Mononuclear Pt(II) and Pd(II) 1,4-dithiolato complexes. Crystal structures of [Pt((−) DIOS) (PPh3)2] and [Pd(S(CH2) 4S)(Ph2P(CH2) 3PPh2)]. Application in styrene hydroformylation

Addition of 1,4-dithiols to dichloromethane solutions of [PtCl2(P-P)] (P-P = (PPh3)2, Ph2P(CH2)3PPh2, Phd2P(CH2)4PPh2; 1,4-dithiols = HS(CH2)4SH, (−)DIOSH2 (2,3-O-isopropylidene-1,4-dithiol-l-threitol), BINASH2 (1,1′-dinaphthalene-2,2′-dithiol)) in the presence of NEt3 yielded the mononuclear complexes [Pt(1,4-dithiolato)(P-P)]. Related palladium(II) complexes [Pd(dithiolato)(P-P)] (P-P=Ph2P(CH2)3PPh2, Ph2P(CH2)4PPh2; dithiolato = −S(CH2)4S−, (−)-DIOS) were prepared by the same method. The structure of [Pt((−)DIOS)(PPh3)2] and [Pd(S(CH2)4S)(Ph2P(CH2)3PPh2)] complexes was determined by X-ray diffraction methods. Pt—dithiolato—SnC12 systems are active in the hydroformylation of styrene. At 100 atm and 125°C [Pt(dithiolate)(P-P)]/SnCl2 (Pt:Sn = 20) systems provided aldehyde conversion up to 80%.

A phosphoinositide 3-kinase (PI3K)-serum- and glucocorticoid-inducible kinase 1 (SGK1) pathway promotes Kv7.1 channel surface expression by inhibiting Nedd4-2 protein

Epithelial cell polarization involves several kinase signaling cascades that eventually divide the surface membrane into an apical and a basolateral part. One kinase, which is activated during the polarization process, is phosphoinositide 3-kinase (PI3K). In MDCK cells, the basolateral potassium channel Kv7.1 requires PI3K activity for surface-expression during the polarization process. Here, we demonstrate that Kv7.1 surface expression requires tonic PI3K activity as PI3K inhibition triggers endocytosis of these channels in polarized MDCK. Pharmacological inhibition of SGK1 gave similar results as PI3K inhibition, whereas overexpression of constitutively active SGK1 overruled it, suggesting that SGK1 is the primary downstream target of PI3K in this process. Furthermore, knockdown of the ubiquitin ligase Nedd4-2 overruled PI3K inhibition, whereas a Nedd4-2 interaction-deficient Kv7.1 mutant was resistant to both PI3K and SGK1 inhibition. Altogether, these data suggest that a PI3K-SGK1 pathway stabilizes Kv7.1 surface expression by inhibiting Nedd4-2-dependent endocytosis and thereby demonstrates that Nedd4-2 is a key regulator of Kv7.1 localization and turnover in epithelial cells.

The impact of ultra thin silicon nitride buffer layer on GaN growth on Si (1 1 1) by RF-MBE

Ultra thin films of pure silicon nitride were grown on a Si (1 1 1) surface by exposing the surface to radio-frequency (RF) nitrogen plasma with a high content of nitrogen atoms. The effect of annealing of silicon nitride surface was investigated with core-level photoelectron spectroscopy. The Si 2p photoelectron spectra reveals a characteristic series of components for the Si species, not only in stoichiometric Si3N4 (Si4+) but also in the intermediate nitridation states with one (Si1+) or three (Si3+) nitrogen nearest neighbors. The Si 2p core-level shifts for the Si1+, Si3+, and Si4+ components are determined to be 0.64, 2.20, and 3.05 eV, respectively. In annealed sample it has been observed that the Si4+ component in the Si 2p spectra is significantly improved, which clearly indicates the crystalline nature of silicon nitride. The high resolution X-ray diffraction (HRXRD), scanning electron microscopy (SEM) and photoluminescence (PL) studies showed a significant improvement of the crystalline qualities and enhancement of the optical properties of GaN grown on the stoichiometric Si3N4 by molecular beam epitaxy (MBE). (C) 2010 Elsevier B.V. All rights reserved.

Addition reactions of nitrones on the reconstructed C(100)-2 x 1 surfaces

In this paper, the reactions of nitrone, N-methyl nitrone, N-phenyl nitrone and their hydroxylamine tautomers (vinyl-hydroxylamine, N-methyl-vinyl-hydroxylamine and N-phenyl-vinyl-hydroxylamine) on the reconstructed C(100)-2 x 1 surface have been investigated using hybrid density functional theory (B3LYP), Moller-Plesset second-order perturbation (MP2) and multi-configuration complete-active-space self-consistent-field (CASSCF) methods. The calculations showed that all the nitrones can react with the surface "dimer" via facile 1.3-dipolar cycloaddition with small activation barriers (less than 12.0 kJ/mol at B3LYP/6-31g(d) level). The [2+2] cycloaddition of hydroxylamine tautomers on the C(100) surface follows a diradical mechanism. Hydroxylamine tautomers first form diradical intermediates with the reconstructed C(I 00)-2 x I surface by overcoming a large activation barrier of 50-60 kJ/mol (B3LYP), then generate [2+2] cycloaddition products via diradical transition states with negligible activation barriers. The surface reactions result in hydroxyl or amino-terminated diamond surfaces, which offers new opportunity for further modifications. (C) 2007 Elsevier B.V. All rights reserved.

