Tristan Tsai Yuan Tan

Precisely integrating MOF powders into patterned electrochemical devices remains a processing challenge, as conventional methods often require masks, manual alignment, or poorly scalable steps and can lead to non‐selective deposition and inefficient material use. While electrophoretic and dielectrophoretic deposition methods for particulate materials and GOx@ZIF‐8/Prussian Blue (PB) glucose biosensors have been reported independently, low‐volume localization of enzyme‐loaded MOFs directly onto active microelectrode transducer regions remains challenging. Here, we develop a mask‐free, DC‐field‐assisted microdroplet strategy that selectively localizes GOx@ZIF‐8 onto PB‐modified interdigitated electrodes (PB@IDEs). The approach uses only 12 µL of GOx@ZIF‐8 suspension and, unlike random drop‐casting, preferentially confines the biocatalytic MOF to the PB transduction interface, minimizing inactive deposition and improving enzyme utilization. The resulting Nafion/GOx@ZIF‐8/PB@IDE biosensor exhibits reproducible spatial localization and approximately threefold higher sensitivity, together with a lower limit of detection, than an otherwise identical drop‐cast electrode. The sensor shows a linear amperometric response over 24–175 µM glucose concentration, overlapping concentrations relevant to sweat glucose analysis. These results demonstrate that electro‐addressable placement of enzyme@MOF particles can improve reaction‐readout coupling while reducing biocatalyst consumption.

Metal–organic framework (MOF) particles are commonly incorporated into polymer composites to impart porosity or functionality, but they often remain as fillers rather than defining the polymer network architecture. Here, we report a new design principle in which UiO‐66‐NH ₂ nanoparticles are used as dynamic covalent crosslinkers for a linear polyimines to form MOF–vitrimer composites. Through imine bond formation between MOF‐bound amines and polymer aldehydes, the MOF becomes an integral network node, yielding free‐standing MOF–vitrimer composite films with high solvent resistance, while the MOF retains crystallinity. This architecture gives rise to properties beyond conventional MOF–polymer composites: dynamic imine exchange enables thermal healing, mechanical reprocessing, and chemical recycling. Furthermore, post‐synthetic tempering redistributes network connectivity and reprograms the mechanical properties from soft and extensible to stiff and strong, enabling material pluripotency and tunability to suit different applications. Unlike conventional organic crosslinkers, the MOF nodes also retain their intrinsic functions, allowing the composites to perform aqueous dye adsorption and organophosphate simulant hydrolysis while remaining easy to handle and recover. This work establishes MOFs as multifunctional dynamic crosslinkers for healable, recyclable, and post‐programmable hybrid materials, expanding MOF–polymer composites beyond passive filler architectures.

A series of gold nanoparticles (AuNPs) stabilized by bidentate acyclic diamino carbenes (ADCs) were synthesized via the reduction of dimeric gold(I) complexes. The resulting ADC-AuNPs were characterized by NMR spectroscopy, UV-vis spectroscopy, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA), revealing nanoparticles with a narrow size distribution and sizes ranging from 1.7 to 3.3 nm. This synthetic approach was extended to an asymmetric dinuclear ADC-gold(I) complex, affording slightly larger AuNPs (∼4 nm) upon reduction. The ADC-AuNPs with shorter linkers exhibited significant catalytic activity for the reduction of 4-nitrophenol, demonstrating a versatile and efficient route to catalytically active gold nanoparticles stabilized by both symmetric and asymmetric ADC ligands.

Polyethylenes (PEs) possess unreactive saturated hydrocarbon backbones, which make chemical recycling highly challenging, even at high temperatures. The insertion of strongly‐hydrogen‐bonding amide linkages into the PE backbone can potentially confer recyclability via amide cleavage and reformation, whilst simultaneously bringing about new material properties for functional upcycling. Herein, it is demonstrated that in‐chain amide insertion can be performed under a variety of reaction conditions, including the usage of p ‐cymene as a bioderived green solvent, with common and low‐cost reagents, on both high‐density (HDPE) and low‐density PEs (LDPE). Approximately 1 amide bond/100 ethylene repeating units can enhance not only the polymers’ tensile properties, but also elicit an unexpected increase in surface hydrophobicity and solid‐state clusteroluminescence that is absent in the parent PEs. Additionally, the hitherto‐overlooked importance of PE structure is uncovered in its chemical recyclability. While low‐branching amide‐containing HDPE could be hydrolysed and reformed for three cycles at ≤150 °C without compromising their tensile properties, attempted chemical recycling of highly‐branched LDPE formed a thermoset‐like crosslinked polymer with greatly enhanced ductility. These findings showcase amide‐insertion as a versatile means to access new functional applications that are originally inaccessible to PEs without requiring additives, with branching‐dependent influences on chemical recyclability for circular polymeric materials design.

