Characterization of Cu species on SiO2 and ZSM-5 by temperature-programmed reduction by ammonia

We studied the temperature-programmed reduction by NH₃ (NH₃-TPR) as a supplement to the temperature-programmed reduction by H₂ (H₂-TPR) for the characterization of supported Cu species. The NH₃-TPR profile of Cu/SiO₂, which contained only bulk CuO, exhibited two peaks for N₂ formation in equal amounts, suggesting stepwise reduction of the bulk CuO. In contrast, the H₂-TPR profile exhibited only one H₂ consumption peak. We also studied Cu-NaZSM-5 samples with various Cu and Na loadings. The Cu ions on ZSM-5 were reduced to Cu⁺ but no further. Kinetic analysis revealed that the NH₃-TPR profile exhibited peaks for separate reductions of isolated and binuclear Cu²⁺ ions. Thus, we found NH₃-TPR to be useful for detailed analysis of the reducibility of Cu²⁺ to Cu⁺ in zeolite pores.     

Preparation of ureido group bearing polymers and their upper critical solution temperature in water

Poly(2‐ureidoethylmethacrylate) (PUEM_n) was synthesized via reversible addition‐fragmentation chain transfer (RAFT) radical polymerization and following polymer reaction. We prepared two PUEM_n samples with different degrees of polymerization (n = 100 and 49). The polymers exhibited upper critical solution temperature (UCST) in phosphate‐buffered saline (PBS) solution. The phase separation temperature (T_p) in PBS can be controlled ranging from 17 to 55 °C by changing molecular weight of the polymer, polymer concentration, and adding NaCl concentration. The polymers in PBS formed coacervate drops by liquid–liquid phase separations below T_p. Results of the dielectric relaxation measurement, the hydration number per monomeric unit was 5 above T_p. Based on a fluorescence study, the polymer formed slightly hydrophobic environments below T_p. The liquid–liquid phase separation was occurred presumably because of weak hydrophobic interactions and intermolecularly hydrogen bonding interactions between the pendant ureido groups. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2845–2854     

Hydration effect on the ion-pair extraction of lithium picrate by hydrophobic benzo-15-crown-5 ether into various less-polar diluents.

The ion-pair formation constant (K(MLA)(0) in mol(-1) dm(3)) for Li(B15C5)(+) with a picrate ion (Pic(-)) in water was determined by potentiometry with a K(+)-selective electrode at 25 degrees C and an ionic strength of 0, where B15C5 denotes benzo-15-crown-5 ether. Using the concentration equilibrium constants, K(MLA), estimated from this value, the extraction constants (mol(-2) dm(6) unit) of about ten diluents were re-calculated from previously reported extraction data. Also, the distribution constants of an ion-pair complex, Li(B15C5)Pic, between water and the diluents were re-estimated. A disagreement in the determined K(MLA) value between a solvent-extraction method and potentiometry was explained in terms of the Scatchard-Hildebrand equation; it came from the fact that the hydration of Li(I) in Li(B15C5)Pic was larger than that of free B15C5 in water. Then, the previously determined value by the former method was re-estimated using the potentiometric K(MLA) value.     

A polyrotaxane gel using boronic acid-appended γ-cyclodextrin as a hybrid cross-linker

A boronic acid-appended γ-cyclodextrin (BA-CyD) was synthesized as a hybrid cross-linker of polyvinyl alcohol (PVA) to form a new type of hydrogel. The CyD moiety of BA-CyD forms an inclusion complex with the PVA chain to produce a mechanically interlocking structure. At the same time, the BA moiety of BA-CyD forms covalent bonds with the 1,3-diol moieties of PVA. On the basis of these two modes of interaction, the hybrid cross-linker connects two PVA chains, thus resulting in the formation of a hydrogel. To investigate the possibility of this hydrogel becoming the basis for an intelligent material for drug delivery, sugar-responsive drug release from the hydrogel was demonstrated.     

Transition-metal-free controlled polymerization for poly(p-aryleneethynylene)s

A transition-metal-free controlled polymerization for the attainment of poly(p-aryleneethynylene)s is developed. The polymerization of 1-pentafluorophenyl-4-[(trimethylsilyl)ethynyl]benzene with a catalytic amount of fluoride anions proceeds in a chain-growth-like manner to afford polymers with controlled molecular weights and low polydispersity indexes. The mechanism involves a pentacoordinated fluorosilicate as a key intermediate. The anionic “living” nature of this process is applied to block copolymerization and also surface-terminated polymerization.