Synthesis and evaluation of nanosized aluminum MOF encapsulating Umbelliferon: assessing antioxidant, anti-inflammatory, and wound healing potential in an earthworm model.

Nanoporous aluminum metal-organic framework (Al-MOF) was synthesized via solvothermal methods and employed as a carrier matrix for in vitro drug delivery of Umbelliferon (Um). The encapsulated Um was gradually released over seven days at 37 °C, using simulated body fluid phosphate-buffered saline (PBS) at pH 7.4 as the release medium. The drug release profile suggests the potential of Al-MOF nanoparticles as effective drug delivery carriers. Structural and chemical analyses of Um-loaded Al-MOF nanoparticles (Um-Al MOF) were conducted using Fourier-transform infrared (FTIR) spectroscopy, X-ray diffractometry (XRD), and ultraviolet-visible (UV-Vis) spectroscopy. Thermal gravimetric analysis (TGA) was employed to investigate the thermal stability of the Al-MOF nanoparticles, while Transmission Electron Microscopy (TEM) was utilized to assess their morphological features. Um-Al MOF nanoparticles demonstrated notable antioxidant and anti-inflammatory properties compared to Um and Al-MOF nanoparticles individually. Moreover, they exhibited significant enhancement in wound healing in an earthworm model. These findings underscore the potential of Al-MOF nanoparticles as a promising drug delivery system, necessitating further investigations to explore their clinical applicability.

Ultra-sensitive electrochemical sensors through self-assembled MOF composites for the simultaneous detection of multiple heavy metal ions in food samples.

Using an assemble-able MOF material, we successfully constructed an ultra-sensitive electrochemical sensor based on Bi2CuO4@Al-MOF@UiO-67 nanocomposite material, in order to investigate the adsorption properties of the Bi2CuO4@Al-MOF@UiO-67 functional material on the heavy metal ion. The Cd2+, Cu2+, Pb2+ and Hg2+ can be detected at the same time. Selective recognition and enrichment of various metal ions on different substrates can be achieved through the assembly of a large number of Al-MOF and UiO-67-MOF nanomaterial composites with small particle sizes on the Bi2CuO4 surface. Based on this, a new type of sensor is researched and prepared, which has been shown to have good stability and reproducibility. Due to its unique assembly structure, large active surface area, excellent adsorption capacity, and high electrical conductivity, Bi2CuO4@Al-MOF@UiO-67 presents outstanding performance. In addition, the sensor also exhibits excellent electrocatalytic redox capacity and high selectivity. The adsorption capacity of Cd2+, Cu2+, Pb2+ and Hg2+ is also significantly improved under the action of the sensor electrode, however, this is not the case. The limits of detection for Cd2+, Cu2+, Pb2+ and Hg2+ were found to be 0.02 pM, 0.032 pM, 0.018 pM and 0.041 pM, respectively. In order to investigate the detection mechanism of Cd2+, Cu2+, Pb2+ and Hg2+ was adsorption properties as well as electrochemical accumulation of Bi2CuO4@Al-MOF@UiO-67 on the metal atoms were investigated. This method has been successfully applied to samples of rice, sorghum, maize, milk, honey, and tea, and has enabled the simultaneous detection of Cd2+, Cu2+, Pb2+ and Hg2+, which is of significant practical value.

Ultrasensitive Visual Tracking of Toxic Cyanide Ions in Biological Samples Using Biocompatible Metal-Organic Frameworks Architectures.

