Microscopic Characterization of Individual Submicron Bubbles during the Layer-by-Layer Deposition: Towards Creating Smart Agents

NASA Astrophysics Data System (ADS)

Kato, Riku; Frusawa, Hiroshi

2015-07-01

We investigated the individual properties of various polyion-coated bubbles with a mean diameter ranging from 300 to 500 nm. Dark field microscopy allows one to track the individual particles of the submicron bubbles (SBs) encapsulated by the layer-by-layer (LbL) deposition of cationic and anionic polyelectrolytes (PEs). Our focus is on the two-step charge reversals of PE-SB complexes: the first is a reversal from negatively charged bare SBs with no PEs added to positive SBs encapsulated by polycations (monolayer deposition), and the second is overcharging into negatively charged PE-SB complexes due to the subsequent addition of polyanions (double-layer deposition). The details of these phenomena have been clarified through the analysis of a number of trajectories of various PE-SB complexes that experience either Brownian motion or electrophoresis. The contrasted results obtained from the analysis were as follows: an amount in excess of the stoichiometric ratio of the cationic polymers was required for the first charge-reversal, whereas the stoichiometric addition of the polyanions lead to the electrical neutralization of the PE-SB complex particles. The recovery of the stoichiometry in the double-layer deposition paves the way for fabricating multi-layered SBs encapsulated solely with anionic and cationic PEs, which provides a simple protocol to create smart agents for either drug delivery or ultrasound contrast imaging.

Microscopic Characterization of Individual Submicron Bubbles during the Layer-by-Layer Deposition: Towards Creating Smart Agents.

PubMed

Kato, Riku; Frusawa, Hiroshi

2015-07-08

We investigated the individual properties of various polyion-coated bubbles with a mean diameter ranging from 300 to 500 nm. Dark field microscopy allows one to track the individual particles of the submicron bubbles (SBs) encapsulated by the layer-by-layer (LbL) deposition of cationic and anionic polyelectrolytes (PEs). Our focus is on the two-step charge reversals of PE-SB complexes: the first is a reversal from negatively charged bare SBs with no PEs added to positive SBs encapsulated by polycations (monolayer deposition), and the second is overcharging into negatively charged PE-SB complexes due to the subsequent addition of polyanions (double-layer deposition). The details of these phenomena have been clarified through the analysis of a number of trajectories of various PE-SB complexes that experience either Brownian motion or electrophoresis. The contrasted results obtained from the analysis were as follows: an amount in excess of the stoichiometric ratio of the cationic polymers was required for the first charge-reversal, whereas the stoichiometric addition of the polyanions lead to the electrical neutralization of the PE-SB complex particles. The recovery of the stoichiometry in the double-layer deposition paves the way for fabricating multi-layered SBs encapsulated solely with anionic and cationic PEs, which provides a simple protocol to create smart agents for either drug delivery or ultrasound contrast imaging.

Surface analysis monitoring of polyelectrolyte deposition on Ba 0.5Sr 0.5TiO 3 thin films

NASA Astrophysics Data System (ADS)

Morales-Cruz, Angel L.; Fachini, Estevão R.; Miranda, Félix A.; Cabrera, Carlos R.

2007-09-01

Thin films are currently gaining interest in many areas such as integrated optics, sensors, friction, reducing coatings, surface orientation layers, and general industrial applications. Recently, molecular self-assembling techniques have been applied for thin film deposition of electrically conducting polymers, conjugated polymers for light-emitting devices, nanoparticles, and noncentrosymmetric-ordered second order nonlinear optical (NOL) devices. Polyelectrolytes self-assemblies have been used to prepare thin films. The alternate immersion of a charged surface in polyannion and a polycation solution leads usually to the formation of films known as polyelectrolyte multilayers. These polyanion and polycation structures are not neutral. However, charge compensation appears on the surface. This constitutes the building driving force of the polyelectrolyte multilayer films. The present approach consists of two parts: (a) the chemisorption of 11-mercaptoundecylamine (MUA) to construct a self-assembled monolayer with the consequent protonation of the amine, and (b) the deposition of opposite charged polyelectrolytes in a sandwich fashion. The approach has the advantage that ionic attraction between opposite charges is the driving force for the multilayer buildup. For our purposes, the multilayer of polyelectrolytes depends on the quality of the surface needed for the application. In many cases, this approach will be used in a way that the roughness factor defects will be diminished. The polyelectrolytes selected for the study were: polystyrene sulfonate sodium salt (PSS), poly vinylsulfate potassium salt (PVS), and polyallylamine hydrochloride (PAH), as shown in Fig. 1. The deposition of polyelectrolytes was carried out by a dipping procedure with the corresponding polyelectrolyte. Monitoring of the alternate deposition of polyelectrolyte bilayers was done by surface analysis techniques such as X-ray photoelectron spectroscopy (XPS), specular reflectance infrared (IR), and atomic force microscopy (AFM). The surface analysis results are presented through the adsorption steps of the polyelectrolytes layer by layer.

Electrostatic interaction between stereocilia: II. Influence on the mechanical properties of the hair bundle.

PubMed

Dolgobrodov, S G; Lukashkin, A N; Russell, I J

2000-12-01

This paper is based on our model [Dolgobrodov et al., 2000. Hear. Res., submitted for publication] in which we examine the significance of the polyanionic surface layers of stereocilia for electrostatic interaction between them. We analyse how electrostatic forces modify the mechanical properties of the sensory hair bundle. Different charge distribution profiles within the glycocalyx are considered. When modelling a typical experiment on bundle stiffness measurements, applying an external force to the tallest row of stereocilia shows that the asymptotic stiffness of the hair bundle for negative displacements is always larger than the asymptotic stiffness for positive displacements. This increase in stiffness is monotonic for even charge distribution and shows local minima when the negative charge is concentrated in a thinner layer within the cell coat. The minima can also originate from the co-operative effect of electrostatic repulsion and inter-ciliary links with non-linear mechanical properties. Existing experimental observations are compared with the predictions of the model. We conclude that the forces of electrostatic interaction between stereocilia may influence the mechanical properties of the hair bundle and, being strongly non-linear, contribute to the non-linear phenomena, which have been recorded from the auditory periphery.

Mixed polyanion glass cathodes: Effect of polyanion content

DOE PAGES

Kercher, Andrew K.; Kolopus, James A.; Sacci, Robert L.; ...

2017-02-18

Mixed polyanion glass cathodes in lithium-ion batteries have very high capacities (200-500 mAh/g), but currently these materials have fundamental problems with 1 st-cycle irreversible loss, cycling efficiency, and capacity fade. It is well established that polyanion substitutions into glasses can dramatically affect their physical properties, but the effect of polyanion content on the electrochemical performance has not been previously established. The proper amount of lithium and borate substitution in copper phosphate/vanadate glasses was shown to nearly eliminate 1 st-cycle irreversible loss and improve cycling efficiency. As a result, Raman and IR spectroscopy were used to identify polyanions that correlated withmore » electrochemical performance changes.« less

Preparation and characterization of chondroitin-sulfate-A-coated magnetite nanoparticles for biomedical applications

NASA Astrophysics Data System (ADS)

Tóth, Ildikó Y.; Illés, Erzsébet; Szekeres, Márta; Tombácz, Etelka

2015-04-01

Polysaccharides are promising candidates for manufacturing biocompatible core-shell nanoparticles with potential in vivo use. Superparamagnetic magnetite nanoparticles (MNPs) have prospective application in both diagnosis and therapy, and so developing a novel polysaccharide shell on MNP core is of great challenge. MNPs were prepared by co-precipitation, then the surface of purified MNPs was coated with chondroitin-sulfate-A (CSA) to obtain core-shell structured magnetite nanoparticles (CSA@MNP). The effect of the added amount of CSA on the surface charging and the aggregation state of MNPs at various pHs and 10 mM NaCl was measured by electrophoresis and dynamic light scattering. The amphoteric behavior of MNPs was fundamentally modified by adsorption of CSA polyanions. A very low CSA-loading induces the aggregation of MNPs, while four times more stabilizes the dispersions over the whole pH-range studied. The coagulation kinetics experiments measured at pH=6.3±0.3 showed that salt tolerance of CSA@MNPs rises up to ~150 mM NaCl.

Cationic cell-penetrating peptide binds to planar lipid bilayers containing negatively charged lipids but does not induce conductive pores.

PubMed

Gurnev, Philip A; Yang, Sung-Tae; Melikov, Kamran C; Chernomordik, Leonid V; Bezrukov, Sergey M

2013-05-07

Using a cation-selective gramicidin A channel as a sensor of the membrane surface charge, we studied interactions of oligoarginine peptide R9C, a prototype cationic cell-penetrating peptide (CPP), with planar lipid membranes. We have found that R9C sorption to the membrane depends strongly on its lipid composition from virtually nonexistent for membranes made of uncharged lipids to very pronounced for membranes containing negatively charged lipids, with charge overcompensation at R9C concentrations exceeding 1 μM. The sorption was reversible as it was removed by addition of polyanionic dextran sulfate to the membrane bathing solution. No membrane poration activity of R9C (as would be manifested by increased bilayer conductance) was detected in the charged or neutral membranes, including those with asymmetric negative/neutral and negative/positive lipid leaflets. We conclude that interaction of R9C with planar lipid bilayers does not involve pore formation in all studied lipid combinations up to 20 μM peptide concentration. However, R9C induces leakage of negatively charged but not neutral liposomes in a process that involves lipid mixing between liposomes. Our findings suggest that direct traversing of CPPs through the uncharged outer leaflet of the plasma membrane bilayer is unlikely and that permeabilization necessarily involves both anionic lipids and CPP-dependent fusion between opposing membranes. Copyright © 2013 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Unconventional Magnetism and Band Gap Formation in LiFePO4: Consequence of Polyanion Induced Non-planarity.

PubMed

Jena, Ajit; Nanda, B R K

2016-01-21

Oxygen plays a critical role in strongly correlated transition metal oxides as crystal field effect is one of the key factors that determine the degree of localization of the valence d/f states. Based on the localization, a set of conventional mechanisms such as Mott-Hubbard, Charge-transfer and Slater were formulated to explain the antiferromagnetic and insulating (AFI) phenomena in many of these correlated systems. From the case study on LiFePO4, through density-functional calculations, we demonstrate that none of these mechanisms are strictly applicable to explain the AFI behavior when the transition metal oxides have polyanions such as (PO4)(3-). The symmetry-lowering of the metal-oxygen complex, to stabilize the polyanion, creates an asymmetric crystal field for d/f states. In LiFePO4 this field creates completely non-degenerate Fe-d states which, with negligible p-d and d-d covalent interactions, become atomically localized to ensure a gap at the Fermi level. Due to large exchange splitting, high spin state is favored and an antiferromagnetic configuration is stabilized. For the prototype LiFePO4, independent electron approximation is good enough to obtain the AFI ground state. Inclusion of additional correlation measures like Hubbard U simply amplifies the gap and therefore LiFePO4 can be preferably called as weakly coupled Mott insulator.

Unconventional Magnetism and Band Gap Formation in LiFePO4: Consequence of Polyanion Induced Non-planarity

PubMed Central

Jena, Ajit; Nanda, B. R. K.

2016-01-01

Oxygen plays a critical role in strongly correlated transition metal oxides as crystal field effect is one of the key factors that determine the degree of localization of the valence d/f states. Based on the localization, a set of conventional mechanisms such as Mott-Hubbard, Charge-transfer and Slater were formulated to explain the antiferromagnetic and insulating (AFI) phenomena in many of these correlated systems. From the case study on LiFePO4, through density-functional calculations, we demonstrate that none of these mechanisms are strictly applicable to explain the AFI behavior when the transition metal oxides have polyanions such as (PO4)3−. The symmetry-lowering of the metal-oxygen complex, to stabilize the polyanion, creates an asymmetric crystal field for d/f states. In LiFePO4 this field creates completely non-degenerate Fe-d states which, with negligible p-d and d-d covalent interactions, become atomically localized to ensure a gap at the Fermi level. Due to large exchange splitting, high spin state is favored and an antiferromagnetic configuration is stabilized. For the prototype LiFePO4, independent electron approximation is good enough to obtain the AFI ground state. Inclusion of additional correlation measures like Hubbard U simply amplifies the gap and therefore LiFePO4 can be preferably called as weakly coupled Mott insulator. PMID:26791249

A High Capacity, Good Safety and Low Cost Na2FeSiO4-Based Cathode for Rechargeable Sodium-Ion Battery.

PubMed

Guan, Wenhao; Pan, Bin; Zhou, Peng; Mi, Jinxiao; Zhang, Dan; Xu, Jiacheng; Jiang, Yinzhu

2017-07-12

Rechargeable sodium-ion batteries (SIBs) are receiving intense interest because the resource abundance of sodium and its lithium-like chemistry make them low cost alternatives to the prevailing lithium-ion batteries in large-scale energy storage devices. Two typical classes of materials including transition metal oxides and polyanion compounds have been under intensive investigation as cathodes for SIBs; however, they are still limited to poor stability or low capacity of the state-of-art. Herein, we report a low cost carbon-coated Na 2 FeSiO 4 with simultaneous high capacity and good stability, owing to the highly pure Na-rich triclinic phase and the carbon-incorporated three-dimensional network morphology. The present carbon-coated Na 2 FeSiO 4 demonstrates the highest reversible capacity of 181.0 mAh g -1 to date with multielectron redox reaction that occurred among various polyanion-based SIBs cathodes, which achieves a close-to-100% initial Coulombic efficiency and a stable cycling with 88% capacity retention up to 100 cycles. In addition, such an electrode shows excellent stability either charged at a high voltage of 4.5 V or heated up to 800 °C. The present work might open up the possibility for developing high capacity, good safety and low cost polyanion-based cathodes for rechargeable SIBs.

Nanocaged enzymes with enhanced catalytic activity and increased stability against protease digestion

NASA Astrophysics Data System (ADS)

Zhao, Zhao; Fu, Jinglin; Dhakal, Soma; Johnson-Buck, Alexander; Liu, Minghui; Zhang, Ting; Woodbury, Neal W.; Liu, Yan; Walter, Nils G.; Yan, Hao

2016-02-01

Cells routinely compartmentalize enzymes for enhanced efficiency of their metabolic pathways. Here we report a general approach to construct DNA nanocaged enzymes for enhancing catalytic activity and stability. Nanocaged enzymes are realized by self-assembly into DNA nanocages with well-controlled stoichiometry and architecture that enabled a systematic study of the impact of both encapsulation and proximal polyanionic surfaces on a set of common metabolic enzymes. Activity assays at both bulk and single-molecule levels demonstrate increased substrate turnover numbers for DNA nanocage-encapsulated enzymes. Unexpectedly, we observe a significant inverse correlation between the size of a protein and its activity enhancement. This effect is consistent with a model wherein distal polyanionic surfaces of the nanocage enhance the stability of active enzyme conformations through the action of a strongly bound hydration layer. We further show that DNA nanocages protect encapsulated enzymes against proteases, demonstrating their practical utility in functional biomaterials and biotechnology.

Nanocaged enzymes with enhanced catalytic activity and increased stability against protease digestion

PubMed Central

Zhao, Zhao; Fu, Jinglin; Dhakal, Soma; Johnson-Buck, Alexander; Liu, Minghui; Zhang, Ting; Woodbury, Neal W.; Liu, Yan; Walter, Nils G.; Yan, Hao

2016-01-01

Cells routinely compartmentalize enzymes for enhanced efficiency of their metabolic pathways. Here we report a general approach to construct DNA nanocaged enzymes for enhancing catalytic activity and stability. Nanocaged enzymes are realized by self-assembly into DNA nanocages with well-controlled stoichiometry and architecture that enabled a systematic study of the impact of both encapsulation and proximal polyanionic surfaces on a set of common metabolic enzymes. Activity assays at both bulk and single-molecule levels demonstrate increased substrate turnover numbers for DNA nanocage-encapsulated enzymes. Unexpectedly, we observe a significant inverse correlation between the size of a protein and its activity enhancement. This effect is consistent with a model wherein distal polyanionic surfaces of the nanocage enhance the stability of active enzyme conformations through the action of a strongly bound hydration layer. We further show that DNA nanocages protect encapsulated enzymes against proteases, demonstrating their practical utility in functional biomaterials and biotechnology. PMID:26861509

Nanocaged enzymes with enhanced catalytic activity and increased stability against protease digestion.

PubMed

Zhao, Zhao; Fu, Jinglin; Dhakal, Soma; Johnson-Buck, Alexander; Liu, Minghui; Zhang, Ting; Woodbury, Neal W; Liu, Yan; Walter, Nils G; Yan, Hao

2016-02-10

Cells routinely compartmentalize enzymes for enhanced efficiency of their metabolic pathways. Here we report a general approach to construct DNA nanocaged enzymes for enhancing catalytic activity and stability. Nanocaged enzymes are realized by self-assembly into DNA nanocages with well-controlled stoichiometry and architecture that enabled a systematic study of the impact of both encapsulation and proximal polyanionic surfaces on a set of common metabolic enzymes. Activity assays at both bulk and single-molecule levels demonstrate increased substrate turnover numbers for DNA nanocage-encapsulated enzymes. Unexpectedly, we observe a significant inverse correlation between the size of a protein and its activity enhancement. This effect is consistent with a model wherein distal polyanionic surfaces of the nanocage enhance the stability of active enzyme conformations through the action of a strongly bound hydration layer. We further show that DNA nanocages protect encapsulated enzymes against proteases, demonstrating their practical utility in functional biomaterials and biotechnology.

Proton and metal ion binding to natural organic polyelectrolytes-I. Studies with synthetic model compounds

USGS Publications Warehouse

Marinsky, J.A.; Reddy, M.M.

1984-01-01

A unified physico-chemical model, based on a modified Henderson-Hasselbalch equation, for the analysis of ion complexation reactions involving charged polymeric systems is presented and verified. In this model pH = pKa+p(??Ka) + log(??/1 - ??) where Ka is the intrinsic acid dissociation constant of the ionizable functional groups on the polymer, ??Ka is the deviation of the intrinsic constant due to electrostatic interaction between the hydrogen ion and the polyanion, and alpha (??) is the polyacid degree of ionization. Using this approach pKa values for repeating acidic units of polyacrylic (PAA) and polymethacrylic (PMA) acids were found to be 4.25 ?? 0.03 and 4.8 ?? 0.1, respectively. The polyion electrostatic deviation term derived from the potentiometric titration data (i.e. p(??Ka)) is used to calculate metal ion concentration at the complexation site on the surface of the polyanion. Intrinsic cobalt-polycarboxylate binding constants (7.5 for PAA and 5.6 for PMA), obtained using this procedure, are consistent with the range of published binding constants for cobalt-monomer carboxylate complexes. In two phase systems incorporation of a Donnan membrane potential term allows determination of the intrinsic pKa of a cross-linked PMA gel, pKa = 4.83, in excellent agreement with the value obtained for the linear polyelectrolyte and the monomer. Similarly, the intrinsic stability constant for cobalt ion binding to a PMA-gel (??CoPMA+ = 11) was found to be in agreement with the linear polyelectrolyte analogue and the published data for cobalt-carboxylate monodentate complexes. ?? 1984.

Polyanionic carbohydrate doxorubicin–dextran nanocomplex as a delivery system for anticancer drugs: in vitro analysis and evaluations

PubMed Central

Yousefpour, Parisa; Atyabi, Fatemeh; Farahani, Ebrahim Vashegani; Sakhtianchi, Ramin; Dinarvand, Rassoul

2011-01-01

This study deals with the preparation and investigation of a nanoscale delivery system for the anticancer drug doxorubicin (DOX) using its complexation with polyanionic carbohydrate dextran sulfate (DS). Dynamic light scattering, SEM, and zeta potential determination were used to characterize nanocomplexes. DOX-DS complexation was studied in the presence of ethanol as a hydrogen-bond disrupting agent, NaCl as an electrostatic shielding agent, and chitosan as a positively charged polymer. Thermodynamics of DOX-DS interaction was studied using isothermal titration calorimetry (ITC). A dialysis method was applied to investigate the release profile of DOX from DOX-DS nanocomplexes. Spherical and smooth-surfaced DOX-DS nanocomplexes (250–500 nm) with negative zeta potential were formed at a DS/DOX (w/w) ratio of 0.4–0.6, with over 90% drug encapsulation efficiency. DOX when complexed with DS showed lower fluorescence emission and 480 nm absorbance plus a 15 nm bathometric shift in its visible absorbance spectrum. Electrostatic hydrogen bonding and π-π stacking interactions are the main contributing interactions in DOX-DS complexation. Thermal analysis of DOX-DS complexation by ITC revealed that each DOX molecule binds with 3 DS glycosyl monomers. Drug release profile of nanocomplexes showed a fast DOX release followed by a slow sustained release, leading to release of 32% of entrapped DOX within 15 days. DOX-DS nanocomplexes may serve as a drug delivery system with efficient drug encapsulation and also may be taken into consideration in designing DOX controlled-release systems. PMID:21796249

Synthesis and characterization of prospective polyanionic electrode materials for high performance energy storage applications

NASA Astrophysics Data System (ADS)

Jayachandran, M.; Durai, G.; Vijayakumar, T.

2018-04-01

In the present study, Polyanionic compound (SO4)-group based on Li2Ni(SO4)2 (Lithium Nickel Sulphate) composite electrodes materials were prepared by a ball-milling method and solid-state reaction route. X-ray diffraction analysis confirmed the formation of a polycrystalline orthorhombic phase of composite Li2Ni(SO4)2 with an average crystallite size of about 50.16 nm. Field Emission Scanning electron microscopy investigation reveals the spherical shape particles with the particle size of around 200–500 nm. Raman and FTIR analysis confirms the structural and functional groups of the synthesized materials and also the formation of Li2Ni(SO4)2. The electrochemical measurements using cyclic voltammetry (CV) and galvanostatic charging-discharging (GCD) techniques were carried out to study the electrochemical supercapacitive performance of the composite Li2Ni (SO4)2 electrodes. From the CV investigations, an areal capacitance of 508 mF cm‑2 was obtained at 10 mV s‑1. The galvanostatic charge-discharge (GCD) measurements exhibited the areal capacitance of 101 mF cm‑2 at a constant current density of 2 mA cm‑2 in 2 M KOH. These GCD profiles were linear and also symmetric in nature with the maximum columbic efficiency of about 85%. The electrochemical performance of the composite Li2Ni(SO4)2 electrode material shows excellent performance for supercapacitor applications.

Molecular interactions in self-assembled nano-structures of chitosan-sodium alginate based polyelectrolyte complexes.

PubMed

Wasupalli, Geeta Kumari; Verma, Devendra

2018-03-16

We report here the self-assembled structures of polyelectrolyte complexes (PECs) of polyanionic sodium alginate with the polycationic chitosan at room temperature. The PECs prepared at different pH values exhibited two distinct morphologies. The chitosan-alginate PECs self-assembled into the fibrous structure in a low pH range of pH3 to 7. The PECs obtained at high pH series around pH8 and above resulted in the formation of colloidal nanoparticles in the range of 120±9.48nm to 46.02±16.66nm. The zeta potential measurement showed that PECs prepared at lower pH (pH<6) exhibited nearly neutral surface charge, whereas PECs prepared at higher pH than 6 exhibited highly negative surface charge. The molecular interactions in nano-colloids and fibers were evaluated using FTIR analysis. The results attest that the ionic state of the chitosan and alginate plays an important role controlling the morphologies of the PECS. The present study has identified the enormous potential of the polyelectrolytes complexes to exploit shape by the alteration of ionic strength. These findings might be useful in the development of novel biomaterial. The produced fibers and nanocolloids could be applied as a biomaterial for tissue engineering and drug delivery. Copyright © 2017. Published by Elsevier B.V.

Polyelectrolyte-Functionalized Nanofiber Mats Control the Collection and Inactivation of Escherichia coli

PubMed Central

Rieger, Katrina A.; Porter, Michael; Schiffman, Jessica D.

2016-01-01

Quantifying the effect that nanofiber mat chemistry and hydrophilicity have on microorganism collection and inactivation is critical in biomedical applications. In this study, the collection and inactivation of Escherichia coli K12 was examined using cellulose nanofiber mats that were surface-functionalized using three polyelectrolytes: poly (acrylic acid) (PAA), chitosan (CS), and polydiallyldimethylammonium chloride (pDADMAC). The polyelectrolyte functionalized nanofiber mats retained the cylindrical morphology and average fiber diameter (~0.84 µm) of the underlying cellulose nanofibers. X-ray photoelectron spectroscopy (XPS) and contact angle measurements confirmed the presence of polycations or polyanions on the surface of the nanofiber mats. Both the control cellulose and pDADMAC-functionalized nanofiber mats exhibited a high collection of E. coli K12, which suggests that mat hydrophilicity may play a larger role than surface charge on cell collection. While the minimum concentration of polycations needed to inhibit E. coli K12 was 800 µg/mL for both CS and pDADMAC, once immobilized, pDADMAC-functionalized nanofiber mats exhibited a higher inactivation of E. coli K12, (~97%). Here, we demonstrate that the collection and inactivation of microorganisms by electrospun cellulose nanofiber mats can be tailored through a facile polyelectrolyte functionalization process. PMID:28773422

A Mussel-Derived One-Component Adhesive Coacervate

PubMed Central

Wei, Wei; Tan, Yerpeng; Rodriguez, N. Martinez; Yu, Jing; Israelachvili, Jacob N.; Waite, J. Herbert

2013-01-01

Marine organisms process and deliver many of their underwater coatings and adhesives as complex fluids. In marine mussels, one such fluid, secreted during the formation of adhesive plaques, consists of a concentrated colloidal suspension of a mussel foot protein (mfp) known as Mfp-3S. Results of this study suggest that Mfp-3S becomes a complex fluid by a liquid-liquid phase separation from equilibrium solution at a pH and ionic strength reminiscent of conditions created by the mussel foot during plaque formation. The pH dependence of phase separation and its sensitivity indicate that inter/intra-molecular electrostatic interactions are partially responsible for driving the phase separation. Hydrophobic interactions between the nonpolar Mfp-3S proteins provide another important driving force for coacervation. As complex coacervation typically results from charge-charge interactions between polyanions and polycations, Mfp-3S is thus unique in being the only known protein that coacervates with itself. The Mfp-3S coacervate was shown to have an effective interfacial energy of ≤ 1 mJ/m2 which explains its tendency to spread over or engulf most surfaces. Of particular interest to biomedical applications is the extremely high adsorption capacity of coacervated Mfp-3S on hydroxyapatite. PMID:24060881

Influence of Layer-by-Layer Polyelectrolyte Deposition and EDC/NHS Activated Heparin Immobilization onto Silk Fibroin Fabric

PubMed Central

Elahi, M. Fazley; Guan, Guoping; Wang, Lu; King, Martin W.

2014-01-01

To enhance the hemocompatibility of silk fibroin fabric as biomedical material, polyelectrolytes architectures have been assembled through the layer-by-layer (LbL) technique on silk fibroin fabric (SFF). In particular, 1.5 and 2.5 bilayer of oppositely charged polyelectrolytes were assembled onto SFF using poly(allylamine hydrochloride) (PAH) as polycationic polymer and poly(acrylic acid) (PAA) as polyanionic polymer with PAH topmost. Low molecular weight heparin (LMWH) activated with 1-ethyl-3-(dimethylaminopropyl) carbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) was then immobilized on its surface. Alcian Blue staining, toluidine blue assay and X-ray photoelectron spectroscopy (XPS) confirmed the presence of heparin on modified SFF surfaces. The surface morphology of the modified silk fibroin fabric surfaces was characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM), and obtained increased roughness. Negligible hemolytic effect and a higher concentration of free hemoglobin by a kinetic clotting time test ensured the improved biological performance of the modified fibroin fabric. Overall, the deposition of 2.5 bilayer was found effective in terms of biological and surface properties of the modified fibroin fabric compared to 1.5 bilayer self-assembly technique. Therefore, this novel approach to surface modification may demonstrate long term patency in future in vivo animal trials of small diameter silk fibroin vascular grafts. PMID:28788601

Layer-by-layer introduction of poly(phenylenevinylene) onto microspheres and probing the influence from the weak/strong polyanion spacer-layers.

PubMed

Song, Jing; Qiu, Tian; Chen, Yun; Zhang, Wei; Fan, Li-Juan

2015-08-15

The layer-by-layer (LBL) technique was employed for preparing fluorescent microspheres with a core-shell structure by the alternating adsorption of positively charged poly(p-phenylenevinylene) precursor (pre-PPV) and the polyanions onto polymer substrate spheres, followed by the thermal elimination to convert pre-PPV into fluorescent poly(p-phenylenevinylene) (PPV). Weak polyelectrolytes poly(acrylic acid) (PAA) (usually in a partly ionized form) and strong polyelectrolytes poly(sodium-p-styrenesulfonate) (PSS) were used as the anions to space the PPV layers and reduce the fluorescence self-quenching. Flow cytometry, combined with spectroscopy and microscopy, were used to study the structure and photophysical properties of the resulting microspheres. Optimization of the processing factors was carried out. PAA and PSS as weak and strong polyelectrolytes, respectively, displayed very different influence on the final emission of the spheres. Such difference was attributed to different inherent characteristics of PAA and PSS after detailed investigation in many aspects. In addition, the fluorescent spheres were found to have excellent photostability and thermal stability. Copyright © 2015 Elsevier Inc. All rights reserved.

Multifunctional enveloped mesoporous silica nanoparticles for subcellular co-delivery of drug and therapeutic peptide.

PubMed

Luo, Guo-Feng; Chen, Wei-Hai; Liu, Yun; Lei, Qi; Zhuo, Ren-Xi; Zhang, Xian-Zheng

2014-08-14

A multifunctional enveloped nanodevice based on mesoporous silica nanoparticle (MSN) was delicately designed for subcellular co-delivery of drug and therapeutic peptide to tumor cells. Mesoporous silica MCM-41 nanoparticles were used as the core for loading antineoplastic drug topotecan (TPT). The surface of nanoparticles was decorated with mitochondria-targeted therapeutic agent (Tpep) containing triphenylphosphonium (TPP) and antibiotic peptide (KLAKLAK)2 via disulfide linkage, followed by coating with a charge reversal polyanion poly(ethylene glycol)-blocked-2,3-dimethylmaleic anhydride-modified poly(L-lysine) (PEG-PLL(DMA)) via electrostatic interaction. It was found that the outer shielding layer could be removed at acidic tumor microenvironment due to the degradation of DMA blocks and the cellular uptake was significantly enhanced by the formation of cationic nanoparticles. After endocytosis, due to the cleavage of disulfide bonds in the presence of intracellular glutathione (GSH), pharmacological agents (Tpep and TPT) could be released from the nanoparticles and subsequently induce specific damage of tumor cell mitochondria and nucleus respectively with remarkable synergistic antitumor effect.

The role of dimension in multivalent binding events: structure-activity relationship of dendritic polyglycerol sulfate binding to L-selectin in correlation with size and surface charge density.

PubMed

Weinhart, Marie; Gröger, Dominic; Enders, Sven; Riese, Sebastian B; Dernedde, Jens; Kainthan, Rajesh K; Brooks, Donald E; Haag, Rainer

2011-08-11

L-, P-, and E-Selectin are cell adhesion molecules that play a crucial role in leukocyte recruitment from the blood stream to the afflicted tissue in an acute and chronic inflammatory setting. Since selectins mediate the initial contact of leukocytes to the vascular endothelium, they have evolved as a valuable therapeutic target in diseases related to inflammation by inhibition of the physiological selectin-ligand interactions. In a previous study, it was demonstrated that dPGS, a fully synthetic heparin analogue, works as an efficient inhibitor towards L- and P-selectin in vitro as well as in vivo. Herein, the focus is directed towards the effect of size and charge density of the polyanion. The efficiency of L-selectin inhibition via an SPR-based in vitro assay and a cell-based flow chamber assay is investigated with dPGS ranging from approximately 4 to 2000 kDa. SPR measurements show that the inhibitory potential of highly sulfated dPGS increases with size and charge density. Thereby, IC(50) values from the micromolar to the low picomolar range are determined. The same tendency could be observed in a cell-based flow chamber assay with three representative dPGS samples. This structure-affinity relationship of dPGS suggests that the strong inhibitory potential of dPGS is not only based on the strong electrostatic interaction with areas of cationic surface potential on L-selectin but is also due to a steric shielding of the carbohydrate binding site by large, flexible dPGS particles. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enantiomeric and Diastereomeric Self-Assembled Multivalent (SAMul) Nanostructures - Understanding the Effects of Chirality on Binding to Polyanionic Heparin and DNA.

PubMed

Thornalley, Kiri; Laurini, Erik; Pricl, Sabrina; Smith, David K

2018-05-15

A family of four self-assembling lipopeptides containing Ala-Lys peptides attached to a C16 aliphatic chain was synthesised. These compounds form two enantiomeric pairs that bear a diastereomeric relationship to one another (C16-L-Ala-L-Lys/C16-D-Ala-D-Lys) and (C16-D-Ala-L-Lys/C16-L-Ala-D-Lys). These diastereomeric pairs have very different critical micelle concentrations (CMCs), with LL/DD < DL/LD suggesting more effective assembly of the former. The self-assembled multivalent (SAMul) systems bind biological polyanions as result of the cationic lysine groups on their surfaces. Polyanion binding was investigated using dye displacement assays and isothermal calorimetry (ITC). On heparin binding, there was no significant enantioselectivity, but there was a binding preference for the diastereomeric assemblies with lower CMCs. Conversely, on binding DNA, there was a significant enantioselective preference for systems displaying D-lysine ligands, with a further slight preference for attachment to L-alanine, with the CMC being irrelevant. Binding to adaptive, ill-defined heparin has a large favourable entropic term, suggesting it depends primarily on the cationic SAMul nanostructure maximising surface contact with heparin, which can adapt, displacing solvent and other ions. Conversely, binding to well-defined, shape-persistent DNA has a larger favourable enthalpic term, and combined with the enantioselectivity, this allows us to suggest that its SAMul binding is based on optimised individual electrostatic interactions at the molecular level, with a preference for binding to D-lysine. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multilayer polyelectrolyte films functionalized by insertion of defensin: a new approach to protection of implants from bacterial colonization.

