Effect Of Charge Distribution Research Articles

Effects of charge distribution and degree of methylesterification of pectin emulsifier on bioaccessibility of curcumin incorporated in nanoemulsions

The objectives of this study were to elucidate the effects of degree of methyl esterification (DM) and charge distribution of pectin on the stability of emulsions and to analyze bioaccessibility of curcumin incorporated in emulsions stabilized by pectins. Three commercial pectins, CP72 (DM72), CP50 (DM50), and CP7 (DM7), were used. MP50 (DM50) with consecutive demethylesterified galacturonic acid residues was prepared from CP72 via demethylesterification to induce different charge distributions. Emulsions containing curcumin were prepared and were stored for 30 days. The CP72 and CP50 emulsions remained relatively stable for 30 days. However, MP50 and CP7 were less effective at forming stable emulsions. When the pectin emulsions passed through each phase of the simulated gastrointestinal tract (GIT), the CP72 and CP50 emulsions retained their initial droplet structures after in vitro mouth and gastric digestion, whereas the MP50 and CP7 emulsions exhibited gel-like clusters, although the gel-like formation of MP50 was distinct from that observed in CP7. MP50 emulsion showed a high degree of final lipid digestion and high bioaccessibility of curcumin while CP72 emulsion displayed a low degree of final lipid digestion. CP50 exhibited low bioaccessibility of curcumin, which might have been contributed by its fast lipid digestion profiles.

Effects of Surface Charge Distribution and Electrolyte Ions on the Nonlinear Spectra of Model Solid-Water Interfaces.

Molecular dynamics simulations of model charged solid/water interfaces were carried out to provide insight about the relationship between the second-order nonlinear susceptibility χ(2) and the structure of the interfacial water layer. The results of the calculations reveal that the density fluctuations of water extend to about 12 Å from the surface regardless of the system, while the orientational ordering of molecules is long-ranged and is sensitive to the presence of electrolytes. The charge localization on the surface was found to affect only the high-frequency part of the Im[χ(2)] spectrum, and the addition of salt has very little effect on the spectrum of the first water layer. For solid/neat water interfaces, the spectroscopically active part of the liquid phase has a thickness largely exceeding the region of density fluctuations, and this long-ranged nonlinear activity is mediated by the electric field of the molecules. The electrolyte ions and their hydration shells act in a destructive way on the molecular field. This effect, combined with the screening of the surface charge by ions, drastically reduces the thickness of the spectroscopic diffuse layer. There is an electrolyte concentration at which the nonlinear response of the diffuse layer is suppressed and the χ(2) spectrum of the interface essentially coincides with that of the first water layer.

Ion current rectification coupled with asymmetric temperature and surface charge in ultrashort conical nanopores

Ion current rectification (ICR) is one of the electrodynamic properties in asymmetric nanochannels, which has been utilized to develop biosensors, heavy metal ion detection, and ion diodes. Previous studies on ICR mainly focused on long nanopores (length >500 nm), and relatively few studies on ion rectification performance in short nanopores. Here, we use a finite element numerical solution to simulate the effect of coupling asymmetric temperature and surface charge distribution on the ion rectification performance of ultrashort conical nanopores (length = 100 nm). The results show that the ion rectification performance is significantly improved when the inner and outer surfaces of the nanopore are charged non-uniformly, which is more than three times that when the inner surface of the nanopore is charged non-uniformly or the outer surface is charged non-uniformly. In addition, the positive temperature difference enhances the ion enrichment and dissipation and improves the ion rectification performance of nanopores. On the contrary, negative temperature difference inhibits ion enrichment and dissipation in pores, which is not conducive to improving ion rectification performance. Abnormal behavior is observed for nanopores non-uniform charged only on the outer wall surface, where the negative temperature gradient enhances the accumulation and dissipation of ions within the pores, thereby increasing the rectification ratio. In addition, in order to more clearly understand the ion transport behavior in the ultrashort nanopore under asymmetric temperature conditions, we further investigated the influence of the tip radius of the nanopore, the solution volume concentration, and the charge type of each surface charge distribution on the ion current rectification performance. The results reveal the ion transport mechanism of ultrashort conical nanopores and provide practical guidance for designing and optimizing nanofluidic devices.

Optimal photoelectron circular dichroism of a model chiral system.

