoyl-2-oleoylphosphatidylcholine, POPC) lipid bilayers measured here. Our findings indicate that OPLS4 reproduces the structure and dehydration response of PC-lipid bilayers fairly well, even slightly outperforming CHARMM36. Both models' main inaccuracies appear in (1) the order parameter magnitudes in the glycerol backbone and unsaturated carbon segments and (2) the qualitatively differing structural response of the PC headgroup to dehydration compared to experiments. In summary, this work underscores the importance of independent validation for (proprietary) force fields and highlights the striking similarities and nuanced differences between OPLS4 and CHARMM36 in describing biomembranes.

Nitrogen-doped modified graphene aerogel enhancing interfacial bonding with lithium aluminium silicate ceramics for broadband microwave absorption

The swift progression of e-communication technology has resulted in significant electromagnetic pollution, necessitating the urgent need for effective microwave-absorbing materials to mitigate this issue. Augmenting heterogeneous phase interfaces and incorporating heteroatoms constitute viable strategies for enhancing the electromagnetic properties of functional materials. In this study, a series of lithium aluminium silicate glass-ceramic/nitrogen-doped graphene (LAS/N-GF) aerogels was synthesised via the hydrothermal and freeze-drying methods. An innovative bonding mechanism for the heterogeneous phase interface was revealed, in which nitrogen doping enabled the formation of lattice defects in LAS ceramic particles and graphene and promoted a closed approach for unsaturated carbon and silicon atoms to form carbon-silicon bonds through the electrostatic force generated by interfacial polarization. Given that covalent bonds are widely recognized as stable carrier channels, the presence of carbon-silicon bonds at the interface facilitates electron migration, ultimately leading to improved microwave absorption. The maximum absorptivity of the LAS/N-GF aerogels could reach −47.98 dB at 8.96 GHz with a filler loading as low as 10 wt%. It is noteworthy that the LAS/N-GF aerogel exhibits an effective absorption bandwidth of 8.34 GHz, which fully spans the entire X-band and more than two-thirds of the Ku-band. Such exceptional performance is rarely observed in dielectric loss materials. Finally, the application potential of the LAS/N-GF aerogels in microwave absorbers was simulated and analysed. The unique chemical phenomenon stemming from the bonding at the carbon material-ceramic interface offers a fresh perspective in interface science, enabling a deeper comprehension of the underlying mechanism of microwave absorption.

Diastereoselective and Enantioselective Hydrophosphinylations of Conjugated Enynes, Allenes and Dienes via Synergistic Pd/Co Catalysis

AbstractDifferent from the reported work focusing on the construction of single P‐ or C‐stereocenter via hydrophosphinylation of unsaturated carbon bonds, the highly diastereo‐ and enantioselective hydrophosphinylation reaction of allenes, conjugated enynes and 1,3‐dienes is achieved via a designed Pd/Co dual catalysis and newly modified masked phosphinylating reagent. A series of allyl motifs bearing both a tertiary C‐ and P‐stereocenter are prepared in generally good yields, >20 : 1 dr, >20 : 1 rr and 99 % ee. The unprecedented diastereo‐ and enantioselective hydrophosphinylation of 1,3‐enynes is established to generate skeletons containing both a P‐stereocenter and a nonadjacent chiral axis. The first stereodivergent hydrophosphinylation reaction is also developed to achieve all four P‐containing stereoisomers. The present protocol features the use of only 3‐minutes reaction time and 0.1 % catalyst, and with the observation of up to 730 TON. A set of mechanistic studies reveal the necessity and roles of two metal catalysts and corroborate the designed synergistic process.

Diastereoselective and Enantioselective Hydrophosphinylations of Conjugated Enynes, Allenes and Dienes via Synergistic Pd/Co Catalysis.

Different from the reported work focusing on the construction of single P- or C-stereocenter via hydrophosphinylation of unsaturated carbon bonds, the highly diastereo- and enantioselective hydrophosphinylation reaction of allenes, conjugated enynes and 1,3-dienes is achieved via a designed Pd/Co dual catalysis and newly modified masked phosphinylating reagent. A series of allyl motifs bearing both a tertiary C- and P-stereocenter are prepared in generally good yields, >20 : 1 dr, >20 : 1 rr and 99 % ee. The unprecedented diastereo- and enantioselective hydrophosphinylation of 1,3-enynes is established to generate skeletons containing both a P-stereocenter and a nonadjacent chiral axis. The first stereodivergent hydrophosphinylation reaction is also developed to achieve all four P-containing stereoisomers. The present protocol features the use of only 3-minutes reaction time and 0.1 % catalyst, and with the observation of up to 730 TON. A set of mechanistic studies reveal the necessity and roles of two metal catalysts and corroborate the designed synergistic process.

