Electroreductive Cobalt‐Catalyzed Carboxylation: Cross‐Electrophile Electrocoupling with Atmospheric CO2

The chemical use of CO₂ as an inexpensive, nontoxic C1 synthon is of utmost topical interest in the context of carbon capture and utilization (CCU). We present the merger of cobalt catalysis and electrochemical synthesis for mild catalytic carboxylations of allylic chlorides with CO₂. Styrylacetic acid derivatives were obtained with moderate to good yields and good functional group tolerance. The thus‐obtained products are useful as versatile synthons of γ‐arylbutyrolactones. Cyclic voltammetry and in operando kinetic analysis were performed to provide mechanistic insights into the electrocatalytic carboxylation with CO₂.     

Nickela‐electrocatalyzed Mild C−H Alkylations at Room Temperature

Direct alkylations of carboxylic acid derivatives are challenging and particularly nickel catalysis commonly requires high reaction temperatures and strong bases, translating into limited substrate scope. Herein, nickel‐catalyzed C?H alkylations of unactivated 8‐aminoquinoline amides have been realized under exceedingly mild conditions, namely at room temperature, with a mild base and a user‐friendly electrochemical setup. This electrocatalyzed C?H alkylation displays high functional group tolerance and is applicable to both the primary and secondary alkylation. Based on detailed mechanistic studies, a nickel(II/III/I) catalytic manifold has been proposed.     

Prediction of tractive response for flexible wheels with application to planetary rovers

Planetary rovers are typically developed for high-risk missions. Locomotion requires traction to provide forward thrust on the ground. In soft soils, traction is limited by the mechanical properties of the soil, therefore lack of traction and wheel slippage cause difficulties during the operation of the rover. A possible solution to increase the traction force is to increase the size of the wheel-ground contact area. Flexible wheels provide this due to the deformation of the loaded wheel and hence this decreases the ground pressure on the soil surface. This study focuses on development of an analytical model which is an extension to the Bekker theory to predict the tractive performance for a metal flexible wheel by using the geometric model of the wheel in deformation. We demonstrate that the new analytical model closely matches experimental results. Hence this model can be used in the design of robust and optimal traction control algorithms for planetary rovers and for the design and the optimisation of flexible wheels.     

On the Roman Bondage Number of Planar Graphs

A Roman dominating function on a graph G is a function f : V(G) → {0, 1, 2} satisfying the condition that every vertex u for which f (u) = 0 is adjacent to at least one vertex v for which f (v) = 2. The weight of a Roman dominating function is the value f (V(G)) = ?_{u ? V(G)} f (u){f (V(G)) = \sum_{u\in V(G)} f (u)}. The Roman domination number, γ _R (G), of G is the minimum weight of a Roman dominating function on G. The Roman bondage number b _R (G) of a graph G with maximum degree at least two is the minimum cardinality of all sets E^￠ í E(G){E^{\prime} \subseteq E(G)} for which γ _R (G − E′) > γ _R (G). In this paper we present different bounds on the Roman bondage number of planar graphs.     

Dipolar and quadrupolar detection using an FT-ICR MS setup at the MPIK Heidelberg

Dipolar and single-phase two-electrode quadrupolar detection schemes have been investigated at a Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) setup built for the KATRIN experiment at the Max-Planck-Institute for Nuclear Physics (MPIK) in Heidelberg. We present first experimental results of ⁷Li^?+? signals from a cylindrical Penning trap configuration for both detection schemes. While the prominent signal of the conventional dipolar detection scheme marks the reduced cyclotron frequency, the main signal for the quadrupolar detection appears at the sum of the reduced cyclotron frequency and the magnetron frequency. For ideal trapping fields, this sum frequency equals the ion cyclotron frequency ?? _c ?=?qB/(2??m). Sidebands due to the combined motions of the cyclotron mode and magnetron mode are observed by quadrupolar detection which allows the determination of the respective combinations of eigenfrequencies.     

Copper–Boxmi Complexes as Highly Enantioselective Catalysts for Electrophilic Trifluoromethylthiolations

The enantioselective trifluoromethylthiolation of β‐ketoesters using chiral copper–boxmi complexes as catalysts is reported. A number of α‐SCF₃‐substituted β‐ketoesters have been obtained with up to >99 % enantiomeric excess (ee), and the trifluoromethylthiolated products were then transformed diastereoselectively to α‐SCF₃‐β‐hydroxyesters with two adjacent quaternary stereocenters.     

Aldehyde‐Assisted Ruthenium(II)‐Catalyzed C?H Oxygenations

Versatile ruthenium(II) complexes allow for site‐selective C H oxygenations with weakly‐coordinating aldehydes. The challenging C H functionalizations proceed with high chemoselectivity by rate‐determining C H metalation. The new method features an ample substrate scope, which sets the stage for the step‐economical preparation of various bioactive heterocycles.     

Knowledge-Based Design of a Biosensor to Quantify Localized ERK Activation in Living Cells

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