A theoretical study of the hydrolysis mechanism of A-234; the suspected novichok agent in the Skripal attack

A-234, [EtO–P( O)(F)–N C(Me)–N(Et)₂], is the suspected A-type nerve agent used in the Skripal attack on the 4th of March 2018. Studies related to the structure and reactivity of this compound are limited. We, therefore, aimed at understanding the underlying hydrolysis mechanism of A-234 within the DFT framework. The attack of the water molecule can occur at the phosphinate and acetoamidine reactive centres. Our theoretical findings indicate that the hydrolysis at the acetoamidine centre is thermodynamically favoured compared to the hydrolysis at the phosphinate centre. The hydrolysis at the acetoamidine moiety may proceed via two pathways, depending on the nitrogen atom participating in the hydrolysis. The main pathway consists of four distinct channels to reach the final product, with the concerted 1,3-proton shift favoured kinetically and thermodynamically in the gas phase and water as solvent. The results are in good agreement with the literature, although some differences in the reaction mechanism were observed.

A theoretical study of the hydrolysis mechanism of A-234 [EtO–P( O)(F)–N C(Me)–N(Et)₂]; the suspected novichok agent in the Skripal attack.     

Theoretical screening of bistriazole-derived energetic salts with high energetic properties and low sensitivity

We designed four series of energetic anions by replacing nitro group (NO₂) with trinitromethyl group (C(NO₂)₃) or by inserting N-bridging groups (–NH–, –NH–NH–, –N N–, –N N(O)–) into the bistriazole frameworks. The properties of 40 energetic salts, based on the bistriazole-derived anions and hydroxylammonium cation, were studied by density functional theory (DFT) and volume-based thermodynamics calculations (VBT). It is found that the newly designed energetic salts have good detonation properties due to their larger nitrogen content and better oxygen balance. And one of their corresponding hydroxylammonium salts exhibits better detonation performance (D = 10.06 km s⁻¹ and P = 48.58 GPa) than CL-20 (D = 9.54 km s⁻¹ and P = 43.36 GPa). Moreover, 10 energetic salts not only exhibit excellent energetic properties superior to CL-20, but also have lower sensitivity than CL-20 (h₅₀ = 13.81 cm). In addition, we rationally selected salt B6 from the 10 salts to predict its crystal structure under pressures. By converting energetic molecules with excellent detonation properties into energetic ions, some highly bistriazole-derived energetic salts with both excellent performance and low sensitivity could be developed strategically.

We designed four series of energetic anions by replacing nitro group (NO₂) with trinitromethyl group (C(NO₂)₃) or by inserting N-bridging groups (–NH–, –NH–NH–, –N N–, –N N(O)–) into the bistriazole frameworks.     

Reactions of triosmium and triruthenium clusters with 2-ethynylpyridine: new modes for alkyne C–C bond coupling and C–H bond activation

The reaction of the trimetallic clusters [H₂Os₃(CO)₁₀] and [Ru₃(CO)₁₀L₂] (L = CO, MeCN) with 2-ethynylpyridine has been investigated. Treatment of [H₂Os₃(CO)₁₀] with excess 2-ethynylpyridine affords [HOs₃(CO)₁₀(μ-C₅H₄NCH=CH)] (1), [HOs₃(CO)₉(μ₃-C₅H₄NC CH₂)] (2), [HOs₃(CO)₉(μ₃-C₅H₄NC CCO₂)] (3), and [HOs₃(CO)₁₀(μ-CH CHC₅H₄N)] (4) formed through either the direct addition of the Os–H bond across the C C bond or acetylenic C–H bond activation of the 2-ethynylpyridine substrate. In contrast, the dominant pathway for the reaction between [Ru₃(CO)₁₂] and 2-ethynylpyridine is C–C bond coupling of the alkyne moiety to furnish the triruthenium clusters [Ru₃(CO)₇(μ-CO){μ₃-C₅H₄NC CHC(C₅H₄N) CH}] (5) and [Ru₃(CO)₇(μ-CO){μ₃-C₅H₄NCCHC(C₅H₄N)CHCHC(C₅H₄N)}] (6). Cluster 5 contains a metalated 2-pyridyl-substituted diene while 6 exhibits a metalated 2-pyridyl-substituted triene moiety. The functionalized pyridyl ligands in 5 and 6 derive via the formal C–C bond coupling of two and three 2-ethynylpyridine molecules, respectively, and 5 and 6 provide evidence for facile alkyne insertion at ruthenium clusters. The solid-state structures of 1–3, 5, and 6 have been determined by single-crystal X-ray diffraction analyses, and the bonding in the product clusters has been investigated by DFT. In the case of 1, the computational results reveal a rare thermodynamic preference for a terminal hydride ligand as opposed to a hydride-bridged Os–Os bond (3c,2e Os–Os–H bond).

