Mono- versus Multi-phosphonic Acid Based PEGylated Polymers for Functionalization and Stabilization of Metal (Ce, Fe, Ti, Al) Oxide Nanoparticles in Biological Media

International audienceFor applications in nanomedicine, particles need to be functionalized to prevent protein corona formation and/or aggregation. Most advanced strategies take advantage of functional polymers and assembly techniques. Nowadays there is an urgent need for coatings that are tailored according to a broad range of surfaces and that can be produced on a large scale. Herein, we synthesize mono-and multi-phosphonic acid based poly(ethylene glycol) (PEG) polymers with the objective of producing efficient coats for metal oxide nanoparticles. Cerium, iron, titanium and aluminum oxide nanoparticles of different morphologies (spheres, platelets, nanoclusters) and sizes ranging from 7 to 40 nm are studied in physiological and in protein rich cell culture media. It is found that the particles coated with mono-functionalized polymers exhibit a mitigated stability over time ( months). With the latter, PEG densities in the range 0.2-0.5 nm-2 and layer thickness about 10 nm provide excellent performances. The study suggests that the proposed coating allows controlling nanomaterial interfa-cial properties in biological environments

Information Guide: Cyprus. March 2015

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Does Satellite Chlorophyll‐a Respond to Southernmost Patagonian Dust? A Multi‐Year, Event‐Based Approach

Mineral aerosols may affect global climate indirectly by enhancing net primary productivity (NPP) upon deposition to the oceans and associated atmosphere-to-ocean CO2 flux. This mechanism is hypothesized to have contributed significantly to the last interglacial-to-glacial climatic transition. However, the dust-NPP connection remains contentious for the present-day climate system. We analyze the impact of southernmost Patagonian dust emissions on southwestern Atlantic Ocean continental shelf and proximal open ocean satellite chlorophyll-a concentration. We use the first decadal time series of surface dust mass flux in southern Patagonia, along with in situ visibility data, to model dust emission, transport, and deposition to the ocean. We then perform a dust event-based analysis of chlorophyll-a time series, using a novel approach by which time series are corrected for post-depositional particle advection due to ocean currents. Finally, we performed chemical analysis of iron in dust samples, a key micronutrient limiting phytoplankton biomass in high-nutrient, low-chlorophyll oceans such as offshore of the 200-m isobath off Patagonia. We find no compelling evidence for an influence of dust as an enhancer of phytoplankton biomass either on shelf or proximal open ocean waters of the southwestern Atlantic Ocean. For open ocean waters this is consistent with a lack of source-inherited bioavailable iron in dust samples. Future case studies addressing similar questions should concentrate on dust sources with identified high contents of bioavailable iron, particularly in the Southern Hemisphere where atmospheric processing of iron is weak.Fil: Cosentino, Nicolas Juan. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigaciones en Ciencias de la Tierra. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas Físicas y Naturales. Centro de Investigaciones en Ciencias de la Tierra; ArgentinaFil: Ruiz Etcheverry, Laura Agustina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones del Mar y la Atmósfera. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones del Mar y la Atmósfera; ArgentinaFil: Bia, Gonzalo Luis. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigaciones en Ciencias de la Tierra. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas Físicas y Naturales. Centro de Investigaciones en Ciencias de la Tierra; ArgentinaFil: Simonella, Lucio Esteban. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Coppo, Renata. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigaciones en Ciencias de la Tierra. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas Físicas y Naturales. Centro de Investigaciones en Ciencias de la Tierra; ArgentinaFil: Torre, Gabriela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigaciones en Ciencias de la Tierra. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas Físicas y Naturales. Centro de Investigaciones en Ciencias de la Tierra; ArgentinaFil: Saraceno, Martin. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones del Mar y la Atmósfera. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones del Mar y la Atmósfera; ArgentinaFil: Tur, Veronica Mabel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigaciones en Ciencias de la Tierra. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas Físicas y Naturales. Centro de Investigaciones en Ciencias de la Tierra; ArgentinaFil: Gaiero, Diego Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigaciones en Ciencias de la Tierra. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas Físicas y Naturales. Centro de Investigaciones en Ciencias de la Tierra; Argentin