PubMed

Etienne, O; Picart, C; Taddei, C; Haikel, Y; Dimarcq, J L; Schaaf, P; Voegel, J C; Ogier, J A; Egles, C

2004-10-01

Infection of implanted materials by bacteria constitutes one of the most serious complications following prosthetic surgery. In the present study, we developed a new strategy based on the insertion of an antimicrobial peptide (defensin from Anopheles gambiae mosquitoes) into polyelectrolyte multilayer films built by the alternate deposition of polyanions and polycations. Quartz crystal microbalance and streaming potential measurements were used to follow step by step the construction of the multilayer films and embedding of the defensin within the films. Antimicrobial assays were performed with two strains: Micrococcus luteus (a gram-positive bacterium) and Escherichia coli D22 (a gram-negative bacterium). The inhibition of E. coli D22 growth at the surface of defensin-functionalized films was found to be 98% when 10 antimicrobial peptide layers were inserted in the film architecture. Noticeably, the biofunctionalization could be achieved only when positively charged poly(l-lysine) was the outermost layer of the film. On the basis of the results of bacterial adhesion experiments observed by confocal or electron microscopy, these observations could result from the close interaction of the bacteria with the positively charged ends of the films, which allows defensin to interact with the bacterial membrane structure. These results open new possibilities for the use of such easily built and functionalized architectures onto any type of implantable biomaterial. The modified surfaces are active against microbial infection and represent a novel means of local host protection.

Antigen size and charge in immune complex glomerulonephritis. II. Passive induction of immune deposits with dextran-anti-dextran immune complexes.

PubMed Central

Isaacs, K. L.; Miller, F.

1983-01-01

Utilizing dextrans of restricted sizes (10,000, 70,000, 500,000 daltons), modified with regard to charge (neutral, polycationic, polyanionic) and an anti-dextran murine IgA myeloma, W3129, the authors have examined a model that may be used in the study of the combined effect of size and charge on renal deposition of immune complexes. Polycationic DEAE dextran complexes, using the 10,000 dalton antigen, showed a mesangiocapillary pattern of deposition. The other antigens showed focal to diffuse mesangial localization of varying degree. This indicates the potential usefulness of this system in examining the factors important in glomerular immune injury. The relevance to other observations, importance of polysaccharide antigens, and role in circulating versus in situ or "planted" immune complex models are considered. Images Figure 3 Figure 4 Figure 5 Figure 6 PMID:6190406

Ionic liquids-mediated interactions between nanorods

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Zhou; Zhang, Fei; Huang, Jingsong

Surface forces mediated by room-temperature ionic liquids (RTILs) play an essential role in diverse applications including self-assembly, lubrication, and electrochemical energy storage. In this work, using molecular simulations we study the interactions between two nanorods immersed in model RTILs at rod-rod separations where both structural and double layer forces are important. The interaction force between neutral rods oscillates as the two rods approach each other, similar to the classical structural forces. Such oscillatory force originates from the density oscillation of RTILs near each rod and is affected by the packing constraints imposed by the neighboring rods. The oscillation period andmore » decay length of the oscillatory force are mainly dictated by the ion density distribution near isolated nanorods. When charges are introduced on the rods, the interaction force remains short-range and oscillatory, similar to the interactions between planar walls mediated by some protic RTILs reported earlier. Nevertheless, introducing net charges to the rods greatly changes the rod-rod interactions, e.g., by delaying the appearance of the first force trough and increasing the oscillation period and decay length of the interaction force. The oscillation period and decay length of the oscillatory force and free energy are commensurate with those of the space charge density near an isolated, charged rod. The free energy of rod-rod interactions reaches local minima (maxima) at rod-rod separations when the space charges near the two rods interfere constructively (destructively). Here, the insight on the short-range interactions between nanorods in RTILs helps guide the design of novel materials, e.g., crystalline ion gels based on rigid-rod polyanions and RTILs.« less

Ionic liquids-mediated interactions between nanorods

DOE PAGES

Yu, Zhou; Zhang, Fei; Huang, Jingsong; ...

2017-10-06

Surface forces mediated by room-temperature ionic liquids (RTILs) play an essential role in diverse applications including self-assembly, lubrication, and electrochemical energy storage. In this work, using molecular simulations we study the interactions between two nanorods immersed in model RTILs at rod-rod separations where both structural and double layer forces are important. The interaction force between neutral rods oscillates as the two rods approach each other, similar to the classical structural forces. Such oscillatory force originates from the density oscillation of RTILs near each rod and is affected by the packing constraints imposed by the neighboring rods. The oscillation period andmore » decay length of the oscillatory force are mainly dictated by the ion density distribution near isolated nanorods. When charges are introduced on the rods, the interaction force remains short-range and oscillatory, similar to the interactions between planar walls mediated by some protic RTILs reported earlier. Nevertheless, introducing net charges to the rods greatly changes the rod-rod interactions, e.g., by delaying the appearance of the first force trough and increasing the oscillation period and decay length of the interaction force. The oscillation period and decay length of the oscillatory force and free energy are commensurate with those of the space charge density near an isolated, charged rod. The free energy of rod-rod interactions reaches local minima (maxima) at rod-rod separations when the space charges near the two rods interfere constructively (destructively). Here, the insight on the short-range interactions between nanorods in RTILs helps guide the design of novel materials, e.g., crystalline ion gels based on rigid-rod polyanions and RTILs.« less

Permeability of the Peritrophic Envelopes of Herbivorous Insects to Dextran Sulfate: a Test of the Polyanion Exclusion Hypothesis.

PubMed

MARTIN, M M.; BARBEHENN, R V.

1997-03-01

We tested the hypothesis that the permeability of the peritrophic envelope in herbivorous insects is greatly reduced for polyanions as a result of an extensive network of anionic sites in the proteoglycans of the matrix. 14C-Dextran sulfate (polyanionic, 8000 M(w)) and fluorescein isothiocyanate-labeled (FITC) dextran (monoanionic, 9400 M(w)) were introduced together into the endoperitrophic space of the midguts of Orgyia leucostigma (Lepidoptera) larvae and Melanoplus sanguinipes (Orthoptera) adults. In all cases more of the 14C-dextran sulfate permeated the peritrophic envelope than the FITC-dextran, the opposite of the result predicted by the polyanion exclusion hypothesis. We conclude that polyanion exclusion is not a mechanism that contributes significantly to the permeability properties of the peritrophic envelopes of these two species, or that explains the failure of tannic acid to cross the peritrophic envelopes of lepidopteran larvae. Copyright 1997 Elsevier Science Ltd. All rights reserved

Cellulose nanoparticles as modifiers for rheology and fluid loss in bentonite water-based fluids.

PubMed

Li, Mei-Chun; Wu, Qinglin; Song, Kunlin; Qing, Yan; Wu, Yiqiang

2015-03-04

Rheological and filtration characteristics of drilling fluids are considered as two critical aspects to ensure the success of a drilling operation. This research demonstrates the effectiveness of cellulose nanoparticles (CNPs), including microfibrillated cellulose (MFC) and cellulose nanocrystals (CNCs) in enhancing the rheological and filtration performances of bentonite (BT) water-based drilling fluids (WDFs). CNCs were isolated from MFC through sulfuric acid hydrolysis. In comparison with MFC, the resultant CNCs had much smaller dimensions, more negative surface charge, higher stability in aqueous solutions, lower viscosity, and less evident shear thinning behavior. These differences resulted in the distinctive microstructures between MFC/BT- and CNC/BT-WDFs. A typical "core-shell" structure was created in CNC/BT-WDFs due to the strong surface interactions among BT layers, CNCs, and immobilized water molecules. However, a similar structure was not formed in MFC/BT-WDFs. As a result, CNC/BT-WDFs had superior rheological properties, higher temperature stability, less fluid loss volume, and thinner filter cakes than BT and MFC/BT-WDFs. Moreover, the presence of polyanionic cellulose (PAC) further improved the rheological and filtration performances of CNC/BT-WDFs, suggesting a synergistic effect between PAC and CNCs.

Crystal structure of undeca-potassium bis-[α-hemi-penta-hydrogen hexa-molybdoplatinate(IV)] dodeca-hydrate.

PubMed

Joo, Hea-Chung; Park, Ki-Min; Lee, Uk

2015-08-01

The title compound, K11[α-Pt(μ3-OH)2(μ3-OH0.5)Mo6(μ3-O)3(μ2-O)6O12]2·12H2O (simplified chemical formula K11[H2.5PtMo6O24]2·12H2O), containing the well-known Anderson-type heteropolyoxomolybdate anion, was obtained by hydro-thermal reaction at pH = ca 6.0. The complete polyanion dimer has 2/m symmetry. The locations of the H atoms with respect to protonated O atoms were obtained from difference Fourier maps, and confirmed by the inter-polyanion hydrogen bonds, bond-length elongation and bond-valence sums (BVSs). The title heteropolyanion has two types of protonated O atoms viz. μ3-OH, {Mo2-O(H)-Pt} and μ3-OH0.5 (disordered H atom). The [H2.5α-PtMo6O24](5.5-) polyanion forms a dimer, [(H2.5α-PtMo6O24)2](11-), held together by two pairs of μ3-O-H⋯μ1-O and of one disordered μ3-O⋯H⋯μ3-O hydrogen bonds. Three K(+) ions are located on special positions (two on twofold rotation axes, one on a mirror plane), and two K(+) ions are located on general positions with a reduced occupancy of 0.5. The remaining K(+) ion has a reduced occupancy of 0.25 for charge balance and reasonable displacement parameters. As a result, the numbers of K(+) and H(+) ions in the title compound are 5.5 and 2.5, respectively.

Solid polymeric electrolytes for lithium batteries

DOEpatents

Angell, Charles A.; Xu, Wu; Sun, Xiaoguang

2006-03-14

Novel conductive polyanionic polymers and methods for their preparion are provided. The polyanionic polymers comprise repeating units of weakly-coordinating anionic groups chemically linked to polymer chains. The polymer chains in turn comprise repeating spacer groups. Spacer groups can be chosen to be of length and structure to impart desired electrochemical and physical properties to the polymers. Preferred embodiments are prepared from precursor polymers comprising the Lewis acid borate tri-coordinated to a selected ligand and repeating spacer groups to form repeating polymer chain units. These precursor polymers are reacted with a chosen Lewis base to form a polyanionic polymer comprising weakly coordinating anionic groups spaced at chosen intervals along the polymer chain. The polyanionic polymers exhibit high conductivity and physical properties which make them suitable as solid polymeric electrolytes in lithium batteries, especially secondary lithium batteries.

Phase behavior and structure of stable complexes between a long polyanion and a branched polycation

NASA Astrophysics Data System (ADS)

Mengarelli, Valentina; Zeghal, Mehdi; Auvray, Loïc; Clemens, Daniel

2011-08-01

The association between oppositely charged branched polyethylenimine (BPEI) and polymethacrylic acid (PMA) in the dilute regime is investigated using turbidimetric titration and electrophoretic mobility measurements. The complexation is controlled by tuning continuously the pH-sensitive charge of the polyacid in acidic solution. The formation of soluble and stable positively charged complexes is a cooperative process characterized by the existence of two regimes of weak and strong complexation. In the regime of weak complexation, a long PMA chain overcharged by several BPEI molecules forms a binary complex. As the charge of the polyacid increases, these binary complexes condense at a well defined charge ratio of the mixture to form large positively charged aggregates. The overcharging and the existence of two regimes of complexation are analyzed in the light of recent theories. The structure of the polyelectrolytes is investigated at higher polymer concentration by small angle neutron scattering. Binary complexes of finite size present an open structure where the polyacid chains connecting a small number of BPEI molecules have shrunk slightly. In the condensed complexes, BPEI molecules, wrapped by polyacid chains, form networks of stretched necklaces.

Bioacceptable and calcification-resistant membranes and interfaces for implantable sensors and devices

NASA Astrophysics Data System (ADS)

Galeska, Izabela Ewa

The rational design and characterization of biocompatible, semipermeable and calcification resistant materials to serve as an outer membrane for implantable glucose biosensors, was the primary focus of this research. Multilayered films of polyanions (i.e. Nafion(TM), a perfluorinated ionomer, and Humic Acids (HAs), naturally occurring biopolymers), fabricated by layer-by-layer self-assembly with oppositely charged ferric ions were investigated as potential membranes. Spectroscopic ellipsometry and quartz crystal microbalance studies point towards a stepwise film growth, with growth rates of 47 and 24.3 nm per layer (for Nafion and HAs respectively) that can be altered depending on the pH and ionic strength of the polyanion solution. Nafion/Fe3+ assembled films exhibited an order of magnitude lower calcification as compared to dip-coated Nafion films and did not require annealing to impart insolubility. Similarly the HAs/Fe3+ films were also devoid of calcification, even after four-week immersion in DMEM cell culture media. Significantly, in vivo studies on the HAs/Fe3 films point to their biocompatibility as demonstrated by mild tissue reaction. These results, along with controllable glucose permeability, could prove vital in prolonging the lifetime of implantable biosensors. Additionally in effort to minimize tissue trauma upon implantation, novel poly(lactic-co-glycolic acid) (PLGA) microsphere/poly(vinyl alcohol) (PVA) hydrogel composites were investigated for dexamethasone delivery. A release rate of 25 to 40% over one month, following a zero order profile, was achieved by preferential adsorption of surface active polyacids (poly(acrylic acid), Nafion and HAs) on the hydrogel dispersed microspheres. Environmental scanning electron microscopy investigation on the degradation mechanism of the microspheres pointed towards their slow homogeneous degradation in the PVA hydrogels that was significantly surface-accelerated in the presence of polyacids. The physico-mechanical properties (fluid uptake and Young's modulus) and release of unencapsulated dexamethasone (80 to 100%) from the hydrogels were related to their crystallinity. Significantly, with Young's modulus in the range of 0.1 to 4 MPa, comparable to human sub-dermal tissue, the hydrated gels provide soft and flexible tissue/sensor interface.

A crystal-chemical classification of borate structures with emphasis on hydrated borates

USGS Publications Warehouse

Christ, C.L.; Clark, J.R.

1977-01-01

The rules governing formation of hydrated borate polyanions that were proposed by C.L. Christ in 1960 are critically reviewed and new rules added on the basis of recent crystal structure determinations. Principles and classifications previously published by others are also critically reviewed briefly. The fundamental building blocks from which borate polyanions can be constructed are defined on the basis of the number n of boron atoms, and the fully hydrated polyanions are illustrated. Known structures are grouped accordingly, and a shorthand notation using n and symbols ?? = triangle, T = tetrahedron is introduced so that the polyanions can be easily characterized. For example, 3:??+2T describes [B3O3(OH)5]2-. Correct structural formulas are assigned borates with known structures whereas borates of unknown structure are grouped separately. ?? 1977 Springer-Verlag.

Polyanion-Type Electrode Materials for Sodium-Ion Batteries.

PubMed

Ni, Qiao; Bai, Ying; Wu, Feng; Wu, Chuan

2017-03-01

Sodium-ion batteries, representative members of the post-lithium-battery club, are very attractive and promising for large-scale energy storage applications. The increasing technological improvements in sodium-ion batteries (Na-ion batteries) are being driven by the demand for Na-based electrode materials that are resource-abundant, cost-effective, and long lasting. Polyanion-type compounds are among the most promising electrode materials for Na-ion batteries due to their stability, safety, and suitable operating voltages. The most representative polyanion-type electrode materials are Na 3 V 2 (PO 4 ) 3 and NaTi 2 (PO 4 ) 3 for Na-based cathode and anode materials, respectively. Both show superior electrochemical properties and attractive prospects in terms of their development and application in Na-ion batteries. Carbonophosphate Na 3 MnCO 3 PO 4 and amorphous FePO 4 have also recently emerged and are contributing to further developing the research scope of polyanion-type Na-ion batteries. However, the typical low conductivity and relatively low capacity performance of such materials still restrict their development. This paper presents a brief review of the research progress of polyanion-type electrode materials for Na-ion batteries, summarizing recent accomplishments, highlighting emerging strategies, and discussing the remaining challenges of such systems.

Experimental study of the effect of polyanionic cellulose on process of filtrate loss of low-solids drilling fluid

NASA Astrophysics Data System (ADS)

yang, P.

2013-12-01

Experimental study of the effect of polyanionic cellulose on process of filtrate loss of low-solids drilling fluid Ping Yang 1,2, Min-hui Wu2, Xue-wen Zhu2, Tao Deng2, Xue-qing Sun2 1. Key Laboratory of Geotechnical and Underground Engineering of Ministry of Education, Tongji University, Shanghai 200092,China 2. Department of Geotechnical Engineering,Tongji University,Shanghai 200092,China Abstract The process of filtrate loss of low-solids drilling fluid was tested by changing the polyanionic cellulose content in low-solids drilling fluid. The effect of polyanionic cellulose on process of filtrate loss of low-solids drilling fluid was analyzed. The test results showed that when time of filtration is same, the volume of filtrate loss decreases linearly with increasing polyanionic cellulose content. When polyanionic cellulose content is same, the rate of filtrate loss decreases nonlinearly with increasing time and the rate of filtrate loss will reach a stable value.The volume of filtrate loss in 7 to 8 minutes can reaches half of the total volume of filtrate loss. At the same time, the rate of filtrate loss of drilling fluid decreases nonlinearly with increasing viscosity.When the apparent viscosity is between 3.5~4.15 MPa.s, decrease speed of rate of filtrate loss of drilling fluid is quick. The results are helpful for characteristics evaluation of filtrate loss of drilling fluid and control of filtrate loss. Keyword Polyanionic Cellulose,Drilling Fluid,Process of Filtrate Loss Acknowledgments This investigation was supported by the National Natural Science Foundation of China (projects No. 41002093 and 41072205); the Fundamental Research Funds for the Central Universities; the Shanghai Leading Academic Discipline Project (project No. B308), Tongji University; and the Program for Young Excellent Talents, Tongji University. The authors are extremely grateful for the financial support from these five organizations.

Macro-hydrogels versus nanoparticles by the controlled assembly of polysaccharides.

PubMed

Costalat, M; Alcouffe, P; David, L; Delair, T

2015-12-10

The controlled assembly of oppositely charged chitosan (CS, Mw ∼ 33 × 10(3) to 600 × 10(3)g mol(-1)) and dextran sulfate (DS, Mw = 1.3 × 10(6)g mol(-1)) or heparin (HP, Mw = 1.8 × 10(4)g mol(-1)) led either to nanoparticles or macro-hydrogels, at room temperature. The control over the electrostatic attractive interactions was achieved using 2 mol L(-1) NaCl in the polyion solutions and subsequent dialysis to let the assembly occur. Macrohydrogels formed with an excess of polyanion. In the presence of an excess of polycation, colloidal gels were exclusively obtained. At salt concentrations lower than 1 mol L(-1), the spontaneous gelation provided macro-hydrogels, whatever the polyion in excess. Rheology measurements showed a similar elastic behaviour for CS-DS and CS-HP hydrogels, though CS-HP hydrogels appeared less cohesive. SAXS experiments revealed an aggregate morphology with internal and surface structure depending on the degree of acetylation (DA) of chitosan. Copyright © 2015 Elsevier Ltd. All rights reserved.

Multifunctional Enveloped Mesoporous Silica Nanoparticles for Subcellular Co-delivery of Drug and Therapeutic Peptide

PubMed Central

Luo, Guo-Feng; Chen, Wei-Hai; Liu, Yun; Lei, Qi; Zhuo, Ren-Xi; Zhang, Xian-Zheng

2014-01-01

A multifunctional enveloped nanodevice based on mesoporous silica nanoparticle (MSN) was delicately designed for subcellular co-delivery of drug and therapeutic peptide to tumor cells. Mesoporous silica MCM-41 nanoparticles were used as the core for loading antineoplastic drug topotecan (TPT). The surface of nanoparticles was decorated with mitochondria-targeted therapeutic agent (Tpep) containing triphenylphosphonium (TPP) and antibiotic peptide (KLAKLAK)2 via disulfide linkage, followed by coating with a charge reversal polyanion poly(ethylene glycol)-blocked-2,3-dimethylmaleic anhydride-modified poly(L-lysine) (PEG-PLL(DMA)) via electrostatic interaction. It was found that the outer shielding layer could be removed at acidic tumor microenvironment due to the degradation of DMA blocks and the cellular uptake was significantly enhanced by the formation of cationic nanoparticles. After endocytosis, due to the cleavage of disulfide bonds in the presence of intracellular glutathione (GSH), pharmacological agents (Tpep and TPT) could be released from the nanoparticles and subsequently induce specific damage of tumor cell mitochondria and nucleus respectively with remarkable synergistic antitumor effect. PMID:25317538

Top-down and Bottom-up Approaches in Production of Aqueous Nanocolloids of Low Soluble Drug Paclitaxel

PubMed Central

Pattekari, P.; Zheng, Z.; Zhang, X.; Levchenko, T.; Torchilin, V.

2015-01-01

Nano-encapsulation of poorly soluble anticancer drug was developed with sonication assisted layer-by-layer polyelectrolyte coating (SLbL). We changed the strategy of LbL-encapsulation from making microcapsules with many layers in the walls for encasing highly soluble materials to using very thin polycation / polyanion coating on low soluble nanoparticles to provide their good colloidal stability. SLbL encapsulation of paclitaxel resulted in stable 100-200 nm diameter colloids with high electrical surface ξ-potential (of -45 mV) and drug content in the nanoparticles of 90 wt %. In the top-down approach, nanocolloids were prepared by rupturing powder of paclitaxel using ultrasonication and simultaneous sequential adsorption of oppositely charged biocompatible polyelectrolytes. In the bottom-up approach paclitaxel was dissolved in organic solvent (ethanol or acetone), and drug nucleation was initiated by gradual worsening the solution with the addition of aqueous polyelectrolyte assisted by ultrasonication. Paclitaxel release rates from such nanocapsules were controlled by assembling multilayer shells with variable thicknesses and are in the range of 10-20 hours. PMID:21442095

76 FR 27294 - Proposed Revocation of the Significant New Use Rule on a Certain Chemical Substance

Federal Register 2010, 2011, 2012, 2013, 2014

2011-05-11

...)(ii) for analogous polyanionic monomers. EPA has received and reviewed aquatic toxicity test data for... environmental effect criteria at Sec. 721.170(b)(4)(ii) for analogous polyanionic monomers. Subsequently, the...

Direct Loading and Tunable Release of Antibiotics from Polyelectrolyte Multilayers To Reduce Bacterial Adhesion and Biofilm Formation.

PubMed

Wang, Bailiang; Jin, Tingwei; Xu, Qingwen; Liu, Huihua; Ye, Zi; Chen, Hao

2016-05-18

Bacteria adhesion on the surface of biomaterials and following biofilm formation are important problems in biomedical applications. The charged antibiotics with small molar mass can hardly deposit alternately with polymers into multilayered films to load the drug. Herein, the (poly(acrylic acid)-gentamicin/poly(ethylenimine))n ((PAA-GS/PEI)n) multilayer film was designed and constructed via a layer-by-layer self-assembly method. Low molar mass GS cations were first combined with polyanion PAA and self-assembled with PEI to form multilayer films showing exponential growth behavior. The GS dosage could be adjusted by changing the layer number of films. Furthermore, the thermal cross-linking method was used to control the release rate of GS in PBS buffer. Owing to the diffusion of GS, a zone of inhibition of about 7.0 mm showed the efficient disinfection activity of the multilayer film. It could also be seen from the biofilm inhibition assay that the multilayer film effectively inhibited bacterial adhesion and biofilm formation. As the drug loading dosage was 160 μg/cm(2), the multilayer films showed very low cytotoxicity against human lens epithelial cells. The present work provides an easy way to load GS into multilayer films which can be applied to surface modification of implants and biomedical devices.

Development and characterization of a novel lipohydrogel nanocarrier: repaglinide as a lipophilic model drug.

PubMed

Ebrahimi, Hossein Ali; Javadzadeh, Yousef; Hamidi, Mehrdad; Barzegar Jalali, Mohammad

2016-04-01

Solid lipid nanoparticles (SLNs) are highly susceptible to phagocytosis by reticuloendothelial system (RES). To overcome this problem, a novel hydrogel-coated SLNs structure was developed and evaluated in this study. Solid lipid nanoparticles surface was coated with chitosan, via electrostatic attraction with the negatively charged SLNs surface. The resulting polymer-coated SLNs then hosted an inorganic poly-anionic agent, tripolyphosphate, to form the final lipohydrogel structure. Compared with the bare SLNs, lipohydrogel nanoparticles (LHNs) showed a significant increase in size and zeta potential. The release profile showed lower burst release and lower release rate for LHNs compared with SLNs. LHNs nanoparticles released the model antidiabetic drug, repaglinide, in a more sustained manner with lower burst effect compared with the corresponding SLN structure. Cytotoxicity studies via cell culture and MTT assay revealed no bio-toxicity of the SLNs and LHNs. In addition, intravenous administration of repaglinide-loaded SLNs and LHNs in rats showed longer drug residence time in circulation for LHNs, a trend also evident for the blood glucose level-time profile. The particle size, zeta potential, FTIR and microscopy data demonstrated the formation of the supposed lipohydrogel nanoparticles. All these benefits of LHNs propose it as a promising candidate for controlled release of the drugs. © 2016 Royal Pharmaceutical Society, Journal of Pharmacy and Pharmacology.

Coating cells with colloidal silica for high yield isolation of plasma membrane sheets and identification of transmembrane proteins.

PubMed

Chaney, L K; Jacobson, B S

1983-08-25

Plasma membrane (PM) can be isolated by binding to a positively charged solid support. Using this concept, we have developed a novel method of PM isolation using cationic colloidal silica. The method is designed for the comparative study of various physiological states of PM and for transbilayer protein mapping. The procedure consists of coating intact cells with a dense pellicle of silica particles and polyanion. Since cells remain intact during pellicle formation, the external face of the PM is selectively coated. The pellicle greatly enhances PM density and stabilizes it against vesiculation or lateral reorientation. Upon cell lysis, large open sheets of PM are rapidly isolated by centrifugation. PM from Dictyostelium discoideum was prepared by this method. Marker enzymes, cell surface labeling and microscopy demonstrate that the PM was isolated in high yield (70-80%) with a 10-17-fold purification and only low levels of cytoplasmic contamination. The pellicle remains intact during cell lysis and membrane isolation, shielding the external surface of the membranes up to 92% from chemical or enzymatic attack. The PM can thus be labeled selectively from inside and/or outside. Transmembrane proteins were identified in Dictyostelium PM by means of lactoperoxidase iodination and autoradiography.

Silica nanogelling of environment-responsive PEGylated polyplexes for enhanced stability and intracellular delivery of siRNA.

PubMed

Gouda, Noha; Miyata, Kanjiro; Christie, R James; Suma, Tomoya; Kishimura, Akihiro; Fukushima, Shigeto; Nomoto, Takahiro; Liu, Xueying; Nishiyama, Nobuhiro; Kataoka, Kazunori

2013-01-01

In this study, poly(ethylene glycol) (PEG)-block-polycation/siRNA complexes (PEGylated polyplexes) were wrapped with a hydrated silica, termed "silica nanogelling", in order to enhance their stability and functionality. Silica nanogelling was achieved by polycondensation of soluble silicates onto the surface of PEGylated polyplexes comprising a disulfide cross-linked core. Formation of silica nanogel layer on the PEGylated cross-linked polyplexes was confirmed by particle size increase, surface charge reduction, and elemental analysis of transmission electron micrographs. Silica nanogelling substantially improved polyplex stability against counter polyanion-induced dissociation under non-reductive condition, without compromising the reductive environment-responsive siRNA release triggered by disulfide cleavage. Silica nanogelling significantly enhanced the sequence-specific gene silencing activity of the polyplexes in HeLa cells without associated cytotoxicity, probably due lower endosomal entrapment (or lysosomal degradation) of delivered siRNA. The lower endosomal entrapment of the silica nanogel system could be explained by an accelerated endosomal escape triggered by deprotonated silanol groups in the silica (the proton sponge hypothesis) and/or a modulated intracellular trafficking, possibly via macropinocytosis, as evidenced by the cellular uptake inhibition assay. Henceforth, silica nanogelling of PEGylated siRNA polyplexes is a promising strategy for preparation of stable and functional siRNA delivery vehicles. Copyright © 2012 Elsevier Ltd. All rights reserved.

Mechanism of Enhancement of Virus Plaques by Cationic Polymers

PubMed Central

Wallis, Craig; Melnick, Joseph L.

1968-01-01

It has been assumed that plaque enhancement by cationic polymers is due to their binding of sulfated polysaccharides in agar. However, viruses that are enhanced by cationic polymers, diethylaminoethyl-dextran, and protamine were found not to be inhibited by polyanions in agar under the usual overlay conditions. In the case of adenovirus, enhancement by protamine seems to be due to the protamine serving as a source of arginine; enzymes released from the cultured cells digest the protamine and provide a reservoir of arginine for the cells. Other viruses (herpes and echovirus types 3, 4, 5, and 6) known to be susceptible to agar inhibitors were found to be enhanced by cationic polymers even under starch gel and methylcellulose overlays, which are free of polyanions. Since cationic polymers enhance the diffusion of virus through agar or starch gel, plaque enhancement seems to be the result of the gel becoming positively charged so that viruses can move effectively through them. The observation that starch gel and methylcellulose enhance plaque formation with viruses known to be inhibited under agar was also reinvestigated. When the consistency of the agar gel was reduced to the same viscosity of starch gel and methylcellulose overlays, the same plaque counts and sizes were observed under all three overlays. PMID:4986901

Hexavalent chromium removal by chitosan modified-bioreduced nontronite

NASA Astrophysics Data System (ADS)

Singh, Rajesh; Dong, Hailiang; Zeng, Qiang; Zhang, Li; Rengasamy, Karthikeyan

2017-08-01

Recent efforts have focused on structural Fe(II) in chemically or biologically reduced clay minerals to immobilize Cr(VI) from aqueous solution, but the coulombic repulsion between the negatively charged clay surface and the polyanionic form of Cr(VI), e.g., dichromate, can hinder the effectiveness of this process. The purpose of this study was to investigate the efficiency and mechanism of Cr(VI) removal by a charge-reversed nontronite (NAu-2), an Fe-rich smectite. Chitosan, a linear polysaccharide derived from chitin found in soil and groundwater, was used to reverse the charge of NAu-2. Intercalation of chitosan into NAu-2 interlayer increased the basal d-spacing of NAu-2 from 1.23 nm to 1.83 nm and zeta potential from -27.17 to +34.13 mV, with the amount of increase depending on chitosan/NAu-2 ratio. Structural Fe(III) in chitosan-exchanged NAu-2 was then biologically reduced by an iron-reducing bacterium Shewanella putrefaciens CN32 in bicarbonate buffer with lactate as the sole electron donor, with and without electron shuttle, AQDS. Without AQDS, the extent of Fe(III) reduction increased from the lowest (∼9%) for the chitosan-free NAu-2 to the highest (∼12%) for the highest chitosan loaded NAu-2 (3:1 ratio). This enhancement of Fe(III) reduction was likely due to the attachment of negatively charged bacterial cells to charge-reversed (e.g., positively charged) NAu-2 surfaces, facilitating the electron transfer between cells and structural Fe(III). With AQDS, Fe(III) reduction extent doubled relative to those without AQDS, but the enhancement effect was similar across all chitosan loadings, suggesting that AQDS was more important than chitosan in enhancing Fe(III) bioreduction. Chitosan-exchanged, biologically reduced NAu-2 was then utilized for removing Cr(VI) in batch experiments with three consecutive spikes of 50 μM Cr. With the first Cr spike, the rate of Cr(VI) removal by charged-reversed NAu-2 that was bioreduced without and with AQDS was ∼1.5 and ∼6 μmol g-1 h-1, respectively. However, the capacity of these clays to remove Cr(VI) was progressively exhausted upon addition of subsequent Cr spikes. X-ray photoelectron spectroscopy (XPS) revealed that the reduction product of Cr(VI) by chitosan-exchanged-bioreduced NAu-2 was Cr(III), possibly in the form of Cr(OH)3. In summary, our results demonstrated that the combined effects of sorption and redox reactions by charge-reversed bioreduced nontronite may offer a feasible in-situ approach for remediating Cr(VI) polluted soil and groundwater.

Translational Mini-Review Series on Complement Factor H: Structural and functional correlations for factor H

PubMed Central

Schmidt, C Q; Herbert, A P; Hocking, H G; Uhrín, D; Barlow, P N

2008-01-01

The 155-kDa glycoprotein, complement factor H (CFH), is a regulator of complement activation that is abundant in human plasma. Three-dimensional structures of over half the 20 complement control protein (CCP) modules in CFH have been solved in the context of single-, double- and triple-module segments. Proven binding sites for C3b occupy the N and C termini of this elongated molecule and may be brought together by a bend in CFH mediated by its central CCP modules. The C-terminal CCP 20 is key to the ability of the molecule to adhere to polyanionic markers on self-surfaces where CFH acts to regulate amplification of the alternative pathway of complement. The surface patch on CCP 20 that binds to model glycosaminoglycans has been mapped using nuclear magnetic resonance (NMR), as has a second glycosaminoglycan-binding patch on CCP 7. These patches include many of the residue positions at which sequence variations have been linked to three complement-mediated disorders: dense deposit disease, age-related macular degeneration and atypical haemolytic uraemic syndrome. In one plausible model, CCP 20 anchors CFH to self-surfaces via a C3b/polyanion composite binding site, CCP 7 acts as a ‘proof-reader’ to help discriminate self- from non-self patterns of sulphation, and CCPs 1–4 disrupt C3/C5 convertase formation and stability. PMID:18081691

Antiviral mechanism of polyanionic carbosilane dendrimers against HIV-1

PubMed Central

Vacas-Córdoba, Enrique; Maly, Marek; De la Mata, Francisco J; Gómez, Rafael; Pion, Marjorie; Muñoz-Fernández, Mª Ángeles

2016-01-01

Nanotechnology-derived platforms, such as dendrimers, are very attractive in several biological applications. In the case of human immunodeficiency virus (HIV) infection, polyanionic carbosilane dendrimers have shown great potential as antiviral agents in the development of novel microbicides to prevent the sexual transmission of HIV-1. In this work, we studied the mechanism of two sulfated and naphthylsulfonated functionalized carbosilane dendrimers, G3-S16 and G2-NF16. They are able to inhibit viral infection at fusion and thus at the entry step. Both compounds impede the binding of viral particles to target cell surface and membrane fusion through the blockage of gp120–CD4 interaction. In addition, and for the first time, we demonstrate that dendrimers can inhibit cell-to-cell HIV transmission and difficult infectious synapse formation. Thus, carbosilane dendrimers’ mode of action is a multifactorial process targeting several proteins from viral envelope and from host cells that could block HIV infection at different stages during the first step of infection. PMID:27103798

DB-PABP: a database of polyanion-binding proteins

PubMed Central

Fang, Jianwen; Dong, Yinghua; Salamat-Miller, Nazila; Russell Middaugh, C.

