The appearance of detritus shed from mountain ranges along the northern margin of the Tibetan Plateau heralds the Cenozoic development of high topography. Current estimates of the age of the basal conglomerate in the Qaidam basin place this event in Paleocene-Eocene. Here we present new magnetostratigraphy and mammalian biostratigraphy that refine the onset of basin fill to ∼25.5 Myr and reveal that sediment accumulated continuously until ∼4.8 Myr. Sediment provenance implies a sustained source in the East Kunlun Shan throughout this time period. However, the appearance of detritus from the Qilian Shan at ∼12 Myr suggests emergence of topography north of the Qaidam occurred during the late Miocene. Our results imply that deformation and mountain building significantly post-date Indo-Asian collision and challenge the suggestion that the extent of the plateau has remained constant through time. Rather, our results require expansion of high topography during the past 25 Myr.

Estrogen sulfotransferase (EST) catalyzes the transfer of the sulfuryl group from 3'-phosphoadenosine 5'-phosphosulfate (PAPS) to 17beta-estradiol (E2). The sulfation of E2 prevents it from binding to, and thereby activating, the estrogen receptor. The regulation of EST appears to be causally linked to tumorigenesis in the breast and endometrium. In this study, recombinant human EST is characterized, and the catalytic mechanism of the transfer reaction is investigated in ligand binding and initial rate experiments. The native enzyme is a dimer of 35-kDa subunits. The apparent equilibrium constant for transfer to E2 is (4.5 +/- 0.2) x 10(3) at pH 6.3 and T = 25 +/- 2 degrees C. Initial rate studies provide the kinetic constants for the reaction and suggest a sequential mechanism. E2 is a partial substrate inhibitor (Ki = 80 +/- 5 nM). The binding of two E2 per EST subunit suggests that the partial inhibition occurs through binding at an allosteric site. In addition to providing the dissociation constants for the ligand-enzyme complexes, binding studies demonstrate that each substrate binds independently to the enzyme and that both the E.PAP.E2S and E.PAP.E2 dead-end complexes form. These results strongly suggest a Random Bi Bi mechanism with two dead-end complexes.

The preparation, characterization, and preliminary biomedical application of various nitric oxide (NO)-releasing fumed silica particles (0.2-0.3 microm) are reported. The tiny NO-releasing particles are synthesized by first tethering alkylamines onto the surface of the silica using amine-containing silylation reagents. These amine groups are then converted to corresponding N-diazeniumdiolate groups via reaction with NO(g) at high pressure in the presence of methoxide bases (e.g., NaOMe). N-Diazeniumdiolate groups were found to form more readily with secondary amino nitrogens than primary amino nitrogens tethered to the silica. Different alkali metal cations of the methoxide bases, however, have little effect on the degree of N-diazeniumdiolate formation. The N-diazeniumdiolate moieties attached on the silica surface undergo a primarily proton-driven dissociation to NO under physiological conditions, with an "apparent" reaction order somewhat greater than 1 owing to local increases in pH at the surface of the particles as free amine groups are generated. The rates of N-diazeniumdiolate dissociation are further related to the parent amine structures and the pH of the soaking buffer. The N-diazeniumdiolate groups also undergo slow thermal dissociation to NO, with zero-order dissociation observed at both -15 and 23 degrees C. It is further shown that the resulting NO-releasing fumed silica particles can be embedded into polymer films to create coatings that are thromboresistant, via the release of NO at fluxes that mimic healthy endothelial cells (EC). For example a polyurethane coating containing 20 wt % of NO-releasing particles prepared with pendant hexane diamine structure (i.e., Sil-2N[6]-N(2)O(2)Na) is shown to exhibit improved surface thromboresistivity (compared to controls) when used to coat the inner walls of extracorporeal circuits (ECC) employed in a rabbit model for extracorporeal blood circulation.

