Persistent spectral hole‐burning study on dendrimer porphyrins

We report the first results of persistent spectral hole burning of dendrimer porphyrins having three‐, four‐, or five‐layered aryl ether dendritic arrays. We evaluate structural relaxations of dendrimer framework around the porphyrin core at low temperatures. A large environmental change around the porphyrin core, as evaluated from the hole area, was suppressed in dendrimer porphyrins of higher generation numbers, whereas a small environmental change, as evaluated from hole width, showed no dependence on the number of generations. The dendrimer porphyrins showed sharp holes at 20 K, suggesting a long dephasing time and the suppression of spontaneous spectral diffusion. The results of dendrimer‐embedded polymer sample indicated that the structural relaxation of polymer chain outside the dendrimer does not have an influence on the resonant frequency of the porphyrin core. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 210–215, 2002     

Rhodium-catalyzed Reformatsky-type reaction of ethyl bromodifluoroacetate

Treatment of a variety of carbonyl compounds with ethyl bromodifluoroacetate and Et₂Zn in the presence of RhCl(PPh₃)₃ in CH₃CN afforded Reformatsky-type products in good to excellent yields in a mild reaction condition. This is a good method to obtain a β-hydroxy-α,α-difluoro carboxylic acid ethyl ester and especially to improve the poor reactivity of ketones.     

Amino acid ester salt recognition by ferrocene-based ditopic receptor bearing oligoethylene glycol with pendant bipy subunits: CV, UV-vis and ESR studies

The novel ferrocene-based ditopic receptor 1 was synthesized. This receptor bears two oligoethylene glycol arms with pendant 2,2'-bipyridine unit at the identical cyclopentadienyl rings, Cu(I) cation binds to 1 to form the 1 : 1 complex (1.Cu(I)) with the cavity consisting of polyether, and the resulting complex acts as a receptor for amino acid ester salts to give the ditopic complex (1.Cu(I).AAOMe-HCl). The 1H NMR spectrum of 1.Cu(I).LeuOMe-HCl exhibits strong broadening at the bipyridine region, and the ESR spectrum of the same sample gives the signals assigned as Cu(II) species. With these data, the binding of 1.Cu(I) towards AAOMe.HCl leads to the conformational change, and the Cu(I) complex is simultaneously oxidized to the Cu(II) complex.     

Convection-aided collection of metal ions using chelating porous flat-sheet membranes

Chelating porous membranes were prepared by radiation-induced graft polymerization of an epoxy-group-containing monomer onto a polyethylene flat sheet and subsequent conversion of the epoxy group to an iminodiacetate group as a chelate-forming group. The chelating group density on the resultant porous flat-sheet membrane of 1.0 mol/kg was comparable to that of commercially available chelating beads. The pure water permeability of the membrane was 40% that of the trunk porous membrane, which was used for microfiltration. During the permeation of a copper chloride solution through the membrane, diffusional mass-transfer resistance of copper ion was negligible, since the ion was transported by convective flow through the pore. The tensile strength and elongation at break of the membranes were measured as a function of dose of electron-beam irradiation, the degree of grafting, and the chelating group density to determine an applicable range for practical use.     

A theoretical study on anomalous temperature dependence of pKw of water

pH, with its well-known value of 7 at ambient condition, is a most basic property of water, with wide implications in chemistry and biology. The pH value is determined by the tendency of autoionization of water molecules into ion pairs, H(+) and OH(-), and is expected to vary extensively with the water condition, which determines the stability of the ion pairs. When temperature rises from the normal to the supercritical region, the pH of water experimentally exhibits complex, nonmonotonic temperature dependence, that is, it first decreases from 7 and then increases rapidly. Accurate theoretical evaluation of pH and microscopic understanding of this anomalous behavior have proven to be a challenging task because the hydration of these ions, especially for OH(-), is very difficult to reproduce. In the present study a molecular simulation is performed to understand this peculiar temperature dependence. The imbalance between the ion-water and the water-water molecular interaction strengths and the concomitant water density enhancement in the hydration shell, observed in the supercritical liquids, serve to put a subtle balance to produce this temperature dependence of the pH value. It is found that the large charge transfers from H(+) and OH(-) to the surrounding water molecules take place. In these transfers, not only water molecules in the neighboring hydration shell but also those in the outer hydration shell play a significant role. The coordination number of water molecules around OH(-) is found to be 4.5 at 300 K, which decreases slowly with temperature, for example, 4 at 800 K, in the present calculation.     

Methoxide of an Anderson-type polyoxometalate and its conversion to a new type of species, [IMo9O32(OH)(OH2)3]4-

A totally new type of polyoxometalate, [IMo(9)O(32)(OH)(OH(2))(3)](4)(-), has been synthesized by reacting [IMo(6)O(22)(OMe)(2)](3)(-) with water. The [IMo(9)O(32)(OH)(OH(2))(3)](4)(-) anion further transforms into [(IMo(7)O(26))(2)](6)(-), a molecular oxide that has a rutile core, in dry acetonitrile, while it stays intact for several hours in wet acetonitrile.     

Tunable photonic band gap crystals based on a liquid crystal-infiltrated inverse opal structure

Composite materials comprised of nematic liquid crystals (LCs) and SiO(2) inverse opal films were fabricated. Their optical properties were quite different from those of inverse opal films without the LCs. The optical properties could be controlled by changing the refractive indices of the LCs, which vary with orientation, phase, and temperature. In particular, the optical properties were drastically changed by thermal or photoinduced isothermal phase transitions of the LCs. This means that the photonic band structure could be controlled, and tunable photonic crystals have been achieved, based on the inverse opal structure. The mechanism of this change was investigated by the evaluation of the effective refractive indices. As a result, it was found that the change in optical properties was derived from the orientation of the LC molecules in the voids in the inverse opal film. Furthermore, once the mechanism was understood, it was also possible to control the position of the reflection peak by changing the alignment of the LCs. Such materials have the possibility for practical use in optical devices and fundamental research systems.     

Metal-modified silica adsorbents for removal of humic substances in water

As novel adsorbents for humic substances, Fe-, Mg-, and Ca-modified silica gels SiO(2)Fe, SiO(2)Mg, and SiO(2)Ca were prepared, and their adsorbabilities to humic and fulvic acids were evaluated in water at 25 degrees C for 20 h. Among these adsorbents, SiO(2)Fe indicated the highest adsorbability, in which removing humic substances in water was accomplished to 80-97%. By calcination at 600 degrees C and washing with water, adsorbabilities of the silica adsorbents deteriorated except for the case of calcination of SiO(2)Ca. This is due to changing metal modification structures and losing chlorine, judging from elemental analysis, TG-DTA, and XPS. Especially, the modifier Fe was tightly fixed on the silica surface of SiO(2)Fe, since the metal content was almost constant even after the calcination and water washing unlike the other adsorbents. Therefore, we found that SiO(2)Fe is the most useful adsorbent among the silica adsorbents and that its modification structure is composed of SiOFe, FeCl, and FeOH. In addition, the adsorption mechanism is explained by an interaction between Fe and humic substance molecule having carboxylate and phenolate groups, accompanied with anion exchange of chloride ion Cl(-) for the humic substance molecule via the silica pores. SiO(2)Fe may be applied to an adsorbent alternative for charcoal in water purification plants, and the used SiO(2)Fe may be further reused as a fertilizer since humic substances have plant-glowing ability and silica strengthens plant parts.