Equilibrium Formation of Stable All‐Silicon Versions of 1,3‐Cyclobutanediyl

Main group analogues of cyclobutane‐1,3‐diyls are fascinating due to their unique reactivity and electronic properties. So far only heteronuclear examples have been isolated. Here we report the isolation and characterization of all‐silicon 1,3‐cyclobutanediyls as stable closed‐shell singlet species from the reversible reactions of cyclotrisilene c‐Si₃Tip₄ (Tip=2,4,6‐triisopropylphenyl) with the N‐heterocyclic silylenes c‐[(CR₂CH₂)(NtBu)₂]Si: (R=H or methyl) with saturated backbones. At elevated temperatures, tetrasilacyclobutenes are obtained from these equilibrium mixtures. The corresponding reaction with the unsaturated N‐heterocyclic silylene c‐(CH)₂(NtBu)₂Si: proceeds directly to the corresponding tetrasilacyclobutene without detection of the assumed 1,3‐cyclobutanediyl intermediate.     

Almost periodic sets and subactions in topological dynamics

Let be a group with subgroup . We show, under certain conditions, that an almost periodic point for the action of is also almost periodic for . This is applied to obtain a theorem of Glasner.

     

The properties of the new Mn(II)–Co(II)–Mn(II)-type hetero-trinuclear oxime metal complexes with N4 and N4O2 ligands

1,3- and 1,2-calix[4]crown-7 and calix[4]crown-9 cone conformers were synthesized in acceptable yields by sequential introduction of two distal or proximal polyethylene glycolic chains with terminal hydroxyls at the lower rim, monotosylation, and intramolecular ring closure reaction. According to the two-phase extraction experiment, the title compounds showed mediocre affinity for alkali and alkaline earth metal picrates. The 1,2-calix[4]crown-9 extracted Sr²⁺ selectively among other alkaline earth metal cations.     

Time-Dependent Shape Factors for Uniform and Non-Uniform Pressure Boundary Conditions

Matrix–fracture transfer functions are the backbone of any dual-porosity or dual-permeability formulation. The chief feature within them is the accurate definition of shape factors. To date, there is no completely accepted formulation of a matrix–fracture transfer function. Many formulations of shape factors for instantly-filled fractures with uniform pressure distribution have been presented and used; however, they differ by up to five times in magnitude. Based on a recently presented transfer function, time-dependent shape factors for water imbibing from fracture to matrix under pressure driven flow are proposed. Also new matrix–fracture transfer pressure-based shape factors for instantly-filled fractures with non-uniform pressure distribution are presented in this article. These are the boundary conditions for a case for porous media with clusters of parallel and disconnected fractures, for instance. These new pressure-based shape factors were obtained by solving the pressure diffusivity equation for a single phase using non-uniform boundary conditions. This leads to time-dependent shape factors because of the transient part of the solution for pressure. However, approximating the solution with an exponential function, one obtains constant shape factors that can be easily implemented in current dual-porosity reservoir simulators. The approximate shape factors provide good results for systems where the transient behavior of pressure is short (a case commonly encountered in fractured reservoirs).     

Planning and approximation models for delivery route based services with price-sensitive demands

Classical vehicle routing problems typically do not consider the impact of delivery price on the demand for delivery services. Existing models seek the minimum sum of tour lengths in order to serve the demands of a given set of customers. This paper proposes approximation models to estimate the impacts of price on delivery services when demand for delivery service is price dependent. Such models can serve as useful tools in the planning phase for delivery service providers and can assist in understanding the economics of delivery services. These models seek to maximize profit from delivery service, where price determines demand for deliveries as well as the total revenue generated by satisfying demand. We consider a variant of the model in which each customer’s delivery volume is price sensitive, as well as the case in which customer delivery volumes are fixed, but the total number of customers who select the delivery service provider is price sensitive. A third model variant allows the delivery service provider to select a subset of delivery requests at the offered price in order to maximize profit.     

