Scientific Highlights
from the Research Department "Biology and Chemistry" (BIO)

Effect of surface charge density on the affinity of oxide nanoparticles for the vapor–water interface

Research Department Biology and Chemistry (BIO), Surface Chemistry Group, Head Markus Ammann. Using in-situ X-ray photoelectron spectroscopy at the vapor-water interface, the affinity of nanometer-sized silica colloids to adsorb at the interface is shown to depend on colloid surface charge density. In aqueous suspensions at pH 10 corrected Debye-Hückel theory for surface complexation calculations predict that smaller silica colloids have increased negative surface charge density that originates from enhanced screening of deprotonated silanol groups by counterions in the condensed ion layer. The increased negative surface charge density results in an electrostatic repulsion from the vapor-water interface that is seen to a lesser extent for larger particles that have a reduced charge density in the XPS measurements. We compare the results and interpretation of the in-situ XPS and corrected Debye-Hückel theory for surface complexation calculations with traditional surface tension measurements. Our results show that controlling the surface charge density of colloid particles can regulate their adsorption to the interface between two dielectrics.

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Advances in the production and chemistry of the heaviest elements

Research Department Biology and Chemistry (BIO), Laboratory of Radiochemistry and Environmental Chemistry, Head Andreas Türler.

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Chemistry: Ten things we need to know about ice and snow

Research Department Biology and Chemistry (BIO), surface chemistry Group, Head Markus Ammann. Understanding the molecular behaviour of frozen water is essential for predicting the future of our planet, says Thorsten Bartels-Rausch.

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44 Ti, 26 Al and 53 Mn samples for nuclear astrophysics: The needs, the possibilities and the sources

Research Department Biology and Chemistry (BIO), RadWaste Analytics Group, Head Dorothea Schumann. Exploration of the physics involved in the production of cosmogenic radionuclides requires experiments using the same rare, radioactive nuclei in sufficient quantities. For this work, such exotic radionuclides have been extracted from previously proton-irradiated stainless steel samples using wet chemistry separation techniques. The irradiated construction material has arisen from an extended material research programme at the Paul Scherrer Institute, called STIP (SINQ Target Irradiation Program), where several thousand samples of different materials were irradiated with protons and neutrons of energies up to 570 MeV. In total, 8 × 10 17 atoms of 44 Ti, ∼10 16 atoms of 26 Al and ∼10 19 atoms of 53 Mn are available from selected samples. These materials may now be used to produce targets or radioactive beams for nuclear reaction studies with protons, neutrons and α-particles. The work is part of the ERAWAST initiative (Exotic Radionuclides from Accelerator Waste for Science and Technology), aimed at facilitating new collaborations between the isotope producers and users from different scientific fields including nuclear astrophysics.

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Variations in diesel soot reactivity along the exhaust after-treatment system, based on the morphology and nanostructure of primary soot particles

Research Department Biology and Chemistry (BIO), Surface Chemistry Group, Head Markus Ammann. The reactivity of soot at different sites of the exhaust after-treatment system of a diesel engine (upstream and downstream of the diesel oxidation catalyst (DOC), downstream of the diesel particulate filter (DPF), as well as inside the DPF) was investigated on the basis of morphology and structure of primary soot particles by high resolution transmission electron microscopy (HRTEM). The results indicate that combustion-formed soot particles are susceptible to further transformations of their morphology within the exhaust system. The same primary soot particles can possess both oxidation-promoting and oxidation-inhibiting morphological features, the particle cores being highly reactive. Most reactivity-promoting features are encountered in pre-DOC and post-DOC primary particles, suggesting that soot can be more easily oxidised before it enters the DPF. The residence time of soot in the DPF contributes to modification of its reactivity by affecting size distribution and nanostructure of primary particles. Partial NO2 oxidation and high temperatures during active regeneration modify the morphology of outer particle shells, thus rendering post-DOC and post-DPF primary soot particles less reactive in this respect. Primary soot particles that pass through the DPF and reach the atmosphere are characterised by the highest graphitisation degree and sizes larger than those entering the DPF. Complementary Near-Edge X-ray Absorption Fine Structure (NEXAFS) analyses proved not as relevant regarding soot reactivity but indicate higher chemical inhomogeneity of pre-DOC than of post-DOC and post-DPF soot and high contents of carboxyl carbon in post-DPF particles.

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Efficacy of a novel 177Lu-chCE7 radioimmunotherapeutic agent for disseminated ovarian cancer therapy

Research Department Biology and Chemistry (BIO), Center for Radiopharmaceutical Sciences,Tumor Targeting Group, Head Eliane Fischer. The L1-cell adhesion molecule (L1-CAM) is highly expressed in various cancer types including ovarian carcinoma but is absent from most normal tissue. A chimeric monoclonal antibody, chCE7, specifically binds to human L1-CAM and exhibits anti-proliferative effects on L1-CAM-expressing tumor cells. The goal of this study was to evaluate the efficacy of a novel 177Lu-chCE7 radioimmunotherapeutic agent and to compare it to a treatment protocol with unlabeled, growth-inhibiting chCE7 in a mouse xenograft model of disseminated ovarian cancer. chCE7agl,an aglycosylated IgG1 variant with improved pharmacokinetics, was conjugated with 1,4,7,10-tetraazacyclododecane-N-N′-N′-N‴-tetraacetic acid (DOTA) and labeled with the low-energy β-emitter 177Lu. Tumor growth and survival were assessed after a single i.v. dose of 8 MBq (60 μg) radioimmunoconjugate in nude mice bearing either subcutaneous or intraperitoneal SKOV3.ip1 human ovarian cancer tumors. Therapeutic efficacy was compared with three times weekly i.p. administration of 10 mg/kg unconjugated chCE7. In vivo analysis of 177Lu-chCE7agl biodistribution demonstrated high and specific accumulation of radioactivity at the tumor site with maximal tumor uptake of up to 48.0 ± 8.1% ID/g at 168 h postinjection. A single treatment with 177Lu-DOTA-chCE7agl caused significant retardation of tumor growth and prolonged median survival from 33 to 71 days, while administration of a nontargeted 177Lu-immunoconjugate had no beneficial effect. Three times weekly i.p. application of unlabeled chCE7 10 mg/kg similarly increased survival from 44 to 72 days. We conclude that a single dose of 177Lu-DOTA-chCE7agl is as effective as repeated administration of nonradioactive chCE7 for treatment of small intraperitoneal tumors expressing L1-CAM.

