Variation Of Charge Density Research Articles

Anomalous scattering and transport in chiral matter

Chiral anomaly modifies the scattering processes in chiral systems. These processes can be investigated using the Maxwell-Chern-Simons theory that couples electrodynamics to the pseudoscalar field θ describing the topological charge induced by external sources. Assuming slow variation of the topological charge density, the fermion scattering cross section is computed in the Born approximation and is found to have a resonance at the scattering angles proportional to the chiral conductivity. As a result, the transport coefficients are suppressed at high temperatures, which may be a reason for the smallness of the Quark Gluon Plasma viscosity. The anisotropy of the cross section arises due to the spatial variation of the topological charge; its effect on the electrical conductivity is discussed.

Efficient Occlusion of Nanoparticles within Inorganic Single Crystals.

In principle, the incorporation of guest nanoparticles within host crystals should provide a straightforward and versatile route to a wide range of nanocomposite materials. However, crystallization normally involves expelling impurities, so nanoparticle occlusion is both counter-intuitive and technically challenging. Clearly, the nanoparticles should have a strong interaction with the growing crystalline lattice, but quantifying such an affinity has been challenging; the basic principles that govern efficient nanoparticle occlusion within inorganic single crystals are rather poorly understood. In the past few years, we have focused on the elucidation of robust design rules for such systems; our progress is summarized in this article.Polymerization-induced self-assembly (PISA) is widely recognized as a powerful platform technology for the preparation of a broad range of model organic nanoparticles. Herein, PISA was exploited to prepare sterically stabilized diblock copolymer nano-objects (e.g., spheres, worms, or vesicles) of varying size using steric stabilizers of well-defined chain length, variable anionic charge density, tunable surface density, and adjustable chemical functionality (e.g., carboxylic acid, phosphate, sulfate or sulfonate groups). Thus, we were able to systematically investigate how such structural parameters influence nanoparticle occlusion. Given its commercial importance for many industrial sectors, calcium carbonate was selected as the model host crystal for nanoparticle occlusion studies. Perhaps surprisingly, the extent of nanoparticle occlusion is not particularly sensitive to nanoparticle size or morphology. However, the steric stabilizer chain length can play a key role: relatively short chains lead to surface-confined occlusion, while sufficiently long chains enable uniform nanoparticle occlusion to be achieved throughout the crystal lattice (albeit sometimes inducing a significant change in crystal morphology). Optimizing the anionic charge density and surface density of the stabilizer chains is required to maximize the extent of nanoparticle occlusion, while steric stabilizer chains comprising anionic carboxylate groups led to greater occlusion compared to those composed of phosphate, sulfate, or sulfonate groups when examining a model vesicle system.Subsequently, our occlusion studies were extended to include functional hybrid nanocomposite crystals. For example, the spatially controlled occlusion of poly(glycerol monomethacrylate)-stabilized gold nanoparticles was achieved within semiconductive ZnO crystals by either controlling the nanoparticle concentration or by delaying their addition to the reaction mixture. Moreover, oil droplets of up to 500 nm have been incorporated into calcite crystals at up to 11% by mass, despite the large mismatch in surface energy between the hydrophobic oil droplets and the ionic crystal lattice. We have also explored a "Trojan horse" strategy, whereby cargos comprising nanoparticles or soluble dye molecules are first encapsulated within anionic block copolymer vesicles prior to their incorporation within calcite crystals. This approach offers a generic and efficient strategy for the occlusion of many types of guest species into single crystals. In summary, we have established important guidelines for efficient nanoparticle occlusion within crystals, which opens up new avenues for the synthesis of next-generation hybrid materials.

Simulation of cations separation through charged porous graphene membrane

Graphene membranes have shown promising prospects in cations separation; however, the underlying separation mechanisms remain elusive. In this study, the permeation of five cations through graphene membranes with variable pore size and surface charge density is explored by molecular simulations. It reveals that negatively charged graphene draws cations closer to the membrane. While positively charged graphene together with small-sized pores generates larger energy barriers, promoting the separation of different cation pairs. Result shows that the separation mechanisms are dominated by electrostatic interaction and steric hindrance. This theoretical work could guide the design of graphene membrane for desalination.

