Facile isolation of bisimines based on 3,3'-diaminobenzidine: direct access to unsymmetrical bimetallic salphen building blocks

Diimines obtained from 3,3'-diaminobenzidine and tert-butyl-substituted salicylaldehydes in MeOH can be readily isolated in 60-90% yield and were obtained as a mixture of geometrical isomers. Two distinct diimine intermediates (4 and 5) with a higher molecular symmetry as related to the other isomeric diimine products were both isolated by crystallization of which 5 was subsequently used to demonstrate that nonsymmetrical bis-salphen complexes with different functional groups and metal centers can be assembled via a three-component one-pot procedure.     

Heterobimetallic [Ru(II)/Fe(II)] complexes: On the formation of trans- and cis-[RuCl2(dppf)(diimines)]

The synthesis and characterization of trans/cis-[RuCl₂(dppf)(diimines)], dppf = 1,1′-bis(diphenylphosphino)ferrocene; diimines = 2,2′-bipyridine (trans/cis-(1)), the new complexes with 4,4′-dimethyl-2,2′-bipyridine (trans/cis-(2)) and 1,10-phenanthroline (cis-(3)) are presented. The complexes were synthesized using two routes and the trans/cis-isomer formation is dependent upon conditions and the precursor applied. The trans-isomer (kinetic) readily isomerizes to the cis-isomer (thermodynamic) when exposed to light (fluorescent) and this process was followed by cyclic voltammetry and UV-vis. The electrochemical studies on these complexes reveal that Fe^(III)/Fe^(II) couples are insensitive to the isomer (trans/cis) formed, but the Ru^(III)/Ru^(II) couples are dependent on the isomer. Transfer-hydrogenation reactions for reduction of acetophenone were conducted using complexes cis-(1) and cis-(2) and the results are compared with that obtained for similar complexes. X-ray structure for cis-(3) are presented and discussed.     

Gas-phase structure, rotational barrier, and vibrational properties of methyl methanethiosulfonate, CH3SO2SCH3: an experimental and computational study

The molecular structure of methyl methanethiosulfonate, CH3SO2SCH3, has been determined in the gas phase from electron-diffraction data supplemented by ab initio (HF, MP2) and density functional theory (DFT) calculations using 6-31G(d), 6-311++G(d,p), and 6-311G(3df,3pd) basis sets. Both experimental and theoretical data indicate that although both anti and gauche conformers are possible by rotating about the S-S bond, the preferred conformation is gauche. The barrier to internal rotation in the CSSC skeleton has been calculated using the RHF/6-31G(d), MP2/6-31G(d), and B3LYP/6-31G(d) methods as well as MP2 with a 6-31G(3df) basis set on sulfur and 6-31G(d) on C, H, and O. A 6-fold decomposition of the rotational barrier has been performed in terms of a Fourier-type expansion, enabling us to analyze the nature of the potential function, showing that the coefficients V1 and V2 are the dominant terms; V1 is associated with nonbonding interactions, and V2 is associated with hyperconjugative interactions. A natural bond orbital analysis showed that the lone pair --> sigma* hyperconjugative interactions favor the gauche conformation. Furthermore, the infrared spectra for the liquid and solid phases and the Raman spectrum for the liquid have been recorded, and the observed bands have been assigned to the vibrational normal modes. The experimental vibrational data, along with calculated theoretical force constants, were used to define a scaled quantum mechanical force field for the target system that enabled us to estimate the measured frequencies with a final root-mean-square deviation of 6 cm-1.     

Glucose oxidation reaction at palladium-carbon nano-onions in alkaline media

Journal of Solid State Electrochemistry - The glucose oxidation reaction, at Pd on unsupported carbon nano-onions (Pd/CNOs), has been studied by using physical and electrochemical characterization...     

New insights about the electrochemical production of ozone

Ozone is a rather attractive oxidant, it is very efficient in the oxidation of pollutants and in the killing of pathogens and does not generate any hazardous waste during its use. Its generation has been constantly sought in an effective way, focusing on obtaining high concentrations of ozone at the lowest possible cost. Recently, electrochemical production of ozone show advantages over conventional corona discharge generation, since this technology do not need very high voltages, feeding oxygen or pure air or dissolving the ozone into wastewater to be treated. However, it is still at early development stage and there is still a long way to reach the high technology readiness levels needed to complete its value chain. Equipment considerations and operation conditions are the key points that need to be understood in order to increase efficiently. Recent novelties in the state of the art of research are summarized in this work.     

