Quasi-Free Electron States Responsible for Single-Molecule Conductance Enhancement in Stable Radical.

Stable organic radicals, which possess half-filled orbitals in the vicinity of the Fermi energy, are promising candidates for electronic devices. In this Letter, using a combination of scanning-tunneling-microscopy-based break junction (STM-BJ) experiments and quantum transport theory, a stable fluorene-based radical is investigated. We demonstrate that the transport properties of a series of fluorene derivatives can be tuned by controlling the degree of localization of certain orbitals. More specifically, radical 36-FR has a delocalized half-filled orbital resulting in Breit-Wigner resonances, leading to an unprecedented conductance enhancement of 2 orders of magnitude larger than the neutral nonradical counterpart (36-FOH). In other words, conversion from a closed-shell fluorene derivative to the free radical in 36-FR opens an electron transport path which massively enhances the conductance. This new understanding of the role of radicals in single-molecule junctions opens up a novel design strategy for single-molecule-based spintronic devices.

Hydrogen-bond-induced quantum interference in single-molecule junctions of regioisomers.

Solvents can play a significant role in tuning the electrical conductance of single-molecule junctions. In this respect, protic solvents offer the potential to form hydrogen bonds with molecular backbones and induce electrostatic gating via their dipole moments. Here we demonstrate that the effect of hydrogen bond formation on conductance depends on whether transport through the junction is controlled by destructive quantum interference (DQI) or constructive quantum interference (CQI). Furthermore, we show that a protic solvent can be used to switch the conductance of single-molecule junctions between the two forms of quantum interference. To explore this possibility, two regioisomers (BIT-Zwitterion and BIT-Neutral) were synthesized and their single-molecule conductances in aprotic and protic solvents were investigated using a scanning-tunneling-microscope-based break junction technique, combined with density functional theory and quantum transport theory. We find that the protic solvent twists the geometry of BIT-Zwitterion by introducing intermolecular hydrogen bonds between the solvent and target molecule. Moreover, it increases the energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the molecule by imposing different electrostatic gating on the delocalized HOMO and localized LUMO, leading to a lower conductance compared to that in aprotic solvent. In contrast, the conductance of BIT-Neutral increases due to a transformation from DQI to CQI originating from a change from a planar to a folded conformation in the protic solvent. In addition, the stacking between the two folded moieties produces an extra through-space transport path, which further contributes to conductance. This study demonstrates that combinations of protic solvents and regioisomers present a versatile route to controlling quantum interference and therefore single-molecule conductance, by enabling control of hydrogen bond formation, electrostatic gating and through-space transport.

Using Lagrangian coherent structures to analyze fluid mixing by cilia.

Motivated by the desire to understand the fluid flow within the airway surface liquid of the lung, we consider the flow generated by a computational model of a motile, internally actuated cilium. The cilium, along with a mucus layer modeled by linear elastic elements, is coupled to a viscous, incompressible fluid. The evolution of this coupled system is captured using an immersed boundary method. The Eulerian velocity field computed on a grid is used to compute finite-time Lyapunov exponent fields, whose maximal ridges identify Lagrangian coherent structures (LCSs). The computed LCS uncovers a barrier that separates a recirculation region of fluid that remains near the beating cilium from fluid that is advected downstream. Moreover, periodic stretching and folding of this region gives rise to complex mixing. Flow structures around a cilium propelling a mucus layer are compared to flow structures around a cilium with no mucus load.

Regiocontrolled dimerization of asymmetric diazaheptacene derivatives toward X-shaped porous semiconductors.

