Catalyst-Free Plasma Enhanced Growth of Graphene from Sustainable Sources.

Details of a fast and sustainable bottom-up process to grow large area high quality graphene films without the aid of any catalyst are reported in this paper. We used Melaleuca alternifolia, a volatile natural extract from tea tree plant as the precursor. The as-fabricated graphene films yielded a stable contact angle of 135°, indicating their potential application in very high hydrophobic coatings. The electronic devices formed by sandwiching pentacene between graphene and aluminum films demonstrated memristive behavior, and hence, these graphene films could find use in nonvolatile memory devices also.

Analysis of Carrier Transport of Organic Devices by Using Nonlinear Optical Polarization.

In this review, we discuss the Maxwell-Wagner (MW) effect model analysis of organic devices and time-resolved optical second harmonic generation (TR-EFISHG) measurement that is available for directly probing carrier motion in organic semiconductor devices. Using these, we show that organic field effect transistor as well organic double-layer device operation is analyzed well, and we can make clear the mechanism of these organic devices' operation. Finally, we conclude that the dielectric physics approach using the MW model analysis and the TR-EFISHG experiment is useful to study carrier transport mechanism of organic devices.

Energetic alignment in nontoxic SnS quantum dot-sensitized solar cell employing spiro-OMeTAD as the solid-state electrolyte.

An environmentally friendly solid-state quantum dot sensitized solar cell (ss-QDSSC) was prepared by combining colloidal SnS QDs as the sensitizer and organic hole scavenger spiro-OMeTAD (2,2',7,7'-tetrakis-(N,N-di-p-methoxyphenylamine)9,9'-spirobifluorene) as the solid-state electrolyte, and the energy alignment of SnS and TiO2 was investigated. The bandgap of colloidal SnS QDs increased with decreasing particle size from 14 to 4 nm due to an upshift of the conduction band and a downshift of the valence band. In TiO2/SnS heterojunctions, the conduction band minimum (CBM) difference between TiO2 and SnS was as large as ∼0.8 eV; this difference decreased with decreasing particle size, but was sufficient for electron injection from SnS nanoparticles of any size into TiO2. Meanwhile, the sensitizer regeneration driving force, that is, the difference between the valence band maximum (VBM) of SnS and the work function of the electrolyte, showed an opposite behaviour with the SnS size due to a downward shift of the SnS VB. Consequently, smaller SnS QDs should result in a more efficient charge transfer in heterojunctions, revealing the advantages of QDs vs larger particles as sensitizers. This prediction was confirmed by the improved photovoltaic performance of ss-QDSSCs modified with SnS nanoparticles, which peaked for 5-6 nm sized SnS nanoparticles due to the balance between electron injection and sunlight absorption.

A Review of Contact Electrification at Diversified Interfaces and Related Applications on Triboelectric Nanogenerator.

The triboelectric nanogenerator (TENG) can effectively collect energy based on contact electrification (CE) at diverse interfaces, including solid-solid, liquid-solid, liquid-liquid, gas-solid, and gas-liquid. This enables energy harvesting from sources such as water, wind, and sound. In this review, we provide an overview of the coexistence of electron and ion transfer in the CE process. We elucidate the diverse dominant mechanisms observed at different interfaces and emphasize the interconnectedness and complementary nature of interface studies. The review also offers a comprehensive summary of the factors influencing charge transfer and the advancements in interfacial modification techniques. Additionally, we highlight the wide range of applications stemming from the distinctive characteristics of charge transfer at various interfaces. Finally, this review elucidates the future opportunities and challenges that interface CE may encounter. We anticipate that this review can offer valuable insights for future research on interface CE and facilitate the continued development and industrialization of TENG.

Novel same-metal three electrode system for cyclic voltammetry studies.

