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A series of poly(aryl ether) dendrimer chloroiron(III) porphyrin complexes (LnTPP)Fe(III)Cl (number of aryl layers [n]=3 to 5) were synthesized, and their Boltzmann temperatures under IR irradiation were evaluated from ratios of Stokes to anti-Stokes intensities of resonance Raman bands. While the Boltzmann temperature of neat solvent was unaltered by IR irradiation (LnTPP)Fe(III)Cl (n=3 to 5), all showed a temperature rise that was larger than that of the solvent and greater as the dendrimer framework was larger. Among vibrational modes of the metalloporphyrin core, the temperature rise of an axial Fe-Cl stretching mode at 355 cm-1 was larger than that for a porphyrin in-plane mode at 390 cm-1. Although most of the IR energy is captured by the phenyl nu8 mode at 1597 cm-1 of the dendrimer framework, an anti-Stokes Raman band of the phenyl nu8 mode was not detected, suggesting the extremely fast vibrational relaxation of the phenyl mode. From these observations, it is proposed that the energy of IR photons captured by the aryl dendrimer framework is transferred to the axial Fe-Cl bond of the iron porphyrin core and then relaxed to the porphyrin macrocycle.

Cobalt(II) complexes of poly(aryl ester) dendrimer porphyrins (m-[Gn]TPP)Co(II) and (p-[Gn]TPP)Co(II) (n = 0-3) underwent AIBN-initiated alkylation (AIBN = 2,2'-azobis(isobutyronitrile)) at the metal center with propargyl alcohol in CDCl(3) at 60 degrees C, where the dendritic substituents did not affect the overall conversion rate but selectivity of the alkylation. With the largest (m-[G3]TPP)Co(II), a single organocobalt(III) species (Co(III)-C(=CH(2))CH(2)OH, 4) was selectively formed in 91% yield, due to a steric protection of 4 by the large dendrimer cage from the access of another molecule of cobalt porphyrin species. In contrast, with other cobalt(II) porphyrins, isomerized compounds such as Co(III)-C(CH(3))=CHOH (5) and Co(III)-CH(CH(3))CHO (6) were formed in addition to 4. A stereochemical investigation with (m-[G3]TPP)Co(II) using AIBN-d(12), in place of nondeuterated AIBN, demonstrated that the alkylation (cobalt(III) hydride addition to propargyl alcohol) is selective to a trans adduct. Results also indicated that this addition step does not involve external activation of propargyl alcohol.

Cobalt(II) complexes of poly(aryl ester) dendrimer porphyrins [(m-[Gn]TPP)Co(II)] (generation number n=0-4), in the presence of azobisisobutyronitrile (AIBN) at 60 degrees C, underwent alkenylation with several alkynes at the metal center. A complete inhibition of double-bond migration (secondary transformation) was observed for [(m-[Gn]TPP)Co(II)] (n=3 and 4), which gave [(m-[Gn]TPP)Co(III)-C(=CH(2))R] (n=3 and 4) exclusively. Overall reaction rates for [(m-[Gn]TPP)Co(II)] (n=0-3) were hardly dependent on the size of the dendritic substituents, while a notable retardation was observed for the largest dendrimer, [(m-[G4]TPP)Co(II)]. Mechanistic studies on double-bond migration with pure [(m-[Gn]TPP)Co(III)-C(=CH(2))Bu] (n=0-4) demonstrated that the secondary transformation involves participation of [(m-[Gn]TPP)Co(III)H] (n=0-4), derived from [(m-[Gn]TPP)Co(II)] and AIBN, rather than [(m-[Gn]TPP)Co(II)] alone. Crossover experiments using [(m-[Gn]TPP)Co(III)-C(=CH(2))Bu] (n=2-4), in combination with nondendritic [(m-[G0]TPP)Co(II)] and AIBN, indicated a high level of steric protection of the active center by a robust [G4]-dendritic cage, as suggested by a (1)H NMR pulse relaxation time profile of m-[G4]TPPH(2).

Gingival tissues obtained from two cases of chronic desquamative gingivitis were examined by scanning electron microscopy (SEM)and transmission electron microscopy (TEM).In case 1 (38 year-old female), SEM revealed peculiar surface characteristics such as flattened, multi-pitted string-like processus appearances. On TEM, there was a thin electron dense band of 3 to 4 μm in width below the outer cell layers pressumed to be prickled cells. This electron dense band was composed of excessive compression of 6 to 7 cell layers. Adittional changes of whorling arrangements of the epithelial cells and occasional multiplications of basal lamina were found near the subepithelial inflammatory regions.In case 2 (53 year-old female), SEM revealed rather regular arrangements of microridge resembled usual surface than unusual. On TEM, there was also a thin electron dense band of about 10μm in width adjacent to the surface areas, and this band was made of moderate compression of cell layers. This band, however, was different to that of case 1, in respect of the degree of compression and characteristics of the outer cells.

慢性剥離性歯肉炎は, その病因や病理発生について未だ明らかにされていない。歯周治療分野では治療の最も困難な病変である。一般的には, 全身的要因によって歯肉上皮に退行性変化が生じ, 二次的に局所の炎症が合併する, とされているが, その本態については不明である。今回, 臨床的に本疾患と診断され, その後追跡可能であった4症例について体験しているので, 臨床経過を主体に報告する。症例はいずれも女性であり, 初診時 Glickman の分類では1例が severe form, 他の3例が moderete form に該当する病変であった。全身的および環境的な面では, 1例は離婚直後の発症, 1例は発症後の子宮筋腫の発見, 1例はヒステリー症状発現とほぼ同時の発症, 1例は妊娠促進の薬物治療時における発症と, いずれも何らかの要因を有していたが, 本疾患との関連性は明らかにできなかった。治療としては, 歯肉病変を二次的に増悪させる局所刺激因子の排除と, 疼痛軽減のための薬物投与など, いわゆる対症療法を主体に試みた。その結果, 皮質ホルモンと抗生物質の含有軟膏の局所塗布, および歯垢, 歯石の除去と0.1%クロールヘキシジンによる含嗽は症状の軽減に有効であった。数年以上に渉る経過中, 3例には症状の改善が認められたが, 1例については初発後6年後の現在も改善はみられず, 病変部歯肉の外科的切除や置換も含めて経過観察中である。