Tow-way regulation strategy for in-situ electropolymerization additives coordinated by double bonds and boric acid groups in lithium secondary batteries

The stability and cycle life of the cathode material directly affect the electrochemical performance of the secondary battery, and the dendrite problem of the anode material greatly destroys its safety. To solve the above problems, here we report a small organic molecule monomer, 2,2-dimethylvinylboronic acid (DEBA) containing carbon–carbon double bonds and boric acid groups as electrolyte additive for lithium secondary battery. The unsaturated carbon–carbon double bonds in DEBA can undergo in-situ electropolymerization during the electrochemical process, forming a polymer network. The electron-deficient boron element can easily combine with the electron-rich lithium salt anion to form a B-F bond. It can promote the transport rate of Li+, alleviate the Li+ concentration gradient at the interface, and achieve uniform and dense deposition on the Li metal surface. The Li//graphite and Li//LiFePO4 half-cell experiments show that DEBA has an excellent tow-way regulation effect. This rationally designed dual-functional electrolyte additive provides a broad prospect for future electrolyte engineering.

Quantum Simulations of Radiation Damage in a Molecular Polyethylene Analog.

An atomic-level understanding of radiation-induced damage in simple polymers like polyethylene is essential for determining how these chemical changes can alter the physical and mechanical properties of important technological materials such as plastics. Ensembles of quantum simulations of radiation damage in a polyethylene analog are performed using the Density Functional Tight Binding method to help bind its radiolysis and subsequent degradation as a function of radiation dose. Chemical degradation products are categorized with a graph theory approach, and occurrence rates of unsaturated carbon bond formation, crosslinking, cycle formation, chain scission reactions, and out-gassing products are computed. Statistical correlations between product pairs show significant correlations between chain scission reactions, unsaturated carbon bond formation, and out-gassing products, though these correlations decrease with increasing atom recoil energy. The results present relatively simple chemical descriptors as possible indications of network rearrangements in the middle range of excitation energies. Ultimately, the work provides a computational framework for determining the coupling between nonequilibrium chemistry in polymers and potential changes to macro-scale properties that can aid in the interpretation of future radiation damage experiments on plasticmaterials.

Sustainable Biocatalytic System for the Enzymatic Epoxidation of Waste Cooking Oil.

The present study is integrated in a global effort to capitalize waste cooking oil (WCO) into versatile compounds by introducing an oxirane ring into the unsaturated carbon chain of fatty acid residues (the epoxidation of double bound). Therefore, an enzymatic method was set up for the epoxidation of artificially adulterated WCO (SFw) and WCO under real conditions (SFr) derived from sunflower biomass. Commercial lipase (Novozyme, NZ) was used as a biocatalyst for generating the peracid requested by the epoxidation pathway. Optimum experimental conditions (e.g., 1.5 wt% NZ, 1:1:0.5 = H2O2/double bonds/peracid precursor (molar ratio) and 12 h reaction time) allowed for the conversion of 90% of the SFw substrate into products with an oxirane ring. Octanoic acid was selected as the best peracid precursor. The versatility of the developed system was tested for olive, milk thistle, hemp and linseed oils as both fresh and WCO samples. The characterization of the oil samples before and after the enzymatic epoxidation allowed for the evaluation of the system performance. SFw/SFr exhibited a better susceptibility to enzymatic epoxidation. In addition, the reusability of the biocatalytic system was investigated. Furthermore, different strategies, such as biocatalyst coating and the addition of organic solvents/buffers were applied, limiting enzyme leaching, for the better recovery of the biocatalyst activity.

Dopamine-Carbonized Coating PtCo Catalyst with Enhanced Durability toward the Oxygen Reduction Reaction.

