Heterogeneous Electrocatalytic Oxygen Evolution Reaction by a Sol-Gel Electrode with Entrapped Na3[Ru2(μ-CO3)4]: The Effect of NaHCO3

The Na₃[Ru₂(μ-CO₃)₄] complex is acting as a water oxidation catalyst in a homogeneous system. Due to the significance of heterogeneous systems and the effect of bicarbonate on the kinetic, we studied the bicarbonate effect on the heterogeneous electrocatalyst by entrapping the Na₃[Ru₂(μ-CO₃)₄] complex in a sol-gel matrix. We have developed two types of sol-gel electrodes, which differ by the precursor, and are demonstrating their stability over a minimum of 200 electrochemical cycles. The pH increases affected the currents and k_cat for both types of electrodes, and their hydrophobicity, which was obtained from the precursor type, influenced the electrocatalytic process rate. The results indicate that NaHCO₃ has an important role in the catalytic activity of the presented heterogeneous systems; without NaHCO₃, the diffusing species is probably OH⁻, which undergoes diffusion via the Grotthuss mechanism. To the best of our knowledge, this is the first study to present a simple and fast one-step entrapment process for the Na₃[Ru₂(μ-CO₃)₄] complex by the sol-gel method under standard laboratory conditions. The results contribute to optimizing the WSP, ultimately helping expand the usage of hydrogen as a green and more readily available energy source.     

Probing Electronic Symmetry Reduction during Charge Migration via Time-Resolved X-Ray Diffraction

The present work focuses on probing ultrafast charge migration after symmetry-breaking excitation using ultrashort laser pulses. LiCN is chosen as prototypical system because it can be oriented in the laboratory frame and it possesses optically-accessible charge transfer states at low energies. The charge migration is simulated within the hybrid time-dependent density functional theory/configuration interaction framework. Time-resolved electronic current densities and simulated time-resolved x-ray diffraction signals are used to unravel the mechanism of charge migration. Our simulations demonstrate that specific choices of laser polarization lead to a control over the symmetry of the induced charge migration. Moreover, time-resolved x-ray diffraction signals are shown to encode transient symmetry reduction at intermediate times.     

Discovery Through Gossip

We study randomized gossip‐based processes in dynamic networks that are motivated by information discovery in large‐scale distributed networks such as peer‐to‐peer and social networks. A well‐studied problem in peer‐to‐peer networks is resource discovery, where the goal for nodes (hosts with IP addresses) is to discover the IP addresses of all other hosts. Also, some of the recent work on self‐stabilization algorithms for P2P/overlay networks proceed via discovery of the complete network. In social networks, nodes (people) discover new nodes through exchanging contacts with their neighbors (friends). In both cases the discovery of new nodes changes the underlying network — new edges are added to the network — and the process continues in the changed network. Rigorously analyzing such dynamic (stochastic) processes in a continuously changing topology remains a challenging problem with obvious applications. This paper studies and analyzes two natural gossip‐based discovery processes. In the push discovery or triangulation process, each node repeatedly chooses two random neighbors and connects them (i.e., “pushes” their mutual information to each other). In the pull discovery process or the two‐hop walk, each node repeatedly requests or “pulls” a random contact from a random neighbor and connects itself to this two‐hop neighbor. Both processes are lightweight in the sense that the amortized work done per node is constant per round, local, and naturally robust due to the inherent randomized nature of gossip. Our main result is an almost‐tight analysis of the time taken for these two randomized processes to converge. We show that in any undirected n‐node graph both processes take rounds to connect every node to all other nodes with high probability, whereas is a lower bound. We also study the two‐hop walk in directed graphs, and show that it takes time with high probability, and that the worst‐case bound is tight for arbitrary directed graphs, whereas Ω(n²) is a lower bound for strongly connected directed graphs. A key technical challenge that we overcome in our work is the analysis of a randomized process that itself results in a constantly changing network leading to complicated dependencies in every round. We discuss implications of our results and their analysis to discovery problems in P2P networks as well as to evolution in social networks. © 2016 Wiley Periodicals, Inc. Random Struct. Alg., 48, 565–587, 2016     

A Novel Trihybrid Material Based on Renewables: An Efficient Recyclable Heterogeneous Catalyst for C−C Coupling and Reduction Reactions

The generation of organic–inorganic hybrid materials from renewable resources and their utilization in basic and applied areas has been at the forefront of research in recent years for sustainable development. Herein, a novel organic–inorganic trihybrid material was synthesized by in situ generation of palladium nanoparticles (PdNPs) in a hybrid gel matrix based on renewable chemicals. Constituents of the hybrid gel included a pentacyclic triterpenoid arjunolic acid extractable from Terminalia arjuna and the leaf extract of Chrysophyllum cainito rich in flavonoids. We took advantage of the presence of flavonoid molecules in this hybrid gel to generate an advanced trihybrid gel through in situ reduction of doped Pd^II salts to stable PdNPs. The xerogel of this trihybrid material was used as a recyclable heterogeneous catalyst for C?C coupling and reduction reactions in aqueous media. We also demonstrated that the in situ generated PdNPs containing trihybrid material was a more efficient catalyst than the trihybrid material generated with presynthesized PdNPs.     