Interaction of zones of flow separation in a centrifugal impeller-stationary vane system

In a radial flow pump operating in off-design conditions, regions of stall can exist on the rotating impeller blade and on the downstream diffuser blade, vane or tongue. Interaction of these stall zones can generate complex patterns of vorticity concentrations. In turn, these vorticity concentrations are related to sources of unsteady stagnation enthalpy. The form of these patterns is strongly dependent on the instantaneous location of the impeller trailing-edge relative to the leading-edge of the vane.Comparison of instantaneous with ensemble-averaged images shows that the flow structure in the gap region between the impeller and the vane is highly repetitive. Away from this region, in particular in the separated shear layer from the vane, the nonrepetitive nature of the vorticity field is manifested in substantial reduction of peak levels of vorticity in the ensemble-averaged image, relative to the instantaneous image.The three-dimensional flow structure resulting from these separation zone interactions was characterized via end views of the flow patterns. Particularly pronounced concentrations of vorticity can occur in this plane. They tend to be located in the shear layer at the outer edge of the large-scale separation zone. These vorticity concentrations are, however, highly non-stationary for successive passages of the impeller blade. Ensemble-averaging reveals that they persist primarily on the endwalls of the diffuser.The authors are grateful to the Office of Naval Research for support of this research program     

Solvent,substituent, and dimerization effects on the ring-opening mechanisms of monosilacyclopropylidenoids: a theoretical study

Density functional theory and ab initio computations elucidated the ring-opening of substituted (R = –CF₃, –CN, –CH₃, –H, –NH₂, –OCH₃, –OH, –SiH₃) 1-bromo–1-lithiosilirane 1 and 2-bromo–2-lithiosilirane 2 to LiBr complexes of 2-silaallene and 1-silaallene, respectively. Formally, two competitive pathways can be considered. The ring-opening reaction can take place through a concerted manner via TS3. Alternatively, the reaction may proceed in a stepwise fashion with the intermediacy of a free silacyclopropylidene–LiBr complex 7. In both cases, the position of the substituents determines the kinetic of the reactions. The structures with an electron-donating group are generally unstable, whereas the silacyclopropylidenoids bearing electron-withdrawing substituents are particularly stable species. Here, we propose the ring-opening of 5a–h to corresponding LiBr complexes of 2-silaallenes can proceed in both concerted and stepwise mechanism except for –H, –CH₃, and –SiH₃. The obtained activation energies for the ring-openings of 5a–h to related 2-silaallenes are too high for a reaction at room temperature with up to 61.4 kcal/mol. In contrast, the activation energy barriers for the isomerization of 6a–h to the LiBr complexes of 1-silaallenes was determined to be relatively low at the B3LYP/6-31+G(d,p), M06/6-31+G(d,p), and MP2/6-31+G(d,p) levels. Moreover, we have also investigated the solvent effect on the unsubstituted models using both implicit and explicit solvation models. The energy barriers of the solvated models are found to be slightly higher than the results of gas phase calculations. Additionally, the ring-opening of dimer 6 (6–Dim) is also calculated for the ring-opening mechanism with the energy barrier of 3.7 kcal/mol at B3LYP/6-31+G(d,p) level of theory.     

Novel hybrid process for the conversion of microcrystalline cellulose to value-added chemicals: part 2: effect of constant voltage on product selectivity

In this study, electrochemical degradation of microcrystalline cellulose (MCC) under hot-compressed water was investigated via application of constant voltage on reaction medium. Constant voltage ranges from 2.5 to 8.0 V was applied between anode (Titanium) and cathode (reactor wall). As an electrolyte and proton source 5–25 mM of H₂SO₄ was used. Reactions were carried out in a specially designed batch reactor (450 mL) made of T316 for 240 min at temperature of 200 °C.MCC decomposition products such as glucose, fructose, furfural, 5-HMF and levulinic acid were detected and quantified by High Performance Liquid Chromatography (HPLC). In the absence of electrolyte, applied voltage (2.5 and 4.0 V) decreased the total organic carbon (TOC) yield, in contrast at 8.0 V, TOC yield increased to 13%. Application of 8.0 V in hydrothermal conditions alter MCC decomposition pathway selectively to furfural (15%). Addition of electrolyte (5 mM, H₂SO₄) and application of 2.5 V potential increased TOC (54%) and changed the decomposition pathway in favor of 5-HMF (30%) and levulinic acid (21%). The structural changes in solid residues of electrochemically reacted MCC was analyzed by Fourier Transform Infrared Spectroscopy (FTIR) and found that MCC particles functionalized by carboxylic acid and sulfonated groups by the application of constant voltage to reaction medium. In the presence of electrolyte, under certain voltage (2.5 V), functionalization of solid particles became more obvious in FTIR spectrum results. Therefore, change in the selectivity values of degradation products were conducted with the functionalization of MCC particles due to applied voltage under sub-critical conditions.