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Metal Organic Frameworks (MOFs) for Sensing Applications

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A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Inorganic Chemistry".

Deadline for manuscript submissions: closed (30 June 2024) | Viewed by 14279

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Dr. Liming Fan

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Shanxi Key Laboratory of Advanced Carbon Based Electrode Materials, Department of Chemistry, School of Chemistry and Chemical Engineering, North University of China, Taiyuan 030051, China
Interests: metal-organic framework; functional coordination polymers; post-synthesis and functionalization; luminescent sensor
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Dear Colleagues,

Metal organic frameworks (MOFs) or porous coordination polymers (PCPs) are crystalline materials with periodic networks constructed from the multidentate organic ligands and metal centers through coordination self-assembly. The outstanding structural characteristics of various structures with a high porosity, large specific surface area, and regular and adjustable confined spaces endow themselves a great potential as functional materials. Considering that MOFs not only have built-in organic ligands and metal ion luminescence centers but also can introduce luminescent guest molecules into a confined space through post-synthesis to realize the luminescence function, the applications of luminescence metal organic frameworks (LMOFs) as luminescence sensors or chemosensors are fascinating, especially in the fields of environmental detection and pollutant monitoring. Up to now, LMOFs have been widely used in the detection of heavy metal ions, highly oxidized metal anions, organic small molecules, volatile pollutants, pesticides, biomarkers, etc. Compared with the traditional detection methods, LMOFs show superior advantages of a rapid response, low cost, high sensitivity, and selectivity. Thus, this Special Issue will focus on the topic of metal organic frameworks (MOFs) for sensing applications and devote itself to the dissemination of research into the design of MOF-based luminescent sensors and their luminescent sensing applications. Various advanced studies regarding the exploration of MOF-based sensors will be covered in our Special Issue. Novel and facile strategies to construct MOF-based sensors are also welcome.

The following categories of manuscripts will be considered for publication: full research articles, short communications, reviews, and mini-reviews. Submissions should not have been previously published. All the submissions will be peer-reviewed before acceptance for publication.

Dr. Liming Fan
Guest Editor

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Keywords

metal-organic framework
coordination polymer
supramolecular chemistry
luminescence sensor
chemosensor
trace detection

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Published Papers (9 papers)

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Research

13 pages, 3706 KiB

Open AccessArticle

Signal-On Detection of Caspase-3 with Methylene Blue-Loaded Metal-Organic Frameworks as Signal Reporters

by Yaliang Huang, Jiaqiang Wang, Yirui Xu, Jiwen Zhang and Ning Xia

Molecules 2024, 29(15), 3700; https://doi.org/10.3390/molecules29153700 - 5 Aug 2024

Cited by 1 | Viewed by 852

Abstract

In this work, we report on an electrochemical method for the signal-on detection of caspase-3 and the evaluation of apoptosis based on the biotinylation reaction and the signal amplification of methylene blue (MB)-loaded metal–organic frameworks (MOFs). Zr-based UiO-66-NH₂ MOFs were used as the nanocarriers to load electroactive MB molecules. Recombinant hexahistidine (His₆)-tagged streptavidin (rSA) was attached to the MOFs through the coordination interaction between the His₆ tag in rSA and the metal ions on the surface of the MOFs. The acetylated peptide substrate Ac-GDEVDGGGPPPPC was immobilized on the gold electrode. In the presence of caspase-3, the peptide was specifically cleaved, leading to the release of the Ac-GDEVD sequence. A N-terminal amine group was generated and then biotinylated in the presence of biotin-NHS. Based on the strong interaction between rSA and biotin, rSA@MOF@MB was captured by the biotinylated peptide-modified electrode, producing a significantly amplified electrochemical signal. Caspase-3 was sensitively determined with a linear range from 0.1 to 25 pg/mL and a limit of detection down to 0.04 pg/mL. Further, the active caspase-3 in apoptosis inducer-treated HeLa cells was further quantified by this method. The proposed signal-on biosensor is compatible with the complex biological samples and shows great potential for apoptosis-related diagnosis and the screening of caspase-targeting drugs. Full article

(This article belongs to the Special Issue Metal Organic Frameworks (MOFs) for Sensing Applications)

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12 pages, 4162 KiB

Open AccessArticle

A Ratiometric Fluorescent Probe Dye-Functionalized MOFs Integrated with Logic Gate Operation for Efficient Detection of Acetaldehyde

by Wenwei Li, Min Liu, Yourong Zhao, Yangchun Fan, Yuting Li, Hongmei Gao, Hongda Li, Daojiang Gao and Zhanglei Ning

Molecules 2024, 29(13), 2970; https://doi.org/10.3390/molecules29132970 - 22 Jun 2024

