Synthesis and Characterization of Bimetallic Nickel Nanoparticles for the Reverse Water Gas Shift Reaction

Eine zentrale Herausforderung des 21. Jahrhunderts ist die Reduktion von Treibhausgasen wie beispielsweise Kohlenstoffdioxid (CO2). Ein vielversprechender Ansatz hierfür ist die katalytische Umsetzung von CO2 zu Synthesegas (CO + H2) über die umgekehrte Wassergas-Shift-Reaktion. Nanopartikel sind ein wichtiges Forschungsgebiet aufgrund ihrer einzigartigen Eigenschaften und vielfältigen Anwendungsmöglichkeiten, einschließlich als Katalysatoren für die umgekehrte Wassergas-Shift-Reaktion. Im Fokus dieser Arbeit steht die Synthese von mono- und bimetallischen Nickel-Nanopartikeln und deren Aktivität für die umgekehrte Wassergas-Shift-Reaktion. Im ersten Teil dieser Arbeit wird das weithin bekannte thermische Reduktionsverfahren zur Herstellung von Nickel-Nanopartikeln vereinfacht und modifiziert. Die monometallischen Nickel-Nanopartikel werden eingehend charakterisiert und der Einfluss der Synthesebedingungen auf die finalen Nanopartikel sowie deren katalytische Aktivität für die Umwandlung von CO2 zu Synthesegas untersucht. In einem zweiten Teil wird das modifizierte Syntheseverfahren auf bimetallische Nickel-Nanopartikel durch Co-Reduktion von Nickel mit entweder Kupfer oder Kobalt übertragen. Die Nanopartikel werden eingehend untersucht und die Kern-Schale-Struktur der Nickel-Kupfer-Nanopartikel wird identifiziert und detailliert charakterisiert. Der Einfluss der Reaktionsparameter auf die finalen Nanopartikel und die Korrelation von Größe, Form und Kupfergehalt der Nanopartikel auf die Aktivität für die umgekehrte Wasser-Gas-Shift-Reaktion werden untersucht.A great challenge of the 21st century is the minimization of greenhouse gases such as CO2. A promising approach is the catalytic conversion of CO2 to synthesis gas (CO + H2) via the reverse water gas shift reaction. Nanoparticles are an important field of research due to their unique properties and variety of applications including catalysts for the reverse water gas shift reaction. This work focusses on the synthesis of mono- and bimetallic nickel nanoparticles and their activity for the reverse water gas shift reaction. In the first part of this work the wellknown thermal reduction procedure for the preparation of nickel nanoparticles is adapted and simplified. The monometallic nickel nanoparticles are characterized thoroughly and the impact of the synthesis conditions on the final nanoparticles and their catalytic activity for the conversion of CO2 to CO are investigated. In a second part the adapted synthesis procedure is transferred to bimetallic nickel nanoparticles by co-reduction of nickel with either copper or cobalt. The nanoparticles are investigated thoroughly and the core-shell structure of nickel copper nanoparticles is identified and characterized in detail. The impact of the reaction parameters on the final nanoparticles as well as the correlation of size, shape and copper content of the nanoparticles on the activity for the reverse water gas shift reaction is investigated

Überwindung der intrinsischen Reaktivität bei aliphatischer C‐H‐Oxidation: Bevorzugte C3/C4‐Oxidation von aliphatischen Ammoniumsubstraten

Die positionsselektive C‐H‐Oxidation von nicht aktivierten Stellen in aliphatischen Ammoniumketten stellt eine enorme synthetische Herausforderung dar, für welche bisher keine Lösung gefunden wurde. Wir berichten hier über die bevorzugte Oxidation der stark deaktivierten C3/C4‐Positionen von aliphatischen Ammoniumsubstraten durch den Einsatz eines neuen supramolekularen Katalysators. Dieser chimäre Katalysator wurde durch die Verknüpfung der gut erforschten katalytischen Fe(pdp)‐Einheit an eine Alkylammonium bindende Pinzette hergestellt. Die Ergebnisse verdeutlichen das enorme Potenzial, die intrinsische Reaktivität in chemischen Reaktionen zu überwinden, indem die Katalyse mithilfe supramolekularer Wirtstrukturen, welche eine exakte Orientierung der Substrate ermöglichen, gesteuert wird

Too much water? Not enough? In situ monitoring of the mechanochemical reaction of copper salts with dicyandiamide

In situ monitoring of mechanochemical reactions between dicyandiamide (DCD) and CuX2 salts (X = Cl-, NO3-), for the preparation of compounds of agrochemical interest, showed the appearance of a number of phases. It is demonstrated that milling conditions, such as the amount of water added in wet grinding and/or the milling frequency, may affect the course of the mechanochemical reactions, and drive the reaction towards the formation of different products. It has been possible to discover by in situ monitored experiments two novel crystalline forms, namely the neutral complexes [Cu(DCD)(2)(OH2)(2)(NO3)(2)] (2) and [Cu(DCD)(2)(OH2)Cl-2]center dot H2O (4), in addition to the previously known molecular salt [Cu(DCD)(2)(OH2)(2)] [NO3](2)center dot 2H(2)O (1, DIVWAG) and neutral complex [Cu(DCD)(2)(OH2)Cl-2] (3, AQCYCU), for which no synthesis conditions were available. Compounds 2 and 4 were fully characterized via a combination of solid-state techniques, including X-ray diffraction, Raman spectroscopy and TGA

Remarks on a Bernstein-type operator of Aldaz, Kounchev and Render

The Bernstein-type operator of Aldaz, Kounchev and Render (2009) is discussed. New direct results in terms of the classical second order modulus as well as in a modification following Marsden and Schoenberg are given

