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La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 (LSCF) - Ce 0.7 Sm 0.3 O 3 (SDC) composite cathodes were investigated for demonstration of SOFCs working at reduced-temperatures of ca. 800°C. Interlayer of SDC or Ce 0.7 Gd 0.3 O 3 (GDC) was inserted between the composite cathode and Sc 0.10 Ce 0.01 Zr 0.89 O 2-α (ScSZ) electrolyte to achieve stable operation. Ni-ScSZ was used as anode. The performance of the composite cathode and the effect of the interlayer were evaluated based on current-voltage and impedance measurements. It was found that insertion of SDC and GDC interlayers was effective in improving power generation characteristics, and especially the SDC interlayer resulted in better performance. In the case of the GDC interlayer, the GDC/LSCF-SDC interface could be responsible for inferior performance to the cell with the SDC interlayer, possibly due to poor adhesion in the GDC/LSCF-SDC interface.

検診によつて発見される無症候性未破裂脳動脈瘤の破裂のリスクは未だ明かではないが,全体としては約1%程度と推定され,直径5mm程度より大きいものではより高いと考えられる.わが国の技術レベルから考えると,これらの症例を積極的に発見,手術することにより,くも膜下出血の発生頻度を減少せしめることが期待される.

The outcome of eight patients with invasive thymoma accompanying pleural dissemination was investigated. Only two patients had mediastinal tumor resection and pleural disseminated tumor excision. Seven patients underwent radiotherapy to the mediastinum and/or disseminated tumors. A clinical response to radiotherapy was achieved in the six patients with evaluable lesions (complete response in five patients and partial response in one). The estimated 5-year survival rate was 87.5%. Four patients were alive more than 10 years. So far, the mediastinal tumors of seven patients have been controlled for periods ranging from 42 to 154 months. Recurrence in six patients appeared as pleural tumors. Four out of the six patients had five courses of radiotherapy to the recurrent pleural tumors, four of which achieved complete response. No distant metastases were observed at any time. These observations suggest that radiotherapy should be the primary mode of treatment in cases of invasive thymoma with pleural dissemination. © 1993 Wiley-Liss, Inc.

The survival and recurrence of 37 patients with small cell lung cancer who underwent surgical resection were compared with those of 32 patients who were excluded from surgical resection but received radiotherapy. All but 2 patients received chemotherapy. The number of patients in the resected and nonresected groups in each pretreatment clinical stage were, respectively, as follows: 13 and 2 in stage I, 12 and 7 in stage II, and 12 and 23 in stage IIIa. The main reasons for exclusion from surgical resection were locally advanced disease in 15 patients, avoidance of pneumonectomy in 7, and poor pulmonary function in 5. In stage II, the mean tumor size was larger and there were fewer patients with peripheral tumors in the nonresected group than in the resected group. In stage IIIa, there were significantly more patients with overt N2 disease and central tumors in the nonresected group than in the resected group. The 5-year survival rate of the resected group in stage I was 67.7%. Although the nonresected group in stages II and IIIa had many adverse prognostic factors, there was no statistically significant difference between the survival of the resected and the nonresected groups. With respect to the site of first recurrence, a similar pattern was observed in the two groups in each stage, whereas local disease in stage I was completely controlled by surgical resection. These observations suggest that surgical resection can be considered a modality of treatment in clinical stage I. However, the treatment role of surgical resection in clinical stages II and IIIa, even in selected patients, remains unclear.

The radiosensitizing effect of the nitroimidazole derivative RK28 and diethyldithiocarbamate (DDC), which is an inhibitor of superoxide dismutase activity, was examined in vitro by using Meth A tumor cells. The radiosensitizing effect of 0.5 mM RK28 was observed in both of 10 Gy and 15 Gy irradiated groups. The addition of 5 x 10(-7) M DDC also enhanced the radiation-induced proliferation inhibition. Marked enhancement of the antiproliferative effect was observed in combined use of 0.2 mM or 0.5 mM RK28 with 2 x 10(-7) M or 5 x 10(-7) M DDC. These results suggest that enhanced oxygen effect could be expected through combined use of the ionizing irradiation with both of these agents.

原発性肺癌患者1180例のうち診断時に骨転移を認めた185例 (15.7%) に対して検討を加えた.組織型では腺癌, 小細胞癌に比べ扁平上皮癌に骨転移が少なく, また腺癌では多発性骨転移が多い傾向にあった.診断面では骨シンチが98.2%の陽性を示したのに対し, 骨X線では69.2%の陽性しか認められなかった.骨転移症例の中間生存期間は5.5カ月で予後は不良であった.放射線治療の有効性は67.7%であった.

