Gemcitabine is a widely used antimetabolite drug of pyrimidine structure, which can exist as a free-base molecular form (Gem). The encapsulated forms of medicinal drugs are of interest for delayed and local drug release. We utilized, for the first time, a novel approach of mechano-chemistry by liquid-assisted grinding (LAG) to encapsulate Gem on a \"matrix\" of porphyrin aluminum metal-organic framework Al-MOF-TCPPH2 (compound 2). The chemical bonding of Gem to compound 2 was studied by ATR-FTIR spectroscopy and powder XRD. The interaction involves the C=O group of Gem molecules, which indicates the formation of the encapsulation complex in the obtained composite. Further, the delayed release of Gem from the composite was studied to phosphate buffered saline (PBS) at 37 °C using an automated drug dissolution apparatus equipped with an autosampler. The concentration of the released drug was determined by HPLC-UV analysis. The composite shows delayed release of Gem due to the bonded form and constant concentration thereafter, while pure Gem shows quick dissolution in less than 45 min. Delayed release of Gem drug from the composite follows the kinetic pseudo-first-order rate law. Further, for the first time, the mechanism of delayed release of Gem was assessed by the variable stirring speed of drug release media, and kinetic rate constant k was found to decrease when stirring speed is decreased (diffusion control). Finally, the prolonged time scale of toxicity of Gem to pancreatic cancer PANC-1 cells was studied by continuous measurements of proliferation (growth) for 6 days, using the xCELLigence real-time cell analyzer (RTCA), for the composite vs. pure drug, and their differences indicate delayed drug release. Aluminum metal-organic frameworks are new and promising materials for the encapsulation of gemcitabine and related small-molecule antimetabolites for controlled delayed drug release and potential use in drug-eluting implants.

Nanoscale science is becoming increasingly important and prominent, and further development will necessitate integration with other material chemistries. In other words, it involves the construction of a methodology to build up materials based on nanoscale knowledge. This is also the beginning of the concept of post-nanotechnology. This role belongs to nanoarchitectonics, which has been rapidly developing in recent years. However, the scope of application of nanoarchitectonics is wide, and it is somewhat difficult to compile everything. Therefore, this review article will introduce the concepts of liquid and interface, which are the keywords for the organization of functional material systems in biological systems. The target interfaces are liquid-liquid interface, liquid-solid interface, and so on. Recent examples are summarized under the categories of molecular assembly, metal-organic framework and covalent organic framework, and living cell. In addition, the latest research on the liquid interfacial nanoarchitectonics of organic semiconductor film is also discussed. The final conclusive section summarizes these features and discusses the necessary components for the development of liquid interfacial nanoarchitectonics.

The sensitivity of immunoassays is generally limited by the low signal reporter/recognition element ratio. Nanomaterials serving as the carriers can enhance the loading number of signal reporters, thus improving the detection sensitivity. However, the general immobilization strategies, including direct physical adsorption and covalent coupling, may cause the random orientation and conformational change in proteins, partially or completely suppressing the enzymatic activity and the molecular recognition ability. In this work, we proposed a strategy to load recognition elements of antibodies and enzyme labels using boronic acid-modified metal-organic frameworks (MOFs) as the nanocarriers for signal amplification. The conjugation strategy was proposed based on the boronate ester interactions between the carbohydrate moieties in antibodies and enzymes and the boronic acid moieties on MOFs. Both enzymes and MOFs could catalyze the oxidation of 3,3\',5,5\'-tetramethylbenzidine (TMB) by H2O2, therefore achieving dual signal amplification. To indicate the feasibility and sensitivity of the strategy, colorimetric immunoassays of prostate specific antigen (PSA) were performed with boronic acid-modified Cu-MOFs as peroxidase mimics to catalyze TMB oxidation and nanocarriers to load antibody and enzyme (horseradish peroxidase, HRP). According to the change in the absorbance intensity of the oxidized TMB (oxTMB), PSA at the concentration range of 1~250 pg/mL could be readily determined. In addition, this work presented a site-specific and oriented conjugation strategy for the modification of nanolabels with recognition elements and signal reporters, which should be valuable for the design of novel biosensors with high sensitivity and selectivity.

