Charge‐Transfer Phase Transition of a Cyanide‐Bridged FeII/FeIII Coordination Polymer

Heterometallic Prussian blue analogues are known to exhibit thermally induced charge transfer, resulting in switching of optical and magnetic properties. However, charge‐transfer phase transitions have not been reported for the simplest FeFe cyanide‐bridged systems. A mixed‐valence Fe^II/Fe^III cyanide‐bridged coordination polymer, {[Fe(Tp)(CN)₃]₂Fe(bpe)?5 H₂O}_n, which demonstrates a thermally induced charge‐transfer phase transition, is described. As a result of the charge transfer during this phase transition, the high‐spin state of the whole system does not change to a low‐spin state. This result is in contrast to FeCo cyanide‐bridged systems that exhibit charge‐transfer‐induced spin transitions.     

Magnetically Alignable Bicelles with Unprecedented Stability Using Tunable Surfactants Derived from Cholic Acid

Five novel surfactants were prepared by modifying the three hydroxy groups of sodium cholate with triethylene glycol chains endcapped with an amide ( SC‐C₁ , SC‐ ⁿ C₄ , and SC‐ ⁿ C₅ ) or a carbamoyl group ( SC‐O ⁿ C₄ and SC‐O ^t C₄ ). The phase behavior of aqueous mixtures of these surfactants with 1,2‐dimyristoyl‐sn‐glycero‐3‐phosphatidylcholine (DMPC) was systematically studied by ³¹P NMR spectroscopy. The surfactants endcapped with carbamate groups ( SC‐O ⁿ C₄ and SC‐O ^t C₄ ) formed magnetically alignable bicelles over unprecedentedly wide ranges of conditions, in terms of temperature (from 21–23 to >90 °C), lipid/surfactant ratio (from 5 to 8), total lipid content (5–20 wt %), and lipid type [DMPC, 1,2‐dilauroyl‐sn‐glycero‐3‐phosphatidylcholine (DLPC), or 1‐palmitoyl‐2‐oleoyl‐sn‐glycero‐3‐phosphatidylcholine (POPC)]. In conjunction with appropriate phospholipids, the carbamate‐endcapped surfactants afforded unique bicelles, characterized by exceptional thermal stabilities (from 0 to >90 °C), biomimetic lipid compositions (DMPC/POPC=25:75 to 50:50), and extremely large ²H quadrupole splittings (up to 71 Hz).     

Five‐State Molecular Shuttling of a Pair of [2]Rotaxanes: Distinct Outputs in Response to Acid and Base Stimuli

In this study we synthesized two acid‐/base‐controllable [2]rotaxanes featuring aminodiazobenzene and aminocoumarin units, respectively, as chromophores and dibenzo[24]crown‐8 and dibenzo[25]crown‐8 units, respectively, as their macrocyclic components. Each [2]rotaxane contained N‐alkylarylamine (ammonium) and N,N‐dialkylamine (ammonium) centers as binding sites for their crown ether components. The absorption patterns of the chromophores were dependent on the position of the encircling macrocyclic component and the degree of protonation, with three distinct states (under acidic, neutral, and basic conditions) evident for each [2]rotaxane. The mixed [2]rotaxane system displayed stepwise and independent molecular shuttling behavior based on the degree of protonation of the amino groups in response to both the amount and strength of added acids or bases; as such, the system provided five different absorption signals as outputs that could be read using UV/Vis spectroscopy.     

Size-selective photocatalytic reactions by titanium(IV) oxide coated with a hollow silica shell in aqueous solutions

A novel core-shell composite photocatalyst, commercially available titanium(IV) oxide (TiO(2)) particles directly incorporated into a hollow amorphous silica shell, was fabricated by successive coating of TiO(2) with a carbon layer and a silica layer followed by heat treatment to remove the carbon layer. The composite induced efficient photocatalytic reactions when relatively small substrates were used, such as methanol dehydration and decomposition of acetic acid, without any reduction in the intrinsic activity of original TiO(2), but did not exhibit efficient photocatalytic activity for decomposition of large substrates, methylene blue and polyvinyl alcohol. The unique size-selective properties of the composites are due to their structural characteristics, i.e., the presence of a pore system and a void space in the silica shell and between the shell and medial TiO(2) particles, respectively. The loading of alkylsilyl groups on the surface of the composite led to highly photostable floatability: the floated sample also induced efficient photocatalytic reaction for decomposition of acetic acid while retaining floatation at the gas/water interface.     

