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Pulmonary glomus tumor is rare and its manifestations on magnetic resonance imaging (MRI) have not, to our knowledge, been reported previously. A round mass was detected in the right upper lung field on a routine chest radiograph. With dynamic contrast-enhanced MRI, the mass showed strong, early-phase peripheral enhancement that expanded in a centripetal direction with time. Postoperative pathologic examination confirmed the diagnosis of glomus tumor.

Aberrant methylation of a sodium co-transporter, solute carrier family 5 member 8 gene (SLC5A8) , has been detected in a subset of colorectal cancers, suggesting SLC5A8 may also serv

The racemic mixture of 2-thiocyanatoneopupukeanane, a marine sesquiterpene-thiocyanate with a tricylo[4.3.1.03,7]decane skeleton, was prepared through a pinacol-type rearrangement of a bicyclo[2.2.2]oct-5-en-2-ol giving a bicyclo[3.2.1]oct-6-en-2-one derivative and an aldol reaction leading to the neopupukeanane framework.

The racemate of junicedranol, a sesquiterpene-alcohol with a novel carbon skeleton, was prepared through a unique anionic [1,3] rearrangement of an 8-methylenebicyclo[3.2.1]oct-6-en-2-ol giving a cyclopentadiene derivative and the facial- and regioselective Diels–Alder reaction of the cyclopentadiene with a ketene equivalent leading to the junicedranol framework.

The anionic [1,3] rearrangement of both stereoisomeric bicyclo[3.2.1]oct-6-en-2-ols by treatment with KN(TMS) 2 in toluene or in diglyme took place as a stereoconvergent route giving each of the stereoisomeric hydroxydiquinanes.

The aromatic oxy-Cope rearrangement including a benzene ring took place when 1-methoxy-2-aryl-bicyclo[2.2.2]oct-5-en-2- exo -ols and 2-(2-methoxyphenyl)-bicyclo[2.2.2]oct-5-en- exo -2-ols were treated with KH in THF.

The reactivities of tricarbonyl(2,4-cycloheptadiene-1,6-dione)iron toward several kinds of nucleophiles and electrophiles were investigated. As a result, it was found that tricarbonyl(2,4-cycloheptadiene-1,6-dione)iron has several reaction sites and undergoes several types of reactions. A new synthetic route to hinokitiol and tricarbonyl-(7,8-diphenylheptariafulvalene-1,6-quinone)iron from (2,4-cycloheptadiene-1,6-dione)iron was explored.

A reaction of 1,4-dimethoxybicyclo[2.2.2]oct-5-en-2-one and R1MgX, followed by treatment with p-toluenesulfonic acid in benzene, gave the 5-methoxybicyclo[3.2.1]oct-6-en-2-one having a substituent (R1) at the C-1 bridgehead. This ketone was converted into the 5-methoxybicyclo[3.2.1]oct-3-en-2-one. By treatment with Li[CuR2], a second bridgehead substituent (R) was introduced at the C-4 position of the conjugated ketone. The product was converted into the corresponding α,β-unsaturated ketone, and then treated with R2Li or DIBAL-H (R2 = H). Acid treatment of the resulting allyl alcohols gave the bicyclo[2.2.2]oct-5-en-2-one having substituents R, R1, and R2 at the C-1, 4, and 5 positions, respectively. This procedure was successfully applied to a formal total synthesis of (±)-modhephene, a propellane-type triquinane sesquiterpene, and that of (±)-isocomene, an angular triquinane sesquiterpene, on the basis of an oxa-di-π methane rearrangement of the bicyclo[2.2.2]oct-5-en-2-ones.

Both enantiomers of 1-methoxybicyclo[2.2.2]oct-5-en-2-ones were prepared in more than 80%ee on the basis of a chemoenzymatic reaction sequence. The optical resolution was achieved by the enantioselective hydrolysis of chloroacetyl esters 1-methoxybicyclo[2.2.2]oct-5-en-endo-2-ols using commercially available lipases.

Synthesis of a propellane sesquiterpene (±)-modhephene ( 23 ) was achieved on the basic of a novel procedure to introduce the desired alkyl groups at both bridgeheads of a bicyclo[2.2.2]oct-5-en-2-one.