Conventional three-electrode systems used in electrochemical measurement demand time-consuming and maintenance intensive procedures to enable accurate and repeatable electrochemical measurements. Traditionally, different metal configurations are used to establish the electrochemical gradient required to acquire the redox activity, and vary between different electrochemical measurement platforms. However, in this work, we report using the same metal (gold) for the counter, working and reference electrodes fabricated on a miniaturized printed circuit board (PCB) for a much simpler design. Potassium ferricyanide, widely used as a redox probe for electrochemical characterization, was utilized to acquire cyclic voltametric profiles using both the printed circuit board-based gold-gold-gold three-electrode and conventional three-electrode systems (glassy carbon electrode or graphite foil as the working electrode, platinum wire as the counter electrode, and Ag/AgCl as the reference electrode). The results show that both types of electrode systems generated similar cyclic voltammograms within the same potential window (-0.5 to +0.7 V). However, the novel PCB-based same-metal three-electrode electrochemical cell only required a few activation cycles and exhibited impressive cyclic voltametric repeatability with higher redox sensitivity and detection window, while using only trace amounts of solutions/analytes.

The use of marine microalgae in microbial fuel cells, photosynthetic microbial fuel cells and biophotovoltaic platforms for bioelectricity generation.

Algal green energy has emerged as an alternative to conventional energy production using fossil fuels. Microbial fuel cells (MFCs), photosynthetic microbial fuel cells (PMFCs) and biophotovoltaic (BPV) platforms have been developed to utilize microalgae for bioelectricity generation, wastewater treatment and biomass production. There remains a lack of research on marine microalgae in these systems, so to the best of our knowledge, all information on their integration in these systems have been gathered in this review, and are used to compare with the interesting studies on freshwater microalgae. The performance of the systems is extremely reliant on the microalgae species and/or microbial community used, the size of the bio-electrochemical cell, and electrode material and distance used. The mean was calculated for each system, PMFC has the highest average maximum power density of 344 mW/m2, followed by MFC (179 mW/m2) and BPV (58.9 mW/m2). In addition, the advantages and disadvantages of each system are highlighted. Although all three systems face the issue of low power outputs, the integration of a suitable energy harvester could potentially increase power efficiency and make them applicable for lower power applications.

Langmuir-Blodgett Graphene-Based Films for Algal Biophotovoltaic Fuel Cells.

The prevalence of photosynthesis, as the major natural solar energy transduction mechanism or biophotovoltaics (BPV), has always intrigued mankind. Over the last decades, we have learned to extract this renewable energy through continuously improving solid-state semiconductive devices, such as the photovoltaic solar cell. Direct utilization of plant-based BPVs has, however, been almost impracticable so far. Nevertheless, the electrochemical platform of fuel cells (FCs) relying on redox potentials of algae suspensions or biofilms on functionalized anode materials has in recent years increasingly been demonstrated to produce clean or carbon-negative electrical power generators. Interestingly, these algal BPVs offer unparalleled advantages, including carbon sequestration, bioremediation and biomass harvesting, while producing electricity. The development of high performance and durable BPVs is dependent on upgraded anode materials with electrochemically dynamic nanostructures. However, the current challenges in the optimization of anode materials remain significant barriers towards the development of commercially viable technology. In this context, two-dimensional (2D) graphene-based carbonaceous material has widely been exploited in such FCs due to its flexible surface functionalization properties. Attempts to economically improve power outputs have, however, been futile owing to molecular scale disorders that limit efficient charge coupling for maximum power generation within the anodic films. Recently, Langmuir-Blodgett (LB) film has been substantiated as an efficacious film-forming technique to tackle the above limitations of algal BPVs; however, the aforesaid technology remains vastly untapped in BPVs. An in-depth electromechanistic view of the fabrication of LB films and their electron transference mechanisms is of huge significance for the scalability of BPVs. However, an inclusive review of LB films applicable to BPVs has yet to be undertaken, prohibiting futuristic applications. Consequently, we report an inclusive description of a contextual outline, functional principles, the LB film-formation mechanism, recent endeavors in developing LB films and acute encounters with prevailing BPV anode materials. Furthermore, the research and scale-up challenges relating to LB film-integrated BPVs are presented along with innovative perceptions of how to improve their practicability in scale-up processes.