2008-01-01

The interactions between polyanions (PAs) and polyanion-binding proteins (PABPs) have been found to play significant roles in many essential biological processes including intracellular organization, transport and protein folding. Furthermore, many neurodegenerative disease-related proteins are PABPs. Thus, a better understanding of PA/PABP interactions may not only enhance our understandings of biological systems but also provide new clues to these deadly diseases. The literature in this field is widely scattered, suggesting the need for a comprehensive and searchable database of PABPs. The DB-PABP is a comprehensive, manually curated and searchable database of experimentally characterized PABPs. It is freely available and can be accessed online at http://pabp.bcf.ku.edu/DB_PABP/. The DB-PABP was implemented as a MySQL relational database. An interactive web interface was created using Java Server Pages (JSP). The search page of the database is organized into a main search form and a section for utilities. The main search form enables custom searches via four menus: protein names, polyanion names, the source species of the proteins and the methods used to discover the interactions. Available utilities include a commonality matrix, a function of listing PABPs by the number of interacting polyanions and a string search for author surnames. The DB-PABP is maintained at the University of Kansas. We encourage users to provide feedback and submit new data and references. PMID:17916573

DB-PABP: a database of polyanion-binding proteins.

PubMed

Fang, Jianwen; Dong, Yinghua; Salamat-Miller, Nazila; Middaugh, C Russell

2008-01-01

The interactions between polyanions (PAs) and polyanion-binding proteins (PABPs) have been found to play significant roles in many essential biological processes including intracellular organization, transport and protein folding. Furthermore, many neurodegenerative disease-related proteins are PABPs. Thus, a better understanding of PA/PABP interactions may not only enhance our understandings of biological systems but also provide new clues to these deadly diseases. The literature in this field is widely scattered, suggesting the need for a comprehensive and searchable database of PABPs. The DB-PABP is a comprehensive, manually curated and searchable database of experimentally characterized PABPs. It is freely available and can be accessed online at http://pabp.bcf.ku.edu/DB_PABP/. The DB-PABP was implemented as a MySQL relational database. An interactive web interface was created using Java Server Pages (JSP). The search page of the database is organized into a main search form and a section for utilities. The main search form enables custom searches via four menus: protein names, polyanion names, the source species of the proteins and the methods used to discover the interactions. Available utilities include a commonality matrix, a function of listing PABPs by the number of interacting polyanions and a string search for author surnames. The DB-PABP is maintained at the University of Kansas. We encourage users to provide feedback and submit new data and references.

Heparin-mimicking multilayer coating on polymeric membrane via LbL assembly of cyclodextrin-based supramolecules.

PubMed

Deng, Jie; Liu, Xinyue; Ma, Lang; Cheng, Chong; Shi, Wenbin; Nie, Chuanxiong; Zhao, Changsheng

2014-12-10

In this study, multifunctional and heparin-mimicking star-shaped supramolecules-deposited 3D porous multilayer films with improved biocompatibility were fabricated via a layer-by-layer (LbL) self-assembly method on polymeric membrane substrates. Star-shaped heparin-mimicking polyanions (including poly(styrenesulfonate-co-sodium acrylate; Star-PSS-AANa) and poly(styrenesulfonate-co-poly(ethylene glycol)methyl ether methacrylate; Star-PSS-EGMA)) and polycations (poly(methyl chloride-quaternized 2-(dimethylamino)ethyl methacrylate; Star-PMeDMA) were first synthesized by atom transfer radical polymerization (ATRP) from β-cyclodextrin (β-CD) based cores. Then assembly of 3D porous multilayers onto polymeric membrane surfaces was carried out by alternating deposition of the polyanions and polycations via electrostatic interaction. The surface morphology and composition, water contact angle, blood activation, and thrombotic potential as well as cell viability for the coated heparin-mimicking films were systematically investigated. The results of surface ATR-FTIR spectra and XPS spectra verified successful deposition of the star-shaped supramolecules onto the biomedical membrane surfaces; scanning electron microscopy (SEM) and atomic force microscopy (AFM) observations revealed that the modified substrate had 3D porous surface morphology, which might have a great biological influence on the biointerface. Furthermore, systematic in vitro investigation of protein adsorption, platelet adhesion, human platelet factor 4 (PF4, indicates platelet activation), activate partial thromboplastin time (APTT), thrombin time (TT), coagulation activation (thrombin-antithrombin III complex (TAT, indicates blood coagulant)), and blood-related complement activation (C3a and C5a, indicates inflammation potential) confirmed that the heparin-mimicking multilayer coated membranes exhibited ultralow blood component activations and excellent hemocompatibility. Meanwhile, after surface coating, endothelial cell viability was also promoted, which indicated that the heparin-mimicking multilayer coating might extend the application fields of polymeric membranes in biomedical fields.

Polyglycerolsulfate Functionalized Gold Nanorods as Optoacoustic Signal Nanoamplifiers for In Vivo Bioimaging of Rheumatoid Arthritis

PubMed Central

Vonnemann, Jonathan; Beziere, Nicolas; Böttcher, Christoph; Riese, Sebastian B.; Kuehne, Christian; Dernedde, Jens; Licha, Kai; von Schacky, Claudio; Kosanke, Yvonne; Kimm, Melanie; Meier, Reinhard; Ntziachristos, Vasilis; Haag, Rainer

2014-01-01

We have synthesized a targeted imaging agent for rheumatoid arthritis based on polysulfated gold nanorods. The CTAB layer on gold nanorods was first replaced with PEG-thiol and then with dendritic polyglycerolsulfate at elevated temperature, which resulted in significantly reduced cytotoxicity compared to polyanionic gold nanorods functionalized by non-covalent approaches. In addition to classical characterization methods, we have established a facile UV-VIS based BaCl2 agglomeration assay to confirm a quantitative removal of unbound ligand. With the help of a competitive surface plasmon resonance-based L-selectin binding assay and a leukocyte adhesion-based flow cell assay, we have demonstrated the high inflammation targeting potential of the synthesized gold nanorods in vitro. In combination with the surface plasmon resonance band of AuNRs at 780 nm, these findings permitted the imaging of inflammation in an in vivo mouse model for rheumatoid arthritis with high contrast using multispectral optoacoustic tomography. The study offers a robust method for otherwise difficult to obtain covalently functionalized polyanionic gold nanorods, which are suitable for biological applications as well as a low-cost, actively targeted, and high contrast imaging agent for the diagnosis of rheumatoid arthritis. This paves the way for further research in other inflammation associated pathologies, in particular, when photothermal therapy can be applied. PMID:24723984

Faconnage de la surface de nanoparticules pour la delivrance de genes

NASA Astrophysics Data System (ADS)

Fortier, Charles

Gene vectorization has become an essential tool in the field of biotechnology. It is also found at the heart of research and development of gene therapies, a specific goal of which is to deliver genetic material in the nuclei of target cells. As the DNA to be delivered is fragile, most vectorization techniques include the use of nanoobjects that are able to encapsulate and protect this delicate cargo. These nanoobjects also facilitate gene transport to the nuclei of target cells whereby its expression can occur. These nanovectors are made from varied materials that include polymers. Particularly, polyplexes form a class of nanovectors that derive from the complexation between DNA and a positively charged polymer. The works presented here are focused on the role of the interface between a model polyplex and the surrounding cellular and physiological environments during the process of gene delivery or transfection. More specifically, in the framework of oncology, systemic delivery has been investigated to enable polyplex accumulation in tumor tissue as well as in ensuing metastases. The stakes are twofold here: it is relevant to decorate polyplexes both with ligands that enable the specific targeting of cancer cells in order to deliver genes at the right place and with a complete surface coating enabling them to circulate more freely in the bloodstream while limiting their elimination by the mononuclear phagocyte system. In a first study, we set up a system to tether ligands at the surface of polyplexes. We based our works on the E/Kcoil tandem: two peptides that enable a stable, oriented and specific tethering between two entities by auto assembly in solution. On the one side, we chose a ligand: a chimeric protein corresponding to the Ecoil peptide fused with the epidermal growth factor (Ecoil-EGF); and on the other side, we engineered a Kcoil peptide-decorated polyplex. In that endeavor, a cationic polymer - branched polyethylenimine (bPEI) - was functionalized with a moiety reactive to the Kcoil peptide. Polyplexes prepared with this activated bPEI could then be decorated at their surface by the covalent grafting of Kcoil. This system enabled us to fine-tune the ligand surface density in order to study its influence on polyplex uptake by cancer-derived EGF receptor (EGFR)-over-expressing A431 cells. Thus, we evidenced a switch effect between the EGFR-specific polyplex uptake rate by A431 cells and the amount of ligand on polyplexes. Then, we carried out a second study that was focused on the electrostatic coating of polyplexes with carboxymethylated dextran (CMD). The objective was to draw relations between the coating structure - defined by the charge density and the molecular weight of the CMD used - and its function relative to the biological environment. We prepared and characterized a chemical library of 26 closely related CMDs by the controlled carboxymethylation of 4 dextrans differing by their molecular weight. A simple and robust electrostatic coating procedure was set up in order to carry out a systematic study of the CMD library. Each coated polyplex formulation was tested on decoupled relevant constituents of the physiological milieu: small ions, DNases, plasma proteins, red blood cells, and target cells. We observed monotonic trends between both parameters and DNA encapsulation. To our great surprise, those observations did not correlate with DNA protection against DNase challenging, the latter correlating with target cells reporter gene expression. Polyplex stability was evaluated at physiological salt concentration; the results of which indicated that both studied parameters had a jointed influence in preventing polyplex aggregation. At the surface of polyplexes, this influence translated in terms of steric and lateral stabilization rather than in terms of surface charge (zeta potential). Conversely, the latter turned out to be a strong predictor of the ability of coated polyplexes to prevent both opsonization and erythrocytes aggregation. Thus, we exposed the complementarity of several relevant interfacial characteristics for the use of polyplexes in vivo, whereby broadening our understanding of the tailoring of the surface of polyplexes with a hydrophilic polyanion. Next, we envisioned the design of a transfection agent comprising of the E/Kcoil system together with a cationic peptide (RRRRRHHHHHC or R5H5) directly grafted on a dextran backbone. This approach was developed in order to take advantage of the growing collection of Ecoil-tagged polypeptides that were being developed and characterized in our group: especially one derived from the vascular endothelial growth factor (Ecoil-VEGF), and the other from the endosomolytic peptide GALA (Ecoil-GALA). In that endeavor, two dextran-peptides conjugates were prepared and characterized: Dextran-R5H5 and Dextran-R5H5,-Kcoil. Their abilities to encapsulate DNA and to form nanoparticles were confirmed. Subsequently, in vitro transfection assays demonstrated no significant gain from controls: Dextran-R5H5 could transfect cells with no greater efficacy than that of linear PEI. We then equipped our polyplexes with Ecoil-GALA in order to facilitate endosomal escape; however we could not evidence any additional gain regarding that latter point or with respect to overall reporter gene expression. In another side study, we evaluated the utility of polyanions such as CMD in transient gene expression (TGE) for the production of r-proteins in bioreactors. We had previously observed that one of the beneficial effects of polyplex coating with CMD was related to the complexation of excess polycation, which had been linked to the cytotoxicity observed during polyplex-mediated transfection. In parallel, we confirmed that the direct use of coated polyplexes did reduce toxicity during transfection, albeit with decreased r-protein yield. We thus conjectured that the addition of polyanion after transfection could attenuate excess polycation-associated toxicity while maintaining high TGE yields, in order to increase the overall r-protein yield. A library of 8 varied polyanions was used in order to test this hypothesis. Although the delay before addition was explored along with the amount of polyanion, no reliable procedure could be brought out. The last study that we carried out dealt with DNA immunization of animals for the generation of antibodies. The hydrodynamic injection of naked plasmid DNA is currently being used in that endeavor for small mammals such as mice. This procedure is effective yet not efficient as it proves lethal for one in four animals in our facility. The direct use of PEI/DNA polyplexes is also limited for it proves even riskier for the animal. These two techniques feature a systemic injection that renders them hardly scalable to larger animals such as llamas, a particularly relevant species in the field of antibodies generation. We first took on setting up a lyophilisation procedure for our most promising coated polyplex formulation for further use in mice. Successful lyophilizing enabled us to prepare in advance polyplexes to be rehydrated in a highly concentrated yet isotonic fashion that was better adapted for systemic injection. We selected appropriate formulations based on the knowledge gained from the analysis of our CMD library. A first assay was carried out with polyplexes coated with CMD70-60, the most stable formulation that was found to comply with every criterion for systemic injection. Corresponding results indicated that no lethal side effect arose, however the resulting gene expression in mice was undetectable. We then carried out a second round of injections on the same mice cohort, with two less stable formulations: a CMD 40-30 coating that still complied with every physiological criterion was chosen for systemic injection; and a CMD40-03 coating that featured better in vitro transfection performances but did not otherwise comply with every physiological criterion was injected subcutaneously. The subcutaneous injection proved lethal to every animal, which suggests that our previous in vitro systematic analysis bears predictive power over in vivo performances.

Chemical and structural indicators for large redox potentials in Fe-based positive electrode materials.

PubMed

Melot, Brent C; Scanlon, David O; Reynaud, Marine; Rousse, Gwenaëlle; Chotard, Jean-Noël; Henry, Marc; Tarascon, Jean-Marie

2014-07-23

Li-ion batteries have enabled a revolution in the way portable consumer-electronics are powered and will play an important role as large-scale electrochemical storage applications like electric vehicles and grid-storage are developed. The ability to identify and design promising new positive insertion electrodes will be vital in continuing to push Li-ion technology to its fullest potential. Utilizing a combination of computational tools and structural analysis, we report new indicators which will facilitate the recognition of phases with the desired redox potential. Most importantly of these, we find there is a strong correlation between the presence of Li ions sitting in close-proximity to the redox center of polyanionic phases and the open circuit voltage in Fe-based cathodes. This common structural feature suggests that the bonding associated with Li may have a secondary inductive effect which increases the ionic character of Fe bonds beyond what is typically expected based purely on arguments of electronegativity associated with the polyanionic group. This correlation is supported by ab initio calculations which show the Bader charge increases (reflecting an increased ionicity) in a nearly linear fashion with the experimental cell potentials. These features are demonstrated to be consistent across a wide variety of compositions and structures and should help to facilitate the design of new, high-potential, and environmentally sustainable insertion electrodes.

Crystallization of calcium oxalate monohydrate at dipalmitoylphosphatidylcholine monolayers in the presence of chondroitin sulfate A

NASA Astrophysics Data System (ADS)

Ouyang, Jian-Ming; Deng, Sui-Ping; Zhong, Jiu-Ping; Tieke, Bernd; Yu, Shu-Hong

2004-10-01

The growth and aggregation of calcium oxalate monohydrate (COM) crystals beneath dipalmitoylphosphatidylcholine (DPPC) monolayers in the presence of chondroitin sulfate A (C4S) was systematically examined under different surface pressure. The results indicated that the addition of C4S can inhibit the crystal growth and prevent the aggregation of COM crystals. Under a DPPC monolayer, well-defined three-dimensional hexagonal prisms and three-dimensional rhombus prisms with sharply angled tips were obtained. The DPPC monolayer at a surface pressure of 10 mN/m can match the Ca2+ distance of the (1 bar 0 1) face of COM better than at 20 mN/m. The addition of C4S could cooperatively modulate the interaction strength between the monolayer (or itself) with the specific morphology determining faces such as (1 bar 0 1) and (0 2 0), and thus results in remarkable stabilization of the (1 bar 0 1) faces. The dramatic changes in morphological details were due to the strong electrostatic interactions between the Ca2+-rich (1 bar 0 1) crystal faces of COM and the polyanionic polysaccharide C4S together with the negatively charged sites of the zwitterionic DPPC monolayers. The increase of the concentration of C4S can further enhance the stabilization of the (1 bar 0 1) face.

Recent achievements on polyanion-type compounds for sodium-ion batteries: Syntheses, crystal chemistry and electrochemical performance

NASA Astrophysics Data System (ADS)

Guo, Sheng-Ping; Li, Jia-Chuang; Xu, Qian-Ting; Ma, Ze; Xue, Huai-Guo

2017-09-01

In the past several years, many efforts have been made to develop polyanion-type cathode materials for sodium ion batteries by chemists and material scientists. These materials are one of the main types of promising cathodes though the studies are still in their infancy. This paper reviews almost all the important advances of polyanion-type cathodes on their syntheses, crystal structures, morphologies, electrochemical performance and Na redox mechanisms. It specifically focuses on their crystal chemistry and electrochemical behaviors. The contents are divided into several categories according to their chemical compositions. After introduction of the synthetic methods, phosphates (ortho-, pyro- and fluoro-), silicates, sulfates, and mixed anions type cathodes are summarized and discussed successively.

Exploiting Conjugated Polyelectrolyte Photophysics toward Monitoring Real-Time Lipid Membrane-Surface Interaction Dynamics at the Single-Particle Level.

PubMed

Calver, Christina F; Liu, Hsiao-Wei; Cosa, Gonzalo

2015-11-03

Herein we report the real-time observation of the interaction dynamics between cationic liposomes flowing in solution and a surface-immobilized charged scaffolding formed by the deposition of conjugated polyanion poly[5-methoxy-2-(3-sulfopropoxy)-1,4-phenylenevinylene (MPS-PPV) onto 100-nm-diameter SiO2 nanoparticles (NPs). Contact of the freely floating liposomes with the polymer-coated surfaces led to the formation of supported lipid bilayers (SLBs). The interaction of the incoming liposomes with MPS-PPV adsorbed on individual SiO2 nanoparticles promoted the deaggregation of the polymer conformation and led to large emission intensity enhancements. Single-particle total internal reflection fluorescence microscopy studies exploited this phenomenon as a way to monitor the deformation dynamics of liposomes on surface-immobilized NPs. The MPS-PPV emission enhancement (up to 25-fold) reflected on the extent of membrane contact with the surface of the NP and was correlated with the size of the incoming liposome. The time required for the MPS-PPV emission to reach a maximum (ranging from 400 to 1000 ms) revealed the dynamics of membrane deformation and was also correlated with the liposome size. Cryo-TEM experiments complemented these results by yielding a structural view of the process. Immediately following the mixing of liposomes and NPs the majority of NPs had one or more adsorbed liposomes, yet the presence of a fully formed SLB was rare. Prolonged incubation of liposomes and NPs showed completely formed SLBs on all of the NPs, confirming that the liposomes eventually ruptured to form SLBs. We foresee that the single-particle studies we report herein may be readily extended to study membrane dynamics of other lipids including cellular membranes in live cell studies and to monitor the formation of polymer-cushioned SLBs.

Two Keggin-type heteropolytungstates with transition metal as a central atom: Crystal structure and magnetic study with 2D-IR correlation spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chai, Feng; Chen, YiPing, E-mail: ypchen007@sina.com; State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002

2013-06-01

Two Keggin-type heteropolytungstates, [Co(phen)₃]₃[CoW₁₂O₄₀]·9H₂O 1 (phen=1,10-phenanthroline) and [Fe(phen)₃]₂[FeW₁₂O₄₀]·H₃O·H₂O 2, have been synthesized via the hydrothermal technique and characterized by single crystal X-ray diffraction analyses, IR, XPS, TG analysis, UV–DRS, XRD, thermal-dependent and magnetic-dependent 2D-COS IR (two-dimensional infrared correlation spectroscopy). Crystal structure analysis reveals that the polyanions in compound 1 are linked into 3D supramolecule through hydrogen bonding interactions between lattice water molecules and terminal oxygen atoms of polyanion units, and [Co(phen)₃]²⁺ cations distributed in the polyanion framework with many hydrogen bonding interactions. The XPS spectra indicate that all the Co atoms in 1 are +2 oxidation state, the Fe atomsmore » in 2 existing with +2 and +3 mixed oxidation states. - Graphical abstract: The magnetic-dependent synchronous 2D correlation IR spectra of 1 (a), 2 (b) over 0–50 mT in the range of 600–1000 cm⁻¹, the obvious response indicate two Keggin polyanions skeleton susceptible to applied magnetic field. Highlights: • Two Keggin-type heteropolytungstates with transition metal as a central atom has been obtained. • Compound 1 forms into 3D supramolecular architecture through hydrogen bonding between water molecules and polyanions. • Magnetic-dependent 2D-IR correlation spectroscopy was introduced to discuss the magnetism of polyoxometalate.« less

CrIII-Substituted Heteropoly-16-Tungstates [CrIII2(B-β-XIVW8O31)2]14- (X = Si, Ge): Magnetic, Biological, and Electrochemical Studies.

PubMed

Liu, Wenjing; Al-Oweini, Rami; Meadows, Karen; Bassil, Bassem S; Lin, Zhengguo; Christian, Jonathan H; Dalal, Naresh S; Bossoh, A Martin; Mbomekallé, Israël M; de Oliveira, Pedro; Iqbal, Jamshed; Kortz, Ulrich

2016-11-07

The dichromium(III)-containing heteropoly-16-tungstates [Cr III 2 (B-β-Si IV W 8 O 31 ) 2 ] 14- (1) and [Cr III 2 (B-β-Ge IV W 8 O 31 ) 2 ] 14- (2) were prepared via a one-pot reaction of the composing elements in aqueous, basic medium. Polyanions 1 and 2 represent the first examples of Cr III -containing heteropolytungstates comprising the octatungstate unit {XW 8 O 31 } (X = Si, Ge). Magnetic studies demonstrated that, in the solid state, the two polyanions exhibit a weak antiferromagnetic interaction between the two Cr III centers with J = -3.5 ± 0.5 cm -1 , with no long-range ordering down to 1.8 K. The ground-state spin of polyanions 1 and 2 was thus deduced to be 0, but the detection of a complex set of EPR signals implies that there are thermally accessible excited states containing unpaired spins resulting from the two S = 3 / 2 Cr III ions. A comprehensive electrochemistry study on 1 and 2 in solution was performed, and biological tests showed that both polyanions display significant antidiabetic and anticancer activities.

Biochemistry-directed hollow porous microspheres: bottom-up self-assembled polyanion-based cathodes for sodium ion batteries

NASA Astrophysics Data System (ADS)

Lin, Bo; Li, Qiufeng; Liu, Baodong; Zhang, Sen; Deng, Chao

2016-04-01

Biochemistry-directed synthesis of functional nanomaterials has attracted great interest in energy storage, catalysis and other applications. The unique ability of biological systems to guide molecule self-assembling facilitates the construction of distinctive architectures with desirable physicochemical characteristics. Herein, we report a biochemistry-directed ``bottom-up'' approach to construct hollow porous microspheres of polyanion materials for sodium ion batteries. Two kinds of polyanions, i.e. Na3V2(PO4)3 and Na3.12Fe2.44(P2O7)2, are employed as cases in this study. The microalgae cell realizes the formation of a spherical ``bottom'' bio-precursor. Its tiny core is subjected to destruction and its tough shell tends to carbonize upon calcination, resulting in the hollow porous microspheres for the ``top'' product. The nanoscale crystals of the polyanion materials are tightly enwrapped by the highly-conductive framework in the hollow microsphere, resulting in the hierarchical nano-microstructure. The whole formation process is disclosed as a ``bottom-up'' mechanism. Moreover, the biochemistry-directed self-assembly process is confirmed to play a crucial role in the construction of the final architecture. Taking advantage of the well-defined hollow-microsphere architecture, the abundant interior voids and the highly-conductive framework, polyanion materials show favourable sodium-intercalation kinetics. Both materials are capable of high-rate long-term cycling. After five hundred cycles at 20 C and 10 C, Na3V2(PO4)3 and Na3.12Fe2.44(P2O7)2 retain 96.2% and 93.1% of the initial capacity, respectively. Therefore, the biochemistry-directed technique provides a low-cost, highly-efficient and widely applicable strategy to produce high-performance polyanion-based cathodes for sodium ion batteries.Biochemistry-directed synthesis of functional nanomaterials has attracted great interest in energy storage, catalysis and other applications. The unique ability of biological systems to guide molecule self-assembling facilitates the construction of distinctive architectures with desirable physicochemical characteristics. Herein, we report a biochemistry-directed ``bottom-up'' approach to construct hollow porous microspheres of polyanion materials for sodium ion batteries. Two kinds of polyanions, i.e. Na3V2(PO4)3 and Na3.12Fe2.44(P2O7)2, are employed as cases in this study. The microalgae cell realizes the formation of a spherical ``bottom'' bio-precursor. Its tiny core is subjected to destruction and its tough shell tends to carbonize upon calcination, resulting in the hollow porous microspheres for the ``top'' product. The nanoscale crystals of the polyanion materials are tightly enwrapped by the highly-conductive framework in the hollow microsphere, resulting in the hierarchical nano-microstructure. The whole formation process is disclosed as a ``bottom-up'' mechanism. Moreover, the biochemistry-directed self-assembly process is confirmed to play a crucial role in the construction of the final architecture. Taking advantage of the well-defined hollow-microsphere architecture, the abundant interior voids and the highly-conductive framework, polyanion materials show favourable sodium-intercalation kinetics. Both materials are capable of high-rate long-term cycling. After five hundred cycles at 20 C and 10 C, Na3V2(PO4)3 and Na3.12Fe2.44(P2O7)2 retain 96.2% and 93.1% of the initial capacity, respectively. Therefore, the biochemistry-directed technique provides a low-cost, highly-efficient and widely applicable strategy to produce high-performance polyanion-based cathodes for sodium ion batteries. Electronic supplementary information (ESI) available: Synthesis, morphology and physical characteristics of reference samples; pore size distribution of the hollow porous microsphere; morphology of the bio-directed Na3.12Fe2.44(P2O7)2 hollow microsphere; comparison of the Rct values for the Na3.12Fe2.44(P2O7)2 composites; TEM images of the cycled materials; lattice parameters and atomic ratio of the samples; calculation process of sodium intercalation coefficients based on the GITT results. See DOI: 10.1039/c6nr00680a

The two-step assemblies of basic-amino-Acid-rich Peptide with a highly charged polyoxometalate.

PubMed

Zhang, Teng; Li, Hong-Wei; Wu, Yuqing; Wang, Yizhan; Wu, Lixin

2015-06-15

Two-step assembly of a peptide from HPV16 L1 with a highly charged europium-substituted polyoxometalate (POM) cluster, accompanying a great luminescence enhancement of the inorganic polyanions, is reported. The mechanism is discussed in detail by analyzing the thermodynamic parameters from isothermal titration calorimetry (ITC), time-resolved fluorescent and NMR spectra. By comparing the actions of the peptide analogues, a binding process and model are proposed accordingly. The driving forces in each binding step are clarified, and the initial POM aggregation, basic-sequence and hydrophobic C termini of peptide are revealed to contribute essentially to the two-step assembly. The present study demonstrates both a meaningful preparation for bioinorganic materials and a strategy using POMs to modulate the assembly of peptides and even proteins, which could be extended to other proteins and/or viruses by using peptides and POMs with similar properties. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrostatic effects on hyaluronic acid configuration

NASA Astrophysics Data System (ADS)

Berezney, John; Saleh, Omar

2015-03-01

In systems of polyelectrolytes, such as solutions of charged biopolymers, the electrostatic repulsion between charged monomers plays a dominant role in determining the molecular conformation. Altering the ionic strength of the solvent thus affects the structure of such a polymer. Capturing this electrostatically-driven structural dependence is important for understanding many biological systems. Here, we use single molecule manipulation experiments to collect force-extension behavior on hyaluronic acid (HA), a polyanion which is a major component of the extracellular matrix in all vertebrates. By measuring HA elasticity in a variety of salt conditions, we are able to directly assess the contribution of electrostatics to the chain's self-avoidance and local stiffness. Similar to recent results from our group on single-stranded nucleic acids, our data indicate that HA behaves as a swollen chain of electrostatic blobs, with blob size proportional to the solution Debye length. Our data indicate that the chain structure within the blob is not worm-like, likely due to long-range electrostatic interactions. We discuss potential models of this effect.

[Chitosan-collagen polymer induced remineralization of tooth hard tissue through self-growing methods].

PubMed

Xun, Ren; Jing, Yao; Qin, Du; Chuhang, Liao; Kun, Tian

2014-10-01

To modify biomacromolecules, such as chitosan and collagen, to synthesize a mineralized template that will induce self-growing remineralization of tooth enamel. Natural polycation polysaccharide chitosan was modified through phosphorylation to synthesize the polyanion derivative ofphosphorylated chitosan. Parent hydrogels com- bined with chitosan and collagen I were built through peptide binding reaction using genipin as a crosslinker. The gels self- assembled on the tooth's inert surface, which was stimulated by ultraviolet radiation. The bionic saliva provided mineralized ion, and then the hydroxyapatite assembled and grew in situ on the tooth. The functional group P04(3-) (3,446 cm(-1)) was grafted on chitosan as confirmed by the Fourier transform infrared spectroscopy. The porous polyelectrolyte complex hydrogel formed by the interaction between the polycation chitosan and the polyanion phosphorylated chitosan could induce hydroxyapatite crystal nucleation and growth on the hydrogel fiber surfaces. The neonatal crystal was hydroxyapatite as confirmed by X-ray diffraction and was tightly connected to the tooth. A continuous structure of column crystals with sizes ranging from 30 nm to 60 nm was observed. The structure was in parallel direction similar to the direction of the enamel rod, and its hardness was close to dentin. The parent hydrogels that were easily obtained and controlled could mimic the template of the enamel mineralization and induce a self-growing hydroxyapatite, which is an important step in the structural bionics of enamel.

Polyacetal Carboxylic Acids: a New Group of Antiviral Polyanions

PubMed Central

Claes, P.; Billiau, A.; De Clercq, E.; Desmyter, J.; Schonne, E.; Vanderhaeghe, H.; De Somer, P.

1970-01-01

Chlorite-oxidized oxypolysaccharides are polyacetal carboxylic acids. They inhibited the cytopathic effect of vesicular stomatitis virus in mouse embryo cell cultures challenged at low input multiplicity. After intraperitoneal injection of these compounds in mice, interferon appeared in the circulation. The compounds also protected mice against lethal mengovirus infection and against the development of experimental pox lesions on the tail. Chlorite-oxidized oxyamylose was antiviral only when at least 64% of the glucopyranose units were oxidized, an observation which suggested a correlation between charge density and antiviral effect. The antiviral activity was also influenced by the molecular weight, as demonstrated by the fact that chlorite-oxidized dextrans which had a high intrinsic viscosity were more active than those with low intrinsic viscosity. PMID:4314553

Poly(l-glutamic acid)-g-poly(ethylene glycol) external layer in polyelectrolyte multilayer films: Characterization and resistance to serum protein adsorption.

PubMed

Szczepanowicz, Krzysztof; Kruk, Tomasz; Świątek, Wiktoria; Bouzga, Aud M; Simon, Christian R; Warszyński, Piotr

2018-06-01

Formation of protein-resistant surfaces is a major challenge in the design of novel biomaterials and an important strategy to prevent protein adsorption is the formation of protein-resistant coatings. It can be achieved by proper modification of surfaces, e.g., by immobilization of hydrophilic polymers such as poly(ethylene glycol) (PEG). An appropriate method to immobilize PEG at charged surfaces is the adsorption of copolymers with PEG chains grafted onto polyelectrolyte backbone. The growing interest in the use of polyelectrolyte multilayer coatings in biomedical applications to improve biocompatibility and/or to prepare coating with antiadhesive properties has been the main reason for these studies. Therefore the aim was to produce protein resistant polyelectrolyte multilayer films. They were formed via the layer-by-layer approach, while their pegylation by the deposition of pegylated polyanion, PGA-g-PEG, as an external layer. The influence of PEG chain length and grafting density of PGA-g-PEG copolymers on the protein antiadhesive properties of pegylated polyelectrolyte multilayer films was investigated. To monitor the formation of pegylated and non-pegylated multilayer films, adsorption of the following proteins: HSA, Fibrinogen, and FBS were measured by quartz crystal microbalance (QCM - D). We found that protein adsorption onto all pegylated polyelectrolyte multilayers was significantly reduced in comparison to non-pegylated ones. Long-term performance tests confirmed the stability and the durability of the protein resistant properties of the pegylated multilayers. Antiadhesive properties of tested surfaces pegylated by PGA-g-PEG were compared to the available data for pegylated polycation PLL-g-PEG. Copyright © 2018 Elsevier B.V. All rights reserved.

Hydrides of Alkaline Earth–Tetrel (AeTt) Zintl Phases: Covalent Tt–H Bonds from Silicon to Tin

DOE Office of Scientific and Technical Information (OSTI.GOV)

Auer, Henry; Guehne, Robin; Bertmer, Marko

Zintl phases form hydrides either by incorporating hydride anions (interstitial hydrides) or by covalent bonding of H to the polyanion (polyanionic hydrides), which yields a variety of different compositions and bonding situations. Hydrides (deuterides) of SrGe, BaSi, and BaSn were prepared by hydrogenation (deuteration) of the CrB-type Zintl phases AeTt and characterized by laboratory X-ray, synchrotron, and neutron diffraction, NMR spectroscopy, and quantum-chemical calculations. SrGeD4/3–x and BaSnD4/3–x show condensed boatlike six-membered rings of Tt atoms, formed by joining three of the zigzag chains contained in the Zintl phase. These new polyanionic motifs are terminated by covalently bound H atoms withmore » d(Ge–D) = 1.521(9) Å and d(Sn–D) = 1.858(8) Å. Additional hydride anions are located in Ae4 tetrahedra; thus, the features of both interstitial hydrides and polyanionic hydrides are represented. BaSiD2–x retains the zigzag Si chain as in the parent Zintl phase, but in the hydride (deuteride), it is terminated by H (D) atoms, thus forming a linear (SiD) chain with d(Si–D) = 1.641(5) Å.« less

Relating voltage and thermal safety in Li-ion battery cathodes: a high-throughput computational study.

PubMed

Jain, Anubhav; Hautier, Geoffroy; Ong, Shyue Ping; Dacek, Stephen; Ceder, Gerbrand

2015-02-28

High voltage and high thermal safety are desirable characteristics of cathode materials, but difficult to achieve simultaneously. This work uses high-throughput density functional theory computations to evaluate the link between voltage and safety (as estimated by thermodynamic O2 release temperatures) for over 1400 cathode materials. Our study indicates that a strong inverse relationship exists between voltage and safety: just over half the variance in O2 release temperature can be explained by voltage alone. We examine the effect of polyanion group, redox couple, and ratio of oxygen to counter-cation on both voltage and safety. As expected, our data demonstrates that polyanion groups improve safety when comparing compounds with similar voltages. However, a counterintuitive result of our study is that polyanion groups produce either no benefit or reduce safety when comparing compounds with the same redox couple. Using our data set, we tabulate voltages and oxidation potentials for over 105 combinations of redox couple/anion, which can be used towards the design and rationalization of new cathode materials. Overall, only a few compounds in our study, representing limited redox couple/polyanion combinations, exhibit both high voltage and high safety. We discuss these compounds in more detail as well as the opportunities for designing safe, high-voltage cathodes.

