Synthesis of Redox-Active Phenanthrene-Fused Heteroarenes by Palladium-Catalyzed C-H Annulation.

Pd-catalyzed C-H annulation reactions of halo- and aryl-heteroarenes were developed using readily available o-bromobiaryls and o-dibromoaryls, respectively. A variety of five-membered heteroarenes rapidly provided the corresponding phenanthrene-fused heteroarenes, which led to the identification of phenanthro-pyrazole and thiazole as new, stable -2 V redox couples. The flexible syntheses and tunability of the redox potentials of these azole-fused phenanthrenes over a wide range are expected to facilitate their application as redox-active organic functional materials.

Regio- and Stereoselective Synthesis of Thiazole-Containing Triarylethylenes by Hydroarylation of Alkynes.

Thiazole-containing π-conjugated moieties are important structural units in the development of new electronic and photochromic materials. We have developed a Pd-catalyzed syn-hydroarylation reaction of diaryl alkynes with thiazoles that provides access to thiazole-containing triarylethylenes. Pd(II) complexes derived from Pd(0) species and carboxylic acids facilitated C-H functionalization of the unsubstituted thiazole with high C5 selectivity. The catalytic system was also compatible with other azoles, such as oxazoles and a pyrazole, allowing the stereoselective syntheses of various trisubstituted olefins.

Aqueous humor concentrations of vascular endothelial growth factor and pigment epithelium-derived factor in high myopic patients.

PURPOSE: To compare the aqueous humor levels of vascular endothelial growth factor (VEGF) and pigment epithelium-derived factor (PEDF) in high myopic eyes and control eyes. METHODS: Aqueous humor samples were collected from 21 highly myopic eyes of 20 patients (high myopia group) and from 30 cataract eyes of 30 patients with no choroidal neovascularization (CNV) or other ocular or systemic diseases (control group). Of the 21 high myopic eyes, 13 had no complications secondary to high myopia (high myopia with no complications group), 3 had posterior staphyloma (high myopia with staphyloma group), and 5 had chorioretinal atrophy (high myopia with chorioretinal atrophy group). The aqueous humor levels of VEGF and PEDF were determined by using commercially available enzyme-linked immunosorbent assay kits. RESULTS: Aqueous humor levels of VEGF were significantly lower in the high myopia group compared to that in the control group (p<0.001). VEGF levels decreased with an increase in the axial length (p<0.001). PEDF levels tended to be higher in the high myopia group compared to that in the control group; however, the difference was not significant. Three high myopia groups had significantly lower VEGF/PEDF ratios than the control group (p=0.000, 0.002, and 0.005). CONCLUSIONS: Aqueous humor levels of VEGF in the high myopia group were significantly lower than those in the control group. The differing levels of VEGF and PEDF in the high myopia and control groups suggest that high myopia disrupts the VEGF/PEDF balance in retinal pigment epithelium (RPE) cells.

Macular hole after intravitreal ranibizumab injection for polypoidal choroidal vasculopathy.

A 67-year-old man visited the clinic presenting with the complaint of decreased vision in his left eye. Visual acuity of the left eye was 6/6. On fundus examination, an orange polypoidal lesion and retinal pigment epithelial (RPE) detachment were seen. Fluorescein angiography and indocyanine green angiography were performed. There was hyper-fluorescence of a clustered polyp-like lesion. The patient was diagnosed with polypoidal choroidal vasculopathy and we recommended that he be seen again in three months. At this visit, visual acuity of the left eye had decreased to 6/9 and the RPE detachment was aggravated. Intravitreal injection of ranibizumab was performed. One month after the injection, visual acuity of his left eye was 6/96. A macular hole was seen in his left eye and vitrectomy of the left eye was performed. Optical coherence tomography was checked and it showed that the macular hole was closed. Two more intravitreal ranibizumab injections were done on the left eye. Visual acuity of his left eye subsequently improved to 6/18.8.

Etiology of invasive bacterial infections in immunocompetent children in Korea (1996-2005): a retrospective multicenter study.

The purpose of this study was to identify the major etiological agents responsible for invasive bacterial infections in immunocompetent Korean children. We retrospectively surveyed invasive bacterial infections in immunocompetent children caused by eight major pediatric bacteria, namely Streptococcus pneumoniae, Haemophilus influenzae, Neisseria meningitidis, Staphylococcus aureus, Streptococcus agalactiae, Streptococcus pyogenes, Listeria monocytogenes, and Salmonella species that were diagnosed at 18 university hospitals from 1996 to 2005. A total of 768 cases were identified. S. agalactiae (48.1%) and S. aureus (37.2%) were the most common pathogens in infants younger than 3 months. S. agalactiae was a common cause of meningitis (73.0%), bacteremia without localization (34.0%), and arthritis (50%) in this age group. S. pneumoniae (45.3%) and H. influenzae (20.4%) were common in children aged 3 months to 5 yr. S. pneumoniae was a common cause of meningitis (41.6%), bacteremia without localization (40.0%), and bacteremic pneumonia (74.1%) in this age group. S. aureus (50.6%), Salmonella species (16.9%), and S. pneumoniae (16.3%) were common in older children. A significant decline in H. influenzae infections over the last 10 yr was noted. S. agalactiae, S. pneumoniae, and S. aureus are important pathogens responsible for invasive bacterial infections in Korean children.

Molecular changes from dysplastic nodule to hepatocellular carcinoma through gene expression profiling.

Progression of hepatocellular carcinoma (HCC) is a stepwise process that proceeds from pre-neoplastic lesions--including low-grade dysplastic nodules (LGDNs) and high-grade dysplastic nodules (HGDNs)--to advanced HCC. The molecular changes associated with this progression are unclear, however, and the morphological cues thought to distinguish pre-neoplastic lesions from well-differentiated HCC are not universally accepted. To understand the multistep process of hepato-carcinogenesis at the molecular level, we used oligo-nucleotide microarrays to investigate the transcription profiles of 50 hepatocellular nodular lesions ranging from LGDNs to primary HCC (Edmondson grades 1-3). We demonstrated that gene expression profiles can discriminate not only between dysplastic nodules and overt carcinoma but also between different histological grades of HCC via unsupervised hierarchical clustering with 10,376 genes. We identified 3,084 grade-associated genes, correlated with tumor progression, using one-way ANOVA and a one-versus-all unpooled t test. Functional assignment of these genes revealed discrete expression clusters representing grade-dependent biological properties of HCC. Using both diagonal linear discriminant analysis and support vector machines, we identified 240 genes that could accurately classify tumors according to histological grade, especially when attempting to discriminate LGDNs, HGDNs, and grade 1 HCC. In conclusion, a clear molecular demarcation between dysplastic nodules and overt HCC exists. The progression from grade 1 through grade 3 HCC is associated with changes in gene expression consistent with plausible functional consequences.