The kinetics of oxygen reduction was studied in acid solutions on Pt monolayers deposited on a Pd(111) surface and on carbon-supported Pd nanoparticles using the rotating disk-ring electrode technique. These electrocatalysts were prepared by a new method for depositing Pt monolayers involving the galvanic displacement by Pt of an underpotentially deposited Cu monolayer on a Pd substrate and characterized by scanning tunneling and transmission electron microscopies. The kinetics of O 2 reduction shows a significant enhancement at Pt monolayers on Pd(111) and Pd nanoparticle surfaces in comparison with the reaction on Pt(111) and Pt nanoparticles. The four-electron reduction, with a first-charge transfer-rate determining step, is operative on both surfaces. The observed increase in the catalytic activity of Pt monolayer surfaces compared with Pt bulk and nanoparticle electrodes may reflect decreased formation of PtOH. An enhanced atomic scale surface roughness and low coordination of some atoms may contribute to the observed activity. The results illustrate that placing a Pt monolayer on a suitable metal nanoparticle substrate is an attractive way of designing better O 2 reduction electrocatalysts. Also, by using this method the Pt content is reduced to very low levels. The Pt mass-specific activity of the Pt/Pd/C electrode is 5-8 times higher than that of the Pt/C electrocatalyst. The noble metal (Pt + Pd) mass-specific activity is two times higher than that of Pt/C.
Regulatory T (Treg) cells, characterized by expression of the transcription factor forkhead box P3 (Foxp3), maintain immune homeostasis by suppressing self-destructive immune responses1–4. Foxp3 operates as a late-acting differentiation factor controlling Treg cell homeostasis and function5, whereas the early Treg-cell-lineage commitment is regulated by the Akt kinase and the forkhead box O (Foxo) family of transcription factors6–10. However, whether Foxo proteins act beyond the Treg-cell-commitment stage to control Treg cell homeostasis and function remains largely unexplored. Here we show that Foxo1 is a pivotal regulatorof Treg cell function. Treg cells express high amounts of Foxo1 and display reduced T-cell-receptor-induced Akt activation, Foxo1 phosphorylation and Foxo1 nuclear exclusion. Mice with Treg-cell-specific deletion of Foxo1 develop a fatal inflammatory disorder similar in severity to that seen in Foxp3-deficient mice, but without the loss of Treg cells. Genome-wide analysis of Foxo1 binding sites reveals ~300 Foxo1-bound target genes, including the pro-inflammatory cytokine Ifng, that do not seem to be directly regulated by Foxp3. These findings show that the evolutionarily ancient Akt–Foxo1 signalling module controls a novel genetic program indispensable for Treg cell function.
An exact quantum master equation formalism is constructed for the efficient evaluation of quantum non-Markovian dissipation beyond the weak system-bath interaction regime in the presence of time-dependent external field. A novel truncation scheme is further proposed and compared with other approaches to close the resulting hierarchically coupled equations of motion. The interplay between system-bath interaction strength, non-Markovian property, and required level of hierarchy is also demonstrated with the aid of simple spin-boson systems.
By introducing the self-energy density functionals for the dissipative interactions between the reduced system and its environment, we develop a time-dependent density-functional theory formalism based on an equation of motion for the Kohn-Sham reduced single-electron density matrix of the reduced system. Two approximate schemes are proposed for the self-energy density functionals, the complete second order approximation and the wide-band limit approximation. A numerical method based on the wide-band limit approximation is subsequently developed and implemented to simulate the steady and transient current through various realistic molecular devices. Simulation results are presented and discussed.
Based on our earlier works [X. Zheng et al., Phys. Rev. B 75, 195127 (2007); J. S. Jin et al., J. Chem. Phys. 128, 234703 (2008)], we propose a rigorous and numerically convenient approach to simulate time-dependent quantum transport from first-principles. The proposed approach combines time-dependent density functional theory with quantum dissipation theory, and results in a useful tool for studying transient dynamics of electronic systems. Within the proposed exact theoretical framework, we construct a number of practical schemes for simulating realistic systems such as nanoscopic electronic devices. Computational cost of each scheme is analyzed, with the expected level of accuracy discussed. As a demonstration, a simulation based on the adiabatic wide-band limit approximation scheme is carried out to characterize the transient current response of a carbon nanotube based electronic device under time-dependent external voltages.
The Fenna-Matthews-Olson (FMO) light-harvesting complex is now one of the primary model systems for the study of excitation energy transfer (EET). However, the mechanism of the EET in this system is still controversial. In this work, molecular dynamics simulations and the electrostatic-embedding quantum-mechanics/molecular-mechanics single-point calculations have been employed to predict the energy transfer pathways utilizing the polarized protein-specific charge (PPC), which provides a more realistic description of Coulomb interaction potential in the protein than conventional mean-field charge scheme. The recently discovered eighth pigment has also been included in this study. Comparing with the conventional mean-field charges, more stable structures of FMO complex were found under PPC scheme during molecular dynamic simulation. Based on the electronic structure calculations, an exciton model was constructed to consider the couplings during excitation. The results show that pigments 3 and 4 dominate the lowest exciton levels whereas the highest exciton level are mainly constituted of pigments 1 and 6. This observation agrees well with the assumption based on the spatial distribution of the pigments. Moreover, the obtained spectral density in this study gives a reliable description of the diverse local environment embedding each pigment.
We use first-principles quantum mechanics to simulate the transient electrical response through carbon nanotube-based conductors under time-dependent bias voltages. The dynamic admittance and time-dependent charge distribution are reported and analyzed. We find that the electrical response of these two-terminal molecular devices can be mapped onto an equivalent classical electric circuit and that the switching time of these end-on carbon nanotube devices is only a few femtoseconds. This result is confirmed by studying the electric response of a simple two-site model device and is thus generalized to other two-terminal molecular electronic devices.
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