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.

Cubes on a string: a series of linear coordination polymers with cubane-like nodes and dicarboxylate linkers.

A series of semicrystalline and amorphous one-dimensional (1D) polymeric chains consisting of cubane-like CoII4L4 units (L = S-1,2-bis(benzimidazol-2-yl)ethanol) and dicarboxylates were synthesized and characterized by single crystal diffraction and X-ray total scattering. The polycationic chains are composed of [Co4L4(dicarboxylate)]2+ monomeric units, while one molecular dicarboxylate counterion is balancing the charge of each monomer. The linear compound series has five members, and the crystal structures were solved for [Co4L4(tph)](tph) and [Co4L4(ndc)](ndc), where tph = terephthalate and ndc = 2,6-naphthalenedicarboxylate. Partly crystalline compounds were produced by slow assembly at elevated temperature (over days), while the amorphous compounds were formed by fast precipitation (within minutes). Pair distribution function (PDF) analysis based on X-ray total scattering data reveals the presence of the cubane-like entity in both the amorphous and semicrystalline samples. While the powders are non-porous, precipitation is a fast and versatile method to produce compounds with cubane-like centres with moderate surface areas of 17-49 m2 g-1 allowing for surface chemical reactions. The powders have a high concentration of Lewis base sites as verified by their selective adsorption of CO2 over N2. The use of an amorphous cubane-like polymer for the electrocatalytic oxygen evolution reaction was demonstrated.

Three-dimensional morphology of anatase nanocrystals obtained from supercritical flow synthesis with industrial grade TiOSO4 precursor.

Anatase TiO2 (a-TiO2) nanocrystals are vital in catalytic applications both as catalysts (e.g. photodegradation) and as a carrier material (e.g. NOx removal from exhaust). The synthesis of a-TiO2 nanocrystals and their properties have been heavily scrutinized, but there exists a clear gap between the scientific literature, and the scale and price expectation of industrial application. Here it is demonstrated that the industrially most attractive Ti precursor, titanyl sulfate (TiOSO4), can be combined with the green, scalable and fast supercritical flow method to produce phase pure and highly crystalline a-TiO2 nanoparticles with high specific surface area. Control of the nanocrystal morphology is important since it is known that certain facets substantially promote catalytic activity. It is, however, in itself challenging to determine nanocrystal morphology to provide a rational basis for the synthesis control. Here we advocate the use of advanced Rietveld refinement of powder X-ray diffraction data including anisotropic size broadening models in aiding to establish the sample three-dimensional morphology. This relatively quick and robust method assists in overcoming the often encountered ambiguity inherent in two-dimensional to three-dimensional reconstruction of selected particle morphologies with transmission electron microscopy and tomography techniques.

Structural changes during water-mediated amorphization of semiconducting two-dimensional thio-stannates.

Owing to their combined open-framework structures and semiconducting properties, two-dimensional thio-stannates show great potential for catalytic and sensing applications. One such class of crystalline materials consists of porous polymeric [Sn3S7 2-] n sheets with molecular cations embedded in-between. The compounds are denoted R-SnS-1, where R is the cation. Dependent on the cation, some R-SnS-1 thio-stannates transition into amorphous phases upon dispersion in water. Knowledge about the fundamental chemical properties of the thio-stannates, including their water stability and the nature of the amorphous products, has not yet been established. This paper presents a time-resolved study of the transition from the crystalline to the amorphous phase of two violet-light absorbing thio-stannates, i.e. AEPz-SnS-1 [AEPz = 1-(2-amino-ethyl)-piperazine] and trenH-SnS-1 [tren = tris-(2-amino-ethyl)-amine]. X-ray total scattering data and pair distribution function analysis reveal no change in the local intralayer coordination during the amorphization. However, a rapid decrease in the crystalline domain sizes upon suspension in water is demonstrated. Although scanning electron microscopy shows no significant decrease of the micrometre-sized particles, transmission electron microscopy reveals the formation of small particles (∼200-400 nm) in addition to the larger particles. The amorphization is associated with disorder of the thio-stannate nanosheet stacking. For example, an average decrease in the interlayer distance (from 19.0 to 15.6 Å) is connected to the substantial loss of the organic components as shown by elemental analysis and X-ray photoelectron spectroscopy. Despite the structural changes, the light absorption properties of the amorphisized R-SnS-1 compounds remain intact, which is encouraging for future water-based applications of such materials.

