Simultaneous electrochemical sensing of heavy metal ions (Zn2+, Cd2+, Pb2+, and Hg2+) in food samples using a covalent organic framework/carbon black modified glassy carbon electrode.

In this study, for the first time, a selective electrochemical sensor by glassy carbon electrode (GCE) modified with the covalent organic framework (COF) and carbon black (CB) was introduced and applied to simultaneous sensing of Zn2+, Cd2+, Pb2+, and Hg2+ via differential pulse anodic stripping voltammetry (DPASV). The COF is supplied through a condensation reaction between melamine and trimesic acid. The COF and CB, which are used to modify the GCE surface, increase electrochemical activity. The linearity to determine ions was achieved as Zn2+: 0.009-1100 nM, Cd2+: 0.005-1100 nM, Pb2+: 0.003-1100 nM, and Hg2+: 0.001-1100 nM. Besides, the detection limits for Zn2+, Cd2+, Pb2+, and Hg2+ have obtained 0.003, 0.002, 0.001 and 0.0003 nM, respectively. The CB-COF/GCE was applied to simultaneously measure the ions in food samples. For validation, atomic absorption spectrometry (AAS) was applied to measure the amount of target metal ions as a standard method in real samples.

Covalent organic framework-sodium alginate-Ca2+-polyacrylic acid composite beads for convenient dispersive solid-phase extraction of neonicotinoid insecticides in fruit and vegetables.

Neonicotinoids, the fastest-growing class of insecticides, have posed a multi-media residue problem with adverse effects on environment, biodiversity and human health. Herein, covalent organic framework-sodium alginate-Ca2+-polyacrylic acid composite beads (CACPs), facilely prepared at room temperature, were used in convenient dispersive solid-phase extraction (dSPE) and combined with high-performance liquid chromatography (HPLC) for the detection of five neonicotinoid insecticides (thiamethoxam, acetamiprid, dinotefuran, clothianidin, imidacloprid). CACPs can be completely separated within 1 min without centrifugation. After seven adsorption/desorption cycles, it maintained high extraction efficiencies (>90%). The developed method exhibited a wide linear range (0.01 âˆ¼ 10 µg mL-1), low limits of detection (LODs, 0.0028 âˆ¼ 0.0031 mg kg-1), and good repeatability (RSD ≤ 8.11%, n = 3). Moreover, it was applied to the determination of five neonicotinoids in fruit and vegetables (peach, pear, lettuce, cucumber, tomato), and recoveries ranged from 73.6% to 116.2%.

Post-synthetic modification of covalent organic framework for efficient adsorption of organochlorine pesticides from cattle's milk.

Analysis of organochlorine pesticides (OCPs) residues in milk faces a significant challenge. Herein, a sea urchin structured covalent organic framework bearing boric acid groups named COF-B(OH)2 was synthesized and applied as a coating material for solid-phase microextraction (SPME) of the OCPs in cattle's milk. Its performance was superior to that of three commonly used commercial SPME fibers, which could be due to the coexistence of hydrogen bonding, halogen bonding, π-stacking and electrostatic interactions. Besides, the fiber coating displayed good stability and reusability. After optimization, a COF-B(OH)2 based SPME coupled with gas chromatography-electron capture detection was established for the sensitive detection of the OCPs from milk samples. The limits of detection (S/N = 3) were between 0.04 and 1.00 µg kg-1. Satisfactory accuracy was achieved with the method recoveries in the range of 87.5 % to 112.5 %. These results manifest the feasibility of the COF-B(OH)2 coated fiber for the enrichment of the trace OCPs from milk samples.

Polyphenol oxidase inactivation from apple juice by Al-based metal-organic frameworks: New anti-browning strategy in fruits and vegetables.

