Etsuko Masuda

Functional metallomacrocycles and their polymers: 34. Kinetics and mechanism of the biomimetic decomposition of hydrogen peroxide catalysed by heterogeneous octacarboxyphthalocyaninato iron(III) supported on amorphous enriched rayon staple fibres

Catalase-like decomposition of hydrogen peroxide with the octacarboxy-phthalocyaninatoiron(III) (Fe(III)-oapc) supported on amorphous enriched rayon staple fibre (degree of crystallinity = 14%) was studied in aqueous solution at pH 7.0 and 25°C. The Fe(III)-oapc supported on the rayon staple fibre is remarkably effective as an immobilized catalyst for decomposition of hydrogen peroxide. The reaction rate was analysed in terms of Michaelis-Menten kinetics, which suggests that the catalysed decomposition of hydrogen peroxide proceeds via the formation of an activated complex. Iron atom distribution of the rayon staple fibre indicated that Fe(III)-oapc existed on the fibre homogeneously. Electronic and e.s.r. spectra of the fibre suggests monomeric Fe(III)-oapc with a distorted rhombic coordinating high spin iron(III) ion. Fe(III)-oapc is considered to be immobilized by hydrogen bonding between carboxylic groups on Fe(III)-oapc and hydroxy groups of cellulose, and a weak coordination bonding of iron with hydroxy groups on cellulose. The immobilization of Fe-oapc to the rayon staple fibre extends its catalytic lifetime and makes the catalyst molecule the monomeric active state.

Functional metallomacrocycle derivatives and their polymers. Part 23. Biaxially orientated Langmuir–Blodgett films of substituted metallophthalocyanines

Soluble metallophthalocyanine compounds (M = NiII or CuII) with alkyloxycarbonyl groups substituted at either the 2 or 3 position of the benzene ring (alkyl = 1- or 2-octyl, or 1-decyl) were synthesized by the reaction of the corresponding metallophthalocyaninetetracarboxyl chlorides with the alkyl alcohols, and monolayers were formed at a water–air interface. All compounds formed stable monolayers at surface pressures higher than ca. 15 mNm–1. In the Langmuir–Blodgett films built up from monolayers of the compounds on Pyrex substrates, the orientation of the phthalocyanine rings was shown to be biaxial from the one-dimensional orientation of the phthalocyanine stacked columns, observed by measurement of polarized visible absorption spectra.

Flame Retardation of Fe(III)-Poly(vinyl Alcohol) Films

was completely hydrolyzed by alkali solution and purified by dialysis. Metal-PVA complexes were prepared in.,the same way as in our previous papers [2, 5]. Kn aqueous solution of Ti(III), Fe(III), and Zn(II) chloride was added to the PVA solution, and the pH of the mixed solution was adjusted to the desired value with KOH. The molar ratios of total metal ions (TM) to monomeric units of PV A(Tud, T,,~/T&dquo;,_

Multinuclear macromolecule metal complexes 2. Preparation and characterization of Prussian blue and its analogs bonded to pofy(vinylamine hydrochloride)

Prussian blue and its analogs bonded to poly(vinylamine hydrochloride) (PVAm · HCl) containing FeII or FeIII and M2+ (M=Fe, Co, Cu) in a 1∶1 molar ratio were obtained by the reaction of [Fe(CN)6]n− (n=3,4) with M2+ ion-PVAm · HCl mixture in aqueous solution. Under a limited polymer concentration (TVAm/TFe over 10), these polymer complexes thus obtained were stable and soluble in water. By casting these solutions, colored films can be produced. The formation of Prussian blue and its analogs bonded to PVAm · HCl was also investigated by the Benesi-Hildebrand method. The molar extinction coefficients of intervalence charge transfer (FeII→FeIII, CoII→FeIII, FeII→CuII) band for MFe(CN)6](n−2)− bound to PVAm · HCl (M=Fe, Co, Cu) were found to be 10,100−9601 · mol−1 · cm−1 at 25 ‡C. The formation constants were found to be in the range of 107 to 1010 M−1. The changes of enthalpy (δH) and entropy (δS) were found to be in the range of −10.4 to −22.5 kJ · mol−1 and 5.7 to 52.9 J · K−1 mol−1 respectively, at 25‡C.

Flame Retardation of Poly(vinyl Alcohol) and Poly(vinyl Chloride) Films Containing Dispersed Metal-Ethylenediamine Complexes

Table I shows that there is not much marked difference in the decrease of cell length and in the increase of cell wall thickness at 1 minute and at 30 minutes of treatment time. Thus it appears that the swelling reaction, which causes the longitudinal shrinkage of the filaments and the increase in cell wall thickness and which is reported to be associated with crimp formation in jute [3, 5], is mostly complete at one minute of treatment time.

Functional metallomacrocycle derivatives and their polymers. XXI Iodine secondary cells using metallophthalocyanine polymers modified electrodes.

金属フタロシアニン (MtPc, Mt=Fe, Co, Ni, Cu) をスチレン-2-ビニルピリジン共重合体 (PSt-co-2Vp) に担持したフロロシアニンポリマー (MtPc-PSt-co-2Vp) で修飾した電極を用いてヨウ素二次電池を形成した. この電池は, 安定した充放電特性を示した. MtPcポリマー修飾電極を用いた際のサイクリックボルタモグラムからこの系は, ポリマー自身の高い導電性のため電池の効率が増加することが示された. MtPcポリマー|3M ZnI2/飽和I2|Znの系において開放電圧, Vocは1.22V, エネルギー密度は135Wh/kgであった. 30回以上充放電を繰返しても, その特性に変化はなかった.