All-atom de novo protein folding with a scalable evolutionary algorithm

The search for efficient and predictive methods to describe the protein folding process at the all-atom level remains an important grand-computational challenge. The development of multi-teraflop architectures, such as the IBM BlueGene used in this study, has been motivated in part by the large computational requirements of such studies. Here we report the predictive all-atom folding of the forty-amino acid HIV accessory protein using an evolutionary stochastic optimization technique. We implemented the optimization method as a master-client model on an IBM BlueGene, where the algorithm scales near perfectly from 64 to 4096 processors in virtual processor mode. Starting from a completely extended conformation, we optimize a population of 64 conformations of the protein in our all-atom free-energy model PFF01. Using 2048 processors the algorithm predictively folds the protein to a near-native conformation with an RMS deviation of 3.43 A in < 24 h.     

Glycal glycosylation and 2-nitroglycal concatenation, a powerful combination for mucin core structure synthesis

A 3,4-O-unprotected galactal derivative having bulky 6-O-TIPS protection (compound 2) could be regioselectively 3-O-glycosylated with O-(galactopyranosyl) trichloroacetimidates; depending on the protecting group pattern stereoselectively alpha- and beta-linked disaccharides were obtained. With O-(2-azido-2-deoxyglucopyransyl) trichloroacetimidate as donor (compound 10A), glycosylation of 2 and of a 6-O-unprotected galactal derivative led in acetonitrile as solvent exclusively to a beta(1-3)- and a beta(1-6)-linked disaccharide, respectively. Nitration of the galactal moieties of the saccharides followed by Michael-type addition of serine and threonine derivatives (7a,b) installed the alpha-galacto-configuration, thus readily furnishing O-glycosyl amino acid building blocks for the incorporation of core 1, core 2, core 3, core 6, and core 8 structures into glycopeptides. 2-Nitrogalactal and 2-nitroglucal derivatives could be also successfully employed in glycoside bond formation via Michael-type addition in a reiterative manner, affording the corresponding core 5, core 7, and core 6 building blocks. In this approach, highly stereoselective glycoside bond formations were based exclusively on Michael-type addition to the nitro-enol ether moiety of the 2-nitroglycals. Hence, 2-nitroglycals are versatile intermediates for base-catalyzed glycoside bond formation.     

Plasma-induced graft copolymerization of poly(methacrylic acid) on electrospun poly(vinylidene fluoride) nanofiber membrane

Electrospun nanofibrous membranes (ENM) which have a porous structure have a huge potential for various liquid filtration applications. In this paper, we explore the viability of using plasma-induced graft copolymerization to reduce the pore sizes of ENMs. Poly(vinylidene) fluoride (PVDF) was electrospun to produce a nonwoven membrane, comprised of nanofibers with diameters in the range of 200-600 nm. The surface of the ENM was exposed to argon plasma and subsequently graft-copolymerized with methacrylic acid. The effect of plasma exposure time on grafting was studied for both the ENM and a commercial hydrophobic PVDF (HVHP) membrane. The grafting density was quantitatively measured with toluidine blue-O. The degree of grafting increased steeply with an increase in plasma exposure time for the ENM, attaining a maximum of 180 nmol/mg after 120 s of plasma treatment. However, the increase in the grafting density on the surface of the HVHP membrane was not as drastic, reaching a plateau of 65 nmol/mg after 60 s. The liquid entry permeation of water dropped extensively for both membranes, indicating a change in surface properties. Field emission scanning electron microscopy micrographs revealed an alteration in the surface pore structure for both membranes after grafting. Bubble point measurements of the ENM reduced from 3.6 to 0.9 um after grafting. The pore-size distribution obtained using the capillary flow porometer for the grafted ENM revealed that it had a similar profile to that of a commercial hydrophilic commercial PVDF (HVLP) membrane. More significantly, water filtration studies revealed that the grafted ENM had a better flux throughput than the HVLP membrane. This suggests that ENMs can be successfully engineered through surface modification to achieve smaller pores while retaining their high flux performance.     

Self-assembled hybrid polymer-TiO2 nanotube array heterojunction solar cells

Films comprised of 4 microm long titanium dioxide nanotube arrays were fabricated by anodizing Ti foils in an ethylene glycol based electrolyte. A carboxylated polythiophene derivative was self-assembled onto the TiO2 nanotube arrays by immersing them in a solution of the polymer. The binding sites of the carboxylate moiety along the polymer chain provide multiple anchoring sites to the substrate, making for a stable rugged film. Backside illuminated liquid junction solar cells based on TiO2 nanotube films sensitized by the self-assembled polymeric layer showed a short-circuit current density of 5.5 mA cm-2, a 0.7 V open circuit potential, and a 0.55 fill factor yielding power conversion efficiencies of 2.1% under AM 1.5 sun. A backside illuminated single heterojunction solid state solar cell using the same self-assembled polymer was demonstrated and yielded a photocurrent density as high as 2.0 mA cm-2. When a double heterojunction was formed by infiltrating a blend of poly(3-hexylthiophene) (P3HT) and C60-methanofullerene into the self-assembled polymer coated nanotube arrays, a photocurrent as high as 6.5 mA cm-2 was obtained under AM 1.5 sun with a corresponding efficiency of 1%. The photocurrent action spectra showed a maximum incident photon-to-electron conversion efficiency (IPCE) of 53% for the liquid junction cells and 25% for the single heterojunction solid state solar cells.