One‐pot fabrication of robust interpenetrating hydrogels via orthogonal click reactions

Interpenetrating polymer network (IPN) hydrogels have been fabricated through a facile one‐pot approach from tetra/bifunctional telechelic macromonomers with epoxy, amine, azide, and alkyne groups by orthogonal double click reactions: epoxy‐amine reaction and copper‐catalyzed azide‐alkyne cycloaddition. Both the crosslinked networks are simultaneously constructed in water from the biocompatible poly (ethylene glycol)‐based macromonomers. The crosslinking density of each network was finely tuned by the macromonomer structure, permitting control of network molecular weights between crosslinks of the final gels. Compared to corresponding single network gels, the IPN gels containing both tightly and loosely crosslinked networks exhibited superior mechanical properties with shear moduli above 15 kPa and fracture stresses over 40 MPa. The synthetic versatility of this one‐pot approach will further establish design principles for the next generation of robust hydrogel materials. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1459–1467     

Development of a certified reference material of nitrous oxide in nitrogen for emission gas measurement

A reference gas mixture of nitrous oxide (N₂O) in nitrogen, filled in a 10-L high-pressure aluminum alloy gas cylinder, has been developed as a certified reference material for emission measurement of exhaust gases from automobiles. As an example of certified values, mole fraction of N₂O is 302.36 μmol/mol. An electronic mass comparator with a home-made automatic cylinder exchanger, gas-filling equipment, and a gas chromatograph with a thermal conductivity detector have been used for the production of this CRM. The gas chromatographic analysis has of sufficient precision. The mole fraction of N₂O has good long-term stability for 10 years and is independent of inner pressure in the gas cylinder. As these results, a relative expanded uncertainty (coverage factor is 2) of the certified value has become 0.28 %. This sufficiently small uncertainty of the N₂O mole fraction will be advantageous in the calibration of analytical instruments for emission gas analysis.     

Combined application of pair potentials and the MM2 force field for the modeling of ionophores

Complexes of alkali and alkaline earth cations with organic compounds are modeled by describing ionligand interaction energies with pair potentials and intraligand as well as interligand energies with the MM2 potential. New pair potentials for the interaction of Li⁺, Na⁺, K⁺, Mg²⁺, and Ca²⁺ ions are derived on the basis of 30,000 ab initio interaction energy values with 70 selected model ligand molecules. Various problems of the combination of these two basically different potentials are discussed. An application for the K⁺ complex of 18-crown-6 is presented. For more flexible ligands the introduction of three-body correction terms of the pair potentials seems necessary.     

Asymmetric 1,3-dipolar cycloaddition reaction of nitrones and acrolein with a bis-titanium catalyst as chiral Lewis acid

A mu-oxo-type chiral bis-Ti(IV) oxide (S,S)-1 can be successfully utilized in the asymmetric 1,3-dipolar cycloaddition reactions between various nitrones 2 and acrolein to give the corresponding isoxazolidines with high to excellent enantioselectivities. For instance, the reaction between nitrone 2 (R = t-Bu) and acrolein in the presence of 10 mol % of bis-Ti(IV) catalyst (S,S)-1 in dichloromethane at -40 degrees C gave the corresponding endo cycloadduct with 97% ee.     

Site selectivity switch in Lewis acid catalysis. Mechanism and kinetic simulation of skeletal rearrangement of cyclobutene-fused homoquinones

[reactions: see text] We investigated the site selectivity switch in BF3-catalyzed dual skeletal rearrangements of cyclobutene-fused diarylhomobenzoquinones by changing the stoichiometric amount of acid concentration. From the lower to the higher equivalency of BF3 x Et2O, the branching product ratios (path A/path B) obeyed nonlinear sigmoid curves against the equivalency of BF3 x Et2O. The observed selectivity profiles were simulated to elucidate factors that govern thermodynamic aspects (binding affinity K of each carbonyl function with acid) and kinetic aspects (rate constants k for the cyclobutene-ring cleavage).     

Oxidizing intermediates from the sterically hindered iron salen complexes related to the oxygen activation by nonheme iron enzymes

Oxidizing intermediates are generated from nonheme iron(III) complexes to investigate the electronic structure and the reactivity, in comparison with the oxoiron(IV) porphyrin pi-cation radical (compound I) as a heme enzyme model. Sterically hindered iron salen complexes, bearing a fifth ligand Cl (1), OH(2) (2), OEt (3), and OH (4), are oxidized both electrochemically and chemically. Stepwise one-electron oxidation of 1 and 2 generates iron(III)-mono- and diphenoxyl radicals, as revealed by detailed spectroscopic investigations, including UV-vis, EPR, M?ssbauer, resonance Raman, and ESIMS spectroscopies. In contrast to the oxoiron(IV) formation from the hydroxoiron(III) porphyrin upon one-electron oxidation, the hydroxo complex 4 does not generate oxoiron(IV) species. Reaction of 2 with mCPBA also results in the formation of the iron(III)-phenoxyl radical. One-electron oxidation of 3 leads to oxidative degradation of the fifth EtO ligand to liberate acetaldehyde even at 203 K. The iron(III)-phenoxyl radical shows high reactivity for alcoxide on iron(III) but exhibits virtually no reactivity for alcohols including even benzyl alcohol without a base to remove an alcohol proton. This study explains unique properties of mononuclear nonheme enzymes with Tyr residues and also the poor epoxidation activity of Fe salen compared to Mn and Cr salen compounds.     

Thermodynamics of the N2/N3- redox couple in a LiBr-KBr-CsBr melt

Nitrogen electrode reaction has been investigated in a LiBr-KBr-CsBr melt containing Li3N. The reaction N3- --> 1/2N2 + 3e- is confirmed by quantitative analysis of anodically evolved gas. The Nernst relation holds for the rest potential of Ni electrodes at a nitrogen gas pressure, pN2, of 0.05-1.0 atm and an anion fraction of the N3- ions, xN3-, of 0.003-0.010 (anion fraction). Then, the standard formal potential of the N2/N3- couple, , is evaluated to be 0.251 +/- 0.009 V versus Li+/Li (pN2 = 1 atm, xN3- = 1) at 673 K. The dependence of on the temperature (570-730 K) gives a linear relation, whose slope is (-0.930 +/- 0.117) x 10(-3) V K(-1). Thermodynamic quantities for the formation of Li3N in the melt are also estimated.