Preparation and characterisation of gelatine hydrogels predisposed to use as matrices for effective immobilisation of biocatalysts

Physical, enzymatic and chemical methods were used to develop an efficient procedure for preparing gelatine hydrogels of appropriate strength and elastic properties for applications as enzyme carriers. The concentrations of the crosslinking enzyme (transglutaminase), the initial amount of gelatine, the production time and the effect of additional crosslinking with glutaraldehyde were examined. As a result, the following conditions were selected: 0.1 g cm^?3 solution of gelatine, 0.01 g cm^?3 of transglutaminase (mTGase), a minimum of 2 h incubation at 4°C and an additional step of crosslinking with 1.0 vol. % of glutaraldehyde. Next, the absorption properties and storage stability of hydrogels so obtained were determined. From these results, it was observed that, with the exception of the physical gel, the remaining materials presented a relatively high resistance to hydrolytic degradation and retained their original spatial structure without any visible damages. The immobilisation experiments indicated gelatine-based hydrogels crosslinked with transglutaminase as suitable for use as matrices for the entrapment of enzymes, which catalyse the conversion of low-molecular mass compounds. In addition to the potential for effective re-use in subsequent batch processes, the essential advantage of the immobilised β-galactosidase obtained in the current study is a marked reduction in its volume under storage conditions of long duration, without any significant decline in catalytic activity.     

Tuning the Photo-electrochemical Performance of RuII-Sensitized Two-Dimensional MoS2

Covalently tethering photosensitizers to catalytically active 1T-MoS₂ surfaces holds great promise for the solar-driven hydrogen evolution reaction (HER). Herein, we report the preparation of two new Ru^II-complex-functionalized MoS₂ hybrids [Ru^II(bpy)₂(phen)]-MoS₂ and [Ru^II(bpy)₂(py)Cl]-MoS₂. The influence of covalent functionalization of chemically exfoliated 1T-MoS₂ with coordinating ligands and Ru^II complexes on the HER activity and photo-electrochemical performance of this dye-sensitized system was studied systematically. We find that the photo-electrochemical performance of this Ru^II-complex-sensitized MoS₂ system is highly dependent on the surface extent of photosensitizers and the catalytic activity of functionalized MoS₂. The latter was strongly affected by the number and the kind of functional groups. Our results underline the tunability of the photovoltage generation in this dye-sensitized MoS₂ system by manipulation of the surface functionalities, which provides a practical guidance for smart design of future dye-sensitized MoS₂ hydrogen production devices towards improved the photofuel conversion efficiency.     

Interaction of Quillaja bark saponins with food-relevant proteins

The surface activity and aggregation behaviour of two Quillaja bark saponins (QBS) are compared using surface tension, conductometry and light scattering. Despite formally of the same origin (bark of the Quillaja saponaria Molina tree), the two QBS show markedly different ionic characters and critical micelle concentrations (7.7 · 10^− 6 mol·dm^− 3 and 1.2 · 10^− 4 mol·dm^− 3). The new interpretation of the surface tension isotherms for both QBS allowed us to propose an explanation for the previous discrepancy concerning the orientation of the saponin molecules in the adsorbed layer.     

Influence of pyridine-based ligands on photostability of MAPbI3 thin films

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Urease adsorption and activity on magnetite nanoparticles functionalized with monofunctional and bifunctional surface layers

The surface of magnetite nanoparticles was coated with functional polysiloxane layers using reaction of hydrolytic copolycondensation of tetraethoxysilane and 3-aminopropyltriethoxysilane (or N-[3-trimethoxysilylpropyl]ethylendiamine), and also that of tetraethoxysilane, 3-aminopropyltriethoxysilane and methyltriethoxysilane (or n-propyltriethoxysilane). It was shown that these functionalized magnetically controllable particles (about 60–150 nm in size as aggregates), as opposed to magnetite, adsorb urease well from aqueous solutions (up to 1 g/g), and that the level of residual activity of adsorbed layers is up to 84 % in the case of a bifunctional sample. It was established that the activity of immobilized urease is normally gradually reduced during storage of the samples, but in the case of ethylenediamine functional group is not decreased for 45 days. The synthesized samples are promising for use as magnetically directed biocatalysts.     

Spatiotemporal Studies of the One-Dimensional Coordination Polymer [Fe(ebtz)2(C2H5CN)2](BF4)2: Tug of War between the Nitrile Reorientation Versus Crystal Lattice as a Tool for Tuning the Spin Crossover Properties**

Reaction of 1,2-di(tetrazol-2-yl)ethane (ebtz) with Fe(BF₄)₂⋅6 H₂O in different nitriles yields one-dimensional coordination polymers [Fe(ebtz)₂(RCN)₂](BF₄)₂⋅nRCN (n=2 for R=CH₃ ( 1 ) and n=0 for R=C₂H₅ ( 2 ) C₃H₇ ( 3 ), C₃H₅ ( 4 ), CH₂Cl ( 5 )) exhibiting spin crossover (SCO). SCO in 1 and 3 – 5 is complete and occurs above 160 K. In 2 , it is shifted to lower temperatures and is accompanied by wide hysteresis (T_1/2^↓=78 K, T_1/2^↑=123 K) and proceeds extremely slowly. Isothermal (80 K) time-resolved single-crystal X-ray diffraction studies revealed a complex nature for the HS→LS transition in 2 . An initial, slow stage is associated with shrinkage of polymeric chains and with reduction of volume at 77 % (in relation to the difference between cell volumes V_HS−V_LS) whereas only 16 % of iron(II) ions change spin state. In the second stage, an abrupt SCO occurs, associated with breathing of the crystal lattice along the direction of the Fe–nitrile bonds, while the nitriles reorient. HS→LS switching triggered by light (808 nm) reveals the coupling of spin state and nitrile orientation. The importance of this coupling was confirmed by studies of [Fe(ebtz)₂(C₂H₅CN/C₃H₇CN)₂](BF₄)₂ mixed crystals ( 2 a , 2 b ), showing a shift of T_1/2 to higher values and narrowing of the hysteresis loop concomitant with an increase of the fraction of butyronitrile. This increase reduces the capability of nitrile molecules to reorient. Density functional theory (DFT) studies of models of 1 – 5 suggest a particular possibility of 2 to adopt a low (140–145°) value of its Fe-N-C(propionitrile) angle.     

A Porous Sulfonated 2D Zirconium Metal–Organic Framework as a Robust Platform for Proton Conduction

By using the strategy of pre-assembly chlorosulfonation applied to a linker precursor, the first sulfonated zirconium metal–organic framework ( JUK-14 ) with two-dimensional (2D) structure, was synthesized. Single-crystal X-ray diffraction reveals that the material is built of Zr₆O₄(OH)₄(COO)₈ oxoclusters, doubly 4-connected by angular dicarboxylates, and stacked in layers spaced 1.5 nm apart by the presence of sulfonic groups. JUK-14 exhibits excellent hydrothermal stability, permanent porosity confirmed by gas adsorption studies, and shows high (>10⁻⁴ S/cm) and low (<10⁻⁸ S/cm) proton conductivity under humidified and anhydrous conditions, respectively. Post-synthesis inclusion of imidazole improves the overall conductivity increasing it to 1.7×10⁻³ S/cm at 60 °C and 90 % relative humidity, and by 3 orders of magnitude at 160 °C. The combination of 2D porous nature with robustness of zirconium MOFs offers new opportunities for exploration of the material towards energy and environmental applications.