The reactivity of 2-ethynylpyridine at low-valent triosmium and triruthenium centers has been investigated.     

FTIR product study of the Cl-initiated oxidation products of CFC replacements: (E/Z)-1,2,3,3,3-pentafluoropropene and hexafluoroisobutylene

A product study of the reactions of (E/Z)-1,2,3,3,3-pentafluoropropene ((E/Z)-CF₃CF CHF) and hexafluoroisobutylene ((CF₃)₂C CH₂) initiated by Cl atoms were developed at 298 ± 2 K and atmospheric pressure. The experiments were carried out in a 1080 L quartz-glass environmental chamber coupled via in situ FTIR spectroscopy to monitor the reactants and products. The main products observed and their yields were as follows: CF₃C(O)F (106 ± 9)% with HC(O)F (100 ± 8)% as a co-product for (E/Z)-CF₃CF CHF, and CF₃C(O)CF₃ (94 ± 5)% with HC(O)Cl (90 ± 7)% as a co-product for (CF₃)₂C CH₂. Atmospheric implications of the end-product degradation are assessed in terms of their impact on ecosystems to help environmental policymakers consider HFOs as acceptable replacements.

An experimental product distribution study and the atmospheric implications of the reactions of Cl with two fluorinated alkenes is provided.     

Probing the supramolecular features via π–π interaction of a di-iminopyrene-di-benzo-18-crown-6-ether compound: experimental and theoretical study

A novel DPyDB-C N-18C6 compound was synthesised by linking a pyrene moiety to each phenyl group of dibenzo-18-crown-6-ether, the crown ether, through –HC N– bonds and characterized by FTIR, ¹H-NMR, ¹³C-NMR, TGA, and DSC techniques. The quantitative ¹³C-NMR analysis revealed the presence of two position isomers. The electronic structure of the DPyDB-C N-18C6 molecule was characterized by UV-vis and fluorescence spectroscopies in four solvents with different polarities to observe particular behavior of isomers, as well as to demonstrate a possible non-bonding chemical association (such as ground- and excited-state associations, namely, to probe if there were forming dimers/excimers). The interpretation of the electronic structure was realized through QM calculations. The TD-CAM-B3LYP functional, at the 6-311+G(d,p) basis set, indicated the presence of predominant π → π* and mixed π → π* + n → π* transitions, in line with the UV-vis experimental data. Even though DPyDB-C N-18C6 computational studies revealed a π-extended conjugation effect with predominantly π → π* transitions, thorough fluorescence analysis was observed a weak emission, as an effect of PET and ACQ. In particular, the WAXD analysis of powder and thin films obtained from n-hexane, 1,2-dichloroethane, and ethanol indicated an amorphous organization, whereas from toluene a smectic ordering was obtained. These results were correlated with MD simulation, and it was observed that the molecular geometry of DPyDB-C N-18C6 molecule played a defining role in the pyrene stacking arrangement.

