Γ-cyclodextrin Metal-organic Frameworks Research Articles

CD-MOF-1 Growth on Polysaccharide Gels through Only C2-OH/C3-OH or C5-O/C6-OH Group Formed Four-Coordinated K+ Ions for Developing Porous Biogels.

The γ-cyclodextrin (γ-CD) metal-organic frameworks (CD-MOF-1) consist of γ-CD and potassium (K+) ions through coordinating an eight-coordinated K+ ion with two C5-linked oxygen and C6-linked hydroxyl (C5-O/C6-OH) groups in the primary faces of adjacent γ-CD units and two C2- and C3-linked hydroxyl (C2-OH/C3-OH) groups in the secondary faces. Herein, we found polysaccharide gels with only C2-OH/C3-OH or C5-O/C6-OH groups in pyranoid rings can form four-coordinated K+ ions and then coordinate γ-CD in a KOH solution for CD-MOF-1 growth. Exposure of C2-OH/C3-OH or C5-O/C6-OH groups in polysaccharide gels is important to form active four-coordinated K+ ions. Mechanism supporting this work is that four-coordinated K+ ion sites are first formed after coordinating C2-OH/C3-OH groups in pectin and then coordinating C5-O/C6-OH groups in the primary faces of γ-CD units. Alternatively, four-coordinated K+ ions with C5-O/C6-OH groups in chitosan can coordinate the C2-OH/C3-OH groups in the secondary faces of γ-CD units. Mechanism of CD-MOF-1 growing on pectin and chitosan gels through the proposed four-coordinated K+ ions is also universally applicable to other polysaccharide gels with similar C2-OH/C3-OH or C5-O/C6-OH groups such as alginate gel. Based on this mechanism, we developed pectin and chitosan gel-based CD-MOF-1 composites and exemplified applications of them in antibacterial and organic dye removal. To help future research and applications of this mechanism, we share our theoretical assumption for further investigations that any matrices with an ortho-hydroxyl carbon chain or ortho-hydroxyl ether structures may form four-coordinated K+ ions for CD-MOF-1 growth. The proposed mechanism will broaden the development of novel CD-MOF-1 composites in various fields.

Enhanced Stability and Solidification of Volatile Eugenol by Cyclodextrin-Metal Organic Framework for Nasal Powder Delivery.

Eugenol (Eug) holds potential as a treatment for bacterial rhinosinusitis by nasal powder drug delivery. To stabilization and solidification of volatile Eug, herein, nasal inhalable γ-cyclodextrin metal-organic framework (γ-CD-MOF) was investigated as a carrier by gas-solid adsorption method. The results showed that the particle size of Eug loaded by γ-CD-MOF (Eug@γ-CD-MOF) distributed in the range of 10-150μm well. In comparison to γ-CD and β-CD-MOF, γ-CD-MOF has higher thermal stability to Eug. And the intermolecular interactions between Eug and the carriers were verified by characterizations and molecular docking. Based on the bionic human nasal cavity model, Eug@γ-CD-MOF had a high deposition distribution (90.07 ± 1.58%). Compared with free Eug, the retention time Eug@γ-CD-MOF in the nasal cavity was prolonged from 5min to 60min. In addition, the cell viability showed that Eug@γ-CD-MOF (Eug content range 3.125-200µg/mL) was non-cytotoxic. And the encapsulation of γ-CD-MOF could not reduce the bacteriostatic effect of Eug. Therefore, the biocompatible γ-CD-MOF could be a potential and valuable carrier for nasal drug delivery to realize solidification and nasal therapeutic effects of volatile oils.

Oral Synergism of Egg-White-Derived Peptides (EWDP) and Curcumin for Colitis Mitigation via Polysaccharide/Cyclodextrin Metal-Organic Framework-Based Assemblies.

