Selective Synthesis of 2,5‐Diformylfuran by Sustainable 4‐acetamido‐TEMPO/Halogen‐Mediated Electrooxidation of 5‐Hydroxymethylfurfural

A new method was developed for the selective gram‐scale synthesis of 2,5‐diformylfuran (DFF), which is an important chemical with a high application potential, via oxidation of biomass‐derived 5‐hydroxylmethylfurfural (HMF) catalyzed by 4‐acetylamino‐2,2,6,6‐tetramethylpiperidine‐1‐oxyl (4‐AcNH‐TEMPO) in a two‐phase system consisting of a methylene chloride and aqueous solution containing sodium hydrogen carbonate and potassium iodide. The key feature of this method is the generation of the I₂ (co‐)oxidant by anodic oxidation of iodide anions during pulse electrolysis. In addition, the electrolyte can be successfully recycled five times while maintaining a 62–65 % yield of DFF. This novel method provides a sustainable pathway for waste‐free production of DFF without the use of metal catalysts and expensive oxidants. An advantage of electrooxidation is utilized in the preparation of demanding chemical.     

The anomalous spectral dependence of polarization in comets

We have found an anomalous (negative) spectral dependence of polarization for split comet 73P/Schwassmann–Wachmann 3, i.e. polarization degree in the I filter is systematically less (4%) than that in the R filter for both B and C subnuclei of the comet. Earlier we revealed a similar effect for comets 21P/Giacobini–Zinner, C/1999 S4 (LINEAR), and 9P/Tempel 1. Together with comet C/1989 X1 (Austin), for which the similar spectral dependence of polarization was also observed, these comets form a group characterized by some peculiar properties of their dust. Since atypical organic composition is a characteristic feature for all these comets, the anomalous spectral dependence of polarization may indicate specifics of origin of these comets. Really, most of these comets (but not all) originated from the Kuiper Belt. Also, most (but not all) of these comets belong to the group of comets depleted in carbon species in the gas phase, which is typical for comets formed in the giant-planet area of the solar system. On the other hand, all of the comets with negative spectral gradient of polarization have the dust dominated by large particles and most of them belong to the Jupiter family. This may indicate that anomalous spectral dependence of their polarization is a result of their evolution. To identify the reason of anomalous polarization, systematic spectropolarimetric observations of Jupiter-family comets are necessary.     

Redox-Active Supramolecular Heteroleptic M4L2L′2 Assemblies with Tunable Interior Binding Site

Three Pt₄L₂L′₂ heteroleptic rectangles ( 1 – 3 ), containing ditopic redox-active bis-pyridine functionalized perylene bisimide (PBI) ligands PBI-pyr₂ ( L ) are reported. Co-ligand L′ is a dicarboxylate spacer of varying length, leading to modified overall size of the assemblies. ¹H NMR spectroscopy reveals a trend in the splitting and upfield chemical shift of the PBI-hydrogens in the rectangles with respect to free PBI, most pronounced with the largest strut length ( 3 ) and least with the smallest strut length ( 1 ). This is attributed to increased rotational freedom of the PBI-pyr ₂ ligand over its longitudinal axis (N_py-N_py), due to increased distance between the PBI-surfaces, which is corroborated by VT-NMR measurements and DFT calculations. The intramolecular motion entails desymmetrization of the two PBI-ligands, in line with cyclic voltammetry (CV) data. The first (overall two-electron) reduction event and re-oxidation for 1 display a subtle peak-to-peak splitting of 60 mV, whilst increased splitting of this event is observed for 2 and 3 . The binding of pyrene in 1 is probed to establish proof of concept of host-guest chemistry enabled by the two PBI-motifs. Fitting the binding curve obtained by ¹H NMR titration with a 1:1 complex formation model led to a binding constant of 964±55 m ⁻¹. Pyrene binding is shown to directly influence the redox-chemistry of 1 , resulting in a cathodic and anodic shift of approximately 46 mV on the first and second reduction event, respectively.     

