Inertia of Technology Stocks: A Technology-Explicit Model for the Transition toward a Low-Carbon Global Aluminum Cycle.

Low-carbon technologies are essential for the aluminum industry to meet its climate targets despite increasing demand. However, the penetration of these technologies is often delayed due to the long lifetimes of the industrial assets currently in use. Existing models and scenarios for the aluminum sector omit this inertia and therefore potentially overestimate the realistic mitigation potential. Here, we introduce a technology-explicit dynamic material flow model for the global primary (smelters) and secondary (melting furnaces) aluminum production capacities. In business-as-usual scenarios, we project emissions from smelters and melting furnaces to rise from 710 Mt CO2-eq./a in 2020 to 920-1400 Mt CO2-eq./a in 2050. Rapid implementation of inert anodes in smelters can reduce emissions by 14% by 2050. However, a limitation of emissions compatible with a 2 °C scenario requires combined action: (1) an improvement of collection and recycling systems to absorb all the available postconsumer scrap, (2) a fast and wide deployment of low-carbon technologies, and (3) a rapid transition to low-carbon electricity sources. These measures need to be implemented even faster in scenarios with a stronger increase in aluminum demand. Lock-in effects are likely: building new capacity using conventional technologies will compromise climate mitigation efforts and would require premature retirement of industrial assets.

Linking Low-Coordinate Ge(II) Centers via Bridging Anionic N-Heterocyclic Olefin Ligands.

We introduce a large-scale synthesis of a sterically encumbered N-heterocyclic olefin (NHO) and illustrate the ability of its deprotonated form to act as an anionic four-electron bridging ligand. The resulting multicenter donating ability has been used to link two low oxidation state Ge(II) centers in close proximity, leading to bridging Ge-Cl-Ge and Ge-H-Ge bonding environments supported by Ge2C2 heterocyclic manifolds. Reduction of a dimeric [RGeCl]2 species (R = anionic NHO, [(MeCNDipp)2C═CH]-; Dipp = 2,6-iPr2C6H3) did not give the expected acyclic RGeGeR analogue of an alkyne, but rather ligand migration/disproportionation transpired to yield the known diorganogermylene R2Ge and Ge metal. This process was examined computationally, and the ability of the reported anionic NHO to undergo atom migration chemistry contrasts with what is typically found with bulky monoanionic ligands (such as terphenyl ligands).

Highly selective AlCl3 initiated intramolecular α-alkylation of α,ß-unsaturated lactams and lactones.

An unprecedented example of AlCl3 initiated intramolecular α-alkylation of α,ß-unsaturated lactams and lactones is reported. A variety of substrates containing an intramolecular diene yield exclusively regioselective six-membered ring products. This reaction protocol generates a new stereo centre which may be of high interest for the functionalization of bioactive coumarin and quinolinone derivatives.

[A survey among family doctors on care reality of patients under oral tyrosine kinase inhibitor therapies]. / Befragung von Hausärzt*innen zur Versorgung von Patienten unter oralen Tyrosinkinaseinhibitoren.

INTRODUCTION: Oral tyrosine kinase inhibitor (TKI) therapies are becoming increasingly more important in the treatment of malignant diseases. Monitoring with focus on adherence, side effects and interactions poses new challenges for medical care. The role and capabilities of family doctors in the care of TKI patients are yet unclear and should be uncovered in a nationwide survey. METHODS: From April to July 2016, 3,000 family doctors in Germany were asked to complete a written questionnaire regarding their capabilities for co-supervision of TKI patients. RESULTS: The response rate was 18% (n=553). The peak age was between 50 and 60 years. 81% were specialists in general medicine, 14% specialists in internal medicine and 5% general practitioners. 98% cared for no or less than 10 TKI patients per quarter. Knowledge of side effects and interaction potential of TKIs was low in over 90%. 83% preferred monitoring by the treating oncologist and 93% felt uncertain about treatment monitoring. The control of adherence was of little importance in 66%. The number of treated TKI patients had a significant impact on knowledge and opportunities for treatment monitoring. There was a significant correlation between knowledge about TKIs and confidence in treatment monitoring. In general, younger doctors tended to be more confident in treatment monitoring, and specialists in internal medicine tended to have more knowledge than specialists in general medicine general practitioners and general practitioners. DISCUSSION: Currently, the low number of TKI patients, little knowledge about TKI, and the desire for specialist care are limiting the possibilities of co-caring for TKI patients by family doctors. CONCLUSION: Although family doctors are generally motivated to care for tumor patients, routine treatment controls of TKI patients conducted by family doctors seem hardly possible at the moment and should currently remain with the specialist.

Exploring different coordination modes of the first tetradentate NHC/1,2,3-triazole hybrid ligand for group 10 complexes.

Synthesis and characterisation of the first tetradentate N-heterocyclic carbene (NHC)/1,2,3-triazole hybrid ligand obtained by means of copper(i) catalyzed "click" chemistry and its application for the synthesis of group 10 complexes is reported. For palladium(ii), two complexes with different ligand coordination modes were obtained. One compound depicts a NCCN coordination sphere with all 1,2,3-triazole and NHC moieties coordinating to the metal, whereas the other one depicts a CCCC coordination sphere resulting from NHC coordination of two ligands. The non-coordinating 1,2,3-triazoles form strong intramolecular hydrogen bonds as proven by SC-XRD. The resulting rigid conformation is retained in solution even at 70 °C as demonstrated by variable temperature NMR spectroscopy. In contrast to palladium(ii), both nickel(ii) and platinum(ii) exclusively form complexes with a CCCC coordination sphere regardless of reaction conditions. Both compounds share characteristics with their palladium(ii) counterpart, including strong intramolecular hydrogen bonds.

A bench stable formal Cu(iii) N-heterocyclic carbene accessible from simple copper(ii) acetate.

For years, Cu(iii)NHCs have been proposed as active intermediates in Cu(i)NHC catalyzed reactions, yielding the desired products by reductive elimination, but until today, no one has ever reported the characterisation of such a compound. When working on the synthesis of biomimetic transition metal (NHC) complexes and their application in homogeneous catalysis, we recently found a highly unusual reactivity for Cu(ii) acetate in the presence of a particular cyclic tetra(NHC) ligand. Therein, the formation of the first stable CuNHC compound, displaying Cu in the formal oxidation state +III, by simple disproportionation of Cu(ii) acetate in dimethyl sulfoxide (DMSO) was observed. At elevated temperatures selective mono-oxidation of the NHC ligand occurs, even under anaerobic conditions. Acetate was identified as the origin of the oxygen atom by 18O-labelling experiments. The remarkably high stability of the title compound was furthermore proven electrochemically by cyclic voltammetry. An in-depth investigation of its reactivity revealed the involvement of four additional compounds. Three of them could be isolated and characterised by 1H/13C-NMR, single crystal XRD, mass spectrometry and elemental analysis. The fourth, a Cu(i)NHC intermediate, formed by formal reductive elimination from the Cu(NHC)3+ compound, was characterised in situ by 1H/13C-NMR and computational methods.