Polyphenol oxidase (PPO) is critical due to enzymatic browning in fruits and vegetables, developing economic impact in fruits industry. Metal-Organic Frameworks (MOF) have shown interesting characteristics such as water stability, low toxicity, and good adsorption yield, making them good candidates for PPO inactivation. Al-based-MOFs, MIL-53(Al), DUT-5, and MIL-110 were tested as PPO inactivators in apple juice by enzyme-MOF interactions at r.t. through two possible mechanisms, i) substrate scavengers (substrates:catechol and 4-methylcatechol) or ii) enzyme activity modifiers. The scavenging behavior of Al-based-MOFs was moderate, in the same magnitude, being catechol adsorption better than 4-methylcatechol. PPO activity was reduced by at least 70% by MIL-53(Al)/DUT-5 in 10/30 min respectively, and MIL-110 inactivated PPO in 50 min with some structural modifications. Enzyme-MOF interactions are major responsible for PPO inactivation. This could be a new applicability of MOFs, as an alternate PPO inactivation process, easily included in juice processing, retaining sensorial/nutritional properties, developed at r.t thus energy-cost-effective.

Immunochromatographic Assay based on Sc-TCPP 3D MOF for the rapid detection of imidacloprid in food samples.

In this work, a highly sensitive immunochromatographic test strip (ITS) based on Scandium-Tetrakis (4-carboxyphenyl) porphyrin (TCPP) metal-organic framework nanocubes (ScTMNs) was developed for ultrasensitive and facile visual determination of imidacloprid (IDP). TCPP as the porphyrin-based planar ligand and Sc3+ as the metal center were applied to form the ScTMNs via coordination chelation. Giving the credit to its excellent optical characteristics, strong affinity with monoclonal antibodies, and favorable biocompatibility, the ScTMNs was selected as a signal tag. Under optimized conditions, the ITS exhibited a great liner relationship in the range of 0.04-3 ng/mL and the detection limit was 0.04 ng/mL for the IDP detection. Additionally, IDP was successfully detected in tomatoes, millet, corn and carrot samples with satisfied recoveries. To the best of our knowledge, this is the first time that ScTMNs have been used in immunochromatography which are expected to have potential applications in detection of other substances.

Fabrication of magnetic covalent organic framework for efficient extraction and determination of phthalate esters in milk samples.

Using two monomers of 4,4″-diamino-p-terphenyl and 1,3,5-triformylphloroglucinol, a co-precipitation structured magnetic covalent organic framework adsorbent was fabricated. After that, a high efficient vortex-assisted magnetic solid-phase extraction method was developed prior to gas chromatography-tandem mass spectrometry analysis for the determination of phthalate esters in milk samples. The fabricated magnetic adsorbent was facilely fabricated, fully characterized, and exhibited high extraction efficiency, which can be attributed to its larger pore size as well as strong hydrophobic and π-π stacking interactions between adsorbent and phthalate esters. Key parameters affecting extraction efficiency were investigated. Under the optimized conditions, the proposed method possessed good linearity (3.0-1000 µg/L), high sensitivity (0.8-2.1 µg/L for limits of detection), and satisfactory recoveries (76.8-99.2%). The relative standard deviations for intra-day was 3.1-4.5% and inter-day was 3.3-6.1%. This work is suitable for high efficient separation/preconcentration of phthalate esters in milk samples.

Novel N-riched covalent organic framework for solid-phase microextraction of organochlorine pesticides in vegetable and fruit samples.

A covalent organic framework named N-COF was successfully constructed by the aldehyde-amine condensation reaction between 2,4,6-tris (4-formyl phenoxy)-1,3,5-triazine and 1,3-bis(4-aminophenyl) urea for the first time. The prepared N-COF exhibited good stability and high affinity to organochlorine pesticides (OCPs). Thus, the N-COF was served as solid phase microextraction fiber coating for extraction of six OCPs from vegetables and fruits including romaine lettuce, cabbage, Chinese cabbage, apple, pear and peach, followed by quantitation with gas chromatography-electron capture detector (GC-ECD). Under the optimal conditions, good linearities for the OCPs existed in the ranges from 0.1 to 1.0 ng g-1 to 100.0 ng g-1 for the samples. The low limits of detection for analytes were obtained in the range of 0.03-0.3 ng g-1. The present work can offer new alternative for sensitive analysis of trace level of OCPs in vegetables and fruits.

Intrinsic Catalytic Activities from Single Enzyme@Metal-Organic Frameworks by Using a Stochastic Collision Electrochemical Technique.