Combination chemotherapy is a leading strategy for advanced cancer treatment, bringing about improved therapeutic responses compared with single-drug chemotherapy. However, achieving the required sequence of drug delivery needed for optimal therapeutic benefits via a single-drug delivery system remains highly challenging, often involving systems of considerable complexities. Herein, we report the design of composites comprising nanoscale metal–organic frameworks (MOFs) and temperature-responsive hydrogels (thermogels) as versatile, modular, yet simple-to-formulate platforms for controlled, localized release of combination chemotherapeutics, which can be used for solid tumor treatment. First, the encapsulation behavior, drug–host interactions, and in vitro release kinetics of four chemotherapeutic drugsgemcitabine (GEM), 5-fluorouracil (5-FU), doxorubicin (DOX), and paclitaxel (PTX)from nanoscale MOF carriers and the bulk gel phase were elucidated. Based on these differences, we designed dual- and even triple-drug formulations that could achieve sustained drug release over 10–18 days, with different rates of drug release that mimic clinically relevant sequential dosage. In all cases, MOF–thermogel multidrug formulations were highly injectable when chilled, potentially allowing minimally invasive and site-specific administration of multidrug cocktails to targeted tumor sites. Our findings establish MOF–thermogel nanocomposites as a highly customizable platform for tailoring multidrug release kinetics, relative rates, sequence, and release duration to meet different therapeutic demands for solid tumor chemotherapy and related applications.

NU-1000, a pyrene-containing benchmark metal–organic framework (MOF), is well-known for its utility and potential across a wide range of applications. Although the extended π-systems in NU-1000 confer favorable properties for diverse photochemical applications, they also increase the susceptibility of the MOF to photodegradation. However, the photostability of NU-1000 has yet to be systematically studied and remains poorly understood. Herein, we report that in the presence of oxygen, water, and light of appropriate energy, extensive oxidation of the pyrene linkers of NU-1000 can occur to yield terephthalic acid as the major decomposition product. Through extensive mechanistic studies, we show that the open framework structure of NU-1000 greatly facilitates linker oxidation, with more than 25-fold greater linker decomposition from the MOF within 3 h of photoirradiation compared to a homogeneous solution of the linker, brought about by rapid generation of pyrene-centred holes. By determining the specific conditions under which the MOF remains stable, our findings offer not just valuable strategies for preserving the integrity of NU-1000 for controlled applications but also reveal its ability to decompose into benign products under ambient light and oxygen, which could provide an eco-friendly route for avoiding environmental accumulation of MOF materials for various applications.

Polyolefins such as polyethylenes and polypropylenes are the most‐produced plastic waste globally, yet are difficult to convert into useful products due to their unreactivity. Pyrolysis is a practical method for large‐scale treatment of mixed, contaminated plastic, allowing for their conversion into industrially‐relevant petrochemicals. Metal–organic frameworks (MOFs), despite their tremendous utility in heterogeneous catalysis, have been overlooked for polyolefin depolymerization due to their perceived thermal instabilities and inability of polyethylenes and polypropylenes to penetrate their pores. Herein, we demonstrate the viability of UiO‐66 MOFs containing coordinatively‐unsaturated zirconium nodes, as effective catalysts for pyrolysis that significantly enhances the yields of valuable liquid and gas hydrocarbons, whilst halving the amounts of residual solids produced. Reactions occur on the Lewis‐acidic UiO‐66 nodes, without the need for noble metals, and yield aliphatic product distributions distinctly different from the aromatic‐rich hydrocarbons that can be obtained from zeolite catalysis. We also demonstrate the first unambiguous characterization of polyolefin penetration into UiO‐66 pores at pyrolytic temperatures, allowing access to the abundant Zr‐oxo nodes within the MOF interior for efficient C−C cleavage. Our work highlights the potential of MOFs as highly‐designable heterogeneous catalysts for depolymerisation of plastics, which can complement conventional catalysts in reactivity.

Polyolefins such as polyethylenes and polypropylenes are the most‐produced plastic waste globally, yet are difficult to convert into useful products due to their unreactivity. Pyrolysis is a practical method for large‐scale treatment of mixed, contaminated plastic, allowing for their conversion into industrially‐relevant petrochemicals. Metal–organic frameworks (MOFs), despite their tremendous utility in heterogeneous catalysis, have been overlooked for polyolefin depolymerization due to their perceived thermal instabilities and inability of polyethylenes and polypropylenes to penetrate their pores. Herein, we demonstrate the viability of UiO‐66 MOFs containing coordinatively‐unsaturated zirconium nodes, as effective catalysts for pyrolysis that significantly enhances the yields of valuable liquid and gas hydrocarbons, whilst halving the amounts of residual solids produced. Reactions occur on the Lewis‐acidic UiO‐66 nodes, without the need for noble metals, and yield aliphatic product distributions distinctly different from the aromatic‐rich hydrocarbons that can be obtained from zeolite catalysis. We also demonstrate the first unambiguous characterization of polyolefin penetration into UiO‐66 pores at pyrolytic temperatures, allowing access to the abundant Zr‐oxo nodes within the MOF interior for efficient C−C cleavage. Our work highlights the potential of MOFs as highly‐designable heterogeneous catalysts for depolymerisation of plastics, which can complement conventional catalysts in reactivity.

We demonstrate the post-synthetic conversion of polyethylene into functional polymer electrolytes for lithium-ion batteries. To avoid end-of-life polymer electrolytes contributing to polymer waste, we further upcycle them into useful organic acids.