Herein, we report the formation of a potential supramolecular arrangement mediated by inter- and intra-molecular interactions between di-iminopyrene-dibenzo-18-crown-6-ether molecules.     

Nitrogen–phosphorus doped graphitic nano onion-like structures: experimental and theoretical studies

Onion-like graphitic structures are of great importance in different fields. Pentagons, heptagons, and octagons are essential features of onion-like graphitic structures that could generate important properties for diverse applications such as anodes in Li metal batteries or the oxygen reduction reaction. These carbon nanomaterials are fullerenes organized in a nested fashion. In this work, we produced graphitic nano onion-like structures containing phosphorus and nitrogen (NP-GNOs), using the aerosol assisted chemical vapor deposition method. The NP-GNOs were grown at high temperature (1020 °C) using ferrocene, trioctylphosphine oxide, benzylamine, and tetrahydrofuran precursors. The morphology, structure, composition, and surface chemistry of NP-GNOs were characterized using different techniques. The NP-GNOs showed diameters of 110–780 nm with Fe-based nanoparticles inside. Thermogravimetric analysis showed that NP-GNOs are thermally stable with an oxidation temperature of 724 °C. The surface chemistry analysis by FTIR and XPS revealed phosphorus–nitrogen codoping, and several functionalities containing C–H, N–H, P–H, P–O, P O, C O, and C–O bonds. We show density functional theory calculations of phosphorus–nitrogen doping and functionalized C₂₄₀ fullerenes. We present the optimized structures, electronic density of states, HOMO, and LUMO wave functions for P-doped and OH-functionalized fullerenes. The P O and P–O bonds attributed to phosphates or hydroxyl groups attached to phosphorus atoms doping the NP-GNOs could be useful in improving supercapacitor function.

Nitrogen–phosphorus doped graphitic nano onion-like structures.     

Boron-doped graphene as a metal-free catalyst for gas-phase oxidation of benzyl alcohol to benzaldehyde

Boron-doped graphene samples (BGs) with tunable boron content of 0–2.90 at% were synthesized and directly used in the gas-phase oxidation of benzyl alcohol to benzaldehyde, and showed excellent performance. XPS results indicated that the graphitic sp² B species (BC₃) is the mainly boron dopant species incorporated in the graphene lattice, which could significantly improve the content of ketone carbonyl groups (C O) on the graphene. For instance, the contents of C O jumped from 1.93 to 4.19 at% while BC₃ doped into the graphene lattice was only 0.35 at%. The C O is the active site of catalytic reaction, so BG has significantly improved catalytic activity. Compared to the un-doped graphene (G), the conversion of benzyl alcohol over BGs increased 2.35 times and the selectivity of benzaldehyde increased from 77.3% to 99.2%. Aerobic–anaerobic exchange experiments revealed that the superior catalytic performance of BG was achieved only under aerobic conditions. The study of the boron-doped carbocatalyst may also provide guidance for the design of surface modified carbon-based catalysts for the selective oxidation dehydrogenation of alcohols by regulating doping elements and their types.

Boron doped graphene for the oxidative dehydrogenation reactions.     

The interaction of dietary flavonoids with xanthine oxidase in vitro: molecular property-binding affinity relationship aspects

The molecular property–affinity relationships of dietary flavonoids binding to xanthine oxidase were investigated in vitro by comparing the binding constants obtained from a fluorescence-quenching method. The inhibitions of dietary flavonoids on xanthine oxidase were also investigated and analyzed, revealing that the binding process was influenced by the structural differences of the flavonoids under investigation. For example, methylation and hydroxylation at the 7- and 5-positions weakened the binding affinities, while hydroxylation at the 3- and 3′-positions mostly improved binding affinities. Glycosylation and hydrogenation of the C₂ C₃ double bond also increased affinities for xanthine oxidase. In addition, galloylated catechins showed higher binding affinities than non-galloylated catechins. Trends in the binding affinities and inhibition of flavonoids during structure modifications were summarized. Affinities for xanthine oxidase and inhibition on xanthine oxidase changed in the opposite direction during the methylation and hydroxylation of flavonoids in the A ring, and the glycosylation and hydrogenation of C₂ C₃. However, affinities and inhibition for xanthine oxidase changed in the same direction during the methylation and hydroxylation of flavonoids in the B ring.

