1,936 research outputs found

    Recent Decisions

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    Comments on recent decisions by Cornelius F. Collins, Joseph P. Summers, Michael E. Phenner, Daniel J. Manelli, Ralph H. Witt, Richard C. Wilbur, and Raymond W. Brown

    Investigating interfacial electron transfer in dye-sensitized NiO using vibrational spectroscopy

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    Understanding what influences the formation and lifetime of charge-separated states is key to developing photoelectrochemical devices. This paper describes the use of time-resolved infrared absorption spectroscopy (TRIR) to determine the structure and lifetime of the intermediates formed on photoexcitation of two organic donor–π–acceptor dyes adsorbed to the surface of NiO. The donor and π-linker of both dyes is triphenylamine and thiophene but the acceptors differ, maleonitrile (1) and bodipy (2). Despite their structural similarities, dye 1 outperforms 2 significantly in devices. Strong transient bands in the fingerprint region (1 and 2) and nitrile region (2300–2000 cm−1) for 1 enabled us to monitor the structure of the excited states in solution or adsorbed on NiO (in the absence and presence of electrolyte) and the corresponding kinetics, which are on a ps–ns timescale. The results are consistent with rapid (<1 ps) charge-transfer from NiO to the excited dye (1) to give exclusively the charge-separated state on the timescale of our measurements. Conversely, the TRIR experiments revealed that multiple species are present shortly after excitation of the bodipy chromophore in 2, which is electronically decoupled from the thiophene linker. In solution, excitation first populates the bodipy singlet excited state, followed by charge transfer from the triphenylamine to the bodipy. The presence and short lifetime (τ ≈ 30 ps) of the charge-transfer excited state when 2 is adsorbed on NiO (2|NiO) suggests that charge separation is slower and/or less efficient in 2|NiO than in 1|NiO. This is consistent with the difference in performance between the two dyes in dye-sensitized solar cells and photoelectrochemical water splitting devices. Compared to n-type materials such as TiO2, less is understood regarding electron transfer between dyes and p-type metal oxides such as NiO, but it is evident that fast charge-recombination presents a limit to the performance of photocathodes. This is also a major challenge to photocatalytic systems based on a “Z-scheme”, where the catalysis takes place on a ”s–s timescale

    Targeting of MuLV Gag to the plasma membrane is mediated by PI(4,5)P2 and PhosphatidylSerine

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    Oral presentationInternational audienceMembrane targeting by the modern human immunodeficiency viruses is dependent on the plasma membrane-located phospholipid PI(4,5)P2. In order to determine if evolutionarily distant retroviruses are targeted by a similar mechanism, we generated mutant Gag constructs in the matrix (MA) domain of the Murine Leukemia Virus (MuLV) and examined their binding to membrane models and phenotypes in cell culture. Mutations in the MA polybasic region altered Gag localization, membrane binding and virion production. In addition, we show that MA binds with good affinity to all the phosphatidylinositol phosphates but displays a strong specificity for PI(4,5)P2 only if enhanced by phophatidylserine. Virus production was strongly impaired by PI(4,5)P2 depletion under 5ptaseIV overexpression. Our results suggest that the N-terminal polybasic region of MA is essential for Gag targeting to the plasma membrane and Gag cellular trafficking. The binding of the MA domain to PI(4,5)P2 appears to be a conserved feature among retroviruses, despite the fact that the MuLV-MA domain is structurally different from that of HIV-1 and -2 and lacks a readily identifiable PI(4,5)P2 binding cleft

    Charge-transfer dynamics at the dye-semiconductor interface of photocathodes for solar energy applications

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    This article describes a comparison between the photophysical properties of two charge-transfer dyes adsorbed onto NiO via two different binding moieties. Transient spectroscopy measurements suggest that the structure of the anchoring group affects both the rate of charge recombination between the dye and NiO surface and the rate of dye regeneration by an iodide/triiodide redox couple. This is consistent with the performance of the dyes in p-type dye sensitised solar cells. A key finding was that the recombination rate differed in presence of the redox couple. This has important implications on the study of electron transfer at dye|semiconductor interfaces for solar energy applications

    Probing the use of long lived intra-ligand π-π * excited states for photocatalytic systems: a study of the photophysics and photochemistry of [ReCl(CO)3(dppz-(CH3)2)]

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    We report the excited state photophysics and photochemistry of [ReCl(CO)3(dppz-(CH3)2)] (dppz-(CH3)2 = 11,12-dimethyl-dipyrido[3,2-a:2’,3’-c]phenazine) in CH3CN using timeresolved infrared (TRIR) and Fourier transform infrared (FTIR) spectroscopy. Excitation of the 1MLCT (metal-to-ligand charge transfer) band of [ReCl(CO)3(dppz-(CH3)2)] populates a 3MLCT excited state which rapidly interconverts on a timescale < 1 ns to a long lived IL (intra-ligand) π-π* excited state with a lifetime of 190 (± 5) ns. In the presence of an electron donor (NEt3), the IL excited state of [ReCl(CO)3(dppz-(CH3)2)] can be reductively quenched to [ReCl(CO)3(dppz-(CH3)2)]− with the radical in the latter localised on the distal phenazine (phz) portion of the dppz ligand. The phz based electron in [ReCl(CO)3(dppz-(CH3)2)]− has minimal interaction with the rhenium metal centre which increases the stability of the photosensitiser in its reduced form. In non-dried, non-degassed CH3CN (1 M NEt3), [ReCl(CO)3(dppz-(CH3)2)]− shows no significant change in the carbonyl region of the IR spectrum for at least 2 hours during continuous photolysis. In addition, we investigate the use of [ReCl(CO)3(dppz-(CH3)2)]− to reduce the previously studied catalyst [NiFe2], with facile electron transfer from [ReCl(CO)3(dppz-(CH3)2)]− to form [NiFe2]–

