Asymmetric cyclopropanation reactions catalyzed by carbohydrate-based crown ethers

Optically active cyclopropane derivatives were prepared by a novel, simple and green approach in high enantioselectivities using monosaccharide-based chiral crown ethers as phase transfer catalysts. The crown ethers having d-glucopyranoside, d-mannopyranoside and d-altropyranoside units proved to be efficient catalyst in a few asymmetric phase transfer cyclopropanation reactions. The Michael-initiated ring closure (MIRC) reactions of diethyl bromomalonate with chalcones took place with complete diastereoselectivity and up to 99% ee. Using benzylidenemalononitrile, 2-arylidenemalononitriles, 2-benzylidene-1,3-indandione, substituted 2-benzylidene-1,3-indandiones, 2-arylidene-1,3-indandiones and 2-benzylidene-1,3-diphenyl-1,3-propanediones enantioselectivities up to 92%, 99%, 54% 93%, 89% and 72%, respectively, were achieved, in the presence of chiral lariat ethers derived from different monosaccharides. The absolute configuration of a cyclopropane diester product was determined by a combined CD spectroscopic and theoretical study.     

An improved method for liquid density measurement using NaI(Tl) detector and low-strength source

In the frame of severe accident topic for pressurized water reactor, the physical-chemistry of Ru fission products were experimentally studied to better understand their behavior inside the reactor coolant system in air or air/steam atmospheres. The tests consisted in vaporizing RuO₂ at 1200 °C and the ruthenium oxides are transported through a controlled thermal gradient tube made of quartz or pre-oxidized stainless steel. Results show that the major part up to 95% is deposited along the tube, the remaining part being transported almost under gaseous form attributed to RuO₄. Impact of carrier gas, temperature profile and nature of the tube are discussed.     

A theoretical kinetic study of the reactions of NH2 radicals with methanol and ethanol and their implications in kinetic modeling

Amino (NH₂) radicals play a central role in the pyrolysis and oxidation of ammonia. Several reports in the literature highlight the importance of the reactions of NH₂ radicals with fuel in NH₃-dual-fuel combustion. Therefore, we investigated the reactions of NH₂ radicals with methanol (CH₃OH) and ethanol (C₂H₅OH) theoretically. We explored the various reaction pathways by exploiting CCSD(T)/cc-pV(T, Q)Z//M06-2X/aug-cc-pVTZ level of theory. The reaction proceeds via complex formation at the entrance and exit channels in an overall exothermic process. We used canonical transition state theory to obtain the high-pressure limiting rate coefficients for various channels over the temperature range of 300–2000 K. We discerned the role of various channels in the potential energy surface (PES) of NH₂ + CH₃OH/C₂H₅OH reactions. For both reactions, the hydrogen abstraction pathway at the OH-site of alcohols plays a minor role in the entire T-range investigated. By including the title reactions into an extensive kinetic model, we demonstrated that the reaction of NH₂ radicals with alcohols plays a paramount role in accurately predicting the low-temperature oxidation kinetics of NH₃-alcohols dual fuel systems (e.g., shortening the ignition delay time). On the contrary, these reactions have negligible importance for high-temperature oxidation kinetics of NH₃-alcohol blends (e.g., not affecting the laminar flame speed). In addition, we calculated the rate coefficients for NH₂ + CH₄ = CH₃ + NH₃ reaction that are in excellent agreement with the experimental data.     

Past and present of electrochemical science in Hungary

Journal of Solid State Electrochemistry - The electrochemistry-related scientific activities in Hungary over the past 3 decades are reviewed. In the first section, we summarize those research areas...     

Resolvent splitting for sums of monotone operators with minimal lifting

Mathematical Programming - In this work, we study fixed point algorithms for finding a zero in the sum of $$nge 2$$ maximally monotone operators by using their resolvents. More precisely, we...     

Photocatalytic generation of a non-heme Fe(iii)-hydroperoxo species with O2 in water for the oxygen atom transfer reaction

Coupling a photoredox module and a bio-inspired non-heme model to activate O₂ for the oxygen atom transfer (OAT) reaction requires a vigorous investigation to shed light on the multiple competing electron transfer steps, charge accumulation and annihilation processes, and the activation of O₂ at the catalytic unit. We found that the efficient oxidative quenching mechanism between a [Ru(bpy)₃]²⁺ chromophore and a reversible electron mediator, methyl viologen (MV²⁺), to form the reducing species methyl viologen radical (MV˙⁺) can convey an electron to O₂ to form the superoxide radical and reset an Fe(iii) species in a catalytic cycle to the Fe(ii) state in an aqueous solution. The formation of the Fe(iii)-hydroperoxo (Fe^III–OOH) intermediate can evolve to a highly oxidized iron-oxo species to perform the OAT reaction to an alkene substrate. Such a strategy allows us to bypass the challenging task of charge accumulation at the molecular catalytic unit for the two-electron activation of O₂. The Fe^III–OOH catalytic precursor was trapped and characterized by EPR spectroscopy pertaining to a metal assisted catalysis. Importantly, we found that the substrate itself can act as an electron donor to reset the photooxidized chromophore in the initial state closing the photocatalytic loop and hence excluding the use of a sacrificial electron donor. Laser Flash Photolysis (LFP) studies and spectroscopic monitoring during photocatalysis lend credence to the proposed catalytic cycle.

A photoinduced iron(III)-hydroperoxo intermediate (Fe^III-OOH) was trapped by bypassing the charge accumulation process, that triggers the oxygen atom transfer reaction to an alkene with O₂ as sole oxygen source in water.     

Synthesis of Polyethylene Glycol–Chitosan–Nano Ag Composites and their Antibacterial Properties

Journal of Applied Spectroscopy - This study showed the synthesis of polyethylene glycol–chitosan–nano Ag (PEG–Chi–Ag) composites to improve the homogeneous distribution of...     

On the volumetric path

We consider the logarithmic and the volumetric barrier functions used in interior point methods. In the case of the logarithmic barrier function, the analytic center of a level set is the point at which the central path intersects that level set. We prove that this also holds for the volumetric path. For the central path, it is also true that the analytic center of the optimal level set is the limit point of the central path. The only known case where this last property for the logarithmic barrier function fails occurs in case of semidefinite optimization in the absence of strict complementarity. For the volumetric path, we show with an example that this property does not hold even for a linear optimization problem in canonical form.