Study of relaxation process of dipalmitoyl phosphatidylcholine monolayers at air-water interface: effect of electrostatic energy.

The instability of organic monolayer composed of polar molecules at the air-water interface has been a spotlight in interface science for many decades. However, the effect of electrostatic energy contribution to the free energy in the system is still not understood. Herein, we investigate the mechanical and electrical properties by studying the isobaric relaxation process of a dipalmitoyl phosphatidylcholine monolayer on water subphase with various concentrations of divalent ions to reveal the effect of electrostatic energy on thermodynamics and kinetics of the collapse mechanism. Our results demonstrate that electrical energy among the dipolar molecules plays an important role in the stability of monolayer and enhances the formation of micelles into subphase under high pressure. In addition, to confirm the electrostatic energy contribution, the well-known thermal effect on the stability of the film is compared. Hence, the general description of the monolayer free energy with contribution of electrostatic energy is suggested to describe the phase transition.

Nonmechanical pumping principle in submicrosized devices.

Dynamic field pumping principle has been developed utilizing the interactions of both the director and velocity fields and temperature-redistribution across a two-dimensional (2D) homogeneously aligned liquid crystal (HALC) film under the influence both of a heat flow directed normal to the upper bounding surface, whereas on the lower bounding surface, the temperature is kept constant, and the normally directed electric field, due to electric double layers, i.e., a shielding layers that is naturally created within the liquid crystal (LC) near a charged surfaces. Calculations, based on the nonlinear extension of the classical Ericksen-Leslie theory, shows that the HALC material under the influence of the heat flow start moving in the horizontal direction. After turning off the heat flow, the HALC drop settles down to the rest, and the temperature field across the LC film is finally downfall to the value of temperature on the lower bounding surface. The role of hydrodynamic flow in the relaxation processes of the temperature field to its equilibrium distribution across the 2D HALC film, containing 4-n-pentyl-4(')-cyanobiphenyl, has been investigated for a number of dynamic regimes.

Dipolar electrostatic energy effect on relaxation process of monolayers at air-water interface: analysis of thermodynamics and kinetics.

In order to understand the effect of electrostatic energy on phase transition from monolayer to multilayer, isobaric relaxation process of Langmuir monolayers composed of stearic acid or ferroelectric polyvinylidene fluoride and trifluoroethylene copolymer with various vinylidene fluoride (VDF) ratios is investigated in terms of thermodynamic and kinetic analysis. A monotonous decreasing tendency of material loss with respect to temperature is observed for stearic acid monolayer, which is due to thermal activation effect on phase transition from monolayer to multilayer. In contrast, for the ferroelectric monolayer it presents a nonmonotonous behavior of losing materials with a peak position near the Curie temperature, which is not only owing to thermal activation but also dipole moment change. This observation is confirmed for the copolymer monolayers with other VDF content ratios. Amazingly, for the ferroelectric monolayers a good correspondence is found for critical temperatures evaluated from several independent methods including the analysis on slow collapse. This finding again tells the fact that the relaxation process, namely phase transition from monolayer to multilayer, is greatly influenced by dipolar electrostatic energy. Moreover, the study of time dependent relaxation process reveals a diffusionlike behavior of multilayer structure formation, which cannot be interpreted by classical models. Hence a new model based on diffusion-driven material transfer is proposed and diffusivity of the copolymer molecules is estimated with a value of 0.4x10(-5) cm(2)/s. As a whole, this research reflects the importance of dipolar electrostatic energy for phase transition of monolayers at air-water interface.

Effect of external electrostatic charge on condensed phase domains at the air-water interface: Experiment and shape equation analysis.

