Exploring the Limits of Frustrated Lewis Pair Chemistry with Alkynes: Detection of a System that Favors 1,1‐Carboboration over Cooperative 1,2‐P/B‐Addition

The zirconocene complex [{(C₆F₅)₂B‐(CH₂)₃‐Cp}(Cp‐PtBu₂)ZrCl₂] ( 6 ; Cp=cyclo‐C₅H₄) was prepared by hydroboration of [(allyl‐Cp)(Cp‐PtBu₂)ZrCl₂] ( 5 ) with HB(C₆F₅)₂ (“Piers’ borane”). It represents a frustrated Lewis pair (FLP) in which both the Lewis acid and the Lewis base were attached at the metallocene framework. Its reaction with 1‐pentyne did not result in the 1,2‐addition of or deprotonation reaction by the FLP, but rather in the 1,1‐carboboration of the triple bond, thereby obtaining a Z/E mixture (1.2:1) of the respective organometallic substituted alkenes 7 . The analogous reaction of 1‐pentyne with the phosphorous‐free system [{(C₆F₅)₂B‐(CH₂)₃‐Cp)}CpZrCl₂] ( 9 ) gave the respective 1,1‐carboboration products ( Z‐10 / E‐10 ≈1.3:1).     

Sheet structure of an L,D-dipeptide aggregate: inclusion compounds of (S)-phenylglycyl-(R)-phenylglycine with amides

A simple dipeptide, (S)-phenylglycyl-(R)-phenylglycine (S,R-1), formed inclusion compounds with a small amide such as formamide, acetamide, N,N-dimethylformamide (DMF), or N,N-dimethylacetamide. By single-crystal X-ray analysis, the inclusion compounds were shown to have a wavy layer structure. The molecules of S,R-1 are arranged in parallel via ionic pairing of the carboxyl and amino groups to construct the wavy layers. The guest molecules were accommodated in a channel cavity between the layers by means of hydrogen bonding with (+)NH(3) of S,R-1. The cavity is surrounded by the phenyl groups of S,R-1 that conformationally rotate so as to make the cavity size fit the guest amide.     

Thermophysical and heat transfer properties of phase change material candidate for waste heat transportation system

A waste heat transportation system––trans-heat (TH) system––is quite attractive that uses the latent heat of a phase change material (PCM). The purpose of this paper is to study the thermophysical properties of various sugars and sodium acetate trihydrate (SAT) as PCMs for a practical TH system and the heat transfer property between PCM selected and heat transfer oil, by using differential scanning calorimetry (DSC), thermogravimetry-differential thermal analysis (TG-DTA) and a heat storage tube. As a result, erythritol, with a large latent heat of 344 kJ/kg at melting point of 117°C, high decomposition point of 160°C and excellent chemical stability under repeated phase change cycles was found to be the best PCM among them for the practical TH system. In the heat release experiments between liquid erythritol and flowing cold oil, we observed foaming phenomena of encapsulated oil, in which oil droplet was coated by solidification of PCM.     

Recognition of Amphiphiles with Many Pendent Galactose Residues byRicinus communisAgglutinin

Amphiphiles which carry many pendent galactose residues as side chains were prepared by telomerization of 2-methacryloyloxyethyl β-D-galactopyranoside (MEGal) or 3-(2-methacryloyl aminoethylthio)propylD-galactopyranoside (MEPGal, α:β = 3.9:1) using a lipophilic radical initiator. The galactose-carrying amphiphiles (DP (degree of polymerization) = 15) incorporated in liposomes were recognized by a lectin fromRicinus communis(RCA₁₂₀), which was proven by the increase in turbidity of the liposome suspension after mixing with the lectin. The recognition was largely affected by the distance between the galactose residues and the polymer main chain, and the surface density of the amphiphile in the liposomes. The liposomes containing these galactolipids were not taken up by mouse peritoneal macrophages, probably due to a steric hindrance of polymer main chains from the uptake of D-galactose receptors on the macrophages.     