Long-afterglow materials have a broad of applications in optoelectronic devices, sensors, medicine and other fields due to their excellent luminescent properties. The host-guest long-afterglow MOFs material combines the advantages of multi-component characteristics and the stability of MOFs, which improves its luminous performance and expands its other properties. This review introduces the classification, synthesis and application of host-guest MOFs materials with long afterglow. Due to their rigid frames and multi-channel characteristics, MOFs can load common guest materials including rare earth metals, organic dyes, carbon dots, etc. The synthesis methods of loading guest materials into MOFs include solvothermal synthesis, post-encapsulation, post-modification, etc. Those long-afterglow host-guest MOFs have a wide range of applications in the fields of sensors, information security and biological imaging.

A novel and robust electrochemical sensing tool for the determination of vismodegib (VIS), an anticancer drug, has been developed by integrating the selective recognition capabilities of molecularly imprinted polymer (MIP) and the sensitivity enhancement capability of metal-organic framework (MOF). Prior to this step, the electrochemical behavior of VIS was investigated using a bare glassy carbon electrode (GCE). It was observed that in 0.5 M H2SO4 solution as electrolyte, VIS has an oxidation peak around 1.3 V and the oxidation mechanism is diffusion controlled. The determination of VIS in a standard solution using a bare GCE showed a linear response in the concentration range from 2.5 μM to 100 μM, with a limit of detection (LOD) of 0.75 μM. Since sufficient sensitivity and selectivity could not be achieved with bare GCE, a MIP sensor was developed in the next step of the study. For this purpose, the GCE surface was first modified by drop casting with as-synthesized Co-MOF. Subsequently, a MIP network was synthesized via a thermal polymerization approach using 2-acrylamido-2-methylpropanesulfonic acid (AMPS) as monomer and VIS as template. MOFs are ideal electrode materials due to their controllable and diverse morphologies and modifiable surface properties. These characteristics enable the development of MIPs with more homogeneous binding sites and high affinity for target molecules. Integrating MOFs could help the performance of sensors with the desired stability and reproducibility. Electrochemical analysis revealed an observable enhancement of the output signal by the incorporation of MOF molecules, which is consistent with the sensitivity-enhancing role of MOF by providing more anchoring sites for the attachment of the polymer texture to the electrode surface. This MOF-MIP sensor exhibited impressive linear dynamic ranges ranging from 0.1 to 1.0 pM for VIS, with detection limits in the low picomolar range. In addition, the MOF-MIP sensor offers high accuracy, selectivity and precision for the determination of VIS, with no interference observed from complex media of serum samples. Additionally, in this study, Analytical GREEnness metric (AGREE), Analytical GREEnness preparation (AGREEprep) and Blue Applicability Grade Index (BAGI) were used to calculate the green profile score.

A three-dimensional (3D) anionic cadmium-organic framework, namely [(CH3)2NH2][Cd1.5(DMTDC)2] ⋅ 2DMA ⋅ 0.5H2O (Cd-MOF; DMA=N,N-dimethylacetamide), was successfully synthesized under solvothermal conditions by using a linear thienothiophene-containing dicarboxylate ligand, 3,4-dimethylthieno [2,3-b]-thiophene-2,5-dicar-boxylic acid (H2DMTDC). Single-crystal X-ray diffraction analysis reveals that Cd-MOF exhibits a 3D anionic framework with pcu α-Po topology, featuring rectangle and rhombus-shaped channels along b- and c- axis direction. Cd-MOF demonstrates selective adsorption of cationic dyes over anionic and neutral dyes. Additionally, Tb3+-loaded Cd-MOF serves as a fast-response fluorescence sensor for the sensitive detection of Fe3+ ions with a low limit of detection (8.90×10-7 M) through fluorescence quenching.