The effect of external electrostatic charge on the shapes of liquid condensed (LC) phase domains in monolayer at the air/water interface was investigated. For this reason the thermodynamic properties, domain size, and spontaneous polarization were analyzed by surface pressure-area isotherms, Brewster angle microscopy (BAM), and Maxwell displacement current technique. The analysis indicated magnesium ions preferred to bond with dipalmitoyl phosphatidylcholine negative head group in liquid expanded phase and/or at domain boundary at low ion concentration and got an access to binding with molecules inside of the LC domains for higher ion concentration. Domain size increase characterized by BAM was discussed in respect to the shape equation on the basis of electrostatic energy contribution. Although molecular repulsive force increased by adding of ions into subphase, the growth of domain size exceeded this tendency. Following shape equation analysis it was suggested that this effect corresponded to change in dipole moment orientation represented by increase in spontaneous polarization in normal projection. This demonstrated impact of local electrostatic field on molecular dipoles and free energy of LC domains.

Anisotropic spatial coherence of ongoing and spontaneous activities in auditory cortex.

We carried out voltage-sensitive dye imaging of the guinea pig auditory cortex to determine whether the ongoing and spontaneous activities of the cortex exhibit spatial coherence reflecting the tonotopic organization of the cortex. We used independent component analysis and a signal-plus-noise model to extract ongoing activities from the observed signals including physiological noise and stimulus-evoked activities. We analyzed the cross-correlations of background activities between all pairs of recording channels and found that ongoing and spontaneous activities in the auditory cortex exhibited anisotropic spatial coherence extending along the isofrequency bands.

Electrostatic Maxwell stress model of the shapes of condensed phase domains in monolayers at the air-water interface.

The formation mechanism of the shapes of condensed phase domains in monolayers at the air-water interface was investigated taking into account the surface pressure, line tension, and electrostatic energy due to the spontaneous polarization generated in normal and in-plane direction. By deriving the shape equation of monolayer domains as the mechanical balance at the domain boundary, we found that the electrostatic energy contributes to the shape equation as electrostatic Maxwell stress. Development of a cusp from condensed phase domains of fatty acid monolayers, which has been experimentally observed, was analyzed by the shape equation. It was found that the development of a cusp originated from the strong Maxwell stress, which was induced by the non-uniform orientational distribution in the fatty acid domain, and that cusped shapes gave a minimum of the free energy of the domain. It demonstrates that the shape equation with Maxwell stress, which is derived in the present study, is useful to study the formation mechanism of the shapes of condensed phase domains in monolayers.

Shear-induced domain deformation in a tilted lipid monolayer: from circle to ellipse and kinked stripe.

The shear-induced domain deformation in a lipid monolayer comprised of tilted molecules is studied as a mechanical balance between surface pressure, line tension, electrostatic energy due to the dipole-dipole interaction, hexatic-elastic stress, and viscous stress. It is found that a simple shear can deform a circular domain into an elliptic shape with the long axis inclined 45 degrees from the shear direction. The "ellipse" is elongated in the long axis as shear rate increases, and evolves to a straight or kinked stripe, which was observed as a "shear band" by Fuller's group [Science 274, 233 (1996)] and "avalanche-like fronts" by Schwaltz's group [Langmuir 17, 3017 (2001)], at a threshold shear rate. The propagation of stripe-shaped domains is discussed in the context of electrostatic energy. The dependence of the threshold shear rate on surface pressure is predicted in good agreement with observation and can be used to estimate surface viscosity. The shear-induced domain deformation is maintained by the effect of the lattice elastic stress when shear ceases.

Publisher Correction: Electronic Properties of Synthetic Shrimp Pathogens-derived DNA Schottky Diodes.

A correction to this article has been published and is linked from the HTML and PDF versions of this paper. The error has not been fixed in the paper.

Electronic Properties of Synthetic Shrimp Pathogens-derived DNA Schottky Diodes.