Stability is the main challenge for the application of PtCo catalysts because Co tends to leach during the electrochemical reaction. Herein, we immerse and adsorb dopamine to densely coat Pt0.8Co0.2 particles and subsequently thermally carbonize the coating into few-layer nitrogen-doped graphene to produce Pt0.8Co0.2@NC. This coating effectively hinders direct contact between Pt0.8Co0.2 particles and the electrolyte, thereby enhancing the stability of the catalyst by preventing Ostwald ripening and suppressing competitive adsorption of toxic species, while also bolstering its antipoisoning ability. Experimental results indicate that the thin coating does not compromise the oxygen reduction reaction activity of the catalyst, showcasing a half-wave potential of 0.81 V in alkaline electrolytes. Spectroscopic results suggest that a strong bonding interaction between Pt and the pyridinic N of N-doped graphene contributes to the generation of a dense coating. The coating layer does not affect the four-electron reaction mechanism of the Pt0.8Co0.2 alloy, and the coordinatively unsaturated carbon atoms on Pt0.8Co0.2@NC serve as active oxygen reduction reaction centers.

Engineered Carbon Nanocatalysts for Homocysteine Catabolism

Cystathionine-β-synthase (CBS) deficiency or homocystinuria (HCU) is a rare inherited disorder with main clinical features of osteoporosis, dislocation of the optic lenses, learning difficulties and thromboembolism. CBS is a key enzyme in methionine catabolism pathway. CBS deficiency impairs the conversion of homocysteine (Hcy) to cystathionine, which leads to extracellular buildup of Hcy in toxic concentrations. Patients with CBS deficiency have elevated plasma Hcy and methionine.Currently, there is no FDA approved drug for CBS deficiency. Clinical treatment options are low-protein diet and betaine for severely affected patients, and vitamin supplementation for mildly affected adults. Artificial protein-based enzymes for Hcy treatment are in clinical trials. However, protein-based artificial enzymes can be immunogenic, prone to intracellular modifications, and the treatment may not be viable after few months.We propose a novel nanotechnology-based approach for the treatment of CBS deficiency. Carbon nanomaterials with multiple unsaturated carbons provide an excellent scaffold for engineering enzyme mimicking catalysts. We have designed carbon nanomaterial based catalytic artificial enzymes (CAEs) by surface engineering to mimic metabolic enzymes that catabolize Hcy under physiological conditions. Using a combination of paper chromatography and H1-NMR, our lab has shown that CAE can breakdown homocysteine and produce hydrogen sulfide similar to CGL enzyme. The degree of surface functionalization as well as surface curvature has profound effect on specificity and catalysis. We have shown that CAE can enter cells and lower homocysteine levels in cellular models. In preliminary studies, CAE was able to lower serum homocysteine levels in a murine model. Further studies will involve safety assessments of CAE as a treatment for HCU.

Investigating the mechanism of Bacillus amyloliquefaciens YUAD7 degrading aflatoxin B1 in alfalfa silage using isotope tracing and nuclear magnetic resonance methods

BackgroundFungal toxins are highly toxic and widely distributed, presenting a considerable threat to global agricultural development. Addressing the issue of aflatoxin B1 (AFB1) contamination in feed, it is crucial to ascertain the effectiveness and mechanisms of microbial strains in degradation.ResultsThis study used isotope tracing and nuclear magnetic resonance (NMR) to investigate the degradation products of Bacillus amyloliquefaciens YUAD7 in complex substrates. By tracing 14C34-AFB1 and utilizing NMR, ultra-performance liquid chromatography–quadrupole time-of-flight/mass spectrometry (UPLC–Q-TOF/MS) purification and identification techniques, it was confirmed that AFB1 was degraded by YUAD7 into C12H14O4, C5H12N2O2, C10H14O2, and C4H12N2O, effectively removing 99.7% of AFB1 (100 μg/kg) from alfalfa silage. YUAD7 targeted the ester bond in the vanillin lactone ring structure, the ether bond in the furan ring structure, and the unsaturated carbon–carbon double bond in the furan ring structure during AFB1 degradation, disrupting the toxic sites responsible for AFB1's carcinogenic, teratogenic, and mutagenic effects and achieving biodegradation. Moreover, B. amyloliquefaciens YUAD7 transformed AFB1 through processes like hydrogenation, enzyme modification, and the loss of the -CO group while also being associated with metabolic pathways such as alanine, aspartate, glutamate metabolism, glutathione metabolism, cysteine and methionine metabolism, and pentose and glucuronate interconversions.ConclusionsThe utilization of isotope tracing allowed for rapid identification of degradation products in complex substrates, while NMR elucidated the structures of these products. This deepens our understanding of AFB1 biodegradation mechanisms, providing technical support for the practical application of these bacteria in degradation, and new insights into studying the biological degradation mechanism. B. amyloliquefaciens YUAD7 can be used as a potential strain for degrading AFB1 in large-scale silage.Graphical

Ligand Tail Controls the Conformation of Indium Sulfide Ultrathin Nanoribbons.