Controlling Surfactant Adsorption on Highly Charged Nanoparticles to Stabilize Bijels.

Bicontinuous particle-stabilized emulsions (bijels) are networks of interpenetrating oil/water channels with applications in catalysis, tissue engineering, and energy storage. Bijels can be generated by arresting solvent transfer induced phase separation (STrIPS) via interfacial jamming of nanoparticles. However, until now, STrIPS bijels have only been formed with silica nanoparticles of low surface charge densities, limiting their potential applications in catalysis and fluid transport. Here, we show how strongly charged silica nanoparticles can stabilize bijels. To this end, we carry out a systematic study employing dynamic light scattering, zeta potential, acid/base titrations, turbidimetry, surface tension, and confocal microscopy. We find that moderating the adsorption of oppositely charged surfactants on the particles is crucial to facilitate particle dispersibility in the bijel casting mixture and bijel stabilization. Our results potentially introduce a general understanding for bijel fabrication with different inorganic nanoparticle materials of variable charge density.

Investigating the Effect of Charged Components on Translocation of DNA Molecules in Track-Etched Nanopores

To understand and improve the translocation dynamics of nanopore based sensors, we studied theoretically the translocation of DNA molecules and compared them with experimental results. In our experimental studies, we used conically shaped track-etched polymer (i.e., PET) membrane and built our model based on its physical properties. Simulations were conducted by varying the surface charges of the nanopore and the particle, particle (i.e., DNA) position and applied potential to examine the translocational behavior of DNA and its effect on current-pulse shape. Our results showed that variations in surface and DNA charge density cause conductive distortions indicating the interaction between the surface and the DNA. It also confirmed that the DNA charge density does not remain in its native form in the solution as well as the pore charge during the translocation.

Contactless probing of graphene charge density variation in a controlled humidity environment

The electronic properties of graphene are highly sensitive to atoms and molecules adsorbed on its surface and to changes in its environment, such as temperature and humidity. In this paper, we examine the effect of humidity on the local carrier concentration of different types of graphene prepared by mechanical exfoliation, chemical vapour deposition and epitaxial growth on SiC, using in-situ Raman spectroscopy. We present a systematic and comparative study of the changes in Raman response using a vector analysis method to produce spatial maps of doping variation as a function of humidity. We also quantify the humidity induced carrier concentration change for different types of graphene. This study illustrates the effects of humidity on the electronic properties of graphene and provides a simple, contactless and quantitative method to directly evaluate water-induced doping effects in graphene, that are crucial for tailored device performance.

Effects of lignin structure and solvent on the formation rate of quinone methide under alkaline conditions

Abstract The purpose of this study was to examine how differences in the type of aromatic nucleus, side-chain structure and type of solvent affect the formation rate of quinone methide (QM) in the alkaline reaction of lignin. The reaction was done at a NaOH concentration of 1.0 mol l−1 and temperature of 75–140°C under an anaerobic condition. The formation rates of QM were in the order: syringyl > guaiacyl > p-hydroxyphenyl, when model compounds with lignin-type aromatic nuclei were compared. This and other results on various phenolic compounds suggested that the formation of QM is rapid from compounds having a high electron density in the aromatic π-electron system. The formation of QM was faster from a C6-C2-type than from a C6-C1-type lignin model compound, which was attributed to the fact that QM is an alkene and hence more stable when an unsaturated carbon in QM has an alkyl substituent, like the C6-C2-type compound. When aqueous 1,4-dioxane solutions with different 1,4-dioxane contents were used, the formation of QM became slower with increasing 1,4-dioxane content. This can be explained by the variation in the negative charge density in the rate-determining step, where the density is larger at the transition than at the initial state and consequently the activation energy is lower in a solvent with higher polarity.

