Strong bidentate coordination for surface passivation and ligand-shell engineering of lead halide perovskite nanocrystals in the strongly quantum confined regime

The surface of lead halide perovskite nanocrystals (PNCs) is unique compared to conventional metal chalcogenide or pnictogenide semiconductor nanoparticles for its ionic character and the dynamic ligand layer, which makes them unstable in stock solutions and hinders the development of surface engineering strategies. This work employs a chelating strategy to form stable coordination on the PNC surface. Through screening a series of heterocyclic aromatic carboxylates, we found the best ligand, picolinate (PIC), with exceptional passivation effect to the surface traps of CsPbBr3 PNCs in the strongly quantum confined regime, resulting in > 0.8 photoluminescence quantum yields. The exciton lifetime in the passivated PNC approaches the radiative decay limit in various solvents. From an NMR titration experiment, the binding affinity of PIC is estimated to be at least 15 to 30 folds stronger than the original ligand from synthesis. The NMR and FTIR spectroscopic data and first-principles calculations elucidate the bidentate nature of the PIC coordination at the surface Pb site and the coadsorption of the ammonium-PIC ion pair. In apolar solvents, such as cyclohexane, the binding of PIC is stoichiometric to the available surface sites, suggesting the structure as a potent candidate for anchoring functional molecular structures to the PNC surface. In polar solvents, the strong affinity of PIC on the PNC surface provides protection for carrying out the precipitation-redissolution purification procedure that removes synthetic residual from the as-synthetic PNC samples. By modifying the purification procedure, we also develop a cation exchange procedure to replace the original oleylammonium cation with desired structures that consist of an ammonium anchoring group. Our results provide a direction for constructing strong interactions to protect the vulnerable surface of PNCs and pave the road for developing surface engineering strategies to functionalize these nanoparticles.

: Strong bidentate coordination for surface passivation and ligand-shell engineering of lead halide perovskite nanocrystals in the strongly quantum confined regime

The surface of lead halide perovskite nanocrystals (PNCs) is unique compared to conventional metal chalcogenide or pnictogenide semiconductor nanoparticles for its ionic character and the dynamic ligand layer, which makes them unstable in stock solutions and hinders the development of surface engineering strategies. This work employs a chelating strategy to form stable coordination on the PNC surface. Through screening a series of heterocyclic aromatic carboxylates, we found the best ligand, picolinate (PIC), with exceptional passivation effect to the surface traps of CsPbBr3 PNCs in the strongly quantum confined regime, resulting in > 0.8 photoluminescence quantum yields. The exciton lifetime in the passivated PNC approaches the radiative decay limit in various solvents. From an NMR titration experiment, the binding affinity of PIC is estimated to be at least 15 to 30 folds stronger than the original ligand from synthesis. The NMR and FTIR spectroscopic data and first-principles calculations elucidate the bidentate nature of the PIC coordination at the surface Pb site and the coadsorption of the ammonium-PIC ion pair. In apolar solvents, such as cyclohexane, the binding of PIC is stoichiometric to the available surface sites, suggesting the structure as a potent candidate for anchoring functional molecular structures to the PNC surface. In polar solvents, the strong affinity of PIC on the PNC surface provides protection for carrying out the precipitation-redissolution purification procedure that removes synthetic residual from the as-synthetic PNC samples. By modifying the purification procedure, we also develop a cation exchange procedure to replace the original oleylammonium cation with desired structures that consist of an ammonium anchoring group. Our results provide a direction for constructing strong interactions to protect the vulnerable surface of PNCs and pave the road for developing surface engineering strategies to functionalize these nanoparticles.

Valorization of cigarette butts for synthesis of levulinic acid as top value-added chemicals

Unprecedented in the literature, levulinic acid (LA), one of the top value-added intermediates of chemical industry, is obtained from cigarette butts as cellulose feedstock by means of a one-pot hydrothermal process carried out at 200 °C for 2 h and catalysed by phosphoric acid. The protocol avoids the use of more aggressive and toxic H2SO4 and HCl, that are generally employed on several cellulose sources (e.g. sludge paper), thus minimizing corrosion phenomena of plants. Neither chemical pre-treatment of butts nor specific purification procedure of LA are required. Notably, by simply modifying acid catalyst (e.g. using CH3COOH), another top value-added fine chemical such as 5-hydroxymethylfuraldehyde (HMF) is obtained, thus widening the scope of the method. Being cigarette filters a waste available in quantities of megatonnes per year, they represent an unlimited at no cost source of cellulose, thus enabling the up-scale to an industrial level of LA production.

