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.     

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.     

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.     

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.     

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.     

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.     

Flexible selection of the functional-group ratio on a polytetrafluoroethylene (PTFE) surface using a single-gas plasma treatment

During plasma treatment of polymers, etching occurs and functional groups are introduced on their surface. We assumed that controlling the etching rate would enable plasma treatment using a single gas to control the ratio of functional groups generated on a polymer''s surface, although previous studies have indicated that several different types of functional groups are formed when the gaseous species are varied. In this study, we selected the base pressure (BP) as a parameter for controlling the etching rate and subjected polytetrafluoroethylene (PTFE) to plasma treatments using only He gas at various BPs. The chemical composition of the surface of the plasma-treated PTFE samples was evaluated by X-ray photoelectron spectroscopy (XPS), and the ratios of fluorine (CF₃, CF₂, C–F), oxygen (O–C O, C O, C–O), and carbon (C–C, C C) groups were quantified from the C 1s-XPS spectra. The fluorine-group ratio decreased and the oxygen- and carbon-group ratios increased with decreasing BP. The results demonstrated that plasma treatment using a single gas enabled flexible selection of the ratio of functional groups generated on PTFE via control of the BP.

During plasma treatment of polymers, etching occurs and functional groups are introduced on their surface.     

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.     

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.     

Corrosion inhibition of carboxylate inhibitors with different alkylene chain lengths on carbon steel in an alkaline solution

The inhibition effects of five organic carboxylate compounds with different alkylene chain lengths on Q235 steel in a simulated carbonation concrete pore solution (pH 11.5) were studied using quantum chemical calculations, electrochemical measurement and surface analysis. The results show that the adsorption capacity of the inhibitors increases with increasing distance between the C C bond and COO– group. As the alkylene chain length increases, the absolute surface charge value increases and the inhibition effectiveness tends to increase. C11 shows the best inhibition. The carboxylate inhibitors adsorb on a steel surface by forming Fe–OOC–C_x compounds and the C C bonds could enhance the adsorption process.

The inhibition effects of carboxylate compounds with different alkylene chain lengths on Q235 steel in simulated carbonation concrete pore solution were studied using quantum chemical calculations, electrochemical measurement and surface analysis.     

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.     

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.     

Inconsistent hydrogen bond-mediated vibrational coupling of amide I

Using infrared spectroscopy and density functional theory (DFT) calculations, we scrutinized an amide (dimethylformamide) as a “model” compound to interpret the interactions of amide 1 with different phenol derivatives (para-chlorophenol (PCP) and para-cresol (CP)) as “model guest molecules”. We established the involvement of amide I in vibrational coupling with symmetric and asymmetric C C modes of different phenolic derivatives and how their coupling was dependent upon different guest aromatic phenolic compounds. Interestingly, substitution of phenol perturbed the pattern of vibrational coupling with amide I. The symmetric and asymmetric C C modes of PC were coupled significantly with amide 1. For PCP, the symmetric C C mode coupled significantly, but the asymmetric mode coupled negligibly, with amide I. Here, we reveal the nature of vibrational coupling based on the structure of a guest molecule hydrogen-bonded with amide I. Our conclusions could be valuable for depiction of the unusual dynamics of coupled amide-I modes as well as the dependency of vibrational coupling on altered factors.

The involvement of amide I in vibrational coupling with symmetric and asymmetric C C modes of different phenolic derivatives.     

The enhanced reduction of bromate by highly reactive and dispersive green nano-zerovalent iron (G-NZVI) synthesized with onion peel extract

In this study, novel green nano-zerovalent iron (G-NZVI) is synthesized for the first time using onion peel extract for the prevention of rapid surface oxidation and the enhancement of particle dispersibility with a high reductive capacity. The results from various surface analyses revealed that the spherical shape of G-NZVI was fully covered by the onion peel extract composed of polyphenolic compounds with C C–C C unsaturated carbon, C C, C–O, and O–H bonds, resulting in high mobility during column chromatography. Furthermore, the obtained G-NZVI showed the complete removal of 50 mg L⁻¹ of bromate (BrO₃⁻) in 2 min under both aerobic (k = 4.42 min⁻¹) and anaerobic conditions (k = 4.50 min⁻¹), showing that G-NZVI had outstanding oxidation resistance compared to that of bare NZVI. Moreover, the observed performance of G-NZVI showed that it was much more reactive than other well-known reductants (e.g., Fe and Co metal organic frameworks), regardless of whether aerobic or anaerobic conditions were used. The effects of G-NZVI loading, the BrO₃⁻ concentration, and pH on the BrO₃⁻ removal kinetics using G-NZVI were also investigated in this study. The results provide the novel insight that organic onion peel waste can be reused to synthesize highly reactive anti-oxidative nanoparticles for the treatment of inorganic chemical species and heavy metals in water and wastewater.