Selective, ultrathin membrane skins prepared by deposition of novel polymer films on porous alumina supports

NASA Astrophysics Data System (ADS)

Balachandra, Anagi Manjula

Membrane-based separations are attractive in industrial processes because of their low energy costs and simple operation. However, low permeabilities often make membrane processes uneconomical. Since flux is inversely proportional to membrane thickness, composite membranes consisting of ultrathin, selective skins on highly permeable supports are required to simultaneously achieve high throughput and high selectivity. However, the synthesis of defect-free skins with thicknesses less than 50 nm is difficult, and thus flux is often limited. Layer-by-layer deposition of oppositely charged polyelectrolytes on porous supports is an attractive method to synthesize ultrathin ion-separation membranes with high flux and high selectivity. The ion-transport selectivity of multilayer polyelectrolyte membranes (MPMs) is primarily due to Donnan exclusion; therefore increase in fixed charge density should yield high selectivity. However, control over charge density in MPMs is difficult because charges on polycations are electrostatically compensated by charges on polyanions, and the net charge in the bulk of these films is small. To overcome this problem, we introduced a templating method to create ion-exchange sites in the bulk of the membrane. This strategy involves alternating deposition of a Cu2+-poly(acrylic acid) complex and poly(allylamine hydrochloride) on a porous alumina support followed by removal of Cu2+ and deprotonation to yield free -COO- ion-exchange sites. Diffusion dialysis studies showed that the Cl-/SO42-. Selectivity of Cu2+-templated membranes is 4-fold higher than that of membranes prepared in the absence of Cu2+. Post-deposition cross-linking of these membranes by heat-induced amide bond formation further increased Cl-/SO42- selectivity to values as high as 600. Room-temperature, surface-initiated atom transfer radical polymerization (ATRP) provides another convenient method for formation of ultrathin polymer skins. This process involves attachment of polymerization initiators to a porous alumina support and subsequent polymerization from these initiators. Because ATRP is a controlled polymerization technique, it yields well-defined polymer films with low polydispersity indices (narrow molecular weight distributions). Additionally, this method is attractive because film thickness can be easily controlled by adjusting polymerization time. Gas-permeability data showed that grafted poly(ethylene glycol dimethacrylate) membranes have a CO 2/CH4 selectivity of 20, whereas poly(2-hydroxyethyl methacrylate) (PHEMA) films grown from a surface have negligible selectivity. However, derivatization of PHEMA with pentadecafluorooctanoyl chloride increases the solubility of CO2 in the membrane and results in a CO2/CH4 selectivity of 9. Although composite PHEMA membranes have no significant gas-transport selectivity, diffusion dialysis studies with PHEMA membranes showed moderate ion-transport selectivities. Cross-linking of PHEMA membranes by reaction with succinyl chloride greatly enhanced anion-transport selectivities while maintaining reasonable flux. The selectivities of these systems demonstrate that alternating polyelectrolyte deposition and surface-initiated ATRP are indeed capable of forming ultrathin, defect-free membrane skins that can potentially be modified for specific separations.

The first Fe-based Na+-ion cathode with two distinct types of polyanions: Fe 3P 5SiO 19

DOE PAGES

Kan, W. H.; Huq, A.; Manthiram, A.

2015-05-15

We report the synthesis, structure, and electrochemistry of the first Na +-ion cathode with two distinct types of polyanions: Fe 3P 5SiO 19. The Fe-based cathode has a reversible capacity of ca. 70 mAh g -1; ca. 1.7 Na + ions per formula can be inserted/extracted at an average voltage of 2.5 V versus Na +/Na.

Conducting electrospun fibres with polyanionic grafts as highly selective, label-free, electrochemical biosensor with a low detection limit for non-Hodgkin lymphoma gene.

PubMed

Kerr-Phillips, Thomas E; Aydemir, Nihan; Chan, Eddie Wai Chi; Barker, David; Malmström, Jenny; Plesse, Cedric; Travas-Sejdic, Jadranka

2018-02-15

A highly selective, label-free sensor for the non-Hodgkin lymphoma gene, with an aM detection limit, utilizing electrochemical impedance spectroscopy (EIS) is presented. The sensor consists of a conducting electrospun fibre mat, surface-grafted with poly(acrylic acid) (PAA) brushes and a conducting polymer sensing element with covalently attached oligonucleotide probes. The sensor was fabricated from electrospun NBR rubber, embedded with poly(3,4-ethylenedioxythiophene) (PEDOT), followed by grafting poly(acrylic acid) brushes and then electrochemically polymerizing a conducting polymer monomer with ssDNA probe sequence pre-attached. The resulting non-Hodgkin lymphoma gene sensor showed a detection limit of 1aM (1 × 10 -18 mol/L), more than 400 folds lower compared to a thin-film analogue. The sensor presented extraordinary selectivity, with only 1%, 2.7% and 4.6% of the signal recorded for the fully non-complimentary, T-A and G-C base mismatch oligonucleotide sequences, respectively. We suggest that such greatly enhanced selectivity is due to the presence of negatively charged carboxylic acid moieties from PAA grafts that electrostatically repel the non-complementary and mismatch DNA sequences, overcoming the non-specific binding. Copyright © 2017 Elsevier B.V. All rights reserved.

Biocompatible Polymeric Nanoparticles as Promising Candidates for Drug Delivery.

PubMed

Łukasiewicz, Sylwia; Szczepanowicz, Krzysztof; Błasiak, Ewa; Dziedzicka-Wasylewska, Marta

2015-06-16

The use of polymeric nanoparticles (NPs) in pharmacology provides many benefits because this approach can increase the efficacy and selectivity of active compounds. However, development of new nanocarriers requires better understanding of the interactions between NPs and the immune system, allowing for the optimization of NP properties for effective drug delivery. Therefore, in the present study, we focused on the investigation of the interactions between biocompatible polymeric NPs and a murine macrophage cell line (RAW 264.7) and a human monocytic leukemia cell line (THP-1). NPs based on a liquid core with polyelectrolyte shells were prepared by sequential adsorption of polyelectrolytes (LbL) using AOT (docusate sodium salt) as the emulsifier and the biocompatible polyelectrolytes polyanion PGA (poly-l-glutamic acid sodium salt) and polycation PLL (poly l-lysine). The average size of the obtained NPs was 80 nm. Pegylated external layers were prepared using PGA-g-PEG (PGA grafted by PEG poly(ethylene glycol)). The influence of the physicochemical properties of the NPs (charge, size, surface modification) on viability, phagocytosis potential, and endocytosis was studied. Internalization of NPs was determined by flow cytometry and confocal microscopy. Moreover, we evaluated whether addition of PEG chains downregulates particle uptake by phagocytic cells. The presented results confirm that the obtained PEG-grafted NPs are promising candidates for drug delivery.

Simple and Rapid Immobilization of Coating Polymers on Poly(dimethyl siloxane)-glass Hybrid Microchips by a Vacuum-drying Method.

PubMed

Kitagawa, Fumihiko; Nakagawara, Syo; Nukatsuka, Isoshi; Hori, Yusuke; Sueyoshi, Kenji; Otsuka, Koji

2015-01-01

A simple and rapid vacuum-drying modification method was applied to several neutral and charged polymers to obtain coating layers for controlling electroosmotic flow (EOF) and suppressing sample adsorption on poly(dimethyl siloxane) (PDMS)-glass hybrid microchips. In the vacuum-dried poly(vinylpyrrolidone) coating, the electroosmotic mobility (μeo) was suppressed from +2.1 to +0.88 × 10(-4) cm(2)/V·s, and the relative standard deviation (RSD) of μeo was improved from 10.2 to 2.5% relative to the bare microchannel. Among several neutral polymers, poly(vinylalcohol) (PVA) and poly(dimethylacrylamide) coatings gave more suppressed and repeatable EOF with RSDs of less than 2.3%. The vacuum-drying method was also applicable to polyanions and polycations to provide accelerated and inversed EOF, respectively, with acceptable RSDs of less than 4.9%. In the microchip electrophoresis (MCE) analysis of bovine serum albumin (BSA) in the vacuum-dried and thermally-treated PVA coating channel, an almost symmetric peak of BSA was obtained, while in the native microchannel a significantly skewed peak was observed. The results demonstrated that the vacuum-dried polymer coatings were effective to control the EOF, and reduced the surface adsorption of proteins in MCE.

Atomic force microscopy of adsorbed proteoglycan mimetic nanoparticles: Toward new glycocalyx-mimetic model surfaces.

PubMed

Hedayati, Mohammadhasan; Kipper, Matt J

2018-06-15

Blood vessels present a dense, non-uniform, polysaccharide-rich layer, called the endothelial glycocalyx. The polysaccharides in the glycocalyx include polyanionic glycosaminoglycans (GAGs). This polysaccharide-rich surface has excellent and unique blood compatibility. We report new methods for preparing and characterizing dense GAG surfaces that can serve as models of the vascular endothelial glycocalyx. The GAG-rich surfaces are prepared by adsorbing heparin or chondroitin sulfate-containing polyelectrolyte complex nanoparticles (PCNs) to chitosan-hyaluronan polyelectrolyte multilayers (PEMs). The surfaces are characterized by PeakForce tapping atomic force microscopy, both in air and in aqueous pH 7.4 buffer, and by PeakForce quantitative nanomechanics (PF-QNM) mode with high spatial resolution. These new surfaces provide access to heparin-rich or chondroitin sulfate-rich coatings that mimic both composition and nanoscale structural features of the vascular endothelial glycocalyx. Copyright © 2018. Published by Elsevier Ltd.

Spectrophotometric determination of various polyanions with polymeric film optodes using microtiter plate reader.

PubMed

Dürüst, Nedime; Meyerhoff, Mark E; Unal, Nazangül; Naç, Sibel

2011-08-05

Polycation-sensitive membrane optodes based on the chromoionophore 2',7'-dichlorofluorescein octadecylester (DCFOE) have previously been developed and used for determination of heparin via a titrimetric method. In this study, it is shown that some other important polyanions such as PPS (pentosan polysulfate), DNA, xanthan, Na-alginate, and carrageenan (food additive) can also be readily determined by using DCFOE-based microtiter plate-format optodes (MPOs) and polycationic titrants that bind these polyanionic species. The optical sensors are prepared with poly(vinyl chloride) (PVC), polyurethane (PU), bis(2-ethylhexyl)sebacate (DOS), and 2',7'-dichlorofluorescein octadecylester (DCFOE) and exhibit reproducible and sensitive absorbance changes in response to the varying polycationic titrant concentrations. Three different polycations; protamine, poly-l-lysine and poly-l-arginine, are employed as titrants. The method has a detection limit of 1 μg mL(-1), and a dynamic range of 1-40 μg mL(-1). After the quantitative determinations are successfully demonstrated in buffered solutions, similar titrations are also performed in real samples. The method is validated by recovery studies in these samples. The average polyanion recoveries were quantitative [99.7(±1.3) % for pastry cream with vanillin (protamine titrant); 100.4 (±3.3) % for pastry gel with strawberry(PLA titrant), and 102.9(±2.0) % for pastry gel with strawberry (PLL titrant)]. Copyright © 2011 Elsevier B.V. All rights reserved.

Actin and DNA Protect Histones from Degradation by Bacterial Proteases but Inhibit Their Antimicrobial Activity

PubMed Central

Sol, Asaf; Skvirsky, Yaniv; Blotnick, Edna; Bachrach, Gilad; Muhlrad, Andras

2016-01-01

Histones are small polycationic proteins located in the cell nucleus. Together, DNA and histones are integral constituents of the nucleosomes. Upon apoptosis, necrosis, and infection – induced cell death, histones are released from the cell. The extracellular histones have strong antimicrobial activity but are also cytotoxic and thought as mediators of cell death in sepsis. The antimicrobial activity of the cationic extracellular histones is inhibited by the polyanionic DNA and F-actin, which also become extracellular upon cell death. DNA and F-actin protect histones from degradation by the proteases of Pseudomonas aeruginosa and Porphyromonas gingivalis. However, though the integrity of the histones is protected, the activity of histones as antibacterial agents is lost. The inhibition of the histone’s antibacterial activity and their protection from proteolysis by DNA and F-actin indicate a tight electrostatic interaction between the positively charged histones and negatively charged DNA and F-actin, which may have physiological significance in maintaining the equilibrium between the beneficial antimicrobial activity of extracellular histones and their cytotoxic effects. PMID:27555840

Grown from lithium flux, the ErCo5Si(3.17) silicide is a combination of disordered derivatives of the UCo5Si3 and Yb6Co30P19 structure types.

PubMed

Stetskiv, Andrij; Rozdzynska-Kielbik, Beata; Misztal, Renata; Pavlyuk, Volodymyr

2015-06-01

A ternary hexaerbium triacontacobalt enneakaidecasilicide, ErCo5Si(3.17), crystallizes as a combination of disordered variants of the hexagonal UCo5Si3 (P6₃/m) and Yb6Co30P19 (P6) structure types and is closely related to the Sc6Co30Si19 and Ce6Rh30Si19 types. The Er, Co and three of the Si atoms occupy sites of m.. symmetry and a fourth Si atom occupies a site of -6.. symmetry. The environment of the Er atom is a 21-vertex pseudo-Frank-Kasper polyhedron. Trigonal prismatic coordination is observed for the Si atoms. The Co atoms are enclosed in heavily deformed cuboctahedra and 11-vertex polyhedra. Crystallochemistry analysis and the data from electronic structure calculations (TB-LMTO-ASA) suggest that the Er atoms form positively charged cations which compensate the negative charge of the [Co12Si9](m-) polyanions.

Effect of buffer at nanoscale molecular recognition interfaces - electrostatic binding of biological polyanions.

PubMed

Rodrigo, Ana C; Laurini, Erik; Vieira, Vânia M P; Pricl, Sabrina; Smith, David K

2017-10-19

We investigate the impact of an over-looked component on molecular recognition in water-buffer. The binding of a cationic dye to biological polyanion heparin is shown by isothermal calorimetry to depend on buffer (Tris-HCl > HEPES > PBS). The heparin binding of self-assembled multivalent (SAMul) cationic micelles is even more buffer dependent. Multivalent electrostatic molecular recognition is buffer dependent as a result of competitive interactions between the cationic binding interface and anions present in the buffer.

Controllable synthesis, crystal structure and magnetic properties of Monomer-Dimer Cocrystallized MnIII Salen-type composite material

NASA Astrophysics Data System (ADS)

Wu, Qiong; Wu, Wei; Wu, Yongmei; Li, Weili; Qiao, Yongfeng; Wang, Ying; Wang, Baoling

2018-04-01

By the reaction of manganese-Schiff-base complexes with penta-anionic Anderson heteropolyanion, a new supramolecular architecture [Mn2(Salen)2(H2O)2][Mn(Salen)(H2O)2]2Na[IMo6O24]·8H2O (1) (salen = N,N‧-ethylene-bis (salicylideneiminate) has been isolated. Compound 1 was characterized by the single-crystal X-ray diffraction, elemental, IR and thermal gravimetric analyses. Structural analysis reveals that the unit cell simultaneously contains MnIII-Salen dimer and monomer cation fragments, for which the Anderson-type polyanions serve as counter anions. In the packing arrangement, all the MnIII dimers are well separated by polyoxometalate units and form tertiary structure together with MnIII monomers. Interestingly, different from the previous work, in the exact same reaction conditions, we are able to template MnIII-Salen complexes into different configurations by varying the charge state of polyanions. Besides, the magnetic properties of 1 were also examined by using both dc and ac magnetic field of the superconducting quantum interference devices. Most importantly, our fitting of the experimental data to a Heisenberg-type spin model shows that there exists a ferromagnetic exchange interaction ∼5 K between the spins (S = 2) on MnIII in the dimer, while antiferromagnetic ones exist among monomers and dimer (∼2 K). This meta-magnetic state could induce a slight spin frustration at low temperature, which would in turn affect the magnetic behavior. In addition, our ac field measurement of the susceptibilities suggests a typical signature for a single-molecule magnet.

Precise engineering of siRNA delivery vehicles to tumors using polyion complexes and gold nanoparticles.

PubMed

Kim, Hyun Jin; Takemoto, Hiroyasu; Yi, Yu; Zheng, Meng; Maeda, Yoshinori; Chaya, Hiroyuki; Hayashi, Kotaro; Mi, Peng; Pittella, Frederico; Christie, R James; Toh, Kazuko; Matsumoto, Yu; Nishiyama, Nobuhiro; Miyata, Kanjiro; Kataoka, Kazunori

2014-09-23

For systemic delivery of siRNA to solid tumors, a size-regulated and reversibly stabilized nanoarchitecture was constructed by using a 20 kDa siRNA-loaded unimer polyion complex (uPIC) and 20 nm gold nanoparticle (AuNP). The uPIC was selectively prepared by charge-matched polyionic complexation of a poly(ethylene glycol)-b-poly(L-lysine) (PEG-PLL) copolymer bearing ∼40 positive charges (and thiol group at the ω-end) with a single siRNA bearing 40 negative charges. The thiol group at the ω-end of PEG-PLL further enabled successful conjugation of the uPICs onto the single AuNP through coordinate bonding, generating a nanoarchitecture (uPIC-AuNP) with a size of 38 nm and a narrow size distribution. In contrast, mixing thiolated PEG-PLLs and AuNPs produced a large aggregate in the absence of siRNA, suggesting the essential role of the preformed uPIC in the formation of nanoarchitecture. The smart uPIC-AuNPs were stable in serum-containing media and more resistant against heparin-induced counter polyanion exchange, compared to uPICs alone. On the other hand, the treatment of uPIC-AuNPs with an intracellular concentration of glutathione substantially compromised their stability and triggered the release of siRNA, demonstrating the reversible stability of these nanoarchitectures relative to thiol exchange and negatively charged AuNP surface. The uPIC-AuNPs efficiently delivered siRNA into cultured cancer cells, facilitating significant sequence-specific gene silencing without cytotoxicity. Systemically administered uPIC-AuNPs showed appreciably longer blood circulation time compared to controls, i.e., bare AuNPs and uPICs, indicating that the conjugation of uPICs onto AuNP was crucial for enhancing blood circulation time. Finally, the uPIC-AuNPs efficiently accumulated in a subcutaneously inoculated luciferase-expressing cervical cancer (HeLa-Luc) model and achieved significant luciferase gene silencing in the tumor tissue. These results demonstrate the strong potential of uPIC-AuNP nanoarchitectures for systemic siRNA delivery to solid tumors.

Enhancement of selectivity and resolution in the enantioseparation of uncharged compounds using mixtures of oppositely charged cyclodextrins in capillary electrophoresis.

PubMed

Abushoffa, Adel M; Fillet, Marianne; Servais, Anne-Catherine; Hubert, Philippe; Crommen, Jacques

2003-01-01

The enantiomeric separation of some nonsteroidal anti-inflammatory drugs (NSAIDs) was investigated in capillary electrophoresis (CE) using dual systems with mixtures of charged cyclodextrin (CD) derivatives. A significant enhancement of selectivity and resolution could be achieved in the enantioseparation of these analytes in their uncharged form by the simultaneous addition of two oppositely charged CD derivatives to the background electrolyte. The combination of the single-isomer cationic CD, permethyl-6-monoamino-6-monodeoxy-beta-CD (PMMAbetaCD) and the single-isomer polyanionic CD, heptakis-6-sulfato-beta-cyclodextrin (HSbetaCD) in a pH 2.5 phosphoric acid-triethanolamine buffer, was designed and employed for the enantioseparation of profens. The improvement in selectivity and resolution can be attributed to the fact that the two CDs, which lead to independent and enantioselective complexation with the analyte enantiomers, have not only opposite effects on the electrophoretic mobility of these compounds but also opposite affinity patterns towards the enantiomers of these compounds. Binding constants for these enantiomers with each CD were determined using linear regression approach, in order to be able to predict the effect of the concentrations of the two CDs on enantiomeric selectivity and resolution in such dual systems.

Fabrication of multilayered thin films via spin-assembly

DOEpatents

Chiarelli, Peter A.; Robinson, Jeanne M.; Casson, Joanna L.; Johal, Malkiat S.; Wang, Hsing-Lin

2007-02-20

An process of forming multilayer thin film heterostructures is disclosed and includes applying a solution including a first water-soluble polymer from the group of polyanionic species, polycationic species and uncharged polymer species onto a substrate to form a first coating layer on the substrate, drying the first coating layer on the substrate, applying a solution including a second water-soluble polymer from the group of polyanionic species, polycationic species and uncharged polymer species onto the substrate having the first coating layer to form a second coating layer on the first coating layer wherein the second water-soluble polymer is of a different material than the first water-soluble polymer, and drying the second coating layer on the first coating layer so as to form a bilayer structure on the substrate. Optionally, one or more additional applying and drying sequences can be repeated with a water-soluble polymer from the group of polyanionic species, polycationic species and uncharged polymer species, so that a predetermined plurality of layers are built up upon the substrate.

6-Peroxo-6-zirconium crown and its hafnium analogue embedded in a triangular polyanion: [M6(O2)6(OH)6(gamma-SiW10O36)3]18- (M = Zr, Hf).

PubMed

Bassil, Bassem S; Mal, Sib Sankar; Dickman, Michael H; Kortz, Ulrich; Oelrich, Holger; Walder, Lorenz

2008-05-28

We have synthesized and structurally characterized the unprecedented peroxo-zirconium(IV) containing [Zr6(O2)6(OH)6(gamma-SiW10O36)3]18- (1). Polyanion 1 comprises a cyclic 6-peroxo-6-zirconium core stabilized by three decatungstosilicate units. We have also prepared the isostructural hafnium(IV) analogue [Hf6(O2)6(OH)6(gamma-SiW10O36)3]18- (2). We investigated the acid/base and redox properties of 1 by UV-vis spectroscopy and electrochemistry studies. Polyanion 1 represents the first structurally characterized Zr-peroxo POM with side-on, bridging peroxo units. The simple, one-pot synthesis of 1 and 2 involving dropwise addition of aqueous hydrogen peroxide could represent a general procedure for incorporating peroxo groups into a large variety of transition metal and lanthanide containing POMs.

The effect of temperature and chitosan concentration during storage on the growth of chitosan nanoparticle produced by ionic gelation method

NASA Astrophysics Data System (ADS)

Handani, Wenny Rinda; Sediawan, Wahyudi Budi; Tawfiequrrahman, Ahmad; Wiratni, Kusumastuti, Yuni

2017-05-01

The objective of this research was to get the mechanism of nano size chitosan particle growth during storage by observing the effect of temperature and initial concentration of chitosan. The products were analyzed using PSA to have the average of particle radius. Nanochitosan solution was prepared by ionic gelation method. This method is described as an electrostatic interaction between positively charged amine with negatively charged polyanion, such as tripolyphosphate (TPP). Chitosan was dissolved in 1% acetic acid and was stirred for 30 minutes. Tween 80 was added to avoid agglomeration. TPP was prepared by dissolving 0.336 g into distilled water. The nano size chitosan was obtained by mixing TPP and chitosan solution dropwise while stirring for 30 minutes. This step was done at 15°C and ambient temperature (about 30°C) and chitosan concentration 0.2%, 0.4% and 0.6%. The results show that temperature during ionic gelation process (15°C and 30°C) does not affect the initial size of the nanoparticles produced as well as the growth of the nanoparticles during storage. On the other hand, initial chitosan concentration strongly affects initial size of the nanoparticles produced and the growth of the nanoparticles during storage. The concentration of chitosan at 0.2%, 0.4%, 0.6% gave initial size of nanoparticle chitosan of 175.3 nm, 337.9 nm, 643.3 nm respectively. On the other hand, the growth mechanism of chitosan nanoparticle depended on its radius(R). At R<500 nm, the growth rate of nanoparticles is controlled by adsorption at the surface of the particles, while at R>500 nm, it is controlled by diffusion in the liquid film around the particles.

Gallium(III)-Containing, Sandwich-Type Heteropolytungstates: Synthesis, Solution Characterization, and Hydrolytic Studies toward Phosphoester and Phosphoanhydride Bond Cleavage.

PubMed

Kandasamy, Balamurugan; Vanhaecht, Stef; Nkala, Fiona Marylyn; Beelen, Tessa; Bassil, Bassem S; Parac-Vogt, Tatjana N; Kortz, Ulrich

2016-09-19

The gallium(III)-containing heteropolytungstates [Ga4(H2O)10(β-XW9O33)2](6-) (X = As(III), 1; Sb(III), 2) were synthesized in aqueous acidic medium by reaction of Ga(3+) ions with the trilacunary, lone-pair-containing [XW9O33](9-). Polyanions 1 and 2 are isostructural and crystallized as the hydrated sodium salts Na6[Ga4(H2O)10(β-AsW9O33)2]·28H2O (Na-1) and Na6[Ga4(H2O)10(β-SbW9O33)2]·30H2O (Na-2) in the monoclinic space group P21/c, with unit cell parameters a = 16.0218(12) Å, b = 15.2044(10) Å, c = 20.0821(12) Å, and β = 95.82(0)°, as well as a = 16.0912(5) Å, b = 15.2178(5) Å, c = 20.1047(5) Å, and β = 96.2(0)°, respectively. The corresponding tellurium(IV) derivative [Ga4(H2O)10(β-TeW9O33)2](4-) (3) was also prepared, by direct reaction of sodium tungstate, tellurium(IV) oxide, and gallium nitrate. Polyanion 3 crystallized as the mixed rubidium/sodium salt Rb2Na2[Ga4(H2O)10(β-TeW9O33)2]·28H2O (RbNa-3) in the triclinic space group P1̅ with unit cell parameters a = 12.5629(15) Å, b = 13.2208(18) Å, c = 15.474(2) Å, α = 80.52(1)°, β = 84.37(1)°, and γ = 65.83(1)°. All polyanions 1-3 were characterized in the solid state by single-crystal XRD, FT-IR, TGA, and elemental analysis, and polyanion 2 was also characterized in solution by (183)W NMR and UV-vis spectroscopy. Polyanion 2 was used as a homogeneous catalyst toward adenosine triphosphate (ATP) and the DNA model substrate 4-nitrophenylphosphate, monitored by (1)H and (31)P NMR spectroscopy. The encapsulated gallium(III) centers in 2 promote the Lewis acidic synergistic activation of the hydrolysis of ATP and DNA model substrates at a higher rate in near-physiological conditions. A strong interaction of 2 with the P-O bond of ATP was evidenced by changes in chemical shift values and line broadening of the (31)P nucleus in ATP upon addition of the polyanion.

Mixed Polyanion Glass Cathodes: Mixed Alkali Effect

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kercher, A. K.; Chapel, A. S.; Kolopus, J. A.

2017-01-01

In lithium-ion batteries, mixed polyanion glass cathodes have demonstrated high capacities (200-500 mAh/g) by undergoing conversion and intercalation reactions. Mixed polyanion glasses typically have the same fundamental issues as other conversion cathodes, i.e.: large hysteresis, capacity fade, and 1st-cycle irreversible loss. A key advantage of glass cathodes is the ability to tailor their composition to optimize the desired physical properties and electrochemical performance. The strong dependence of glass physical properties (e.g., ionic diffusivity, electrical conductivity, and chemical durability) on the composition of alkali mixtures in a glass is well known and has been named the mixed alkali effect. The mixedmore » alkali effect on battery electrochemical properties is reported here for the first time. Depending on glass composition, the mixed alkali effect is shown to improve capacity retention during cycling (from 39% to 50% after 50 cycle test), to reduce the 1st-cycle irreversible loss (from 41% to 22%), and improve the high power (500 mA/g) capacity (from 50% to 67% of slow discharge capacity).« less

Synthesis and PPy loading for enhanced visible-light photocatalytic activity of new POMOFs containing silver chains

NASA Astrophysics Data System (ADS)

Sha, Jing-Quan; Yang, Xi-Ya; Sheng, Ning; Liu, Guo-Dong; Li, Ji-Sen; Yang, Jian-Bo

2018-07-01

A new polyoxometalate based hybrid compound containing Ag-Ag chain, [Ag29(trz)18][SiWV7WVI5O40] (Ag29SiW12), was synthesized by the simple one-step hydrothermal reaction of silver nitrate, 1, 2, 3- triazole (trz), and [SiW12O40]4- polyanion. Single crystal X-ray diffraction analysis shows that the [SiW12O40]4- polyanions as coordinating guests were successfully encapsulated into the metal-organic framework host matrix. The Keggin [SiW12O40]n- polyanions as templates and trz molecules as the small and delicate ligands play the decisive factors to the formation of silver chain. In addition, to improve the photocatalytic activity of the new compound Ag29SiW12, its polypyrrole (PPy) composite (PPy@Ag29SiW12) has been prepared and exhibits excellent photocatalytic activity (93.1% for MB and 48.8% for RhB) and selectivity adsorption (16.2 mg/g for MB and 1.60 mg/g for RhB) for organic dyes under the visible light radiation.

Copper Selenidophosphates Cu4P2Se6, Cu4P3Se4, Cu4P4Se3, and CuP2Se, Featuring Zero-, One-, and Two-Dimensional Anions.

PubMed

Kuhn, Alexander; Schoop, Leslie M; Eger, Roland; Moudrakovski, Igor; Schwarzmüller, Stefan; Duppel, Viola; Kremer, Reinhard K; Oeckler, Oliver; Lotsch, Bettina V

2016-08-15

Five new compounds in the Cu/P/Se phase diagram have been synthesized, and their crystal structures have been determined. The crystal structures of these compounds comprise four previously unreported zero-, one-, and two-dimensional selenidophosphate anions containing low-valent phosphorus. In addition to two new modifications of Cu4P2Se6 featuring the well-known hexaselenidohypodiphosphate(IV) ion, there are three copper selenidophosphates with low-valent P: Cu4P3Se4 contains two different new anions, (i) a monomeric (zero-dimensional) selenidophosphate anion [P2Se4](4-) and (ii) a one-dimensional selenidophosphate anion [Formula: see text], which is related to the well-known gray-Se-like [Formula: see text] Zintl anion. Cu4P4Se3 contains one-dimensional [Formula: see text] polyanions, whereas CuP2Se contains the 2D selenidophosphate [Formula: see text] polyanion. It consists of charge-neutral CuP2Se layers separated by a van der Waals gap which is very rare for a Zintl-type phase. Hence, besides black P, CuP2Se constitutes a new possible source of 2D oxidized phosphorus containing layers for intercalation or exfoliation experiments. Additionally, the electronic structures and some fundamental physical properties of the new compounds are reported. All compounds are semiconducting with indirect band gaps of the orders of around 1 eV. The phases reported here add to the structural diversity of chalcogenido phosphates. The structural variety of this family of compounds may translate into a variety of tunable physical properties.

Phosphorylation-mediated RNA/peptide complex coacervation as a model for intracellular liquid organelles

NASA Astrophysics Data System (ADS)

Aumiller, William M.; Keating, Christine D.

2016-02-01

Biological cells are highly organized, with numerous subcellular compartments. Phosphorylation has been hypothesized as a means to control the assembly/disassembly of liquid-like RNA- and protein-rich intracellular bodies, or liquid organelles, that lack delimiting membranes. Here, we demonstrate that charge-mediated phase separation, or complex coacervation, of RNAs with cationic peptides can generate simple model liquid organelles capable of reversibly compartmentalizing biomolecules. Formation and dissolution of these liquid bodies was controlled by changes in peptide phosphorylation state using a kinase/phosphatase enzyme pair. The droplet-generating phase transition responded to modification of even a single serine residue. Electrostatic interactions between the short cationic peptides and the much longer polyanionic RNAs drove phase separation. Coacervates were also formed on silica beads, a primitive model for localization at specific intracellular sites. This work supports phosphoregulation of complex coacervation as a viable mechanism for dynamic intracellular compartmentalization in membraneless organelles.

Insight into the ionotropic gelation of chitosan using tripolyphosphate and pyrophosphate as cross-linkers.

PubMed

Sacco, Pasquale; Paoletti, Sergio; Cok, Michela; Asaro, Fioretta; Abrami, Michela; Grassi, Mario; Donati, Ivan

2016-11-01

Ionotropic gelation of chitosan by means of opposite charged ions represents an efficient alternative to covalent reticulation because of milder condition of use and, in general, higher biocompatibility of the resulting systems. In this work 90° light scattering (turbidimetry), circular dichroism (CD) and 1 H NMR measurements have been performed to study the interactions between the biopolymer and ionic cross-linkers tripolyphosphate (TPP) and pyrophosphate (PPi) in dilute solutions. Thereafter, a dialysis-based technique was exploited to fabricate tridimensional chitosan hydrogels based on both polyanions. Resulting matrices showed a different mechanical behavior because of their peculiar mesh-texture at micro/nano-scale: in the present contribution we demonstrate that TPP and PPi favor the formation of homogeneous and inhomogeneous systems, respectively. The different texture of networks could be exploited in future for the preparation of systems for the controlled release of molecules. Copyright © 2016 Elsevier B.V. All rights reserved.

Identification and characterization of podocalyxin--the major sialoprotein of the renal glomerular epithelial cell

PubMed Central

1984-01-01

The glomerular epithelial polyanion is a specialized cell surface component found on renal glomerular epithelial cells (podocytes) that is rich in sialoprotein(s), as detected by staining with cationic dyes (colloidal iron, alcian blue) and wheat germ agglutinin (WGA). We have isolated rat glomeruli and analyzed their protein composition by SDS PAGE in 5-10% gradient gels. When the gels were stained with alcian blue or "Stains All," a single band with an apparent Mr of 140,000 was detected that also stained very prominently with silver, but not with Coomassie Blue. This band predominated in fluorograms of gels of isolated glomeruli that had been labeled in their sialic acid residues by periodate-[3H]borohydride. In lectin overlays, the 140-kilodalton (kd) band was virtually the only one that bound [125I]wheat germ agglutinin, and this binding could be prevented by predigestion with neuraminidase. [125I]Peanut lectin bound exclusively to the 140-kd band after neuraminidase treatment. An antibody was prepared that specifically recognizes only the 140-kd band by immunoprecipitation and immuneoverlay. By immunoperoxidase and immunogold techniques, it was localized to the surface coat of the glomerular epithelium and, less extensively, to that of endothelial cells. When analyzed (after electroelution from preparative SDS gels), the 140-kd band was found to contain approximately 20% hexose and approximately 4.5% sialic acid. These findings indicate that the 140-kd protein is the major sialoprotein of the glomerulus, and it is the only component of glomerular lysates with an affinity for cationic dyes and lectins identical to that defined histochemically for the epithelial polyanion in situ. Since this molecule is a major component of the cell coat or glycocalyx of the podocytes, we have called it "podocalyxin." PMID:6371025

Antibacterial Performance of Alginic Acid Coating on Polyethylene Film

PubMed Central

Karbassi, Elika; Asadinezhad, Ahmad; Lehocký, Marian; Humpolíček, Petr; Vesel, Alenka; Novák, Igor; Sáha, Petr

2014-01-01

Alginic acid coated polyethylene films were examined in terms of surface properties and bacteriostatic performance against two most representative bacterial strains, that is, Escherichia coli and Staphylococcus aureus. Microwave plasma treatment followed by brush formation in vapor state from three distinguished precursors (allylalcohol, allylamine, hydroxyethyl methacrylate) was carried out to deposit alginic acid on the substrate. Surface analyses via various techniques established that alginic acid was immobilized onto the surface where grafting (brush) chemistry influenced the amount of alginic acid coated. Moreover, alginic acid was found to be capable of bacterial growth inhibition which itself was significantly affected by the brush type. The polyanionic character of alginic acid as a carbohydrate polymer was assumed to play the pivotal role in antibacterial activity. The cell wall composition of two bacterial strains along with the substrates physicochemical properties accounted for different levels of bacteriostatic performance. PMID:25196604

Formation and stability of water-soluble, molecular polyelectrolyte complexes: effects of charge density, mixing ratio, and polyelectrolyte concentration.

