Selective Crystallization of Linkage Isomers, [RhIII(NCS)(SCN)5]3- and [RhIII(SCN)6]3-, to Investigate Structural Trans Influence and Thermal Stability.

Linkage isomers of homoleptic complexes, [RhIII(SCN)6]3- and [RhIII(NCS)(SCN)5]3-, formed in aqueous solution were successfully separated by employing methyltriphenylphosphonium (MePPh3+) and 1-ethylquinolinium (EtQu+) ions as countercations, respectively. The single-crystal X-ray analysis of (MePPh3)3[RhIII(SCN)6] (1) indicated that all of the SCN- ligands coordinate to the RhIII ion by S atoms with an octahedral symmetry, where the average bond length of Rh-S is 2.374(7) Å. On the other hand, the RhIII ion of (EtQu)3[RhIII(NCS)(SCN)5]·H2O (2) is coordinated by five S atoms and one N atom of the SCN- ligands with a C4v symmetry. Structural trans influence was observed in the shorter bond length of Rh-S at the trans position of Rh-N. The Rh-S bond length is 2.3398(13) Å significantly shorter than those of 1 by ca. 0.04 Å, although DFT calculations based on the crystal structures indicated that the effective bond order of Rh-N is higher than those of Rh-S. Thermal stability examination by thermogravimetric and differential thermal analyses (TG/DTA) and IR spectroscopy indicated that the linkage isomerization of [RhIII(SCN)6]3- to [RhIII(NCS)(SCN)5]3- proceeded after melting around 174 °C. These results clearly indicate that [RhIII(NCS)(SCN)5]3- is thermodynamically more stable than [RhIII(SCN)6]3- in solid states, although further linkage isomerization hardly occurs.

Synthesis, crystal structure and photophysical properties of chlorido-[(E)-3-hy-droxy-2-methyl-6-(quinolin-8-yldiazen-yl)phenolato]copper(II) monohydrate.

The reaction between copper(II) chloride dihydrate and the (E)-2-methyl-4-(quinolin-8-yldiazen-yl)benzene-1,3-diol ligand in aceto-nitrile leads to the formation of the title compound, [Cu(C16H12N3O2)Cl]·H2O. The ligand is deprotonated and coordinates with three donor atoms (tridentate) to the CuII ion. Individual mol-ecules of the CuII complex are connected by chloride bridges, forming a one-dimensional coordination polymer. No photoisomerization to the cis isomer of the azo ligand was observed upon irradiation with UV light.

Ultrasonography Improves Glycemic Control by Detecting Insulin-Derived Localized Amyloidosis.

We examined the feasibility of ultrasound diagnosis of insulin-derived localized amyloidosis (IDLA). In addition to ultrasound detectability and findings, the insulin absorption rate, insulin dosage and hemoglobin A1c (HbA1c) levels before and after shifting the insulin injection site were investigated for 22 cases of IDLA. The detectability of IDLA on ultrasound was 100%; 59.1% was palpable lumps and 40.9% was not palpable. The palpable type had lower echo intensity and were harder than the non-palpable type. Blood flow decreased in IDLA, especially in the palpable type. IDLA, especially the palpable type, had a low insulin absorption rate. HbA1c level and insulin dosage decreased after shifting the injection site. The palpable type had more insulin reduction than the non-palpable type. Characteristic ultrasound images of IDLA were acquired. As the non-palpable type could be identified by ultrasound, its diagnosis encourages changing the insulin injection site; hence, ultrasound diagnosis of IDLA can enhance insulin treatment.

Localized Subcutaneous Insulin-Derived Amyloidosis Excised after Evaluation Using Ultrasonography in a Patient with Type 2 Diabetes Mellitus.

A 62-year-old man with type 2 diabetes mellitus, who had been on insulin therapy for the past 20 years, was found to have subcutaneous mass formation in the abdomen during a workup of worsened glycemic control. Because of suspected amyloid deposition, he was advised to avoid injections to the mass, which led to improvement of glycemic control. However, he strongly requested mass excision and was hospitalized. After evaluation using ultrasonography and computed tomography, a total mass excision was performed, and a diagnosis of insulin-derived amyloidosis was made. Comparison of the ultrasonographic and histopathological findings demonstrated that the location of the amyloid deposition nearly corresponded to the hypoechoic region. This case highlights that ultrasonography, which is a noninvasive imaging modality, can be useful for detection of insulin-derived amyloidosis.