Weak polyelectrolyte brushes: re-entrant swelling and self-organization.

We have studied the combined influence of pH and ionic strength on the properties of brushes of a weak polyion, poly(acrylic acid), in conditions of grafting density close to the mushroom-brush crossover. By combining atomic force microscopy AFM and quartz crystal microbalance, we show that at low ionic strengths the conformational change of grafted polyions is non-monotonic with increasing pH due to the counterintuitive variation of the ionization degree. Thus, reentrant swelling of the polymer chains is observed with increasing pH. This effect is more important at low polymer grafting densities, when it is accompanied by in-plane heterogeneous distribution at intermediate pH values. In addition, we observed self-assembly on the polymer brush (formation of holes and islands) at pH values below pKa, due to the short-range attractive interaction between uncharged grafted chains. The sensitivity of the ionization of grafted chains to the physicochemical environment was also studied by measuring the interaction force between a silica tip and polymer brushes by atomic force microscopy. The dependence of the ionization of polyions on the presence of the tip points toward important charge regulation effects, in particular at pH values corresponding to partial ionization of the polyion.

Measurements and simulations of surface radiation damage effects on IFX and HPK test structures

Radiation damage effects at High Luminosity LHC (HL-LHC) expected fluences and total ionizing doses (TID) will impose very stringent constraints in terms of radiation resistance of silicon detectors. In this work, we address the effects of surface damage on detectors fabricated on p-type substrates by two different foundries. Starting from standard test structure measurements, the interface trap state density and the oxide charge can be extracted for each specific foundry before and after irradiation with X-rays with doses ranging from 0.05 to 100 Mrad(SiO2). These parameters are then used as inputs to the Technology-CAD simulation tools, aiming at evaluating the effects of oxide charge density and interface trap density variation with the dose on MOS capacitor capacitances and interstrip resistances. The good agreement between simulation results and measurements would support the use of the model as a predictive tool to optimize the design and the operation of novel silicon detectors in the HL-LHC scenario.

Field-Flow Fractionation of Cationic Cellulose Derivatives

The asymmetric flow field-flow fractionation (AF4) method was developed for cationic cellulose derivatives. AF4 is the method of choice especially for high-molar mass samples, which are challenging to characterize with conventional chromatographic techniques such as size-exclusion chromatography (SEC). The cationic charge of macromolecules also complicates the size-based separations where no interaction between the analytes and the column stationary phase (SEC) or membrane (AF4) should occur. However, many column matrices and membranes carry negative charge and thus preventing interactions between cationic analytes and negatively charged separation support should be taken into consideration when doing method development. In this study, two eluent compositions, neutral and acidic, were tested for AF4 separation of cationic hydroxyethyl celluloses with varying charge densities. The eluent composition with a pH below the isoelectric point of regenerated cellulose membrane, which was used in this AF4 study, enabled the size-based separation with close to 100% analysis recovery. Macromolecular parameters (molar mass and radius of gyration) and conformation were investigated by coupling a multi-angle light scattering detector and differential refractometer to the AF4 system.

Optical manifestations of domains with constant topological charge density

Domains of finite topological charge density can exist in chiral materials and chiral matter. Spatial and temporal variation of the average topological charge density, represented by the $\theta$-field, induces anomalous currents that are responsible for the chiral magnetic effect, the anomalous Hall effect and other phenomena that are intimately related to the chiral anomaly. We consider domains with constant average topological charge density. We argue that even though the Maxwell equations in the bulk are not altered, the chiral anomaly manifests itself by the way of the boundary conditions. This is illustrated by several examples. The first example deals with the refraction of plane electromagnetic wave on a surface of a constant-$\theta$ domain. We derive the modified Fresnel equations and discuss the effect of the chiral anomaly on the amplitude and polarization of the reflected and transmitted waves. In particular, we argue that the Brewster's angle is sensitive to the value of $\theta$. In the second example we compute the spectrum of the transition radiation at high frequencies and show that it is enhanced at finite $\theta$.