Of 471 patients undergoing a complete resection for non-small-cell carcinoma of the lung between 1972 and 1989, 40 patients (8.5%) had local recurrences without extrathoracic distant metastasis. Excluding 8 patients who had malignant pleural effusion, we selected 32 patients (24 with hilar-mediastinal lymph node, 6 with bronchial stump, and 2 with chest wall recurrence) from the 40 patients and assessed the significance of local control by radiotherapy. The median length of survival after disease recurrence for these 32 patients was 19 months. Of 29 patients given radiation treatment, 16 who responded to the treatment survived significantly longer than nonresponders (median survival time 27 months versus 6 months, p0.01). Univariate analyses of survival after recurrences in relation to various factors revealed that sex and disease-free intervals were significant prognostic factors (p0.05) other than the effect of radiotherapy. A multivariate analysis showed that the effect of radiotherapy was the predominant prognostic factor. From these results, we conclude that local control with radiation is beneficial in patients with solely locally recurrent tumors in terms of improved survival.

A case of prolonged survival after radiotherapy for primary tracheal squamous cell carcinoma and the subsequent brain metastases is reported. The patient is alive and well without any sign of relapse, approximately six years after the onset of brain metastases from tracheal carcinoma. Radiotherapy proved useful in the treatment of both the primary tracheal carcinoma and the brain metastases.

[2.2]Metacyclophane ( 1 ) undergoes a variety of reactions according to the reagents and conditions. These include (1) substitution (path a), (2) transannular dehydrogenation (path b and c), (3) cycloisomerization (path d) and (4) transannular hydrogenation. A brief summary of these reactions is presented. The diversity of the reactions of 1 is further explored using benzoyl peroxide (BPO), cupric chloride, aluminum chloride, other metal salts, H 2 SO 4 and FSO 3 H. With BPO or cupric chloride, one-electron transfer mechanism is postulated. This involves a tautomeric ion pair formed by the intramolecular arylation with an aryl cation radical. A supporting evidence in favor of the mechanism is presented from experiments using various metal salts in different solvents. On the contrary, the reaction with aluminum chloride gives decahydropyrene ( 8 ) and octahydropyrene ( 11 ) together with cycloisomerization product 5 and dehydrogenation products 2 , 3 and 4 . When treated with AlCl 3 HCl 1 gives similar products as above but the product ratios are quite different. The major product is 5 but only a trace amount of 8 is formed. The reaction with H 2 SO 4 or FSO 3 H also produce 2 , 4 , 5 and 11 . Some mechanistic evidence in favor of the disproportionation reaction is presented.

Reviewing the outcome of 70 cases of clinically localized small cell lung cancer (SCLC) treated with combined modality treatment, we attempted to define the role of resection in this disease. The survival rate for all cases was 37 per cent at 2 years and 23 per cent at 3 years with a median survival time (MST) of 14 months. For 25 resected cases the overall 5-year survival rate was 37 per cent with an MST of 26 months. According to clinical staging, 5-year survival was 64 per cent for stage I and 20 per cent for stage II. However, none of the stage III cases achieved long-term survival, of over 3 years. In 45 non-resected cases, the overall response rate was 84 per cent with a 44 per cent complete response. The overall survival rate was 27 per cent at 2 years and 14 per cent at 3 years with an MST of 11 months. The 20 cases who achieved complete response had an MST of 26 months with 51 per cent alive at 2 years and 19 per cent at 5 years. Thus, we consider that lung resection is definitely indicated in cases with stage I and probably stage II SCLC. For stage III, however, particularly in cases with N2 disease, resection seems to offer no special benefit in favor of survival compared to combination chemotherapy and radiotherapy.

肺小細胞癌67例に対して化学療法と放射線療法の同時ならびに交替併用治療を行った.有効率は79%(CR37%, PR42%) であった.この有効率はLD例がED例より, また強力化学療法と放射線交替併用群が軽い化学療法と放射線同時併用群より高かった.全体の遠隔成績は, MSTが8.5ヶ月, 2年生存17%, 3年生存8%であったが, 個々の成績は治療効果, 病巣の進展度, 一般状態により異った.特にLDのCR例の予後が良好で, MST19ヶ月, 2年生存38%, 3年生存23%であった.

