Bottom-up construction of efficient active sites in transition metal–nitrogen–carbon (M–N–C) catalysts for oxygen reduction reaction (ORR) from single molecular building blocks remains one of the most difficult challenges. Herein, we report a bottom-up approach to produce a highly active Cu–N4–C catalyst with well-defined Cu–N4 coordination sites derived from a small molecular copper complex containing Cu–N4 moieties. The Cu–N4 moieties were found to be covalently integrated into graphene sheets to create the Cu–N4 active sites for ORR. Furthermore, the activity was boosted by tuning the structure of active sites. We find that the high ORR activity of the Cu–N4–C catalyst is related to the Cu–N4 center linked to edges of the graphene sheets, where the electronic structure of the Cu center has the right symmetry for the degenerate π* orbital of the O2 molecule. These findings point out the direction for the synthesis of the M–N–C catalysts at the molecular level.

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The question whether the emitter of yellow-green firefly bioluminescence is the enol or keto-constrained form of oxyluciferin (OxyLH(2)) still has no definitive answer from experiment or theory. In this study, Arg220, His247, adenosine monophosphate (AMP), Water324, Phe249, Gly343, and Ser349, which make the dominant contributions to color tuning of the fluorescence, are selected to simulate the luciferase (Luc) environment and thus elucidate the origin of firefly bioluminescence. Their respective and compositive effects on OxyLH(2) are considered and the electronic absorption and emission spectra are investigated with B3LYP, B3PW91, and PBE1KCIS methods. Comparing the respective effects in the gas and aqueous phases revealed that the emission transition is prohibited in the gas phase but allowed in the aqueous phase. For the compositive effects, the optimized geometry shows that OxyLH(2) exists in the keto(-1) form when Arg220, His247, AMP, Water324, Phe249, Gly343, and Ser349 are all included in the model. Furthermore, the emission maximum wavelength of keto(-1)+Arg+His+AMP+H(2)O+Phe+Gly+Ser is close to the experimental value (560 nm). We conclude that the keto(-1) form of OxyLH(2) is a possible emitter which can produce yellow-green bioluminescence because of the compositive effects of Arg220, His247, AMP, Water324, Phe249, Gly343, and Ser349 in the luciferase environment. Moreover, AMP may be involved in enolization of the keto(-1) form of OxyLH(2). Water324 is indispensable with respect to the environmental factors around luciferin (LH(2)).

Is the resonance-based anionic keto form of oxyluciferin the chemical origin of multicolor bioluminescence? Can it modulate green into red luminescence? There is as yet no definitive answer from experiment or theory. The resonance-based anionic keto forms of oxyluciferin have been proposed as a cause of multicolor bioluminescence in the firefly. We model the possible structures by adding sodium or ammonium cations and investigating the ground- and excited-state geometries as well as the electronic absorption and emission spectra. A role for the resonance structures is obvious in the gas phase. The absorption and emission spectra of the two structures are quite different--one in the blue and another in the red. The differences in the spectra of the models are small in aqueous solution, with all the absorption and emission spectra in the yellow-green region. The resonance-based anionic keto form of oxyluciferin may be one origin of the red-shifted luminescence but is not the exclusive explanation for the variation from green (approximately 530 nm) to red (approximately 635 nm). We study the geometries, absorption, and emission spectra of the possible protonated compounds of keto(-1) in the excited states. A new emitter keto(-1)'-H is considered.

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Poly(1-amino-5-chloroanthraquinone) (PACA) was firstly synthesized by a chemically oxidative interfacial polymerization. The PACA has been developed as a fluorescent sensor for the determination of Fe(III) in semi-aqueous solution at pH 7.0. The sensor exhibited remarkably high sensitivity toward Fe(3+) since the fluorescence of the polymer could be significantly quenched even though trace Fe(3+) was added. The sensor showed a linear fluorescence emission response over a wide concentration range from 1.0 × 10(-10) to 1.0 × 10(-4) M, with an ultra-low detection limit of 2.0 × 10(-11) M. The quenching of the fluorescence was found to be static one due to the formation of non-fluorescent complex in the ground state.

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Poly(1-amino-5-chloroanthraquinone) (PACA) nanofibrils were applied as novel nanoadsorbents for highly toxic mercury removal from aqueous solutions. A series of batch adsorption experiments were conducted to study the effect of adsorbent dose, pH, contact time, and metal concentration on Hg(II) uptake by PACA nanofibrils. Kinetic data indicated that the adsorption process of PACA nanofibrils for Hg(II) achieved equilibrium within 2 h following a pseudo-second-order rate equation. The adsorption mechanism of PACA nanofibrils for Hg(II) was investigated by Fourier transform-infrared (FT-IR) spectra and X-ray photoelectron spectroscopy (XPS) analyses. The adsorption isotherm of Hg(II) fitted well the Langmuir model, exhibiting superb adsorption capacity of 3.846 mmol of metal per gram of adsorbent. Lastly, we found out that the as-synthesized PACA nanofibrils are efficient in Hg(II) removal from real wastewater. Furthermore, five consecutive adsorption-desorption cycles demonstrated that the PACA nanofibrils were suitable for repeated use without considerable changes in the adsorption capacity.