Polymer coated cerium oxide nanoparticles as oxidoreductase-like catalysts

Cerium oxide nanoparticles have been shown to mimic oxidoreductase enzymes by catalyzing the decomposition of organic substrates and reactive oxygen species. This mimicry can be found in superoxide radicals and hydrogen peroxides, harmful molecules produced in oxidative stress asso-ciated diseases. Despite the fact that nanoparticle functionalization is mandatory in the context of nanomedicine, the influence of polymer coatings on their enzyme-like catalytic activity is poorly understood. In this work, six polymer coated cerium oxide nanoparticles are prepared by associa-tion of 7.8 nm cerium oxide cores with two poly(sodium acrylate) and four poly(ethylene glycol) (PEG) grafted copolymers with different terminal or anchoring end groups, such as phosphonic acids. The superoxide dismutase-, catalase-, peroxidase- and oxidase-like catalytic activities of the coated nanoparticles were systematically studied. It is shown that the polymer coatings do not af-fect the superoxide dismutase-like, impair the catalase-like and oxidase-like and surprisingly im-proves peroxidase-like catalytic activities of cerium oxide nanoparticles. It is also demonstrated that the particles coated with the PEG-grafted copolymers perform better than the poly(acrylic acid) coated ones as oxidoreductase-like enzymes, a result that confirms the benefit of having phosphon-ic acids as anchoring groups at the particle surface.Comment: 23 pages, 8 figures, 3 table

Ratios of dijet production cross sections as a function of the absolute difference in rapidity between jets in proton-proton collisions at √s = 7TeV

A study of dijet production in proton-proton collisions was performed at root s = 7 TeV for jets with p(T) > 35 GeV and vertical bar y vertical bar < 4.7 using data collected with the CMS detector at the LHC in 2010. Events with at least one pair of jets are denoted as "inclusive". Events with exactly one pair of jets are called "exclusive". The ratio of the cross section of all pairwise combinations of jets to the exclusive dijet cross section as a function of the rapidity difference between jets vertical bar Delta y vertical bar is measured for the first time up to vertical bar Delta y vertical bar = 9.2. The ratio of the cross section for the pair consisting of the most forward and the most backward jet from the inclusive sample to the exclusive dijet cross section is also presented. The predictions of the Monte Carlo event generators PYTHIA6 and PYTHIA8 agree with the measurements. In both ratios the HERWIG++ generator exhibits a more pronounced rise versus vertical bar Delta y vertical bar than observed in the data. The BFKL-motivated generators CASCADE and HEJ+ARIADNE predict for these ratios a significantly stronger rise than observed

Prebiotic Synthesis of 2-Deoxy-D-Ribose from Interstellar Building Blocks Promoted by Amino Esters or Amino Nitriles

Understanding the prebiotic genesis of 2-deoxy-D-ribose, which forms the backbone of DNA, is of crucial importance to unravelling the origins of life, yet remains open to debate. Here we demonstrate that 20 mol% of proteinogenic amino esters promote the selective formation of 2-deoxy-D-ribose over 2-deoxy-D-threopentose in combined yields of ≥ 4%. We also demonstrate the first aldol reaction promoted by prebiotically-relevant proteinogenic amino nitriles (20 mol%) for the enantioselective synthesis of D-glyceraldehyde with 6 %e.e., and its subsequent conversion into 2-deoxy-D-ribose in yields of ≥ 5%. Finally, we explore the combination of these two steps in a one-pot process using 20 mol% of an amino ester or amino nitrile promoter. It is hence demonstrated that three interstellar starting materials, when mixed together with an appropriate promoter, can directly lead to the formation of a mixture of higher carbohydrates, including 2-deoxy-D-ribos

Persistent luminescence nanoparticles functionalized by polymers bearing phosphonic acid anchors: synthesis, characterization, and in vivo behaviour

International audienceOptical in vivo imaging has become a widely used technique and is still under development for clinical diagnostics and treatment applications. For further development of the field, researchers have put much effort into the development of inorganic nanoparticles (NPs) as imaging probes. In this trend, our laboratory developed ZnGa1.995O4Cr0.005 (ZGO) nanoparticles, which can emit a bright persistent luminescence signal through the tissue transparency window for dozens of minutes and can be activated in vivo with visible irradiation. These properties endow them with unique features, allowing us to recover information over a long-time study with in vivo imaging without any background. To target tissues of interest, ZGO must circulate long enough in the blood stream, a phenomenon which is limited by the mononuclear phagocyte system (MPS). Depending on their size, charge and coating, the NPs are sooner or later opsonized and stored into the main organs of the MPS (liver, spleen, and lungs). The NPs therefore have to be coated with a hydrophilic polymer to avoid this limitation. To this end, a new functionalization method using two different polyethylene glycol phosphonic acid polymers (a linear one, later named lpPEG and a branched one, later named pPEG) has been studied in this article. The coating has been optimized and characterized in various aqueous media. The behaviour of the newly functionalized NPs has been investigated in the presence of plasmatic proteins, and an in vivo biodistribution study has been performed. Among them ZGOpPEG exhibits a long circulation time, corresponding to low protein adsorption, while presenting an effective one-step process in aqueous medium with a low hydrodynamic diameter increase. This new method is much more advantageous than another strategy we reported previously that used a two-step PEG silane coating performed in an organic solvent (dimethylformamide) for which the final hydrodynamic diameter was twice the initial diameter