In this study, novel green nano-zerovalent iron (G-NZVI) is synthesized for the first time using onion peel extract for the prevention of rapid surface oxidation and the enhancement of particle dispersibility with a high reductive capacity.     

Computational design and molecular modeling of the interaction of nicotinic acid hydrazide nickel-based complexes with H2S gas

The application of nickel complexes of nicotinic acid hydrazide ligand as a potential gas-sensor and adsorbent material for H₂S gas was examined using appropriate density functional theory (DFT) calculations with the ωB97XD/Gen/6-311++G(d,p)/LanL2DZ method. The FT-IR spectrum of the synthesized ligand exhibited a medium band at 3178 cm⁻¹ attributed to ν(NH) stretching vibrations and strong bands at 1657 and 1600 cm⁻¹ corresponding to the presence of ν(C O) and ν(C N) vibration modes. In the spectrum of the nickel(ii) complex, the ν(C O) and ν(C N) vibration bands experience negative shifts to 1605 cm⁻¹ and 1580 cm⁻¹, respectively, compared to the ligand. This indicates the coordination of the carbonyl oxygen and the azomethine nitrogen atoms to the Ni²⁺ ion. Thus, the sensing mechanism of the complexes indicated a short recovery time and that the work function value increases for all complexes, necessitating an excellent H₂S gas sensor material. Thus, a profound assertion was given that the complex sensor surfaces exhibited very dense stability with regards to their relevant binding energies corresponding to various existing studies.

We demonstrate the efficacy of nicotinic acid hydrazide as adsorbent/sensor materials for H₂S gas.     

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.     

Influence of flaxseed flour as a partial replacement for wheat flour on the characteristics of Chinese steamed bread

This study investigated the effects of partially replacing wheat flour with flaxseed flour (FF) on the quality parameters of Chinese Steamed Bread (CSB). FF was utilized as a functional ingredient of CSB at varying levels. The pasting properties of flour blends, the rheological and microstructural characteristics of dough, the textural and quality characteristics and functional group structure of CSB were analyzed. Results showed that FF addition influenced the pasting characteristics of wheat flour by decreasing the final viscosity, breakdown and setback values, but had little effect on the rheological properties of the dough. The microstructure of the dough indicated that the disruption degree of the gluten matrix increased with the increase of FF. Besides, FF addition increased the hardness and chewiness of CSB, while decreasing the cohesiveness and springiness. Additional characteristic peaks were observed at 1745, 2854, and 3006 cm⁻¹ and associated with –C O, –CH₂, and cis-C CH bond stretching vibrations of flaxseed. Results suggested 12% FF exhibited the best acceptability.

Chinese steamed bread supplemented with flaxseed flour can be recommended as a dietary product with health benefits.     

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.     

Retro Diels Alder protocol for regioselective synthesis of novel [1,2,4]triazolo[4,3-a]pyrimidin-7(1H)-ones

Reactions of diastereochemically varied norbornene-condensed 2-thioxopyrimidin-4-ones 6 and 10 with variously functionalized hydrazonoyl chlorides 2a–h gave regioselectively angular norbornene-based [1,2,4]triazolo[4,3-a]pyrimidin-7(1H)-ones 7a–h and 11a,c–e, respectively. Thermal retro Diels–Alder (RDA) reaction of 7a–h and 11a,c–e resulted in the target compounds 4a–h as single products. On the other hand, reactions of thiouracil 1 and hydrozonoyl chlorides 2a–e gave regioselectively [1,2,4]triazolo[4,3-a]pyrimidinone-5(1H)-ones 3a–e. The opposite regioselectivity of thiouracil 1 and norbornene-condensed 2-thioxopyrimidin-4-ones 6 and 10 was attributed to electronic factors according to DFT calculations. The angular structure of norbornene based [1,2,4]triazolo[4,3-a]pyrimidin-7(1H)-ones was confirmed by single crystal X-ray crystallography.

Norbornene is an efficient motif for blocking the electronic effect of the C C bond to invert the stereochemistry outcome. Then, using the RDA strategy the C C bond was recovered to obtain the target compound with a definite stereochemistry.