Energetics and kinetics of Li intercalation in irradiated graphene scaffolds

In the present study we investigate the irradiation-defects hybridized graphene scaffold as one potential building material for the anode of Li-ion batteries. Designating the Wigner V22 defect as a representative, we illustrate the interplay of Li atoms with the irradiation-defects in graphene scaffolds. We examine the adsorption energetics and diffusion kinetics of Li in the vicinity of a Wigner V22 defect using density functional theory calculations. The equilibrium Li adsorption sites at the defect are identified and shown to be energetically preferable to the adsorption sites on pristine (bilayer) graphene. Meanwhile the minimum energy paths and corresponding energy barriers for Li migration at the defect are determined and computed. We find that while the defect is shown to exhibit certain trapping effects on Li motions on the graphene surface, it appears to facilitate the interlayer Li diffusion and enhance the charge capacity within its vicinity because of the reduced interlayer spacing and characteristic symmetry associated with the defect. Our results provide critical assessment for the application of irradiated graphene scaffolds in Li-ion batteries.Comment: 23 pages, 5 figure

Scheduling with Rate Adaptation under Incomplete Knowledge of Channel/Estimator Statistics

In time-varying wireless networks, the states of the communication channels are subject to random variations, and hence need to be estimated for efficient rate adaptation and scheduling. The estimation mechanism possesses inaccuracies that need to be tackled in a probabilistic framework. In this work, we study scheduling with rate adaptation in single-hop queueing networks under two levels of channel uncertainty: when the channel estimates are inaccurate but complete knowledge of the channel/estimator joint statistics is available at the scheduler; and when the knowledge of the joint statistics is incomplete. In the former case, we characterize the network stability region and show that a maximum-weight type scheduling policy is throughput-optimal. In the latter case, we propose a joint channel statistics learning - scheduling policy. With an associated trade-off in average packet delay and convergence time, the proposed policy has a stability region arbitrarily close to the stability region of the network under full knowledge of channel/estimator joint statistics.Comment: 48th Allerton Conference on Communication, Control, and Computing, Monticello, IL, Sept. 201

Strong and Confined Acids Enable a Catalytic Asymmetric Nazarov Cyclization of Simple Divinyl Ketones

We report a catalytic asymmetric Nazarov cyclization of simple, acylic, alkyl-substituted divinyl ketones using our recently disclosed strong and confined imidodiphosphorimidate Brønsted acids. The corresponding monocyclic cyclopentenones are formed in good yields and excellent regio-, diastereo-, and enantioselectivities. Further, the chemical utility of the obtained enantiopure cyclopentenones is demonstrated

Tetanic Stimulation Leads to Increased Accumulation of Ca^(2+)/Calmodulin-Dependent Protein Kinase II via Dendritic Protein Synthesis in Hippocampal Neurons

mRNA for the ɑ-subunit of CaMKII is abundant in dendrites of neurons in the forebrain (Steward, 1997). Here we show that tetanic stimulation of the Schaffer collateral pathway causes an increase in the concentration of ɑ-CaMKII in the dendrites of postsynaptic neurons. The increase is blocked by anisomycin and is detected by both quantitative immunoblot and semiquantitative immunocytochemistry. The increase in dendritic ɑ-CaMKII can be measured 100-200 µm away from the neuronal cell bodies as early as 5 min after a tetanus. Transport mechanisms for macromolecules from neuronal cell bodies are not fast enough to account for this rapid increase in distal portions of the dendrites. Therefore, we conclude that dendritic protein synthesis must produce a portion of the newly accumulated CaMKII. The increase in concentration of dendritic CaMKII after tetanus, together with the previously demonstrated increase in autophosphorylated CaMKII (Ouyang et al., 1997), will produce a prolonged increase in steady-state kinase activity in the dendrites, potentially influencing mechanisms of synaptic plasticity that are controlled through phosphorylation by CaMKII

Visualization of the distribution of autophosphorylated calcium/calmodulin-dependent protein kinase II after tetanic stimulation in the CA1 area of the hippocampus

Autophosphorylation of calcium/calmodulin-dependent protein kinase II (CaMKII) at threonine-286 produces Ca2+-independent kinase activity and has been proposed to be involved in induction of long-term potentiation by tetanic stimulation in the hippocampus. We have used an immunocytochemical method to visualize and quantify the pattern of autophosphorylation of CaMKII in hippocampal slices after tetanization of the Schaffer collateral pathway. Thirty minutes after tetanic stimulation, autophosphorylated CaM kinase II (P-CaMKII) is significantly increased in area CA1 both in apical dendrites and in pyramidal cell somas. In apical dendrites, this increase is accompanied by an equally significant increase in staining for nonphosphorylated CaM kinase II. Thus, the increase in P-CaMKII appears to be secondary to an increase in the total amount of CaMKII. In neuronal somas, however, the increase in P-CaMKII is not accompanied by an increase in the total amount of CaMKII. We suggest that tetanic stimulation of the Schaffer collateral pathway may induce new synthesis of CaMKII molecules in the apical dendrites, which contain mRNA encoding its alpha-subunit. In neuronal somas, however, tetanic stimulation appears to result in long-lasting increases in P-CaMKII independent of an increase in the total amount of CaMKII. Our findings are consistent with a role for autophosphorylation of CaMKII in the induction and/or maintenance of long-term potentiation, but they indicate that the effects of tetanus on the kinase and its activity are not confined to synapses and may involve induction of new synthesis of kinase in dendrites as well as increases in the level of autophosphorylated kinase