PubMed

Shovsky, Alexander; Varga, Imre; Makuska, Ricardas; Claesson, Per M

2009-06-02

The formation of complexes with stoichiometric (1:1) as well as nonstoichiometric (2:1) and (1:2) compositions between oppositely charged synthetic polyelectrolytes carrying strong ionic groups and significantly different molecular weights is reported in this contribution. Poly(sodium styrenesulfonate) (NaPSS) was used as polyanion, and a range of copolymers with various molar ratios of the poly(methacryloxyethyltrimethylammonium) chloride, poly(METAC), and the nonionic poly(ethylene oxide) ether methacrylate, poly(PEO45MEMA), were used as polycations. Formation and stability of PECs have been investigated by dynamic and static light scattering (LS), turbidity, and electrophoretic mobility measurements as a function of polyelectrolyte solution concentration, charge density of the cationic polyelectrolyte, and mixing ratio. The data obtained demonstrate that in the absence of PEO45 side chains the 100% charged polymer (polyMETAC) formed insoluble PECs with PSS that precipitate from solution when exact stoichiometry is achieved. In nonstoichiometric complexes (1:2) and (2:1) large colloidally stable aggregates were formed. The presence of even a relatively small amount of PEO45 side chains (25%) in the cationic copolymer was sufficient for preventing precipitation of the formed stoichiometric and nonstoichiometric complexes. These PEC's are sterically stabilized by the PEO45 chains. By further increasing the PEO45 side-chain content (50 and 75%) of the cationic copolymer, small, water-soluble molecular complexes could be formed. The data suggest that PSS molecules and the charged backbone of the cationic brush form a compact core, and with sufficiently high PEO45 chain density (above 25%) molecular complexes are formed that are stable over prolonged times.

Polyelectrolyte Properties in Mono and Multi-Valent Ionic Media: Brushes and Complex Coacervates

NASA Astrophysics Data System (ADS)

Farina, Robert M.

Materials composed of polyelectrolytes have unique and interesting physical properties resulting primarily from their charged monomer segments. Polyelectrolytes, which exist in many different biological and industrial forms, have also been shown to be highly responsive to external environmental changes. Here, two specific polyelectrolyte systems, brushes and complex coacervates, are discussed in regards to how their properties can be tailored by adjusting the surrounding ionic environment with mono and multi-valent ions. End-tethered polyelectrolyte brushes, which constitute an interesting and substantial portion of polyelectrolyte applications, are well known for their ability to provide excellent lubrication and low friction when coated onto surfaces (e.g. articular cartilage and medical devices), as well as for their ability to stabilize colloidal particles in solution (e.g. paint and cosmetic materials). These properties have been extensively studied with brushes in pure mono-valent ionic media. However, polyelectrolyte brush interactions with multi-valent ions in solution are much less understood, although highly relevant considering mono and multi-valent counterions are present in most applications. Even at very low concentrations of multi-valent ions in solution, dramatic polyelectrolyte brush physical property changes can occur, resulting in collapsed chains which also adhere to one another via multi-valent bridging. Here, the strong polyelectrolyte poly(sodium styrene sulfonate) was studied using the Surface Forces Apparatus (SFA) and electrochemistry in order to investigate brush height and intermolecular interactions between two brushes as a function of multi-valent counterion population inside a brush. Complex coacervates are formed when polyanions and polycations are mixed together in proper conditions of an aqueous solution. This mixing results in a phase separation of a polymer-rich, coacervate phase composed of a chain network held together via electrostatic interactions. Complex coacervates are highly regarded for their extremely low interfacial energy resulting in an ability to spread and adhere to surfaces under water, utilized by marine organisms (e.g. mussels and tubeworms), as well as many encapsulation applications (e.g. pigment encapsulation for carbon-less paper and electronic paper displays). Here, the interfacial energy of coacervates composed of oppositely charged polypeptides, poly(L-lysine) and poly(L-glutamic acid), was investigated using the SFA in regards to changes in bulk mono-valent salt concentrations.

Photophysics of aggregated 9-methylthiacarbocyanine bound to polyanions

NASA Astrophysics Data System (ADS)

Chibisov, Alexander K.; Görner, Helmut

2002-05-01

The photophysical properties of 3,3 '-diethyl-9-methylthiacarbocyanine (DTC) were studied in the presence of polystyrene sulfonate (PSS), polyacrylic acid (PAA) and polymethacrylic acid (PMA). The absorption spectra reflect a monomer/dimer equilibrium in neat aqueous solution and a shift towards bound H-aggregates, bound dimers and bound monomers on increasing the ratio of polyanion residue to dye concentrations ( r). These equilibria also determine the photodeactivation modes of DTC. The fluorescence intensity is reduced, when dimers and aggregates are present and strongly enhanced for low dye loading ( r=10 4). In contrast, the quantum yield of intersystem crossing is enhanced for bound dimers ( r=10 3).

Precipitation of a monoclonal antibody by soluble tungsten.

PubMed

Bee, Jared S; Nelson, Stephanie A; Freund, Erwin; Carpenter, John F; Randolph, Theodore W

2009-09-01

Tungsten microparticles may be introduced into some pre-filled syringes during the creation of the needle hole. In turn, these microcontaminants may interact with protein therapeutics to produce visible particles. We found that soluble tungsten polyanions formed in acidic buffer below pH 6.0 can precipitate a monoclonal antibody within seconds. Soluble tungsten in pH 5.0 buffer at about 3 ppm was enough to cause precipitation of a mAb formulated at 0.02 mg/mL. The secondary structure of the protein was near-native in the collected precipitate. Our observations are consistent with the coagulation of a monoclonal antibody by tungsten polyanions. Tungsten-induced precipitation should only be a concern for proteins formulated below about pH 6.0 since tungsten polyanions are not formed at higher pHs. We speculate that the heterogenous nature of particle contamination within the poorly mixed syringe tip volume could mean that a specification for tungsten contamination based on the entire syringe volume is not appropriate. The potential potency of tungsten metal contamination is highlighted by the small number of particles that would be required to generate soluble tungsten levels needed to coagulate this antibody at pH 5.0.

Precipitation of a Monoclonal Antibody by Soluble Tungsten

PubMed Central

Bee, Jared S.; Nelson, Stephanie A.; Freund, Erwin; Carpenter, John F.; Randolph, Theodore W.

2009-01-01

Tungsten microparticles may be introduced into some pre-filled syringes during the creation of the needle hole. In turn, these microcontaminants may interact with protein therapeutics to produce visible particles. We found that soluble tungsten polyanions formed in acidic buffer below pH 6.0 can precipitate a monoclonal antibody within seconds. Soluble tungsten in pH 5.0 buffer at about 3 ppm was enough to cause precipitation of a mAb formulated at 0.02 mg/mL. The secondary structure of the protein was near-native in the collected precipitate. Our observations are consistent with the coagulation of a monoclonal antibody by tungsten polyanions. Tungsten-induced precipitation should only be a concern for proteins formulated below about pH 6.0 since tungsten polyanions are not formed at higher pHs. We speculate that the heterogenous nature of particle contamination within the poorly mixed syringe tip volume could mean that a specification for tungsten contamination based on the entire syringe volume is not appropriate. The potential potency of tungsten metal contamination is highlighted by the small number of particles that would be required to generate soluble tungsten levels needed to coagulate this antibody at pH 5.0. PMID:19230018

Characterization of Escherichia coli K1 colominic acid-specific murine antibodies that are cross-protective against Neisseria meningitidis groups B, C, and Y.

PubMed

Park, In Ho; Lin, Jisheng; Choi, Ji Eun; Shin, Jeon-Soo

2014-06-01

The capsular polysaccharide (PS) of Neisseria meningitidis serogroup B (NMGB) is α(2-8)-linked N-acetylneuraminic acid (Neu5Ac), which is almost identical to the O-acetylated colominic acid (CA) of Escherichia coli K1 Although E. coli K1 has long been known to elicit cross-protective antibodies against NMGB, limited information on these highly cross-reactive antibodies is available. In the present study, six new monoclonal antibodies (mAbs) specific to both E. coli K1 CA and NMGB PS were produced by immunizing Balb/c mice with E. coli K1, and their serological and molecular properties were characterized, together with 12 previously reported hybridoma mAbs. Among the bactericidal mAbs against NMGB, both HmenB5 and HmenB18, which are genetically identical though of different mouse origins, were able to kill serogroup C and Y meningococci. Based on SPR sensograms, the binding affinity of HmenB18 for PS was suggested to be associated with at least two different binding forces: the polyanionicity of Neu5Ac and an interaction with the O-acetyl groups of Neu5Ac. Molecular analysis showed that similar to most mAbs presenting a few restricted V region germline genes, the V region genes of HmenB18 were 979% and 986% identical to the closest IGHV1-1401 and IGLV15-10301 germline gene alleles, respectively, and V-D-J editing in this mAb generated an unusually long VH-CDR3 sequence (17 amino acid residues), containing one basic arginine, two hydrophobic isoleucine residues and a 'YAMDY' motif. Models of the mAb combining sites demonstrate that most of the mAbs exhibited a wide, shallow groove with a high overall positive charge, as seen in mAb735, which is specific for a polyanionic helical epitope. In contrast, the combining site of HmenB18 was shown to be wide but to present a relatively weak positive charge, consistent with the extensive recognition by HmenB18 of the various structural epitopes formed with the Neu5Ac residue and its O-acetylation. Copyright © 2014 Elsevier Ltd. All rights reserved.

Polyelectrolyte multilayer assembly as a function of pH and ionic strength using the polysaccharides chitosan and heparin.

PubMed

Boddohi, Soheil; Killingsworth, Christopher E; Kipper, Matt J

2008-07-01

The goal of this work is to explore the effects of solution ionic strength and pH on polyelectrolyte multilayer (PEM) assembly, using biologically derived polysaccharides as the polyelectrolytes. We used the layer-by-layer (LBL) technique to assemble PEM of the polysaccharides heparin (a strong polyanion) and chitosan (a weak polycation) and characterized the sensitivity of the PEM composition and layer thickness to changes in processing parameters. Fourier-transform surface plasmon resonance (FT-SPR) and spectroscopic ellipsometry provided in situ and ex situ measurements of the PEM thickness, respectively. Vibrational spectroscopy and X-ray photoelectron spectroscopy (XPS) provided details of the chemistry (i.e., composition, electrostatic interactions) of the PEM. We found that when PEM were assembled from 0.2 M buffer, the PEM thickness could be increased from less than 2 nm per bilayer to greater than 4 nm per bilayer by changing the solution pH; higher and lower ionic strength buffer solutions resulted in narrower ranges of accessible thickness. Molar composition of the PEM was not very sensitive to solution pH or ionic strength, but pH did affect the interactions between the sulfonates in heparin and amines in chitosan when PEM were assembled from 0.2 M buffer. Changes in the PEM thickness with pH and ionic strength can be interpreted through descriptions of the charge density and conformation of the polyelectrolyte chains in solution.

pH-controlled drug loading and release from biodegradable microcapsules.

PubMed

Zhao, Qinghe; Li, Bingyun

2008-12-01

Microcapsules made of biopolymers are of both scientific and technological interest and have many potential applications in medicine, including their use as controlled drug delivery devices. The present study makes use of the electrostatic interaction between polycations and polyanions to form a multilayered microcapsule shell and also to control the loading and release of charged drug molecules inside the microcapsule. Micron-sized calcium carbonate (CaCO3) particles were synthesized and integrated with chondroitin sulfate (CS) through a reaction between sodium carbonate and calcium nitrate tetrahydrate solutions suspended with CS macromolecules. Oppositely charged biopolymers were alternately deposited onto the synthesized particles using electrostatic layer-by-layer self-assembly, and glutaraldehyde was introduced to cross-link the multilayered shell structure. Microcapsules integrated with CS inside the multilayered shells were obtained after decomposition of the CaCO3 templates. The integration of a matrix (i.e., CS) permitted the subsequent selective control of drug loading and release. The CS-integrated microcapsules were loaded with a model drug, bovine serum albumin labeled with fluorescein isothiocyanate (FITC-BSA), and it was shown that pH was an effective means of controlling the loading and release of FITC-BSA. Such CS-integrated microcapsules may be used for controlled localized drug delivery as biodegradable devices, which have advantages in reducing systemic side effects and increasing drug efficacy.

Crystal structure of catena-poly[N,N,N′,N′-tetra­methyl­guanidinium [(chlorido­cadmate)-di-μ-chlorido

PubMed Central

Ndiaye, Mamadou; Samb, Abdoulaye; Diop, Libasse; Maris, Thierry

2016-01-01

In the structure of the title salt, {(C5H14N3)[CdCl3]}n, the CdII atom of the complex anion is five-coordinated by one terminal and four bridging Cl atoms. The corresponding coordination polyhedron is a distorted trigonal bipyramid, with Cd—Cl distances in the range 2.4829 (4)–2.6402 (4) Å. The bipyramids are condensed into a polyanionic zigzag chain extending parallel to [101]. The tetra­methyl­guanidinium cations are situated between the polyanionic chains and are linked to them through N—H⋯Cl hydrogen bonds, forming a layered network parallel to (010). PMID:26870572

Quantum mechanical design of efficient second-order nonlinear optical materials based on heteroaromatic imido-substituted hexamolybdates: first theoretical framework of POM-based heterocyclic aromatic rings.

PubMed

Janjua, Muhammad Ramzan Saeed Ashraf

2012-11-05

This work was inspired by a previous report (Janjua et al. J. Phys. Chem. A 2009, 113, 3576-3587) in which the nonlinear-optical (NLO) response strikingly improved with an increase in the conjugation path of the ligand and the nature of hexamolybdates (polyoxometalates, POMs) was changed into a donor by altering the direction of charge transfer with a second aromatic ring. Herein, the first theoretical framework of POM-based heteroaromatic rings is found to be another class of excellent NLO materials having double heteroaromatic rings. First hyperpolarizabilities of a large number of push-pull-substituted conjugated systems with heteroaromatic rings have been calculated. The β components were computed at the density functional theory (DFT) level (BP86 geometry optimizations and LB94 time-dependent DFT). The largest β values are obtained with a donor (hexamolybdates) on the benzene ring and an acceptor (-NO(2)) on pyrrole, thiophene, and furan rings. The pyrrole imido-substituted hexamolybdate (system 1c) has a considerably large first hyperpolarizability, 339.00 × 10(-30) esu, and it is larger than that of (arylimido)hexamolybdate, calculated as 0.302 × 10(-30) esu (reference system 1), because of the double aromatic rings in the heteroaromatic imido-substituted hexamolybdates. The heteroaromatic rings act as a conjugation bridge between the electron acceptor (-NO(2)) and donor (polyanion). The introduction of an electron donor into heteroaromatic rings significantly enhances the first hyperpolarizabilities because the electron-donating ability is substantially enhanced when the electron donor is attached to the heterocyclic aromatic rings. Interposing five-membered auxiliary fragments between strong donor (polyanion) or acceptor (-NO(2)) groups results in a large computed second-order NLO response. The present investigation provides important insight into the NLO properties of (heteroaromatic) imido-substituted hexamolybdate derivatives because these compounds exhibit enhanced hyperpolarizabilities compared to typical NLO arylimido hexamolybdates and heterocyclic aromatic rings reported in the literature.

Identification of a major sialoprotein in the glycocalyx of human visceral glomerular epithelial cells.

PubMed Central

Kerjaschki, D; Poczewski, H; Dekan, G; Horvat, R; Balzar, E; Kraft, N; Atkins, R C

1986-01-01

Glomerular visceral epithelial cells are endowed with a sialic acid-rich surface coat (the "glomerular epithelial polyanion"), which in rat tissue contains the sialoprotein podocalyxin. We have identified a major membrane sialoprotein in human glomeruli that is similar to rat podocalyxin in its sialic acid-dependent binding of wheat germ agglutinin and in its localization on the surface of glomerular epithelial and endothelial cells, as shown by immunoelectron microscopy, using the monoclonal antibody PHM5. Differences in the sialoproteins of the two species are indicated by the discrepancy of their apparent molecular weights in sodium dodecyl sulfate gels, by the lack of cross reactivity of their specific antibodies, and by the lack of homology of their proteolytic peptide maps. It is therefore possible that the human glomerular sialoprotein and rat podocalyxin are evolutionarily distinct, but have similar functions. Images PMID:3533998

Importance of Diffuse Metal Ion Binding to RNA

PubMed Central

Tan, Zhi-Jie; Chen, Shi-Jie

2016-01-01

RNAs are highly charged polyanionic molecules. RNA structure and function are strongly correlated with the ionic condition of the solution. The primary focus of this article is on the role of diffusive ions in RNA folding. Due to the long-range nature of electrostatic interactions, the diffuse ions can contribute significantly to RNA structural stability and folding kinetics. We present an overview of the experimental findings as well as the theoretical developments on the diffuse ion effects in RNA folding. This review places heavy emphasis on the effect of magnesium ions. Magnesium ions play a highly efficient role in stabilizing RNA tertiary structures and promoting tertiary structural folding. The highly efficient role goes beyond the mean-field effect such as the ionic strength. In addition to the effects of specific ion binding and ion dehydration, ion-ion correlation for the diffuse ions can contribute to the efficient role of the multivalent ions such as the magnesium ions in RNA folding. PMID:22010269

Importance of diffuse metal ion binding to RNA.

PubMed

Tan, Zhi-Jie; Chen, Shi-Jie

2011-01-01

RNAs are highly charged polyanionic molecules. RNA structure and function are strongly correlated with the ionic condition of the solution. The primary focus of this article is on the role of diffusive ions in RNA folding. Due to the long-range nature of electrostatic interactions, the diffuse ions can contribute significantly to RNA structural stability and folding kinetics. We present an overview of the experimental findings as well as the theoretical developments on the diffuse ion effects in RNA folding. This review places heavy emphasis on the effect of magnesium ions. Magnesium ions play a highly efficient role in stabilizing RNA tertiary structures and promoting tertiary structural folding. The highly efficient role goes beyond the mean-field effect such as the ionic strength. In addition to the effects of specific ion binding and ion dehydration, ion-ion correlation for the diffuse ions can contribute to the efficient role of the multivalent ions such as the magnesium ions in RNA folding.

NAA-modified DNA oligonucleotides with zwitterionic backbones: stereoselective synthesis of A-T phosphoramidite building blocks.

PubMed

Schmidtgall, Boris; Höbartner, Claudia; Ducho, Christian

2015-01-01

Modifications of the nucleic acid backbone are essential for the development of oligonucleotide-derived bioactive agents. The NAA-modification represents a novel artificial internucleotide linkage which enables the site-specific introduction of positive charges into the otherwise polyanionic backbone of DNA oligonucleotides. Following initial studies with the introduction of the NAA-linkage at T-T sites, it is now envisioned to prepare NAA-modified oligonucleotides bearing the modification at X-T motifs (X = A, C, G). We have therefore developed the efficient and stereoselective synthesis of NAA-linked 'dimeric' A-T phosphoramidite building blocks for automated DNA synthesis. Both the (S)- and the (R)-configured NAA-motifs were constructed with high diastereoselectivities to furnish two different phosphoramidite reagents, which were employed for the solid phase-supported automated synthesis of two NAA-modified DNA oligonucleotides. This represents a significant step to further establish the NAA-linkage as a useful addition to the existing 'toolbox' of backbone modifications for the design of bioactive oligonucleotide analogues.

High Temperature Electronic and Thermal Transport Properties of EuGa2- x In x Sb2

NASA Astrophysics Data System (ADS)

Chanakian, Sevan; Weber, Rochelle; Aydemir, Umut; Ormeci, Alim; Fleurial, Jean-Pierre; Bux, Sabah; Snyder, G. Jeffrey

2017-08-01

The Zintl phase EuGa2Sb2 was synthesized via ball milling followed by hot pressing. The crystal structure of EuGa2Sb2 is comprised of a 3-D network of polyanionic [Ga2Sb2]2- tunnels filled with Eu cations that provide charge balance (Eu2+[Ga2Sb2]2-). Here we report the temperature-dependent resistivity, Hall Effect, Seebeck coefficient and thermal conductivity for EuGa2- x In x Sb2 ( x = 0, 0.05, 0.1) from 300 K to 775 K. Experimental results demonstrate that the material is a p-type semiconductor. However, a small band gap (˜0.1 eV) prevents EuGa2Sb2 from having high zT at higher temperatures. Isoelectronic substitution of In on the Ga site leads to point defect scattering of holes and phonons, thus reducing thermal conductivity and resulting in a slight improvement in zT.

Control superstructure of rigid polyelectrolytes in oppositely charged hydrogels via programmed internal stress

NASA Astrophysics Data System (ADS)

Takahashi, Riku; Wu, Zi Liang; Arifuzzaman, Md; Nonoyama, Takayuki; Nakajima, Tasuku; Kurokawa, Takayuki; Gong, Jian Ping

2014-08-01

Biomacromolecules usually form complex superstructures in natural biotissues, such as different alignments of collagen fibres in articular cartilages, for multifunctionalities. Inspired by nature, there are efforts towards developing multiscale ordered structures in hydrogels (recognized as one of the best candidates of soft biotissues). However, creating complex superstructures in gels are hardly realized because of the absence of effective approaches to control the localized molecular orientation. Here we introduce a method to create various superstructures of rigid polyanions in polycationic hydrogels. The control of localized orientation of rigid molecules, which are sensitive to the internal stress field of the gel, is achieved by tuning the swelling mismatch between masked and unmasked regions of the photolithographic patterned gel. Furthermore, we develop a double network structure to toughen the hydrogels with programmed superstructures, which deform reversibly under large strain. This work presents a promising pathway to develop superstructures in hydrogels and should shed light on designing biomimetic materials with intricate molecular alignments.

Dithallium(III)-Containing 30-Tungsto-4-phosphate, [Tl2Na2(H2O)2(P2W15O56)2]16-: Synthesis, Structural Characterization, and Biological Studies.

PubMed

Ayass, Wassim W; Fodor, Tamás; Farkas, Edit; Lin, Zhengguo; Qasim, Hafiz M; Bhattacharya, Saurav; Mougharbel, Ali S; Abdallah, Khaled; Ullrich, Matthias S; Zaib, Sumera; Iqbal, Jamshed; Harangi, Sándor; Szalontai, Gábor; Bányai, István; Zékány, László; Tóth, Imre; Kortz, Ulrich

2018-06-18

Here we report on the synthesis and structural characterization of the dithallium(III)-containing 30-tungsto -4-phosphate [Tl 2 Na 2 (H 2 O) 2 {P 2 W 15 O 56 } 2 ] 16- (1) by a multitude of solid-state and solution techniques. Polyanion 1 comprises two octahedrally coordinated Tl 3+ ions sandwiched between two trilacunary {P 2 W 15 } Wells-Dawson fragments and represents only the second structurally characterized, discrete thallium-containing polyoxometalate to date. The two outer positions of the central rhombus are occupied by sodium ions. The title polyanion is solution-stable as shown by 31 P and 203/205 Tl NMR. This was also supported by Tl NMR spectra simulations including several spin systems of isotopologues with half-spin nuclei ( 203 Tl, 205 Tl, 31 P, 183 W). 23 Na NMR showed a time-averaged signal of the Na + counter cations and the structurally bonded Na + ions. 203/205 Tl NMR spectra also showed a minor signal tentatively attributed to the trithallium-containing derivative [Tl 3 Na(H 2 O) 2 (P 2 W 15 O 56 ) 2 ] 14- , which could also be identified in the solid state by single-crystal X-ray diffraction. The bioactivity of polyanion 1 was also tested against bacteria and Leishmania.

Nozzleless Fabrication of Oil-Core Biopolymeric Microcapsules by the Interfacial Gelation of Pickering Emulsion Templates.

PubMed

Leong, Jun-Yee; Tey, Beng-Ti; Tan, Chin-Ping; Chan, Eng-Seng

2015-08-05

Ionotropic gelation has been an attractive method for the fabrication of biopolymeric oil-core microcapsules due to its safe and mild processing conditions. However, the mandatory use of a nozzle system to form the microcapsules restricts the process scalability and the production of small microcapsules (<100 μm). We report, for the first time, a nozzleless and surfactant-free approach to fabricate oil-core biopolymeric microcapsules through ionotropic gelation at the interface of an O/W Pickering emulsion. This approach involves the self-assembly of calcium carbonate (CaCO3) nanoparticles at the interface of O/W emulsion droplets followed by the addition of a polyanionic biopolymer into the aqueous phase. Subsequently, CaCO3 nanoparticles are dissolved by pH reduction, thus liberating Ca(2+) ions to cross-link the surrounding polyanionic biopolymer to form a shell that encapsulates the oil droplet. We demonstrate the versatility of this method by fabricating microcapsules from different types of polyanionic biopolymers (i.e., alginate, pectin, and gellan gum) and water-immiscible liquid cores (i.e., palm olein, cyclohexane, dichloromethane, and toluene). In addition, small microcapsules with a mean size smaller than 100 μm can be produced by selecting the appropriate conventional emulsification methods available to prepare the Pickering emulsion. The simplicity and versatility of this method allows biopolymeric microcapsules to be fabricated with ease by ionotropic gelation for numerous applications.

Oligonucleotides as probes for studying polymerization reactions in dilute aqueous solution

NASA Technical Reports Server (NTRS)

Kolb, V.; Orgel, L. E.; Miller, S. L. (Principal Investigator)

1994-01-01

We have prepared a [32P]-labled oligonucleotide probe carrying a free primary amine at its 3'-terminus. This probe is used to initiate polymerization of aziridine (ethyleneimine) in aqueous solution. The nature of the oligomeric products and the kinetics of their formation are then monitored by gel electrophoresis. Our results are generally consistent with those obtained using conventional techniques. We have also investigated the effect of polyanionic templates on the rate of oligomerization of aziridine. We find that water-soluble polyanions generally accelerate the polymerization. The sodium salt of polymethacrylic acid is the most effective of the templates that we studied. The methods introduced in this paper should be applicable to a variety of polymerization reactions in aqueous solution. They should greatly simplify the screening of potentially prebiotic polymerization reactions.

Grafting transition metal-organophosphonate fragments onto heteropolyoxomolybdate: activity in photocatalysis.

PubMed

Sun, Xiaopeng; Liang, Zhijie; Ma, Pengtao; Ban, Ran; Jiang, Mingshuang; Zhang, Dongdi; Wang, Jingping; Niu, Jingyang

2015-10-28

A novel organophosphonate-functionalized heteropolyoxomolybdate incorporated nickel cluster, CsNa9[H2{Ni3O2(H2O)6}(PMo6O21)2{Ni(OOCCH2NHCH2PO3)2}3]·21H2O (1), has been synthesized, which represents the first member of the family of oxomolybdenum organophosphonate containing hexa-nuclear Ni(ii) in a polyanion framework. The polyanion comprises a unique ladder-type {Ni3O10(H2O)6} cluster and three {Ni(OOCCH2NHCH2PO3)2} bridgings, which are capped on either end by a {PMo6O28} group. Photocatalytic experiments indicate that 1 exhibits catalytic activity for the photodegradation of RhB solution. Furthermore, magnetic studies indicate that 1 displays antiferromagnetic interactions.

pH-controlled drug loading and release from biodegradable microcapsules

PubMed Central

Zhao, Qinghe; Li, Bingyun

2013-01-01

Microcapsules made of biopolymers are of both scientific and technological interest and have many potential applications in medicine including their use as controlled drug delivery devices. The present study employs the electrostatic interaction between polycations and polyanions to form a multilayered microcapsule shell and also to control the loading and release of charged drug molecules inside the microcapsule. Micron-sized CaCO3 particles were synthesized and integrated with chondroitin sulfate (CS) through a reaction between Na2CO3 and Ca(NO3)2 solutions suspended with CS macromolecules. Oppositely-charged biopolymers were alternately deposited onto the synthesized particles using electrostatic layer-by-layer self-assembly, and glutaraldehyde was introduced to crosslink the multilayered shell structure. Microcapsules integrated with CS inside the multilayered shells were obtained after decomposition of the CaCO3 templates. The integration of a matrix, i.e. CS, enabled the subsequent selective control of drug loading and release. The CS integrated microcapsules were loaded with a model drug, i.e. bovine serum albumin labeled with fluorescein isothiocyanate (FITC-BSA), and it was shown that pH was an effective means of controlling the loading and release of FITC-BSA. Such CS integrated microcapsules may be used for controlled localized drug delivery as biodegradable devices, which have advantages in reducing systemic side effects and increasing drug efficacy. PMID:18657478

Direct detection of hyaluronidase in urine using cationic gold nanoparticles: a potential diagnostic test for bladder cancer.

PubMed

Nossier, Ahmed Ibrahim; Eissa, Sanaa; Ismail, Manal Fouad; Hamdy, Mohamed Ahmed; Azzazy, Hassan Mohamed El-Said

2014-04-15

Hyaluronidase (HAase) was reported as a urinary marker of bladder cancer. In this study, a simple colorimetric gold nanoparticle (AuNP) assay was developed for rapid and sensitive detection of urinary HAase activity. Charge interaction between polyanionic hyaluronic acid (HA) and cationic AuNPs stabilized with cetyl trimethyl ammonium bromide (CTAB) led to formation of gold aggregates and a red to blue color shift. HAase digests HA into small fragments preventing the aggregation of cationic AuNPs. The nonspecific aggregation of AuNPs in urine samples was overcome by pre-treatment of samples with the polycationic chitosan that was able to agglomerate all negatively charged interfering moieties before performing the assay. The developed AuNP assay was compared with zymography for qualitative detection of urinary HAase activity in 40 bladder carcinoma patients, 11 benign bladder lesions patients and 15 normal individuals, the assay sensitivity was 82.5% vs. 65% for zymography, while the specificity for both assays was 96.1%. The absorption ratio, A530/A620 of the reacted AuNP solution was used to quantify the HAase activity. The best cut off value was 93.5 μU/ng protein, at which the sensitivity was 90% and the specificity was 80.8%.The developed colorimetric AuNP HAase assay is simple, inexpensive, and can aid noninvasive diagnosis of bladder cancer. © 2013 Elsevier B.V. All rights reserved.

Enhancing siRNA-based cancer therapy using a new pH-responsive activatable cell-penetrating peptide-modified liposomal system

PubMed Central

Xiang, Bai; Jia, Xue-Li; Qi, Jin-Long; Yang, Li-Ping; Sun, Wei-Hong; Yan, Xiao; Yang, Shao-Kun; Cao, De-Ying; Du, Qing; Qi, Xian-Rong

2017-01-01

As a potent therapeutic agent, small interfering RNA (siRNA) has been exploited to silence critical genes involved in tumor initiation and progression. However, development of a desirable delivery system is required to overcome the unfavorable properties of siRNA such as its high degradability, molecular size, and negative charge to help increase its accumulation in tumor tissues and promote efficient cellular uptake and endosomal/lysosomal escape of the nucleic acids. In this study, we developed a new activatable cell-penetrating peptide (ACPP) that is responsive to an acidic tumor microenvironment, which was then used to modify the surfaces of siRNA-loaded liposomes. The ACPP is composed of a cell-penetrating peptide (CPP), an acid-labile linker (hydrazone), and a polyanionic domain, including glutamic acid and histidine. In the systemic circulation (pH 7.4), the surface polycationic moieties of the CPP (polyarginine) are “shielded” by the intramolecular electrostatic interaction of the inhibitory domain. When exposed to a lower pH, a common property of solid tumors, the ACPP undergoes acid-catalyzed breakage at the hydrazone site, and the consequent protonation of histidine residues promotes detachment of the inhibitory peptide. Subsequently, the unshielded CPP would facilitate the cellular membrane penetration and efficient endosomal/lysosomal evasion of liposomal siRNA. A series of investigations demonstrated that once exposed to an acidic pH, the ACPP-modified liposomes showed elevated cellular uptake, downregulated expression of polo-like kinase 1, and augmented cell apoptosis. In addition, favorable siRNA avoidance of the endosome/lysosome was observed in both MCF-7 and A549 cells, followed by effective cytoplasmic release. In view of its acid sensitivity and therapeutic potency, this newly developed pH-responsive and ACPP-mediated liposome system represents a potential platform for siRNA-based cancer treatment. PMID:28405163

Super-reduced polyoxometalates: excellent molecular cluster battery components and semipermeable molecular capacitors.

PubMed

Nishimoto, Yoshio; Yokogawa, Daisuke; Yoshikawa, Hirofumi; Awaga, Kunio; Irle, Stephan

2014-06-25

Theoretical investigations are presented on the molecular and electronic structure changes that occur as α-Keggin-type polyoxometalate (POM(3-)) clusters [PM12O40](3-) (M = Mo, W) are converted toward their super-reduced POM(27-) state during the discharging process in lithium-based molecular cluster batteries. Density functional theory was employed in geometry optimization, and first-principles molecular dynamics simulations were used to explore local minima on the potential energy surface of neutral POM clusters adorned with randomly placed Li atoms as electron donors around the cluster surface. On the basis of structural, electron density, and molecular orbital studies, we present evidence that the super-reduction is accompanied by metal-metal bond formation, beginning from the 12th to 14th excess electron transferred to the cluster. Afterward, the number of metal-metal bonds increases nearly linearly with the number of additionally transferred excess electrons. In α-Keggin-type POMs, metal triangles are a prominently emerging structural feature. The origin of the metal triangle formation during super-reduction stems from the formation of characteristic three-center two-electron bonds in triangular metal atom sites, created under preservation of the POM skeleton via "squeezing out" of oxygen atoms bridging two metal atoms when the underlying metal atoms form covalent bonds. The driving force for this unusual geometrical and electronic structure change is a local Jahn-Teller distortion at individual transition-metal octahedral sites, where the triply degenerate t2 d orbitals become partially filled during reduction and gain energy by distortion of the octahedron in such a way that metal-metal bonds are formed. The bonding orbitals show strong contributions from mixing with metal-oxygen antibonding orbitals, thereby "shuffling away" excess electrons from the cluster center to the outside of the cage. The high density of negatively charged yet largely separated oxygen atoms on the surface of the super-reduced POM(27-) polyanion allows the huge Coulombic repulsion due to the presence of the excess electrons to be counterbalanced by the presence of Li countercations, which partially penetrate into the outer oxygen shell. This "semiporous molecular capacitor" structure is likely the reason for the effective electron uptake in POMs.

