In situ fabricated MOF-cellulose composite as an advanced ROS deactivator-convertor: Fluoroswitchable bi-phasic tweezers for free chlorine detoxification and size-exclusive catalytic insertion of aqueous H2O2
- Title
- In situ fabricated MOF-cellulose composite as an advanced ROS deactivator-convertor: Fluoroswitchable bi-phasic tweezers for free chlorine detoxification and size-exclusive catalytic insertion of aqueous H2O2
- Creator
- Goswami R.; Bankar B.D.; Rajput S.; Seal N.; Pillai R.S.; Biradar A.V.; Neogi S.
- Description
- Combining the merits of structural diversity, and purposeful implantation of task-specific functionalities, metal-organic frameworks (MOFs) instigate targeted reactive oxygen species (ROS) scavenging and concurrent detoxification via self-calibrated emission modulation. Then again, grafting of catalytically active sites in MOFs can benefit developing a greener protocol to convert ROS generators to technologically important building blocks, wherein tailorable MOF-composite fabrication is highly sought for practical applications, yet unexplored. The chemo-robust and hydrogen-bonded framework encompassing free -NH2 moiety affixed pores serves as an ultra-fast and highly regenerable fluoro-probe for selective detection of toxic ROS producers hypochlorite ion (ClO-) and H2O2 with record-level nanomolar sensitivity. While the bio-relevant antioxidant l-ascorbic acid (AA) imparts notable quenching to the MOF, a significant 3.5 fold emission enhancement with bi-phasic colorimetric variation ensues when it selectively scavenges ClO- from uni-directional porous channels through an unprecedented molecular tweezer approach. Apart from a battery of experimental evidence, density functional theory (DFT) results validate "on-off-on"fluoroswitching from redistribution of MOF orbital energy levels, and show guest-mediated exclusive transition from "Tight state"to "Loose state". The coordination frustrated metal site engineered pore-wall benefits the dual-functionalized MOF in converting the potential ROS generator H2O2via selective alkene epoxidation under mild-conditions. Importantly, sterically encumbered substrates exhibit poor conversion and demonstrate first-ever pore-fitting-induced size selectivity for this benign oxidation. Judiciously planned control experiments in combination with DFT-optimized intermediates provide proof-of-concept to the ionic route of ROS conversion. Considering an effective way to broaden the advanced applications of this crystalline material, reconfigurable MOF@cotton fiber (CF) is fabricated via in situ growth, which scavenges free chlorine and concomitantly squeezes it upon exposure to AA with obvious colorimetric changes over multiple real-life platforms. Furthermore, multi-cyclic alkene epoxidation by MOF@CF paves the way to futuristic continuous flow reactors that truly serves this smart composite as a bimodal ROS deactivator-convertor and explicitly denotes it as an advanced promising analogue from contemporary state-of-the-art materials. The Royal Society of Chemistry.
- Source
- Journal of Materials Chemistry A, Vol-10, No. 8, pp. 4316-4332.
- Date
- 2022-01-01
- Publisher
- Royal Society of Chemistry
- Coverage
- Goswami R., Academy of Scientific and Innovative Research (AcSIR), Ghaziabad, 201002, India, Inorganic Materials and Catalysis Division, CSIR-Central Salt and Marine Chemicals Research Institute, Gujarat, Bhavnagar, 364002, India; Bankar B.D., Academy of Scientific and Innovative Research (AcSIR), Ghaziabad, 201002, India, Inorganic Materials and Catalysis Division, CSIR-Central Salt and Marine Chemicals Research Institute, Gujarat, Bhavnagar, 364002, India; Rajput S., Inorganic Materials and Catalysis Division, CSIR-Central Salt and Marine Chemicals Research Institute, Gujarat, Bhavnagar, 364002, India; Seal N., Academy of Scientific and Innovative Research (AcSIR), Ghaziabad, 201002, India, Inorganic Materials and Catalysis Division, CSIR-Central Salt and Marine Chemicals Research Institute, Gujarat, Bhavnagar, 364002, India; Pillai R.S., Department of Chemistry, Christ University, Bangalore, 560029, India; Biradar A.V., Academy of Scientific and Innovative Research (AcSIR), Ghaziabad, 201002, India, Inorganic Materials and Catalysis Division, CSIR-Central Salt and Marine Chemicals Research Institute, Gujarat, Bhavnagar, 364002, India; Neogi S., Academy of Scientific and Innovative Research (AcSIR), Ghaziabad, 201002, India, Inorganic Materials and Catalysis Division, CSIR-Central Salt and Marine Chemicals Research Institute, Gujarat, Bhavnagar, 364002, India
- Rights
- Restricted Access
- Relation
- ISSN: 20507488; CODEN: JMCAE
- Format
- Online
- Language
- English
- Type
- Article
Collection
Citation
Goswami R.; Bankar B.D.; Rajput S.; Seal N.; Pillai R.S.; Biradar A.V.; Neogi S., “In situ fabricated MOF-cellulose composite as an advanced ROS deactivator-convertor: Fluoroswitchable bi-phasic tweezers for free chlorine detoxification and size-exclusive catalytic insertion of aqueous H2O2,” CHRIST (Deemed To Be University) Institutional Repository, accessed February 24, 2025, https://archives.christuniversity.in/items/show/15207.