Classification of finite groups according to the number of conjugacy classes II

In the following,G denotes a finite group,r(G) the number of conjugacy classes ofG, β(G) the number of minimal normal subgroups ofG andα(G) the number of conjugate classes ofG not contained in the socleS(G). Let Φ _j = {G|β(G) =r(G) −j}. In this paper, the family Φ₁₁ is classified. In addition, from a simple inspection of the groups withr(G) =b conjugate classes that appear in ϒ _j ^=1/11 Φ _j , we obtain all finite groups satisfying one of the following conditions: (1)r(G) = 12; (2)r(G) = 13 andβ(G) > 1; …; (9)r(G) = 20 andβ(G) > 8; (10)r(G) =n andβ(G) =n −a with 1 ≦a ≦ 11, for each integern ≧ 21. Also, we obtain all finite groupsG with 13 ≦r(G) ≦ 20,β(G) ≦r(G) − 12, and satisfying one of the following conditions: (i) 0 ≦α(G) ≦ 4; (ii) 5 ≦α(G) ≦ 10 andS(G) solvable.     

Gompertz zero-inflated cure rate regression models applied to credit risk data

In the financial market, it is important to consider that there is a proportion of customers that have settled their debt in time zero, immediately recovering their ability to pay. In this context, in this paper, we propose a survival analysis methodology that allows the insertion of times equal to zero in scenarios where credit risk is observed. The proposed model addresses the survival analysis model of the zero-inflated cure rate which incorporates the heterogeneity of three subgroups (individuals having events in the initial time, and individuals not susceptible and susceptible to the event). In our proposal, all available survival data of customers are modeled considering that the number of competitive causes follows a Poisson distribution and the baseline risk function follows a Gompertz distribution. The model parameter estimation is obtained by the maximum likelihood estimation procedure and simulation studies are conducted to evaluate the estimators' performance. The studied methodology will be applied to a credit database provided by a financial institution in Brazil.     

Structural and Thermodynamic Peculiarities of Core-Shell Particles at Fluid Interfaces from Triangular Lattice Models

A triangular lattice model for pattern formation by core-shell particles at fluid interfaces is introduced and studied for the particle to core diameter ratio equal to 3. Repulsion for overlapping shells and attraction at larger distances due to capillary forces are assumed. Ground states and thermodynamic properties are determined analytically and by Monte Carlo simulations for soft outer- and stiffer inner shells, with different decay rates of the interparticle repulsion. We find that thermodynamic properties are qualitatively the same for slow and for fast decay of the repulsive potential, but the ordered phases are stable for temperature ranges, depending strongly on the shape of the repulsive potential. More importantly, there are two types of patterns formed for fixed chemical potential—one for a slow and another one for a fast decay of the repulsion at small distances. In the first case, two different patterns—for example clusters or stripes—occur with the same probability for some range of the chemical potential. For a fixed concentration, an interface is formed between two ordered phases with the closest concentration, and the surface tension takes the same value for all stable interfaces. In the case of degeneracy, a stable interface cannot be formed for one out of four combinations of the coexisting phases, because of a larger surface tension. Our results show that by tuning the architecture of a thick polymeric shell, many different patterns can be obtained for a sufficiently low temperature.     

Stabilization of mixture of two rigid solids modeling temperature and porosity

In this paper we investigate the asymptotic behavior of solutions to the initial boundary value problem for a mixture of two rigid solids modeling temperature and porosity. Our main result is to establish conditions which ensure the analyticity and the exponential stability of the corresponding semigroup.     

On coderivatives and Lipschitzian properties of the dual pair in optimization

In this paper, we apply the concept of coderivative and other tools from the generalized differentiation theory for set-valued mappings to study the stability of the feasible sets of both the primal and the dual problem in infinite-dimensional linear optimization with infinitely many explicit constraints and an additional conic constraint. After providing some specific duality results for our dual pair, we study the Lipschitz-like property of both mappings and also give bounds for the associated Lipschitz moduli. The situation for the dual shows much more involved than the case of the primal problem.