Postsynthetic Metal and Ligand Exchange in MFU‐4l: A Screening Approach toward Functional Metal–Organic Frameworks Comprising Single‐Site Active Centers

The isomorphous partial substitution of Zn²⁺ ions in the secondary building unit (SBU) of MFU‐4l leads to frameworks with the general formula [M_xZn_(5–x)Cl₄(BTDD)₃], in which x≈2, M=Mn^II, Fe^II, Co^II, Ni^II, or Cu^II, and BTDD=bis(1,2,3‐triazolato‐[4,5‐b],[4′,5′‐i])dibenzo‐[1,4]‐dioxin. Subsequent exchange of chloride ligands by nitrite, nitrate, triflate, azide, isocyanate, formate, acetate, or fluoride leads to a variety of MFU‐4l derivatives, which have been characterized by using XRPD, EDX, IR, UV/Vis‐NIR, TGA, and gas sorption measurements. Several MFU‐4l derivatives show high catalytic activity in a liquid‐phase oxidation of ethylbenzene to acetophenone with air under mild conditions, among which Co‐ and Cu derivatives with chloride side‐ligands are the most active catalysts. Upon thermal treatment, several side‐ligands can be transformed selectively into reactive intermediates without destroying the framework. Thus, at 300 °C, Co^II‐azide units in the SBU of Co‐MFU‐4l are converted into Co^II‐isocyanate under continuous CO gas flow, involving the formation of a nitrene intermediate. The reaction of Cu^II‐fluoride units with H₂ at 240 °C leads to Cu^I and proceeds through the heterolytic cleavage of the H₂ molecule.     

On the chemical characteristics and dynamics of n-alkane low-temperature multistage diffusion flames

We demonstrate experimentally, perhaps for the first time, the existence of low-temperature multistage diffusion flames of n-alkanes. Multistage diffusion flames of n-heptane, n-decane, and n-dodecane are established in an atmospheric counterflow burner. Planar laser-induced fluorescence, chemiluminescence, and thermometry are used to probe the structures of such flames. In the first flame zone, the majority of the fuel is partially oxidized via low-temperature peroxy chemistry. In the second flame zone, the intermediate species produced are further oxidized via intermediate-temperature chemistry. The two stages of the flame are coupled such that significant fuel and oxidizer leakage occur, respectively, from the first and second reaction zones. The fuel is then further consumed, in the second stage, after the radical pool is replenished by the oxidation of the intermediates. The structure of the n-alkane multistage flame is found to be consistent with that previously observed for acyclic ethers. Owing to the different classes of temperature-dependent chemistries dominating the first and second stages, the reaction zone structure of multistage diffusion flames is dramatically influenced by the reactant concentrations and flame temperatures. The first stage is relatively favored at lower temperatures whereas the second stage is favored at elevated temperatures. Moreover, near extinction where the flame temperature is low, the multistage flame dynamics are controlled by the first oxidation stage, governed by peroxy chemistry, whereas the second oxidation stage, governed by intermediate chemistry, is dominant near high-temperature ignition conditions. Finally, by doping the oxidizer with ozone, we demonstrate the role of ozone doping on the multistage flame structure and the existence of a separate low-temperature ozone-assisted burning mode.     

Non-perturbative QEG corrections to the Yang–Mills beta function

We discuss the non-perturbative renormalization group evolution of the gauge coupling constant by using a truncated form of the functional flow equation for the effective average action of the Yang–Mills-gravity system. Our result is consistent with the conjecture that quantum Einstein gravity (QEG) is asymptotically safe and has a vanishing gauge coupling constant at the non-trivial fixed point.     

Selective Uptake of Cylindrical Poly(2‐Oxazoline) Brush‐AntiDEC205 Antibody‐OVA Antigen Conjugates into DEC‐Positive Dendritic Cells and Subsequent T‐Cell Activation

To achieve specific cell targeting by various receptors for oligosaccharides or antibodies, a carrier must not be taken up by any of the very many different cells and needs functional groups prone to clean conjugation chemistry to derive well‐defined structures with a high biological specificity. A polymeric nanocarrier is presented that consists of a cylindrical brush polymer with poly‐2‐oxazoline side chains carrying an azide functional group on each of the many side chain ends. After click conjugation of dye and an anti‐DEC205 antibody to the periphery of the cylindrical brush polymer, antibody‐mediated specific binding and uptake into DEC205⁺‐positive mouse bone marrow‐derived dendritic cells (BMDC) was observed, whereas binding and uptake by DEC205^? negative BMDC and non‐DC was essentially absent. Additional conjugation of an antigen peptide yielded a multifunctional polymer structure with a much stronger antigen‐specific T‐cell stimulatory capacity of pretreated BMDC than application of antigen or polymer–antigen conjugate.