No abstract

Seventeen fibrous glasses of diverse type or dimensional distribution induced different incidences of malignant mesenchymal neoplasms when implanted in the pleurae of female Osborne-Mendel rats for periods of more than 1 year. Neoplastic response correlated well with the dimensional distribution of fibers. Fibers less than or equal to 1.5 mu in diameter and greater than 8 mu in length yielded the highest probability of pleural sarcomas, and probability trends suggested that pleural sarcoma incidence increased with increasing lengths of fibers with diameters of less than 1.5 mu, Morphologic observations indicated that fibers less than or equal to 8 mu in length were inactivated by phagocytosis. In fibers greater than 8 mu in length, the correlation of carcinogenicity witth increasing length was difficult to explain. Since neoplastic response to a variety of types of durable fibers, particularly asbestos fibers, was similar, our experiments reinforce the idea that the carcinogenicity of fibers depends on dimension and durability rather than physicochemical properties and emphasize that all respirable fibers be viewed with caution.

Difluoromethylene-containing compounds have attracted substantial research interest over the past decades for their ability to mimic biological functions of traditional functional groups while providing a wide variety of pharmacological benefits bestowed by the C–F bond. We report a novel strategy to access RCF2Br-containing heterocycles by regio- and enantioselective bromocyclization of difluoroalkenes enabled by chiral anion phase-transfer catalysis. The utility of this methodology was highlighted through a synthesis of an analogue of efavirenz, a drug used for treating HIV. Additionally, the synthetic versatility of the CF2Br intermediates was showcased through functionalization to a variety of enantioenriched α,α-difluoromethylene-containing products.

No abstract

Despite considerable research performed on forested catchments in the Ouachita Mountains of Oklahoma and Arkansas, little information on hydrological processes in operation is available. Based on catchment physical characteristics, subsurface flow was thought to be an important hydrological process in the region. Therefore, this study was undertaken to determine the occurrence, rates, timing and volumes of subsurface flow, and to estimate the importance of subsurface flow as a streamflow generating process. Subsurface flow was collected from three hillslope sites on a 7.7 ha forested catchment. Hillslope sites drained through natural seepage faces located near stream channels. Subsurface flow was collected from three depths at each hillslope site, below the litter layer, below the A horizon, and within the B horizon (Bt21). Subsurface flow occurred and was measured during 11 of 31 rainfall events. Subsurface flow responded rapidly to the initiation of and to changes in intensity of rainfall a t all depths. The rapid response was indicative of flow through soil macropores. B horizon subsurface flow commenced within 10 to 180 min of the initiation of rainfall. Multiple linear regression showed that the volume of subsurface flow generated during a given storm was directly related to rainfall depth and a 7-day antecedent precipitation index used to represent antecedent water content. About 67 per cent of the total subsurface flow collected during the study was produced in one large storm under wet antecedent conditions. The storm was equal to the 2-year, 24-hour storm for the region. Measured subsurface flow volumes were extended to the watershed scale to provide estimates of catchment-wide contributions to streamflow. It was estimated that subsurface flow contributed from 1 to 48 per cent of total quickflow measured at the catchment outlet. Based on the timing of subsurface flow, it was estimated that subsurface flow may contribute up to 70 per cent of quickflow before and soon after peak flow.

Clear-cut harvest and site preparation, including crushing the residual vegetation, burning, and contour ripping, were applied to three small watersheds in Oklahoma. Three undisturbed forested watersheds served as controls. First-year sediment losses averaged 282 and 36 kg/ha and storm flow water yields averaged 22.9 and 31.7 cm on clear-cut and uncut watersheds, respectively. The lower water yield on cut watersheds may have been due to contour ripping. Treatment differences in sediment yield were significant the second and third, but not the fourth, year following treatment. Storm flow water yield from clear-cut watersheds was significantly higher than from uncut watersheds the second year but not the third or fourth years. Absolute levels of sediment yield from clear-cut and control watersheds were relatively low in all years of the study. The overall impact of harvest and site preparation on total suspended solids levels in runoff was small and short-lived. of elimination of vegetation on stream water quantity and quality, Publ. 96, pp. 311-328, Int. Assoc. Sci. Hydrol. Gentbrugge, Belgium, 1970. Soil Survey Staff, Soil taxonomy: A basic system of soil classification for making and interpreting soil surveys, Handb. 436,

No abstract

The defined structure of molecules bearing multiple stereogenic axes is of increasing relevance to materials science, pharmaceuticals, and catalysis. However, catalytic enantioselective approaches to control multiple stereogenic axes remain synthetically challenging. We report the catalytic synthesis of two-axis terphenyl atropisomers, with complementary strategies to both chlorinated and brominated variants, formed with high diastereo-and enantioselectivity. The chemistry proceeds through a sequence of two distinct dynamic kinetic resolutions: first, an atroposelective ring-opening of Bringmann-type lactones produces a product with one established axis of chirality; second, a stereoselective arene halogenation delivers the product with the second axis of chirality established. In order to achieve these results, a class of Brønsted basic guanidinylated peptides, which catalyze an efficient atroposelective chlorination, is reported for the first time. In addition, a complementary bromination is reported, which also establishes the second stereogenic axis. These bromo-terphenyls are accessible following the discovery that chiral anion phase transfer catalysis by C 2 -symmetric phosphoric acids allows catalyst control in the second stereochemistry-determining event. Accordingly, we established the fully catalyst-controlled stereodivergent synthesis of all possible chlorinated stereoisomers, while also demonstrating diastereodivergence in the brominated variants, with significant levels of enantioselectivity in both cases.