Steric effects upon transition states of radical addition polymerizations

Transition states (TSs) of radical addition homopolymerization reactions of methyl acrylate, methyl methacrylate, dimethyl itaconate, and N-methyl itaconimide were examined with two-unit radical models using MOPAC (PM3 UHF) semiempirical method. Calculated activation energies (E_as) show good correlations with experimental values. Calculated activation entropies (−ΔS^‡s) are found to be well proportional to E_as. The entropy terms play an important role as well as E_a in radical additions. E_a depends on the angle (θ_rs) between reaction points of radical and of monomer at TS. The bond length between reaction points at TS is constant regardless of monomers studied. The geometries and thermodynamical properties calculated here for TS indicate the importance of steric effects caused by substituted group(s) rather than electronic perturbation energies reported previously. © 1996 John Wiley & Sons, Inc.     

Linear polybiurets: Facile synthesis and characteristic properties

Linear polybiurets have been synthesized by polyaddition of benzyloxyamine and diisocyanates, and properties of the novel polymeric materials have been elucidated. Prior to polymerization, model reactions between benzyloxyamine and phenyl isocyanate were examined in detail and proved to be controlled by the molar ratio of reagents and by catalysts to give the urea (1:1 adduct) and/or biuret (1:2 adduct). Under appropriate conditions, the biuret was synthesized in a quantitative yield. Polymerization of equimolar amounts of benzyloxyamine and diphenylmethane or hexamethylene diisocyanate proceeded smoothly to give polybiurets with inherent viscosities up to 0.52 dL/g. The benzyl group of the model biuret and polybiuret could be removed by catalytic hydrogenation. Both the N-benzyloxy-type and N-hydroxy-type polybiurets showed excellent solubility in common organic solvents. The two kinds of polybiurets as well as model biurets adsorbed metal cations efficiently. The N-hydroxybiuret structure exhibited particularly high affinity for iron(III) and was useful for selective removal of iron from metal cation mixtures. © 1996 John Wiley & Sons, Inc.     

Removal of phosphate from solution by adsorption and precipitation of calcium phosphate onto monohydrocalcite

The sorption behavior and mechanism of phosphate on monohydrocalcite (CaCO₃?H₂O: MHC) were examined using batch sorption experiments as a function of phosphate concentrations, ionic strengths, temperatures, and reaction times. The mode of PO₄ sorption is divisible into three processes depending on the phosphate loading. At low phosphate concentrations, phosphate is removed by coprecipitation of phosphate during the transformation of MHC to calcite. The sorption mode at the low-to-moderate phosphate concentrations is most likely an adsorption process because the sorption isotherm at the conditions can be fitted reasonably with the Langmuir equation. The rapid sorption kinetics at the conditions is also consistent with the adsorption reaction. The adsorption of phosphate on MHC depends strongly on ionic strength, but slightly on temperature. The maximum adsorption capacities of MHC obtained from the regression of the experimental data to the Langmuir equation are higher than those reported for stable calcium carbonate (calcite or aragonite) in any conditions. At high phosphate concentrations, the amount of sorption deviates from the Langmuir isotherm, which can fit the low-to-moderate phosphate concentrations. Speciation–saturation analyses of the reacted solutions at the conditions indicated that the solution compositions which deviate from the Langmuir equation are supersaturated with respect to a certain calcium phosphate. The obtained calcium phosphate is most likely amorphous calcium phosphate (Ca₃(PO₄)₂?xH₂O). The formation of the calcium phosphate depends strongly on ionic strength, temperature, and reaction times. The solubility of MHC is higher than calcite and aragonite because of its metastability. Therefore, the higher solubility of MHC facilitates the formation of the calcium phosphates more than with calcite and aragonite.     

Self-regulated Ni cluster formation on the TiO2(1 1 0) terrace studied using scanning tunneling microscopy

We have studied the growth mode and morphology of Ni clusters on a TiO₂(1 1 0) surface with a wide terrace using scanning tunneling microscopy (STM) at a low coverage (less than 3 atoms nm⁻²). The Ni clusters are formed on the terrace at the low coverage of 0.2 atoms nm⁻². Their average dimensions are constant in three directions up to 1 atoms nm⁻². The Ni clusters have an oval shape with average sizes of 1.8 nm (along [0 0 1]) × 1.4 nm (along (in the [1 1 0] directions). Above the coverage of 1.0 atoms nm⁻², an increase in the cluster height occurs, retaining an almost constant lateral size. It is proposed that the interaction of the Ni cluster and the support surface regulates the Ni cluster size.     