Recently, oral deliverable strategies of multiple nutraceuticals for ulcerative colitis (UC) mitigation have attracted increasing attention. This study aimed to fabricate facile oral assemblies loaded with egg-white-derived peptides (EWDP) and curcumin based on carboxymethyl chitosan (CMCS) and an γ-cyclodextrin metal-organic framework (MOF). Herein, outer CMCS could coassemble with EWDP (both nutraceuticals and building blocks) into cobweb-like fibrils to promote bridging with inner MOF via coordinative noncovalent interactions (hydrogen bonding, hydrophobic interaction, and electrostatic interaction). Compared with conventional γ-cyclodextrin/MOF-based composites, the above coassembly could also endow the biocompatible assemblies with superior nanoscale colloidal properties, processing applicability (curcumin storage stability, bioaccessibility, and aqueous solubility), and bioactivity. Moreover, the oral synergism of EWDP and curcumin (initially nonsynergistic) for UC mitigation was achieved by alleviating inflammatory damage and gut microbiota imbalance. Overall, the novel assemblies could be a promising amplifier and platform to facilitate oral formulations of various nutraceuticals for food processing and UC relief.

Rapid isolation of extracellular vesicles using covalent organic frameworks combined with microfluidic technique

Extracellular vesicles (EVs) are nano-sized lipid-membrane vesicles involved in intercellular communication and reflecting the physiological and pathological processes of their parental cells. Rapid isolation of EVs with low cost is an essential precondition for downstream function exploration and clinical applications. In this work, we designed a novel EVs isolation device based on the boronated organic framework (BOF) coated recyclable microfluidic chip (named EVs-BD) to separate EVs from cell culture media. Using a reactive oxygen species responsive phenylboronic ester compound, the highly porous BOF with a pore size in the range of 10–300 nm was prepared by crosslinking γ-cyclodextrin metal-organic frameworks. A mussel-inspired polydopamine (PDA)/polyethyleneimine (PEI) coating was employed to pattern BOF on the PDMS substrate of microfluidic channels. The EVs-BD was demonstrated to offer distinct advantages over the traditional ultracentrifugation method, such as operation simplicity and safety, reduced time and expense, and low expertize requirements. All things considered, a novel approach of EV acquisition has been successfully developed, which can be customized easily to meet the requirements of various EV-relevant research.

Synthesis of Nanosized γ-Cyclodextrin Metal-Organic Frameworks as Carriers of Limonene for Fresh-Cut Fruit Preservation Based on Polycaprolactone Nanofibers.

To address the issue of bacterial growth on fresh-cut fruits, this paper reports the synthesis of nanosized γ-cyclodextrin metal-organic frameworks (CD-MOFs) using an ultrasound-assisted method and their application as carriers of limonene for antibacterial active packaging. The effects of the processing parameters on the morphology and crystallinity of the CD-MOFs are investigated, and the results prove that the addition of methanol is the key to producing nanosized CD-MOFs. The limonene loading content of the nanosized CD-MOFs can reach approximately 170mg g-1. The sustained-release behaviors of limonene in the CD-MOFs are evaluated. Molecular docking simulations reveal the distribution and binding sites of limonene in the CD-MOFs. CD-MOFs are deposited on the surfaces of polycaprolactone (PCL) nanofibers via an immersion method, and limonene-loaded CD-MOF@PCL nanofibers are prepared. The morphology, crystallinity, thermal stability, mechanical properties, and antibacterial activity of the nanofibers are also studied. The nanofiber film effectively inhibits bacterial growth and prolongs the shelf life of fresh-cut apples. This study provides a novel strategy for developing antibacterial active packaging materials based on CD-MOFs and PCL nanofibers.