The molecular property–affinity relationships between flavonoids and xanthine oxidase were investigated through comparing binding constants obtained via fluorescence quenching measurements.     

Insights into the nucleophilic substitution of pyridine at an unsaturated carbon center

Bimolecular nucleophilic substitution (S_N2) is a fundamental reaction that has been widely studied. So far, the nucleophiles are mainly anionic species in S_N2 reactions. In this study, we use density functional theory calculations to assess the mechanisms of substitution of carbonyl, imidoyl, and vinyl compounds with a neutral nucleophile, pyridine. Charge decomposition analysis is performed to explore the main components of the transition state''s LUMO. For reactions of imidoyl or carbonyl compounds with pyridine or Cl⁻, the LUMOs of the transition states are composed of mixed orbitals originating from the nucleophile and the substrate. Considering the unique mixed nature of the orbitals, the reaction mode is termed S_Nm (m means mix). Moreover, the main components of the transition state''s LUMO are pure σ*_C–Cl MO in the reactions of H₂C CHCl with pyridine or Cl⁻. Computations were also performed for RY CHX substrates with different X and Y groups (X= Cl⁻, Br⁻, or F⁻; Y = O, N, or C).

The nucleophilic substitution of carbonyl, imidoyl, and vinyl carbon centers with pyridine or halides is investigated in this paper.     

tBuOK-triggered bond formation reactions

Recently, inexpensive and readily available tBuOK has seen widespread use in transition-metal-free reactions. Herein, we report the use of tBuOK for S–S, S–Se, N N and C N bond formations, which significantly extends the scope of tBuOK in chemical synthesis. Compared with traditional methods, we have realized mild and general methods for disulfide, azobenzenes imine etc. synthesis.

Inexpensive and readily available ^tBuOK can trigger a series of bond formation reactions, including S–S, S–Se, Se–Se, and N N and C N bonds.     

Experimental and theoretical investigation of oxidative methane activation on Pd–Pt catalysts

Density functional theory (DFT) and measurements of rate are used to provide evidence for the rate determining step (RDS) and requirements of the active site for CH₄ combustion on Pd–Pt bimetallic catalysts in five different distinct kinetic regimes. These five regimes exhibit different rate equations for methane combustion due to the reaction rate constants and diverse dominant adsorbed species for these different kinetically relevant steps. Oxygen chemical potential at the Pd–Pt surface was replaced by oxygen pressure, reflecting the kinetic coupling between C–H and O O bond cleavage steps. C–H bond cleavage occurs on different active sites in five of these kinetic regimes, evolving from vacancy–vacancy (*–*) to oxygen–vacancy (O*–*), oxygen–oxygen (O*–O*) site pairs, monolayer Pd–O, and ultimately to oxide bulk with Pd–O site pairs as the oxygen chemical potential increases. It is easier to form a metallic surface at low oxygen pressure, implying minimal O* coverage. The sole kinetically relevant step on uncovered Pd–Pt surfaces for methane combustion is O O bond cleavage. The supply of oxygen is obviously more important than the supply of methane in regime (I). As vacancies become less available on metallic surfaces, C–H bond cleavage occurs via O*–* paired sites, the energy barrier of which is much higher than that on uncovered Pd–Pt surfaces. In this regime (II), O O bond cleavage is still an irreversible process because O* will be consumed by the rapidly formed products of methane dissociation. For the oxygen saturated surfaces in regime (III), C–H bond cleavage occurs on two adjacent adsorbed oxygens that form OH and weak CH₃–O bond interactions, resulting in a low activity for methane combustion. On the oxidation surfaces (IV and V), exposed metal atoms and their adjacent exposed lattice oxygen were the active sites, leading to a large decrease in C–H bond cleavage energy barrier, deduced from both experiment and theory. The increase of the metallic oxide thickness (increase of oxygen potential) increases the methane combustion turnover rates on Pd–Pt catalysts.