Image analysis of the spatial distribution of paramagnetic Pr3+ ions in a polymer gel by a 1H-chemical shift NMR imaging method

¹H-chemical shift NMR imaging patterns of a poly(methacrylic acid) gel containing water with paramagnetic praseodymium ions(Pr³⁺) were successfully observed, in order to elucidate spatial distribution of Pr³⁺ ions in the gel. The ¹H chemical shift of water associated with Pr³⁺ ions in the gel moves largely downfield. By analyzing these experimental results, the immersion process of Pr³⁺ ions into the network of the polymer gel was spatially clarified. Further, it is shown that the chemical shift NMR imaging method is a useful means for determining the spatial distribution of paramagnetic metal ions in polymer gels.     

The Exergy Losses Analysis in Adiabatic Combustion Systems including the Exhaust Gas Exergy

The entropy generation analysis of adiabatic combustion systems was performed to quantify the exergy losses which are mainly the exergy destroyed during combustion inside the chamber and in the exhaust gases. The purpose of the present work was therefore: (a) to extend the exergy destruction analysis by including the exhaust gas exergy while applying the hybrid filtered Eulerian stochastic field (ESF) method coupled with the FGM chemistry tabulation strategy; (b) to introduce a novel method for evaluating the exergy content of exhaust gases; and (c) to highlight a link between exhaust gas exergy and combustion emissions. In this work, the adiabatic Sandia flames E and F were chosen as application combustion systems. First, the numerical results of the flow and scalar fields were validated by comparison with the experimental data. The under-utilization of eight stochastic fields (SFs), the flow field results and the associated scalar fields for the flame E show excellent agreement contrary to flame F. Then, the different exergy losses were calculated and analyzed. The heat transfer and chemical reaction are the main factors responsible for the exergy destruction during combustion. The chemical exergy of the exhaust gases shows a strong relation between the exergy losses and combustion emission as well as the gas exhaust temperature.     

Solubility of gallium(III) oxyhydroxide in aqueous NaCl solutions at 100°C

The hydrolysis-precipitation equilibrium reaction of aqueous gallium(III) solution was investigated in 0–3 mol-kg^-1 NaCl media at low pH at 100°C using a pressure-tight glass vessel. All precipitates were identified as GaOOH. The results were analyzed with a nonlinear least-squares computer program to obtain the solubility product K_so for gallium(III) oxyhydroxide using a single-parameter type of Debye-Hückel equation. The value of log K_so for GaOOH(s) + 3H⁺ ⇆ Ga³⁺ + 2H₂O was -0.60 at 100°C. The solubility product calculated from thermodynamic data was compared with the experimental result.     

The effect of the addition of polypropylene-grafted SiO2 nanoparticle on the thermal conductivity of isotactic polypropylene

The thermal conductivity of Isotactic polypropylene (iPP)/silica particle (SiO₂, 26 nm) nanocomposite has been investigated. The untreated SiO₂ and iPP grafted onto SiO₂ were dispersed in the iPP (M _w = 2.5 × 10⁵) matrix. The molecular mass of the iPP-grafted chain, M _n, was precisely controlled to be 5.8 × 10³, 1.2 × 10⁴, and 4.6 × 10⁴. It was found that the thermal conductivities of graft-treated nanocomposites were higher than that of untreated SiO₂ composites. This implied that it is possible to achieve even higher thermal conductivity using the graft treatment. A thermal conductivity analysis conducted using a three-phase model, with considerations for thermal conductivity at interfacial layers, showed that the thermal conductivity of the interfacial layer increased significantly when a graft chain was incorporated. Moreover, the thermal conductivity per graft chain was proportional to the 1/2 power of the molecular mass ( \( M_{\text{n}}^{0.5} \) ). The results strongly suggest that the thermal conductivity pathway of interfacial layer was the main chain direction of iPP-grafted molecular chains.     

Cooperative Catalysis: Enantioselective Propargylic Alkylation of Propargylic Alcohols with Enecarbamates Using Ruthenium/Phosphoramide Hybrid Catalysts

The diastereo‐ and enantioselective propargylic alkylation of propargylic alcohols with E‐enecarbamates in the presence of a catalytic amount of thiolate‐bridged diruthenium complexes bearing an optically active phosphoramide moiety gives the corresponding propargylic alkylated products (up to 97 % ee).