Interleukin-2 gene transfer potentiates the alpha-galactosylceramide-stimulated antitumor effect by the induction of TRAIL in NKT and NK cells in mouse models of subcutaneous and metastatic carcinoma.

Alpha-Galactosylceramide (alpha-GalCer) is a potent CD1d ligand that activates natural killer like T-cells (NKT), leading to the production of helper T (Th) 1 and Th2 cytokines that mediate various immunemodulatory and antitumor effects. Here, we determined whether the administration of adenovirus-vector-encoding mouse interleukin-2 (AdmIL-2) can augment the antitumor effect of alpha-GalCer on subcutaneous and metastatic tumors in mice. Mice were intraperitoneally injected with alpha-GalCer on days 7, 10 and 13 after tumor inoculation, with or without intratumoral injection of AdmIL-2 on day 7. alpha-GalCer treatment increased the serum levels of interferon-gamma, while intratumoral injection of AdmIL-2 elevated serum IL-2 levels. A combination of alpha-GalCer and AdmIL-2 (alpha-GalCer/AdmIL-2) inhibited the in vivo tumor growth and improved the survival of tumor-bearing mice, as compared to the use of a single agent. Experiments on spontaneous metastasis models revealed that alpha-GalCer/AdmIL-2 reduced lung metastasis and prolonged survival, as compared to control groups. In addition, the splenic and liver mononuclear cells from mice treated with alpha-GalCer/AdmIL-2 showed enhanced cytolytic activity against NK-sensitive YAC-1 and NK-resistant 3LL tumors. Moreover, alpha-GalCer/AdmIL-2 treatment expanded the absolute numbers of lung and liver NK, NKT and T-cells as well as the TNF-related apoptosis-inducing ligand (TRAIL) expression of these cells. This study shows the efficacy of alpha-GalCer/AdmIL-2 immunomodulatory therapy, and provides a cellular mechanism on how it exerts the antitumor effects.

[Telangiectatic focal nodular hyperplasia accompanied with hemorrhage and necrosis during the course: report of a case].

A tumor, which was 10 cm in diameter, was found in the lateral segment of the liver of a 42-year-old man in October, 2004. The lesion was clinically diagnosed as focal nodular hyperplasia (FNH). In March, 2006, the patient admitted our hospital complaining epigastralgia, back pain, and fever. Hemorrhage and necrotic region was revealed within the tumor, hence lateral segmentectomy was carried out. The lesion was pathologically diagnosed as a telangiectatic FNH (T-FNH). A possibility that hemorrhage or necrosis may be induced within a T-FNH during its progress should be taken into consideration.

[Undifferentiated pleomorphic sarcoma detected in the descending colon: report of a case].

Undifferentiated pleomorphic sarcoma was a well-known tumor that usually involves the soft tissues. However, in the alimentary tract, it was seldom reported. A 55-year-old man was admitted to our hospital with lower abdominal pain. Endoscopic examination showed a protruding tumor occupied the lumen of the descending colon. Because of the colon obstruction by the tumor, a left hemicolectomy with en bloc lymph node dissection was performed. Main occupied lesion of the tumor was mesenterium and submucosa, with no epithelial dysplasia. Also, dissemination of the tumor was recognized in the mesenterium and greater omentum. Based on histological and immunohistological studies, the tumor was diagnosed as undifferentiated pleomorphic sarcoma.

Inhibition of type I procollagen production by tRNAVal CTE-HSP47 ribozyme.

BACKGROUND: Fibrosis characteristically occurs in the advanced stages of chronic inflammatory diseases, occasionally as the primary lesion, and frequently determines the disease prognosis. Fibrotic lesions consist mostly of collagen, and therefore it may be possible to prevent or treat fibrosis by inhibiting collagen production. Of the currently available therapeutic approaches, however, none is sufficiently effective and specific for inhibition of collagen. Heat shock protein 47 (HSP47) is a collagen-specific molecular chaperone that has been reported to play a pivotal role in secretion of procollagen molecules. Therefore, we have tried to suppress its function to inhibit these various types of collagen. METHODS: We have developed a novel type of ribozyme by ligating a hammerhead sequence to a tRNA(Val) promoter to facilitate displacing the ribozyme from nucleus to cytoplasm and to constitutive transport element, a binding motif of helicase which unwinds mRNA to render the target sequence on the mRNA accessible to the ribozyme. RESULTS: The ribozyme thus constructed showed strong activity to cleave HSP47 mRNA and suppress the secretion of type I procollagen in the human primary fibroblast. CONCLUSION: We suggest applicability of this ribozyme as a new modality for antifibrosis therapy.