Density functional theory and measurements of rate are used to provide evidence for the rate determining step and requirements of the active site for CH₄ combustion on Pd–Pt bimetallic catalysts in five different distinct kinetic regimes.     

Insights into the promotion role of phosphorus doping on carbon as a metal-free catalyst for low-temperature selective catalytic reduction of NO with NH3

The catalytic reduction of NO with NH₃ (NH₃-SCR) on phosphorus-doped carbon aerogels (P-CAs) was studied in the temperature range of 100–200 °C. The P-CAs were prepared by a one-pot sol–gel method by using phosphoric acid as a phosphorus source followed by carbonization at 600–900 °C. A correlation between catalytic activity and surface P content is observed. The P-CA-800_vac sample obtained via carbonization at 800 °C and vacuum treatment at 380 °C shows the highest NO conversion of 45.6–76.8% at 100–200 °C under a gas hourly space velocity of 500 h⁻¹ for the inlet gas mixture of 500 ppm NO, 500 ppm NH₃ and 5.0 vol% O₂. The coexistence of NH₃ and O₂ is essential for the high conversion of NO on the P-CA carbon catalysts, which can decrease the spillover of NO₂ and N₂O. The main Brønsted acid sites derived from P-doping and contributed by the C–OH group at edges of carbon sheets are beneficial for NH₃ adsorption. In addition, the C₃–P O configuration seems to have the most active sites for favorable adsorption and dissociation of O₂ and facilitates the formation of NO₂. Therefore, the simultaneous presence of acidic groups for NH₃ adsorption and the C₃–P O active sites for NO₂ generation due to the activation of O₂ molecules is likely responsible for the significant increase in the NH₃-SCR activity over the P–CAs. The transformation of C₃–P O to C–O–P functional groups after the reaction is found, which could be assigned to the oxidation of C₃–P O by the dissociated O*, resulting in an apparent decrease of catalytic activity for P-CAs. The C–O–P based functional groups are also active in the NH₃-SCR reaction.

P species can effectively enhance the catalytic activity of carbon aerogels for NO reduction at low temperature.     

Selective production of bio-based aromatics by aerobic oxidation of native soft wood lignin in tetrabutylammonium hydroxide

Aerobic oxidation of native soft wood lignin in an aqueous solution of Bu₄NOH facilitates efficient production of vanillin (4-hydroxy-3-methoxybenzaldehyde), which is one of the platform chemicals in industry. Oxidation of Japanese cedar (Cryptomeria japonica) wood flour at 120 °C for 4 h under O₂ in Bu₄NOH-based aqueous solutions produced vanillin in 23.2 wt% yield based on the Klason lignin content of the starting material. This yield was comparable to that in alkaline nitrobenzene oxidation of the same material (27.2%), which indicated that our aerobic oxidation exploited the full potential of the wood flour for vanillin production. Further mechanical investigation with lignin model compounds suggested that the vanillin formation occurred mainly through following successive reactions: alkaline-catalyzed degradation of β-ether linkages in middle units of lignin polymer to form a glycerol end group, oxidation of the glycerol end group by O₂ to a HC_α O moiety, and release of vanillin from the HC_α O end. One of the reasons for the high performance of Bu₄NOH for the vanillin production was explained by the general understanding in organic chemistry that Bu₄OH is a stronger base than simple alkali, e.g. NaOH. The other more fundamental mechanical aspect was that Bu₄N⁺ suppressed disproportionation of the vanillin precursor (the C_αHO end group) probably due to strong interaction between the cation and the HC_α O end group.