Influence of polyelectrolyte structure and type on the degree of flocculation and rheological behavior of industrial MBR sludge

The influence of polyelectrolyte's type and structure on the rheological characteristics of industrial highly stable membrane bioreactor (MBR) sludge have been investigated and were related to its degree of flocculation and dewatering. The polyelectrolytes used for the conditioning of MBR sludge were polyacrylamides (PAMs) of varying charge density (CD), molecular weight (Mw) and molecular architecture, polydiallyldimethylammonium chloride (polyDADMAC) and polyamine. Rheological measurements showed that the MBR sludge with/without conditioning has a thixotropic (time-dependent) behavior with measurable yield stress. It exhibited a non-Newtonian shear thinning behavior and well represented by the Bingham model. The measurements of elastic (G′) and viscous (G″) moduli proved the viscoelastic solid-like behavior of the MBR sludge with/without conditioning (G′ > G″). Bingham yield stress, τo, viscosity, µ, and G′, were used for examining the rheological behavior of the conditioned MBR sludge. About 77–94% higher in τo, 86–96% in µ, and 76–92% in G′ were obtained by conditioning the sludge with different types of PAMs. These percentages vary depending on the type and structure of the PAMs. The highest τo, µ, and G′ was obtained by using a linear structure PAM, FO 4690 SSH. This behavior was in good agreement with flocs size, D50, zeta potential, ζ, and capillary suction time, CST. The results obtained by conditioning MBR sludge with different PAMs were compared with those obtained by conditioning with polyamine and polyDADMAC. Polyamine and polyDADMAC have raised the τo, µ and G′ of the MBR sludge by 52%, 84%, and 63%, respectively. Overall, MBR sludge conditioned with PAMs having a high CD in the case of high Mw (FO 4690 SSH, FO 4698 SSH) and low CD in the case of low Mw (FO 4498 XXR), resulted in greater τo, µ and G′ compare to those formed with polyamine and polyDADMAC. Therefore, PAMs are building a more compact network that highly reduces the trapped water within the sludge flocs.

Enhancement of Charge Transport in Polythiophene Semiconducting Polymer by Blending with Graphene Nanoparticles.

This paper describes a study on the charge transport in a composite of liquid-exfoliated graphene nanoparticles (GNPs) and a polythiophene semiconducting polymer. While the former component is highly conducting, although it consists of isolated nanostructures, the latter offers an efficient charge transport path between the individual GNPs within the film, overall yielding enhanced charge transport properties of the resulting bi-component system. The electrical characteristics of the composite layers were investigated by means of measurements of time-of-flight photoconductivity and transconductance in field-effect transistors. In order to analyze both phenomena separately, charge density and charge mobility contributions to the conductivity were singled out. With the increasing GNP concentration, the charge mobility was found to increase, thereby reducing the time spent by the carriers on the polymer chains. In addition, for GNP loading above 0.2 % (wt.), an increase of free charge density was observed that highlights an additional key role played by doping. Variable-range hopping model of a mixed two- and three-dimensional transport is explained using temperature dependence of mobility and free charge density. The temperature variation of free charge density was related to the electron transfer from polythiophene to GNP, with an energy barrier of 24 meV.

Strategic improvement of second and third harmonic generation in multifunctional Cu-Sn-S3 ternary semiconducting thin films