Alizarin-embedded γ-cyclodextrin-based metal-organic framework in a methylcellulose/polyvinyl alcohol film for maintaining and monitoring grass carp freshness

Multifunctional packaging films that monitor and maintain fish freshness hold significant potential for use in the food industry. This study introduces a multifunctional intelligent packaging film comprising alizarin (ALI)-embedded cubic γ-cyclodextrin metal-organic frameworks (γ-CD-MOFs) (denoted as γ-CD-MOFs@ALI) in a methylcellulose/polyvinyl alcohol (MP)-based matrix to achieve colorimetric monitoring and enhanced preservation of fish freshness. The MP/γ-CD-MOFs@ALI reveals a rapid color transition in 3 min from yellow color progressively darkens to purple as the pH increases from 2.0 to 10.0. And it is proved that the as-prepared film owns high antibacterial activity against Gram-positive bacteria (S. aureus), impressive ABTS+ radical scavenging rates of 85.54 ± 1.25 %, and effective ALI sustained-release properties. The intelligent packaging film exhibits an excellent colorimetric response to total volatile basic nitrogen and provides exceptional freshness preservation performance, effectively prolonging the shelf life of Ctenopharyngodon idella (grass carp) under 25 °C to 42 h.

A functional Pickering emulsion coating based on octadecenylsuccinic anhydride modified γ-cyclodextrin metal-organic frameworks for food preservation

In the rapidly advancing field of colloid and interface chemistry, food-grade nanoparticles are garnering increased attention for their potential applications in food preservation and innovative material development. Pickering emulsions, stabilized by solid particles, are especially noteworthy for their versatile applicability, spanning from food preservation to innovative material engineering. However, crafting a reliable, application-specific Pickering emulsion that amalgamates both stability and functionality poses a substantial challenge. In this research, we present an in-depth analysis of octadecenylsuccinic anhydride (ODSA) modified γ-cyclodextrin metal-organic frameworks (OCMs) stabilized ODSA Pickering emulsions, probing their stability across varying pH values and ionic strengths, and evaluating their groundbreaking applications, notably in paper coating and enhancing food shelf life. Our results unequivocally indicate a pronounced improvement in paper water resistance and fruit preservation after treatment with the OCMs-ODSA emulsion, heralding a novel methodology in these areas. Additionally, our studies illuminate the intrinsic antimicrobial attributes of OCMs, accentuating their cardinal role in augmenting the emulsion's preservation capabilities and heralding potential widespread applications in microbial mitigation, decay deterrence, and beyond.

Enhanced stability of anthocyanins by cyclodextrin–metal organic frameworks: Encapsulation mechanism and application as protecting agent for grape preservation

Anthocyanins are promising naturally occurring food preservatives for enhancing the quality of food products due to their excellent antioxidant properties. However, their low stability hinders their food packaging application. Here, we propose a facile strategy to achieve the improved stability of anthocyanins encapsulated in γ-cyclodextrin metal-organic frameworks (CD-MOFs) with an in-depth exploration of their structure–property relationships. The adsorbed anthocyanins in CD-MOFs are stabilized by multiple cooperative non-covalent interactions including hydrogen bonding and van der Waals (vdW) interactions as demonstrated by density functional theory (DFT) calculations and spectroscopy analysis. Particularly, by ion-exchange of acetate ions into the pores of CD-MOFs, the resulting CD-MOFs (CD-MOF_OAc) shows a higher anthocyanins adsorption rate with a maximum loading capacity of 83.7 % at 1 min. Besides, CD-MOF_OAc possesses the more effective protecting effect on anthocyanins with at least two-fold enhancement of stability in comparison of free anthocyanins under heating and light irradiation. The anthocyanins encapsulated CD-MOFs films for fruit freshness was validated by the Kyoho experiment. This novel encapsulation system provides a new possibility for the potential use of CD-MOFs as the encapsulating material for anthocyanins in fruit preservation.