We optimize the internuclear geometry and electronic structure of a model chiral system to achieve a maximal photoelectron circular dichroism (PECD) in its one-photon ionization by circularly polarized light. The electronic structure calculations are performed by the single center method, while the optimization is done using quantum alchemy employing a Taylor series expansion. Thereby, the effect of bond lengths and uncompensated charge distributions on the chiral response of the model is investigated theoretically in some detail. It is demonstrated that manipulating a chiral asymmetry of the ionic potential may enhance the dichroic parameter (i.e., the PECD) of the randomly oriented model system well beyond β1 = 25%. Furthermore, we demonstrate that quantum alchemy is applicable to PECD despite the unusually strong coupling of spatial and electronic degrees of freedom and discuss the relative impact of the individual degrees of freedom in this model system. We define the necessary conditions for the computational design of PECD for real (non-model) chiral molecules using our approach.

Osteogenic differentiation of human mesenchymal stem cells on electroactive substrates

This study investigates the effect of electroactivity and electrical charge distribution on the biological response of human bone marrow stem cells (hBMSCs) cultured in monolayer on flat poly(vinylidene fluoride), PVDF, substrates. Differences in cell behaviour, including proliferation, expression of multipotency markers CD90, CD105 and CD73, and expression of genes characteristic of different mesenchymal lineages, were observed both during expansion in basal medium before reaching confluence and in confluent cultures in osteogenic induction medium. The crystallisation of PVDF in the electrically neutral α-phase or in the electroactive phase β, both unpoled and poled, has been found to have an important influence on the biological response. In addition, the presence of a permanent positive or negative surface electrical charge distribution in phase β substrates has also shown a significant effect on cell behaviour.

Numerical Simulation of the Influence of Non-Uniform ζ Potential on Interfacial Flow.

Zeta potential (ζ potential) is a significant parameter to characterize the electric property of the electric double layer (EDL), which is important at the solid-liquid interface. Non-uniform ζ potential could be developed on a chemically uniform solid-liquid interface due to external flow. However, its influence on the flow has never been concerned. In this investigation, we numerically studied the influence of non-uniform 2D ζ potential on the flow at the solid-liquid interface. It is found, that even without any external electric field and only considering the influence of 2D ζ potential distribution, swirling flow can be generated near EDL, according to the rotational electric volume force. The streamwise vortices, which are important in the turbulent boundary layer, are theoretically predicted in this laminar flow model when considering the 2D distribution of ζ potential, implying the necessity of considering the origin of streamwise vortices of the turbulent boundary layer from the perspective of electrokinetic flow. In addition, the ζ potential distribution can promote the wall shear stress. Therefore, more attention must be paid to shear-sensitivity circumstances, like biomedical, medical devices, and in vivo. We hope that the current investigation can help us to better understand the effect of charge distribution on interfacial flow and provide theoretical guidance for the development of related applications in the future.

Electrically driven coalescence of charged conical droplet in non-uniform electric field

The dynamic behaviors of charged droplet coalescence in electric field has drawn much attention over the past decades due to its complex underlying physics and potential industrial application. This work experimentally investigated asymmetric coalescence dynamics of conical droplets in non-uniform electric field. With the effect of electric field, the cone apexes of deformed droplets merged with each other to form a liquid bridge that initially expanded but then retracted back gradually. It was found that the bridge length increased fast at initial conical coalescence and shrank slowly at retraction stage in various conditions. In addition, the effect of electric charge distribution and transportation on liquid bridge evolution behaviors was analyzed. The characteristics of cone angle and contact distance during droplet conical coalescence and recoil processes were quantitatively discussed with consideration of different parameters. Besides, the phase diagram for determining droplet coalescence and recoil was illustrated based on contact distance and electric Bond number, where the critical transition boundary was figured out with a linear increasing trend.

