A Fluorinated BODIPY-Based Zirconium Metal-Organic Framework for In Vivo Enhanced Photodynamic Therapy.

Photodynamic therapy (PDT), an emergent noninvasive cancer treatment, is largely dependent on the presence of efficient photosensitizers (PSs) and a sufficient oxygen supply. However, the therapeutic efficacy of PSs is greatly compromised by poor solubility, aggregation tendency, and oxygen depletion within solid tumors during PDT in hypoxic microenvironments. Despite the potential of PS-based metal-organic frameworks (MOFs), addressing hypoxia remains challenging. Boron dipyrromethene (BODIPY) chromophores, with excellent photostability, have exhibited great potential in PDT and bioimaging. However, their practical application suffers from limited chemical stability under harsh MOF synthesis conditions. Herein, we report the synthesis of the first example of a Zr-based MOF, namely, 69-L2, exclusively constructed from the BODIPY-derived ligands via a single-crystal to single-crystal post-synthetic exchange, where a direct solvothermal method is not applicable. To increase the PDT performance in hypoxia, we modify 69-L2 with fluorinated phosphate-functionalized methoxy poly(ethylene glycol). The resulting 69-L2@F is an oxygen carrier, enabling tumor oxygenation and simultaneously acting as a PS for reactive oxygen species (ROS) generation under LED irradiation. We demonstrate that 69-L2@F has an enhanced PDT effect in triple-negative breast cancer MDA-MB-231 cells under both normoxia and hypoxia. Following positive results, we evaluated the in vivo activity of 69-L2@F with a hydrogel, enabling local therapy in a triple-negative breast cancer mice model and achieving exceptional antitumor efficacy in only 2 days. We envision BODIPY-based Zr-MOFs to provide a solution for hypoxia relief and maximize efficacy during in vivo PDT, offering new insights into the design of promising MOF-based PSs for hypoxic tumors.

Hetero-interpenetrated metal-organic frameworks.

Interpenetrated metal-organic frameworks (MOFs) comprise two or more lattices that are mutually entangled. Interpenetration can be used to tune the structures and pore architectures of MOFs to influence, for example, their stability or interactions with guest molecules. The interpenetrating sublattices are typically identical, but hetero-interpenetrated MOFs, which consist of sublattices that are different from one another, have also been serendipitously produced. Here we describe a strategy for the deliberate synthesis of hetero-interpenetrated MOFs. We use the cubic α-MUF-9 framework as a host sublattice to template the growth of a second sublattice within its pores. Three different secondary sublattices are grown-two of which are not known as standalone MOFs-leading to three different hetero-interpenetrated MOFs. This strategy may serve to combine different properties into one material. We produce an asymmetric catalysis by allocating separate roles to the interpenetrating sublattices in a hetero-interpenetrated MOF: an achiral secondary amine on one sublattice provides the catalytic activity, while the chiral α-MUF-10 host imparts asymmetry to aldol and Henry reactions.

Science Teachers' Attitudes towards Computational Modeling in the Context of an Inquiry-Based Learning Module.

This study focuses on science teachers' first encounter with computational modeling in professional development workshops. It examines the factors shaping the teachers' self-efficacy and attitudes towards integrating computational modeling within inquiry-based learning modules for 9th grade physics. The learning modules introduce phenomena, the analysis of measurement data, and offer a method for coordinating the experimental findings with a theory-based computational model. Teachers' attitudes and self-efficacy were studied using survey questions and workshop activity transcripts. As expected, prior experience in physics teaching was related to teachers' self-efficacy in teaching physics in 9th grade. Also, teachers' prior experience with programming was strongly related to their self-efficacy regarding the programming component of model construction. Surprisingly, the short interaction with computational modeling increased the group's self-efficacy, and the average rating of understanding and enjoyment was similar among teachers with and without prior programming experience. Qualitative data provides additional insights into teachers' predispositions towards the integration of computational modeling into the physics teaching.

Controlled partial interpenetration in metal-organic frameworks.

Interpenetration, the entwining of multiple lattices, is a common phenomenon in metal-organic frameworks (MOFs). Typically, in interpenetrated MOFs the sub-lattices are fully occupied. Here we report a family of MOFs in which one sub-lattice is fully occupied and the occupancy level of the other can be controlled during synthesis to produce frameworks with variable levels of partial interpenetration. We also report an 'autocatenation' process, a transformation of non-interpenetrated lattices into doubly interpenetrated frameworks via progressively higher degrees of interpenetration that involves no external reagents. Autocatenation maintains crystallinity and can be triggered either thermally or by shear forces. The ligand used to construct these MOFs is chiral, and both racemic and enantiopure partially interpenetrated frameworks can be accessed. X-ray diffraction, nonlinear optical microscopy and theoretical calculations offer insights into the structures and dynamic behaviour of these materials and the growth mechanisms of interpenetrated MOFs.

Postcomplexation synthetic routes to dipyrrin complexes.

We report a postfunctionalization synthetic route to dipyrrin complexes that gives access to a broad range of new complexes. This route involves the coordination of a 5-methylthiodipyrrinato ligand to a metal centre followed by displacement of the thiomethyl moiety by a nucleophile. Using rhenium(I) as a platform and amine nucleophiles, we show how complexes that would be difficult or impossible to synthesize via traditional methods can now be accessed.