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Finally, the suprastructures can be disassembled into single-compartment units by applying ultra-sonication, switching their release to a burst-release mode. These findings open up exciting opportunities to fabricate multi-compartment suprastructures incorporating diverse functionalities for materials with emerging properties.This Perspective outlines the results obtained at the University of Bologna by applying crystal engineering strategies to develop nature inspired organic-inorganic materials to tackle challenges in the health and environment sectors. It is shown by means of a number of examples that co-crystallization of inorganic salts, such as alkali and transition metal halides, with organic compounds, such as amino acids, urea, thiourea and quaternary ammonium salts, can be successfully used for (i) chiral resolution and conglomerate formation from racemic compounds, (ii) inhibition of soil enzyme activity in order to reduce urea decomposition and environmental pollution, and (iii) preparation of novel agents to tackle antimicrobial resistance. All materials described in this Perspective have been obtained by mechanochemical solvent-free or slurry methods and characterized by solid state techniques. The fundamental idea is that a crystal engineering approach based on the choice of intermolecular interactions (coordination and hydrogen bonds) between organic and inorganic compounds allows obtaining materials with collective properties that are different, and often very much superior to those of the separate components. It is also demonstrated that the success of this strategy depends crucially on cross-disciplinary synergistic exchange with expert scientists in the areas of bioinorganics, microbiology, and chirality application-oriented developments of these novel materials.The treatment of nuclear spent fuels, especially the separation of minor actinides, is an imperative task for the healthy development of the nuclear industry. Up to now, it still remains a worldwide challenge to separate trivalent An3+ from Ln3+ because of their similar chemical properties. Therefore, investigating the mechanism behind the selective extraction of An3+ by theoretical methods is necessary. In this work, three phosphine oxide ligands with the same side structures but different bridging frameworks, Ph2PyPO, Ph2BipyPO and Ph2PhenPO, were investigated theoretically, and compared with each other using relativistic density functional theory. The results of QTAIM and MBO suggest that the Am-N bonds in the studied complexes have more covalent character than those in the Eu-N bonds, whereas the PDOS analysis indicates that more overlap exists between Am-5f and the Ph2PyPO's N-2p orbital than between Am-5f and Ph2BipyPO's N-2p, and Am-5f and Ph2PhenPO's N-2p orbital. However, the studied ligands all possess stronger affinities towards Am3+ than Eu3+, which partly results in the Am3+ selectivity towards Eu3+ in these three ligands. The calculated reaction free energy can reproduce the Am/Eu separation ability difference of three ligands well. This work offers some useful information for An/Ln separation of phosphine oxide ligands, and may help to design more efficient An3+/Ln3+ separation ligands.Laboratory studies of the radiation chemistry occurring in astrophysical ices have demonstrated the dependence of this chemistry on a number of experimental parameters. One experimental parameter which has received significantly less attention is that of the phase of the solid ice under investigation. In this present study, we have performed systematic 2 keV electron irradiations of the amorphous and crystalline phases of pure CH3OH and N2O astrophysical ice analogues. Radiation-induced decay of these ices and the concomitant formation of products were monitored in situ using FT-IR spectroscopy. A direct comparison between the irradiated amorphous and crystalline CH3OH ices revealed a more rapid decay of the former compared to the latter. Interestingly, a significantly lesser difference was observed when comparing the decay rates of the amorphous and crystalline N2O ices. These observations have been rationalised in terms of the strength and extent of the intermolecular forces present in each ice. The strong and extensive hydrogen-bonding network that exists in crystalline CH3OH (but not in the amorphous phase) is suggested to significantly stabilise this phase against radiation-induced decay. Conversely, although alignment of the dipole moment of N2O is anticipated to be more extensive in the crystalline structure, its weak attractive potential does not significantly stabilise the crystalline phase against radiation-induced decay, hence explaining the smaller difference in decay rates between the amorphous and crystalline phases of N2O compared to those of CH3OH. Our results are relevant to the astrochemistry of interstellar ices and icy Solar System objects, which may experience phase changes due to thermally-induced crystallisation or space radiation-induced amorphisation.A new class of nickel(II) oxyquinoline-bipyridine complexes, namely, [Ni(La1)2(Lb6)] (Ni1), [Ni(La1)2(Lb2)] ·CH3OH (Ni2), [Ni(La7)2(Lb11)]·2H2O (Ni3), [Ni(La1)2(Lb9)] (Ni4), [Ni(La1)2(Lb8)] (Ni5), [Ni(La2)2(Lb1)] (Ni6), [Ni(La2)2(Lb6)]·CH3OH (Ni7), [Ni(La2)2(Lb11)]·CH3OH (Ni8), [Ni(La2)2(Lb3)] (Ni9), [Ni(La2)2(Lb2)]·CH3OH (Ni10), [Ni(La2)2(Lb5)]·CH3OH (Ni11), [Ni(La2)2(Lb7)] (Ni12), [Ni(La3)2(Lb2)] (Ni13), [Ni(La4)2(Lb4)]·2CH3OH (Ni14), [Ni(La4)2(Lb8)]·2.5CH3OH (Ni15), [Ni(La4)2(Lb11)]·1.5CH3OH (Ni16), [Ni(La5)2(Lb7)] (Ni17), [Ni(La5)2(Lb10)]·CH3OH (Ni18), [Ni(La6)2(Lb11)]·3CH3OH (Ni19), [Ni(La7)2(Lb7)]·2CH3OH (Ni20), [Ni(La7)2(Lb8)]·2CH3OH (Ni21) and [Ni(La7)2(Lb1)]·2CH3OH (Ni22) bearing oxyquinoline (H-La1-H-La7) and bipyridine derivatives (Lb1-Lb11) were synthesized and characterized by elemental analysis, X-ray crystallography, infrared (IR) spectroscopy and electrospray mass spectrometry (ESI-MS). An MTT method suggested that the IC50 values of Ni1-Ni22 for A549/DDP tumor cells were 0.25-25.14 μM, but these complexes exhibited low cytotoxicity toward normal HL-7702 cells (>50 μM). Ni2 could induce A549/DDP tumor cell apoptosis, cause a decrease in the mitochondrial membrane potential (MMP, ΔΨm), and increase the intracellular [Ca2+] and reactive oxygen species (ROS) levels better than Ni10, Ni13, and Ni14. Autophagic and western blot assays showed that Ni2, Ni10, Ni13, and Ni14 could induce autophagy and regulate the expression of LC3 II/I, Beclin1, P62, PINK1, and Parkin proteins, and the inducibility activities were in the order of Ni2 > Ni14 > Ni13 > Ni10. Taken together, these results revealed that the nickel(II) oxyquinoline-bipyridine complex Ni2 inhibited cell growth in A549/DDP tumor cells via mitophagy pathways.A dual-phase transition metal nitride (TMN) based Co4N-WNx system has been fabricated using nitridation of CoWO4. The interface between centrosymmetric Co4N and non-centrosymmetric WNx promotes charge carrier separation. This system also shows piezoelectric behavior. The piezoelectric property has been proved using piezoelectric force microscopy (PFM) measurements. In addition, modulating the non-centrosymmetric structure of Co4N-WNx allows a hydrogen production rate of about 262.7 μmol g-1 h-1 in pure water. We also show that the piezocatalytic hydrogen evolution efficiency is satisfactory. Co4N-WNx can also help achieve simultaneous piezocatalytic hydrogen production and RhB degradation. This work provides a novel strategy for designing efficient piezocatalytic materials.Photocatalytic synthesis has emerged as an efficient route to transform CO2 into functionalized organic carbamates by photocatalysis. Herein, a catalyst-free carbamoyloxylation of arylacetones with CO2 and amines under visible light was developed for the synthesis of O-β-oxoalkyl carbamates in yields up to 93%. This protocol proceeded smoothly with the assistance of inexpensive carbon tetrabromide at room temperature under atmospheric CO2 pressure, leading to simultaneous construction of C-O and C-N bonds. Mechanism studies suggested the photoinduced hydrogen atom transfer (HAT) pathway followed by radical addition or single electron transfer (SET).Enzyme-free isothermal amplification reactions for nucleic acid analysis usually take several hours to obtain sufficient detection sensitivity, which limits their practical applications. Herein, we report a butanol dehydration-based method to greatly improve both the efficiency and the sensitivity of nucleic acid detections by three types of enzyme-free isothermal amplification reactions. The reaction time has been shortened from 3 h to 5-20 min with higher sensitivities. Especially in the DNAzyme-based amplification, the detection limit can be lowered over 16 000-fold to 3 × 10-17 mol L-1 in 2 h compared to the normal 3 h-reaction. We demonstrate that the high amplification efficiencies are attributed to the greatly accelerated reaction rates in the extremely concentrated reaction solutions caused by the butanol dehydration. This approach enhances the potential of applications of isothermal amplification reactions in clinical rapid tests, nanostructure synthesis, etc. and is promising to expand to other types of chemical reactions.The formation of a rare type of diphosphazenium cation is described. Its synthesis features a unique oxidative dealkylation of an iminophosphorane-phosphole by a silver(I) salt. DFT study of this compound reveals the low valent character of the N(I) center.This study compared the surface properties and rising velocities of pristine and weathered plastic production pellets, to evaluate impacts of environmental conditions. Rising velocities were measured for 140 weathered pellets collected from a Spanish beach and compared with pristine low-density polyethylene, high-density polyethylene and polypropylene pellets. Selleckchem MM-102 A subset of 49 weathered pellets were analysed by Fourier-transform infrared spectroscopy (FTIR), with all found to be polyethylene. Experimental rising velocities for the weathered pellets varied widely, from (2.36 ± 0.01) cm s-1 to (10.56 ± 0.26) cm s-1, with a mean value of (5.79 ± 0.06) cm s-1. Theoretical rising velocities were consistently higher than experimental velocities for all pellet types on average 136% of experimental values for weathered pellets. This discrepancy was more distinct for less spherical pellets, which were often more weathered. Flatter pellets often oscillated as they rose, which explains at least some of this finding. Atomic force microscopy (AFM) analysis revealed that the roughness of the pristine and weathered pellets was (59 ± 11) nm, and (74 ± 26) nm respectively. X-ray photoelectron spectroscopy (XPS) analysis showed that the proportion of surface oxidised carbon species were 2.3% and 4.0% of the total carbon signal for a pristine and a weathered pellet, respectively; consistent with photochemical reactions changing the surface chemistry of weathered pellets. As determined by density column, weathered pellets had slightly lower experimental densities than pristine pellets. Overall, this study illustrates why it is important that modelling studies on the environmental fate and/or movements of microplastics validate or correct predictions using experimental data.

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