    Multiple drugs compete for transport via the Plasmodium falciparum chloroquine resistance transporter at distinct but interdependent sites

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    Mutations in the "chloroquine resistance transporter" (PfCRT) are a major determinant of drug resistance in the malaria parasite Plasmodium falciparum. We have previously shown that mutant PfCRT transports the antimalarial drug chloroquine away from its target, whereas the wild-type form of PfCRT does not. However, little is understood about the transport of other drugs via PfCRT or the mechanism by which PfCRT recognizes different substrates. Here we show that mutant PfCRT also transports quinine, quinidine, and verapamil, indicating that the protein behaves as a multidrug resistance carrier. Detailed kinetic analyses revealed that chloroquine and quinine compete for transport via PfCRT in a manner that is consistent with mixed-type inhibition. Moreover, our analyses suggest that PfCRT accepts chloroquine and quinine at distinct but antagonistically interacting sites. We also found verapamil to be a partial mixed-type inhibitor of chloroquine transport via PfCRT, further supporting the idea that PfCRT possesses multiple substratebinding sites. Our findings provide new mechanistic insights into the workings of PfCRT, which could be exploited to design potent inhibitors of this key mediator of drug resistance

    Organic and inorganic mercurials have distinct effects on cellular thiols, metal homeostasis, and Fe-binding proteins in Escherichia coli

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    The protean chemical properties of the toxic metal mercury (Hg) have made it attractive in diverse applications since antiquity. However, growing public concern has led to an international agreement to decrease its impact on health and the environment. During a recent proteomics study of acute Hg exposure in E. coli, we also examined the effects of inorganic and organic Hg compounds on thiol and metal homeostases. On brief exposure, lower concentrations of divalent inorganic mercury Hg(II) blocked bulk cellular thiols and protein-associated thiols more completely than higher concentrations of monovalent organomercurials, phenylmercuric acetate (PMA) and merthiolate (MT). Cells bound Hg(II) and PMA in excess of their available thiol ligands; X-ray absorption spectroscopy indicated nitrogens as likely additional ligands. The mercurials released protein-bound iron (Fe) more effectively than common organic oxidants and all disturbed the Na(+)/K(+) electrolyte balance, but none provoked efflux of six essential transition metals including Fe. PMA and MT made stable cysteine monothiol adducts in many Fe-binding proteins, but stable Hg(II) adducts were only seen in CysXxx(n)Cys peptides. We conclude that on acute exposure: (a) the distinct effects of mercurials on thiol and Fe homeostases reflected their different uptake and valences; (b) their similar effects on essential metal and electrolyte homeostases reflected the energy dependence of these processes; and (c) peptide phenylmercury-adducts were more stable or detectable in mass spectrometry than Hg(II)-adducts. These first in vivo observations in a well-defined model organism reveal differences upon acute exposure to inorganic and organic mercurials that may underlie their distinct toxicology

    XO-2b: Transiting Hot Jupiter in a Metal-rich Common Proper Motion Binary

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    We report on a V=11.2 early K dwarf, XO-2 (GSC 03413-00005), that hosts a Rp=0.98+0.03/-0.01 Rjup, Mp=0.57+/-0.06 Mjup transiting extrasolar planet, XO-2b, with an orbital period of 2.615857+/-0.000005 days. XO-2 has high metallicity, [Fe/H]=0.45+/-0.02, high proper motion, mu_tot=157 mas/yr, and has a common proper motion stellar companion with 31" separation. The two stars are nearly identical twins, with very similar spectra and apparent magnitudes. Due to the high metallicity, these early K dwarf stars have a mass and radius close to solar, Ms=0.98+/-0.02 Msolar and Rs=0.97+0.02/-0.01 Rsolar. The high proper motion of XO-2 results from an eccentric orbit (Galactic pericenter, Rper<4 kpc) well confined to the Galactic disk (Zmax~100 pc). In addition, the phase space position of XO-2 is near the Hercules dynamical stream, which points to an origin of XO-2 in the metal-rich, inner Thin Disk and subsequent dynamical scattering into the solar neighborhood. We describe an efficient Markov Chain Monte Carlo algorithm for calculating the Bayesian posterior probability of the system parameters from a transit light curve.Comment: 14 pages, 10 Figures, Accepted in ApJ. Negligible changes to XO-2 system properties. Removed Chi^2 light curve analysis section, and simplified MCMC light curve analysis discussio
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