Catalytic C1 Alkylation with Methanol and Isotope‐Labeled Methanol

A metal‐catalyzed methylation process has been developed. By employing an air‐ and moisture‐stable manganese catalyst together with isotopically labeled methanol, a series of D‐, CD₃‐, and ¹³C‐labeled products were obtained in good yields under mild reaction conditions with water as the only byproduct.     

Photocatalytic Reduction of Nicotinamide Co-factor by Perylene Sensitized RhIII Complexes**

The ambitious goal of artificial photosynthesis is to develop active systems that mimic nature and use light to split water into hydrogen and oxygen. Intramolecular design concepts are particularly promising. Herein, we firstly present an intramolecular photocatalyst integrating a perylene-based light-harvesting moiety and a catalytic rhodium center ( Rh^IIIphenPer ). The excited-state dynamics were investigated by means of steady-state and time-resolved absorption and emission spectroscopy. The studies reveal that photoexcitation of Rh^IIIphenPer yields the formation of a charge-separated intermediate, namely Rh^IIphenPer ⋅ ⁺ , that results in a catalytically active species in the presence of protons.     

Pyrimidoquinazolinophenanthroline Opens Next Chapter in Design of Bridging Ligands for Artificial Photosynthesis**

The synthesis and detailed characterization of a new Ru polypyridine complex containing a heteroditopic bridging ligand with previously unexplored metal-metal distances is presented. Due to the twisted geometry of the novel ligand, the resultant division of the ligand in two distinct subunits leads to steady state as well as excited state properties of the corresponding mononuclear Ru(II) polypyridine complex resembling those of prototype [Ru(bpy)₃]²⁺ (bpy=2,2'-bipyridine). The localization of the initially optically excited and the nature of the long-lived excited states on the Ru-facing ligand spheres is evaluated by resonance Raman and fs-TA spectroscopy, respectively, and supported by DFT and TDDFT calculations. Coordination of a second metal (Zn or Rh) to the available bis-pyrimidyl-like coordination sphere strongly influences the frontier orbitals, apparent by, for example, luminescence quenching. Thus, the new bridging ligand motif offers electronic properties, which can be adjusted by the nature of the second metal center. Using the heterodinuclear Ru−Rh complex, visible light-driven reduction of NAD⁺ to NADH was achieved, highlighting the potential of this system for photocatalytic applications.     

Regiodivergent C−H Acylation of Arenes by Switching from Ionic- to Radical-Type Chemistry Using NHC Catalysis

The Friedel–Crafts acylation reaction, which belongs to the class of electrophilic aromatic substitutions is a highly valuable and versatile reaction in synthesis. Regioselectivity is predictable and determined by electronic as well as steric factors of the (hetero)arene substrate. Herein, a radical approach for the acylation of arenes and heteroarenes is presented. C−H acylation is achieved through mild cooperative photoredox/NHC radical catalysis with the cross-coupling of an arene radical cation with an NHC-bound ketyl radical as a key step. As compared to the classical Friedel–Crafts acylation, a regiodivergent outcome is observed upon switching from the ionic to the radical mode. In these divergent reactions, aroyl fluorides act as the acylation reagents in both the ionic as well as the radical process.     

Protection of flows under targeted attacks

We present a new robust optimization model for the problem of maximizing the amount of flow surviving the attack of an interdictor. Given some path flow, our model allows the interdictor to specify the amount of flow removed from each path individually. In contrast to previous models, for which no efficient algorithms are known, the most important basic variants of our model can be solved in poly-time. We also consider extensions where there is a budget to set the interdiction costs.     

