An investigation into the electro-oxidation of ethanol and 2-propanol for application in direct alcohol fuel cells (DAFCs)

A comparative study of the electro-oxidation of ethanol and 2-propanol was carried out on carbon-supported platinum particles. Cyclic voltammetry, steady state polarisation, and electrochemical impedance spectroscopy were used to investigate the oxidation reactions. A difference in the mechanistic behaviour of the oxidation of ethanol and 2-propanol on Pt was observed, thereby highlighting the fact that the molecular structure of the alcohol has great influence on its electroreactivity. The study emphasizes the fact that 2-propanol is a promising fuel candidate for a direct alcohol fuel cell.     

Probing electrochemical surface/interfacial reactions with liquid cell transmission electron microscopy: a challenge or an opportunity?

Understanding electrochemical reactions at material surfaces and interfaces is crucial for the development of next-generation battery electrodes and electrocatalysts — two key areas in global CO₂ mitigation strategies. By allowing these dynamic reactions to be captured on an atomic level and in real-time, the liquid cell transmission electron microscopy (LC-TEM) technique has carved itself a niche in energy materials research. Several key problems are being investigated, ranging from addressing dendrite growth in lithium-ion batteries that cause a thermal runaway, to understanding mass loss of expensive platinum catalysts in native hydrogen fuel-cell environments. Unfortunately, as with any emerging technology, LC-TEM is not without its share of problems. Undesired electron beam interactions with the liquid, low containable liquid volumes, and poor spatial resolution due to plural scattering are only some of the many problems which must still be fully resolved.This short review highlights the strengths and weaknesses behind LC-TEM while providing updates on the latest applications and technical advances in the areas of dose-minimization strategies, improvements in analytical abilities, and novel closed-cell design. Notable future opportunities include off-axis holography, diffraction tomography, and pump-probe laser excitations — all carried out in liquids.     

“Seems Bad Turns Good” – traces of precursor in dicationic ionic liquid lead to analytical application

Research on Chemical Intermediates - We explored a geminal dicationic ionic liquid (DCIL), 1′-(propane-1,3-diyl)bis(4-aminopyridin-1-ium) dibromide, [C3(Amp)2][Br]2, as a fluorescent probe...     

Locating order-chaos-order transition in elastic pendulum

An undamped elastic pendulum being a nonintegrable Hamiltonian system always has some chaotic trajectories observable on choosing appropriate initial conditions. This is true even if the pendulum is in libration with small amplitude; in this situation, the pendulum may be seen as a nearly integrable system. Since the measure of the set of the local chaotic trajectories in the phase space may be very small, the trajectories are hard to locate. However, the emergence of widespread chaos when the elastic pendulum is at autoparametric resonance is well-documented. The transition from the local and the widespread chaos is typically established through the Chirikov overlap criterion that approximates the phase portrait around a resonance using a one degree-of-freedom pendulum Hamiltonian. We argue in this paper that the aforementioned transition in the elastic pendulum is due to interaction between two resonances of same kind and their coexistence can be analytically located using perturbation methods, like the method of averaging, whereas the technique of the pendulum Hamiltonian is inapplicable. Furthermore, in the course of validating the result numerically, we also showcase the order-chaos-order transition in the elastic pendulum using the fast Lyapunov indicator.

     

Gram-Scale Synthesis of the 1,1,n,n-Tetramethyl[n](2,11)teropyrenophanes

A gram-scale synthesis of a series of 1,1,n,n-tetramethyl[n](2,11)teropyrenophanes (n=7–9) has been accomplished as well as the first synthesis of the next higher homologue 1,1,10,10-tetramethyl[10](2,11)teropyrenophane. The scale-up of the original small-scale synthesis required the development of several heavily modified synthetic methods, including a chlorination/Friedel–Crafts alkylation protocol and an iodination/Wurtz coupling protocol, which were performed on 25–30 g and 30–60 g scales, respectively. Two separate sets of conditions for the key teropyrene-forming cyclodehydrogenation reaction at the end of the synthetic pathway were developed, an acid-promoted one for the two less strained congeners and an acid-free method for the two more strained homologues.     