Reversible photoswitching of ferromagnetic FePt nanoparticles at room temperature

There has been a great interest in developing photoswitchable magnetic materials because of their possible applications for future high-density information storage media. In fact, however, the examples reported so far did not show ferromagnetic behavior at room temperature. From the viewpoint of their practical application to magnetic recording systems, the ability to fix their magnetic moments such that they still exhibit room-temperature ferromagnetism is an absolute requirement. Here, we have designed reversible photoswitchable ferromagnetic FePt nanoparticles whose surfaces were coated with azobenzene-derivatized ligands. On the surfaces of core particles, reversible photoisomerization of azobenzene in the solid state was realized by using spacer ligands that provide sufficient free volume. These photoisomerizations brought about changes in the electrostatic field around the core-FePt nanoparticles. As a result, we have succeeded in controlling the magnetic properties of these ferromagnetic composite nanoparticles by alternating the photoillumination in the solid state at room temperature.     

Nanostructural control of cup-stacked carbon nanotubes with 1-benzyl-1,4-dihydronicotinamide dimer via photoinduced electron transfer

The photoinduced electron-transfer reduction of cup-stacked carbon nanotubes (CSCNTs) with 1-benzyl-1,4-dihydronicotinamide dimer [(BNA)2] results in the electrostatic destacking of CSCNTs to afford CSCNTs with uniform size.     

Highly emissive pi-conjugated alkynylpyrene oligomers: their synthesis and photophysical properties

We newly prepared para- and meta-linked alkynylpyrene oligomers and examined their photophysical properties. Oligomerization of monomeric building blocks was performed by CuI-promoted oxidative coupling reaction. The resulting oligomers mainly consist of 2-mer to 6-mer that were assigned on the basis of MALDI-TOF mass spectra, and the 2-mer, 3-mer, and 4-mer were isolated and fully characterized. From their absorption and fluorescence spectra, the para-linked oligomers were found to be somewhat pi-conjugated compared with meta-linked ones, and the fluorescence quantum yields decreased with increasing oligomer length (Phif = 0.79-0.55).     

Determination of gallium by graphite furnace atomic absorption spectrometry with combined use of a tungsten-coated L'vov platform tube and a chemical modification technique

Tungsten-coated non-pyrolytic graphite (NPG), pyrolytic graphite (PG) and pyrolytic L'vov platform graphite (PPG) tubes were prepared, and their analytical performances were compared. The coating process simply involved injecting 100 μl of a sodium tungstate solution (0.01 mol l⁻¹) into each graphite tube, followed by heating according to a temperature programme similar to an atomisation cycle for the determination of gallium. This procedure for coating was repeated at least 12, 25, and 7 times towards NPG, PG, and PPG tubes, respectively. Among these tubes, the tungsten-coated PPG tube showed excellent performance for the determination of gallium. By combined use of a chemical modifier such as aluminium(III) or nickel(II) a detection limit (3σ) of 6 pg and sensitivity (1% absorption) of 3–4 pg were achieved. The practical potential of the proposed technique was demonstrated for the determination of gallium in several samples of alloys and fresh water.     

A novel approach to the characterization of end groups in styrene–methyl methacrylate copolymers by pyrolysis–gas chromatography

The end groups of styrene–methyl methacrylate (St‐MMA) copolymers polymerized radically with 2,2′‐azobisisobutyronitrile (AIBN) as an initiator, which are difficult to characterize even by NMR, were investigated by pyrolysis–gas chromatography. On the resulting pyrograms, characteristic products that formed from the end‐group moiety due to AIBN, such as 2‐cyanopropane, 2‐cyanopropen, and various compounds consisting of an isobutyronitrile group and a monomer unit, were observed together with those from the main chain, such as St and MMA monomers and various dimeric and trimeric products. The relative abundance between the recombination and disproportionation termination reactions in the copolymerization process was estimated from the relative intensities between the characteristic peaks of the end group and those of the main chain. Thus, the estimated abundance for the termination reactions suggested that the polymerization process for this particular copolymer system terminated preferentially by recombination rather than by disproportionation. Furthermore, the relative abundance between the monomer units adjacent to the chain‐end AIBN residues was estimated on the basis of the peak intensities of the products consisting of an isobutyronitrile group and either monomer unit, which reflected the penultimate neighboring structure of the end group in the polymer chain. Thus, the observed results suggested that the isobutyronitrile radical formed by the dissociation of AIBN in the initiation reaction was predominantly adjoined by St monomer rather than by MMA monomer. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1880–1888, 2000