The extraordinary accumulation of cyanide ions within biological cells is a severe health risk. Detecting and tracking toxic cyanide ions within these cells by simple and ultrasensitive methodologies are of immense curiosity. Here, continuous tracking of ultimate levels of CN--ions in HeLa cells was reported employing biocompatible branching molecular architectures (BMAs). These BMAs were engineered by decorating colorant-laden dendritic branch within and around the molecular building hollows of the geode-shelled nanorods of organic-inorganic Al-frameworks. Batch-contact methods were utilized to assess the potential of hollow-nest architecture for inhibition/evaluation of toxicant CN--ions within HeLa cells. The nanorod BMAs revealed significant potential capabilities in monitoring and tracking of CN- ions (88 parts per trillion) in biological trials within seconds. These results demonstrated sufficient evidence for the compatibility of BMAs during HeLa cell exposure. Under specific conditions, the BMAs were utilized for in-vitro fluorescence tracking/sensing of CN- in HeLa cells. The cliff swallow nest with massive mouths may have the potential to reduce the health hazards associated with toxicant exposure in biological cells.

New easily recycled carrier based polyurethane foam by loading Al-MOF and biochar for selective removal of fluoride ion from aqueous solutions.

The production of Integrated circuits (ICs) generates wastewater with a high concentration of residual fluoride ions, necessitating highly efficient fluorine removal methods. In this study, a novel composite carrier was developed using a hydrothermal synthesis method to load Al-MOF and biochar (BC) onto polyurethane foam (PUF), resulting in the composite foam of Al-MOF-PUF@BC. The results showed that the composite carrier exhibited a stable fluoride removal effect, with a maximum adsorption capacity of 16.52 mg/g at room temperature. The adsorption isotherm curves were consistent with the Langmuir isotherm model, and the adsorption kinetics were well-described by the pseudo-first-order model. The mechanism of fluorine adsorption on Al-MOF-PUF@BC was ligand exchange with hydroxyl groups and the formation of FAl bonds. Density functional theory (DFT) calculations revealed that the adsorption energy reached -246.7 eV, indicating stable adsorption for fluoride ions. The composite foam demonstrated excellent regenerative properties and was effective for fluoride removal in actual IC wastewater.

Alternate Storage of Opposite Charges in Multisites for High-Energy-Density Al-MOF Batteries.

The limited active sites of cathode materials in aluminum-ion batteries restrict the storage of more large-sized Al-complex ions, leading to a low celling of theoretical capacity. To make the utmost of active sites, an alternate storage mechanism of opposite charges (AlCl4 - anions and AlCl2 + cations) in multisites is proposed herein to achieve an ultrahigh capacity in Al-metal-organic framework (MOF) battery. The bipolar ligands (oxidized from 18π to 16π electrons and reduced from 18π to 20π electrons in a planar cyclic conjugated system) can alternately uptake and release AlCl4 - anions and AlCl2 + cations in charge/discharge processes, which can double the capacity of unipolar ligands. Moreover, the high-density active Cu sites (Cu nodes) in the 2D Cu-based MOF can also store AlCl2 + cations for a higher capacity. The rigid and extended MOF structure can address the problems of high solubility and poor stability of small organic molecules. As a result, three-step redox reactions with two-electron transfer in each step are demonstrated in charge/discharge processes, achieving high reversible capacity (184 mAh g-1 ) and energy density (177 Wh kg-1 ) of the optimized cathode in an Al-MOF battery. The findings provide a new insight for the rational design of stable high-energy Al-MOF batteries.

GNP/Al-MOF nanocomposite as an efficient fiber coating of headspace solid-phase micro-extraction for the determination of organophosphorus pesticides in food samples.

The synthesis and utilization of a high porous nanocomposite comprising MIL-53(Al) metal-organic framework (Al-MOF) and graphene nanopowder (GNP) is reported as a fiber coating for headspace solid-phase micro-extraction (HS-SPME) of selected organophosphorus pesticides (OPPs) from apple, potato, grape juice, tomato, and river water. The adsorbed OPPs on the coated fiber were subsequently determined using GC-MS. Several parameters affecting the efficiency of extraction including time and temperature of extraction, desorption condition of extracted analytes, pH and agitation of sample solution, and salt concentration were investigated. The optimum extraction condition was achieved at 70 °C with an extraction time of 40 min, pH = 4-8, and NaCl concentration of 6.0% (w/v). The best condition of desorption were observed at 280 °C for 2.0 min under a flow of helium gas in the GC inlet. Under optimal conditions, the detection limits ranged from 0.2 to 1.5 ng g-1 and the linear ranges between 0.8 and 600 ng g-1. The proposed method showed very good repeatability with RSD values ranging from 4.5 to 7.3% (n = 5). The relative recoveries were between 88% and 109% at the spiked level of 25.0 ng g-1 for the tomato sample. The fabricated fiber exhibited good enrichment factor (62-195) at optimum condition of HS-SPME. The applied HS-SPME technique is facile, fast, and inexpensive. The thermally stable GNP/Al-MOF exhibited a high sensitivity toward OPPs. So, this nanocomposite can be considered as a sorbent for the micro-extraction of other pesticides in food.