Structural analysis of an impurity of the drug landiolol

In a course of development and preparation of landiolol (1a), a known ultra‐short‐acting β‐blocker, process quality control by HPLC and LC‐MS analysis consistently showed an impurity peak ranging from 0.05% to 0.15 % and exhibiting a molecular mass m/z 887. To identify the hitherto unknown impurity, we prepared one of the possible landiolol derivatives with the same molecular mass for proper spectral characterization (NMR and MS). Its equivalence with the unknown impurity was then confirmed by LC‐MS analysis. Ultimately, using fragmentation patterns in LC‐MS and selective two‐dimensional NMR experiments, the structure of the impurity was assigned as [(4S)‐2,2‐dimethyl‐1,3‐dioxolan‐4‐yl]methyl 3‐{4‐[(2S)‐2‐hydroxy‐3‐(3‐{4‐[(2S)‐2‐hydroxy‐3‐[(2‐{[(morpholin‐4‐yl)carbonyl]amino}ethyl)amino]propoxy]phenyl}‐N‐(2‐{[(morpholin‐4‐yl)carbonyl]amino}ethyl)propanamido)propoxy]phenyl}propanoate (2). It was found that the impurity was present in two rotameric forms at room temperature. The synthesis and NMR characterization of (2) are discussed. Copyright © 2014 John Wiley & Sons, Ltd.     

Eco-friendly synthesis of 2-aryl-1-arylmethyl-1H-benzimidazoles using alumina-sulfuric acid as a heterogeneous reusable catalyst

A cost-effective and eco-friendly synthesis of 2-aryl-1-arylmethyl-1H-benzimidazoles has been developed through the condensation of different aldehydes with o-phenylenediamine using alumina-sulfuric acid as a recyclable heterogeneous solid acid catalyst. Morphological properties of the catalyst have been investigated. Effect of different solvents and comparison of alumina-sulfuric acid with different acid catalysts have also been studied. A plausible mechanistic pathway has been proposed on the basis of the isotope labelling experiments where catalytic behaviour of alumina-sulfuric acid has been explained.     

ZnII‐ and AuI‐Catalyzed Regioselective Hydrative Oxidations of 3‐En‐1‐ynes with Selectfluor: Realization of 1,4‐Dioxo and 1,4‐Oxohydroxy Functionalizations

Catalytic 1,4‐dioxo functionalizations of 3‐en‐1‐ynes to (Z)‐ and (E)‐2‐en‐1,4‐dicarbonyl compounds are described. This regioselective difunctionalization was achieved in one‐pot operation through initial alkyne hydration followed by in situ Selectfluor oxidation. The presence of pyridine alters the reaction chemoselectivity to give 4‐hydroxy‐2‐en‐1‐carbonyl products instead. A cooperative action of pyridine and Zn^II assists the hydrolysis of key oxonium intermediate.     

Facile and efficient synthesis of carbohybrids as stereodivergent druglike small molecules

A facile and efficient one-pot synthesis of acyclic polyols fused with pyrazolo[1,5-a]pyrimidines and 1,2,4-triazolo[1,5-a]pyrimidines as novel carbohybrids with regioselectivity was achieved through the condensation of 2-C-formyl glycals with 3-aminopyrazoles and 3-amino-1,2,4-triazoles in excellent yields under the microwave irradiation.     

Near‐IR Emitting Iridium(III) Complexes with Heteroaromatic β‐Diketonate Ancillary Ligands for Efficient Solution‐Processed OLEDs: Structure–Property Correlations

Three NIR‐emitting neutral Ir^III complexes [Ir(iqbt)₂(dpm)] ( 1 ), [Ir(iqbt)₂(tta)] ( 2 ), and [Ir(iqbt)₂(dtdk)] ( 3 ) based on the 1‐(benzo[b]thiophen‐2‐yl)‐isoquinolinate (iqtb) were synthesized and characterized (dpm=2,2,6,6‐tetramethyl‐3,5‐heptanedionate; tta=2‐thienoyltrifluoroacetonate; dtdk=1,3‐di(thiophen‐2‐yl)propane‐1,3‐dionate). The compounds emit between λ=680 and 850 nm with high luminescence quantum yields (up to 16 %). By combining electrochemistry, photophysical measurements, and computational modelling, the relationship between the structure, energy levels, and properties were investigated. NIR‐emitting, solution‐processed phosphorescent organic light‐emitting devices (PHOLEDs) were fabricated using the complexes. The devices show remarkable external quantum efficiencies (above 3 % with 1 ) with negligible efficiency roll‐off values, exceeding the highest reported values for solution‐processible NIR emitters.