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Three centuries of eastern european and Altai lead emissions recorded in a belukha ice core

Research Department Biology and Chemistry (BIO), Analytical Chemistry Group, Head Margit Schwikowski. Human activities have significantly altered atmospheric Pb concentrations and thus, its geochemical cycle, for thousands of years. Whereas historical Pb emissions from Western Europe, North America, and Asia are well documented, there is no equivalent data for Eastern Europe. Here, we present ice-core Pb concentrations for the period 1680–1995 from Belukha glacier in the Siberian Altai, assumed to be representative of emissions in Eastern Europe and the Altai. Pb concentrations and Pb-207/Pb-206 ratios were strongly enhanced during the period 1935–1995 due to the use of Pb additives in Russian gasoline mined in the Rudny Altai. Comparable to Western Europe and North America, Eastern European Pb emissions peaked in the 1970s. However, the subsequent downward trend in Eastern Europe was mainly caused by the economic crisis in the U.S.S.R. and not by a phase-out of leaded gasoline. Pb concentrations in the period 1680–1935, preceding the era of intensified industrialization in Russia, reflect the history of local emissions from Rudny Altai mining and related metallurgical processing primarily for the production of Russian coins. During this time, Altai ore Pb contributed about 40% of the regional atmospheric Pb.

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Gas uptake and chemical aging of semisolid organic aerosol particles

Research Department Biology and Chemistry (BIO), Surface Chemistry Group, Head Markus Ammann. Organic substances can adopt an amorphous solid or semisolid state, influencing the rate of heterogeneous reactions and multiphase processes in atmospheric aerosols. Here we demonstrate how molecular diffusion in the condensed phase affects the gas uptake and chemical transformation of semisolid organic particles. Flow tube experiments show that the ozone uptake and oxidative aging of amorphous protein is kinetically limited by bulk diffusion. The reactive gas uptake exhibits a pronounced increase with relative humidity, which can be explained by a decrease of viscosity and increase of diffusivity due to hygroscopic water uptake transforming the amorphous organic matrix from a glassy to a semisolid state (moisture-induced phase transition). The reaction rate depends on the condensed phase diffusion coefficients of both the oxidant and the organic reactant molecules, which can be described by a kinetic multilayer flux model but not by the traditional resistor model approach of multiphase chemistry. The chemical lifetime of reactive compounds in atmospheric particles can increase from seconds to days as the rate of diffusion in semisolid phases can decrease by multiple orders of magnitude in response to low temperature or low relative humidity. The findings demonstrate that the occurrence and properties of amorphous semisolid phases challenge traditional views and require advanced formalisms for the description of organic particle formation and transformation in atmospheric models of aerosol effects on air quality, public health, and climate.

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The role of long-lived reactive oxygen intermediates in the reaction of ozone with aerosol particles

Research Department Biology and Chemistry (BIO), Surface Chemistry Group, Head Markus Ammann. The heterogeneous reactions of ozone with aerosol particles are of central importance to air quality. They are studied extensively, but the molecular mechanisms and kinetics remain unresolved. Based on new experimental data and calculations, we show that long-lived reactive oxygen intermediates (ROIs) are formed. The chemical lifetime of these intermediates exceeds 100 seconds, which is much longer than the surface residence time of molecular ozone (~ ns). The ROIs explain and resolve apparent discrepancies between earlier quantum mechanical calculations and kinetic experiments. They play a key role in the chemical transformation and adverse health effects of toxic and allergenic air-particulate matter, such as soot, polycyclic aromatic hydrocarbons and proteins. ROIs may also be involved in the decomposition of ozone on mineral dust and in the formation and growth of secondary organic aerosols. Moreover, ROIs may contribute to the coupling of atmospheric and biospheric multiphase processes.

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Recent increase in black carbon concentrations
from a Mt. Everest ice core spanning 1860–2000 AD

Research Department Biology and Chemistry (BIO), Analytical Chemistry Group, Head Margit Schwikowski. A Mt. Everest ice core spanning 1860–2000 AD and analyzed at high resolution for black carbon (BC) using a Single Particle Soot Photometer demonstrates strong seasonality, with peak concentrations during the winter‐spring, and low concentrations during the summer monsoon season. BC concentrations from 1975–2000 relative to 1860–1975 have increased approximately threefold, indicating that BC from anthropogenic sources is being transported to high elevation regions of the Himalaya. The timing of the increase in BC is consistent with BC emission inventory data from South Asia and the Middle East, however since 1990 the ice core BC record does not indicate continually increasing BC concentrations. The Everest BC and dust records provide information about absorbing impurities that can contribute to glacier melt by reducing the albedo of snow and ice. There is no increasing trend in dust concentrations since 1860, and estimated surface radiative forcing due to BC in snow exceeds that of dust in snow. This suggests that a reduction in BC emissions may be an effective means to reduce the effect of absorbing impurities on snow albedo and melt, which affects Himalayan glaciers and the availability of water resources in major Asian rivers.

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