Dissolution kinetics of octadecanethiolate monolayers electro-adsorbed on Au(1 1 1)

Monolayers of octadecanethiolate on Au(1 1 1) surface were formed under electrochemical control. The influence of the formation time on the reductive desorption process was studied by cyclic voltammetry and chronoamperometry. When the formation time is increased, the reductive desorption peak observed on the voltammograms is significantly shifted in the negative direction, while the cathodic charge is only slightly affected. This behaviour is attributed to a higher degree of organisation of the monolayers for longer formation times, highlighting the role of defect sites in promoting the dissolution. A good agreement was found between our experimental chronoamperograms and theoretical models describing the dissolution process by a shrinkage mechanism. It is demonstrated that a reorganisation process takes place, consisting in the merging of small condensed domains into larger ones. This annealing phenomenon is time and potential dependent, the largest condensed domains being obtained for the longest formation times and least negative potentials. © 2008 Elsevier B.V. All rights reserved.

Structure and reactivity of the Ru(0 0 0 1) electrode towards fuel cell electrocatalysis

The reactivity of the Ru(0 0 0 1) electrode towards the adsorption and electrooxidation of CO and methanol has been studied by variable-temperature in situ FTIR spectroscopy in both perchloric acid and sodium hydroxide solution, and the results interpreted in terms of the surface chemistry of the Ru(0 0 0 1) electrode. Both linear (CO) and threefold hollow (CO) binding CO adsorbates (bands at 1970-2040 and 1770-1820 cm, respectively) were observed on the Ru(0 0 0 1) electrode in both 0.1 M HClO and 0.1 M NaOH solutions from the CO adsorption. In the acid solution, CO was detected as the main adsorbed species on Ru(0 0 0 1) surface over all the potential region studied. In contrast, in the alkaline solution, more CO than CO was detected at lower potentials, whilst increasing the potential resulted in the transformation of CO to CO. At higher potentials, the oxidation of the adsorbed CO took place via reaction with the active (1 × 1)-O oxide/hydroxide. It was found that no dissociative adsorption or electrooxidation of methanol took place at the Ru(0 0 0 1) at potentials below 900 mV vs Ag/AgCl in perchloric acid solution at both 20 and 55°C. However, in the alkaline solution, methanol did undergo dissociative adsorption, to form linearly adsorbed CO (CO) with little or no CO adsorbed at threefold hollow sites (CO) at both 20 and 55°C. Increasing the temperature from 20 to 55°C clearly facilitated the methanol dissociative adsorption to CO and also enhanced the electrooxidation of the CO. At the higher potentials, significant oxidation of methanol to CO and methyl formate in acid solution and to bicarbonate and formate in alkaline solution, was observed, which was attributed to the formation of an active RuO phase on the Ru(0 0 0 1) surface, in agreement with our previous studies. © 2003 Elsevier Ltd. All right reserved.

PECAM-1 expression and activity negatively regulate multiple platelet signaling pathways

Platelet endothelial cell adhesion molecule-1 (PECAM-1) inhibits platelet response to collagen and may also inhibit two other major platelet agonists ADP and thrombin although this has been less well explored. We hypothesized that the combined effect of inhibiting these three platelet activating pathways may act to significantly inhibit thrombus formation. We demonstrate a negative relationship between PECAM-1 surface expression and platelet response to cross-linked collagen related peptide (CRP-XL) and ADP, and an inhibitory effect of PECAM-1 clustering on platelet response to CRP-XL, ADP and thrombin. This combined inhibition of multiple signaling pathways results in a marked reduction in thrombus formation. (C) 2009 Federation of European Biochemical Societies. Published by Elsevier B. V. All rights reserved.

Synergetic effects of the Cu/Pt{110} surface alloy: enhanced reactivity of water and carbon monoxide

We have used synchrotron-based high-resolution X-ray photoelectron spectroscopy in combination with ab initio density functional theory calculations to investigate the characteristics of water and CO adsorption on the bimetallic Cu/Pt{110}-(2 x 1) surface at a Cu coverage near 0.5 ML. Cu fills the troughs of the reconstructed clean surface forming nanowires, which are stable up to 830 K. Their presence dramatically influences the adsorption of water and CO. Water adsorption changes from intact to partially dissociated while the desorption temperature of CO on this surface increases by up to 27 K with respect to the clean Pt{110} surface. Ab initio calculations and experimental valence band spectra reveal that the Cu 3d-band is narrowed and shifted upward with respect to bulk Cu surfaces. This and electron donation to surface Pt atoms cause the increase in the bond strength between CO and the Pt surface atoms. The pathway for water dissociation occurs via Cu surface atoms. The heat of adsorption of water bonding to Cu surface atoms was calculated to be 0.82 eV, which is significantly higher than on the clean Pt{110} surface; the activation energy for partial dissociation is 0.53 eV (not corrected for zero point energy).