Validation of Recombinant Chicken Liver Bile Acid Binding Protein as a Tool for Cholic Acid Hosting

Bile acids (BAs) are hydroxylated steroids derived from cholesterol that act at the intestinal level to facilitate the absorption of several nutrients and also play a role as signaling molecules. In the liver of various vertebrates, the trafficking of BAs is mediated by bile acid-binding proteins (L-BABPs). The ability to host hydrophobic or amphipathic molecules makes BABPs suitable for the distribution of a variety of physiological and exogenous substances. Thus, BABPs have been proposed as drug carriers, and more recently, they have also been employed to develop innovative nanotechnology and biotechnology systems. Here, we report an efficient protocol for the production, purification, and crystallization of chicken liver BABP (cL-BABP). By means of target expression as His6-tag cL-BABP, we obtained a large amount of pure and homogeneous proteins through a simple purification procedure relying on affinity chromatography. The recombinant cL-BABP showed a raised propensity to crystallize, allowing us to obtain its structure at high resolution and, in turn, assess the structural conservation of the recombinant cL-BABP with respect to the liver-extracted protein. The results support the use of recombinant cL-BABP for the development of drug carriers, nanotechnologies, and innovative synthetic photoswitch systems.

Valorization of cigarette butts for top value-added chemicals: Levulinic Acid

Levulinic acid (LA), one of the top value-added intermediates of chemical industry, can be obtained by thermal hydrolysis (at 200 °C) from cigarette butts (as cellulose feedstock) catalysed by phosphoric acidic. The protocol avoids the use of more aggressive H2SO4 and HCl, that are generally employed on several cellulose sources (e.g. sludge paper), thus minimizing corrosion phenomena of plants. Neither chemical pre-treatment of butts nor specific purification procedure of LA are required. Notably, by simply modifying acid catalyst (e.g. using CH3COOH), another top value-added fine chemical such as 5-hydroxymethylfuraldehyde (HMF) is obtained, thus widening the scope of the method.Being cigarette filters a waste available in quantities of megatonnes per year, they represent an unlimited at no cost source of cellulose, thus enabling the up-scale to an industrial level of LA production.

Cyclotron Production of 225Ac from an electroplated 226Ra Target

Purpose We demonstrate a cyclotron production of high-quality 225Ac using an electroplated 226Ra target. Methods All 226Ra used in this work was extracted from legacy Ra sources using a chelating resin. The subsequent ion-exchange purification gave pure 226Ra with a certain amount of carrier Ba. The radium target was prepared by electroplating. We successfully deposited about 1 mg (mCi) of 226Ra on a target box. Activation was performed by 16.5 MeV protons (on the target) at 20 µA for 5 h as the maximum. Purification of 225Ac as well as 226Ra recovery was performed using two functional resins with various concentrations of nitric acid. Cooling of the intermediate 225Ac for 2–3 weeks decayed the major byproduct of 226Ac and increased the radionuclidic purity of 225Ac. Then the same separation protocol was repeated to provide high-quality 225Ac. Results We obtained 225Ac at a yield of about 2.4 MBq (65 µCi) at EOB, and the subsequent primal purification gave 1.7 MBq (48 µCi) of 225Ac with 226Ac/225Ac ratio of < 4% at 4 d from EOB. Additional cooling time coupled with the repeated separation procedure (secondary purification) effectively increased the 225Ac (4n + 1 series) radionuclidic purity up to 99+%, which showed a similar identification to a commercially available 225Ac originating from a 229Th/225Ac generator. Conclusion The 226Ra(p,2n)225Ac reaction and the appropriate purification procedure has the potential to be a major alternative pathway for 225Ac production and can be performed in any facility with a compact cyclotron to address the increasing demand for 225Ac.

Multipartite entanglement and topology in holography

Starting from the entanglement wedge of a multipartite mixed state we describe a purification procedure which involves the gluing of several copies. The resulting geometry has non-trivial topology and a single oriented boundary for each original boundary region. In the purified geometry the original multipartite entanglement wedge cross section is mapped to a minimal surface of a particular non-trivial homology class. In contrast, each original bipartite entanglement wedge cross section is mapped to the minimal wormhole throat around each boundary. Using the bit thread formalism we show how maximal flows for the bipartite and multipartite entanglement wedge cross section can be glued together to form maximal multiflows in the purified geometry. The defining feature differentiating the flows is given by the existence of threads which cross between different copies of the original entanglement wedge. Together these demonstrate a possible connection between multipartite entanglement and the topology of holographic spacetimes.