Dual regulations on texture and water mobility of shrimp surimi gel with sustained-release epigallocatechin-3-gallate in γ-cyclodextrin metal organic frameworks: Insights into functionality and mechanisms

Epigallocatechin-3-gallate (EGCG) could demonstrate crosslinking effects on myofibrillar proteins, yet its proneness to self-aggregation could bring excessive crosslinking and water loss within gels, hindering its application as an additive during thermal gelation process. Here, encapsulation with the γ-cyclodextrin metal organic framework (γ-CD-MOF) before the use of EGCG was found to play a dual role: alleviating over-crosslinking of proteins and elevating water retention within gels. Results showed that EGCG got a sustainable release throughout the thermal process due to the gradual fracture of O-K coordinate bounds and structural collapse of γ-CD-MOF. Mechanism insights revealed that the use of EGCG loaded γ-CD-MOF (EGCG@γ-CD-MOF) could regulate formation efficiency on disulfide bounds and promote protonation transition of the amino groups in proteins. Moreover, EGCG@γ-CD-MOF brought a higher retention of phenols within gels through preventing oxidative transformation of phenols towards quinones, which were verified to display a higher affinity towards myosin via molecular calculations.

Cyclodextrin MOFs modified dry powder inhalers quadruple bioavailability of luteolin to ameliorate fibrosing interstitial lung disease

Fibrosing interstitial lung disease (ILD) is a pathological condition that is highly heterogeneous and lethal, and has few effective treatment choices. Other than pirfenidone and nintedanib for the therapy of idiopathic pulmonary fibrosis, no medications are currently licensed for the treatment of ILD. Luteolin is a common flavonoid with multiple biological effects such as anti-inflammation but with poor solubility and absorption. In this study, we loaded luteolin into γ-cyclodextrin metal–organic frameworks (CD-MOFs) to deliver the medicine to the lungs using dry powder inhalers; in vitro pulmonary deposition results showed LUT@CDMOF had a high fine particle fraction (FPF) (59.77 ± 3.48%). LUT@CDMOF effectively inhibited ILD progression in the BLM-induced fibrosing ILD model rats. When compared to oral administration, the inhalation of LUT@CDMOF dry powder in rats showed considerable improvements in absorption and bioavailability, with a tmax of 0.08 h and a high absolute bioavailability (82%) of LUT (The AUC(0-t) and Cmax of inhal. LUT@CDMOF respectively increased about 4.03 times and 9.11 times, when compared with the i.g. LUT group). These studies demonstrate the potent anti-inflammatory activities of LUT@CDMOF. The inhaled LUT@CDMOF might be considered as a promising new strategy in the treatment of fibrosing ILD.

Chiral MOF Derived Wearable Logic Sensor for Intuitive Discrimination of Physiologically Active Enantiomer.

Chiral sensors have attracted growing interest due to their application in health monitoring. However, rational design of wearable logic chiral sensors remains a great challenge. In this work, a dual responsive chiral sensor RT@CDMOF is prepared through in situ self-assembly of chiral γ-cyclodextrin metal-organic framework (CDMOF), rhodamine 6G hydrazide (RGH), and tetracyanovinylindane (TCN). The embedded RGH and TCN inherit the chirality of host CDMOF, producing dual changes both in fluorescence and reflectance. RT@CDMOF is explored as a dual channel sensor for chiral discrimination of lactate enantiomers. Comprehensive mechanistic studies reveal the chiral binding process, and carboxylate dissociation is confirmed by impedance and solid-state 1 H nuclear magnetic resonance (NMR). A flexible membrane sensor is successfully fabricated based on RT@CDMOF for wearable health monitoring. Practical evaluation confirms the potential of fabricated membrane sensor in point-of-care health monitoring by indexing the exercise intensity. Based on above, a chiral IMPLICATION logic unit can be successfully achieved, demonstrating the promising potential of RT@CDMOF in design and assembly of novel smart devices. This work may open a new avenue to the rational design of logic chiral sensors for wearable health monitoring applications.