Aerobic oxidation of native soft wood lignin in an aqueous solution of Bu₄NOH facilitates efficient production of vanillin (4-hydroxy-3-methoxybenzaldehyde), which is one of the platform chemicals in industry.     

Correction: Mid-infrared spectroscopy and microscopy of subcellular structures in eukaryotic cells with atomic force microscopy – infrared spectroscopy

Correction for ‘Mid-infrared spectroscopy and microscopy of subcellular structures in eukaryotic cells with atomic force microscopy – infrared spectroscopy’ by Luca Quaroni et al., RSC Adv., 2018, 8, 2786–2794.

In the article the assignment of two IR absorption bands, at 3010 and at 3070 cm⁻¹ has been confused by us in the text, resulting in two incorrect statements. The misstatement does not change any of the conclusions of the work, and can be corrected by restating the following sentences.The following sentence (p. 2790, column 1, line 10):A weak but sharp band can be seen at 3010 cm⁻¹, corresponding to the stretching mode of C–H bonds on unsaturated C C bonds in acyl chains.must be corrected to:A weak but sharp band can be seen at 3010 cm⁻¹, corresponding to the stretching mode of C–H₃ bonds on choline headgroups.In addition, the following sentence (p. 2792, column 1, line 25):Observation of a sharp band at 3010 cm⁻¹ indicates that at least part of the acyl chains have unsaturated C C bonds.must be changed to:Observation of a band at 3070 cm⁻¹, corresponding to the stretching mode of C–H bonds on unsaturated C C bonds in acyl chains, indicates that at least part of the acyl chains have unsaturated C C bonds.The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers.     

Revisiting salicylidene-based anion receptors

Several salicylidene-based colorimetric and fluorimetric anion sensors are known in the literature. However, our ¹H-NMR experimental results (in DMSO-d₆) showed hydrolysis of imine (–N CH–) bonds in salicylidene-based receptors (SL, CL1 and CL2) in the presence of quaternary ammonium salts (n-Bu₄N⁺) of halides (Cl⁻ and Br⁻) and oxo-anions (H₂PO₄⁻, HSO₄⁻ and CH₃COO⁻). The mono-salicylidene compound CL1 showed the most extensive –N CH– bond hydrolysis in the presence of anions. In contrast, the di-salicylidene compound CL2 and the tris-salicylidene compound SL showed comparatively slow hydrolysis of –N CH– bonds in the presence of anions. Anion-induced imine bond cleavage in salicylidene compounds could easily be detected in ¹H-NMR due to the appearance of the salicylaldehyde –CHO peak at 10.3 ppm which eventually became more intense over time, and the –N CH– peak at 8.9–9.0 ppm became considerably weaker. Furthermore, the formation of the salicylidene O–H⋯X⁻ (X⁻ = Cl⁻/Br⁻) hydrogen-bonded complex, peak broadening due to proton-exchange processes and keto–enol tautomerism have also been clearly observed in the ¹H-NMR experiments. Control ¹H-NMR experiments revealed that the presence of moisture in the organic solvents could result in gradual hydrolysis of the salicylidene compounds, and the rate of hydrolysis has further been enhanced significantly in the presence of an anion. Based on ¹H-NMR results, we have proposed a general mechanism for the anion-induced hydrolysis of imine bonds in salicylidene-based receptors.

Salicylidene Schiff bases undergo imine bond hydrolysis in the presence of halides and oxo-anions in aprotic media, raising fundamental questions on the applicability of salicylidene-based receptors as anion sensors.     

Ancillary ligand effects on α-olefin polymerization catalyzed by zirconium metallocene: a computational study

The polymerization of α-olefins catalyzed by zirconium metallocene catalyst was systematically studied through experiments and density functional theory (DFT) calculations. Having achieved an agreement between theory and experiment, it was found that the effect of the catalyst ligand on the C C insertion reaction was significantly greater than that on the β-H elimination reaction. Therefore, the molecular weight of polymers can be increased by improving the activity of the C C insertion. In addition, in comparison with propylene, the chain length of α-olefins can directly affect the stereotacticity of polymerization products, owing to steric hindrance between the polymer chain and monomer.

