Advancing MXene Electrocatalysts for Energy Conversion Reactions: Surface,Stoichiometry, and Stability

MXenes, due to their tailorable chemistry and favourable physical properties, have great promise in electrocatalytic energy conversion reactions. To exploit fully their enormous potential, further advances specific to electrocatalysis revolving around their performance, stability, compositional discovery and synthesis are required. The most recent advances in these aspects are discussed in detail: surface functional and stoichiometric modifications which can improve performance, Pourbaix stability related to their electrocatalytic operating conditions, density functional theory and advances in machine learning for their discovery, and prospects in large scale synthesis and solution processing techniques to produce membrane electrode assemblies and integrated electrodes. This Review provides a perspective that is complemented by new density functional theory calculations which show how these recent advances in MXene material design are paving the way for effective electrocatalysts required for the transition to integrated renewable energy systems.     

Synthesis and characterization of some Schiff-base-containing polyimides

The diamine, 4-aminophenyloxy-N-4-[(4-amiophenyloxy)benzylidene]aniline, was prepared via the nucleophilic substitution reaction and was polymerized with different dianhydrides either by one-step solution polymerization reaction or two-step procedure. The latter includes ring-opening polyaddition to give poly(amic acid), followed by cyclodehydration to polyimides. The inherent viscosity ranges from 0.61–0.79 dl/g. Some of the polymers were soluble in most of the organic solvents such as DMSO, DMF, DMAc, NMP, and m-cresol even at room temperature. The degradation temperature of the resultant polymers falls in the ranges from 240–500 °C in nitrogen with only 10% weight loss. Specific heat capacity at 200 °C ranges from 1.0929–2.6275 J g⁻¹ k⁻¹. The temperature at which the maximum degradation of the polymer occurs ranges from 600–630 °C. The glass transition temperature (Tg) values of the polyimides ranged from 185 to 272 °C. The activation energy and enthalpy of the polyimides ranged from 47.5–55.0 kJ/mole and 45.7–53.0 kJ/mole and the moisture absorption in the range of 0.23–0.72%.     

A New Method for Assessment of Performing Mechanical Works of Energetic Compounds by the Cylinder Test

A new method is introduced for assessment of performing mechanical works of energetic compounds by cylinder wall velocities of CHNOFCl energetic compounds on the basis of the cylinder test. Four suitable decomposition paths are used to evaluate the number of moles of gaseous detonation products per gram of explosive, the average molecular weight of these gases, and the heat of detonation in calories per gram by considering different decomposition products HF, HCl, CO, N₂, H₂O, H₂, and CO₂. For CHNO and fluoro energetic compounds, the predicted cylinder wall velocities of these compounds give more reliable results than one of the best available empirical methods. The predicted root mean square (rms) deviations of cylinder wall velocities of the new model for some chloro explosives at actual radial expansions 0.6 and 1.9 mm are 0.010 and 0.062 km · s^–1, which show high reliability of the new method.     

A highly stereoselective synthesis of (-)-(ent)-julifloridine from the cyclization of an alanine-derived chloroamine with an acetylenic sulfone

The cyclization of gamma-chloroamine 11, derived from l-alanine, and acetylenic sulfone 12 afforded the dehydropiperidine 19 via conjugate addition followed by intramolecular alkylation of the corresponding sulfone-stabilized anion. An unexpected acid-catalyzed desulfonylation of 19 occurred in one step via desilylation and tautomerization of the enamine moiety to the corresponding aldehyde, followed by elimination of p-toluenesulfinic acid. The highly stereoselective reduction of the resulting unsaturated aldehyde 25 with sodium cyanoborohydride produced piperidine 23 with a diastereomeric ratio of >98:2. (-)-(ent)-Julifloridine (8) was obtained by Swern oxidation of 23, followed by Wittig olefination and hydrogenation/debenzylation.     