We propose a low-cost approach for the synthesis of multifunctional CuSnS3 (CTS) ternary compound thin film via spray pyrolysis technique. By varying Sn and S doping concentrations, a high energy absorber layers of CuSnS3 thin films were deposited on a glass substrate at a substrate temperature of 405 °C. The prepared samples were analysed with respect to their optical, structural and electrical and nonlinear optical properties. X-Ray diffraction (XRD) analysis reveals that the films exhibit a tetragonal crystal structure with a preferential growth orientation along (1 1 2). The surface morphology of the films was explored by atomic force microscopy (AFM) in tapping mode configuration. Variation in the carrier charge density and electrical properties were observed for different Sn and S combination. The analysis of the Raman spectra indicates the presence of multiple phases apart from CuSnS3. The obtained Raman spectra were assigned to phonon mode as per zone centre phonon representation of optical and acoustic modes and identified to dominant “A” symmetry modes. The maximal laser stimulated induced second harmonic generation (SHG) signal was observed for the CTS 3 film and the corresponding second order nonlinear optical susceptibility which was equal to about 0.89 pm/V at 1064 nm and the minimal SHG signal was found for the CTS 2 film (about 0.22 pm/V). This strategic improvement in SHG and third harmonic generation (THG) signal efficiency endorses the role of Sn and S in modulating second and third harmonic generations in CuSnS3 compound.

Surface charging on HVDC spacers considering time-varying effect of temperature and electric fields

The dynamic behavior of surface charging on spacers in DC-GILs can be influenced by multi-factors including the non-uniform distributed electric field as well as the time-varying temperature gradient. In this paper, the time-varying effect of surface charging phenomenon on spacers is studied and a time-varying mathematical model is established, based on the influence of temperature and electric field on the ion mobility at the gas phase and the bulk conductivity in the solid phase. The results verify that the bulk conductivity can be greatly influenced by temperature, which leads to an increase in the surface charge density on the spacer. This allows the surface charge accumulation to stabilize more quickly. However, the ion mobility from the gas phase is less affected by temperature. When the non-uniform distributed electric field changes from 1.3 to 6.4 kV/mm, ion mobility is less influenced and the surface charge density on the spacer varies slightly. In this case, the effects of the non-uniformly distributed electric field in surface charge density variation is much smaller and can be ignored.

A Theoretical Treatment of THz Resonances in Semiconductor GaAs p-n Junctions.

Semiconductor heterostructures are suitable for the design and fabrication of terahertz (THz) plasmonic devices, due to their matching carrier densities. The classical dispersion relations in the current literature are derived for metal plasmonic materials, such as gold and silver, for which a homogeneous dielectric function is valid. Penetration of the electric fields into semiconductors induces locally varying charge densities and a spatially varying dielectric function is expected. While such an occurrence renders tunable THz plasmonics a possibility, it is crucial to understand the conditions under which propagating resonant conditions for the carriers occur, upon incidence of an electromagnetic radiation. In this manuscript, we derive a dispersion relation for a p–n heterojunction and apply the methodology to a GaAs p–n junction, a material of interest for optoelectronic devices. Considering symmetrically doped p- and n-type regions with equal width, the effect of certain parameters (such as doping and voltage bias) on the dispersion curve of the p–n heterojunction were investigated. Keeping in sight the different effective masses and mobilities of the carriers, we were able to obtain the conditions that yield identical dielectric functions for the p- and n-regions. Our results indicated that the p–n GaAs system can sustain propagating resonances and can be used as a layered plasmonic waveguide. The conditions under which this is feasible fall in the frequency region between the transverse optical phonon resonance of GaAs and the traditional cut-off frequency of the diode waveguide. In addition, our results indicated when the excitation was slightly above the phonon resonance frequency, the plasmon propagation attained low-loss characteristics. We also showed that the existence or nonexistence of the depletion zone between the p- and n- interfaces allowed certain plasmon modes to propagate, while others decayed rapidly, pointing out the possibility for a design of selective filters.

