Biosensing is of vital importance for advancing public health through monitoring abnormalities in biological systems, which may be potentially associated with certain body dysfunctions. A wide range of luminescent materials have been actively pursued in the fabrication of biosensing platforms, particularly ones that can function in complex biological fluids with high selectivity and sensitivity. Recently, metal-organic frameworks (MOFs) have experienced rapid growth due to their tunable structures, large surface area, and being prone to surface engineering, etc. These virtues endow MOF materials with immense feasibility in the target-oriented construction of sensing platforms for specific applications. In this review, we extrapolated six sensing mechanisms for MOF-based photoluminescent biosensing platforms, including photoelectron transfer (PET), resonance energy transfer (RET), competition absorption (CA), structural transformation (ST), chemical conversion (CC), and quencher detachment (QD). Accordingly, recent progress of MOF-based materials in photoluminescence sensing of biomolecules, biomarkers, drugs, and toxins was highlighted. The objective of this review is to provide readers with an extensive overview of the design and synthesis of MOF materials for photoluminescence biosensing. The challenges and outlook are briefly discussed at the end.

Metal-organic frameworks as photoluminescent biosensing platforms: mechanisms and applications.

The successful use of electrochemiluminescence (ECL) in immunoassay for clinical diagnosis requires development of novel ECL signal probes. Herein, we report lanthanide (Ln) metal-organic frameworks (LMOFs) as ECL signal emitters in the ECL immunoassay. The LMOFs were prepared from precursors containing Eu (III) ions and 5-boronoisophthalic acid (5-bop), which could be utilized to adjust optical properties. Investigations of ECL emission mechanisms revealed that 5-bop was excited with ultraviolet photons to generate a triplet-state, which then triggered Eu (III) ions for red emission. The electron-deficient boric acid decreased the energy-transfer efficiency from the triplet-state of 5-bop to Eu (III) ions; consequently, both were excited with high-efficiency at single excitation. In addition, by progressively tailoring the atomic ratios of Ni/Fe, NiFe composites (Ni/Fe 1:1) were synthesized with more available active sites, enhanced stability, and excellent conductivity. As a result, the self-luminescent europium LMOFs displayed excellent performance characteristics in an ECL immunoassay with a minimum detectable limit of 0.126 pg mL-1, using Cytokeratins21-1 (cyfra21-1) as the target detection model. The probability of false positive/false negative was reduced dramatically by using LMOFs as signal probes. This proposed strategy provides more possibilities for the application of lanthanide metals in analytical chemistry, especially in the detection of other disease markers.

Self-Luminescent Lanthanide Metal-Organic Frameworks as Signal Probes in Electrochemiluminescence Immunoassay.

Investigation of macromolecular structure and dynamics is fundamental to understanding how macromolecules carry out their functions in the cell. Significant advances have been made toward this end in silico, with a growing number of computational methods proposed yearly to study and simulate various aspects of macromolecular structure and dynamics. This review aims to provide an overview of recent advances, focusing primarily on methods proposed for exploring the structure space of macromolecules in isolation and in assemblies for the purpose of characterizing equilibrium structure and dynamics. In addition to surveying recent applications that showcase current capabilities of computational methods, this review highlights state-of-the-art algorithmic techniques proposed to overcome challenges posed in silico by the disparate spatial and time scales accessed by dynamic macromolecules. This review is not meant to be exhaustive, as such an endeavor is impossible, but rather aims to balance breadth and depth of strategies for modeling macromolecular structure and dynamics for a broad audience of novices and experts.

/pdf/principles-and-overview-of-sampling-methods-for-modeling-znr1ol4lhn.pdf

Principles and Overview of Sampling Methods for Modeling Macromolecular Structure and Dynamics

Metal–organic frameworks (MOFs) have been frequently used as photocatalysts for the hydrogen evolution reaction (HER) using sacrificial agents with UV–vis or visible light irradiation. The aim of the present review is to summarize the use of MOFs as solar-driven photocatalysts targeting to overcome the current efficiency limitations in overall water splitting (OWS). Initially, the fundamentals of the photocatalytic OWS under solar irradiation are presented. Then, the different strategies that can be implemented on MOFs to adapt them for solar photocatalysis for OWS are discussed in detail. Later, the most active MOFs reported until now for the solar-driven HER and/or oxygen evolution reaction (OER) are critically commented. These studies are taken as precedents for the discussion of the existing studies on the use of MOFs as photocatalysts for the OWS under visible or sunlight irradiation. The requirements to be met to use MOFs at large scale for the solar-driven OWS are also discussed. The last section of this review provides a summary of the current state of the field and comments on future prospects that could bring MOFs closer to commercial application.

https://pubs.acs.org/doi/pdf/10.1021/acs.chemrev.2c00460

Metal–Organic Frameworks as Photocatalysts for Solar-Driven Overall Water Splitting

Metal–orgainc frameworks (MOFs) are a class of hybrid inorganic/organic framework materials and have been widely used in smart sensing. Among them, MOF-based monochromatic luminescent sensors display a limited detecting accuracy due to their easily disturbed signal. Combining the merits of lanthanide (Ln) luminescence with a porous skeleton, Ln-functionalized dual/multiple-emitting metal–organic frameworks (MOFs) have exhibited potential applications in ratiometric luminescence sensing with high accuracy, antijamming, sensitivity, and selectivity. Through rational design or post-modification, MOFs can be endowed with intrinsic emissions from Ln ions, ligands, or other luminescent materials and served as advanced detection materials for a wide variety of analytes via the linear variation of the ratio of luminescence intensities. Herein, we have summarized the recent progress of Ln-functionalized MOF-based ratiometric probes in sensing analytes in organic solvents, aqueous systems, and gas phase as well as in detecting temperature and pH. According to the possible origin of emissions, three strategies, including embedding additional luminescent species, modulating “antenna effect”, and mixed-Ln-based MOFs, are put forward for the construction of dual-emitting materials with high sensing performance.

Lanthanide-functionalized metal–organic frameworks as ratiometric luminescent sensors

Photoluminescence of metal–organic frameworks (MOFs) is sensitive to the structure and concentration of chemical species in the surroundings since MOFs combine the advantages of highly ordered porous structures, varied luminescence origins and diversified host–guest interactions. The diversity and combination flexibility of the organic and inorganic components together with the voids within MOFs offer ample possibilities for tuning their luminescence properties. On the basis of their intrinsic framework structures and biocompatible building blocks, MOFs have stimulated great interest in the area of biosensors. By elaborating on these points, this review will provide up-to-date developments in luminescent MOFs (LMOFs) with emphasis on synthetic approaches and their application in sensing biomolecules. The design outline of LMOFs including functionalization with fluorescent linkers and metal centers and incorporating fluorescent guest molecules within MOFs is presented, and the sensing properties of LMOFs for biomolecules such as DNA/RNA, enzymes/proteins, amino acids, glucose, ascorbic acid, and antibiotics are summarized.

Photoluminescent metal–organic frameworks and their application for sensing biomolecules

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Photoluminescent metal–organic frameworks and their application for sensing biomolecules

New aniline derivatives from the volva of Phallus rubrovolvatus and their anti-inflammatory activity

Structural Analysis of the Binding of Type I, I1/2, and II Inhibitors to Eph Tyrosine Kinases.