Carbon nitride photocatalyzes regioselective aminium radical addition to the carbonyl bond and yields N-fused pyrroles.

Addition of N-centered radicals to C=C bonds or insertion into C-H bonds is well represented in the literature. These reactions have a tremendous significance, because they afford polyfunctionalized organic molecules. Despite the tetrahydroisoquinoline (THIQ) moiety widely occurring in natural biologically active compounds, N-unsubstituted THIQs as a source of N-centered radicals are not studied. Herein, we report a photocatalytic reaction between tetrahydroisoquinoline and chalcones that gives N-fused pyrroles-1,3-disubstituted-5,6-dihydropyrrolo[2,1-a]isoquinolines (DHPIQ). The mechanism includes at least two photocatalytic events in one pot: (1) C-N bond formation; (2) C-C bond formation. In this process potassium poly(heptazine imide) is used as a visible light active heterogeneous and recyclable photocatalyst. Fifteen N-fused pyrroles are reported with 65-90% isolated yield. DHPIQs are characterized by UV-vis and fluorescence spectroscopy, while the fluorescence quantum efficiency of fluorinated DHPIQs reaches 24%.

Graphene inclusion controlling conductivity and gas sorption of metal-organic framework.

A general approach to prepare composite films of metal-organic frameworks and graphene has been developed. Films of copper(ii)-based HKUST-1 and HKUST-1/graphene composites were grown solvothermally on glassy carbon electrodes. The films were chemically tethered to the substrate by diazonium electrografting resulting in a large electrode coverage and good stability in solution for electrochemical studies. HKUST-1 has poor electrical conductivity, but we demonstrate that the addition of graphene to HKUST-1 partially restores the electrochemical activity of the electrodes. The enhanced activity, however, does not result in copper(ii) to copper(i) reduction in HKUST-1 at negative potentials. The materials were characterised in-depth: microscopy and grazing incidence X-ray diffraction demonstrate uniform films of crystalline HKUST-1, and Raman spectroscopy reveals that graphene is homogeneously distributed in the films. Gas sorption studies show that both HKUST-1 and HKUST-1/graphene have a large CO2/N2 selectivity, but the composite has a lower surface area and CO2 adsorption capacity in comparison with HKUST-1, while CO2 binds stronger to the composite at low pressures. Electron paramagnetic resonance spectroscopy reveals that both monomeric and dimeric copper units are present in the materials, and that the two materials behave differently upon hydration, i.e. HKUST-1/graphene reacts slower by interaction with water. The changed gas/vapour sorption properties and the improved electrochemical activity are two independent consequences of combining graphene with HKUST-1.

Light absorption engineering of a hybrid (Sn3S72-)n based semiconductor - from violet to red light absorption.

The crystalline two-dimensional thiostannate Sn3S7(trenH)2 [tren = tris(2-aminoethyl)amine] consists of negatively charged (Sn3S72-)n polymeric sheets with trenH+ molecular species embedded in-between. The semiconducting compound is a violet light absorber with a band gap of 3.0 eV. In this study the compound was synthesized and functionalized by introducing the cationic dyes Methylene Blue (MB) or Safranin T (ST) into the crystal structure by ion exchange. Dye capacities up to approximately 45 mg/g were obtained, leading to major changes of the light absorption properties of the dye stained material. Light absorption was observed in the entire visible light region from red to violet, the red light absorption becoming more substantial with increasing dye content. The ion exchange reaction was followed in detail by variation of solvent, temperature and dye concentration. Time-resolved studies show that the ion exchange follows pseudo-second order kinetics and a Langmuir adsorption mechanism. The pristine and dye stained compounds were characterized by powder X-ray diffraction and scanning electron microscopy revealing that the honeycomb hexagonal pore structure of the host material was maintained by performing the ion exchange in the polar organic solvent acetonitrile, while reactions in water caused a break-down of the long-range ordered structure.