Comparison of monomethoxy‐, dimethoxy‐, and trimethoxysilane anchor groups for surface‐initiated RAFT polymerization from silica surfaces

The immobilization of reversible addition–fragmentation chain transfer (RAFT) agents on silica for surface‐initiated RAFT polymerizations (SI‐RAFT) via the Z‐group approach was studied systematically in dependence of the functionality of the RAFT‐agent anchor group. Monoalkoxy‐, dialkoxy‐, and trialkoxy silyl ether groups were incorporated into trithiocarbonate‐type RAFT agents and bound to planar silica surfaces as well as to silica nanoparticles. The immobilization efficiency and the structure of the bound RAFT‐agent film varied strongly in dependence of the used solvent (toluene vs. 1,2‐dimethoxyethane) and the anchor group functionality, as evidenced by atomic force microscopy, transmission electron microscopy, dynamic light scattering, and UV/Vis spectroscopy. Surface‐initiated RAFT polymerizations using functionalized silica nanoparticles revealed that grafted oligomers, which often occur in SI‐RAFT, are not formed within the crosslinked structures that originate from the immobilization, and that RAFT‐agent films that show less aggregation during the immobilization are more efficient during SI‐RAFT in terms of polymer grafting density. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 103–113     

Popular branchings and their dual certificates

Mathematical Programming - Let G be a digraph where every node has preferences over its incoming edges. The preferences of a node extend naturally to preferences over branchings, i.e., directed...     

Dijkstra meets Steiner: a fast exact goal-oriented Steiner tree algorithm

We present a new exact algorithm for the Steiner tree problem in edge-weighted graphs. Our algorithm improves the classical dynamic programming approach by Dreyfus and Wagner. We achieve a significantly better practical performance via pruning and future costs, a generalization of a well-known concept to speed up shortest path computations. Our algorithm matches the best known worst-case run time and has a fast, often superior, practical performance: on some large instances originating from VLSI design, previous best run times are improved upon by orders of magnitudes. We are also able to solve larger instances of the d-dimensional rectilinear Steiner tree problem for \(d \in \{3, 4, 5\}\), whose Hanan grids contain up to several millions of edges.     

Retrosynthetic accessibility score (RAscore) – rapid machine learned synthesizability classification from AI driven retrosynthetic planning

Computer aided synthesis planning (CASP) is part of a suite of artificial intelligence (AI) based tools that are able to propose synthesis routes to a wide range of compounds. However, at present they are too slow to be used to screen the synthetic feasibility of millions of generated or enumerated compounds before identification of potential bioactivity by virtual screening (VS) workflows. Herein we report a machine learning (ML) based method capable of classifying whether a synthetic route can be identified for a particular compound or not by the CASP tool AiZynthFinder. The resulting ML models return a retrosynthetic accessibility score (RAscore) of any molecule of interest, and computes at least 4500 times faster than retrosynthetic analysis performed by the underlying CASP tool. The RAscore should be useful for pre-screening millions of virtual molecules from enumerated databases or generative models for synthetic accessibility and produce higher quality databases for virtual screening of biological activity.

The retrosynthetic accessibility score (RAscore) is based on AI driven retrosynthetic planning, and is useful for rapid scoring of synthetic feasability and pre-screening of large datasets of virtual/generated molecules.     

Merging of a Perylene Moiety Enables a RuII Photosensitizer with Long-Lived Excited States and the Efficient Production of Singlet Oxygen

Multichromophoric systems based on a Ru^II polypyridine moiety containing an additional organic chromophore are of increasing interest with respect to different light-driven applications. Here, we present the synthesis and detailed characterization of a novel Ru^II photosensitizer, namely [(tbbpy)₂Ru((2-(perylen-3-yl)-1H-imidazo[4,5-f][1,10]-phenanthrolline))](PF₆)₂ RuipPer , that includes a merged perylene dye in the back of the ip ligand. This complex features two emissive excited states as well as a long-lived (8 μs) dark state in acetonitrile solution. Compared to prototype [(bpy)₃Ru]²⁺-like complexes, a strongly altered absorption (ϵ=50.3×10³ M⁻¹ cm⁻¹ at 467 nm) and emission behavior caused by the introduction of the perylene unit is found. A combination of spectro-electrochemistry and time-resolved spectroscopy was used to elucidate the nature of the excited states. Finally, this photosensitizer was successfully used for the efficient formation of reactive singlet oxygen.