In Situ X-ray Diffraction Investigation of the Crystallisation of Perfluorinated CeIV-Based Metal–Organic Frameworks with UiO-66 and MIL-140 Architectures**

We report on the results of an in situ synchrotron powder X-ray diffraction study of the crystallisation in aqueous medium of two recently discovered perfluorinated Ce^IV-based metal–organic frameworks (MOFs), analogues of the already well investigated Zr^IV-based UiO-66 and MIL-140A, namely, F4_UiO-66(Ce) and F4_MIL-140A(Ce). The two MOFs were originally obtained in pure form in similar conditions, using ammonium cerium nitrate and tetrafluoroterephthalic acid as reagents, and small variations of the reaction parameters were found to yield mixed phases. Here, we investigate the crystallisation of these compounds, varying parameters such as temperature, amount of the protonation modulator nitric acid and amount of the coordination modulator acetic acid. When only HNO₃ is present in the reaction environment, only F4_MIL-140A(Ce) is obtained. Heating preferentially accelerates nucleation, which becomes rate determining below 57 °C. Upon addition of AcOH to the system, alongside HNO₃, mixed-phased products are obtained. F4_UiO-66(Ce) is always formed faster, and no interconversion between the two phases occurs. In the case of F4_UiO-66(Ce), crystal growth is always the rate-determining step. A higher amount of HNO₃ favours the formation of F4_MIL-140A(Ce), whereas increasing the amount of AcOH favours the formation of F4_UiO-66(Ce). Based on the in situ results, a new optimised route to achieving a pure, high-quality F4_MIL-140A(Ce) phase in mild conditions (60 °C, 1 h) is also identified.     

Multidentate,V-Shaped Pyridine Building Blocks as Tectons for Crystal Engineering

The formation of supramolecular structural units through self-assembly is a powerful method to design new architectures and materials endowed with specific properties. With the aim of adding a group of versatile tectons to the toolkit of crystal engineers, we have devised and synthesised four new V-shaped building blocks characterised by an aryl acetylene scaffold comprising three substituted pyridine rings connected by two triple bonds. The judicious choice of different substituents on the pyridine rings provides these tectons with distinctive steric, electrostatic and self-assembly properties, which influence their crystal structures and their ability to form co-crystals. Co-crystals of the tectons with tetraiododifluorobenzene were obtained both via traditional and mechanochemical crystallisation strategies, proving their potential use in crystal engineering. The energetic contributions of the supramolecular interactions at play in the crystal lattice have also been evaluated to better understand their nature and strength and to rationalise their role in designing molecular crystals.     

Characterization of PEGylated Asparaginase: New Opportunities from NMR Analysis of Large PEGylated Therapeutics

Resonance assignment and structural characterization of pharmacologically relevant proteins promise to improve understanding and safety of these proteins by rational design. However, the PEG coating that is used to evade the immune system also causes these molecules to “evade” the standard structural biology methodologies. We here demonstrate that it is possible to obtain the resonance assignment and a reliable structural model of large PEGylated proteins through an integrated approach encompassing NMR and X-ray crystallography.     

Fluorescence Emission of Self-assembling Amyloid-like Peptides: Solution versus Solid State

Analysis of the intrinsic UV-visible fluorescence exhibited by self-assembling amyloid-like peptides in solution and in solid the state highlights that their physical state has a profound impact on the optical properties. In the solid state, a linear dependence of the fluorescence emission peaks as a function of excitation wavelength is detected. On the contrary, an excitation-independent emission is observed in solution. The present findings constitute a valuable benchmark for current and future explanations of the fluorescence emission by amyloids.     

Tight Fluctuations of Weight-Distances in Random Graphs with Infinite-Variance Degrees

Journal of Statistical Physics - We prove results for first-passage percolation on the configuration model with degrees having asymptotic finite mean, infinite variance and i.i.d. edge-weights with...     

Metal Nanoparticle–Microbe Interactions: Synthesis and Antimicrobial Effects

Metal nanoparticles (NPs), chalcogenides, and carbon quantum dots can be easily synthesized from whole microorganisms (fungi and bacteria) and cell-free sterile filtered spent medium. The particle size distribution and the biosynthesis time can be somewhat controlled through the biomass/metal solution ratio. The biosynthetic mechanism can be explained through the ion-reduction theory and UV photoconversion theory. Formation of biosynthetic NPs is part of the detoxification strategy employed by microorganisms, either in planktonic or biofilm form, to reduce the chemical toxicity of metal ions. In fact, most reports on NP biosynthesis show extracellular metal ion reduction. This is important for environmental and industrial applications, particularly in biofilms, as it allows in principle high biosynthetic rates. The antimicrobial and antifungal effect on biosynthetic NPs can be explained in terms of reactive oxygen species and can be enhanced by the capping agents attached to the NP during the biosynthesis process. Industrial applications of NP biosynthesis are still lagging, due to the difficulty of controlling NP size and low titer. Further, the environmental assessment of biosynthetic NPs has not yet been carried out. It is expected that further advancements in biosynthetic NP research will lead to applications, particularly in environmental biotechnology.     

Visible-Light Controlled Divergent Catalysis Using a Bench-Stable Cobalt(I) Hydride Complex

While the use of visible light in conjunction with transition metal catalysis offers powerful opportunities to switch between on/-off states of catalytic activity, the next frontier would be the ability to switch the actual function of the catalyst and resulting products. Here we report such an example of multi-dimensional catalysis. Featuring an easily prepared, bench-stable cobalt(I) hydride complex in conjunction with pinacolborane, we can switch the reaction outcome between two widely employed transformations, olefin migration and hydroboration, with visible light as the trigger.