Enzymes encapsulated in metal-organic frameworks (enzyme@MOFs), as a promising immobilized enzyme, were investigated for intrinsic catalytic activities at the single entity level via a stochastic collision electrochemical technique. Zeolitic imidazolate frameworks with amorphous (aZIF-8) and crystalline (ZIF-8) structures were chosen as model MOFs to encapsulate glucose oxidase (GOx). We carried out single enzyme@MOF nanoparticle (NP) collision experiments using the carbon ultramicroelectrode (CUME), which demonstrated that the catalytic activity of GOx@ZIF-8 NPs was much less than GOx@aZIF-8 NPs. Meanwhile, the kcat and TON per GOx in aZIF-8 NPs were obtained, revealing the intrinsic catalytic activity of GOx in aZIF-8 NPs at the single entity level. This strategy is the first approach for investigating enzyme@MOFs at a single entity level, which can not only broaden the horizons of single entity electrochemistry (SEE) but also provide further insights into research on electrochemistry, catalysis, and nanocomposites.

Application of HKUST-1 metal-organic framework as coating for headspace solid-phase microextraction of some addictive drugs.

In the present study, a copper-based metal-organic framework (HKUST-1) was used first time for preconcentration trace amounts of addictive drugs in biological samples. HKUST-1 was synthesized and coated onto the surface of stainless steel wire. The prepared coating was used in headspace solid-phase microextraction method coupled with gas chromatography-mass spectrometry for preconcentration and determination of some addictive drugs in biological fluids. Prepared coating shows good extraction efficiency due to large surface area, and π-π stacking interaction with selected analytes. Under optimum conditions, the method was validated with a reasonable determination coefficient (R2  > 0.9961) and suitable linear dynamic range (0.5-1000 µg L-1 ). Also, the limits of detections were obtained in the range of 0.1-0.4, 0.2-0.6, and 0.4-0.7 µg L-1 for water, urine, and plasma samples, respectively. The limits of quantification of present method were obtained in the range 0.5-1.3, 0.7-1.5, and 1.0-1.9 µg L-1 in water, urine, and plasma samples, respectively. The intra-day and inter-dye single fiber and fiber to fiber relative standard deviations were observed in the range 3.0-13.9% and 3.5-12.3%, respectively. Finally, the present method was applied for the determination of the drugs in biological samples.

Advanced materials on sample preparation for safety analysis of aquatic products.

Safety analysis of aquatic products has been a challenge in recent years due to the serious matrix interference, complex characteristics, and ultra-low content of analytes. Introducing advanced materials to sample preparation technique can greatly improve the extraction, enrichment, and separation for further qualification and quantification of target analytes by coupling with consequent analytical technologies. Based on this scope, this review is mainly introducing advanced materials on the sample preparation for safety analysis of aquatic products in the past decade. After introducing the importance of the corresponding advanced materials, advanced materials are used for the sample preparation and in the improvement of safety analysis result of aquatic products. Advanced materials for sample preparation of aquatic products were reviewed including carbon materials, metal organic frameworks, covalent organic frameworks, molecularly/ions imprinted polymers, etc. Then, applications of the advanced materials for the analysis of specific fishery analytes (antibiotics, anesthetic, preservatives, etc.) were briefly introduced. Conclusions and perspectives on advanced materials for sample preparation and safety analysis of aquatic products were also presented.

Recent applications of covalent organic frameworks and their multifunctional composites for food contaminant analysis.

Food safety issues are a great concern of the international community. Many methods to analyze and detect food contaminants have been widely researched because both biological and chemical contaminants in food can cause severe damage to human health. Several adsorbent materials have been utilized in the complicated procedure of food sample pretreatment. Covalent organic frameworks (COFs) present enormous application potential due to their tailorable skeletons and pores and fascinating features. In this review, recent applications of COF-based adsorbents for the extraction and analysis of food contaminants, including polycyclic aromatic hydrocarbons, biogenic amines, pesticides, endocrine-disrupting chemicals, heavy metal ions, illegal additives, and biotoxins, from complex samples are summarized. Current challenges and future prospects are also discussed.