Copper removal using electrosterically stabilized nanocrystalline cellulose.

PubMed

Sheikhi, Amir; Safari, Salman; Yang, Han; van de Ven, Theo G M

2015-06-03

Removal of heavy metal ions such as copper using an efficient and low-cost method with low ecological footprint is a critical process in wastewater treatment, which can be achieved in a liquid phase using nanoadsorbents such as inorganic nanoparticles. Recently, attention has turned toward developing sustainable and environmentally friendly nanoadsorbents to remove heavy metal ions from aqueous media. Electrosterically stabilized nanocrystalline cellulose (ENCC), which can be prepared from wood fibers through periodate/chlorite oxidation, has been shown to have a high charge content and colloidal stability. Here, we show that ENCC scavenges copper ions by different mechanisms depending on the ion concentration. When the Cu(II) concentration is low (C0≲200 ppm), agglomerates of starlike ENCC particles appear, which are broken into individual starlike entities by shear and Brownian motion, as evidenced by photometric dispersion analysis, dynamic light scattering, and transmission electron microscopy. On the other hand, at higher copper concentrations, the aggregate morphology changes from starlike to raftlike, which is probably due to the collapse of protruding dicarboxylic cellulose (DCC) chains and ENCC charge neutralization by copper adsorption. Such raftlike structures result from head-to-head and lateral aggregation of neutralized ENCCs as confirmed by transmission electron microscopy. As opposed to starlike aggregates, the raftlike structures grow gradually and are prone to sedimentation at copper concentrations C0≳500 ppm, which eliminates a costly separation step in wastewater treatment processes. Moreover, a copper removal capacity of ∼185 mg g(-1) was achieved thanks to the highly charged DCC polyanions protruding from ENCC. These properties along with the biorenewability make ENCC a promising candidate for wastewater treatment, in which fast, facile, and low-cost removal of heavy metal ions is desired most.

Ultrasonication assisted Layer-by-Layer technology for the preparation of multi-functional anticancer drugs paclitaxel and lapatinib

NASA Astrophysics Data System (ADS)

Zhang, Xingcai

In this dissertation, ultrasonication assisted Layer-by-Layer (LbL) technology for the preparation of multifunctional poorly water-soluble anticancer drug nanoparticles, paclitaxel and lapatinib, has been developed. Many FDA approved drugs are very low soluble in water; therefore, it is very difficult to load and control their release and targeting efficiently, which greatly confines their application. The development of this method will pave the way for the development and application of those low soluble anticancer drugs. In the first part of this dissertation, the first approach for powerful ultrasonication, the top-down approach (sonicating bulk drug crystals in polyelectrolyte solution), was successfully applied for the preparation of the nanoparticles of paclitaxel. For this approach, a 200 nm diameter was a kind of "magic" barrier for colloidal particles prepared. This diameter barrier may be related to the nucleation size of the solvent vapor microbubbles. Consequently, agents enhancing bubbling formation (such as NH4HCO3) were applied to decrease paclitaxel colloid particles to 100-120 nm. Those paclitaxel nanoparticles were Layer-by-Layer coated with a 10-20 nm polycation/polyanion shell to provide aqueous colloidal stability and slower particle dissolution. However, a large obstacle of these powerful ultrasonication methods was a necessity of long ca 45 minutes high power ultrasonication which resulted in TiO2 contamination from titanium electrode. The small amount of TiO2 contamination from ultrasonication did negatively affect the in vivo testing of this system in mice, and had to be removed before low toxicity of the Layer-by-Layer coated paclitaxel nanoparticles were observed. In the second part of the dissertation, the second approach for sonication, the bottom-up approach (sonicating drug in a water-miscible organic solvent followed by slow water add-in) was successfully applied for the preparation of the nanoparticles of lapatinib and paclitaxel with less powerful sonication. By using polymeric excipients combined with non-ionic and anionic surfactants along with regular sonication, the prepared particle sizes was uniform at around 140-150 nm. Less sonication time (ca 15 minutes) and lower sonication power avoided TiO2 contamination. The amphiphiles attached to the hydrophobic nanoparticles and served as anchors for LbL shell. The inner LbL layers and surfactants minimized the surface free energy, thereby preventing crystal form changes and nanoparticles coalescence, while the outermost layers enhanced colloidal stability. In the third part of the dissertation, LbL shells with PEGylation (using a block copolymer of poly-L-lysine (PLL) and PEG) for lapatinib were developed for enhanced colloidal stability in high molarity PBS buffer. In the above proposed paclitaxel and lapatinib formulation, we obtained 150-200 nm with high drug content of 80-90% due to very thin capsule walls (ca 10 nm). The drug release time from the LbL capsules was found to be between 10 and 20 hours depending on the shell thickness. Washless Layer-by-Layer assembly was used: 1) addition of polycation in the amount that is enough to reverse surface charge of the dispersion to a high positive (+30 mV) value; 2) addition of polyanion in the amount that is enough to reverse surface charge of the dispersion to a high negative (-30 mV) value. No intermediate washing of nanoparticles was done until the shell was complete. The washless method had the advantage of time and energy saving, preservation of the sample structure and no losses of sample. In the last part of the dissertation, we elaborated nanoformulation of two drugs in one nanocapsule locating paclitaxel in the core and lapatinib on the shell periphery. With this formulation, combining in one nanoparticle dual drugs, we reached the drugs' efficiency synergy. In a multidrug-resistant (MDR) ovarian cancer cell line, OVCAR-3, LbL lapatinib/paclitaxel nanocolloids mediated an enhanced cell growth inhibition in comparison with the LbL paclitaxel-only and LbL lapatinib-only treatment, not to say the free one drug treatment.

Calcium intercalation into layered fluorinated sodium iron phosphate

DOE PAGES

Lipson, Albert L.; Kim, Soojeong; Pan, Baofei; ...

2017-10-09

Here, the energy density and cost of battery systems could be improved by moving to alternative battery chemistries such as Ca-ion. However, in order to switch chemistries many problems need to be solved including the identification of cathode materials with high energy density, and electrolytes that can plate and strip calcium metal. Herein, the feasibility and cycling performance of Ca 2+ intercalation into a desodiated layered Na 2FePO 4F host is described. This is the first demonstration of Ca 2+ intercalation into a polyanionic framework, which implies that other polyanionic framework materials may be active for Ca 2+ intercalation. Althoughmore » substantial effort is still needed to identify a high energy density cathode material, this study and others demonstrate the feasibility of Ca 2+ intercalation into multiple materials making it more probable that such a cathode material can be found.« less

Calcium intercalation into layered fluorinated sodium iron phosphate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lipson, Albert L.; Kim, Soojeong; Pan, Baofei

Here, the energy density and cost of battery systems could be improved by moving to alternative battery chemistries such as Ca-ion. However, in order to switch chemistries many problems need to be solved including the identification of cathode materials with high energy density, and electrolytes that can plate and strip calcium metal. Herein, the feasibility and cycling performance of Ca 2+ intercalation into a desodiated layered Na 2FePO 4F host is described. This is the first demonstration of Ca 2+ intercalation into a polyanionic framework, which implies that other polyanionic framework materials may be active for Ca 2+ intercalation. Althoughmore » substantial effort is still needed to identify a high energy density cathode material, this study and others demonstrate the feasibility of Ca 2+ intercalation into multiple materials making it more probable that such a cathode material can be found.« less

Polyanion Driven Antiferromagnetic and Insulating Ground State of Olivine Phosphates: LiMPO4

NASA Astrophysics Data System (ADS)

Jena, Ajit Kumar; Nanda, B. R. K.; Condensed Matter Theory; Computation Team

Through density functional calculations we have investigated the electronic and magnetic properties of LiMPO4, where M is a 3d transition metal element. We find that contrary to many transition metal oxides, in these Olivine phosphates the band gap is originated due to crystal field anisotropy as well as weak O-p - M-d covalent interaction. Both of them are attributed to the presence of PO43- polyanion. The anisotropic crystal field, in the absence of covalent interactions, creates atomically localized non-degenerate M-d states and therefore the gap is a natural outcome. Onsite repulsion, due to strong correlation effect, further enhances the gap. These localized d states favor high-spin configuration which leads to antiferromagnetic ordering due to Hund's coupling. Experimentally observed low Neel temperature of this family of compounds is explained from the DFT obtained spin exchange interaction parameters. Work supported by Nissan Research Program.

Reactions in glass-ionomer cements: IV. Effect of chelating comonomers on setting behavior.

PubMed

Wilson, A D; Crisp, S; Ferner, A J

1976-01-01

The oscillating rheometer is a valuable instrument for studying the effects of additives on the setting behavior of a cement system. Using this instrument, it was found that certain chelating comonomers, the hydroxycarboxylic acids, could improve the setting characteristics of the glass-ionomer cement system when added to the PAA solution. The acid chelates probably assign the extraction of metal ions from the glass and also tend to hold them in solution, preventing premature ion binding of the polyanion chains. The effect is to increase the rate of hardening without reducing the working time, which may indeed by slightly increased. Tartaric acid, the most effective of the comonomers, can form a chelate bridge between aluminum atoms, and this metal complex probably acts as a flexible bridge structure linking polyanion chains. This mechanism offers some steric advantages over a simple salt bridge.

Quantification of alginate by aggregation induced by calcium ions and fluorescent polycations.

PubMed

Zheng, Hewen; Korendovych, Ivan V; Luk, Yan-Yeung

2016-01-01

For quantification of polysaccharides, including heparins and alginates, the commonly used carbazole assay involves hydrolysis of the polysaccharide to form a mixture of UV-active dye conjugate products. Here, we describe two efficient detection and quantification methods that make use of the negative charges of the alginate polymer and do not involve degradation of the targeted polysaccharide. The first method utilizes calcium ions to induce formation of hydrogel-like aggregates with alginate polymer; the aggregates can be quantified readily by staining with a crystal violet dye. This method does not require purification of alginate from the culture medium and can measure the large amount of alginate that is produced by a mucoid Pseudomonas aeruginosa culture. The second method employs polycations tethering a fluorescent dye to form suspension aggregates with the alginate polyanion. Encasing the fluorescent dye in the aggregates provides an increased scattering intensity with a sensitivity comparable to that of the conventional carbazole assay. Both approaches provide efficient methods for monitoring alginate production by mucoid P. aeruginosa. Copyright © 2015 Elsevier Inc. All rights reserved.

Activity and lifetime of urease immobilized using layer-by-layer nano self-assembly on silicon microchannels.

PubMed

Forrest, Scott R; Elmore, Bill B; Palmer, James D

2005-01-01

Urease has been immobilized and layered onto the walls of manufactured silicon microchannels. Enzyme immobilization was performed using layer-by-layer nano self-assembly. Alternating layers of oppositely charged polyelectrolytes, with enzyme layers "encased" between them, were deposited onto the walls of the silicon microchannels. The polycations used were polyethylenimine (PEI), polydiallyldimethylammonium (PDDA), and polyallylamine (PAH). The polyanions used were polystyrenesulfonate (PSS) and polyvinylsulfate (PVS). The activity of the immobilized enzyme was tested by pumping a 1 g/L urea solution through the microchannels at various flow rates. Effluent concentration was measured using an ultraviolet/visible spectrometer by monitoring the absorbance of a pH sensitive dye. The architecture of PEI/PSS/PEI/urease/PEI with single and multiple layers of enzyme demonstrated superior performance over the PDDA and PAH architectures. The precursor layer of PEI/PSS demonstrably improved the performance of the reactor. Conversion rates of 70% were achieved at a residence time of 26 s, on d 1 of operation, and >50% at 51 s, on d 15 with a six-layer PEI/urease architecture.

Ion distribution in dry polyelectrolyte multilayers: a neutron reflectometry study.

PubMed

Ghoussoub, Yara E; Zerball, Maximilian; Fares, Hadi M; Ankner, John F; von Klitzing, Regine; Schlenoff, Joseph B

2018-02-28

Ultrathin films of complexed polycation poly(diallyldimethylammonium), PDADMA, and polyanion poly(styrenesulfonate), PSS, were prepared on silicon wafers using the layer-by-layer adsorption technique. When terminated with PDADMA, all films had excess PDADMA, which was balanced by counterions. Neutron reflectivity of these as-made multilayers was compared with measurements on multilayers which had been further processed to ensure 1 : 1 stoichiometry of PDADMA and PSS. The compositions of all films, including polymers and counterions, were determined experimentally rather than by fitting, reducing the number of fit parameters required to model the reflectivity. For each sample, acetate, either protiated, CH 3 COO - , or deuterated, CD 3 COO - , served as the counterion. All films were maintained dry under vacuum. Scattering length density profiles were constrained to fit reflectivity data from samples having either counterion. The best fits were obtained with uniform counterion concentrations, even for stoichiometric samples that had been exposed to PDADMA for ca. 5 minutes, showing that surprisingly fast and complete transport of excess cationic charge occurs throughout the multilayer during its construction.

Fission of Polyanionic Metal Clusters

NASA Astrophysics Data System (ADS)

König, S.; Jankowski, A.; Marx, G.; Schweikhard, L.; Wolfram, M.

2018-04-01

Size-selected dianionic lead clusters Pbn2 -, n =34 - 56 , are stored in a Penning trap and studied with respect to their decay products upon photoexcitation. Contrary to the decay of other dianionic metal clusters, these lead clusters show a variety of decay channels. The mass spectra of the fragments are compared to the corresponding spectra of the monoanionic precursors. This comparison leads to the conclusion that, in the cluster size region below about n =48 , the fission reaction Pbn2 -→Pbn-10 -+Pb10- is the major decay process. Its disappearance at larger cluster sizes may be an indication of a nonmetal to metal transition. Recently, the pair of Pb10- and Pbn-10 - were observed as pronounced fragments in electron-attachment studies [S. König et al., Int. J. Mass Spectrom. 421, 129 (2017), 10.1016/j.ijms.2017.06.009]. The present findings suggest that this combination is the fingerprint of the decay of doubly charged lead clusters. With this assumption, the dianion clusters have been traced down to Pb212 -, whereas the smallest size for the direct observation was as high as n =28 .

Anionic poly(p-phenylenevinylene)/layered double hydroxide ordered ultrathin films with multiple quantum well structure: a combined experimental and theoretical study.

PubMed

Yan, Dongpeng; Lu, Jun; Ma, Jing; Wei, Min; Wang, Xinrui; Evans, David G; Duan, Xue

2010-05-18

The sulfonated phenylenevinylene polyanion derivate (APPV) and exfoliated Mg-Al-layered double hydroxide (LDH) monolayers were alternatively assembled into ordered ultrathin films (UTFs) employing a layer-by-layer method, which shows uniform yellow luminescence. UV-vis absorption and fluorescence spectroscopy present a stepwise and regular growth of the UTFs upon increasing deposited cycles. X-ray diffraction, atomic force microscopy, and scanning electron microscopy demonstrate that the UTFs are orderly periodical layered structure with a thickness of 3.3-3.5 nm per bilayer. The APPV/LDH UTFs exhibit well-defined polarized photoemission characteristic with the maximum luminescence anisotropy of approximately 0.3. Moreover, the UTF exhibit longer fluorescence lifetime (3-3.85-fold) and higher photostability than the drop-casting APPV film under UV irradiation, suggesting that the existence of a LDH monolayer enhances the optical performance of the APPV polyanion. A combination study of electrochemistry and periodic density functional theory was used to investigate the electronic structure of the APPV/LDH system, illustrating that the APPV/LDH UTF is a kind of organic-inorganic hybrid multiple quantum well (MQW) structure with a low band energy of 1.7-1.8 eV, where the valence electrons of APPV can be confined into the energy wells formed by the LDH monolayers effectively. Therefore, this work not only gives a feasible method for fabricating a luminescence ultrathin film but also provides a detailed understanding of the geometric and electronic structures of photoactive polyanions confined between the LDH monolayers.

Surface charge accumulation of solid insulator under nanosecond pulse in vacuum: 3D distribution features and mechanism

NASA Astrophysics Data System (ADS)

Qi, Bo; Gao, Chunjia; Sun, Zelai; Li, Chengrong

2017-11-01

Surface charge accumulation can incur changes in electric field distribution, involved in the electron propagation process, and result in a significant decrease in the surface flashover voltage. The existing 2D surface charge measurement fails to meet the actual needs in real engineering applications that usually adopt the 45° conical frustum insulators. The present research developed a novel 3D measurement platform to capture surface charge distribution on solid insulation under nanosecond pulse in a vacuum. The results indicate that all surface charges are positive under a positive pulse and negative under a negative pulse. Surface charges tend to accumulate more near the upper electrode. Surface charge density increases significantly with the increase in pulse counts and amplitudes. Accumulation of surface charge results in a certain decrease of flashover voltage. Taking consideration of the secondary electron emission for the surface charge accumulation, four materials were obtained to demonstrate the effects on surface charge. Combining the effect incurred by secondary electron emission and the weighty action taken by surface charge accumulation on the flashover phenomena, the discharge mechanism along the insulator surface under nanosecond pulse voltage was proposed.

Surface modification of protein enhances encapsulation in chitosan nanoparticles

NASA Astrophysics Data System (ADS)

Koyani, Rina D.; Andrade, Mariana; Quester, Katrin; Gaytán, Paul; Huerta-Saquero, Alejandro; Vazquez-Duhalt, Rafael

2018-04-01

Chitosan nanoparticles have a huge potential as nanocarriers for environmental and biomedical purposes. Protein encapsulation in nano-sized chitosan provides protection against inactivation, proteolysis, and other alterations due to environmental conditions, as well as the possibility to be targeted to specific tissues by ligand functionalization. In this work, we demonstrate that the chemical modification of the protein surface enhances the protein loading in chitosan nanocarriers. Encapsulation of green fluorescent protein and the cytochrome P450 was studied. The increase of electrostatic interactions between the free amino groups of chitosan and the increased number of free carboxylic groups in the protein surface enhance the protein loading, protein retention, and, thus, the enzymatic activity of chitosan nanoparticles. The chemical modification of protein surface with malonic acid moieties reduced drastically the protein isoelectric point increasing the protein interaction with the polycationic biomaterial and chitosan. The chemical modification of protein does not alter the morphology of chitosan nanoparticles that showed an average diameter of 18 nm, spheroidal in shape, and smooth surfaced. The strategy of chemical modification of protein surface, shown here, is a simple and efficient technique to enhance the protein loading in chitosan nanoparticles. This technique could be used for other nanoparticles based on polycationic or polyanionic materials. The increase of protein loading improves, doubtless, the performance of protein-loaded chitosan nanoparticles for biotechnological and biomedical applications.

Hydrogel Walkers with Electro-Driven Motility for Cargo Transport.

PubMed

Yang, Chao; Wang, Wei; Yao, Chen; Xie, Rui; Ju, Xiao-Jie; Liu, Zhuang; Chu, Liang-Yin

2015-08-28

In this study, soft hydrogel walkers with electro-driven motility for cargo transport have been developed via a facile mould-assisted strategy. The hydrogel walkers consisting of polyanionic poly(2-acrylamido-2-methylpropanesulfonic acid-co-acrylamide) exhibit an arc looper-like shape with two "legs" for walking. The hydrogel walkers can reversibly bend and stretch via repeated "on/off" electro-triggers in electrolyte solution. Based on such bending/stretching behaviors, the hydrogel walkers can move their two "legs" to achieve one-directional walking motion on a rough surface via repeated "on/off" electro-triggering cycles. Moreover, the hydrogel walkers loaded with very heavy cargo also exhibit excellent walking motion for cargo transport. Such hydrogel systems create new opportunities for developing electro-controlled soft systems with simple design/fabrication strategies in the soft robotic field for remote manipulation and transportation.

X-ray microanalysis of black piedra.

PubMed

Figueras, M J; Guarro, J

1997-11-01

The elements present in the fungal structures produced by Piedraia hortae in vivo and in vitro have been investigated using electron microscopy X-ray microanalysis. Phosphorus, sulphur and calcium were detected in the nodules which developed on hair and on colonies on culture. These elements belong to the extracellular material that compacts the pseudoparenchymatous organization of the fungus. They may be present due to the capacity of melanin-like pigments to sequester ions and/or they may form part of the sulphates and phosphates of the polyanionic mucopolysaccharides that constitute the extracellular material. Environmental contaminants such as aluminium, silicon and iron were detected exclusively on the surface of the nodule. They were deposited or linked to the residual molecules produced during the breakdown of the cuticular keratin. The advantages of these techniques for elucidating the chemical nature of fungal structures are discussed.

Generation of Anaphylatoxins by Human β-Tryptase from C3, C4, and C51

PubMed Central

Fukuoka, Yoshihiro; Xia, Han-Zhang; Sanchez-Muñoz, Laura B.; Dellinger, Anthony L.; Escribano, Luis; Schwartz, Lawrence B.

2009-01-01

Both mast cells and complement participate in innate and acquired immunity. The current study examines whether β-tryptase, the major protease of human mast cells, can directly generate bioactive complement anaphylatoxins. Important variables included pH, monomeric vs tetrameric forms of β-tryptase, and the β-tryptase-activating polyanion. The B12 mAb was used to stabilize β-tryptase in its monomeric form. C3a and C4a were best generated from C3 and C4, respectively, by monomeric β-tryptase in the presence of low molecular weight dextran sulfate or heparin at acidic pH. High molecular weight polyanions increased degradation of these anaphylatoxins. C5a was optimally generated from C5 at acidic pH by β-tryptase monomers in the presence of high molecular weight dextran sulfate and heparin polyanions, but also was produced by β-tryptase tetramers under these conditions. Mass spectrometry verified that the molecular mass of each anaphylatoxin was correct. Both β-tryptase-generated C5a and C3a (but not C4a) were potent activators of human skin mast cells. These complement anaphylatoxins also could be generated by β-tryptase in releasates of activated skin mast cells. Of further biologic interest, β-tryptase also generated C3a from C3 in human plasma at acidic pH. These results suggest β-tryptase might generate complement anaphylatoxins in vivo at sites of inflammation, such as the airway of active asthma patients where the pH is acidic and where elevated levels of β-tryptase and complement anaphylatoxins are detected. PMID:18424754

Layered Structures and Disordered Polyanionic Nets in the Cation-Poor Polar Intermetallics CsAu 1.4 Ga 2.8 and CsAu 2 Ga 2.6

DOE PAGES

Smetana, Volodymyr; Steinberg, Simon; Mudring, Anja-Verena

2016-12-27

Gold intermetallics are known for their unusual structures and bonding patterns. Two new compounds have been discovered in the cation-poor part of the Cs–Au–Ga system. We obtained both compounds directly by heating the elements at elevated temperatures. Structure determinations based on single-crystal X-ray diffraction analyses revealed two structurally and compositionally related formations: CsAu 1.4Ga 2.8 (I) and CsAu 2Ga 2.6 (II) crystallize in their own structure types (I: Rmore » $$\\bar{3}$$, a = 11.160(2) Å, c = 21.706(4) Å, Z = 18; II: R$$\\bar{3}$$, a = 11.106(1) Å, Å, c = 77.243(9) Å, Z = 54) and contain hexagonal cationic layers of cesium. Furthermore, this is a unique structural motif, which has never been observed for the other (lighter) alkali metals in combination with Au and post transition elements. The polyanionic part is characterized in contrast by Au/Ga tetrahedral stars, a structural feature that is characteristic for light alkali metal representatives, and disordered sites with mixed Au/Ga occupancies that occur in both structures with a more significant disorder in the polyanionic component of CsAu 2Ga 2.6. Examinations of the electronic band structure for a model approximating the composition of CsAu 1.4Ga 2.8 have been completed using density-functional-theory-based methods and reveal a deep pseudogap at E F. Bonding analysis by evaluating the crystal orbital Hamilton populations show dominant heteroatomic Au–Ga bonds and only a negligible contribution from Cs pairs.« less

Quantification of surface charge density and its effect on boundary slip.

PubMed

Jing, Dalei; Bhushan, Bharat

2013-06-11

Reduction of fluid drag is important in the micro-/nanofluidic systems. Surface charge and boundary slip can affect the fluid drag, and surface charge is also believed to affect boundary slip. The quantification of surface charge and boundary slip at a solid-liquid interface has been widely studied, but there is a lack of understanding of the effect of surface charge on boundary slip. In this paper, the surface charge density of borosilicate glass and octadecyltrichlorosilane (OTS) surfaces immersed in saline solutions with two ionic concentrations and deionized (DI) water with different pH values and electric field values is quantified by fitting experimental atomic force microscopy (AFM) electrostatic force data using a theoretical model relating the surface charge density and electrostatic force. Results show that pH and electric field can affect the surface charge density of glass and OTS surfaces immersed in saline solutions and DI water. The mechanisms of the effect of pH and electric field on the surface charge density are discussed. The slip length of the OTS surface immersed in saline solutions with two ionic concentrations and DI water with different pH values and electric field values is measured, and their effects on the slip length are analyzed from the point of surface charge. Results show that a larger absolute value of surface charge density leads to a smaller slip length for the OTS surface.

An equivalent body surface charge model representing three-dimensional bioelectrical activity

NASA Technical Reports Server (NTRS)

He, B.; Chernyak, Y. B.; Cohen, R. J.

1995-01-01

A new surface-source model has been developed to account for the bioelectrical potential on the body surface. A single-layer surface-charge model on the body surface has been developed to equivalently represent bioelectrical sources inside the body. The boundary conditions on the body surface are discussed in relation to the surface-charge in a half-space conductive medium. The equivalent body surface-charge is shown to be proportional to the normal component of the electric field on the body surface just outside the body. The spatial resolution of the equivalent surface-charge distribution appears intermediate between those of the body surface potential distribution and the body surface Laplacian distribution. An analytic relationship between the equivalent surface-charge and the surface Laplacian of the potential was found for a half-space conductive medium. The effects of finite spatial sampling and noise on the reconstruction of the equivalent surface-charge were evaluated by computer simulations. It was found through computer simulations that the reconstruction of the equivalent body surface-charge from the body surface Laplacian distribution is very stable against noise and finite spatial sampling. The present results suggest that the equivalent body surface-charge model may provide an additional insight to our understanding of bioelectric phenomena.

Fabrication of pullulan and pectin submicron fibers by electrospinning

USDA-ARS?s Scientific Manuscript database

Pullulan (PUL), a food grade polysaccharide, was fabricated into fibrous mats from fibers of submicron size by electrospinning. The effects of inorganic salts and polyanions present in the electrospinning solution on the properties of the resultant fibers was investigated. The inclusion of exogenous...

Synthesis of tetra- and octa-aurated heteroaryl complexes towards probing aromatic indoliums

PubMed Central

Yuan, Jun; Sun, Tingting; He, Xin; An, Ke; Zhu, Jun; Zhao, Liang

2016-01-01

Polymetalated aromatic compounds are particularly challenging synthetic goals because of the limited thermodynamic stability of polyanionic species arising from strong electrostatic repulsion between adjacent carbanionic sites. Here we describe a facile synthesis of two polyaurated complexes including a tetra-aurated indole and an octa-aurated benzodipyrrole. The imido trinuclear gold(I) moiety exhibits nucleophilicity and undergoes an intramolecular attack on a gold(I)-activated ethynyl to generate polyanionic heteroaryl species. Their computed magnetic properties reveal the aromatic character in the five-membered ring. The incorporation of the aurated substituents at the nitrogen atom can convert non-aromaticity in the parent indolium into aromaticity in the aurated one because of hyperconjugation. Thus, the concept of hyperconjugative aromaticity is extended to heterocycles with transition metal substituents. More importantly, further analysis indicates that the aurated substituents can perform better than traditional main-group substituents. This work highlights the difference in aromaticity between polymetalated aryls and their organic prototypes. PMID:27186982

Modeling competitive substitution in a polyelectrolyte complex

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peng, B.; Muthukumar, M., E-mail: muthu@polysci.umass.edu

2015-12-28

We have simulated the invasion of a polyelectrolyte complex made of a polycation chain and a polyanion chain, by another longer polyanion chain, using the coarse-grained united atom model for the chains and the Langevin dynamics methodology. Our simulations reveal many intricate details of the substitution reaction in terms of conformational changes of the chains and competition between the invading chain and the chain being displaced for the common complementary chain. We show that the invading chain is required to be sufficiently longer than the chain being displaced for effecting the substitution. Yet, having the invading chain to be longermore » than a certain threshold value does not reduce the substitution time much further. While most of the simulations were carried out in salt-free conditions, we show that presence of salt facilitates the substitution reaction and reduces the substitution time. Analysis of our data shows that the dominant driving force for the substitution process involving polyelectrolytes lies in the release of counterions during the substitution.« less

Mucoadhesive ophthalmic vehicles: evaluation of polymeric low-viscosity formulations.

PubMed

Saettone, M F; Monti, D; Torracca, M T; Chetoni, P

1994-01-01

A series of polyanionic natural or semi-synthetic polymers (polygalacturonic acid, hyaluronic acid, carboxymethylamylose, carboxymethylchitin, chondroitin sulfate, heparan sulfate and mesoglycan) were evaluated as potential mucoadhesive carriers for ophthalmic drugs. Solutions containing cyclopentolate (CY) or pilocarpine (PI) as salts (or polyanionic complexes) with the acidic polymers, all showing a low viscosity, were tested for miotic (resp. mydriatic) activity in albino rabbits. In the case of some polymeric complexes, small but significant increases of the areas under the activity vs. time curves (AUC) over reference cyclopentolate hydrochloride (CYHC1) or pilocarpine nitrate (PINO3) vehicles, and significant AUC decreases after removal of precorneal mucin by treatment with N-acetylcysteine were observed. A correlation was found between these data, considered indicative of the occurrence of a mucoadhesive interaction "in vivo", and "in vitro" viscometric data expressing the polymers-mucin force of interaction. The advantages and limitations of the mucoadhesive non-viscous approach in the formulation of ophthalmic vehicles are presented and discussed.

Calcium intercalation into layered fluorinated sodium iron phosphate

NASA Astrophysics Data System (ADS)

Lipson, Albert L.; Kim, Soojeong; Pan, Baofei; Liao, Chen; Fister, Timothy T.; Ingram, Brian J.

2017-11-01

The energy density and cost of battery systems, relative to the current state-of-the art, can be improved by developing alternative chemistries utilizing multivalent working ions such as calcium. Many challenges must be overcome, such as the identification of cathode materials with high energy density and an electrolyte with a wide electrochemical stability window that can plate and strip calcium metal, before market implementation. Herein, the feasibility and cycling performance of Ca2+ intercalation into a desodiated layered Na2FePO4F host is described. This is the first demonstration of Ca2+ intercalation into a polyanionic framework, which implies that other polyanionic framework materials may be active for Ca2+ intercalation. Although substantial effort is expected in order to develop a high energy density cathode material, this study demonstrates the feasibility of Ca2+ intercalation into multiple host structures types, thereby extending opportunities for development of Ca insertion host structures, suggesting such a cathode material can be identified and developed.

Atomic-Level Structural Dynamics of Polyoxoniobates during DMMP Decomposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Qi; Chapleski, Robert C.; Plonka, Anna M.

Ambient pressure in situ synchrotron-based spectroscopic techniques have been correlated to illuminate atomic-level details of bond breaking and formation during the hydrolysis of a chemical warfare nerve agent simulant over a polyoxometalate catalyst. Specifically, a Cs 8[Nb 6O 19] polyoxoniobate catalyst has been shown to react readily with dimethyl methylphosphonate (DMMP). The atomic-level transformations of all reactant moieties, the [Nb 6O 19] 8- polyanion, its Cs + counterions, and the DMMP substrate, were tracked under ambient conditions by a combination of X-ray absorption fine structure spectroscopy, Raman spectroscopy, and X-ray diffraction. Results reveal that the reaction mechanism follows general basemore » (in contrast to specific base) hydrolysis. Together with computational results, the work demonstrates that the ultimate fate of DMMP hydrolysis at the Cs 8[Nb 6O 19] catalyst is strong binding of the (methyl) methylphosphonic acid ((M)MPA) product to the polyanions, which ultimately inhibits catalytic turnover.« less

Atomic-Level Structural Dynamics of Polyoxoniobates during DMMP Decomposition

DOE PAGES

Wang, Qi; Chapleski, Robert C.; Plonka, Anna M.; ...

2017-04-10

Ambient pressure in situ synchrotron-based spectroscopic techniques have been correlated to illuminate atomic-level details of bond breaking and formation during the hydrolysis of a chemical warfare nerve agent simulant over a polyoxometalate catalyst. Specifically, a Cs 8[Nb 6O 19] polyoxoniobate catalyst has been shown to react readily with dimethyl methylphosphonate (DMMP). The atomic-level transformations of all reactant moieties, the [Nb 6O 19] 8- polyanion, its Cs + counterions, and the DMMP substrate, were tracked under ambient conditions by a combination of X-ray absorption fine structure spectroscopy, Raman spectroscopy, and X-ray diffraction. Results reveal that the reaction mechanism follows general basemore » (in contrast to specific base) hydrolysis. Together with computational results, the work demonstrates that the ultimate fate of DMMP hydrolysis at the Cs 8[Nb 6O 19] catalyst is strong binding of the (methyl) methylphosphonic acid ((M)MPA) product to the polyanions, which ultimately inhibits catalytic turnover.« less

Elution Is a Critical Step for Recovering Human Adenovirus 40 from Tap Water and Surface Water by Cross-Flow Ultrafiltration

PubMed Central

Shi, Hang; Xagoraraki, Irene; Bruening, Merlin L.

