Hypervalent iodine in synthesis 64:Syntheses of diaryl selenides and alkyl aryl selenides by palladium-catalyzed arylation of areneselenyl or alkaneselenyl magnesium bromide with diaryliodonium salt

Areneselenyl or alkaneselenyl magnesium bromide reacts rapidly with diaryliodonium salt to give the corresponding diaryl or alkyl aryl selenide in the presence of catalytic amounts of Pd-(PPh3)4 in good yield.

Novel reaction products from the hypervalent iodine oxidation of hydroxylated stilbenes and isoflavones

Novel reaction pathways for the hypervalent iodine-mediated oxidation of bioactive phenols containing extended conjugated π-systems are described. Oxidation of 4-hydroxystilbenes in methanol using a hypervalent iodine-based oxidant led to the formal 1,2-addition of methoxy groups across the central stilbene double bond. Treatment of the structurally related 4-hydroxyisoflavone with di(trifluoroacetoxy)iodobenzene leads to the surprising formation of 2,4′-dihydroxybenzil. Potential mechanisms for these new reaction pathways are discussed, and the X-ray crystal structure of 2,4′-dihydroxybenzil is presented. In contrast, oxidation of the corresponding 3-hydroxystilbenes and 3-hydroxyisoflavone led to conventional dienone oxidation products. The antitumour implications of these oxidation processes are briefly highlighted; the novel 4-substituted phenolic oxidation products were found to be inactive in terms of in vitro antitumour cellular activity, whereas the 3-substituted phenol products gave novel agents with potent and enhanced antitumour activity in the HCT 116 cancer cell line. © The Royal Society of Chemistry 2005.

A randomized trial comparing the diagnostic accuracy of visual inspection with acetic acid to Visual Inspection with Lugol's Iodine for cervical cancer screening in HIV-infected women.

Visual inspection with Acetic Acid (VIA) and Visual Inspection with Lugol’s Iodine (VILI) are increasingly recommended in various cervical cancer screening protocols in low-resource settings. Although VIA is more widely used, VILI has been advocated as an easier and more specific screening test. VILI has not been well-validated as a stand-alone screening test, compared to VIA or validated for use in HIV-infected women. We carried out a randomized clinical trial to compare the diagnostic accuracy of VIA and VILI among HIV-infected women. Women attending the Family AIDS Care and Education Services (FACES) clinic in western Kenya were enrolled and randomized to undergo either VIA or VILI with colposcopy. Lesions suspicious for cervical intraepithelial neoplasia 2 or greater (CIN2+) were biopsied. Between October 2011 and June 2012, 654 were randomized to undergo VIA or VILI. The test positivity rates were 26.2% for VIA and 30.6% for VILI (p = 0.22). The rate of detection of CIN2+ was 7.7% in the VIA arm and 11.5% in the VILI arm (p = 0.10). There was no significant difference in the diagnostic performance of VIA and VILI for the detection of CIN2+. Sensitivity and specificity were 84.0% and 78.6%, respectively, for VIA and 84.2% and 76.4% for VILI. The positive and negative predictive values were 24.7% and 98.3% for VIA, and 31.7% and 97.4% for VILI. Among women with CD4+ count < 350, VILI had a significantly decreased specificity (66.2%) compared to VIA in the same group (83.9%, p = 0.02) and compared to VILI performed among women with CD4+ count ≥ 350 (79.7%, p = 0.02). VIA and VILI had similar diagnostic accuracy and rates of CIN2+ detection among HIV-infected women.

(Table 1) Organic acid analyses from ODP Leg 125 interstitial waters

For the first time, short-chain organic acids are described from serpentine-associated interstitial waters. In this geologic setting, formate typically dominates the organic acid assemblage. Within the forearc setting, the organic acids are associated only with unconsolidated serpentine. Their existence may be the result of alkaline hydrolysis of ester linkages in organic matter that has been entrained in the serpentine diapir.

(Table 1) Strontium isotopic ratios of interstitial waters from ODP Leg 125 holes

The strontium isotopic data presented here are from interstitial waters squeezed from unconsolidated serpentine, an unusual type of substrate that was recovered from Mariana and Bonin forearc seamounts and has not been previously drilled by the Deep Sea Drilling Project or Ocean Drilling Program. The texture and composition of some of these serpentine deposits from Conical Seamount, located on the Mariana forearc, indicate emplacement as low- or high-viscosity, cold gravitational flows, which are therefore neither sediment nor igneous rock. The strontium isotopic ratios of the interstitial waters from the unconsolidated serpentine range from 0.70912 to 0.70525 and trend toward a relatively less radiogenic composition with increasing sub-bottom depth. These strontium isotopic ratios are derived from at least two strontium sources: seawater and igneous. The strontium isotopic gradients from the interstitial waters from the Leg 125 sites are probably the result of diffusive transport of strontium from an igneous source deep within the lithosphere that may be contaminated with subducted or underplated sediment.

(Table 1) Framework-grain composition of ODP Leg 125 sediment samples

This report presents petrographic data that will be used to characterize spatial and temporal changes in the provenance of Izu-Bonin forearc sediments recovered during Ocean Drilling Program Leg 125. These data document the history of the Izu-Bonin arc system as reflected in the framework mineralogy of supra-subduction zone sediments. Subsequent analysis will reveal the record of arc-splitting events as well as the spatial and temporal episodes in forearc volcanism, in source type, and in source area that are preserved in these sediments.

(Table 1) Composition of interstitial waters from ODP Leg 125 sites

Pore waters were collected from nine sites during Leg 125 of the Ocean Drilling Program (ODP). The first four sites (778-781) were drilled in the Mariana forearc on and near Conical Seamount, an active serpentine "mud volcano" located about 80 km behind the trench axis and 120 km in front of the active island arc. The last five sites (782-786) were drilled in the Izu-Bonin forearc between the trench and the outer arc high. Pore waters from the five sites from both areas that penetrated serpentine silts (Sites 778,779,780,783, and 784) are discussed in detail by Mottl (this volume). Here we report analyses of the pore waters from all nine sites for Li, Rb, Sr, Ba, Mn, B, and the sulfur isotopic ratio of dissolved sulfate. Sampling methods and results of analyses for major and minor species determined aboard ship were presented by Fryer, Pearce, Stokking, et al. (1990, doi:10.2973/odp.proc.ir.125.1990).