Functionalized cyclodextrin metal‐organic framework materials with excellent photocatalytic performance for removal of organic dyes from water

Driven by the global water crisis, the necessity for wastewater treatment has become more important than ever. Herein, γ-cyclodextrin metal-organic frameworks (CD-MOF) generated by solvent diffusion method serve as a carrier, and glycol glycidyl ether acts as the cross-linking agent, Crosslinked-CD-MOF (CCM) has been successfully designed. Benefiting from tunable size and fine water stability, CCM used as a framework allows ZnO for a large-area space loading. The resultant ZnO/CCM exhibits well-defined shapes, a narrower band gap, excellent chemical stability, and photocatalytic performance for dye removal. Apart from that, the antibacterial activity was further explored. The study confirmed that ZnO/CCM-3 could degrade above 93% methylene blue (MB) under ultraviolet or visible light irradiation, particularly in five cyclic tests. This straightforward yet general approach offers potential applications for CD-MOF-based materials in sewage remediation.

γ-Cyclodextrin-based metal-organic frameworks for lactonic sophorolipid application in enhanced oil recovery

Lactonic sophorolipid (LSL) exhibits numerous surfactant activities, such as emulsification, wetting action, dispersion effect, and oil-washing activities. Nevertheless, LSLs have poor water solubility, which restrains their application in the petroleum industry. In this research, a new compound, lactonic sophorolipid cyclodextrin metal-organic framework (LSL-CD-MOFs), was obtained by loading LSL into γ-cyclodextrin metal-organic frameworks (γ-CD-MOFs). The LSL-CD-MOFs were characterized by N2 adsorption analysis, X-ray powder diffraction analysis, Fourier transform infrared spectroscopy, and thermogravimetric analysis. Loading LSL into γ-CD-MOFs significantly increased the apparent water solubility of LSL. However, the critical micelle concentration of LSL-CD-MOFs was similar to that of LSL. Furthermore, LSL-CD-MOFs effectively reduced the viscosities and improved the emulsification indices of oil–water mixtures. Oil-washing tests, which were conducted using oil sands, revealed that the LSL-CD-MOFs yielded an oil-washing efficiency of 85.82 % ± 2.04 %. Overall, γ-CD-MOFs are promising carriers for LSL, and LSL-CD-MOFs are a potential, low-cost, new, green surfactant for enhanced oil recovery.

Highly efficient pulmonary delivery of levo-tetrahydropalmatine using γ-cyclodextrin metal-organic framework as a drug delivery platform

Highly efficient pulmonary delivery of levo-tetrahydropalmatine using γ-cyclodextrin metal-organic framework as a drug delivery platform

Efficient controlled release of cannabinoids loaded in γ-CD-MOFs and DPPC liposomes as novel delivery systems in oral health

Olivetol (OLV), as a cannabidiol (CBD) analog, was incorporated in γ-cyclodextrin metal-organic frameworks (γ-CD-MOFs) and 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) liposomes as potential analgesic drug delivery systems (DDS) for dental hypersensitivity (DH) treatment. These DDS have been scarcely employed in oral health, being the first time in case of MOFs loaded with cannabinoids. In vitro experiments using bovine teeth were performed to verify if the drug is able to reach the dentin, where it can flow to the pulp tissues and exert its analgesic effect; enamel and dentin regions were analyzed by synchrotron radiation-based FTIR microspectroscopy. Principal component analysis (PCA) was used to process the spectroscopic data as a powerful chemometric tool, and it revealed a similar behavior in both regions. The studied DDS have been characterized by different techniques, and is was demonstrated that DDS is an efficient way to carry the drug through dental tissues without compromising their structure.Graphical

Cyclodextrin Metal-Organic Framework as a Broad-Spectrum Potential Delivery Vehicle for the Gasotransmitters.

The important role of gasotransmitters in physiology and pathophysiology suggest employing gasotransmitters for biomedical treatment. Unfortunately, the difficulty in storage and controlled delivery of these gaseous molecules hindered the development of effective gasotransmitters-based therapies. The design of a safe, facile, and wide-scale method to delivery multiple gasotransmitters is a great challenge. Herein, we use an ultrasonic assisted preparation γ-cyclodextrin metal organic framework (γ-CD-MOF) as a broad-spectrum delivery vehicle for various gasotransmitters, such as SO2, NO, and H2S. The release rate of gasotransmitters could be tuned by modifying the γ-CD-MOF with different Pluronics. The biological relevance of the exogenous gasotransmitters produced by this method is evidenced by the DNA cleavage ability and the anti-inflammatory effects. Furthermore, the γ-CD-MOF composed of food-grade γ-CD and nontoxic metal salts shows good biocompatibility and particle size (180 nm). Therefore, γ-CD-MOF is expected to be an excellent tool for the study of co-delivery and cooperative therapy of gasotransmitters.

