The major impediments to the implementation of cancer immunotherapies are the sustained immune effect and the targeted delivery of these therapeutics, as they have life-threatening adverse effects. In this work, biomimetic metal-organic frameworks [zeolitic imidazolate frameworks (ZIFs)] are used for the controlled delivery of nivolumab (NV), a monoclonal antibody checkpoint inhibitor that was U.S. Food and Drug Administration–approved back in 2014. The sustained release behavior of NV-ZIF has shown a higher efficacy than the naked NV to activate T cells in hematological malignancies. The system was further modified by coating NV-ZIF with cancer cell membrane to enable tumor-specific targeted delivery while treating solid tumors. We envisage that such a biocompatible and biodegradable immunotherapeutic delivery system may promote the development and the translation of hybrid superstructures into smart and personalized delivery platforms.
Distillation-free separations of haloalkanes isomers represents a persistent challenge for the chemical industry. Several classic molecular sorbents show high selectivity in the context of such separations; however, most suffer from...
The impact of OH• generation during the oxidative coupling of methane (OCM) was simulated using state-of-the-art gas-phase chemistry and a comprehensive chemical kinetic model. The inclusion of the quasi-equilibrated formation of OH• from a H2O-O2 mixture into the combustion chemistry network enhanced the CH4 conversion rate and C2 selectivity, consistent with the previously proposed mechanism involving catalytically generated OH•. The OH-pathway increased the CH3• concentration resulting in an enhanced transformation rate from CH3• to C2H6 (second-order in CH3•) more than to CO (first-order in CH3•). Relative to other H-abstracting radical species, the OH• weakened the sensitivity of the H abstraction rate constant to C-H bond energy, or lower 2 6 4 C H CH / kk , which comparatively slows the C2H6 conversion rate relative to CH4, thus enhancing C2 selectivity. Concurrent dehydrogenation of C2H6 to C2H4 may maximize the C2H4 selectivity even after O2 depletion. With the involvement of the OH•-mediated pathway, this study addresses the effects of Received: ((will be filled in by the editorial staff)) Revised: ((will be filled in by the editorial staff))
This study simulates a high-temperature reaction in a plug-flow reactor (PFR) for the aromatization of methane via oxidative coupling of methane (OCM) using a state-of-the-art gas-phase chemical kinetic mechanism. Benzene is formed from a methane-oxygen (CH4-O2) feed via formation of ethylene through OCM followed by homogeneous gas-phase aromatization of C2H4 after O2 depletion. Because both OCM and C2H4 aromatization are exothermic reactions, the process is advantageous over an endothermic non-oxidative methane aromatization reaction. For the OCM reaction, the previously reported mechanism in which the catalyst achieves the quasiequilibrated formation of OH• from an H2O-O2 mixture was included in the combustion chemistry network. It was evident that OH• formation increased benzene yield as a consequence of enhanced C2H4 yield from the OCM. The influence of temperature, CH4/O2 ratio and contact time on benzene yield was elucidated, and reaction pathways leading to aromatic formation were analyzed. The maximum benzene yield on a carbon basis at a total pressure of 1 atm reached 10% at CH4/O2 ratios from 3 to 6 and temperatures of 800 to 900ºC (isothermal). Our analysis on the differential rates of production suggest that benzene is formed from the benzyl radical via toluene and from the reaction between allyl and propargyl. Adiabatic operations were found to be beneficial for reducing external heat supply (i.e., inlet temperature) by utilizing the exothermic reactions. ASSOCIATED CONTENT Supporting Information. Reaction profiles without OH• contribution Figure S1, Table S1; Water addition effects on adiabatic reactor temperature profiles Figure S2.
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