Tc and Other Cuprate Properties in Relation to Planar Charges as Measured by NMR

Nuclear magnetic resonance (NMR) in cuprate research is a prominent bulk local probe of magnetic properties. NMR also, as was shown over the last years, actually provides a quantitative measure of local charges in the CuO 2 plane. This has led to fundamental insights, e.g., that the maximum T c is determined by the sharing of the parent planar hole between Cu and O. Using bonding orbital hole contents on planar Cu and O measured by NMR, instead of the total doping x, the thus defined two-dimensional cuprate phase diagram reveals significant differences between the various cuprate materials. Even more importantly, the reflected differences in material chemistry appear to set a number of electronic properties as we discuss here, for undoped, underdoped and optimally doped cuprates. These relations should advise attempts at a theoretical understanding of cuprate physics as well as inspire material chemists towards new high- T c materials. Probing planar charges, NMR is also sensitive to charge variations or ordering phenomena in the CuO 2 plane. Thereby, local charge order on planar O in optimally doped YBCO could recently be proven. Charge density variations seen by NMR in both planar bonding orbitals with amplitudes between 1% to 5% appear to be omnipresent in the doped CuO 2 plane, i.e., not limited to underdoped cuprates and low temperatures.

Role of Protein Self-Association on DNA Condensation and Nucleoid Stability in a Bacterial Cell Model.

Bacterial cells do not have a nuclear membrane that encompasses and isolates the genetic material. In addition, they do not possess histone proteins, which are responsible for the first levels of genome condensation in eukaryotes. Instead, there is a number of more or less specific nucleoid-associated proteins that induce DNA bridging, wrapping and bending. Many of these proteins self-assemble into oligomers. The crowded environment of cells is also believed to contribute to DNA condensation due to excluded volume effects. Ribosomes are protein-RNA complexes found in large concentrations in the cytosol of cells. They are overall negatively charged and some DNA-binding proteins have been reported to also bind to ribosomes. Here the effect of protein self-association on DNA condensation and stability of DNA-protein complexes is explored using Monte Carlo simulations and a simple coarse-grained model. The DNA-binding proteins are described as positively charged dimers with the same linear charge density as the DNA, described using a bead and spring model. The crowding molecules are simply described as hard-spheres with varying charge density. It was found that applying a weak attractive potential between protein dimers leads to their association in the vicinity of the DNA (but not in its absence), which greatly enhances the condensation of the model DNA. The presence of neutral crowding agents does not affect the DNA conformation in the presence or absence of protein dimers. For weakly self-associating proteins, the presence of negatively charged crowding particles induces the dissociation of the DNA-protein complex due to the partition of the proteins between the DNA and the crowders. Protein dimers with stronger association potentials, on the other hand, stabilize the nucleoid, even in the presence of highly charged crowders. The interactions between protein dimers and crowding agents are not completely prevented and a few crowding molecules typically bind to the nucleoid.

Charge-Density-Dominated Phase Behavior and Viscoelasticity of Polyelectrolyte Complex Coacervates

The composition dependence of the phase behavior and viscoelasticity of polyelectrolyte complex coacervates was investigated in a series of model acrylamide copolymers with varying charge density a...

Excited state intermolecular hydrogen bond’s effect on the luminescent behaviour of the 2D covalent organic framework (PPy-COF): A TDDFT insight

ABSTRACTThe theoretical investigation of electronically excited stated intermolecular hydrogen bonding dynamics of the 2D luminescent polypyrene covalent organic framework and methanol molecule (PPy-COF-MeOH) was performed using the density functional theory (DFT) and time-dependent (TD-DFT) method. The strengthening of Hydrogen bonds C-H---O-H and B-O---H-O upon photoexcitation was confirmed via comparison of geometric structures, electronic transition energies, 1H-NMR, binding energies, UV-Vis and infrared spectra in S0 and S1 states. Frontier molecular orbitals (MOs) analysis, electronic configuration, Mulliken charge analysis; and the charge density variation in hydrogen bonding proximity demonstrated that the strengthened hydrogen bonds facilitate the nonradiative path which may consequently proceed the luminescence quenching. Hence, the molecular material property prediction package (MOMAP) programme verified the fluorescence quenching because PPy-COF-MeOH complex showed a lower fluorescent rate constant compared to isolated PPy-COF fragment. The S1-T1 energy gap analysis also revealed the possibility of the Intersystem crossing (ISC). Above results significantly highlighted the role of the hydrogen bonding dynamics on luminescence property of the PPy-COF.