Refining antimicrobial photodynamic therapy: effect of charge distribution and central metal ion in fluorinated porphyrins on effective control of planktonic and biofilm bacterial forms

Antibiotic resistance represents a pressing global health challenge, now acknowledged as a critical concern within the framework of One Health. Photodynamic inactivation of microorganisms (PDI) offers an attractive, non-invasive approach known for its flexibility, independence from microbial resistance patterns, broad-spectrum efficacy, and minimal risk of inducing resistance. Various photosensitizers, including porphyrin derivatives have been explored for pathogen eradication. In this context, we present the synthesis, spectroscopic and photophysical characteristics as well as antimicrobial properties of a palladium(II)-porphyrin derivative (PdF2POH), along with its zinc(II)- and free-base counterparts (ZnF2POH and F2POH, respectively). Our findings reveal that the palladium(II)-porphyrin complex can be classified as an excellent generator of reactive oxygen species (ROS), encompassing both singlet oxygen (Φ△ = 0.93) and oxygen-centered radicals. The ability of photosensitizers to generate ROS was assessed using a variety of direct (luminescence measurements) and indirect techniques, including specific fluorescent probes both in solution and in microorganisms during the PDI procedure. We investigated the PDI efficacy of F2POH, ZnF2POH, and PdF2POH against both Gram-negative and Gram-positive bacteria. All tested compounds proved high activity against Gram-positive species, with PdF2POH exhibiting superior efficacy, leading to up to a 6-log reduction in S. aureus viability. Notably, PdF2POH-mediated PDI displayed remarkable effectiveness against S. aureus biofilm, a challenging target due to its complex structure and increased resistance to conventional treatments. Furthermore, our results show that PDI with PdF2POH is more selective for bacterial than for mammalian cells, particularly at lower light doses (up to 5 J/cm2 of blue light illumination). This enhanced efficacy of PdF2POH-mediated PDI as compared to ZnF2POH and F2POH can be attributed to more pronounced ROS generation by palladium derivative via both types of photochemical mechanisms (high yields of singlet oxygen generation as well as oxygen-centered radicals). Additionally, PDI proved effective in eliminating bacteria within S. aureus-infected human keratinocytes, inhibiting infection progression while preserving the viability and integrity of infected HaCaT cells. These findings underscore the potential of metalloporphyrins, particularly the Pd(II)-porphyrin complex, as promising photosensitizers for PDI in various bacterial infections, warranting further investigation in advanced infection models.Graphical abstract

Nuclear charge distribution effect on the shape for some even-even nuclide

Nuclear charge distribution effect on the shape for some even-even nuclide

Interfacial Se-O Bonds Modulating Spatial Charge Distribution in FeSe2/Nb:Fe2O3 with Rapid Hole Extraction for Efficient Photoelectrochemical Water Oxidation.

Surface engineering is an effective strategy to improve the photoelectrochemical (PEC) catalytic activity of hematite, and the defect states with abundant coordinative unsaturation atoms can serve as anchoring sites for constructing intimate connections between semiconductors. On this basis, we anchored an ultrathin FeSe2 layer on Nb5+-doped Fe2O3 (FeSe2/Nb:Fe2O3) via interfacial Se-O chemical bonds to tune the surface potential. Density functional theory (DFT) calculations indicate that amorphous FeSe2 decoration could generate electron delocalization over the composite photoanodes so that the electron mobility was improved to a large extent. Furthermore, electrons could be transferred via the newly formed Se-O bonds at the interface and holes were collected at the surface of electrode for PEC water oxidation. The desired charge redistribution is in favor of suppressing charge recombination and extracting effective holes. Later, work function calculations and Mott-Schottky (M-S) plots demonstrate that a type-II heterojunction was formed in FeSe2/Nb:Fe2O3, which further expedited carrier separation. Except for spatial carrier modulation, the amorphous FeSe2 layer also provided abundant active sites for intermediates adsorption according to the d band center results. In consequence, the target photoanodes attained an improved photocurrent density of 2.42 mA cm-2 at 1.23 V versus the reversible hydrogen electrode (RHE), 2.5 times as that of the bare Fe2O3. This study proposed a defect-anchoring method to grow a close-connected layer via interfacial chemical bonds and revealed the spatial charge distribution effects of FeSe2 on Nb:Fe2O3, giving insights into rational designation in composite photoanodes.