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[1] Based on field investigations, aerial-photo morphological analysis, topographic profiling, and optically stimulated luminescence (OSL) dating of alluvial surfaces, we estimate vertical components of the slip rate along the South Heli Shan thrust fault, which lies on the northern margin of the Hexi Corridor and the northeastern edge of the Tibetan Plateau. The fault consists of three segments with scarp heights ranging from less than 1 m to more than 16 m. OSL dating indicates that most of the alluvial fans cut by fault scarps formed during the transition from the last glacial stage to the present interglacial stage from 19 to~9 ka along southern Heli Shan and from~27 ka to~22 ka along its northern margin. In addition, remnants of older alluvial fan have been abandoned after~67 ka. Scarp heights increase from west to east and reach a maximum of more than 16 m near the eastern end. Using three approaches, we calculate late Quaternary slip rates for each of the three fault segments along the southern margin and the fault on the northern flank. These approaches yield maximum vertical slip rates from 0.18 to 0.2 mm/a for the western segment, 0.3 to 0.43 mm/a for the central segment, 0.36 to 0.53 mm/a for the eastern segment, and 0.21 mm/a for the Wutongjing Fault, which lies on the north side of the Heli Shan. For a range of likely fault dips, these correspond to 0.1-0.2 mm/a of average horizontal shortening for the western segment, and increase to 0.4-0.5 mm/a across the eastern segment of the southern Heli Shan Fault. Combining the height of the eastern parts of the Heli Shan (Daqing Peak) above the Hei He (a major river that incised the western end of the range) and the vertical component of the slip rate of the eastern segment, we suggest that the Heli Shan was uplifted by motion on the South Heli Shan Fault beginning sometime between 1 and 4 Ma, most likely since~2 Ma. This age suggests that the Tibetan Plateau continues to grow northeastward across the Hexi Corridor.

We used airborne light detection and ranging (LiDAR) data to reevaluate the singleevent offsets of the 1920 Haiyuan Ms 8.5 earthquake and the cumulative offsets along the western and middle segments of the coseismic surface rupture zone. Our LiDAR data indicate that the offset observations along both the western and middle segments fall into groups. The group with the minimum slip amount is associated with the 1920 Haiyuan Ms 8.5 earthquake, which ruptured both the western and middle segments. Our research highlights two new interpretations: First, the previously reported maximum displacement of the 1920 earthquake was likely due to at least two earthquakes; second, our results reveal that the cumulative offset probability density (COPD) peaks of the same offset amounts on the western and middle segments do not correspond to one another one-to-one. We suggest that any discussion of the rupture pattern of a certain fault based on the offset data should also consider fault segmentation and paleoseismological data. Therefore, the COPD peaks should be computed and analyzed on fault subsections and not entire fault zones to study the number of paleoearthquakes and their rupture patterns.

The uplift processes of the Qilian Shan (northern Tibetan Plateau) play a central role in our understanding of the dynamics of outward and upward growth of Tibet due to sustained convergence of the Indian and Asian plates. We employ apatite fission track chronology and geological mapping to reveal the time and pattern of the deformation along the Qilian Shan. Our results indicate that the emergence of the Tuolai Shan in the central Qilian Shan occurred at 17-14 Ma, that northern Qilian Shan thrusting began at 10-8 Ma, and that the Laojunmiao anticline formed ca. 3.6 Ma. Together with previous results that show that uplift of the southern Qilian Shan began in the Oligocene, we suggest that the Qilian Shan has undergone progressively northward expansion in the Cenozoic due to significant crustal shortening driven by Qilian Shan thrust fault systems.

2-Cyanoacrylate is an important kind of herbicide targeted in photosystem II. Starting from cyano ethyl acetate, the chiral title compounds were synthesized under microwave irradiation, which has the advantages of shorter reaction time, higher yield, and simpler procedure. A half-leaf method was used to determine the inhibition and curative efficacies of the eight chiral products against tobacco mosaic virus in vivo. It was found that chiral compound IIc-R possesses moderate inhibition and curative effect in vivo with rates of 89.1 and 43.1%, respectively. In the MTT test, these new chiral compounds were found to possess weak antiproliferation activities to PC3 and A431 cells.