Nanocomposite Hydrogel of Pd@ZIF-8 and Laponite®: Size-Selective Hydrogenation Catalyst under Mild Conditions

The composite hydrogel of a nanoscale metal–organic framework (NMOF) and nanoclay has emerged as a new soft-material with advanced properties and applications. Herein, we report a facile synthesis of a hydrogel nanocomposite by charge-assisted self-assembly of Pd@ZIF-8 nanoparticles with Laponite^® nanoclay which coat the surface of Pd@ZIF-8 nanoparticles. Such surface coating significantly enhanced the thermal stability of the ZIF-8 compared to the pristine framework. Further, the Pd@ZIF-8+LP hydrogel nanocomposite shows better size-selective catalytic hydrogenation of olefins than Pd@ZIF-8 nanoparticles based on selective diffusion of the substrate.     

Waste Cleaning Waste: Combining Alginate with Biowaste-Derived Substances in Hydrogels and Films for Water Cleanup

Biowaste-derived substances isolated from green compost (BBS-GC) are environmentally friendly reactants similar to humic substances, which contain multiple functionalities, that are suitable for adsorbing different kinds of pollutants in wastewater. Herein, sodium alginate (derived from brown algae) cross-linked with both Ca²⁺ ions and BBS-GC in the form of hydrogels and dried films are proposed as green, easy-to-form, and handleable materials for tertiary water treatments. The results show that both hydrogels and films are mechanically stable and can effectively remove differently charged dyes through an adsorption mechanism that can be described by the Freundlich model. BBS-GC-containing gels always performed better than samples prepared without BBS-GC, revealing that such unconventional materials can integrate waste valorization and water decontamination, potentially providing social and environmental benefits.     

Infrared Responsive Choline Phosphate Lipids for Synergistic Cancer Therapy

Choline phosphate lipids have been designed and developed as new-generation zwitterionic nanocarriers with excellent biocompatibility and bioorthogonality to provide a more programmable performance for cancer therapy. However, there is a lack of spatiotemporal and reversible control for drug release at target tumor cells, which can lead to severe adverse effects to normal tissue and discounted treatment outcome. Here, light-inducible Lip-cRGDfk/ICG/Dox liposomes were developed for synergistic cancer therapy. ICG can effectively convert light energy into selective heating in a local environment upon laser irradiation, thus inducing thermal ablation of tumor cells, and further reversibly trigger the spatiotemporal release of anticancer drugs (Dox) at tumor cells due to the conformation transformation of CP lipids to synergistically kill tumor cells. That Lip-cRGDfk/ICG/Dox exhibited a significant improvement for breast cancer therapy in vitro and in vivo is also demonstrated, thus it can serve as an efficient platform to noninvasively and spatiotemporally control the activation of cytotoxicity at tumor cells for precision cancer therapy.     

Amine-Directed Palladium-Catalyzed C−H Halogenation of Phenylalanine Derivatives

An efficient primary-amine-directed, palladium-catalyzed C−H halogenation (X=I, Br, Cl) of phenylalanine derivatives is reported on a range of quaternary amino acid (AA) derivatives thanks to suitable conditions employing trifluoroacetic acid as additive. The extension of this original native functionality-directed ortho-selective halogenation was even demonstrated with the more challenging native phenylalanine as tertiary AA.     

From the {FeIII2Ln2} Butterfly's Perspective: the Magnetic Benefits and Challenges of Cooperativity within 3 d–4 f Based Coordination Clusters

In this Review we discuss the tuning handles which can be used to steer the magnetic properties of Fe^III-4 f “butterfly” compounds. The majority of presented compounds were produced in the context of project A3 “Di- to tetranuclear compounds incorporating highly anisotropic paramagnetic metal ions” within the SFB/TRR88 “3MET”. These contain {Fe^III₂Ln₂} cores encapsulated in ligand shells which are easy to tune in a “test-bed” system. We identify the following advantages and variables in such systems: (i) the complexes are structurally simple usually with one crystallographically independent Fe^III and Ln^III, respectively. This simplifies theory and anaylsis; (ii) choosing Fe allows ⁵⁷Fe Mössbauer spectroscopy to be used as an additional technique which can give information about oxidation levels and spin states, local moments at the iron nuclei and spin-relaxation and, more importantly, about the anisotropy not only of the studied isotope, but also of elements interacting with this isotope; (iii) isostructural analogues with all the available (i. e. not Pm) 4 f ions can be synthesised, enabling a systematic survey of the influence of the 4 f ion on the electronic structure; (iv) this cluster type is obtained by reacting [Fe^III₃O(O₂CR)₆(L)₃](X) (X=anion, L=solvent such as H₂O, py) with an ethanolamine-based ligand L′ and lanthanide salts. This allows to study analogues of [Fe^III₂Ln₂(μ₃-OH)₂(L′)₂(O₂CR)₆] using the appropriate iron trinuclear starting materials. (v) the organic main ligand can be readily functionalised, facilitating a systematic investigation of the effect of organic substituents on the ligands on the magnetic properties of the complexes. We describe and discuss 34 {M^III₂Ln₂} (M=Fe or in one case Al) butterfly compounds which have been reported up to 2020. The analysis of these gives perspectives for designing new SMM systems with specific electronic and magnetic signatures