Inner-filter effect induced fluorescent sensor based on fusiform Al-MOF nanosheets for sensitive and visual detection of nitrofuran in milk.

Developing highly sensitive and visual methods for rapid detection of antibiotics is significant to ensure food quality and safety. To meet the requirement of nitrofuran antibiotics detection, luminescent fusiform Al(III)-containing metal-organic frameworks (Al-MOF) nanosheets were successfully synthesized by one-step hydrothermal method. And then, the nanosheet served as a fluorescent probe to detect nitrofuran via the inner-filter effect mechanism. The developed sensor allowed sensitive and selective detection of nitrofuran with good linear relationships. And, the detection limit (LOD) values were estimated to be 0.53, 0.838 and 0.583 µM for nitrofurazone, nitrofurantoin and furazolidone detection, respectively. The practical application of the proposed system was verified by HPLC in spiked milk samples with satisfying recoveries ranging from 88.14 to 126.21% and low relative standard deviations of 2.85 ~ 8.13%. Moreover, we designed fluorescent test papers for semi-quantitative detection of nitrofuran via naked-eye colorimetric assay. The established method provides an alternative strategy for semiquantitative detection of nitrofuran.

Synthesis of Al-Based Metal-Organic Framework in Water With Caffeic Acid Ligand and NaOH as Linker Sources With Highly Efficient Anticancer Treatment.

In this study, novel nanostructures of aluminum base metal-organic framework (Al-MOF) samples were synthesized using a sustainable, non-toxic, and cost-effective green synthesis route. Satureja hortensis extract was used as an effective source of linker for the development of the Al-MOF structures. The Fourier-transformed infrared (FTIR) spectrum confirmed the presence of characterization bonds related to the Al-MOF nanostructures synthesized by the green synthesis route. The scanning electron microscopy (SEM) and transmission electron microscopy (TEM) analyses revealed that the sample synthesized by Na2-CA was composed of multilayers, although it was agglomerated, but it had dispersed and occurred in spherical particles, indicating active organic matter. N2 adsorption/desorption isotherms demonstrated the significant porosity of the Al-MOF samples that facilitate the high potential of these nanostructures in medical applications. The anticancer treatment of Al-MOF samples was performed with different concentrations using the MTT standard method with untreated cancer cells for 24 and 48 h periods. The results exhibited the significant anticancer properties of Al-MOF samples developed in this study when compared with other MOF samples. Thus, the development of a novel Al-MOF and its application as a natural linker can influence the anticancer treatment of the samples. According to the results, the products developed in this study can be used in more applications such as biosensors, catalysts, and novel adsorbents.

A Multi-response Aluminum Metal-organic Frameworks for Fluorescence Sensing of Fe3+, Sr2+, SiO32-and Toluene.

A new Aluminum metal-organic frameworks(Al-MOF) based on tricarboxylate ligands(L){L = 2,2',2'-([1,3,5]-triazine-2,4,6-triimino)tribenzoic acid)} has been designed and synthesized. It can be served as a platform of multi-responsive fluorescence sensor for Fe3+, Sr2+and SiO32-in water, which is mainly due to the significant enhancement effect of these ions on the fluorescence intensity of Al-MOF. Especially, Fe3+ions are rarely able to induce MOFs fluorescence enhancement. The limit of detection for three kinds of ions is 6.62* 10-6M, 5.37* 10-6M, 6.85* 10-10M respectively. Meanwhile, It can also be used as a multi-response fluorescence probe to detect toluene in DMF solution, limit of detection is 9.16* 10-3M respectively. The structure of Al-MOF was characterized by FTIR,1H NMR, SEM, TAG, PXRD and element analysis. The PXRD showed that the structure of Al-MOF remained the high water stability and pH stability. The application of water samples and vegetables showed that Al-MOF had high sensitive detection for Fe3+ions.