(Table 1) Minerals of bulk sediment at DSDP Holes 64-480 and 64-481

This paper provides a brief, descriptive, sedimentological background for the chapters on hydraulic piston core Site 480 in this symposium, and supplements data given in the site chapter for Sites 479-480 (this volume, Pt. 1). Sediments are composed primarily of planktonic diatoms, with minor numbers of silicoflagellates, radiolarians, and varying amounts of both benthic and planktonic foraminifers, along with a large terrigenous component of olive brown, silty clay. The section contains meter-thick intervals of finely laminated facies alternating with nonlaminated zones. A few paleoenvironmental events are documented within the generally uniform sequence by sporadic occurrences of thin turbidites, phosphatic concretions, fish debris concentrations, an ash layer, and a thin layer of diagenetic dolomite. The distribution of nonlaminated and laminated zones is attributed to fluctuations of bottom-water oxygen content caused by variations in circulation, fertility, and productivity. Homogeneous sections are interpreted as coinciding with cooler climatic periods, whereas laminated sections seem to correspond to upwelling conditions during drier periods.

SPC3, a synthetic peptide derived from the V3 domain of human immunodeficiency virus type 1 (HIV-1) gp120, inhibits HIV-1 entry into CD4+ and CD4- cells by two distinct mechanisms.

The third variable region (V3 loop) of gp120, the HIV-1 surface envelope glycoprotein, plays a key role in HIV-1 infection and pathogenesis. Recently, we reported that a synthetic multibranched peptide (SPC3) containing eight V3-loop consensus motifs (GPGRAF) inhibited HIV-1 infection in both CD4+ and CD4- susceptible cells. In the present study, we investigated the mechanisms of action of SPC3 in these cell types--i.e., CD4+ lymphocytes and CD4- epithelial cells expressing galactosylceramide (GalCer), an alternative receptor for HIV-1 gp120. We found that SPC3 was a potent inhibitor of HIV-1 infection in CD4+ lymphocytes when added 1 h after initial exposure of the cells to HIV-1, whereas it had no inhibitory effect when present only before and/or during the incubation with HIV-1. These data suggested that SPC3 did not inhibit the binding of HIV-1 to CD4+ lymphocytes but interfered with a post-binding step necessary for virus entry. In agreement with this hypothesis, SPC3 treatment after HIV-1 exposure dramatically reduced the number of infected cells without altering gp120-CD4 interaction or viral gene expression. In contrast, SPC3 blocked HIV-1 entry into CD4-/GalCer+ human colon epithelial cells when present in competition with HIV-1 but had no effect when added after infection. Accordingly, SPC3 was found to inhibit the binding of gp120 to the GalCer receptor. Thus, the data suggest that SPC3 affects HIV-1 infection by two distinct mechanisms: (i) prevention of GalCer-mediated HIV-1 attachment to the surface of CD4-/GalCer+ cells and (ii) post-binding inhibition of HIV-1 entry into CD4+ lymphocytes.

Replies from executive departments and Federal agencies to inquiry regarding use of advisory committees (January 1, 1953-January 1, 1956).

Errata slip inserted in pt. 1.

Automobile marketing practices : hearings, Eighty-fourth Congress, second session pursuant to S. Res. 13 continued by S. Res. 163... January 19,20,23, and February 21,22,23,29, March 1,6,7,8,9,10, 1956.

pt. 1. January 19, 20, 23, February 21-23, 29, March 1, 6-10, 1956. 1225 p.--pt. 2. June 4-6, 12, 21, 1956. pp. 1227-1533.

Town records of Salem Massachusetts. [v.1]- 1634-

"These records were copied from the original by Miss Martha O. Howes. The copy was verified by Sidney Perley, esq., who also made the index."--Verso of t-p., v. 2

A compendium of the properties of materials at low temperatures (Phase 1- )

"Materials Central. Contract no. AF 33 (616)-58-4, Project no. 7360."

Geologie des Erongo im Hererolande (Geologische Beobachtungen in Südafrika, Teil II.) Vorläufige Mitteilungen. Mit einer Karte 1:300 000,6 Textzeichnungen und einer Schichtentafel.

Pt. 1 of Cloos' Geologische Beobachtungen in Südafrika appeared in Neues Jahrbuch für Mineralogie, Geologie und Paläontologie, Beilage - Band 32, p. 49 - 70 (Stuttgart, 1911)