Pinacol-type rearrangement of 2-substituted 1-methoxybicyclo[2.2.2]oct-5-en-exo-2-ols (1) by treatment with p-toluenesulfonic acid in boiling benzene gave bicyclo[3.2.1]oct-6-en-2ones (2) and -3en-2-ones (4) in a ratio of ≥ 10 to 1 along with small amounts of dehydration products. Treatment of the endo isomers (3) under the same conditions gave 2, 4, and the dehydration products. The ratios of 2 to 4, in this case were within a certain range and were influenced by the substituent at the C-2 position. The ratio of the relative disappearance rate constant of 1 to that of the corresponding 3 was less than 10. This observation suggests that the unsaturated bridge does not offer remarkable anchimeric assistance in the reaction of 1. A similar acid treatment of the dehydration products gave 2 and 4 and their ratio was somewhat affected by the substituent. A mechanism is proposed for the pinacol-type rearrangement.

A direct diazo transfer reaction to bicyclo[3.2.1]oct-6-en-2-ones and related compounds was accomplished by treatments with 2,4,6-triisopropylbenzenesulfonyl azide and potassium t-butoxide at −78 °C in THF. A Wolff rearrangement of the resulting α-diazoketones in the presence of water gave ring-contraction products, bicyclo[2.2.1]heptenecarboxylic acids. Using these two transformations the total synthesis of (±)-camphorenone was achieved stereoselectively, starting from 1-methoxybicyclo[2.2.2]oct-5-en-2-one.

An adduct formed from 2-trichlorostannyl-3-pentanone and phenylethynyltrichlorotin was isolated, and the structure was determined by spectroscopy and X-ray crystallography. It provides a direct evidence for the carbostannylation of alkynyl metals.

Lewis acid-catalyzed reactions of an N-acylaldimine with allyltriisopropylsilane gave [2+2] azetidine annulation products, while those of an N-ethoxycarbonylaldimine gave an allylated product.

Synthesis of a propellane sesquiterpene (±)-modhephene ( 23 ) was achieved on the basic of a novel procedure to introduce the desired alkyl groups at both bridgeheads of a bicyclo[2.2.2]oct-5-en-2-one.

Treatment of an 8-methylene-endo-2-vinylbicyclo[3.2.1]oct-6-en-exo-2-ol with KH in THF gave mainly a [5-6] fused-ring compound via [1,3] sigmatropy with retention of the configuration in the migrating group.

Treatment of 2-vinylbicyclo[3.2.1]oct-6-en-2-ols with KH in toluene gave mainly [5-5] fused-ring compounds through a [1,3] sigmatropic shift.

The aromatic oxy-Cope rearrangement including a benzene ring took place when 1-methoxy-2-aryl-bicyclo[2.2.2]oct-5-en-2- exo -ols and 2-(2-methoxyphenyl)-bicyclo[2.2.2]oct-5-en- exo -2-ols were treated with KH in THF.

The reactivities of tricarbonyl(2,4-cycloheptadiene-1,6-dione)iron toward several kinds of nucleophiles and electrophiles were investigated. As a result, it was found that tricarbonyl(2,4-cycloheptadiene-1,6-dione)iron has several reaction sites and undergoes several types of reactions. A new synthetic route to hinokitiol and tricarbonyl-(7,8-diphenylheptariafulvalene-1,6-quinone)iron from (2,4-cycloheptadiene-1,6-dione)iron was explored.

The anionic [1,3] rearrangement of both stereoisomeric bicyclo[3.2.1]oct-6-en-2-ols by treatment with KN(TMS) 2 in toluene or in diglyme took place as a stereoconvergent route giving each of the stereoisomeric hydroxydiquinanes.

The racemate of junicedranol, a sesquiterpene-alcohol with a novel carbon skeleton, was prepared through a unique anionic [1,3] rearrangement of an 8-methylenebicyclo[3.2.1]oct-6-en-2-ol giving a cyclopentadiene derivative and the facial- and regioselective Diels–Alder reaction of the cyclopentadiene with a ketene equivalent leading to the junicedranol framework.

