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In this paper, we report a facile strategy to fabricate fluorescent porous thin film on the surface of U-bent poly(methyl methacrylate) optical fiber (U-bent POF) in situ via "click" polymerization for vapor phase sensing of explosives. Upon irradiation of evanescent UV light transmitting within the fiber under ambient condition, a porous film (POSS-thiol cross-linking film, PTCF) is synthesized on the side surface of the fiber by a thiol-ene "click" reaction of vinyl-functionalized polyhedral oligomeric silsesquioxanes (POSS-V8) and alkane dithiols. When vinyl-functionalized porphyrin, containing four allyl substituents at the periphery, is added into precursors for the polymerization, fluorescence porphyrin can be covalently bonded into the cross-linked network of PTCF. This "fastened" way reduces the aggregation-induced fluorescence self-quenching of porphyrin and enhances the physicochemical stability of the porous film on the surface of U-bent POF. Fluorescent signals of the PTCF/U-bent POF probe made by this method exhibit high fluorescence quenching toward trace TNT and DNT vapor and the highest fluorescence quenching efficiency is observed for 1, 6-hexanedimercaptan-based film. In addition, because of the presence of POSS-V8 with multi cross-linkable groups, PTCF exhibits well-organized pore network and stable dye dispersion, which not only causes fast and sensitive fluorescence quenching against vapors of nitroaromatic compounds, but also provides a repeatability of the probing performance.
ACS Appl Mater Interfaces 2015 Jan 14
PMID:Fluorescent porous film modified polymer optical fiber via "click" chemistry: stable dye dispersion and trace explosive detection. 2548 15

We synthesized three conjugated polycarbazole porous organic frameworks named o-Cz-POF, m-Cz-POF, and p-Cz-POF for hydrocarbon fuels' adsorptive desulfurization. The carbazole building blocks possessed ortho, meta, and para steric configuration, which resulted in POFs exhibiting adjustable specific surface area and pore structure. Adsorption kinetics experiments and DFT calculations were carried out to understand the competitive adsorption of 3-methylthiophene and octane in the Cz-POF. The instantaneous adsorption rate and adsorption energy calculation analyses gave a convincing demonstration on preferential selective adsorption of 3-methylthiophene in Cz-POFs. Furthermore, the fixed bed breakthrough experiment demonstrated that the Cz-POFs can selectively adsorb 3-methylthiophene efficiently, and hydrocarbon fuel with sulfide content close to 0 ppm was obtained. The features of high stability and high desulfurization efficiency of Cz-POFs make them hold the promise as a new type of porous adsorbent for ultradeep adsorption desulfurization.
ACS Appl Mater Interfaces 2019 Oct 30
PMID:High-Efficiency Separation of Aromatic Sulfide from Liquid Hydrocarbon Fuel in Conjugated Porous Organic Framework with Polycarbazole Unit. 3158 97

The introduction of a trimethylsilyl (TMS) motif in electrolyte additives for lithium-ion batteries is regarded as an effectual approach to remove corrosive hydrofluoric acid (HF) that structurally and compositionally damages the electrode-electrolyte interface and gives rise to transition metal dissolution from the cathode. Herein, we present that electrolyte additives with TMS moieties lead to continued capacity loss of polycrystalline (PC)-LiNi0.8Co0.1Mn0.1O2 (NCM811) cathodes coupled with graphite anodes compared to additives without TMS as the cycle progresses. Through a comparative study using electrolyte additives with and without TMS moieties, it is revealed that the TMS group is prone to react with residual lithium compounds, in particular, lithium hydroxide (LiOH) on the PC-NCM811 cathode, and the resulting TMS-OH triggers the decomposition of PF5 created by the autocatalytic decomposition of LiPF6 that generates reactive species, namely, HF and POF3. This work aims to offer a way to build favorable interface structures for Ni-rich cathodes covered with residual lithium compounds through a study to figure out the roles of TMS moieties of electrolyte additives.
ACS Appl Mater Interfaces 2020 Sep 30
PMID:Unanticipated Mechanism of the Trimethylsilyl Motif in Electrolyte Additives on Nickel-Rich Cathodes in Lithium-Ion Batteries. 3288 53