Viewed by 818

Abstract

Volatile organic compounds (VOCs) are a class of hazardous gases that are widely present in the atmosphere and cause great harm to human health. In this paper, a ratiometric fluorescent probe (Dye@Eu-MOFs) based on a dye-functionalized metal–organic framework was designed to detect VOCs, which showed high sensitivity and specificity for acetaldehyde solution and vapor. A linear correlation between the integrated fluorescence intensity (I₅₁₀/I₆₁₆) and the concentration of acetaldehyde was investigated, enabling a quantitative analysis of acetaldehyde in the ranges of 1 × 10⁻⁴~10⁻⁵ μL/mL, with a low detection limit of 8.12 × 10⁻⁴ mg/L. The selective recognition of acetaldehyde could be clearly distinguished by the naked eye under the excitation of UV light. The potential sensing mechanism was also discussed. Significantly, a molecular logic gate was constructed based on the whole system, and finally, a molecular logic network system for acetaldehyde detection connecting basic and integrated logic operations was realized. This strategy provided an effective guiding method for constructing a molecular-level logic gate for acetaldehyde detection on a simple platform. Full article

(This article belongs to the Special Issue Metal Organic Frameworks (MOFs) for Sensing Applications)

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11 pages, 6064 KiB

Open AccessArticle

Stereoselective Solid-State Synthesis of Biologically Active Cyclobutane and Dicyclobutane Isomers via Conformation Blocking and Transference

by Zhen Qin, Yunqiong Gu, Davidjames Young, Feilong Hu and Zhirong Luo

Molecules 2024, 29(12), 2909; https://doi.org/10.3390/molecules29122909 - 19 Jun 2024

Viewed by 998

Abstract

Conformations in the solid state are typically fixed during crystallization. Transference of “frozen” C=C conformations in 3,5-bis((E)-2-(pyridin-4-yl)vinyl)methylbenzene (CH₃-3,5-bpeb) by photodimerization selectively yielded cyclobutane and dicyclobutane isomers, one of which (Isomer 2) exhibited excellent in vitro anti-cancer activity towards T-24, 7402, MGC803, [...] Read more.

(This article belongs to the Special Issue Metal Organic Frameworks (MOFs) for Sensing Applications)

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13 pages, 5222 KiB

Open AccessArticle

A Benzothiadiazole-Based Zn(II) Metal–Organic Framework with Visual Turn-On Sensing for Anthrax Biomarker and Theoretical Calculation

by Jing Ru, Yi-Xuan Shi, Qing-Yun Yang, Teng Li, Hai-Ying Wang, Fan Cao, Qiang Guo and Yan-Lan Wang

Molecules 2024, 29(12), 2755; https://doi.org/10.3390/molecules29122755 - 9 Jun 2024

Viewed by 1138

Abstract

2,6-pyridine dicarboxylic acid (DPA) is an exceptional biomarker of notorious anthrax spores. Therefore, the rapid, sensitive, and selective quantitative detection of DPA is extremely significant and urgent. This paper reports a Zn(II) metal–organic framework with the formula of {[Zn₆(NDA)₆(DPBT)₃] 2H₂O·3DMF}_n (MOF-1), which consists of 2,6-naphthalenedicarboxylic acid (2,6-NDA), 4,7-di(4-pyridyl)-2,1,3-benzothiadiazole (DPBT), and Zn(II) ions. Structural analysis indicated that MOF-1 is a three-dimensional (3D) network which crystallized in the monoclinic system with the C2/c space group, revealing high pH, solvent, and thermal stability. Luminescence sensing studies demonstrated that MOF-1 had the potential to be a highly selective, sensitive, and recyclable fluorescence sensor for the identification of DPA. Furthermore, fluorescent test paper was made to detect DPA promptly with color changes. The enhancement mechanism was established by the hydrogen-bonding interaction and photoinduced electron transfer transition between MOF-1 and DPA molecules. Full article

(This article belongs to the Special Issue Metal Organic Frameworks (MOFs) for Sensing Applications)

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13 pages, 3513 KiB

Open AccessArticle

Robust Thiazole-Linked Covalent Organic Frameworks for Water Sensing with High Selectivity and Sensitivity

by Kewei Wang, Zhaoxia Wu, Na Ji, Tingxia Wang, Yongxin Gu, Zhixiang Zhao, Yong Guo, Xiaoyan Wang, Zhifang Jia and Bien Tan

Molecules 2024, 29(7), 1677; https://doi.org/10.3390/molecules29071677 - 8 Apr 2024