NMR studies indicatethe hydrophobic pocket formedby the internalfour-stand β-sheet of apoprotein bindsNCS-chr with the conformation in wich its naphthoate moiety sits on the bottom of the pocket and the aminosugar and the carbonate group face outwards.

The purpose of the present study was to explore structural relationships among health behavior and health consciousness and to delineate latent factors underlying them.Data used in this study were obtained from a mail survey conducted by Toshima City Government, Tokyo, in 2002. The subjects were 3,000 community residents, living in the city, ranging in age from 20 to 79 years. The response rate was 54.3%. The data for 1,301 respondents without missing observations were analyzed. A second-order factor model utilizing 23 items of health behavior and health consciousness as observed indicators was developed for the analysis.Covariance structure analysis showed that a model consisting of 23 observed indicators, 9 latent first-order factors, and one second-order factor fitted well and explained the structure of health behavior and health consciousness: the 23 items of health behavior and health consciousness were indicatives of the latent second-order factor named Health-oriented Attitude. The second-order factor score was significantly higher in respondents willing to participate in programs of public health agencies than in those not willing.The results imply that reinforcement of the health-oriented attitude may bring about improved health consciousness and practice of health behavior. They also suggest the necessity to reconsider traditional programs of public health agencies because persons with a weak health-oriented attitude are less likely to participate.

Since the advent of imatinib mesylate (IM), its clinical efficacy against gastrointestinal stromal tumor (GIST) has been widely acknowledged, and therapeutic strategies for this disease have undergone great changes. We recently experienced a case of giant GIST of the stomach that was successfully treated with IM neoadjuvant therapy prior to surgical resection, but liver metastasis recurred 1 year and 7 months after the operation. The patient was a 65-year-old male who presented at our department with the chief complaints of dizziness, malaise, and fever in April 2002. An abdominal CT revealed a mass with a maximum diameter of 17 cm, as well as a cystic septate mass, 12 cm in diameter, with a thick capsule in the left lobe of the liver. The patient was diagnosed with GIST of the stomach and liver metastasis. Since radical operation was considered difficult at that point, IM (400 mg/day) was started on May 9. The result of treatment was determined to be PR, and radical operation was considered feasible. On March 18, 2003, total gastrectomy and left hepatic lobectomy/S 6 partial lobectomy were performed in the surgery department of our hospital. The postoperative course was favorable and oral administration of IM was resumed soon after the operation. However, the drug was discontinued for financial reasons and a decreased white blood cell count (grade 3) 2 months after the operation. Recurrence in the liver and abdominal wall was found in October 2004, and oral administration of IM was resumed again. Currently, treatment with IM is ongoing. Case reports on the efficacy of IM neoadjuvant therapy are occasionally found in the literature, but there are few reports on its long-term prognosis. We report this case with a discussion of future therapeutic options.

BNIP3 protein is a proapoptotic member of the Bcl-2 family that is expressed in hypoxic regions of tumors. To examine its role in the progression of gastrointestinal cancer, we examined the expression and DNA methylation status of BNIP3 gene in a panel of colorectal and gastric cancer cell lines. BNIP3 was not expressed in 14 of the 24 cell lines tested, and its absence was not caused by gene mutation or by altered expression of hypoxia inducible factor-1, a key transcription factor that regulates BNIP3 expression. On the other hand, methylation of the 5′ CpG island of BNIP3 was closely correlated with silencing the gene. Moreover, treating methylated cells with the methyltransferase inhibitor 5-aza-2′-deoxycytidine restored hypoxia-induced expression of BNIP3 mRNA and protein, which in turn led to cell death. Aberrant methylation of BNIP3 was also detected in 66% of primary colorectal and 49% of primary gastric cancers, but not in normal tissue samples collected from areas adjacent to the tumors. Apparently, epigenetic alteration of BNIP3 is a frequent and cancer-specific event, which suggests that inactivation of BNIP3 likely plays a key role in the progression of some gastrointestinal cancers and that it may be a useful molecular target for therapy.