We reviewed the brain metastases, after treatment, of 45 patients with limited small cell lung cancer who achieved complete remission by radiochemotherapy or curative operation. No patient received prophylactic cranial irradiation. The incidence of subsequent brain metastases was classified according to pretreatment staging as follows: two of 13 (15 percent) patients in stage I; two of ten (20 percent) in stage II; nine of 17 (53 percent) in stage IIIa; and four of five (80 percent) in stage IIIb. The brain metastases occurred from seven to 29 months after the start of treatment, and the median time of the occurrence was 13 months. Of 17 patients who developed brain metastases and who subsequently received cranial irradiation, there were two in whom relapse had occurred at no other site except the brain and who survived 26 and 79 months after the relapse, respectively. These data indicate that not all patients with limited SCLC achieving CR due to treatment necessarily benefit from PCI.

The oxidation of 2-methyloxirane and propionaldehyde on ZnO has been studied by infrared spectroscopy. It was found that 2-methyloxirane was adsorbed on ZnO to form alkoxide species by scission of the α bond (OCH) of the epoxy ring. With time of adsorption, this alkoxide was dehydrogenated to form the enolate complex (CH 3 CH..CH..O) The enolate complex was oxidized to formate and acetate ions at about 400 °K in the presence of oxygen. In the case of oxidation by nitrous oxide, only propionate ions were formed. In the case of propionaldehyde, the adsorption occurred on zinc oxide by coordination of the carbonyl group. Upon oxidation by oxygen or nitrous oxide, scission of the CC bond of adsorbed species took place to a much smaller extent compared to 2-methyloxirane, the majority of the carboxylate species formed being propionate ions.

The preparation of [ m . n ]metacyclophane sulfur analogs with ring size up to 14 are described. They include 11- and 12-membered sulfides, sulfoxides, and sulfones as well as 12- and 14-membered rings having disulfide linkages. Through PMR spectral studies, including variable temperature spectroscopy, their conformation and conformational mobility are examined in relation to structural variation. While the parent compound of this series, [2,2]metacyclophane, has rigid system (ΔG ‡ > 27 kcal/mol), an increase in ring size lowers the energy barrier, ΔG ‡ 's found for 2-thia[3.2]- and 2,11-dithia[3.3)metacyclophanes are 13 and less than 9 kcal/mol, respectively. With the [3.2] system an increase in ΔG ‡ is observed in the sequence as going from sulfide to sulfoxide and then sulfone. A large effect of Me substitution in an aromatic ring on ΔG ‡ in the [3.3] system is attributable to buttressing effect, from which inversion mechanism is deduced. A highly substituted [3.3] system is found to exist in a stable cisoid geometry as well as transoid one. The UV spectrum of a series of compounds is examined to detect possible transannular interactions between the two benzene rings.

The reaction of dimethyl sulfoxide-polyphosphoric acid mixture with benzylic alcohols has been shown to afford a complex mixture of the products; this is in contrast to the case of aliphatic alcohols, which yield the corresponding acetal as the major product. By carrying out reactions using several benzylic alcohols and a series of benzyl alcohols, it was found that, in addition to the acetal formation reaction, dehydration and oxidation reactions, as well as a methyl thioether-formation reaction, were occurring. Possible pathways for the formation of these products are presented.

Several 1′- and 2-substituted 1-methylferrocenes were prepared, and their NMR spectra were measured. From the consideration of the chemical shifts, the transmission coefficient of the electronic effect through the ferrocene nucleus was calculated to be 0.28. 1′-Substituted 1-acetylferrocenes were also prepared, and their NMR spectra were discussed in connection with those of methylferrocenes.

This paper will describe the reaction of benzyl alcohol in the presence of various kinds of modified stabilized nickel catalysts, which had been prepared from the mother catalyst by treating it with solutions of appropriate metal chlorides. The catalytic activities of each modified catalyst for the formation of benzene, toluene, and benzaldehyde were compared in terms of the fH,fCH3, and fCHO values; the selectivities for the formation of benzene and toluene against that of benzaldehyde, SH and SCH3, were also evaluated. In general, the formation of toluene and benzene was greatly affected both by the kind and by the amount of metal chlorides used as additives. The reaction was promoted by the addition of a proper quantity of alkali metal chloride. In the cases of the reactions by lowlymodified catalysts, the decreasing order of the fH and fCH3 values according to the kind of metal ion adsorbed on the catalyst was as follows: Na+≥K+>Co2+>Ca2+>Cd2+>Ba2+>Hg2+>Cu2+. On the other hand, in the higher degrees o...

The condensation reactions of ferrocene with various ketones and with trichloroacetaldehyde in the presence of aluminum chloride were investigated. The formation of carbinol (7) as an intermediate was postulated in these reactions. In the reaction of acetone with ferrocene, the intermediate carbinol underwent further condensation with other ferrocene molecules to give oligomers (9). On the other hand, in the cases of methyl ethyl ketone, acetophenone, propiophenone, cyclohexanone, and trichloroacetaldehyde, the condensation reactions produced olefinic compounds via the intermediate carbinols. The intermediate carbinol was isolated together with the olefin in the reaction with trichloroacetaldehyde.