The polymerization of α-olefins catalyzed by zirconium metallocene catalyst was systematically studied through experiments and density functional theory (DFT) calculations.     

Formation of bicyclic polycyclic aromatic hydrocarbons (PAHs) from the reaction of a phenyl radical with cis-3-penten-1-yne

The formation of polycyclic aromatic hydrocarbons (PAHs) on the C₁₁H₁₁ potential energy surface involved in the reactions of a phenyl radical (C₆H₅) with cis-3-penten-1-yne (cis-C¹H C²–C³H C⁴H–C⁵H₃, referred to as C₅H₆) and its three radicals (CH C–Ċ CH–CH₃, CH C–CH Ċ–CH₃, and cis-CH C–CH CH–ĊH₂, referred to as the C³-, C⁴-, and C⁵-radicals with the same chemical components, C₅H₅) assisted by H atoms is investigated by performing combined density functional theory (DFT) and ab initio calculations. Five potential pathways for the formation of PAHs have been explored in detail: Pathways I–II correspond to the reaction of C₆H₅ with C₅H₆ at the C¹ and C² position, and Pathways III–V involve the reaction of C₆H₅ with the C³-, C⁴-, and C⁵-radicals with the assistance of H atoms. The initial association of C₆H₅ with C₅H₆ or C₅H₅ is found to be highly exothermic with only minor barriers (1.4–7.1 kcal mol⁻¹), which provides a large driving force for the formation of PAHs. The hydrogen atom is beneficial for the ring enlargement and ring formation processes. The present calculations predict 9 potential PAHs, six (CS6, CS10, CS13, CS26, CS28 and CS29) of which are indicated to be energetically more favorable along Pathways I, III, IV and V at low temperature. The calculated barriers for the formation of these PAHs are around 19.2–38.0 kcal mol⁻¹. All PAHs products could be formed at flame temperature, for the medium barriers are easily overcome in various flame conditions. The theoretical results supplement the PAH formation pathway and provide help to understand PAH growth mechanism.

The formation of PAHs within 4-, 5-, 6- and 7-membered rings on the C₆H₅ + C₅H₆ potential energy surface.     

Production of renewable long-chained cycloalkanes from biomass-derived furfurals and cyclic ketones

Developing renewable long-chain cycloalkanes from lignocellulosic biomass is of significance because it offers huge resource storage, wide applications in aviation/diesel fuels and mitigation of CO₂ emissions. In this paper, cycloalkanes with carbon chain lengths of 13–18 were produced from biomass-derived furfural species (furfural and 5-hydroxymethylfurfural) and cyclic ketones (cyclopentanone and cyclohexanone) via aldol condensation, followed by hydrogenation to saturate the C C and C O bonds, and hydrodeoxygenation to remove oxygen atoms. The aldol condensation of the furfural species with cyclic ketones was catalyzed by NaOH and the target condensation intermediates were obtained in yields of more than 90% at room temperature (30 °C) with a short reaction time (40 min). By using amorphous zirconium phosphate combined with Pd/C as the catalyst, liquid cycloalkanes were produced at the optimal conditions with a yield of 76%. When the combined solid catalyst was reused, the target products reduced after the second run but the initial yield could be largely recovered by recalcination of the spent zirconium phosphate. Considering that cyclopentanone and cyclohexanone can be easily produced from furfural (originating from hemicellulose) and phenol (originating from lignin), respectively, this condensation has the potential to achieve the integrated conversion of biomass-derived cellulose, hemicellulose and lignin to jet fuel and/or diesel additives.