The residues of organophosphorus pesticides (OPs) are increasing environmental pollution and public health concerns. Thus, the development of simple, convenient and sensitive method for detection of OPs is crucial. Herein, a multifunctional Fe-based MOF with fluorescence, catalytic and adsorption, is synthesized by a simple one-pot hydrothermal method. The ratiometric fluorescence sensor for detection of OPs is constructed by using only one multifunctional sensing material. The NH2-MIL-101(Fe) is able catalyze the o-phenylenediamine (OPD) into 2,3-diaminophenazine (DAP) in the presence of H2O2. The generated DAP can significantly quench the intrinsic fluorescence of NH2-MIL-101(Fe) by the fluorescence resonance energy transfer (FRET) and internal filtration effect (IFE), while producing a new measurable fluorescence. Without immobilization or molecular imprinting, pyrophosphate ion (PPi) can inhibit the peroxidase-like activity of the NH2-MIL-101(Fe) by chelating with Fe3+/Fe2+ redox couple. Moreover, PPi can also be hydrolyzed by alkaline phosphatase (ALP), the presence of OPs inhibits the activity of ALP, resulting in the increase of extra PPi preservation and signal changes of ratiometric fluorescence, the interactions of ALP with different OPs are explored by molecular docking, the OPs (e.g., glyphosate) interact with crucial amino acid residues (Asp, Ser, Ala, Lys and Arg) are indicated. The proposed sensor exhibits excellent detection performance for OPs with the detection limit of 18.7 nM, which provides a promising strategy for detection of OPs.

Immobilized laccases are widely used as green biocatalysts for bioremediation of phenolic pollutants and wastewater treatment. Metal-organic frameworks (MOFs) show potential application for immobilization of laccase. Their unique adsorption properties provide a synergic effect of adsorption and biodegradation. This review focuses on bioremediation of wastewater pollutants using laccase-MOF composites, and summarizes the current knowledge and future perspective of their biodegradation and the enhancement strategies of enzyme immobilization. Mechanistic strategies of preparation of laccase-MOF composites were mainly investigated via physical adsorption, chemical binding, and de novo/co-precipitation approaches. The influence of architecture of MOFs on the efficiency of immobilization and bioremediation were discussed. Moreover, as sustainable technology, the integration of laccases and MOFs into wastewater treatment processes represents a promising approach to address the challenges posed by industrial pollution. The MOF-laccase composites can be promising and reliable alternative to conventional techniques for the treatment of wastewaters containing pharmaceuticals, dyes, and phenolic compounds. The detailed exploration of various immobilization techniques and the influence of MOF architecture on performance provides valuable insights for optimizing these composites, paving the way for future advancements in environmental biotechnology. The findings of this research have the potential to influence industrial wastewater treatment and promoting cleaner treatment processes and contributing to sustainability efforts.

This study focused on detecting streptomycin (STR) residues using a luminescent aptasensor encapsulated with aptamer. Utilizing MOF-74-Co with peroxidase-like activity, luminol was enclosed in its pores. The specific STR aptamer acted as a gatekeeper, ensuring excellent performance. Upon exposure to STR, the aptamers detached, releasing luminol and amplifying the luminescent signal through MOF-74-Co catalytic activity. A linear relationship between fluorescence intensity and STR concentration (50 nM ∼ 5 × 106 nM) was established, with a limit of detection of 0.065 nM. The sensor exhibited high selectivity for STR even in the presence of other aminoglycoside antibiotics. Applied to tea, egg, and honey samples, the sensor showed recovery rates of 91.38-100.2%, meeting safety standards. This MOF-based aptasensor shows promise for detecting harmful residues.

Due to their abundant active sites and porous structures, metal-organic frameworks (MOFs) have garnered significant interest as oxygen evolution reaction (OER) electrocatalysts. Nevertheless, the development of MOF-based electrocatalysts with efficient OER activity and excellent stability simultaneously still faces challenges. Herein, a cathodic activation strategy was used to enhance the OER electrocatalytic performance of M-HHTP for the first time, where M refers to Ni, Cu, Co, Fe, while HHTP denotes 2, 3, 6, 7, 10, 11-hexahydroxytriphenylene. As a prototype, the activated Ni-HHTP (HA-Ni-HHTP) demonstrates outstanding OER performance, with an overpotential as low as 140 mV at 20 mA cm-2 and a small Tafel slope of 78.7 mV-1, surpassing commercial RuO2 and rivaling state-of-the-art MOFs-based electrocatalysts. Characterizations and density functional theory calculations reveal that the superior performance of HA-Ni-HHTP is primarily ascribed to changes in semiconductor type, contact angle, and oxygen vacancy content induced by cathodic activation. Electrochemical impedance spectroscopy analysis using the transmission line model confirms that cathodic activation accelerates charge transport, enhancing the OER process. Furthermore, the cathodic activation strategy holds promise for improving the water oxidation performance of other MOFs such as Fe-HHTP, Co-HHTP, and Cu-HHTP.