Viewed by 1665

Abstract

The rational design of covalent organic frameworks (COFs) with hydrochromic properties is of significant value because of the facile and rapid detection of water in diverse fields. In this report, we present a thiazole-linked COF (TZ-COF-6) sensor with a large surface area, ultrahigh stability, and excellent crystallinity. The sensor was synthesized through a simple three-component reaction involving amine, aldehyde, and sulfur. The thiazole and methoxy groups confer strong basicity to TZ-COF-6 at the nitrogen sites, making them easily protonated reversibly by water. Therefore, TZ-COF-6 displayed color change visible to the naked eye from yellow to red when protonated, along with a red shift in absorption in the ultraviolet-visible diffuse reflectance spectra (UV-vis DRS) when exposed to water. Importantly, the water-sensing process was not affected by polar organic solvents, demonstrating greater selectivity and sensitivity compared to other COF sensors. Therefore, TZ-COF-6 was used to detect trace amounts of water in organic solvents. In strong polar solvents, such as N,N-dimethyl formamide (DMF) and ethanol (EtOH), the limit of detection (LOD) for water was as low as 0.06% and 0.53%, respectively. Even after 8 months of storage and 15 cycles, TZ-COF-6 retained its original crystallinity and detection efficiency, displaying high stability and excellent cycle performance. Full article

(This article belongs to the Special Issue Metal Organic Frameworks (MOFs) for Sensing Applications)

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10 pages, 3656 KiB

Open AccessArticle

Highly Water-Stable Zinc Based Metal–Organic Framework: Antibacterial, Photocatalytic Degradation and Photoelectric Responses

by Congying Yuan, Yadi Miao, Yinhang Chai, Xiaojun Zhang, Xiaojing Dong and Ying Zhao

Molecules 2023, 28(18), 6662; https://doi.org/10.3390/molecules28186662 - 16 Sep 2023

Cited by 3 | Viewed by 1588

Abstract

A reported water-stable Zn-MOF ([Zn(L)₂(bpa)(H₂O)₂]·2H₂O, H₂L = 5-(2-cyanophenoxy) isophthalic acid has been prepared via a low-cost, general and efficient hydrothermal method. It is worth noting the structural features of Zn-MOF which exhibit the unsaturated metal site and the main non-covalent interactions including O⋯H, N⋯H and π-π stacking interactions, which lead to strong antibacterial and good tetracycline degradation ability. The average diameter of the Zn-MOF inhibition zone against Escherichia coli and Staphylococcus aureus was 12.22 mm and 10.10 mm, respectively. Further, the water-stable Zn-MOF can be employed as the effective photocatalyst for the photodegradation of tetracycline, achieving results of 67% within 50 min, and it has good cyclic stability. In addition, the photodegradation mechanism was studied using UV-vis diffuse reflection spectroscopy (UV-VIS DRS) and valence-band X-ray photoelectron spectroscopy (VB-XPS) combined with the ESR profile of Zn-MOF, which suggest that ·O₂⁻ is the main active species responsible for tetracycline photodegradation. Also, the photoelectric measurement results show that Zn-MOF has a good photocurrent generation performance under light. This provides us with a new perspective to investigate Zn-MOF materials as a suitable multifunctional platform for future environmental improvement applications. Full article

(This article belongs to the Special Issue Metal Organic Frameworks (MOFs) for Sensing Applications)

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14 pages, 2646 KiB

Open AccessArticle

Heterometallic ZnHoMOF as a Dual-Responsive Luminescence Sensor for Efficient Detection of Hippuric Acid Biomarker and Nitrofuran Antibiotics

by Jingrui Yin, Wenqian Li, Wencui Li, Liying Liu, Dongsheng Zhao, Xin Liu, Tuoping Hu and Liming Fan

Molecules 2023, 28(17), 6274; https://doi.org/10.3390/molecules28176274 - 27 Aug 2023

Cited by 38 | Viewed by 1705

Abstract

Developing efficient and sensitive MOF-based luminescence sensors for bioactive molecule detection is of great significance and remains a challenge. Benefiting from favorable chemical and thermal stability, as well as excellent luminescence performance, a porous Zn(II)Ho(III) heterometallic–organic framework (ZnHoMOF) was selected here as a bifunctional luminescence sensor for the early diagnosis of a toluene exposure biomarker of hippuric acid (HA) through “turn-on” luminescence enhancing response and the daily monitoring of NFT/NFZ antibiotics through “turn-off” quenching effects in aqueous media with high sensitivity, acceptable selectivity, good anti-interference, exceptional recyclability performance, and low detection limits (LODs) of 0.7 ppm for HA, 0.04 ppm for NFT, and 0.05 ppm for NFZ. Moreover, the developed sensor was employed to quantify HA in diluted urine samples and NFT/NFZ in natural river water with satisfactory results. In addition, the sensing mechanisms of ZnHoMOF as a dual-response chemosensor in efficient detection of HA and NFT/NFZ antibiotics were conducted from the view of photo-induced electron transfer (PET), as well as inner filter effects (IFEs), with the help of time-dependent density functional theory (TD-DFT) and spectral overlap experiments. Full article