Renewable cyclic alkanes were produced in high yield via condensation of biomass-based furfurals and cyclic ketones followed by hydrodeoxygenation.     

Enhancing the conversion of ethyl levulinate to γ-valerolactone over Ru/UiO-66 by introducing sulfonic groups into the framework

The conversion of ethyl levulinate (EL) to γ-valerolactone (GVL) is an important reaction in biomass conversion. This process undergoes two consecutive reactions: hydrogenation and transesterification of the intermediate compound, i.e. ethyl 4-hydroxypentanoate, which are catalyzed by metal nanoparticles and acid sites, respectively. In this study, we explored the catalytic activity of Ru supported on metal organic frameworks aiming to develop efficient metal–acid bifunctional catalysts for this green process. UiO-66 and its analogues with various substituted groups (–SO₃H, –NH₂ and –NO₂) were employed in this study. The Ru particle size, oxidation state and reducibility were characterized by TEM, H₂-TPR, and XPS. The results suggest that the introduction of functional groups reduces the hydrogenation activity of pristine Ru/UiO-66 to various extents. Catalyst modified with –SO₃H group shows much higher acidic catalytic performance while showing hydrogenation activity towards C O bonds, thus improving the overall transformation of EL to GVL due to the presence of strong Brønsted acid sites.

Ru/UiO-66 modified with –SO₃H groups shows good acidic catalytic performance while also showing hydrogenation activity towards C O bonds, thus improving the overall transformation of EL to GVL due to the presence of strong Brønsted acid sites.     

Study of the thermal decomposition mechanism of FOX-7 by molecular dynamics simulation and online photoionization mass spectrometry

The thermal decomposition mechanism of energetic materials is important for analyzing the combustion mechanisms of propellants and evaluating the safety of propellants during transport and storage. 1,1-Diamino-2,2-dinitroethylene (FOX-7) is an important insensitive energetic material that can be used as an oxidizer in propellants. However, the initial decomposition mechanism of FOX-7 is not clear to date. The ReaxFF molecular dynamics method is widely used in the investigation of the thermal decomposition mechanisms of energetic materials. Meanwhile, the combination of thermogravimetry with online photoionization time-of-flight mass spectrometry (TG-PI-TOF-MS) and online single-photon ionization time-of-flight mass spectrometry (SPI-TOF-MS) can reveal the decomposition products, which may be integrated with the results of the simulation. In this study, the primary thermal decomposition mechanism of 1,1-diamino-2,2-dinitroethylene (FOX-7) was studied by the ReaxFF molecular dynamics simulations and online photoionization mass spectrometry. The results of the molecular dynamics simulations showed that the primary decomposition step of FOX-7 is C–NO₂ cleavage; after this, C O formation occurs via a three-membered ring transition state, followed by NO elimination. The remaining structure loses NH₂ and H, resulting in the formation of the NHC C O structure, which finally breaks down into HNC and CO. NH₂ reacts with an H atom to produce NH₃. A reversible intramolecular hydrogen transfer was also observed at 2500 K; however, it failed to dominate the decomposition reaction. During the decomposition of FOX-7, the major products are N₂, NH₃, CO₂, and H₂N₂ and the minor products are H₂O, HN₂, and H₂. The TG-PI-TOF-MS spectrum shows three signals, i.e., m/z = 18, 28, and 30, which can be assigned to H₂O, CO, and NO, respectively. Moreover, four signals at m/z = 72.72, 55.81, 45.79, and 29.88 corresponding to the products (NH₂)₂C C O, (NH₂)C C O, NO₂, and NO have been obtained in the SPI-TOF-MS spectrum. The experimental data obtained via online photoionization mass spectrometry further validated the results of the molecular dynamics simulations.

In this work, the primary thermal decomposition mechanism of 1,1-diamino-2,2-dinitroethylene (FOX-7) was studied by ReaxFF molecular dynamics simulations and online photoionization mass spectrometry.