2016-01-01

ABSTRACT This paper examines the recovery of the enteric adenovirus human adenovirus 40 (HAdV 40) by cross-flow ultrafiltration and interprets recovery values in terms of physicochemical interactions of virions during sample concentration. Prior to ultrafiltration, membranes were either blocked by exposure to calf serum (CS) or coated with a polyelectrolyte multilayer (PEM). HAdV 40 is a hydrophobic virus with a point of zero charge between pH 4.0 and pH 4.3. In accordance with predictions from the extended Derjaguin-Landau-Verwey-Overbeek theory, the preelution recovery of HAdV (rpre) from deionized water was higher with PEM-coated membranes (rprePEM = 74.8% ± 9.7%) than with CS-blocked membranes (rpreCS = 54.1% ± 6.2%). With either membrane type, the total virion recovery after elution (rpost) was high for both deionized water (rpostPEM = 99.5% ± 6.6% and rpostCS = 98.8% ± 7.7%) and tap water (rpostPEM = 89% ± 15% and rpostCS = 93.7% ± 6.9%). The nearly 100% recoveries suggest that the polyanion (sodium polyphosphate) and surfactant (Tween 80) in the eluent disrupt electrostatic and hydrophobic interactions between the virion and the membrane. Addition of EDTA to the eluent greatly improved the elution efficacy (rpostCS = 88.6% ± 4.3% and rpostPEM = 87.0% ± 6.9%) with surface water, even when the organic carbon concentration in the water was high (9.4 ± 0.1 mg/liter). EDTA likely disrupts cation bridging between virions and particles in the feed water matrix or the fouling layer on the membrane surface. For complex water matrices, the eluent composition is the most important factor for achieving high virion recovery. IMPORTANCE Herein we present the results of a comprehensive physicochemical characterization of HAdV 40, an important human pathogen. The data on HAdV 40 surface properties enabled rigorous modeling to gain an understanding of the energetics of virion-virion and virion-filter interactions. Cross-flow filtration for concentration and recovery of HAdV 40 was evaluated, with postelution recoveries from ultrapure water (99%), tap water (∼91%), and high-carbon-content surface water (∼84%) being demonstrated. These results are significant because of the very low adenovirus recoveries that have been reported, to date, for other methods. The recovery data were interpreted in terms of specific interactions, and the eluent composition was designed accordingly to maximize HAdV 40 recovery. PMID:27287319

Upregulation of BMSCs Osteogenesis by Positively-Charged Tertiary Amines on Polymeric Implants via Charge/iNOS Signaling Pathway

PubMed Central

Zhang, Wei; Liu, Na; Shi, Haigang; Liu, Jun; Shi, Lianxin; Zhang, Bo; Wang, Huaiyu; Ji, Junhui; Chu, Paul K.

2015-01-01

Positively-charged surfaces on implants have a similar potential to upregulate osteogenesis of bone marrow-derived mesenchymal stem cells (BMSCs) as electromagnetic therapy approved for bone regeneration. Generally, their osteogenesis functions are generally considered to stem from the charge-induced adhesion of extracellular matrix (ECM) proteins without exploring the underlying surface charge/cell signaling molecule pathways. Herein, a positively-charged surface with controllable tertiary amines is produced on a polymer implant by plasma surface modification. In addition to inhibiting the TNF-α expression, the positively-charged surface with tertiary amines exhibits excellent cytocompatibility as well as remarkably upregulated osteogenesis-related gene/protein expressions and calcification of the contacted BMSCs. Stimulated by the charged surface, these BMSCs display high iNOS expressions among the three NOS isoforms. Meanwhile, downregulation of the iNOS by L-Can or siRNA inhibit osteogenic differentiation in the BMSCs. These findings suggest that a positively-charged surface with tertiary amines induces osteogenesis of BMSCs via the surface charge/iNOS signaling pathway in addition to elevated ECM protein adhesion. Therefore, creating a positively-charged surface with tertiary amines is a promising approach to promote osseointegration with bone tissues. PMID:25791957

The pre-ulcerative phase of carrageenan-induced colonic ulceration in the guinea-pig.

PubMed Central

Marcus, S. N.; Marcus, A. J.; Marcus, R.; Ewen, S. W.; Watt, J.

1992-01-01

The pre-ulcerative phase of carrageenan-induced colonic ulceration was investigated in guinea-pigs supplied 3% degraded carrageenan as an aqueous solution as drinking fluid for 2 or 3 days during which no ulceration of the bowel was observed with the naked eye or dissecting microscope. Mucosal microscopic changes, from caecum to rectum, were multifocal and included cellular infiltrates, dilatation of glands, crypt abscesses, micro-ulcers and sulphated polysaccharide in the lamina propria. Sulphated polysaccharide was also demonstrated histologically for the first time within the surface epithelium and showed ultrastructural features similar to carrageenan. The results indicate that colonic epithelium in the guinea-pig is capable of macromolecular absorption. Carrageenan, a highly active polyanionic electrolyte, within the surface epithelial cells is most likely a primary factor in the breakdown of mucosal integrity. Macromolecular absorption causing enteropathy of the large bowel is a new pathophysiological concept which may have implications in man, particularly in the pathology of large bowel disease. Images Fig. 7 Fig. 1 Fig. 2 Fig. 3 Fig. 4 Fig. 5 Fig. 6 PMID:1356411

Modulation of protein stability and aggregation properties by surface charge engineering.

PubMed

Raghunathan, Govindan; Sokalingam, Sriram; Soundrarajan, Nagasundarapandian; Madan, Bharat; Munussami, Ganapathiraman; Lee, Sun-Gu

2013-09-01

An attempt to alter protein surface charges through traditional protein engineering approaches often affects the native protein structure significantly and induces misfolding. This limitation is a major hindrance in modulating protein properties through surface charge variations. In this study, as a strategy to overcome such a limitation, we attempted to co-introduce stabilizing mutations that can neutralize the destabilizing effect of protein surface charge variation. Two sets of rational mutations were designed; one to increase the number of surface charged amino acids and the other to decrease the number of surface charged amino acids by mutating surface polar uncharged amino acids and charged amino acids, respectively. These two sets of mutations were introduced into Green Fluorescent Protein (GFP) together with or without stabilizing mutations. The co-introduction of stabilizing mutations along with mutations for surface charge modification allowed us to obtain functionally active protein variants (s-GFP(+15-17) and s-GFP(+5-6)). When the protein properties such as fluorescent activity, folding rate and kinetic stability were assessed, we found the possibility that the protein stability can be modulated independently of activity and folding by engineering protein surface charges. The aggregation properties of GFP could also be altered through the surface charge engineering.

Molecular simulation study of feruloyl esterase adsorption on charged surfaces: effects of surface charge density and ionic strength.

PubMed

Liu, Jie; Peng, Chunwang; Yu, Gaobo; Zhou, Jian

2015-10-06

The surrounding conditions, such as surface charge density and ionic strength, play an important role in enzyme adsorption. The adsorption of a nonmodular type-A feruloyl esterase from Aspergillus niger (AnFaeA) on charged surfaces was investigated by parallel tempering Monte Carlo (PTMC) and all-atom molecular dynamics (AAMD) simulations at different surface charge densities (±0.05 and ±0.16 C·m(-2)) and ionic strengths (0.007 and 0.154 M). The adsorption energy, orientation, and conformational changes were analyzed. Simulation results show that whether AnFaeA can adsorb onto a charged surface is mainly controlled by electrostatic interactions between AnFaeA and the charged surface. The electrostatic interactions between AnFaeA and charged surfaces are weakened when the ionic strength increases. The positively charged surface at low surface charge density and high ionic strength conditions can maximize the utilization of the immobilized AnFaeA. The counterion layer plays a key role in the adsorption of AnFaeA on the negatively charged COOH-SAM. The native conformation of AnFaeA is well preserved under all of these conditions. The results of this work can be used for the controlled immobilization of AnFaeA.

Effect of Surface Hydration on Antifouling Properties of Mixed Charged Polymers.

PubMed

Leng, Chuan; Huang, Hao; Zhang, Kexin; Hung, Hsiang-Chieh; Xu, Yao; Li, Yaoxin; Jiang, Shaoyi; Chen, Zhan

2018-05-07

Interfacial water structure on a polymer surface in water (or surface hydration) is related to the antifouling activity of the polymer. Zwitterionic polymer materials exhibit excellent antifouling activity due to their strong surface hydration. It was proposed to replace zwitterionic polymers using mixed charged polymers because it is much easier to prepare mixed charged polymer samples with much lower costs. In this study, using sum frequency generation (SFG) vibrational spectroscopy, we investigated interfacial water structures on mixed charged polymer surfaces in water, and how such structures change while exposing to salt solutions and protein solutions. The 1:1 mixed charged polymer exhibits excellent antifouling property while other mixed charged polymers with different ratios of the positive/negative charges do not. It was found that on the 1:1 mixed charged polymer surface, SFG water signal is dominated by the contribution of the strongly hydrogen bonded water molecules, indicating strong hydration of the polymer surface. The responses of the 1:1 mixed charged polymer surface to salt solutions are similar to those of zwitterionic polymers. Interestingly, exposure to high concentrations of salt solutions leads to stronger hydration of the 1:1 mixed charged polymer surface after replacing the salt solution with water. Protein molecules do not substantially perturb the interfacial water structure on the 1:1 mixed charged polymer surface and do not adsorb to the surface, showing that this mixed charged polymer is an excellent antifouling material.

Effects of Discrete Charge Clustering in Simulations of Charged Interfaces.

PubMed

Grime, John M A; Khan, Malek O

2010-10-12

A system of counterions between charged surfaces is investigated, with the surfaces represented by uniform charged planes and three different arrangements of discrete surface charges - an equispaced grid and two different clustered arrangements. The behaviors of a series of systems with identical net surface charge density are examined, with particular emphasis placed on the long ranged corrections via the method of "charged slabs" and the effects of the simulation cell size. Marked differences are observed in counterion distributions and the osmotic pressure dependent on the particular representation of the charged surfaces; the uniformly charged surfaces and equispaced grids of discrete charge behave in a broadly similar manner, but the clustered systems display a pronounced decrease in osmotic pressure as the simulation size is increased. The influence of the long ranged correction is shown to be minimal for all but the very smallest of system sizes.

Interfacial characterization and supercapacitive properties of polyaniline-Gum arabic nanocomposite/graphene oxide LbL modified electrodes

NASA Astrophysics Data System (ADS)

Oliveira, Rafaela D.; Santos, Cleverson S.; Ferreira, Rodolfo T.; Marciniuk, Gustavo; Marchesi, Luís F.; Garcia, Jarem R.; Vidotti, Marcio; Pessoa, Christiana A.

2017-12-01

In this manuscript, we describe the synthesis and electrochemical characterization of polyaniline-gum arabic nanocomposites and graphene oxide (PANI-GA/GO) modified electrodes with a detailed study concerning their supercapacitive properties. The electrode modification was carried out by using the Layer-by-Layer technique (LbL), where the PANI-GA nanocomposite dispersion was used as polycation and the GO colloidal dispersion as polyanion. The bilayer growth was followed by both UV-vis spectroscopy and cyclic voltammetry, and an increase in the characteristic PANI absorption and in the electrochemical signal was verified, confirming the electrode build up. Galvanostatic charge-discharge curves (GCDC) were performed to evaluate the supercapacitive properties of the modified electrodes, these results showed the dependence of the specific capacitance with the number of bilayers, where values of CS around 15 mF cm-2 (i = 0.1 mA cm-2) were found. Electrochemical impedance spectroscopy confirmed the pseudocapacitive properties of the modified electrodes, showing an increase in the low-frequency capacitance with the number of bilayers. Hereby the (PANI-GA/GO)-LbL electrodes were shown to be good candidates for active materials in supercapacitors.

Binding of anti-prion agents to glycosaminoglycans: Evidence from electronic absorption and circular dichroism spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zsila, Ferenc; Gedeon, Gabor

2006-08-11

The polyanionic glycosaminoglycans (GAGs) are intimately involved in the pathogenesis of protein conformational disorders such as amyloidosis and prion diseases. Several cationic agents are known to exhibit anti-prion activity but their mechanism of action is poorly understood. In this study, UV absorption and circular dichroism (CD) spectroscopic techniques were used to investigate the interaction between heparin and chondroitin-6-sulfate and anti-prion drugs including acridine, quinoline, and phenothiazine derivatives. UV band hypochromism of ({+-})-quinacrine, ({+-})-primaquine, tacrine, quinidine, chlorpromazine, and induced CD spectra of ({+-})-quinacrine upon addition of GAGs provided evidence for the GAG binding of these compounds. The association constants ({approx}10{sup 6}-10{supmore » 7} M{sup -1}) estimated from the UV titration curves show high-affinity drug-heparin interactions. Ionic strength-dependence of the absorption spectra suggested that the interaction between GAGs and the cationic drugs is principally electrostatic in nature. Drug binding differences of heparin and chondroitin-6-sulfate were attributed to their different negative charge density. These results call the attention to the alteration of GAG-prion/GAG-amyloid interactions by which these compounds might exert their anti-prion/anti-amyloidogenic activities.« less

Prediction of selectivity for enantiomeric separations of uncharged compounds by capillary electrophoresis involving dual cyclodextrin systems.

PubMed

Abushoffa, Adel M; Fillet, Marianne; Hubert, Phillipe; Crommen, Jacques

2002-03-01

The single-isomer polyanionic cyclodextrin (CD) derivative heptakis-6-sulfato-beta-cyclodextrin (HSbetaCD) has been tested as chiral additive for the enantioseparation of non-steroidal anti-inflammatory drugs, such as fenoprofen, flurbiprofen, ibuprofen and ketoprofen, in capillary electrophoresis, using a pH 2.5 phosphoric acid-triethanolamine buffer in the reversed polarity mode. In most cases, the enantiomers of these acidic compounds, present in uncharged form at that pH, were only poorly resolved with HSbetaCD alone. However, the use of HSbetaCD in combination with the neutral CD derivative, heptakis-(2,3,6-tri-O-methyl)-beta-cyclodextrin (TMbetaCD), which has a particularly high enantioselectivity towards these compounds, has led to complete enantioresolution in reasonably low migration times in most cases. Affinity constants for the enantiomers with the two cyclodextrins were determined, using linear regression in a two-step approach. Affinity constants with the charged HSbetaCD were first calculated in single systems while those with the neutral TMbetaCD were determined in dual systems. Selectivity for the enantiomeric separation of these compounds in dual CD systems could be predicted using recently developed mathematical models.

Encapsulation of selenium in chitosan nanoparticles improves selenium availability and protects cells from selenium-induced DNA damage response

USDA-ARS?s Scientific Manuscript database

Selenium, an essential mineral, plays important roles in optimizing human health. Chitosan is an effective, naturally oriented material for synthesizing nanoparticles with polyanions and exhibit preferable properties such as biocompatibility, biodegradation and resistance to certain enzymes. We have...

Na2MnSiO4 as an attractive high capacity cathode material for sodium-ion battery

NASA Astrophysics Data System (ADS)

Law, Markas; Ramar, Vishwanathan; Balaya, Palani

2017-08-01

Here we report a polyanion-based cathode material for sodium-ion batteries, Na2MnSiO4, registering impressive sodium storage performances with discharge capacity of 210 mAh g-1 at an average voltage of 3 V at 0.1 C, along with excellent long-term cycling stability (500 cycles at 1 C). Insertion/extraction of ∼1.5 mol of sodium ion per formula unit of the silicate-based compound is reported and the utilisation of Mn2+ ⇋ Mn4+ redox couple is also demonstrated by ex-situ XPS. Besides, this study involves a systematic investigation of influence of the electrolyte additive (with different content) on the sodium storage performance of Na2MnSiO4. The electrolyte additive forms an optimum protective passivation film on the electrode surface, successfully reducing manganese dissolution.

Modular Small Diameter Vascular Grafts with Bioactive Functionalities

PubMed Central

Neufurth, Meik; Wang, Xiaohong; Tolba, Emad; Dorweiler, Bernhard; Schröder, Heinz C.; Link, Thorben; Diehl-Seifert, Bärbel; Müller, Werner E. G.

2015-01-01

We report the fabrication of a novel type of artificial small diameter blood vessels, termed biomimetic tissue-engineered blood vessels (bTEBV), with a modular composition. They are composed of a hydrogel scaffold consisting of two negatively charged natural polymers, alginate and a modified chitosan, N,O-carboxymethyl chitosan (N,O-CMC). Into this biologically inert scaffold two biofunctionally active biopolymers are embedded, inorganic polyphosphate (polyP) and silica, as well as gelatin which exposes the cell recognition signal, Arg-Gly-Asp (RGD). These materials can be hardened by exposure to Ca2+ through formation of Ca2+ bridges between the polyanions, alginate, N,O-CMC, and polyP (alginate-Ca2+-N,O-CMC-polyP). The bTEBV are formed by pressing the hydrogel through an extruder into a hardening solution, containing Ca2+. In this universal scaffold of the bTEBV biomaterial, polycations such as poly(l-Lys), poly(d-Lys) or a His/Gly-tagged RGD peptide (three RGD units) were incorporated, which promote the adhesion of endothelial cells to the vessel surface. The mechanical properties of the biopolymer material (alginate-Ca2+-N,O-CMC-polyP-silica) revealed a hardness (elastic modulus) of 475 kPa even after a short incubation period in CaCl2 solution. The material of the artificial vascular grafts (bTEBVs with an outer size 6 mm and 1.8 mm, and an inner diameter 4 mm and 0.8 mm, respectively) turned out to be durable in 4-week pulsatile flow experiments at an alternating pressure between 25 and 100 mbar (18.7 and 75.0 mm Hg). The burst pressure of the larger (smaller) vessels was 850 mbar (145 mbar). Incorporation of polycationic poly(l-Lys), poly(d-Lys), and especially the His/Gly-tagged RGD peptide, markedly increased the adhesion of human, umbilical vein/vascular endothelial cells, EA.HY926 cells, to the surface of the hydrogel. No significant effect of the polyP samples on the clotting of human plasma is measured. We propose that the metabolically degradable polymeric scaffold bTEBV is a promising biomaterial for future prosthetic vascular grafts. PMID:26204529

Studies of Surface Charging of Polymers by Indirect Triboelectrification

NASA Astrophysics Data System (ADS)

Mantovani, James; Calle, Carlos; Groop, Ellen; Buehler, Martin

2001-03-01

Charge is known to develop on the surface of an insulating polymer by frictional charging through direct physical contact with another material. We will present results of recent triboelectrification studies of polymer surfaces that utilized an indirect method of frictional charging. This method first involves placing a grounded thin metal foil in stationary contact over the polymer surface. The exposed metal foil is then rubbed with the surface of the material that generates the triboelectric charge. Data is presented for five types of polymers: fiberglass/epoxy, polycarbonate (Lexan), polytetraflouroethylene (Teflon), Rulon J, and polymethylmethacrylate (PMMA, Lucite). The amount of charge that develops on an insulator's surface is measured using the MECA Electrometer, which was developed jointly by NASA Kennedy Space Center and the Jet Propulsion Laboratory to study the electrostatic properties of soil on the surface of Mars. Even though the insulator's surface is electrically shielded from the rubbing material by the grounded metal foil, charge measurements obtained by the MECA Electrometer after the metal foil is separated from the insulator's surface reveal that the insulator's surface does accumulate charge by indirect frictional charging. A possible explanation of the observations will be presented based on a simple contact barrier model.

Current-voltage characteristics influenced by the nanochannel diameter and surface charge density in a fluidic field-effect-transistor.

PubMed

Singh, Kunwar Pal; Guo, Chunlei

2017-06-21

The nanochannel diameter and surface charge density have a significant impact on current-voltage characteristics in a nanofluidic transistor. We have simulated the effect of the channel diameter and surface charge density on current-voltage characteristics of a fluidic nanochannel with positive surface charge on its walls and a gate electrode on its surface. Anion depletion/enrichment leads to a decrease/increase in ion current with gate potential. The ion current tends to increase linearly with gate potential for narrow channels at high surface charge densities and narrow channels are more effective to control the ion current at high surface charge densities. The current-voltage characteristics are highly nonlinear for wide channels at low surface charge densities and they show different regions of current change with gate potential. The ion current decreases with gate potential after attaining a peak value for wide channels at low values of surface charge densities. At low surface charge densities, the ion current can be controlled by a narrow range of gate potentials for wide channels. The current change with source drain voltage shows ohmic, limiting and overlimiting regions.

Effective Electrostatic Interactions Between Two Overall Neutral Surfaces with Quenched Charge Heterogeneity Over Atomic Length Scale

NASA Astrophysics Data System (ADS)

Zhou, S.

2017-12-01

Using Monte Carlo results as a reference, a classical density functional theory ( CDFT) is shown to reliably predict the forces between two heterogeneously charged surfaces immersed in an electrolyte solution, whereas the Poisson-Boltzmann ( PB) theory is demonstrated to deteriorate obviously for the same system even if the system parameters considered fall within the validity range of the PB theory in the homogeneously charged surfaces. By applying the tested CDFT, we study the effective electrostatic potential of mean force ( EPMF) between two face-face planar and hard surfaces of zero net charge on which positive and negative charges are separated and considered to present as discontinuous spots on the inside edges of the two surfaces. Main conclusions are summarized as follows: (i) strength of the EPMF in the surface charge separation case is very sensitively and positively correlated with the surface charge separation level and valency of the salt ion. Particularly, the charge separation level and the salt ion valency have a synergistic effect, which makes high limit of the EPMF strength in the surface charge separation case significantly go beyond that of the ideal homogeneously charged surface counterpart at average surface charge density similar to the average surface positive or negative charge density in the charge separation case. (ii) The surface charge distribution patterns mainly influence sign of the EPMF: symmetrical and asymmetrical patterns induce repulsive and attractive (at small distances) EPMF, respectively; but with low valency salt ions and low charge separation level the opposite may be the case. With simultaneous presence of both higher valency cation and anion, the EPMF can be repulsive at intermediate distances for asymmetrical patterns. (iii) Salt ion size has a significant impact, which makes the EPMF tend to become more and more repulsive with the ion diameter regardless of the surface charge distribution patterns and the valency of the salt ion; whereas if the 1:1 type electrolyte and the symmetrical patterns are considered, then the opposite may be the case. All of these findings can be explained self-consistently from several perspectives: an excess adsorption of the salt ions (induced by the surface charge separation) serving to raise the osmotic pressure between the plates, configuration fine-tuning in the thinner ion adsorption layer driven by the energy decrease principle, direct Coulombic interactions operating between charged objects on the two face-to-face plates involved, and net charge strength in the ion adsorption layer responsible for the net electrostatic repulsion.

Pretreatment-dependent surface chemistry of wood nanocellulose for pH-sensitive hydrogels.

PubMed

Chinga-Carrasco, Gary; Syverud, Kristin

2014-09-01

Nanocellulose from wood is a promising material with potential in various technological areas. Within biomedical applications, nanocellulose has been proposed as a suitable nano-material for wound dressings. This is based on the capability of the material to self-assemble into 3D micro-porous structures, which among others have an excellent capacity of maintaining a moist environment. In addition, the surface chemistry of nanocellulose is suitable for various applications. First, OH-groups are abundant in nanocellulose materials, making the material strongly hydrophilic. Second, the surface chemistry can be modified, introducing aldehyde and carboxyl groups, which have major potential for surface functionalization. In this study, we demonstrate the production of nanocellulose with tailor-made surface chemistry, by pre-treating the raw cellulose fibres with carboxymethylation and periodate oxidation. The pre-treatments yielded a highly nanofibrillated material, with significant amounts of aldehyde and carboxyl groups. Importantly, the poly-anionic surface of the oxidized nanocellulose opens up for novel applications, i.e. micro-porous materials with pH-responsive characteristics. This is due to the swelling capacity of the 3D micro-porous structures, which have ionisable functional groups. In this study, we demonstrated that nanocellulose gels have a significantly higher swelling degree in neutral and alkaline conditions, compared to an acid environment (pH 3). Such a capability can potentially be applied in chronic wounds for controlled and intelligent release of antibacterial components into biofilms. © The Author(s) 2014 Reprints and permissions: sagepub.co.uk/journalsPermissions.nav.

Pretreatment-dependent surface chemistry of wood nanocellulose for pH-sensitive hydrogels

PubMed Central

Syverud, Kristin

2014-01-01

Nanocellulose from wood is a promising material with potential in various technological areas. Within biomedical applications, nanocellulose has been proposed as a suitable nano-material for wound dressings. This is based on the capability of the material to self-assemble into 3D micro-porous structures, which among others have an excellent capacity of maintaining a moist environment. In addition, the surface chemistry of nanocellulose is suitable for various applications. First, OH-groups are abundant in nanocellulose materials, making the material strongly hydrophilic. Second, the surface chemistry can be modified, introducing aldehyde and carboxyl groups, which have major potential for surface functionalization. In this study, we demonstrate the production of nanocellulose with tailor-made surface chemistry, by pre-treating the raw cellulose fibres with carboxymethylation and periodate oxidation. The pre-treatments yielded a highly nanofibrillated material, with significant amounts of aldehyde and carboxyl groups. Importantly, the poly-anionic surface of the oxidized nanocellulose opens up for novel applications, i.e. micro-porous materials with pH-responsive characteristics. This is due to the swelling capacity of the 3D micro-porous structures, which have ionisable functional groups. In this study, we demonstrated that nanocellulose gels have a significantly higher swelling degree in neutral and alkaline conditions, compared to an acid environment (pH 3). Such a capability can potentially be applied in chronic wounds for controlled and intelligent release of antibacterial components into biofilms. PMID:24713295

Rectification of nanopores at surfaces

PubMed Central

Sa, Niya

2011-01-01

At the nanoscale, methods to measure surface charge can prove challenging. Herein we describe a general method to report surface charge through the measurement of ion current rectification of a nanopipette brought in close proximity to a charged substrate. This method is able to discriminate between charged cationic and anionic substrates when the nanopipette is brought within distances from ten to hundreds of nanometers from the surface. Further studies of the pH dependence on the observed rectification support a surface-induced mechanism and demonstrate the ability to further discriminate between cationic and nominally uncharged surfaces. This method could find application in measurement and mapping of heterogeneous surface charges and is particularly attractive for future biological measurements, where noninvasive, noncontact probing of surface charge will prove valuable. PMID:21675734

The electrokinetic behavior of calcium oxalate monohydrate in macromolecular solutions

NASA Technical Reports Server (NTRS)

Curreri, P. A.; Onoda, G. Y., Jr.; Finlayson, B.

1988-01-01

Electrophoretic mobilities were measured for calcium oxalate monohydrate (COM) in solutions containing macromolecules. Two mucopolysaccharides (sodium heparin and chrondroitin sulfate) and two proteins (positively charged lysozyme and negatively charged bovine serum albumin) were studied as adsorbates. The effects of pH, calcium oxalate surface charge (varied by calcium or oxalate ion activity), and citrate concentration were investigated. All four macromolecules showed evidence for chemical adsorption. The macromolecule concentrations needed for reversing the surface charge indicated that the mucopopolysacchrides have greater affinity for the COM surface than the proteins. The amount of proteins that can chemically adsorb appears to be limited to approximately one monomolecular layer. When the surface charge is high, an insufficient number of proteins can chemically adsorb to neutralize or reverse the surface charge. The remaining surface charge is balanced by proteins held near the surface by longer range electrostatic forces only. Citrate ions at high concentrations appear to compete effectively with the negative protein for surface sites but show no evidence for competing with the positively charged protein.

Protein adsorption at charged surfaces: the role of electrostatic interactions and interfacial charge regulation.

PubMed

Hartvig, Rune A; van de Weert, Marco; Østergaard, Jesper; Jorgensen, Lene; Jensen, Henrik

2011-03-15

The understanding of protein adsorption at charged surfaces is important for a wide range of scientific disciplines including surface engineering, separation sciences and pharmaceutical sciences. Compared to chemical entities having a permanent charge, the adsorption of small ampholytes and proteins is more complicated as the pH near a charged surface can be significantly different from the value in bulk solution. In this work, we have developed a phenomenological adsorption model which takes into account the combined role of interfacial ion distribution, interfacial charge regulation of amino acids in the proximity of the surface, electroneutrality, and mass balance. The model is straightforward to apply to a given set of experimental conditions as most model parameters are obtained from bulk properties and therefore easy to estimate or are directly measurable. The model provides a detailed understanding of the importance of surface charge on adsorption and in particular of how changes in surface charge, concentration, and surface area may affect adsorption behavior. The model is successfully used to explain the experimental adsorption behavior of the two model proteins lysozyme and α-lactalbumin. It is demonstrated that it is possible to predict the pH and surface charge dependent adsorption behavior from experimental or theoretical estimates of a preferred orientation of a protein at a solid charged interface.

The Charging Events in Contact-Separation Electrification.

PubMed

Musa, Umar G; Cezan, S Doruk; Baytekin, Bilge; Baytekin, H Tarik

2018-02-06

Contact electrification (CE)-charging of surfaces that are contacted and separated, is a common phenomenon, however it is not completely understood yet. Recent studies using surface imaging techniques and chemical analysis revealed a 'spatial' bipolar distribution of charges at the nano dimension, which made a paradigm shift in the field. However, such analyses can only provide information about the charges that remained on the surface after the separation, providing limited information about the actual course of the CE event. Tapping common polymers and metal surfaces to each other and detecting the electrical potential produced on these surfaces 'in-situ' in individual events of contact and separation, we show that, charges are generated and transferred between the surfaces in both events; the measured potential is bipolar in contact and unipolar in separation. We show, the 'contact-charges' on the surfaces are indeed the net charges that results after the separation process, and a large contribution to tribocharge harvesting comes, in fact, from the electrostatic induction resulting from the generated CE charges. Our results refine the mechanism of CE providing information for rethinking the conventional ranking of materials' charging abilities, charge harvesting, and charge prevention.

Charged particle detectors with active detector surface for partial energy deposition of the charged particles and related methods

DOEpatents

Gerts, David W; Bean, Robert S; Metcalf, Richard R

2013-02-19

A radiation detector is disclosed. The radiation detector comprises an active detector surface configured to generate charge carriers in response to charged particles associated with incident radiation. The active detector surface is further configured with a sufficient thickness for a partial energy deposition of the charged particles to occur and permit the charged particles to pass through the active detector surface. The radiation detector further comprises a plurality of voltage leads coupled to the active detector surface. The plurality of voltage leads is configured to couple to a voltage source to generate a voltage drop across the active detector surface and to separate the charge carriers into a plurality of electrons and holes for detection. The active detector surface may comprise one or more graphene layers. Timing data between active detector surfaces may be used to determine energy of the incident radiation. Other apparatuses and methods are disclosed herein.

Adsorption of a cationic dye molecule on polystyrene microspheres in colloids: effect of surface charge and composition probed by second harmonic generation.

PubMed

Eckenrode, Heather M; Jen, Shih-Hui; Han, Jun; Yeh, An-Gong; Dai, Hai-Lung

2005-03-17

Nonlinear optical probe, second harmonic generation (SHG), of the adsorption of the dye molecule malachite green (MG), in cationic form at pH < or = 5, on polystyrene microspheres in aqueous solution is used to study the effect of surface charge and composition on molecular adsorption. Three types of polystyrene microspheres with different surface composition are investigated: (1) a sulfate terminated, anionic surface, (2) a neutral surface without any functional group termination, and (3) an amine terminated, cationic surface. The cationic dye was found to adsorb at all three surfaces, regardless of surface charge. The adsorption free energies, DeltaG's, measured for the three surfaces are -12.67, -12.39, and -10.46 kcal/mol, respectively, with the trend as expected from the charge interactions. The adsorption density on the anionic surface, where attractive charge-charge interaction dominates, is determined by the surface negative charge density. The adsorption densities on the neutral and cationic surfaces are on the other hand higher, perhaps as a result of a balance between minimizing repulsive charge interaction and maximizing attractive molecule-substrate and intermolecular interactions. The relative strength of the SH intensity per molecule, in combination of a model calculation, reveals that the C(2) axis of the MG molecule is nearly perpendicular to the surface on the anionic surface and tilts away from the surface norm when the surface is neutral and further away when cationic. Changing the pH of the solution may alter the surface charge and subsequently affect the adsorption configuration and SH intensity.

NASA charging analyzer program: A computer tool that can evaluate electrostatic contamination

NASA Technical Reports Server (NTRS)

Stevens, N. J.; Roche, J. C.; Mandell, M. J.

1978-01-01

A computer code, the NASA Charging Analyzer Program (NASCAP), was developed to study the surface charging of bodies subjected to geomagnetic substorm conditions. This program will treat the material properties of a surface in a self-consistent manner and calculate the electric fields in space due to the surface charge. Trajectories of charged particles in this electric field can be computed to determine if these particles enhance surface contamination. A preliminary model of the Spacecraft Charging At The High Altitudes (SCATHA) satellite was developed in the NASCAP code and subjected to a geomagnetic substorm environment to investigate the possibility of electrostatic contamination. The results indicate that differential voltages will exist between the spacecraft ground surfaces and the insulator surfaces. The electric fields from this differential charging can enhance the contamination of spacecraft surfaces.

Effect of alterations in glomerular charge on deposition of cationic and anionic antibodies to fixed glomerular antigens in the rat.

PubMed

Adler, S; Baker, P; Pritzl, P; Couser, W G

1985-07-01

Reduction of the negative charge of the glomerular capillary wall alters its charge- and size-selective properties. To investigate the effect of alteration in glomerular charge properties on antibody localization, we prepared cationic and anionic fractions of antibodies to subepithelial and glomerular basement membrane (GBM) antigens, and compared their deposition in normal rats and rats treated with protamine sulfate or aminonucleoside of puromycin to reduce capillary wall charge. IgG antibodies were eluted from kidneys of rats with active Heymann's nephritis (AICN), passive Heymann's nephritis (PHN), or anti-GBM nephritis (NTN), separated into cationic and anionic fractions, and radiolabeled with iodine 125 or iodine 131. Relative antibody content of each fraction was determined by incubation with an excess of glomerular antigen. Varying amounts of cationic and anionic IgG eluted from kidneys of rats with AICN or PHN were injected into 24 normal or protamine sulfate-treated rats. Glomerular binding of all antibodies was highly correlated with IgG delivery to the kidney. The ratio of cationic to anionic antibody deposited in the glomeruli of normal rats after 4 hours was 1.08 +/- 0.07 for AICN eluate and 0.37 +/- 0.04 for PHN eluate. The ratios were not significantly different in animals pretreated with protamine sulfate (1.15 +/- 0.06 and 0.44 +/- 0.06, respectively; P greater than 0.05). Varying amounts of cationic and anionic IgG eluted from kidneys of rats with NTN were injected into 10 normal rats and four rats treated with aminonucleoside of puromycin. Glomerular binding of antibody was again highly correlated with IgG delivery to the kidney. The ratio of cationic to anionic antibody deposited in the glomeruli of normal rats after 1 hour was 1.03 +/- 0.06, and was not significantly altered in rats treated with aminonucleoside of puromycin (1.05 +/- 0.03, P greater than 0.5). Proteinuria in PHN rats was also unaffected by treatment with protamine sulfate for 5 days (controls: 68 +/- 21 mg/day; protamine sulfate-treated: 65 +/- 14 mg/day; n = 25, P greater than 0.08). These results demonstrate that treatment to reduce glomerular polyanion does not significantly alter the ratio of cationic to anionic antibodies to fixed glomerular antigens that deposit in the glomerulus, or reduce proteinuria caused by deposition of antibody to a fixed subepithelial antigen.