(This article belongs to the Special Issue Metal Organic Frameworks (MOFs) for Sensing Applications)

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13 pages, 3408 KiB

Open AccessArticle

Tunable Non-Enzymatic Glucose Electrochemical Sensing Based on the Ni/Co Bimetallic MOFs

by Qi Wang, Qi Jia, Peng Hu and Liudi Ji

Molecules 2023, 28(15), 5649; https://doi.org/10.3390/molecules28155649 - 26 Jul 2023

Cited by 7 | Viewed by 1819

Abstract

Constructing high-performance glucose sensors is of great significance for the prevention and diagnosis of diabetes, and the key is to develop new sensitive materials. In this paper, a series of Ni₂Co₁-L MOFs (L = H₂BPDC: 4,4′-biphenyldicarboxylic acid; H₂NDC: 2,6-naphthalenedicarboxylic acid; H₂BDC: 1,4-benzenedicarboxylic acid) were synthesized by a room temperature stirring method. The effects of metal centers and ligands on the structure, compositions, electrochemical properties of the obtained Ni₂Co₁-L MOFs were characterized, indicating the successful preparation of layered MOFs with different sizes, stacking degrees, electrochemical active areas, numbers of exposed active sites, and glucose catalytic activity. Among them, Ni₂Co₁-BDC exhibits a relatively thin and homogeneous plate-like morphology, and the Ni₂Co₁-BDC modified glassy carbon electrode (Ni₂Co₁-BDC/GCE) has the highest electrochemical performance. Furthermore, the mechanism of the enhanced glucose oxidation signal was investigated. It was shown that glucose has a higher electron transfer capacity and a larger apparent catalytic rate constant on the Ni₂Co₁-BDC/GCE surface. Therefore, tunable non-enzymatic glucose electrochemical sensing was carried out by regulating the metal centers and ligands. As a result, a high-sensitivity enzyme-free glucose sensing platform was successfully constructed based on the Ni₂Co₁-BDC/GCE, which has a wide linear range of 0.5–2899.5 μM, a low detection limit of 0.29 μM (S/N = 3), and a high sensitivity of 3925.3 μA mM⁻¹ cm⁻². Much more importantly, it was also successfully applied to the determination of glucose in human serum with satisfactory results, demonstrating its potential for glucose detection in real samples. Full article

(This article belongs to the Special Issue Metal Organic Frameworks (MOFs) for Sensing Applications)

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15 pages, 5938 KiB

Open AccessArticle

Ultrasensitive and Simple Dopamine Electrochemical Sensor Based on the Synergistic Effect of Cu-TCPP Frameworks and Graphene Nanosheets

by Liudi Ji, Qi Wang, Xiaqing Gong, Jiamin Chen, Xiaoming Zhu, Zeyu Li and Peng Hu

Molecules 2023, 28(6), 2687; https://doi.org/10.3390/molecules28062687 - 16 Mar 2023

Cited by 3 | Viewed by 2032

Abstract

Dopamine (DA) is an important neurotransmitter. Abnormal concentration of DA can result in many neurological diseases. Developing reliable determination methods for DA is of great significance for the diagnosis and monitoring of neurological diseases. Here, a novel and simple electrochemical sensing platform for quantitative analysis of DA was constructed based on the Cu-TCPP/graphene composite (TCPP: Tetrakis(4-carboxyphenyl)porphyrin). Cu-TCPP frameworks were selected in consideration of their good electrochemical sensing potential. The graphene nanosheets with excellent conductivity were then added to further improve the sensing efficiency and stability of Cu-TCPP frameworks. The electrochemical properties of the Cu-TCPP/graphene composite were characterized, showing its large electrode active area, fast electron transfer, and good sensing performance toward DA. The signal enhancement mechanism of DA was explored. Strong accumulation ability and high electrocatalytic rate were observed on the surface of Cu-TCPP/graphene-modified glassy carbon electrode (Cu-TCPP/graphene/GCE). Based on the synergistic sensitization effect, an ultrasensitive and simple DA electrochemical sensor was developed. The linear range is 0.02–100 and 100–1000 µM, and the detection limit is 3.6 nM for the first linear range. It was also successfully used in detecting DA in serum samples, and a satisfactory recovery was obtained. Full article

(This article belongs to the Special Issue Metal Organic Frameworks (MOFs) for Sensing Applications)

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