Ferrocene derivatives with one or two glycidyl substituents, desired for the formation of polymeric ferrocene compounds, were synthesized by the epoxidation of chlorohydrin compounds obtained from the products of the addition of ferrocenyllithium to epichlorohydrin at −40–−78°C. In the course of this synthesis, mono- and di-chlorohydrin compound and a disubstituted ferrocene with a 3-chloro-2-hydroxypropyl and a glycidyl substituent were isolated. All of them are stable liquid compounds. The investigation of the relationship between the reaction conditions and the yield of glycidylferrocenes revealed that the larger molar ratio of each reactant to ferrocene at each reaction step causes a higher conversion into glycidylferrocenes. In the epoxidation reaction of chlorohydrins with caustic alkali, a small amount of ethers, formed by the reaction of epoxides and the solvent ethanol, was obtained under some reaction conditions. In all cases, a small amount of biferrocenyl was isolated; the formation of this co...

The reactions of 1-iodo-2-ferrocenyl-1-nitroethylene (1) and β-bromo-β-nitrostyrene (5) with various sodium alkoxides were investigated. The reaction in the presence of an excess of alkoxides gave nitroketones, (2) and (6), and nitroacetals (3) and (7). The thermal decomposition of the nitroacetals in a nitrogen atmosphere afforded β-alkoxynitroolefins (8), which were found to be useful for obtaining asymmetric nitroacetals (9) with different alkoxy groups. The reaction mechanism was discussed by postulating the intervention of a nitrocarbene (12) and β-alkoxynitroolefin (8). The intermediacy of the nitrocarbene was supported by an experiment using vinylferrocene as a carbene scavenger.

The reaction of bromoferrocene with copper(I) chloride - pyridine complex was found to be second-order, that is, first-order in each of bromoferrocene and copper(I) chloride-pyridine complex. The results obtained from the competitive reactions between bromoferrocene and bromobenzene indicated that bromoferrocene was 103 times more reactive than bromobenzene in the halogen-exchange reaction. The effects of the pyridine bases on the halogen-exchange reaction of bromoferrocene were examined, and the trend of the results was found to be different from that of bromobenzene. The reason for this was discussed on the basis of the reaction mechanism.

The ppt-metal-catalyzed reduction, which is performed by refluxing the substrates with water in the presence of ppt-metals, was investigated in detail. The participation of water as a hydrogen donor was demonstrated by the fact that benzaldehyde was reduced to the corresponding deuterated alcohols when heated with D2O in the presence of ppt-Ni. The scope of the reduction was established by the reaction of cyclohexanone with ppt-metals and water. The most preferable H2O/cyclohexanone molar ratio was found to be about 15 : 1. The reaction was accelerated when a 0.25N aqueous solution of sodium chloride was used instead of water. It was found that the order of the abilities of various ppt-metals to decompose water is different from that of the abilities to catalyze the reduction of cyclohexanone. The values of the activation energies for the reduction catalyzed by ppt-Ni and ppt-Ni,Co were found to be 4.0 kcal/mol and 7.5 kcal/mol respectively. From these facts, it was concluded that the ppt-metal-catalyzed ...

The condensation reaction of haloferrocenes with various carboxylic acids in the presence of copper(I) oxide was studied extensively. The reaction generally afforded the corresponding ferrocenyl carboxylates, along with a comparable amount of ferrocene. The change in the distribution of the reaction products was examined under various conditions in the reaction of bromoferrence with benzoic acid. From the discussion of the reaction mechanism, it was concluded that the ferrocenyl ester and ferrocene are produced through different active species. The reaction under proper conditions was found to be useful for the preparation of ferrocenyl esters.

The condensation reaction of formylferrocene with simple aliphatic and alicyclic ketones, as acetone, ethyl methyl ketone, isobutyl methyl ketone, and cyclohexanone, in the presence of piperidine as a condensing agent afforded seven kinds of β-ferrocenyl-α,β-unsaturated ketones. The geometric configurations of the unsaturated ketones were discussed on the basis of their NMR spectra, and the influences of the ferrocenyl group on the π-π* transition bands in their UV spectra were also discussed.

The NMR spectra of [2.2]metacyclophane have been shown to be held unchanged over a wide range of temperature, ca. −80 to 190°C, indicating that the ten-membered ring system undergoes no inversion and is frozen in a chair conformation. It may, then, be expected that suitably substituted derivatives of [2.2]metacyclophane would become disymmetric due to restricted inversion; such was proved to be the case by carrying out the optical resolution of the 4, 14-di-substituted derivatives. The 4,14-dimethyl derivative was resolved by means of a complex formation with Newman’s reagent, [α]57826=−3.4 and +4.2°. 4,14-Dicarboxylic acid was also resolved by converting it to the quinine salt, [α]D22=+5.0°.