Identifiability of kinetic models of isotope transient tracing in fixed bed plug flow reactors

A novel method is presented to address the identifiability of a class of kinetic models of monoatomic isotope transient tracing in plug flow reactors. It is shown that the identifiability of these models can be addressed solely from a knowledge of the rate functions. Dedicated to Professor Pál Tétényi on the occasion of his 70th birthday     

Effects of Thermal Radiation and Slip Mechanism on Mixed Convection Flow of Williamson Nanofluid Over an Inclined Stretching Cylinder

The current investigation highlights the mixed convection slip flow and radiative heat transport of uniformly electrically conducting Williamson nanofluid yield by an inclined circular cylinder in the presence of Brownian motion and thermophoresis parameter.A Lorentzian magnetic body force model is employed and magnetic induction effects are neglected.The governing equations are reduced to a system of nonlinear ordinary differential equations with associated boundary conditions by applying scaling group transformations.The reduced nonlinear ordinary differential equations are then solved numerically by Runge-Kutta-Fehlberg fifth-order method with shooting technique.The effects of magnetic field,Prandtl number,mixed convection parameter,buoyancy ratio parameter,Brownian motion parameter,thermophoresis parameter,heat generation/absorption parameter,mass transfer parameter,radiation parameter and Schmidt number on the skin friction coefficient and local Nusselt are analyzed and discussed.It is found that the velocity of the fluid decreases with decrease in curvature parameter,whereas it increases with mixed convection parameter.Further,the local Nusselt number decreases with an increase in the radiation parameter.The numerical comparison is also presented with the existing published results and found that the present results are in excellent agreement which also confirms the validity of the present methodology.     

Perfluoropentaphenylborole

Komplett fluoriert : Vollständig fluoriertes Pentaphenylborol (siehe Struktur) wurde durch aufeinander folgende Transmetallierungsreaktionen unter Beteiligung von Zr‐ und Sn‐Heterocyclen synthetisiert. Das hoch feuchtigkeitsempfindliche Borol ist ein neues Mitglied der Familie der Perfluorarylborane, einer Klasse von antiaromatischen Verbindungen mit grundlegender Bedeutung für Aromatizitätskonzepte.

     

9‐Boraanthracene Derivatives Stabilized by N‐Heterocyclic Carbenes

2009: A boraanthracene odyssey : General routes to boraanthracene derivatives—long proposed, but never observed—are disclosed, along with the structural and photophysical properties of these compounds and their remarkable reactivity towards oxygen.

     

1H and 13C NMR assignments and X-ray structures for three monocyclic benzoannelated dilactam polyethers

Three monocyclic polyether dilactams, 17,18-dihydro-5H, 9H-dibenzo[e,n]1,4,10,7,13trioxadiazacyclopentadecine-6,10(7H,11H)-dione (1); 9,10,20,21-tetrahydro-5H, 12H-dibenzo[e,q]1,4,10,13,7,16tetraoxadiazacyclooctadecine-6, 13(7H,14H)-dione (2); and 6,7,9,10-tetrahydro-16H, 20H-dibenzo[h,q]1,4,7,13, 10,16tetraoxadiazacyclooctadecine-17, 21(18H,22H)-dione (3) were isolated during the synthesis of several benzoannelated cryptands. The complete assignments of the 1H and 13C NMR spectra of 1, 2 and 3 in CDCl3 were made using gCOSY, gHMBC, gHMQC, HMQC, HSQC, and NOESY 1D techniques. The ortho (H2) benzene protons show significant downfield shifts (1.16-1.43 ppm) that are consistent with an exodentate orientation for the amide carbonyl groups. The X-ray crystal structures of 1, 2 and 3 show that the carbonyl groups adopt an exodentate conformation in the solid state.     

Influence of crosslinker identity and position on gas-phase dissociation of lys-lys crosslinked peptides

A systematic study of the dissociation patterns of crosslinked peptides analyzed by tandem mass spectrometry is reported. A series of 11-mer peptides was designed around either a polyalanine or polyglycine scaffold with arginine at the C terminus. One or two lysine residues were included at various locations within the peptides to effect inter- or intra-molecular crosslinking, respectively. Crosslinked species were generated with four commonly used amine-specific chemical crosslinking reagents: disuccinimidyl suberate (DSS), disuccinimidyl tartarate (DST), dithiobis(succinimidylpropionate) (DSP), and disuccinimidyl glutarate (DSG). The influence of precursor charge state, location of crosslink, and specific crosslinking reagent on the MS/MS dissociation pattern was examined. Observed trends in the dissociation patterns obtained for these species will allow for improvements to software used in the automated interpretation of crosslinked peptide MS/MS data.