Identification and Directed Development of Non‐Organic Catalysts with Apparent Pan‐Enzymatic Mimicry into Nanozymes for Efficient Prodrug Conversion

Nanozymes, nanoparticles that mimic the natural activity of enzymes, are intriguing academically and are important in the context of the Origin of Life. However, current nanozymes offer mimicry of a narrow range of mammalian enzymes, near‐exclusively performing redox reactions. We present an unexpected discovery of non‐proteinaceous enzymes based on metals, metal oxides, 1D/2D‐materials, and non‐metallic nanomaterials. The specific novelty of these findings lies in the identification of nanozymes with apparent mimicry of diverse mammalian enzymes, including unique pan‐glycosidases. Further novelty lies in the identification of the substrate scope for the lead candidates, specifically in the context of bioconversion of glucuronides, that is, human metabolites and privileged prodrugs in the field of enzyme‐prodrug therapies. Lastly, nanozymes are employed for conversion of glucuronide prodrugs into marketed anti‐inflammatory and antibacterial agents, as well as “nanozyme prodrug therapy” to mediate antibacterial measures.     

Semi‐heterogeneous Dual Nickel/Photocatalysis using Carbon Nitrides: Esterification of Carboxylic Acids with Aryl Halides

Cross‐coupling reactions mediated by dual nickel/photocatalysis are synthetically attractive but rely mainly on expensive, non‐recyclable noble‐metal complexes as photocatalysts. Heterogeneous semiconductors, which are commonly used for artificial photosynthesis and wastewater treatment, are a sustainable alternative. Graphitic carbon nitrides, a class of metal‐free polymers that can be easily prepared from bulk chemicals, are heterogeneous semiconductors with high potential for photocatalytic organic transformations. Here, we demonstrate that graphitic carbon nitrides in combination with nickel catalysis can induce selective C?O cross‐couplings of carboxylic acids with aryl halides, yielding the respective aryl esters in excellent yield and selectivity. The heterogeneous organic photocatalyst exhibits a broad substrate scope, is able to harvest green light, and can be recycled multiple times. In situ FTIR was used to track the reaction progress to study this transformation at different irradiation wavelengths and reaction scales.     

Recognition of derivability for the Lambek calculus with one division

A polynomial algorithm for determination of derivability in the Lambek calculus with one division is described in the paper.     

Electron Deficient Monomers that Optimize Nucleation and Enhance the Photocatalytic Redox Activity of Carbon Nitrides

Polymeric carbon nitride (PCN) is usually synthesized from nitrogen‐rich monomers such as cyanamide, melamine, and urea, but is rather disordered in many cases. Now, a new allotrope of carbon nitride with internal heterostructures was obtained by co‐condensation of very electron poor monomers (for example, 5‐amino‐tetrazole and nucleobases) in the presence of mild molten salts (for example, NaCl/KCl) to mediate the polymerization kinetics and thus modulate the local structure, charge carrier properties, and most importantly the HOMO and LUMO levels. Results reveal that the as‐prepared NaK‐PHI‐A material shows excellent photo‐redox activities because of a nanometric hetero‐structure which enhances visible light absorption and promotes charge separation in the different domains.     

Structural analogs of adenosine receptor inhibitors in the series of 1,2,4-triazolo[1,5-<Emphasis Type="Italic">a</Emphasis>]pyrimidines

A universal method was developed for the synthesis of 7-alkylamino-6-nitro-1,2,4-triazolo-[1,5-a]pyrimidines by the chlorodeoxygenation of the corresponding triazolopyrimidones.