Effect of two additional doses of intrathecal methotrexate during induction therapy on serious infectious toxicity in pediatric patients with acute lymphoblastic leukemia

Although initial central nervous system (CNS) involvement is rarely detected in childhood acute lymphoblastic leukemia (ALL), risk-adapted CNS-directed therapy is essential for all patients. Treatment intensity depends on the initial CNS status. In the AIEOP-BFM ALL 2009 trial, patients with cytomorphologic detection of leukemic blasts in initial cerebrospinal fluid were classified as CNS2 or CNS3 and received five intrathecal doses of methotrexate (MTX) in induction therapy compared to patients with CNS1 status (no blasts detected) who received three doses. The impact of additional intrathecal (IT) MTX on systemic toxicity in induction therapy is unknown. Between June 1st 2010 and February 28th 2017, a total of 6,136 ALL patients aged 1-17 years were enrolled onto the AIEOP-BFM ALL 2009 trial. The effect of three versus five doses of IT MTX during induction therapy on the incidence of severe infectious complications was analyzed. Among 4,706 patients treated with three IT MTX doses, 77 (1.6%) had a life-threatening infection during induction as compared to 59 of 1,350 (4.4%) patients treated with five doses (P<0.001; Odds Ratio 2.86 [95% Confidence Interval 1.99-4.13]). In a multivariate regression model, treatment with additional IT MTX proved to be the strongest risk factor for life-threatening infections (Odds Ratio 2.85 [1.96-4.14]). Fatal infections occurred in 16 (0.3%) and 38 (1.6%) patients treated with three or five IT MTX doses, respectively (P<0.001). As the relevance of additional intrathecal MTX in induction for relapse prevention in CNS2 patients is unclear, doses of intrathecal therapy have been reduced for these patients. (Clinicaltrials.gov identifiers: NCT01117441 and NCT00613457)

Genome-Wide Meta-Analysis in Alopecia Areata Resolves HLA Associations and Reveals Two New Susceptibility Loci

Alopecia areata (AA) is a prevalent autoimmune disease with ten known susceptibility loci. Here we perform the first meta-analysis in AA by combining data from two genome-wide association studies (GWAS), and replication with supplemented ImmunoChip data for a total of 3,253 cases and 7,543 controls. The strongest region of association is the MHC, where we fine-map 4 independent effects, all implicating HLA-DR as a key etiologic driver. Outside the MHC, we identify two novel loci that exceed statistical significance, containing ACOXL/BCL2L11(BIM) (2q13); GARP (LRRC32) (11q13.5), as well as a third nominally significant region SH2B3(LNK)/ ATXN2 (12q24.12). Candidate susceptibility gene expression analysis in these regions demonstrates expression in relevant immune cells and the hair follicle. We integrate our results with data from seven other autoimmune diseases and provide insight into the alignment of AA within these disorders. Our findings uncover new molecular pathways disrupted in AA, including autophagy/apoptosis, TGFß/Tregs and JAK kinase signaling, and support the causal role of aberrant immune processes in AA

Hybrid bioactive hydrogels containing single-walled carbon nanotubes covalently integrated via strain-promoted azide-alkyne cycloaddition

A non-photochemical and metal-free orthogonal route for the covalent incorporation of single-walled carbon nanotubes into a κ-carrageenan-based bioactive hydrogel scaffold is reported. The characterization of materials was carried out by usual analytical techniques and hybrid biohydrogels were evaluated for in vitro cytotoxicity on HeLa cell lines. The results revealed a significant antiproliferative effect instead of additional cytotoxicity with respect to native hydrogels.Peer reviewe

The Global Stratotype Sections and Points for the bases of the Selandian (Middle Paleocene) and Thanetian (Upper Paleocene) stages at Zumaia, Spain

The global stratotype sections and points for the bases of the Selandian (Middle Paleocene) and Thanetian (Upper Paleocene) stages have been defined in the coastal cliff along the Itzurun Beach at the town of Zumaia in the Basque Country, northern Spain. In the hemipelagic section exposed at Zumaia the base of the Selandian Stage has been placed at the base of the Itzurun Formation, ca. 49 m above the Cretaceous/ Paleogene boundary. At the base of the Selandian, marls replace the succession of Danian red limestone and limestone-marl couplets. The best marine, global correlation criterion for the basal Selandian is the second radiation of the important calcareous nannofossil group, the fasciculiths. Species such as Fasciculithus ulii, F. billii, F. janii, F. involutus, F.pileatus and F. tympaniformis have their first appearance in the interval from a few decimetres below up to 1.1 m above the base of the Selandian. The marker species for nannofossil Zone NP5, F. tympaniformis, first occurs 1.1 m above the base. Excellent cyclostratigraphy and magnetostratigraphy in the section creates further correlation potential, with the base of the Selandian occuring 30 precession cycles (630 kyr) above the top of magnetochron C27n. Profound changes in sedimentology related to a major sea-level fall characterize the Danian-Selandian transition in sections along the margins of the North Atlantic. The base of the Thanetian Stage is placed in the same section ca. 78 m above the Cretaceous/Paleogene boundary. It is defined at a level 2.8 m or eight precession cycles above the base of the core of the distinct clay-rich interval associated with the Mid-Paleocene Biotic Event, and it corresponds to the base of magnetochron C26n in the section. The base of the Thanetian is not associated with any significant change in marine micro-fauna or flora. The calcareous nannofossil Zone NP6, marked by the first occurrence of Heliolithus kleinpelli starts ca. 6.5 m below the base of the Thanetian. The definitions of the global stratotype points for the bases of the Selandian and Thanetian stages are in good agreements with the definitions in the historical stratotype sections in Denmark and England, respectively