Modification of activated carbon by MIL-53(Al) MOF to develop a composite framework adsorbent for CO2 capturing.

In this research, a novel composite is synthesized based on activated carbon and MIL-53(Al) through the solution mixing method at different MOF weight fractions, and the CO2 loading of prepared samples are measured in the batch and continuous apparatus. The structure, crystallinity, surface area, and chemical functionality of activated carbon, MIL-53(Al), and developed composite are characterized through BET, X-ray diffraction (XRD), scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR). The CO2 and N2 adsorption capacity of activated carbon, MIL-53(Al), and composites are examined in an isothermal batch reactor at the pressure range 0-110 kPa and equilibrium temperature 305 K. The adsorption isotherm of CO2 is correlated by the Langmuir and Toth models. Besides, the performance of composite is compared with MIL-53(Al) and activated carbon in a continuous packed bed at flow rate range 15-25 ml min-1 and temperature 32 °C, and the breakthrough curves are developed. The results show that increasing MOF content in the composite increases CO2 adsorption capacity, so the CO2 loading of synthesized composite containing 10%, 20%, and 30% MOF is 1.608, 1.704, and 1.792 mmol gr-1, respectively.

Preparation of poly(4-vinylpyridine)-functionalized magnetic Al-MOF for the removal of naproxen from aqueous solution.

In this work, a novel poly(4-vinylpyridine)-functionalized magnetic Al-MOF (Al-MOF-Fe3O4@P4VP) was synthesized successfully as an adsorbent for the adsorption of naproxen from aqueous solution. The resulting adsorbent was characterized with scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, vibrating sample magnetometer (VSM), BET surface area and X-ray photoelectron spectroscopy (XPS). Al-MOF-Fe3O4@P4VP had high surface area (123.68 m2/g), porous structure, rough surface and magnetic property. The maximum adsorption capacity of Al-MOF-Fe3O4@P4VP for naproxen could reach up to 31.67 mg/g and the adsorption process was well described by the Freundlich isotherm. The adsorption rate of naproxen on Al-MOF-Fe3O4@P4VP was very fast and the kinetics could be well modeled by the pseudo-second-order model. The adsorbent exhibited good adsorption ability even after ten adsorption-desorption cycles. Al-MOF-Fe3O4@P4VP had the characteristics of high removal efficiency, fast adsorption speed, good reusability and easy separation, making it a novel environment-friendly and effective magnetic nanomaterial in adsorbing naproxen from wastewater.

Highly stable aluminum-based metal-organic frameworks as biosensing platforms for assessment of food safety.

Two unique immunosensors made of aluminum-based metal-organic frameworks (MOFs), namely, 515- and 516-MOFs, with 4,4',4''-nitrilotribenzoic acid (H3NTB) were successfully obtained to efficiently assess food safety. The as-prepared 515- and 516-MOFs exhibited superior thermal and physicochemical stability, high electrochemical activity, and good biocompatibility. Among these immunosensors, 516-MOF showed a preferable biosensing ability toward analytes determined by electrochemical techniques. The developed 516-MOF-based electrochemical biosensor not only demonstrated high sensitivity with low detection limits of 0.70 and 0.40pgmL-1 toward vomitoxin and salbutamol, respectively, but also showed good selectivity in the presence of other interferences. Therefore, with the advantages of high sensitivity, good selectivity, and simple operation, this new strategy is believed to exhibit great potential for simple and convenient detection of poisonous and harmful residues in food.