Existence and Blow-up for a Parabolic System from?Combustion Theory

We study the stability of the Solid Fuel Model, which represents a thermal reaction of a solid material. This model corresponds to a nonlinear eigenvalue problem of two strongly coupled nonlinear reaction–diffusion equations, with different boundary conditions on each unknown. We obtain a strong bifurcation criterion for the steady problem and estimates for the blow-up time in the unsteady case. In addition, numerical solutions of both the steady and unsteady problem are presented to illustrate the results.     

π-dimerization of pleiadiene radical cations at low temperatures revealed by UV–vis spectroelectrochemistry and quantum theory

One-electron oxidation of the non-alternant polycyclic aromatic hydrocarbon pleiadiene and related cyclohepta[c,d]pyrene and cyclohepta[c,d]fluoranthene in THF produces corresponding radical cations detectable in the temperature range of 293–263 K only on the subsecond time scale of cyclic voltammetry. Although the EPR-active red-coloured pleiadiene radical cation is stable according to the literature in concentrated sulfuric acid, spectroelectrochemical measurements reported in this study provide convincing evidence for its facile conversion into the green-coloured, formally closed shell and, hence, EPR-silent π-bound dimer dication stable in THF at 253 K. The unexpected formation of the thermally unstable dimeric product featuring a characteristic intense low-energy absorption band at 673 nm (1.84 eV; logε _max = 4.0) is substantiated by ab initio calculations on the parent pleiadiene molecule and the PF₆⁻ salts of the corresponding radical cation and dimer dication. The latter is stabilized with respect to the radical cation by 14.40 kcal mol⁻¹ (DFT B3LYP) [37.64 kcal mol⁻¹ (CASPT2/DFT B3LYP)]. An excellent match has been obtained between the experimental and TD-DFT-calculated UV–vis spectra of the PF₆⁻ salt of the pleiadiene dimer dication, considering solvent (THF) effects.     

Transport properties of graphite/epoxy composites: Thermal, permeability and dielectric characterization

In this study nanocomposites were prepared by dispersing three different grades of graphite particles, expanded graphite, commercial graphene nanoplatelets and natural graphite, in a commercial epoxy matrix. Dielectric properties, thermal conductivity and permeability to oxygen of the composites were studied and compared to those of the unfilled epoxy matrix. An increase of all properties is obtained using expanded graphite, suggesting the presence of a good dispersion of the filler in the matrix and a strong polar interactions of the filler with the matrix, attributed to the partially oxidised surfaces of the expanded graphite. All the measured transport properties were fitted with simple mathematical models obtaining good agreement between the experimental results and theoretical predictions. The model parameters were related to the aspect ratio of the filler, defined as the ratio between the in-plane average dimension and the thickness of the reinforcement. An aspect ratio between 1250 and 1550 indicates that graphite thin platelets (or graphene stacks), characterized by a thickness of the order of a few tens of nanometers, were dispersed in the epoxy matrix.     

Regioselective Acylations of Aldono-1,4-lactones

Abstract

Partial benzoylation or pivaloylation of D-gulono-l,4-lactone (1) with 3.3-3.6 molar equivalents of the acyl chloride afforded 2,5,6-tri-O-benzoyl- (3) or 2,5,6-tri-O-pivaloyl-D-gulono-1,4-lactone (5), which were isolated crystalline from the reaction mixture in yields of 54% and 84.5 %, respectively. Similarly, partial pivaloylation of L-mannono-1,4-lactone (6) gave crystalline 2,5,6-tri-O-pivaloyl-L-mannono-l,4-lactone (9) in 50% yield. Under the same conditions of acylation, D-galactono-l,4-lactone (11) gave a mixture of products, which were separated by column chromatography. On benzoylation, 2,3,5,6-tetra-O-benzoyl- (12); 2,5,6-tri-O-benzoyl- (13); 2,3,6-tri-O-benzoyl- (14) and 2,6-di-O-benzoyl-D-galactono-l,4-lactone (15) were obtained in 47%, 16.4%, 8%, and 14% yield, respectively. Pivaloylation of 11 afforded 2,3,5,6-tetra-O-pivaloyl- (16), 2,5,6-tri-O-pivaloyl- (17), 2,3,6-tri-O-pivaloyl (18) and 2,6-di-O-pivaloyl-D-galactono-l,4-lactone (19) in 21.6%, 9.7%, 2.6%, and 30.0%, respectively.     

Synthetic Utility of α-Stannyl α,β-Unsaturated Esters as Reagents for β-Substituted Acrylate α-Anion Synthons: Tin-Lithium Exchange and Palladium-Catalized Coupling Reactions

The tin-lithium exchange and the palladium-catalized coupling reactions of the title compounds have been studied. The latter reaction was found to be more efficient for functionalizing the α-carbon of these esters.     