Photoredox‐Catalyzed Alkenylation of Benzylsulfonium Salts

Visible light‐mediated radical alkenylation of benzylsulfonium salts was achieved by means of fac‐Ir(ppy)₃ as a photocatalyst, giving allylbenzenes as products. A variety of functional groups, such as halogen, ester, and cyano, were well tolerated in this transformation. Starting benzylsulfonium salts could be readily prepared from benzyl alcohols by an acid‐mediated substitution, increasing the synthetic utility of this transformation.     

Synthesis of Porphyrinquinone and Doubly‐Fused Diporphyrin Quinone Through Oxidation of Diarylporphyrins Using a Hypervalent Iodine Compound

Treatment of a meso‐diarylporphyrin with PhI(OAc)₂ in the presence of BF₃ ? OEt₂ and propionic acid affords the corresponding porphyrinquinone in a high yield (91%). A novel quinone derived from meso‐meso β–β doubly‐fused diporphyrin was obtained as the sole byproduct (16% yield), which exhibits strong panchromatic absorption between 300 and 1000 nm. It has a low HOMO‐LUMO gap owing to expanded and low‐symmetry π‐planes.     

Molecular chaperone-like properties of sodium caseinate to suppress the pressure-induced aggregation of β-lactoglobulin

ABSTRACT

The objective of this study was to determine whether sodium caseinate can inhibit the aggregation of whey protein induced by pressure treatment. Solutions of β-lactoglobulin (β-Lg, 0.2%, w/v) and mixtures containing 0.2% (w/v) β-Lg and 0–0.5% (w/v) sodium caseinate (NaCas) were pressurized at 400–800?MPa. NaCas suppressed the aggregation of β-Lg induced by pressure treatment, and this function was dependent on the concentration of NaCas. Furthermore, NaCas altered the aggregation process of β-Lg by suppressing the transition of the aggregate from the soluble phase to the insoluble phase and, as a result, the fraction of insoluble aggregates was decreased. During this process, NaCas formed stable complexes with the denatured β-Lg, and the formation of complexes prevented further aggregation of β-Lg. These results indicate that NaCas exhibits a chaperone-like activity under high pressure.     

Well-crystallized zinc oxide quantum dots with narrow size distribution

In this study, pulsed laser ablation, online annealing, and following size classification using a differential mobility analyzer (DMA) were employed to fabricate quantum dots (QDs) of zinc oxide (ZnO). The irregularly shaped ZnO particles were obtained at annealing temperature less than 873 K, which gradually transformed into spherical QDs with increasing the annealing temperature. Finally, ZnO QDs with narrow size distribution having spherical shapes were successfully obtained at temperatures above 1173 K under the DMA classification at a nominal size of 10 nm. TEM observation demonstrated that the ZnO QDs obtained by this process were well-crystallized single crystallites with a wurtzite structure. Further, ZnO QDs with average sizes in the range of 4.8–8.1 nm were successfully fabricated by reducing the specified sizes of DMA. These features of the fabricated ZnO QDs are favorable for investigation of intrinsic quantum size effect in ZnO.     

A satellite of the grand Furuta inequality and its application

The grand Furuta inequality has the following satellite (SGF;$t\in [0\text{,}1]$), given as a mean theoretic expression:$A?B>0\text{,}t\in [0\text{,}1]?A^{-r+t}{\#}_{\frac{1-t+r}{(p-t)s+r}}(A^t{?}_s{B}^p)?B\text{for}r?t\text{;}p\text{,}s?1\text{,}$where ${\#}_{\alpha }$ is the $\alpha$-geometric mean and ${?}_s$ ($s?[0\text{,}1]$) is a formal extension of ${\#}_{\alpha }$. It is shown that (SGF; $t\in [0\text{,}1]$) has the Löwner–Heinz property, i.e. (SGF; $t=1$) implies (SGF;t) for every $t\in [0\text{,}1]$. Furthermore, we show that a recent further extension of (GFI) by Furuta himself has also the Löwner–Heinz property.