17322-97-3Relevant articles and documents
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
Bankar, Balasaheb D.,Biradar, Ankush V.,Goswami, Ranadip,Neogi, Subhadip,Pillai, Renjith S.,Rajput, Sonal,Seal, Nilanjan
, p. 4316 - 4332 (2022/03/07)
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.
Epoxidation of Cyclooctene Using Water as the Oxygen Atom Source at Manganese Oxide Electrocatalysts
Jin, Kyoungsuk,Maalouf, Joseph H.,Lazouski, Nikifar,Corbin, Nathan,Yang, Dengtao,Manthiram, Karthish
supporting information, p. 6413 - 6418 (2019/05/02)
Epoxides are useful intermediates for the manufacture of a diverse set of chemical products. Current routes of olefin epoxidation either involve hazardous reagents or generate stoichiometric side products, leading to challenges in separation and significant waste streams. Here, we demonstrate a sustainable and safe route to epoxidize olefin substrates using water as the oxygen atom source at room temperature and ambient pressure. Manganese oxide nanoparticles (NPs) are shown to catalyze cyclooctene epoxidation with Faradaic efficiencies above 30%. Isotopic studies and detailed product analysis reveal an overall reaction in which water and cyclooctene are converted to cyclooctene oxide and hydrogen. Electrokinetic studies provide insights into the mechanism of olefin epoxidation, including an approximate first-order dependence on the substrate and water and a rate-determining step which involves the first electron transfer. We demonstrate that this new route can also achieve a cyclooctene conversion of ~50% over 4 h.
Regiocontrolled syntheses of FAHFAs and LC-MS/MS differentiation of regioisomers
Balas, Laurence,Bertrand-Michel, Justine,Viars, Fanny,Faugere, Julien,Lefort, Corinne,Caspar-Bauguil, Sylvie,Langin, Dominique,Durand, Thierry
supporting information, p. 9012 - 9020 (2016/10/07)
An efficient regiospecific total synthesis of several branched fatty acyl hydroxyl-fatty acids (FAHFA) has been achieved from available terminal alkenes and alkynes. The key steps feature a boron trifluoride mediated epoxide ring opening with acetylide carbanions, followed by hydrogenation of the alkyne function. The carboxylic acid of the hydroxylated chains is introduced at the last step of the synthesis to allow the esterification of the branched hydroxyl group by fatty acids beforehand. The chemical syntheses of a "linear" FAHFA and a branched FAHFA analog containing a Z-olefin in the hydroxyl-fatty acid chain are also reported. A LC-MS/MS method has been developed. Several reversed phase columns were compared. Regioisomers were separated.