It was found that various organic compounds were reduced in good yields by refluxing them with precipitated metals in water. Water was proved to be indispensable as a hydrogen donor. The reduction of compounds which are insoluble in water was facilitated by using a mixture of dioxane and water. It is of interest that the reduction of nitriles with this catalyst afforded the hydrochlorides of the corresponding primary amines. The results imply the participation of the chloride ion on the ppt-metal catalyst. A selective reduction of C=C was observed in some α,β-unsaturated ketones, such as mesityl oxide and 1,3-diferrocenyl-2-buten-1-one. The relative activity of the various precipitated metals depends not only upon the kinds of the metals but also upon their combination. It is assumed that the surface of the ppt-Ni is acidic as a result of the coexisting chloride ion, which might participate in the catalytic reaction.

The condensation reactions of β-ferrocenylnitroethylene (1), with various aromatic aldehydes in the presence of an excess of sodium methoxide were investigated. The main products of these reactions were ferrocenylnitroalkenols (2), which were obtained from precursory sodium salts by the acidification of the reaction mixture. Sodium nitroalkanolate (4) was postulated as an intermediate in these reactions. On the other hand, the reaction of 1 with acetophenone resulted in a different condensation, one giving 1-benzoyl-2-ferrocenyl-3-nitropropane (11) and 1-benzoyl-2-ferrocenylethylene (12).

The geometrical and conformational isomerism of various β-ferrocenyl-α,β-unsaturated ketones, most of which had been reported in a previous paper, was discussed on the basis of their IR spectra in the 1700–1600 cm−1 range and their NMR spectra. An unusually strong IR absorption of the olefinic double bond was observed in comparison with that of the carbonyl group. Considering the IR and NMR data, it was concluded that 3-ferrocenyl-1-(p-substituted phenyl)-2-propen-1-ones may mostly exist in a s-cis conformation.

The nitration reaction of [2.2]metacyclophane was carried out using dilute nitric acid or benzoyl nitrate under various conditions. Dilute nitric acid afforded 2-nitro-4, 5, 9, 10-tetrahydro-pyrene as the sole product, confirming Allinger’s original experiments, whereas benzoyl nitrate furnished a complex mixture consisting of 4, 5, 9, 10-tetrahydropyrene, 4, 5-dihydropyrene and pyrene, together with the nitration product. A series of experiments established that 4, 5, 9, 10-tetrahydropyrene, which was formed by the 1, 4-elimination reaction of Allinger’s intermediate, was the initial product of the reaction. Two competitive reactions, nitration and dehydrogenation reactions of the tetrahydropyrene, were assumed to be occurring, thus accounting for the experimental results.

Dimethyl sulfoxide (DMSO), under acidic conditions, is known to yield formaldehyde as one of its decomposition products. A new method of synthesizing dialkoxymethanes, which consists of the treatment of alcohols with a DMSO-PPA (polyphosphoric acid) mixture, has been shown to be convenient and also generally applicable. Under mild conditions, five primary alcohols and four secondary alcohols are converted to the corresponding formals in 50—80 and 30—40% yields respectively. Dimethyl disulfide, bis(methylthio) methane and methylthiomethyl ether and an oxidation product of the alcohol have been shown to be the main by-products in this reaction. The examination of the NMR spectra has revealed that the acetal methylene protons of dialkoxymethanes made from (±)-secondary alcohols are observed as an AB quartet and as a singlet, each arising from meso and racemic compounds, respectively.

Electronic effects on the photochemical conversion of o-terphenyl to triphenylene were examined by comparing the ultraviolet irraiation reaction, carried out in a benzene solution using iodine as an oxidant, of three classes of o-terphenyl derivatives, 4- (3) and 4′-substituted (4) and 4,4″-disubstituted derivatives (5). While a strong electron-withdrawing group such as nitro group, hindered the cyclization reaction to occur, methoxy, fluoro, chloro and bromo compounds afforded the corresponding triphenylene derivatives. With bromo and iodo compounds, however, a complex mixture of the products resulted due to photochemical cleavage of a carbon-halogen bonding, which led to the formation of phenylation products and hence phenyltriphenylenes together with reduction products. Further, with iodo compounds, it was found that no oxidant was necessary to effect the cyclodehydrogenation reaction since iodine was liberated during the photolysis. Possible pathways for the formation of the photolysis products from b...