Pancreatic cancer cells often show resistance to hypoxia-mediated apoptosis, but the molecular mechanism underlying that resistance remains unknown. The purpose of the present study, therefore, was to examine the role of epigenetic gene alteration in the resistance to hypoxia-mediated apoptosis among pancreatic cancer cells.Reverse transcription-polymerase chain reaction (RT-PCR) was used to examine the expression of five genes associated with hypoxia-mediated apoptosis (PUMA, Caspase-8 [CASP8], APAF-1, BNIP3, and BNIP3L) in a panel of pancreatic cancer cell lines. Protein expression was examined by Western blot analysis, using lysates from cells incubated under normoxic or hypoxic conditions. The methylation status of the genes was determined using bisulfite-PCR and sequencing. The percentages of cells that were apoptotic were determined using flow cytometry.Under normoxic conditions, the expression of the BNIP3 gene varied among the 12 pancreatic cancer cell lines tested, with 50% of them showing no BNIP3 expression at all, whereas expression of the other four genes was readily detected in all 12 cell lines. DNA methylation of BNIP3's CpG island in the region around the transcription start site of the gene was closely associated with its silencing. The expression of BNIP3 was restored by the methyltransferase inhibitor 5-aza-deoxycytidine (5-aza-dC), as was the hypoxia-mediated pancreatic cancer cell death.BNIP3 expression is silenced in some pancreatic cancer cells by the methylation of its CpG island. Demethylation of BNIP3, using a methyltransferase inhibitor, restores the gene's expression and induces hypoxia-mediated cell death. BNIP3 may thus be a useful target for new therapies aimed at treating pancreatic cancer.

Aberrant methylation of a sodium co-transporter, solute carrier family 5 member 8 gene (SLC5A8), has been detected in a subset of colorectal cancers, suggesting SLC5A8 may also serve as a tumor suppressor. To further investigate the role of epigenetic inactivation of SLC5A8 expression in gastric cancer, we determined the methylation status of the SLC5A8 5' CpG island (CGI) in a panel of gastric cancer cell lines and primary gastric cancers. We detected methylation of the 5'CGI in ten of twelve gastric cancer cell lines, and five of those showed dense methylation, which correlated with the absence of SLC5A8 transcription. Aberrant methylation of SLC5A8 was also detected in 23 of 71 (30%) primary gastric cancers, indicating that epigenetic inactivation of SLC5A8 is not a cell-line-specific phenomenon. SLC5A8 expression was restored in methylated cell lines by treatment with 5-aza-2'-deoxycytidine, a methyltransferase inhibitor. In addition, chromatin immunoprecipitation assays showed that acetylation of histone H3 in the 5' region of the gene correlated directly with SLC5A8 expression and inversely with DNA methylation. It thus appears that aberrant methylation of its 5'CGI and histone deacetylation play key roles in silencing SLC5A8 expression in gastric cancers.

The racemic mixture of 2-thiocyanatoneopupukeanane, a marine sesquiterpene-thiocyanate with a tricylo[4.3.1.03,7]decane skeleton, was prepared through a pinacol-type rearrangement of a bicyclo[2.2.2]oct-5-en-2-ol giving a bicyclo[3.2.1]oct-6-en-2-one derivative and an aldol reaction leading to the neopupukeanane framework.

OBJECTIVE We report MR findings in three patients with dysembryoplastic neuroepithelial tumor (DNT), which is a recently described benign tumor in childhood or young adolescents. MATERIALS AND METHODS The MR studies of three patients with surgically proven DNT were reviewed. All cases presented with partial complex seizures. Axial and coronal T1- and T2-weighted MR imaging of the head was performed using a 1.5 T MR unit. T1-weighted imaging after Gd-DTPA was also performed. RESULTS The tumors were located mainly in the cortical to subcortical area with very little perifocal mass effects on MR imaging. They were essentially hypointense on T1-weighted imaging and hyperintense well-demarcated mass on T2-weighted imaging and retained a thick gyrus-like configuration within the lesions. None of them exhibited contrast enhancement after administration of Gd-DTPA. CONCLUSION Differentiation of DNT from gangliogliomas or other low grade gliomas is possible using these MR features and is important because DNT does not recur after epilepsy surgery, therefore postoperative radiation and chemotherapy are not needed.