Physical, structural, and rheological properties of γ-cyclodextrin metal-organic framework emulgels

AbstractThis study aimed to develop and characterise emulgels based on aqueous γ-cyclodextrin metal-organic framework (γ-CD-MOF) solutions with sunflower oil in the presence of Tween 20, 40, and 60 emulsifiers. The main physical, structural, and rheological properties of γ-CD-MOF emulgels were investigated. The emulgels prepared with 5% and 10% γ-CD-MOF were durable. The X-ray diffraction patterns proved the existence of β polymorph type lipid crystals. The rheological analyses showed that the gel strength increased with increased γ-CD-MOF concentration, and thixotropic behaviour was observed depending on the gel strength at 10 °C. In addition, the samples were heat resistant proved by rheological temperature ramp tests. Finally, addition of the emulsifiers did not cause any change in the centrifuge stability and colour properties of the emulgels. These samples could be used to prepare different emulsion type food products.

Synthesis of γ-cyclodextrin metal-organic framework as ethylene absorber for improving postharvest quality of kiwi fruit

In this study, we developed an edible metal-organic framework (MOF) based on K+ and γ-cyclodextrin (γ-CD), named γ-CD-MOF-K, using ultrasonication. A structural analysis demonstrated that MOF had good adsorption performance for ethylene gas: 56% ± 0.67% (w/w). Molecular docking technology found that γ-CD-MOF-K had a spindle cavity structure, which can effectively adsorb and store ethylene gas. The results showed that the material could effectively absorb ethylene gas in storage packaging and delay red kiwi fruit ripening. Therefore, MOF exhibits great potential to improve the postharvest quality of fruits and vegetables.

Optimal Polyethyleneimine Molecular Weight and Arrangement for Modification of γ-Cyclodextrin Metal Organic Frameworks (γ-CD-MOFs) for Post-Combustion CO2 Capture

Modified γ-cyclodextrin metal organic frameworks (γ-CD-MOFs) are a promising eco-friendly sorbents for post-combustion CO2 capture. Polyethyleneimine (PEI) has been widely used for modifying MOFs to enhance their CO2 sorption capacity and selectivity through the introduction of CO2 selective amine groups. The main objective of this study was to determine the optimal PEI molecular weight and arrangement (linear or branched) to enhance γ-CD-MOF’s CO2 sorption capacity. γ-CD-MOFs were impregnated with linear as well as branched PEI with molecular weights of 600, 1200 or 10,000. The CO2 sorption capacity of the PEI-impregnated γ-CD-MOFs was determined using a quartz crystal microbalance assembly at CO2 partial pressures from 0.35–1.0 atm. Impregnation with 600 g/mole branched PEI achieved the highest CO2 sorption capacity of 0.9 mmole/g CO2 at 1 atm, followed by the linear PEI (0.12 mmol/g). Modification with the other branched PEI molecular weights did not achieve detectable CO2 sorption, likely because of pore blockage with the relatively larger PEI molecular weights, as demonstrated by molecular docking simulations. Furthermore, the control γ-CD-MOFs did not sorb CO2, likely because of the lower attraction forces between CO2 and the large pore volume of the unmodified MOFs.

Crystalline γ-cyclodextrin metal organic framework nano-containers for encapsulation of benzaldehyde and their host–guest interactions

Crystalline γ-cyclodextrin metal organic framework nano-containers for encapsulation of benzaldehyde and their host–guest interactions