We report the conformational control of 2D ultrathin indium sulfide nanoribbons by tuning their amine ligands' alkyl chain. The initial orthorhombic InS nanoribbons bare n-octylamine ligands and display a highly curved geometry with a characteristic figure of eight shapes. Exchanging the native ligand by oleylamine induces their complete unfolding to yield flat board-shaped nanoribbons. Significant strain variations in the InS crystal structure accompany this shape-shifting. By tuning the linear alkyl chain length from 4 to 18 carbon atoms, we show using small-angle X-ray scattering in solution and transmission electron microscopy that the curvature of the nanoribbon subtly depends on the ligand-ligand interactions at the nanoribbon's surface. The curvature decreases gradually as the chain length increases, while carbon unsaturation has an unexpectedly significant effect at constant chain length. These experiments shed light on the critical role of the ligand monolayer on the curvature of ultrathin 2D crystalline nanosheets and demonstrate that weak supramolecular forces within the organic part of colloidal nanocrystals can dramatically impact their shape. This transduction mechanism, in which changes in the organic monolayer impact the shape of a nanocrystal, will help to devise new strategies to design stimuli-responsive systems that take advantage of both the flexibility of organic moieties and the physical properties of the inorganic core.

Nitrogen-doped activated carbon composite electrode for deionization of phosphate removal and DFT model adsorption of phosphates

Phosphate discharge in sewage can result in water eutrophication, posing a threat to aquatic ecosystems. Membrane capacitive deionization (MCDI) has demonstrated outstanding performance and significant potential for salt removal and nutrient recovery. In this study, a nitrogen-doped activated carbon electrode material (NAC) was synthesized through one-step pyrolysis to selectively remove phosphate from MCDI. At a voltage of 1.2V, a flow rate of 20 mL/min, and a pH of 6.51, the phosphate adsorption capacity of the NAC electrode was determined to be 1.60 mg/g. The study revealed that NAC pHpzc increased from 4.14 to 6.44, effectively broadening the pH range for phosphate removal. In the presence of competing ions (NO3−, Cl−, and SO42−) at a concentration of 0.5 M, the electroadsorption capacity of phosphate decreased to 1.21 mg/g, 1.14 mg/g, and 1.02 mg/g, respectively. The kinetic parameters of adsorption indicated that NAC electroadsorbed phosphate through physical adsorption, with the maximum adsorption capacity achieved at 303K. Data from the Freundlich isothermal model suggested that phosphate adsorption by the NAC electrode involves a multilayer adsorption process. A carbon structure model of density functional theory (DFT), incorporating doped nitrogen, was constructed based on XPS analysis. Following nitrogen doping, the electrostatic potential (ESP) of unsaturated carbon atoms became more positive, enhancing the ability of nitrogen-doped activated carbon to adsorb phosphate. This study provides compelling evidence that nitrogen doping facilitates the adsorption of phosphate by carbon materials.

Density functional theory and ReaxFF MD study on steam-induced nitrogen migration mechanism during char gasification

The formation of nitrogen-containing species during char gasification is crucial for emission of nitrogenous pollutants. In this work, the detailed nitrogen migration mechanism during char gasification is studied. Density functional theory (DFT) coupled with ReaxFF MD methods are used to conduct an in-depth analysis on the intrinsic reaction mechanism during Char(N) and steam interaction. DFT results show that orbital electrons of carbon atoms on char surface are driven towards nitrogen atoms by nitrogen functional groups. The electron density of adjacent carbon atoms is weakened, which has a positive charge. Orbital electron properties show that the band energy gaps of three Char(N) models are 3.063 eV, 1.092 eV and 3.328 eV, indicating the reactivity order for three Char(N) models is as follows: Char(N)-2＞Char(N)-1＞Char(N)-3. DFT calculation indicates that the interaction between Char(N) and steam reduces unsaturated carbon atoms and lower the char decomposition activity, which will inhibit the yield of HCN. In contrast, through hydrogen transfer reactions, nitrogen atoms are easily combined with hydrogen atoms, which is more conducive to the formation of ammonia. ReaxFF MD modeling proves that HCN is the main product for Char(N) decomposition under inert atmosphere. Under steam atmosphere, nitrogen atoms in char are more likely to be converted into amino products. The induction of steam provides a large number of active hydrogen radicals, which is able to attack the nitrogen atoms of char and form N–H bonds, thus promoting the formation of ammonia.