A simple approach to simulate corona-charged electret filters

This paper presents a novel computational model devised to simulate how different ways of corona-charging a fibrous filter can impact its aerosol collection efficiency. The model assigns different bipolar charges to the fibers in the media based on how the corona-generated negative ions impact these fibers they travel from the corona needles towards the grounded surface underneath the media. The charge assignment process is based on observations made from simulating the electrohydrodynamic field around the corona needles. With the fibers virtually charged, the trajectory of positively and negatively charged aerosol particles, ranging in size from 30 to 500 nm, were simulated across the filter thickness to quantify the effect of fiber charge distribution on the filter efficiency. The performance of our virtual filter was found to be better when it was exposed to the corona ions on both the face and back sides. More interestingly, it was found that the filtration efficiency of the filter was dependent on the order by which its face and back sides were charged. The filter was observed to capture smaller particles (less than 150 nm) more efficiently when it was first charged on the face side and then charged on the back side. The opposite effect was observed when the charging order was reversed. This difference in filtration performance was found to arise from the differences in the solid volume fraction of the filter across its thickness.

Adsorption of a Polyelectrolyte Chain at Dielectric Surfaces: Effects of Surface Charge Distribution and Relative Dielectric Permittivity

Adsorption of a Polyelectrolyte Chain at Dielectric Surfaces: Effects of Surface Charge Distribution and Relative Dielectric Permittivity

(Invited) Understanding the Effects of Charge Distribution on the Oxidation of Water

Water oxidation is an important first step of photosynthesis. Presently, it remains a challenge to carry out this reaction efficiently using low-cost materials. Among the questions that remain to be answered are the influences by charge distribution at or on the catalyst surfaces where water oxidation takes place. Recent literature has shown that the reaction can be sensitive to the charge density or the charge potential or both. Generally, high charge density or high charge potential favors faster kinetic constants. However, the existing studies face challenges as most of them were carried out on different materials that feature different chemical catalytic properties, as well. As such, it is not yet possible to definitely conclude the observed differences in water oxidation kinetics is necessarily a function of charge properties but not the inherent chemical catalytic differences. The study we plan to present addresses this issue. We used a catalyst system that features a well-defined catalytic center but employed supports that feature varying charge redistribution properties. This system allowed us to systematically compare how charge redistribution affects the water oxidation reactions. It was observed that when charge redistribution indeed plays an important role in defining the reaction kinetics, but it is so only when the subsequent chemical steps are fast. For the first time, we found a different dependence of the reaction kinetics on temperatures. Under otherwise identical conditions, comparable reaction kinetics were measured on ITO support and CeO2 support at room temperature. When the temperature increased to 50ºC, the reaction rate on ITO support increased to twice that on CeO2 support. The results shed new light on the role played by charge redistribution in governing reactions such as water oxidation.

A molecular dynamics study of cell-penetrating peptide transportan-10 (TP10): Binding, folding and insertion to transmembrane state in zwitterionic membrane

Transportan 10 (TP10) is a 21-residue, cationic, α-helical cell-penetrating peptide that can be used as a delivery vector for various bioactive molecules. Based on recent confocal microscopy studies, it is believed that TP10 can translocate across neutral lipid membrane passively, possibly as a monomer, without the formation of permanent pore. Here, we performed extensive molecular dynamics (MD) simulations of TP10W (Y3W variant of TP10) to find the microscopic details of binding, folding and insertion of TP10W to transmembrane state in POPC bilayer. Binding study with CHARMM36 force field showed that TP10W initially binds to the membrane surface in unstructured configuration, but it spontaneously folds into α-helical conformation under the lipid head groups. Further insertion of TP10W, changing from a surface bound state to a vertically oriented transmembrane state, was investigated via umbrella simulations. The resulting free energy profile shows a relatively small barrier between two states, suggesting a possible translocation pathway as a monomer. In fact, unbiased simulation of transmembrane TP10W revealed how a charged Lys side chain can move from one leaflet to the other without a significant free energy cost. Finally, we compared the results of TP10W simulations with those of point mutated variants (TP10W-K12A18 and TP10W-K19L) to understand the effect of charge distribution on the peptide. It was observed that such a conservative mutation can cause noticeable changes in the conformations of both surface bound and transmembrane states. The results of present study will be discussed in relation to the experimentally observed activities of TP10W against neutral membrane.

Charge equilibration model with shielded long-range Coulomb for reactive molecular dynamics simulations.

