Verification of German methane emission inventories and their recent changes based on atmospheric observations

Continuous methane concentration records and stable isotope observations measured in the suburbs of Heidelberg, Germany, are presented. While delta13C-CH4 shows a significant trend of -0.14 permil per year, towards more depleted values, no trend is observed in the concentration data. Comparison of the Heidelberg records with clean air observations in the North Atlantic at Izana station (Tenerife) allows the determination of the continental methane excess at Heidelberg, decreasing by 20% from 190 ppb in 1992 to 150 ppb in 1997. The isotope ratio which is associated with this continental methane pile-up in the Heidelberg catchment area shows a significant trend to more depleted values from delta13C (source) = -47.4 ± 1.2 permil in 1992 to 52.9 ± 0.4 permil in 1995/96, pointing to a significant change in the methane source mix. Total methane emissions in the Heidelberg catchment area are estimated using the 222Radon (222Rn) tracer method: from the correlations of half hourly 222Rn and CH4 mixing ratios from 1995 to 1997, and the mean 222Rn exhalation rate from typical soils in the Rhine valley, a mean methane flux of 0.24 ± 0.5 g CH4 km-2 s-1 is derived. For the Heidelberg catchment area with an estimated radius of approximately 150 km, Core Inventories Air 1990 (CORINAIR90) emission estimates yield a flux of 0.47 g CH4 km-2 s-1, which is about 40% higher than the 222Rn derived number if extrapolated to 1990. The discrepancy can be explained by over-estimated emissions from waste management in the CORINAIR90 statistical assessment. The observed decrease in total emissions can be accounted for by decreasing contributions from fossil sources (mainly coal mining) and from cattle breeding. This finding is also supported by the observed decrease in mean source isotopic signatures

Advances in rheumatology: new targeted therapeutics

Treatment of inflammatory arthritides - including rheumatoid arthritis, ankylosing spondylitis, and psoriatic arthritis - has seen much progress in recent years, partially due to increased understanding of the pathogenesis of these diseases at the cellular and molecular levels. These conditions share some common mechanisms. Biologic therapies have provided a clear advance in the treatment of rheumatological conditions. Currently available TNF-targeting biologic agents that are licensed for at east one of the above-named diseases are etanercept, infliximab, adalimumab, golimumab, and certolizumab. Biologic agents with a different mechanism of action have also been approved in rheumatoid arthritis (rituximab, abatacept, and tocilizumab). Although these biologic agents are highly effective, there is a need for improved management strategies. There is also a need for education of family physicians and other healthcare professionals in the identification of early symptoms of inflammatory arthritides and the importance of early referral to rheumatologists for diagnosis and treatment. Also, researchers are developing molecules - for example, the Janus kinase inhibitor CP-690550 (tofacitinib) and the spleen tyrosine kinase inhibitor R788 (fostamatinib) - to target other aspects of the inflammatory cascade. Initial trial results with new agents are promising, and, in time, head-to-head trials will establish the best treatment options for patients. The key challenge is identifying how best to integrate these new, advanced therapies into daily practice

Heterodimers of heterometallic rings

Nine new complexes are reported involving linked heterometallic rings; one ring is designed as a ligand for the second, and the compounds produced can be regarded as molecular prototypes for implementing quantum gates featuring two subtly different qubits.We are grateful to the EPSRC (UK) for funding, especially of the National EPR Facility. M. Albring is a member of the EPSRC supported Centre for Doctoral Training NoWNANO. We acknowledge financial support also from the FIRB Project No. RBFR12RPD1 of the Italian Ministry of Education and Research. This work has been partially supported by EC through the FET-Proactive Project “MoQuaS”, contract N.610449.Peer Reviewe

XAS of Ni and Cu Quinoxaline-2,3-Dithiolene Complexes in Solution using a Novel In Situ Electrochemical Cell

A novel electrochemical cell for XAS is presented. Using this cell XANES and EXAFS studies have been recorded of unstable redox active species in solution. In particular, changes in the immediate environment of the metal that occur upon oxidation of the metal dithiolene complexes [Ni(qdf)2]2- and [Cu(qdt)2]2- (where qdt = quinoxaline-2-3-dithioIate) have been studied. The position of the edge has been used to determine the site of the redox process and analysis of the EXAFS shows changes in the M-S bond length upon oxidation

Observation of the influence of dipolar and spin frustration effects on the magnetocaloric properties of a trigonal prismatic {Gd7} molecular nanomagnet

We report the synthesis and structure of a molecular {Gd7} cage of the formula (iPr2NH2)6[Gd7(μ3-OH)3(CO3)6(O2CtBu)12] which has crystallographic C3h symmetry. Low temperature specific heat and adiabatic demagnetization experiments (the latter achieving temperatures below 100 mK), lead to the observation of the effects of both intramolecular dipolar interactions and geometric spin frustration. The dipolar interaction leads to a massive rearrangement of energy levels such that specific heat and entropy below 2 K are strongly modified while magnetic susceptibility and magnetization above 2 K are not affected. The consequences of these phenomena for low temperature magnetocaloric applications are discussed.EMP thanks the Panamanian agency SENACYT-IFARHU. KZ thanks the KRG-Scholarship program in “Human Capacity Development (HCDP)”. JS thanks the Deutsche Forschungsgemeinschaft (DFG SCHN 615/20-1) for continuous support. Supercomputing time at the LRZ Garching is gratefully acknowledged. GL and ME thank Spanish MINECO (MAT2015-68204-R). We also thank EPSRC (UK) for funding an X-ray diffractometer (grant number EP/K039547/1).Peer Reviewe