Functionalization of unsaturated carbon–carbon bonds by continuous-flow ozonolysis

Functionalization of unsaturated carbon–carbon bonds by continuous-flow ozonolysis

Investigation on the steam gasification mechanism of different chars using isotopic tracing method

Gasification can provide syn-gas for consequent chemical production from carbon resources. The control of CO2 emission produced from gasification calls for the lower temperature and the more biomass char for the feed compared with traditional gasification, and the mechanism for steam gasification of different chars is more important. The gasification behaviors of four biomass chars and four coal chars are studied. The mechanism is probed using H216O/H218O period step tracing method coupled with various solid-state analyses on char structures. The increment of intermediates with increasing conversion demonstrate other slow step exists during gasification, and the solid state spectra of chars after and before gasification demonstrates that the condensation of poly-aromatic clusters in chars occurs accompanied with gasification. The addition reactions of radicals generated from gasifying agents and unsaturated carbon bonds C = C in chars is the slower step during gasification and enhancing the addition of radicals to unsaturated C = C bonds may be helpful for the higher gasification rate.

Constructing Ni-Pt Bimetallic Catalysts for Catalytic Hydrogenation and Rearrangement of Furfural into Cyclopentanone with Insight in H/D Exchange by D2O Labeling.

Developing a metallic catalyst for converting furfural (FAL) to highly valuable products such as cyclopentanone (CPO) is important for fine chemical synthesis by the efficient utilization of biomass resources. The presence of diverse unsaturated carbon atoms in FAL and the rearrangement of oxygen atoms hinder the production of CPO. We developed an optimal nickel (Ni)-to-platinum (Pt) molar ratio (1:0.007) for a bimetallic Ni-Pt/alumina (Al2O3) catalyst with a low Pt loading via an impregnation method to efficiently catalyze the selective hydrogenation of FAL in an aqueous solution to form CPO. The comprehensive characterizations by X-ray diffraction and X-ray absorption near edge structure analyses elucidated the formation of Ni0/Pt0 and Ni2+/Pt4+ after reduction by H2. The addition of a low amount of the Pt-Ni/Al2O3 catalyst resulted in an alleviation of H2 reduction behavior detected by hydrogen temperature-programmed reduction, accompanied by low H2 desorption ability observed by hydrogen temperature-programmed desorption. The catalytic activity of Ni-Pt/Al2O3 was higher than those of Ni/Al2O3 and Pt/Al2O3 catalysts. The maximum CPO yield was 66% with 93% FAL conversion under the optimized conditions (160 °C, 20 bar of H2 pressure, and 2 h). Isotopic deuterium oxide (D2O) labeling revealed the transfer of deuterium (D) atoms from D2O to the intermediates and products during hydrogenation and rearrangement, which confirmed that water was a medium for rearrangement and the source of hydrogen for the reaction. This study developed an efficient catalyst for the catalytic hydrogenation and ring rearrangement of FAL into CPO.

How the addition of atomic hydrogen to a multiple bond can be catalyzed by water molecules.

Observational data show complex organic molecules in the interstellar medium (ISM). Hydrogenation of small unsaturated carbon double bond could be one way for molecular complexification. It is important to understand how such reactivity occurs in the very cold and low-pressure ISM. Yet, there is water ice in the ISM, either as grain or as mantle around grains. Therefore, the addition of atomic hydrogen on double-bonded carbon in a series of seven molecules have been studied and it was found that water catalyzes this reaction. The origin of the catalysis is a weak charge transfer between the π MO of the unsaturated molecule and H atom, allowing a stabilizing interaction with H2O. This mechanism is rationalized using the non-covalent interaction and the quantum theory of atoms in molecules approaches.