The exciting discovery of the semiconducting-like properties of deoxyribonucleic acid (DNA) and its potential applications in molecular genetics and diagnostics in recent times has resulted in a paradigm shift in biophysics research. Recent studies in our laboratory provide a platform towards detecting charge transfer mechanism and understanding the electronic properties of DNA based on the sequence-specific electronic response, which can be applied as an alternative to identify or detect DNA. In this study, we demonstrate a novel method for identification of DNA from different shrimp viruses and bacteria using electronic properties of DNA obtained from both negative and positive bias regions in current-voltage (I-V) profiles. Characteristic electronic properties were calculated and used for quantification and further understanding in the identification process. Aquaculture in shrimp industry is a fast-growing food sector throughout the world. However, shrimp culture in many Asian countries faced a huge economic loss due to disease outbreaks. Scientists have been using specific established methods for detecting shrimp infection, but those methods do have their significant drawbacks due to many inherent factors. As such, we believe that this simple, rapid, sensitive and cost-effective tool can be used for detection and identification of DNA from different shrimp viruses and bacteria.

Optical second harmonic generation imaging for visualizing in-plane electric field distribution.

The electric field distribution in electronic devices, particularly in the organic devices, was visualized by the optical second harmonic generation (SHG) imaging technique on the basis of electric field induced SHG (EFISHG). Two-dimensional SHG images from organic field effect transistor using pentacene were taken with a cooled CCD camera, and the SHG images showed the electric field was successfully visualized with a resolution of 1 mum. The SHG imaging method provides us a novel technique for visualizing the electric field distribution in actual devices under device operation.

Effect of backflow on the orientational and dissipation processes in Langmuir films.

The numerical study of the system of hydrodynamic equations that include both director motion and fluid flow, for a number of dynamic regimes in the 4-n -pentyl- 4' -cyanobiphenyl multilayer film on the water surface has been carried out. Calculations show that the relaxation time over which the torques exerted per unit of liquid crystals volume puts the director n[over] to be normal to the air-water interface, is one order of magnitude less in the case of accounting for the backflow effect than without accounting for that effect. The role of the charged water surface potential on the orientational relaxation process in the 5CB multilayer film on the water surface also has been investigated.

Dynamic disorder in receptor-ligand forced dissociation experiments.

Recently experiments showed that some biological noncovalent bonds increase their lifetimes when they are stretched by an external force, and their lifetimes will decrease when the force increases further. Several specific quantitative models have been proposed to explain the intriguing transitions from the "catch bond" to the "slip bond." In this work we propose that the dynamic disorder of the force-dependent dissociation rate can account for the counterintuitive behaviors of the bonds. A Gaussian stochastic rate model is used to quantitatively describe the transitions observed recently in the single bond P-selctin glycoprotein ligand 1-P-selectin force rupture experiment [Marshall, Nature 423, 190 (2003)]. Our model agrees well with the experimental data. We conclude that the catch bonds could arise from the stronger positive correlation between the height of the intrinsic energy barrier and the distance from the bound state to the barrier; classical pathway scenario or a priori catch bond assumption is not essential.

Optical second-harmonic generation measurement for probing organic device operation.

We give a brief overview of the electric-field induced optical second-harmonic generation (EFISHG) technique that has been used to study the complex behaviors of organic-based devices. By analyzing EFISHG images of organic field-effect transistors, the in-plane two-dimensional distribution of the electric field in the channel can be evaluated. The susceptibility tensor of the organic semiconductor layer and the polarization of the incident light are considered to determine the electric field distribution. EFISHG imaging can effectively evaluate the distribution of the vectorial electric field in organic films by selecting a light polarization. With the time-resolved technique, measurement of the electric field originating from the injected carriers allows direct probing of the carrier motion under device operation, because the transient change of the electric field distribution reflects the carrier motion. Some applications of the EFISHG technique to organic electronic devices are reviewed.