Unraveling the Bonding Nature Along the Photochemically Activated Paterno-Büchi Reaction Mechanism

The photochemically activated Paterno-Büchi reaction mechanism following the singlet excited-state reaction path was analyzed based on a bonding evolution framework. The electronic rearrangements, which describe the mechanism of oxetane formation via carbon-oxygen attack (C−O), comprises of the electronic activation of formaldehyde and accumulation of pairing density on the O once the reaction system is approaching the conical intersection point. Our theoretical evidence based on the ELF topology shows that the C−O bond is formed in the ground-state surface (via C−O attack) returning from the S₁ surface accompanied by 1,4-singlet diradical formation. Subsequently, the reaction center is fully activated near the transition state (TS), and the ring-closure (yielding oxetane) involves the C−C bond formation after the TS. For the carbon-carbon attack (C−C), both reactants (formaldehyde and ethylene) are activated, leading to C−C bond formation in the S₁ excited state before reaching the conical intersection region. Finally, the C−O formation occurs in the ground-state surface, resulting from the pair density flowing primarily from the C to O atom.     

A Bibliometric Evaluation of the Top 100 Cited Dimethyl Fumarate Articles

Dimethyl fumarate is a cytoprotective and immunomodulatory drug used in the treatment of multiple sclerosis. We performed a bibliometric study examining the characteristics and trends of the top 100 cited articles that include dimethyl fumarate in the title. On 21 September 2020 we carried out an electronic search in the Web of Science (WOS), seeking articles that include the following terms within the title: dimethyl fumarate, BG-12, or Tecfidera. To focus our investigation on original research, we refined the search to include only articles, early access, others, case report, and clinical trials. We obtained a total of 1115 items, which were cited 7169 times, had a citation density of 6.43 citations/item, and an h-index of 40. Around 2010, there was a jump in the number of published articles per year, rising from 5 articles/year up to 12 articles/year. We sorted all the items by the number of citations and selected the top 100 most cited (T100). The T100 had 4164 citations, with a density of 37 citations/year and contained 16 classic research articles. They were published between 1961 and 2018; the years 2010–2018 amassed nearly 80% of the T100. We noted 17 research areas with articles in the T100. Of these, the number one ranking went to neurosciences/neurology with 39 articles, and chemistry ranked second on the T100 list with 14 items. We noticed that the percentage of articles belonging to different journals changed depending on the time period. Chemistry held the highest number of papers during 1961–2000, while pharmacology andneurosciences/neurology led the 2001–2018 interval. A total of 478 authors from 145 institutions and 25 countries were included in the T100 ranking. The paper by Gold R et al. was the most successful with 14 articles, 1.823 citations and a density of 140.23 citations/year. The biotechnological company Biogen led the T100 list with 20 articles. With 59 published articles, the USA was the leading country in publications. We concluded that this study analyzed the use of and research on dimethyl fumarate from a different perspective, which will allow the readership (expert or not) to understand the relevance of classic and recent literature on this topic.     

A modified Leslie–Gower predator–prey model with ratio‐dependent functional response and alternative food for the predator

In this work, a modified Leslie–Gower predator–prey model is analyzed, considering an alternative food for the predator and a ratio‐dependent functional response to express the species interaction. The system is well defined in the entire first quadrant except at the origin ( 0 , 0 ) . Given the importance of the origin ( 0 , 0 ) as it represents the extinction of both populations, it is convenient to provide a continuous extension of the system to the origin. By changing variables and a time rescaling, we obtain a polynomial differential equations system, which is topologically equivalent to the original one, obtaining that the non‐hyperbolic equilibrium point ( 0 , 0 ) in the new system is a repellor for all parameter values. Therefore, our novel model presents a remarkable difference with other models using ratio‐dependent functional response. We establish conditions on the parameter values for the existence of up to two positive equilibrium points; when this happen, one of them is always a hyperbolic saddle point, and the other can be either an attractor or a repellor surrounded by at least one limit cycle. We also show the existence of a separatrix curve dividing the behavior of the trajectories in the phase plane. Moreover, we establish parameter sets for which a homoclinic curve exits, and we show the existence of saddle‐node bifurcation, Hopf bifurcation, Bogdanov–Takens bifurcation, and homoclinic bifurcation. An important feature in this model is that the prey population can go to extinction; meanwhile, population of predators can survive because of the consumption of alternative food in the absence of prey. In addition, the prey population can attain their carrying capacity level when predators go to extinction. We demonstrate that the solutions are non‐negatives and bounded (dissipativity and permanence of population in many other works). Furthermore, some simulations to reinforce our mathematical results are shown, and we further discuss their ecological meanings. Copyright © 2017 John Wiley & Sons, Ltd.     

On a New Class of Abstract Neutral Integro-Differential Equations and Applications

In this paper we introduce a new class of abstract integro-differential equations with delay and we study the existence of strict solutions. An application involving the heat equation with memory is presented.     

Adaptive control of local errors for elliptic problems using weighted Sobolev norms

We develop an a posteriori error estimator which focuses on the local H¹ error on a region of interest. The estimator bounds a weighted Sobolev norm of the error and is efficient up to oscillation terms. The new idea is very simple and applies to a large class of problems. An adaptive method guided by this estimator is implemented and compared to other local estimators, showing an excellent performance. © 2016 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 33: 1266–1282, 2017