Well-defined air-stable palladium HASPO complexes for efficient Kumada-Corriu cross-couplings of (hetero)aryl or alkenyl tosylates

Palladium complexes of representative heteroatom-substituted secondary phosphine oxide (HASPO) preligands were synthesized and fully characterized, including X-ray crystal structure analysis. Importantly, these well-defined complexes served as highly efficient catalysts for Kumada-Corriu cross-coupling reactions of aryl, alkenyl, and even heteroaryl tosylates. Particularly, an air-stable catalyst derived from inexpensive PinP(O)H displayed a remarkably high catalytic efficacy, which resulted in cross-couplings at low catalyst loadings under exceedingly mild reaction conditions with ample scope.     

Resolving the EPR Spectra in the Cytochrome bc 1 Complex from Saccharomyces cerevisiae

Quinone molecules are ubiquitous in living organisms. They are found either within the lipid phase of the biological membrane (quinone pool) or are bound in specific binding sites within membrane-bound protein complexes. The biological function of such bound quinones is determined by their ability to be reduced and/or oxidized in two successive one-electron steps. As a result, quinones are involved as one- or two-electron donors or acceptors in a large number of biological electron-transfer steps occurring during respiratory or photosynthetic processes. The intermediate formed by a one-electron reduction step is a semiquinone, which is paramagnetic and can be studied by electron paramagnetic resonance (EPR) spectroscopy. Detailed studies of such states can provide important structural information on these intermediates in such electron-transfer processes. In this study, we focus on the redox-active ubiquinone-6 of the yeast cytochrome bc ₁ complex (QCR, ubiquinol: cytochrome c oxidoreductase) from Saccharomyces cerevisiae at the so-called Q_i site. Although the location of the Q_i binding pocket is quite well known, details about its exact binding are less clear. Currently, three different X-ray crystallographic studies suggest three different binding geometries for Q_i. Recent studies in the bacterial system (Rhodobacter sphaeroides) have suggested a direct coordination to histidine as proposed in the chicken heart crystal structure model. Using the yeast system we apply EPR and especially relaxation filtered hyperfine (REFINE) spectroscopy to study the Q_i binding site. ¹⁴N-electron spin-echo envelope modulation spectroscopy together with an inversion-recovery filter (REFINE) is applied to resolve the question of whether ¹⁴N modulations arise from interactions to Q _i ^·? or to the Rieske iron–sulphur center. These results are discussed with regard to the location and potential function of Q_i in the enzyme.     

CUPID-0: the first array of enriched scintillating bolometers for 0$$\nu \beta \beta $$ decay investigations

The CUPID-0 detector hosted at the Laboratori Nazionali del Gran Sasso, Italy, is the first large array of enriched scintillating cryogenic detectors for the investigation of \(^{82}\)Se neutrinoless double-beta decay (\(0\nu \beta \beta \)). CUPID-0 aims at measuring a background index in the region of interest (RoI) for \(0\nu \beta \beta \) at the level of 10\(^{-3}\) counts/(keV kg years), the lowest value ever measured using cryogenic detectors. CUPID-0 operates an array of Zn\(^{82}\)Se scintillating bolometers coupled with bolometric light detectors, with a state of the art technology for background suppression and thorough protocols and procedures for the detector preparation and construction. In this paper, the different phases of the detector design and construction will be presented, from the material selection (for the absorber production) to the new and innovative detector structure. The successful construction of the detector lead to promising preliminary detector performance which is discussed here.     

Modeling and Simulation of an Energy Integrated Distillation Column in a Bond Graph Approach

The bond graph methodology for modelling an integrated energy distillation column is applied in this paper. The distillation column is built by five trays for a binary mixture. However, due to its modular construction in a bond graph, the number of trays can be increased. In order to link the analysis tools of systems modeled in the bond graph to the mathematical model given to a distillation column, a junction structure of the proposed bond graph is presented. Hence, this junction structure is a way to obtain the state space representation of the modeled column in bond graphs. Likewise, it is well known that distillation columns determine a class of nonlinear systems, so throughout this paper, these systems in a bond graph approach can be analyzed. In order to learn the behavior of the distillation column in the physical domain, simulation results using 20-Sim software are shown. In addition, with the simulation of two case studies consisting of two mixtures with different relative volatilities, the versatility of the column model in a bond graph is presented. In both cases, the increase in the feed flow, the mole fraction of the light component in the feed or the distillate reflux that enriches the concentration of light in the column determine an increase in the mole fraction of light in the distillate and in the bottom reflow. Further, the control design for a distillation column in the physical domain can be extended.     

Electroanalytical performance of a Bismuth/Antimony composite glassy carbon electrode in detecting lead and cadmium

This work reports on the electroanalytical performance of a glassy carbon electrode (GCE) modified with antimony and bismuth (Sb/Bi-GCE) in detecting heavy metal ions using lead and cadmium as model analytes. The electroanalytical performance of the Sb/Bi-GCE surface was compared to the bismuth modified glassy carbon electrode (Bi-GCE) as well as the antimony modified glassy carbon electrode (Sb-GCE). The Sb/Bi-GCE exhibited excellent figures of merit compared to Bi-GCE and Sb-GCE surfaces. For example, the limit of detection for lead was 0.01 ppb using Sb/Bi-GCE and 0.1 and 1 ppb on Bi-GCE and Sb-GCE, respectively.