A full structural assignment of the neutral, protonated, and deprotonated histidine conformers in the gas phase is presented. A total of 3024 unique trial structures were generated by all combinations of internal single-bond rotamers of these species and optimized at the B3LYP/6-311G* level and further optimized at the B3LYP/6-311++G** level. A set of unique conformers is found, and their relative energies, free energies, dipole moments, rotational constants, electron affinities, ionization energies, and harmonic frequencies are determined. The population ratio of histidine and its tautomer is 1:0.16 at 298 K. Massive conformational changes are observed due to protonation and deprotonation, and the intramolecular H-bonds are characterized with the atoms in molecules theory. The calculated proton dissociation energy, gas-phase acidity, proton affinity, and gas-phase basicity are in excellent agreement with the experiments. The deprotonation and protonation of gaseous histidine both occur on the imidazole ring, explaining the versatile biofunctions of histidine in large biomolecules. The UV spectra of neutral and singly and doubly protonated histidine are investigated with the TDDFT/B3LYP/6-311+G(2df,p) calculations. The S0-S1, S0-S2, and S0-S3 excitations of histidine are mixed pipi*/npi* transitions at 5.37, 5.44, and 5.69 eV, respectively. The three excitation energies for histidine tautomer are 4.85, 5.47, and 5.52 eV, respectively. The three excitations for protonated histidine are mainly npi* transitions at 5.45, 5.67, and 5.82 eV, respectively. The S0-S1 excitation of protonated histidine produces ImH-CbetaH2-CalphaH(COOH)-NH2+, while the S0-S2 and S0-S3 transitions produce ImH-CbetaH2-CalphaH(NH2)-(COOH)+. These data may help to understand the mechanisms of the UV fragmentation of biomolecules.

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HIGHLIGHTS • A novel N-doped strategy of C 2 N 3 − in situ trimerization between the 2D MXene interlayers was first proposed. • The ultra-fast pseudocapacitive behavior of Ti 3 C 2 T x /Na 3 TCM anode was managed and verified. • The as-fabricated sodium-ion capacitor delivers excellent electrochemical performance by anode/cathode mass matching. ABSTRACT 2D MXenes are attractive for energy storage applications because of their high electronic conductivity. However, it is still highly challenging for improving the sluggish sodium (Na)-ion transport kinetics within the MXenes interlayers. Herein, a novel nitrogen-doped Ti 3 C 2 T x MXene was synthesized by introducing the in situ polymeric sodium dicyanamide (Na-dca) to tune the complex terminations and then utilized as intercalation-type pseudocapacitive anode of Na-ion capacitors (NICs). The Na-dca can intercalate into the interlayers of Ti 3 C 2 T x nanosheets and simultaneously form sodium tricyanomelaminate (Na 3 TCM) by the catalyst-free trimerization. The as-prepared Ti 3 C 2 T x /Na 3 TCM exhibits a high N-doping of 5.6 at.% in the form of strong TiN bonding and stabilized triazine ring structure. Consequently, coupling Ti 3 C 2 T x /Na 3 TCM anode with different mass of activated carbon cathodes, the asymmetric MXene//carbon NICs are assembled. It is able to deliver high energy density (97.6 Wh kg −1), high power output (16.5 kW kg −1), and excellent cycling stability (≈ 82.6% capacitance retention after 8000 cycles).

Lithium−sulfur (Li−S) batteries have attracted a great deal of attention for the next-generation energy storage devices due to their inherently high theoretical energy density, high natural abundance, and low cost. However, the dissolution of polysulfides in electrolytes and their undesirable shuttle behavior lead to poor cycling performance, which obstructs practical application. Herein, we report a dual-sulfur-fixing mechanism of epoxy/allyl compound/sulfur system to prepare poly(sulfur-random-4-vinyl-1,2-epoxycyclohexane) (SVE) copolymers as powerful cathode materials. Benefiting from the stable C−S bond and a uniform distribution of ultrafine Li 2 S/S 8 in the SVE-based polymer matrix, the SVE electrodes exerted an embedding effect to reduce polysulfides migration. The thiosulfate/polythionate protective layer derived from the terminal hydroxyl group of SVE also ensured the cycle stability of SVE electrodes during cycling. As a result, optimized SVE electrodes deliver a high reversible specific capacity of 1248 mA h g −1 at rates of 0.1 C, together with a stable cycling performance of no capacity decay per cycle over more than 400 cycles. This work provides an effective strategy for the practical application of organosulfur polymers Li−S batteries and inspires the exploration of the reaction mechanism of epoxy/allyl compound/sulfur system.

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Graphene oxide has become an attractive electrode-material candidate for supercapacitors thanks to its higher specific capacitance compared to graphene. The quantum capacitance makes relative contributions to the specific capacitance, which is considered as the major limitation of graphene electrodes, while the quantum capacitance of graphene oxide is rarely concerned. This study explores the quantum capacitance of graphene oxide, which bears epoxy and hydroxyl groups on its basal plane, by employing density functional theory (DFT) calculations. The results demonstrate that the total density of states near the Fermi level is significantly enhanced by introducing oxygen-containing groups, which is beneficial for the improvement of the quantum capacitance. Moreover, the quantum capacitances of the graphene oxide with different concentrations of these two oxygen-containing groups are compared, revealing that more epoxy and hydroxyl groups result in a higher quantum capacitance. Notably, the hydroxyl concentration has a considerable effect on the capacitive behavior.

N, S-co-doped hierarchical porous carbon with stable sodium storage were prepared by designing the precursors and changing the reaction temperature.