Atomic description of electrochemical systems requires reactive interaction potential to explicitly describe the chemistry between atoms and molecules and the evolving charge distribution and polarization effects. Calculating Coulomb electrostatic interactions and polarization effects requires a better estimate of the partial charge distribution in molecular systems. However, models such as reactive force fields and charge equilibration (QEq) include Coulomb interactions up to a short-distance cutoff for better computational speeds. Ignoring long-distance electrostatic interaction affects the ability to describe electrochemistry in large systems. We studied the long-range Coulomb effects among charged particles and extended the QEq method to include long-range effects. By this extension, we anticipate a proper account of Coulomb interactions in reactive molecular dynamics simulations. We validate the approach by computing charges on a series of metal-organic frameworks and some simple systems. Results are compared to regular QEq and quantum mechanics calculations. The study shows slightly overestimated charge values in the regular QEq approach. Moreover, our method was combined with Ewald summation to compute forces and evaluate the long-range effects of simple capacitor configurations. There were noticeable differences between the calculated charges with/without long-range Coulomb interactions. The difference, which may have originated from the long-range influence on the capacitor ions, makes the Ewald method a better descriptor of Coulomb electrostatics for charged electrodes. The approach explored in this study enabled the atomic description of electrochemical systems with realistic electrolyte thickness while accounting for the electrostatic effects of charged electrodes throughout the dielectric layer in devices like batteries and emerging solid-state memory.

A Temperature and Voltage Coupling Equivalent Electrical Behavior Model of Lithium‐Ion Battery Pack for Electric Unmanned Aerial Vehicle under Variable Load Conditions

It is a valuable and challenge problem to reveal the coupling mechanism between heat and electricity in lithium‐ion battery under variable load conditions. A temperature–voltage coupling equivalent electrical behavior model for lithium‐ion battery under variable load conditions is established to describe the electrical behavior of the battery by analyzing the effect of temperature on particle motion, the effect of particle motion on charge distribution, and the effect of charge distribution on the electrical behavior of the battery and to accurately portray the temperature and voltage coupling mechanism. In the model, heat is taken as the state variable of lithium‐ion battery, and the relationship between the external temperature and voltage is described. The model is verified by simulation and measured data of lithium‐ion battery used in electric unmanned aerial vehicles. The results indicate that the established temperature–voltage coupling model can accurately describe the electrical behavior of the battery and can accurately reveal the coupling relationship between temperature and voltage, and the effect of temperature on the electrical behavior of the battery reflected by the model is basically consistent (voltage and temperature mean absolute percentage error is 5.50% and 2.02%, respectively) with the measured data.

Molecular dynamics simulation of desalination process using polyoxometalate ionic liquid confined in carbon nanotubes

In this work, the effect of positioning of [Keggin][emim]3 ionic liquid (IL) into carbon nanotubes (CNTs) with different concentrations has been examined in the desalination process at different external pressures using molecular dynamics (MD) simulations. Another membrane was also modelled composed of four similar CNTs with almost equal space from each other. Using of only Keggin anions into the charged CNT was also studied in the desalination process. To study the mechanism of the water and ions fluxes, the potential of mean force, average number of hydrogen bonds, and self-diffusion coefficient have been also computed and discussed. The results showed that the placing of [Keggin][emim]3 IL into a CNT decreases the water flux (Nwaterns=74at150MPa) relative to the empty CNT (Nwaterns=834). However, the four CNTs configuration shows increase in the water flux (Nwaterns=183at150MPa) than the one CNT system. The placing of one polyoxometallate IL into the CNT increases the salt rejection 10 to 20 times than the empty-CNT system at low and high pressures, respectively. Moreover, positioning of the two ILs results in the complete salt rejection at all pressures. These results indicate that the use of polyoxometalate ILs into the CNT efficiently increases the salt rejection. The self-diffusion of confined water molecules in the single IL-CNT composite (D = 0.73 × 10-9 m2/s) is also smaller than the empty CNT at 150 MPa (D = 1.89 × 10-9 m2/s). The results also indicated that using of the Keggin anions into the charged CNT leads to the more water flux (Nwaterns=250at150MPa) and complete salt rejection relative to the fixing of [Keggin][emim]3 IL into the uncharged CNT. The effects of CNT charge distributions, temperature, and CNT chirality have been also examined on the desalination process.