Conformationally rigid X-shaped PAHs are attracting interest due to their self-assembly into unique networks and as models to study through-space exciton and charge delocalization in one single molecule. We report here the synthesis of X-shaped PAHs by dimerization of diazaheptacene diimides. The diimide groups are employed to effectively direct the self-assembly into antiparallel dimer aggregates, which assist the compounds to undergo a regiocontrolled [4 + 4] dimerization, leading to an X-shaped conformation bearing electron-poor and -rich subunits. The resulting PAHs are found to pack in 2D layers with large open channels and infinite π⋯π arrays. Furthermore, these highly crystalline porous materials serve as electron-transporting materials in OFETs due to the long-range π-stacked arrays in the layers. This work presents a potentially generalizable strategy, which may provide a unique class of porous semiconductors for organic devices, taking advantage of their open channels.

The correlations among wastewater internal energy, energy consumption and energy recovery/production potentials in wastewater treatment plant: An assessment of the energy balance.

Given the economic and environmental importance of energy use in wastewater treatment plants (WWTPs), the need to assess the energy balance of WWTPs has become a growing concern. Previous studies have suggested that energy balance or even net energy production may be achieved in WWTPs under specific conditions. However, information regarding the energy consumption and the energy recovery/production potential in WWTPs as a function of the influent characteristics is still very limited. In this paper, by exploring the correlations among wastewater internal energy, energy consumption and energy recovery in WWTPs, a novel net energy consumption (NEC) model was developed for predicting the energy self-sufficiency level of WWTPs. From our results, exponential regression showed a high accuracy in predicting the annual energy consumption, the annual excess sludge production and the bioreactor footprints in WWTPs. Wastewater with more internal energy which is determined by influent chemical oxygen demand (COD) concentration and flow rate, not only leads to higher energy consumption in WWTPs, but also results in an increase in the excess sludge production, bioreactor footprints and wastewater volume. This means that the WWTPs could achieve energy saving or even net energy production by incorporating sludge incineration, photovoltaic (PV) generation and thermal energy recovery. By combing regression analysis with theoretical formula, the annual net energy demand of WWTPs reached -0.187-0.466 kWh·m-3 in the range of wastewater condition studied (the influent COD concentration range of 60-800 mg·L-1 and the flow rate range of 1296-100,000 m3·d-1). The NEC model reveals that the net zero energy consumption may be achieved by integrating the better understandings of wastewater internal energy, energy conversion methods and environmental media energy, which is of value to policy makers for the planning of new WWTPs and provides theoretical support for the selection of available energy recovery methods.

Fluid dynamic models of flagellar and ciliary beating.

We have developed a fluid-mechanical model of a eucaryotic axoneme that couples the internal force generation of dynein molecular motors, the passive elastic mechanics of microtubules, and forces due to nexin links with a surrounding incompressible fluid. This model has been used to examine both ciliary beating and flagellar motility. In this article, we show preliminary simulation results for sperm motility in both viscous and viscoelastic fluids, as well as multiciliary interaction with a mucus layer.

An integrative computational model of multiciliary beating.

The coordinated beating of motile cilia is responsible for ovum transport in the oviduct, transport of mucus in the respiratory tract, and is the basis of motility in many single-celled organisms. The beating of a single motile cilium is achieved by the ATP-driven activation cycles of thousands of dynein molecular motors that cause neighboring microtubule doublets within the ciliary axoneme to slide relative to each other. The precise nature of the spatial and temporal coordination of these individual motors is still not completely understood. The emergent geometry and dynamics of ciliary beating is a consequence of the coupling of these internal force-generating motors, the passive elastic properties of the axonemal structure, and the external viscous, incompressible fluid. Here, we extend our integrative model of a single cilium that couples internal force generation with the surrounding fluid to the investigation of multiciliary interaction. This computational model allows us to predict the geometry of beating, along with the detailed description of the time-dependent flow field both near and away from the cilia. We show that synchrony and metachrony can, indeed, arise from hydrodynamic coupling. We also investigate the effects of viscosity and neighboring cilia on ciliary beat frequency. Moreover, since we have precise flow information, we also measure the dependence of the total flow pumped per cilium per beat upon parameters such as viscosity and ciliary spacing.