Effective enrichment and detection of plant growth regulators in fruits and vegetables using a novel magnetic covalent organic framework material as the adsorbents.

The present research reported a facile strategy for the synthesis of a novel magnetic covalent organic frameworks (Fe3O4@COF(TpDA)) material and applied it as a sorbent for magnetic solid phase extraction of plant growth regulators from fruits and vegetables. The prepared Fe3O4@COF materials showed many attractive features involving large specific surface area (180.2 m2/g) and high saturation magnetization (62.3 emu/g), which enabled it an ideal sorbent for sample pretreatment. The experimental conditions affecting the extraction performance were optimized systematically, including eluent, amount of sorbent, adsorption time and desorption time. The extracted samples were detected by HPLC-DAD. Under the optimized conditions, the proposed method exhibited good linearity (R ≥ 0.9990) and low limits of detection (4.68-7.51 µg/L). Satisfactory recoveries were calculated to be 83.0-105.0%. Finally, the proposed method was successfully applied to determination of plant growth regulators in fruits and vegetables, indicating the potential prospect of the Fe3O4@COF(TpDA) materials in sample pretreatment.

Metal-Ligand Coordination Nanomaterials for Biomedical Imaging.

Over the past two decades, amorphous nanoscale coordination polymers (NCPs) and crystalline nanoscale metal-organic frameworks (NMOFs) have emerged as attractive nanomaterials in biomedical applications, especially in drug delivery, biomedical imaging, and biosensing. The biodegradability, tunable composition, and feasible functionality of NCPs/NMOFs make them excellent contrast agents or nanocarriers for biomedical imaging, including magnetic resonance (MR) imaging, positron emission tomography (PET), computed tomography (CT), optical imaging, and photoacoustic (PA) imaging. In this Topical Review, we will summarize the recent advances of NCPs/NMOFs in biomedical imaging with emphasis on research over the past three years. A variety of imaging technologies based on NCPs/NMOFs will be discussed, followed by the introduction of the application of NCPs/NMOFs in multimodal imaging where optical/MR imaging is highlighted. In the final part, we will make concluding remarks and point out the challenges and prospects for the further development in this area of research.

Metal-Organic Frameworks for Food Safety.

Food safety is a prevalent concern around the world. As such, detection, removal, and control of risks and hazardous substances present from harvest to consumption will always be necessary. Metal-organic frameworks (MOFs), a class of functional materials, possess unique physical and chemical properties, demonstrating promise in food safety applications. In this review, the synthesis and porosity of MOFs are first introduced by some representative examples that pertain to the field of food safety. Following that, the application of MOFs and MOF-based materials in food safety monitoring, food processing, covering preservation, sanitation, and packaging is overviewed. Future perspectives, as well as potential opportunities and challenges faced by MOFs in this field will also be discussed. This review aims to promote the development and progress of MOF chemistry and application research in the field of food safety, potentially leading to novel solutions.

Comprehensive evaluation of the removal mechanism of carbamazepine and ibuprofen by metal organic framework.

Pharmaceutical products (PhACs) in water sources are considered to be a severe environmental issue. To mitigate this issue, we used a metal-organic framework (MOF) as an adsorbent to remove selected PhACs (i.e., carbamazepine (CBM) and ibuprofen (IBP)). This work was carried out to characterize the MOF, then confirm its feasibility for removing the selected PhACs. In particular, based on practical considerations, we investigated the effects of various water quality conditions, such as solution temperature, pH, ionic strength/background ions, and humic acid. MOF exhibited better removal rates than commercial powder activated carbon (PAC), considering pseudo-second order kinetic model. We clarified the competitive PhACs adsorption mechanisms based on the results obtained under various water quality conditions and found that hydrophobic interactions were the most important factors for both adsorbates. To confirm the practicality of MOF adsorption, we carried out regeneration tests with four adsorption and desorption cycles using acetone as a cleaning solution. Furthermore, to support the results of our regeneration tests, we characterized the MOF samples before and after adsorbate exposure using Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy. Overall, MOF can be used in practical applications as efficient adsorbents to remove PhACs from water sources.