Analytical and Numerical Investigation of Nanowire Transistor X-ray Detector

Recently, nanowire detectors have been attracting increasing interest thanks to their advantages of high resolution and gain. The potential of using nanowire detectors is investigated in this work by developing a physically based model for Indium Phosphide (InP) phototransistor as well as by performing TCAD simulations. The model is based on solving the basic semiconductor equations for bipolar transistors and considering the effects of charge distribution on the bulk and on the surface. The developed model also takes into consideration the impact of surface traps, which are induced by photogenerated carriers situated at the surface of the nanowire. Further, photogating phenomena and photodoping are also included. Moreover, displacement damage (DD) is also investigated; an issue arises when the detector is exposed to repeated doses. The presented analytical model can predict the current produced from the incident X-ray beam at various energies. The calculation of the gain of the presented nanowire carefully considers the different governing effects at several values of energies as well as biasing voltage and doping. The proposed model is built in MATLAB, and the validity check of the model results is achieved using SILVACO TCAD device simulation. Comparisons between the proposed model results and SILVACO TCAD device simulation are provided and show good agreement.

Computational study of physicochemical, optical, and thermodynamic properties of 2,2-dimethylchromene derivatives.

A large number of heterocyclic compounds are used as drugs, mainly due to the duality of lipophilicity playing in hydrophobic interactions and solubility with at least one hydrogen bond acceptor. The study of electronic properties is then important to better understand not only these charge distribution effects but also some other physicochemical properties involved in bioactivity to directly assess the bioavailability of these compounds and a possible classification in related applications. Phytomolecules such as chromenes are very accessible molecules exhibiting a bioactivity. Our study is focused on the impact of a number of functional groups acting on some 2,2-dimethylchromene derivatives, namely their global reactivity from the frontier molecular orbitals and local reactivity from the Fukui functions, where the carbonyl group acting as an electron withdrawal group has the most relevant effect, the solubility from the partition coefficient Log P strongly depending on the charge distribution and electronegative sites, the optical effects from the delocalization in the vinyl group, as well as the evaluation of the entropy associated with the molecular flexibility also acting on the bioactivity. Despite the effects of the wave function or density methods on the order of magnitude of these properties, these compounds are consistent with the rules for a potential oral drug candidate. The calculations of the electronic properties were performed through two levels of theory: Hartree-Fock level as a wave function-based method as an ab initio reference including some physically consistent eigenvalues and density functional theory DFT as a correlation consistent method using different functionals: hybrid or with a long-range correction. The basis set used is a 6-311++G(d,p) Pople basis set including diffuse and polarization basis functions. The basis set is adapted to the size of the molecules and consequently to the degree of electronic localization. Gaussian 09 software was used for the computation.

The Effect of Positive Charge Distribution on the Cryoprotective Activity of Dehydrins.

Dehydrins are intrinsically disordered proteins expressed ubiquitously throughout the plant kingdom in response to desiccation. Dehydrins have been found to have a cryoprotective effect on lactate dehydrogenase (LDH) in vitro, which is in large part influenced by their hydrodynamic radius rather than the order of the amino acids within the sequence (alternatively, this may be a sequence specific effect). However, it seems that a different mechanism may underpin the cryoprotection that they confer to the cold-labile yeast frataxin homolog-1 (Yfh1). Circular dichroism spectroscopy (CD) was used to assess the degree of helicity of Yfh1 at 1 °C, both alone and in the presence of several dehydrin constructs. Three constructs were compared to the wild type: YSK2-K→R (lysine residues substituted with arginine), YSK2-Neutral (locally neutralized charge), and YSK2-SpaceK (evenly distributed positive charge). The results show that sequence rearrangements and minor substitutions have little impact on the ability of the dehydrin to preserve LDH activity. However, when the positive charge of the dehydrin is locally neutralized or evenly distributed, the dehydrin becomes less efficient at promoting structure in Yfh1 at low temperatures. This suggests that a stabilizing, charge-based interaction occurs between dehydrins and Yfh1. Dehydrins are intrinsically disordered proteins, expressed by certain organisms to improve desiccation tolerance. These proteins are thought to serve many cellular roles, such as the stabilization of membranes, DNA, and proteins. However, the molecular mechanisms underlying the function of dehydrins are not well understood. Here, we examine the importance of positive charges in dehydrin sequences by making substitutions and comparing their effects in the cryoprotection of two different proteins.