A nucleoside catalyzing the oxidoreduction of NADH and K{sub 3}Fe(CN){sub 6} was isolated from Torula yeast RNA and also obtained in 0.05{percent} yield by a series of steps: SDS-phenol extraction, nuclease P{sub 1} digestion, alkaline phosphatase digestion, anion exchange chromatography, and HPLC on an ODS column. Its chemical structure was clearly determined at 5-hydroxycytidine, from the results of FAB-MS and {sup 1}H and {sup 13}C NMR spectroscopies. The mass spectra, chromatographic behavior, UV spectra, and NMR spectra of this nucleoside from natural and synthetic sources were identical. This is the first report of an RNA catalyst having catalytic activity except for the cleavage and ligation of phosphodiester bonds of RNA. That an RNA has oxidoreduction activity indicates new possibilities for RNAs as living molecules. 5-hydroxycytidine may be a vestige of RNAs that formerly possessed metabolizing ability.

Treatment of 2-vinylbicyclo[3.2.1]oct-6-en-2-ols with KH in toluene gave mainly [5-5] fused-ring compounds through a [1,3] sigmatropic shift.

Treatment of an 8-methylene-endo-2-vinylbicyclo[3.2.1]oct-6-en-exo-2-ol with KH in THF gave mainly a [5-6] fused-ring compound via [1,3] sigmatropy with retention of the configuration in the migrating group.

Lewis acid-catalyzed reactions of an N-acylaldimine with allyltriisopropylsilane gave [2+2] azetidine annulation products, while those of an N-ethoxycarbonylaldimine gave an allylated product.

1,6-Diethynylcyclohepta-1,3,5-triene 27 was synthesized from 1,6-diacetylcyclohepta-1,3,5-triene 24. Oxidative coupling of the diacetylene 27 with copper(II) acetate in pyridine (Eglinton conditions) led to the cyclic ‘dimer’, a dimethano-bridged octadehydro[20]annulene 28, in 18% yield and the cyclic ‘trimer’, a trimethano-bridged dodecadehydro[30]annulene 29, in 19% yield. Both compounds 28 and 29 consisted of an equilibrating mixture of two conformers which differed in the relative disposition of the methano bridges. Oxidative coupling of compound 27 with oxygen, copper(I) chloride and ammonium chloride (Glaser conditions) afforded 2,3,4,5-tetrachloro-1,6-methano[10]annulene 32 in 3.5% yield together with compounds 28 and 29.

10,11,12,13-Tetradehydro-9,14-dimethyl[14]-, 10,11,12,13-tetradehydro-9,14-dimethyl[16]annuleno[a]azulene and their 3-isopropyl derivatives have been synthesized. The effect of annelation of a 10π-azulene ring onto the monocyclic [4n+ 2]π- and [4n]π-electron systems is discussed on the basis of 1H NMR and electronic spectra.

3-Hydroxy-(I, X = β- and α-OH; Y = H) and 2 β-senecioyloxy-(I, X = H; Y = OCOCH=CMe2) eremophilenolides were synthesized stereoselectively starting from ethylenedioxy octalone derivative (II, X = H2). The present synthetic study demonstrates unequivocally that the positions of ester groups of petasitolides should be located at C2- rather than C3- exposition.

交叉共役系の非ベンゼン系芳香族炭化水素として最も基本的な分子の一つである“カリセン”の安定な誘導体として1,2,3,4-テトラクロル-5,6-ジフェニルカリセンをテトラクロルシクロペンタジエンとジフェニルシクロプロペノンとの縮合によって合成し,この紫外,赤外,核磁気共鳴スペクトルの検討から,基底状態における極性構造の寄与の大きいことを明らかにした。またこの物質の塩基性に関連してpKを測定して-4.7を得た。更に双極子能率の測定からμ=7.97Dの極めて大きな値を持つことを明かにした。結合交替を考慮したHuckel MOによる取扱いを行なって基底電子状態を説明すると共に,テトラシアノエチレンとの分子化合物の電荷移動スペクトルの測定から最高被占軌道エネルギーを実験的に推定した。

Diels-Alder adducts of 2-methyl-2-cyclohexenone and substituted butadienes were obtained in a high yield in the presence of catalytic aluminum chloride.

Diels-Alder adducts of 2-methyl-2-cyclohexenone and substituted butadienes were obtained in a high yield in the presence of catalytic aluminum chloride.