Adhesion of osteoblasts to a nanorough titanium implant surface

PubMed Central

Gongadze, Ekaterina; Kabaso, Doron; Bauer, Sebastian; Slivnik, Tomaž; Schmuki, Patrik; van Rienen, Ursula; Iglič, Aleš

2011-01-01

This work considers the adhesion of cells to a nanorough titanium implant surface with sharp edges. The basic assumption was that the attraction between the negatively charged titanium surface and a negatively charged osteoblast is mediated by charged proteins with a distinctive quadrupolar internal charge distribution. Similarly, cation-mediated attraction between fibronectin molecules and the titanium surface is expected to be more efficient for a high surface charge density, resulting in facilitated integrin mediated osteoblast adhesion. We suggest that osteoblasts are most strongly bound along the sharp convex edges or spikes of nanorough titanium surfaces where the magnitude of the negative surface charge density is the highest. It is therefore plausible that nanorough regions of titanium surfaces with sharp edges and spikes promote the adhesion of osteoblasts. PMID:21931478

Effects of image charges, interfacial charge discreteness, and surface roughness on the zeta potential of spherical electric double layers.

PubMed

Gan, Zecheng; Xing, Xiangjun; Xu, Zhenli

2012-07-21

We investigate the effects of image charges, interfacial charge discreteness, and surface roughness on spherical electric double layer structures in electrolyte solutions with divalent counterions in the setting of the primitive model. By using Monte Carlo simulations and the image charge method, the zeta potential profile and the integrated charge distribution function are computed for varying surface charge strengths and salt concentrations. Systematic comparisons were carried out between three distinct models for interfacial charges: (1) SURF1 with uniform surface charges, (2) SURF2 with discrete point charges on the interface, and (3) SURF3 with discrete interfacial charges and finite excluded volume. By comparing the integrated charge distribution function and the zeta potential profile, we argue that the potential at the distance of one ion diameter from the macroion surface is a suitable location to define the zeta potential. In SURF2 model, we find that image charge effects strongly enhance charge inversion for monovalent interfacial charges, and strongly suppress charge inversion for multivalent interfacial charges. For SURF3, the image charge effect becomes much smaller. Finally, with image charges in action, we find that excluded volumes (in SURF3) suppress charge inversion for monovalent interfacial charges and enhance charge inversion for multivalent interfacial charges. Overall, our results demonstrate that all these aspects, i.e., image charges, interfacial charge discreteness, their excluding volumes, have significant impacts on zeta potentials of electric double layers.

On the physics of both surface overcharging and charge reversal at heterophase interfaces.

PubMed

Wang, Zhi-Yong; Zhang, Pengli; Ma, Zengwei

2018-02-07

The conventional paradigm for characterizing surface overcharging and charge reversal is based on the so-called Stern layer, in which surface dissociation reaction and specific chemical adsorption are assumed to take place. In this article, a series of Monte Carlo simulations have been applied to obtain useful insights into the underlying physics responsible for these two kinds of anomalous phenomena at the interface of two dielectrics, with special emphasis on the case of divalent counterions that are more relevant in natural and biological environments. At a weakly charged surface, it is found that independent of the type of surface charge distribution and the dielectric response of the solution, the overcharging event is universally driven by the ion size-asymmetric effect. Exceptionally, the overcharging still persists when the surface is highly charged but is only restricted to the case of discrete surface charge in a relatively low dielectric medium. As compared to the adsorption onto the homogeneously smeared charge surface that has the same average affinity for counterions, on the other hand, charge reversal under the action of a dielectric response can be substantially enhanced in the discrete surface charge representation due to strong association of counterions with interfacial groups, and the degree of enhancement depends in a nontrivial way on the reduction of the medium dielectric constant and the steric effects of finite ion size. Rather interestingly, the charge reversal is of high relevance to the overcharging of interfaces because the overwhelming interfacial association forces the coions closer to the surface due to their smaller size than the counterions. Upon the addition of a monovalent salt to the solution, the interfacial association with divalent counterions makes surface overcharging and charge reversal widely unaffected, in contrast to the prevailing notion that screening of surface charge of a homogeneous nature is determined by the competitive effects between size-exclusion effects and energetic contributions. Overall, the present work highlights that the complex interplay between the electrostatic and steric interactions should be coupled to the realistic character of surface charge to establish a faithful description of the overcharging and charge reversal at heterophase interfaces.

Nanopipette delivery: influence of surface charge.

PubMed

Shi, Wenqing; Sa, Niya; Thakar, Rahul; Baker, Lane A

2015-07-21

In this report, transport through a nanopipette is studied and the interplay between current rectification and ion delivery for small pipettes is examined. First, surface charge dependence of concentration polarization effects in a quartz nanopipette was investigated. Electrical characterization was performed through current-potential (I-V) measurements. In addition, fluorescein (an anionic fluorescent probe) was utilized to optically map ion enrichment and ion depletion in the nanopipette tip. Bare nanopipettes and polyethylenimine (PEI)-modified nanopipettes were examined. Results confirm that concentration polarization is a surface charge dependent phenomenon and delivery can be controlled through modification of surface charge. The relationship between concentration polarization effects and voltage-driven delivery of charged electroactive species was investigated with a carbon ring/nanopore electrode fabricated from pyrolyzed parylene C (PPC). Factors such as surface charge polarity of the nanopipette, electrolyte pH, and electrolyte concentration were investigated. Results indicate that with modification of surface charge, additional control over delivery of charged species can be achieved.

Polarization-induced surface charges in hydroxyapatite ceramics

NASA Astrophysics Data System (ADS)

Horiuchi, N.; Nakaguki, S.; Wada, N.; Nozaki, K.; Nakamura, M.; Nagai, A.; Katayama, K.; Yamashita, K.

2014-07-01

Calcium hydroxyapatite (HAp; Ca10(PO4)6(OH)2) is a well-known biomaterial that is the main inorganic component of bones and teeth. Control over the surface charge on HAp would be a key advance in the development of the material for tissue engineering. We demonstrate here that surface charge can be induced by an electrical poling process using the Kelvin method. Positive and negative charges were induced on the HAp surface in response to the applied electric field in the poling process. The surface charging is attributed to dipole polarization that is homogeneously distributed in HAp. Additionally, the surface charging is considered to originate from the organization of OH- ions into a polar phase in the structure.

New iron-based mixed-polyanion cathodes for lithium and sodium rechargeable batteries: combined first principles calculations and experimental study.

PubMed

Kim, Hyungsub; Park, Inchul; Seo, Dong-Hwa; Lee, Seongsu; Kim, Sung-Wook; Kwon, Woo Jun; Park, Young-Uk; Kim, Chul Sung; Jeon, Seokwoo; Kang, Kisuk

2012-06-27

New iron-based mixed-polyanion compounds Li(x)Na(4-x)Fe(3)(PO(4))(2)(P(2)O(7)) (x = 0-3) were synthesized, and their crystal structures were determined. The new compounds contained three-dimensional (3D)sodium/lithium paths supported by P(2)O(7) pillars in the crystal. First principles calculations identified the complex 3D paths with their activation barriers and revealed them as fast ionic conductors. The reversible electrode operation was found in both Li and Na cells with capacities of one-electron reaction per Fe atom, 140 and 129 mAh g(-1), respectively. The redox potential of each phase was ∼3.4 V (vs Li) for the Li-ion cell and ∼3.2 V (vs Na) for the Na-ion cell. The properties of high power, small volume change, and high thermal stability were also recognized, presenting this new compound as a potential competitor to other iron-based electrodes such as Li(2)FeP(2)O(7), Li(2)FePO(4)F, and LiFePO(4).

Interfering lipoproteins in magnetic field-assisted agglutination of superparamagnetic particles immunoassay.

PubMed

Cauet, Gilles; Daynès, Aurélien; Temurok, Nevzat

2016-04-01

The technology of magnetic field-assisted immuno-agglutination of superparamagnetic particles allows sensitive detection of biomarkers in whole blood. However, we observed non-specific agglutination (NSA), due to interfering plasma proteins, that negatively affects C-reactive protein immunoassay. The objective of the study was to identify the plasma proteins involved and to eliminate these interferences. Plasma was fractionated by size exclusion HPLC and each fraction was tested for non-specific agglutination. In addition, plasma proteins bound to magnetic particles were analyzed by SDS-gel electrophoresis and identified by mass spectrometry. We found that NSA was due to the binding of some lipoproteins to the particles. NSA was observed in the presence of purified LDL and VLDL but not HDL. NSA was mediated by the binding of ApoB100 to magnetic particles through its heparin binding sites. These interferences could be eliminated by addition of heparin or other polyanions like dextran sulfate to the assay buffer. NSA results from the binding of some plasma lipoproteins to magnetic particles. The use of a polyanion to eliminate these interferences allows the formulation of a stable reagent.

Poisson-Boltzmann theory of the charge-induced adsorption of semi-flexible polyelectrolytes.

PubMed

Ubbink, Job; Khokhlov, Alexei R

2004-03-15

A model is suggested for the structure of an adsorbed layer of a highly charged semi-flexible polyelectrolyte on a weakly charged surface of opposite charge sign. The adsorbed phase is thin, owing to the effective reversal of the charge sign of the surface upon adsorption, and ordered, owing to the high surface density of polyelectrolyte strands caused by the generally strong binding between polyelectrolyte and surface. The Poisson-Boltzmann equation for the electrostatic interaction between the array of adsorbed polyelectrolytes and the charged surface is solved for a cylindrical geometry, both numerically, using a finite element method, and analytically within the weak curvature limit under the assumption of excess monovalent salt. For small separations, repulsive surface polarization and counterion osmotic pressure effects dominate over the electrostatic attraction and the resulting electrostatic interaction curve shows a minimum at nonzero separations on the Angstrom scale. The equilibrium density of the adsorbed phase is obtained by minimizing the total free energy under the condition of equality of chemical potential and osmotic pressure of the polyelectrolyte in solution and in the adsorbed phase. For a wide range of ionic conditions and charge densities of the charged surface, the interstrand separation as predicted by the Poisson-Boltzmann model and the analytical theory closely agree. For low to moderate charge densities of the adsorbing surface, the interstrand spacing decreases as a function of the charge density of the charged surface. Above about 0.1 M excess monovalent salt, it is only weakly dependent on the ionic strength. At high charge densities of the adsorbing surface, the interstrand spacing increases with increasing ionic strength, in line with the experiments by Fang and Yang [J. Phys. Chem. B 101, 441 (1997)]. (c) 2004 American Institute of Physics.

Method for Estimating the Charge Density Distribution on a Dielectric Surface.

PubMed

Nakashima, Takuya; Suhara, Hiroyuki; Murata, Hidekazu; Shimoyama, Hiroshi

2017-06-01

High-quality color output from digital photocopiers and laser printers is in strong demand, motivating attempts to achieve fine dot reproducibility and stability. The resolution of a digital photocopier depends on the charge density distribution on the organic photoconductor surface; however, directly measuring the charge density distribution is impossible. In this study, we propose a new electron optical instrument that can rapidly measure the electrostatic latent image on an organic photoconductor surface, which is a dielectric surface, as well as a novel method to quantitatively estimate the charge density distribution on a dielectric surface by combining experimental data obtained from the apparatus via a computer simulation. In the computer simulation, an improved three-dimensional boundary charge density method (BCM) is used for electric field analysis in the vicinity of the dielectric material with a charge density distribution. This method enables us to estimate the profile and quantity of the charge density distribution on a dielectric surface with a resolution of the order of microns. Furthermore, the surface potential on the dielectric surface can be immediately calculated using the obtained charge density. This method enables the relation between the charge pattern on the organic photoconductor surface and toner particle behavior to be studied; an understanding regarding the same may lead to the development of a new generation of higher resolution photocopiers.

Lunar Surface Charging during Solar Energetic Particle Events

NASA Astrophysics Data System (ADS)

Halekas, Jasper S.; Delory, G. T.; Mewaldt, R. A.; Lin, R. P.; Fillingim, M. O.; Brain, D. A.; Lee, C. O.; Stubbs, T. J.; Farrell, W. M.; Hudson, M. K.

2006-09-01

The surface of the Moon, not protected by any substantial atmosphere, is directly exposed to the impact of both solar UV and solar wind plasma and energetic particles. This creates a complex lunar electrostatic environment, with the surface typically charging slightly positive in sunlight, and negative in shadow. Observations from the Apollo era and theoretical considerations strongly suggest that surface charging leads to dust electrification and transport, posing a potentially significant hazard for exploration. The most significant charging effects should occur when the Moon is exposed to high-temperature plasmas like those encountered in the terrestrial plasmasheet or in solar storms. We now present evidence for kilovolt-scale negative charging of the shadowed lunar surface during solar energetic particle (SEP) events, utilizing data from the Lunar Prospector Electron Reflectometer (LP ER). We find that SEP events are associated with the most extreme lunar surface charging observed during the LP mission - rivaled only by previously reported charging during traversals of the terrestrial plasmasheet. The largest charging event observed by LP is a 4 kV negative surface potential (as compared to typical values of V) during a SEP event in May 1998. We characterize lunar surface charging during several SEP events, and compare to energetic particle measurements from ACE, Wind, and SOHO in order to determine the relationship between SEP events and extreme lunar surface charging. Space weather events are already considered by NASA to be a significant hazard to lunar exploration, due to high-energy ionizing radiation. Our observations demonstrate that plasma interactions with the lunar surface during SEP events, causing extreme surface charging and potentially significant dust electrification and transport, represent an additional hazard associated with space weather.

Charge-Spot Model for Electrostatic Forces in Simulation of Fine Particulates

NASA Technical Reports Server (NTRS)

Walton, Otis R.; Johnson, Scott M.

2010-01-01

The charge-spot technique for modeling the static electric forces acting between charged fine particles entails treating electric charges on individual particles as small sets of discrete point charges, located near their surfaces. This is in contrast to existing models, which assume a single charge per particle. The charge-spot technique more accurately describes the forces, torques, and moments that act on triboelectrically charged particles, especially image-charge forces acting near conducting surfaces. The discrete element method (DEM) simulation uses a truncation range to limit the number of near-neighbor charge spots via a shifted and truncated potential Coulomb interaction. The model can be readily adapted to account for induced dipoles in uncharged particles (and thus dielectrophoretic forces) by allowing two charge spots of opposite signs to be created in response to an external electric field. To account for virtual overlap during contacts, the model can be set to automatically scale down the effective charge in proportion to the amount of virtual overlap of the charge spots. This can be accomplished by mimicking the behavior of two real overlapping spherical charge clouds, or with other approximate forms. The charge-spot method much more closely resembles real non-uniform surface charge distributions that result from tribocharging than simpler approaches, which just assign a single total charge to a particle. With the charge-spot model, a single particle may have a zero net charge, but still have both positive and negative charge spots, which could produce substantial forces on the particle when it is close to other charges, when it is in an external electric field, or when near a conducting surface. Since the charge-spot model can contain any number of charges per particle, can be used with only one or two charge spots per particle for simulating charging from solar wind bombardment, or with several charge spots for simulating triboelectric charging. Adhesive image-charge forces acting on charged particles touching conducting surfaces can be up to 50 times stronger if the charge is located in discrete spots on the particle surface instead of being distributed uniformly over the surface of the particle, as is assumed by most other models. Besides being useful in modeling particulates in space and distant objects, this modeling technique is useful for electrophotography (used in copiers) and in simulating the effects of static charge in the pulmonary delivery of fine dry powders.

Atomistic and molecular effects in electric double layers at high surface charges

DOE PAGES

Templeton, Jeremy Alan; Lee, Jonathan; Mani, Ali

2015-06-16

Here, the Poisson–Boltzmann theory for electrolytes near a charged surface is known to be invalid due to unaccounted physics associated with high ion concentration regimes. In order to investigate this regime, fluids density functional theory (f-DFT) and molecular dynamics (MD) simulations were used to determine electric surface potential as a function of surface charge. Based on these detailed computations, for electrolytes with nonpolar solvent, the surface potential is shown to depend quadratically on the surface charge in the high charge limit. We demonstrate that modified Poisson–Boltzmann theories can model this limit if they are augmented with atomic packing densities providedmore » by MD. However, when the solvent is a highly polar molecule water an intermediate regime is identified in which a constant capacitance is realized. Simulation results demonstrate the mechanism underlying this regime, and for the salt water system studied here, it persists throughout the range of physically realistic surface charge densities so the potential’s quadratic surface charge dependence is not obtained.« less

Surface charge mapping with a nanopipette.

PubMed

McKelvey, Kim; Kinnear, Sophie L; Perry, David; Momotenko, Dmitry; Unwin, Patrick R

2014-10-01

Nanopipettes are emerging as simple but powerful tools for probing chemistry at the nanoscale. In this contribution the use of nanopipettes for simultaneous surface charge mapping and topographical imaging is demonstrated, using a scanning ion conductance microscopy (SICM) format. When a nanopipette is positioned close to a surface in electrolyte solution, the direct ion current (DC), driven by an applied bias between a quasi-reference counter electrode (QRCE) in the nanopipette and a second QRCE in the bulk solution, is sensitive to surface charge. The charge sensitivity arises because the diffuse double layers at the nanopipette and the surface interact, creating a perm-selective region which becomes increasingly significant at low ionic strengths (10 mM 1:1 aqueous electrolyte herein). This leads to a polarity-dependent ion current and surface-induced rectification as the bias is varied. Using distance-modulated SICM, which induces an alternating ion current component (AC) by periodically modulating the distance between the nanopipette and the surface, the effect of surface charge on the DC and AC is explored and rationalized. The impact of surface charge on the AC phase (with respect to the driving sinusoidal signal) is highlighted in particular; this quantity shows a shift that is highly sensitive to interfacial charge and provides the basis for visualizing charge simultaneously with topography. The studies herein highlight the use of nanopipettes for functional imaging with applications from cell biology to materials characterization where understanding surface charge is of key importance. They also provide a framework for the design of SICM experiments, which may be convoluted by topographical and surface charge effects, especially for small nanopipettes.

High resolution printing of charge

DOEpatents

Rogers, John; Park, Jang-Ung

2015-06-16

Provided are methods of printing a pattern of charge on a substrate surface, such as by electrohydrodynamic (e-jet) printing. The methods relate to providing a nozzle containing a printable fluid, providing a substrate having a substrate surface and generating from the nozzle an ejected printable fluid containing net charge. The ejected printable fluid containing net charge is directed to the substrate surface, wherein the net charge does not substantially degrade and the net charge retained on the substrate surface. Also provided are functional devices made by any of the disclosed methods.

Photoelectric charging of partially sunlit dielectric surfaces in space

NASA Technical Reports Server (NTRS)

De, B. R.; Criswell, D. R.

1977-01-01

Sunlight-shadow effects may substantially alter the charging situation for a dielectric surface. The sunlight-shadow boundary tends to be the site of intense multipole electric fields. Charges on a sunlit dielectric surface have a finite effective mobility. The charge distribution tends to resemble that on a conducting surface. A boundary between a conducting and a dielectric surface may not represent a conductivity discontinuity when this boundary is sunlit; charges may migrate at a nontrivial rate across the boundary. A contracting or expanding sunlit area may experience a supercharging.

Effect of the surface charge discretization on electric double layers: a Monte Carlo simulation study.

PubMed

Madurga, Sergio; Martín-Molina, Alberto; Vilaseca, Eudald; Mas, Francesc; Quesada-Pérez, Manuel

2007-06-21

The structure of the electric double layer in contact with discrete and continuously charged planar surfaces is studied within the framework of the primitive model through Monte Carlo simulations. Three different discretization models are considered together with the case of uniform distribution. The effect of discreteness is analyzed in terms of charge density profiles. For point surface groups, a complete equivalence with the situation of uniformly distributed charge is found if profiles are exclusively analyzed as a function of the distance to the charged surface. However, some differences are observed moving parallel to the surface. Significant discrepancies with approaches that do not account for discreteness are reported if charge sites of finite size placed on the surface are considered.

Luminescent systems based on the isolation of conjugated PI systems and edge charge compensation with polar molecules on a charged nanostructured surface

DOEpatents

Ivanov, Ilia N.; Puretzky, Alexander A.; Zhao, Bin; Geohegan, David B.; Styers-Barnett, David J.; Hu, Hui

2014-07-15

A photoluminescent or electroluminescent system and method of making a non-luminescent nanostructured material into such a luminescent system is presented. The method of preparing the luminescent system, generally, comprises the steps of modifying the surface of a nanostructured material to create isolated regions to act as luminescent centers and to create a charge imbalance on the surface; applying more than one polar molecule to the charged surface of the nanostructured material; and orienting the polar molecules to compensate for the charge imbalance on the surface of the nanostructured material. The compensation of the surface charge imbalance by the polar molecules allows the isolated regions to exhibit luminescence.

Characterization of the surface charge distribution on kaolinite particles using high resolution atomic force microscopy

NASA Astrophysics Data System (ADS)

Kumar, Naveen; Zhao, Cunlu; Klaassen, Aram; van den Ende, Dirk; Mugele, Frieder; Siretanu, Igor

2016-02-01

Most solid surfaces, in particular clay minerals and rock surfaces, acquire a surface charge upon exposure to an aqueous environment due to adsorption and/or desorption of ionic species. Macroscopic techniques such as titration and electrokinetic measurements are commonly used to determine the surface charge and ζ -potential of these surfaces. However, because of the macroscopic averaging character these techniques cannot do justice to the role of local heterogeneities on the surfaces. In this work, we use dynamic atomic force microscopy (AFM) to determine the distribution of surface charge on the two (gibbsite-like and silica-like) basal planes of kaolinite nanoparticles immersed in aqueous electrolyte with a lateral resolution of approximately 30 nm. The surface charge density is extracted from force-distance curves using DLVO theory in combination with surface complexation modeling. While the gibbsite-like and the silica-like facet display on average positive and negative surface charge values as expected, our measurements reveal lateral variations of more than a factor of two on seemingly atomically smooth terraces, even if high resolution AFM images clearly reveal the atomic lattice on the surface. These results suggest that simple surface complexation models of clays that attribute a unique surface chemistry and hence homogeneous surface charge densities to basal planes may miss important aspects of real clay surfaces.

Proximity charge sensing for semiconductor detectors

DOEpatents

Luke, Paul N; Tindall, Craig S; Amman, Mark

2013-10-08

A non-contact charge sensor includes a semiconductor detector having a first surface and an opposing second surface. The detector includes a high resistivity electrode layer on the first surface and a low resistivity electrode on the high resistivity electrode layer. A portion of the low resistivity first surface electrode is deleted to expose the high resistivity electrode layer in a portion of the area. A low resistivity electrode layer is disposed on the second surface of the semiconductor detector. A voltage applied between the first surface low resistivity electrode and the second surface low resistivity electrode causes a free charge to drift toward the first or second surface according to a polarity of the free charge and the voltage. A charge sensitive preamplifier coupled to a non-contact electrode disposed at a distance from the exposed high resistivity electrode layer outputs a signal in response to movement of free charge within the detector.

Probing the Surface Charge on the Basal Planes of Kaolinite Particles with High-Resolution Atomic Force Microscopy

PubMed Central

2017-01-01

High-resolution atomic force microscopy is used to map the surface charge on the basal planes of kaolinite nanoparticles in an ambient solution of variable pH and NaCl or CaCl2 concentration. Using DLVO theory with charge regulation, we determine from the measured force–distance curves the surface charge distribution on both the silica-like and the gibbsite-like basal plane of the kaolinite particles. We observe that both basal planes do carry charge that varies with pH and salt concentration. The silica facet was found to be negatively charged at pH 4 and above, whereas the gibbsite facet is positively charged at pH below 7 and negatively charged at pH above 7. Investigations in CaCl2 at pH 6 show that the surface charge on the gibbsite facet increases for concentration up to 10 mM CaCl2 and starts to decrease upon further increasing the salt concentration to 50 mM. The increase of surface charge at low concentration is explained by Ca2+ ion adsorption, while Cl– adsorption at higher CaCl2 concentrations partially neutralizes the surface charge. Atomic resolution imaging and density functional theory calculations corroborate these observations. They show that hydrated Ca2+ ions can spontaneously adsorb on the gibbsite facet of the kaolinite particle and form ordered surface structures, while at higher concentrations Cl– ions will co-adsorb, thereby changing the observed ordered surface structure. PMID:29140711

Probing the Surface Charge on the Basal Planes of Kaolinite Particles with High-Resolution Atomic Force Microscopy.

PubMed

Kumar, N; Andersson, M P; van den Ende, D; Mugele, F; Siretanu, I

2017-12-19

High-resolution atomic force microscopy is used to map the surface charge on the basal planes of kaolinite nanoparticles in an ambient solution of variable pH and NaCl or CaCl 2 concentration. Using DLVO theory with charge regulation, we determine from the measured force-distance curves the surface charge distribution on both the silica-like and the gibbsite-like basal plane of the kaolinite particles. We observe that both basal planes do carry charge that varies with pH and salt concentration. The silica facet was found to be negatively charged at pH 4 and above, whereas the gibbsite facet is positively charged at pH below 7 and negatively charged at pH above 7. Investigations in CaCl 2 at pH 6 show that the surface charge on the gibbsite facet increases for concentration up to 10 mM CaCl 2 and starts to decrease upon further increasing the salt concentration to 50 mM. The increase of surface charge at low concentration is explained by Ca 2+ ion adsorption, while Cl - adsorption at higher CaCl 2 concentrations partially neutralizes the surface charge. Atomic resolution imaging and density functional theory calculations corroborate these observations. They show that hydrated Ca 2+ ions can spontaneously adsorb on the gibbsite facet of the kaolinite particle and form ordered surface structures, while at higher concentrations Cl - ions will co-adsorb, thereby changing the observed ordered surface structure.

Characterizing the surface charge of synthetic nanomembranes by the streaming potential method

PubMed Central

Datta, Subhra; Conlisk, A. T.; Kanani, Dharmesh M.; Zydney, Andrew L.; Fissell, William H.; Roy, Shuvo

2010-01-01

The inference of the surface charge of polyethylene glycol (PEG)-coated and uncoated silicon membranes with nanoscale pore sizes from streaming potential measurements in the presence of finite electric double layer (EDL) effects is studied theoretically and experimentally. The developed theoretical model for inferring the pore wall surface charge density from streaming potential measurements is applicable to arbitrary pore cross-sectional shapes and accounts for the effect of finite salt concentration on the ionic mobilities and the thickness of the deposited layer of PEG. Theoretical interpretation of the streaming potential data collected from silicon membranes having nanoscale pore sizes, with/without pore wall surface modification with PEG, indicates that finite electric double layer (EDL) effects in the pore-confined electrolyte significantly affect the interpretation of the membrane charge and that surface modification with PEG leads to a reduction in the pore wall surface charge density. The theoretical model is also used to study the relative significance of the following uniquely nanoscale factors affecting the interpretation of streaming potential in moderate to strongly charged pores: altered net charge convection by applied pressure differentials, surface-charge effects on ionic conduction, and electroosmotic convection of charges. PMID:20462592

Electronically shielded solid state charged particle detector

DOEpatents

Balmer, D.K.; Haverty, T.W.; Nordin, C.W.; Tyree, W.H.

1996-08-20

An electronically shielded solid state charged particle detector system having enhanced radio frequency interference immunity includes a detector housing with a detector entrance opening for receiving the charged particles. A charged particle detector having an active surface is disposed within the housing. The active surface faces toward the detector entrance opening for providing electrical signals representative of the received charged particles when the received charged particles are applied to the active surface. A conductive layer is disposed upon the active surface. In a preferred embodiment, a nonconductive layer is disposed between the conductive layer and the active surface. The conductive layer is electrically coupled to the detector housing to provide a substantially continuous conductive electrical shield surrounding the active surface. The inner surface of the detector housing is supplemented with a radio frequency absorbing material such as ferrite. 1 fig.

Electronically shielded solid state charged particle detector

DOEpatents

Balmer, David K.; Haverty, Thomas W.; Nordin, Carl W.; Tyree, William H.

1996-08-20

An electronically shielded solid state charged particle detector system having enhanced radio frequency interference immunity includes a detector housing with a detector entrance opening for receiving the charged particles. A charged particle detector having an active surface is disposed within the housing. The active surface faces toward the detector entrance opening for providing electrical signals representative of the received charged particles when the received charged particles are applied to the active surface. A conductive layer is disposed upon the active surface. In a preferred embodiment, a nonconductive layer is disposed between the conductive layer and the active surface. The conductive layer is electrically coupled to the detector housing to provide a substantially continuous conductive electrical shield surrounding the active surface. The inner surface of the detector housing is supplemented with a radio frequency absorbing material such as ferrite.

Strong coupling electrostatics for randomly charged surfaces: antifragility and effective interactions.

PubMed

Ghodrat, Malihe; Naji, Ali; Komaie-Moghaddam, Haniyeh; Podgornik, Rudolf

2015-05-07

We study the effective interaction mediated by strongly coupled Coulomb fluids between dielectric surfaces carrying quenched, random monopolar charges with equal mean and variance, both when the Coulomb fluid consists only of mobile multivalent counterions and when it consists of an asymmetric ionic mixture containing multivalent and monovalent (salt) ions in equilibrium with an aqueous bulk reservoir. We analyze the consequences that follow from the interplay between surface charge disorder, dielectric and salt image effects, and the strong electrostatic coupling that results from multivalent counterions on the distribution of these ions and the effective interaction pressure they mediate between the surfaces. In a dielectrically homogeneous system, we show that the multivalent counterions are attracted towards the surfaces with a singular, disorder-induced potential that diverges logarithmically on approach to the surfaces, creating a singular but integrable counterion density profile that exhibits an algebraic divergence at the surfaces with an exponent that depends on the surface charge (disorder) variance. This effect drives the system towards a state of lower thermal 'disorder', one that can be described by a renormalized temperature, exhibiting thus a remarkable antifragility. In the presence of an interfacial dielectric discontinuity, the singular behavior of counterion density at the surfaces is removed but multivalent counterions are still accumulated much more strongly close to randomly charged surfaces as compared with uniformly charged ones. The interaction pressure acting on the surfaces displays in general a highly non-monotonic behavior as a function of the inter-surface separation with a prominent regime of attraction at small to intermediate separations. This attraction is caused directly by the combined effects from charge disorder and strong coupling electrostatics of multivalent counterions, which dominate the surface-surface repulsion due to the (equal) mean charges on the two surfaces and the osmotic pressure of monovalent ions residing between them. These effects can be quite significant even with a small degree of surface charge disorder relative to the mean surface charge. The strong coupling, disorder-induced attraction is typically much stronger than the van der Waals interaction between the surfaces, especially within a range of several nanometers for the inter-surface separation, where such effects are predicted to be most pronounced.

Effect of surface material on electrostatic charging of houseflies (Musca domestica L).

PubMed

McGonigle, Daniel F; Jackson, Chris W

2002-04-01

Houseflies (Musca domestica L) accumulated electrostatic charges when walking over clean, uncharged dielectric surfaces. The charges elicited on a walking housefly by a range of materials were quantified, allowing a triboelectric series to be determined relative to M domestica. This ranged from surfaces that charged individuals positively, e.g. Correx (corrugated polypropylene) [.1 (+/- 4.2)pC], to those that applied a negative charge, e.g. clear cast acrylic [-14.9 (+/- 2.9)pC]. Maximum positive and negative charges accumulated by individual M domestica were +73 and -27 pC. Replicate measurements on the same fly and surface showed little variation. Variation between individuals was not related to sex and was not consistent between surfaces. Different materials charged M domestica significantly differently and individual flies had significantly different charging properties. Variation in temperature between 21.3 degrees C and 24.7 degrees C and humidity between 24% and 41% RH significantly affected charge accumulated by M domestica on some surfaces, although further experimentation is needed to confirm this. The implications of this work are discussed in relation to insect trap design and pollination biology.

Oil Contact Angles in a Water-Decane-Silicon Dioxide System: Effects of Surface Charge

NASA Astrophysics Data System (ADS)

Xu, Shijing; Wang, Jingyao; Wu, Jiazhong; Liu, Qingjie; Sun, Chengzhen; Bai, Bofeng

2018-04-01

Oil wettability in the water-oil-rock systems is very sensitive to the evolution of surface charges on the rock surfaces induced by the adsorption of ions and other chemical agents in water flooding. Through a set of large-scale molecular dynamics simulations, we reveal the effects of surface charge on the oil contact angles in an ideal water-decane-silicon dioxide system. The results show that the contact angles of oil nano-droplets have a great dependence on the surface charges. As the surface charge density exceeds a critical value of 0.992 e/nm2, the contact angle reaches up to 78.8° and the water-wet state is very apparent. The variation of contact angles can be confirmed from the number density distributions of oil molecules. With increasing the surface charge density, the adsorption of oil molecules weakens and the contact areas between nano-droplets and silicon dioxide surface are reduced. In addition, the number density distributions, RDF distributions, and molecular orientations indicate that the oil molecules are adsorbed on the silicon dioxide surface layer-by-layer with an orientation parallel to the surface. However, the layered structure of oil molecules near the silicon dioxide surface becomes more and more obscure at higher surface charge densities.

Oil Contact Angles in a Water-Decane-Silicon Dioxide System: Effects of Surface Charge.

PubMed

Xu, Shijing; Wang, Jingyao; Wu, Jiazhong; Liu, Qingjie; Sun, Chengzhen; Bai, Bofeng

2018-04-19

Oil wettability in the water-oil-rock systems is very sensitive to the evolution of surface charges on the rock surfaces induced by the adsorption of ions and other chemical agents in water flooding. Through a set of large-scale molecular dynamics simulations, we reveal the effects of surface charge on the oil contact angles in an ideal water-decane-silicon dioxide system. The results show that the contact angles of oil nano-droplets have a great dependence on the surface charges. As the surface charge density exceeds a critical value of 0.992 e/nm 2 , the contact angle reaches up to 78.8° and the water-wet state is very apparent. The variation of contact angles can be confirmed from the number density distributions of oil molecules. With increasing the surface charge density, the adsorption of oil molecules weakens and the contact areas between nano-droplets and silicon dioxide surface are reduced. In addition, the number density distributions, RDF distributions, and molecular orientations indicate that the oil molecules are adsorbed on the silicon dioxide surface layer-by-layer with an orientation parallel to the surface. However, the layered structure of oil molecules near the silicon dioxide surface becomes more and more obscure at higher surface charge densities.

Critical Dipole Length for the Wetting Transition Due to Collective Water-dipoles Interactions

PubMed Central

Wang, Chunlei; Zhou, Bo; Tu, Yusong; Duan, Manyi; Xiu, Peng; Li, Jingye; Fang, Haiping

2012-01-01

The wetting behavior of water on the solid surfaces is fundamental to various physical, chemical and biological processes. Conventionally, the surface with charges or charge dipoles is hydrophilic, whereas the non-polar surface is hydrophobic though some exceptions were recently reported. Using molecular dynamics simulations, we show that there is a critical length of the charge dipoles on the solid surface. The solid surface still exhibited hydrophobic behavior when the dipole length was less than the critical value, indicating that the water molecules on the solid surface seemed not “feel” attractive interactions from the charge dipoles on the solid surface. Those unexpected observations result from the collective interactions between the water molecules and charge dipoles on the solid surface, where the steric exclusion effect between water molecules greatly reduces the water-dipole interactions. Remarkably, the steric exclusion effect is also important for surfaces with charge dipole lengths greater than this critical length. PMID:22496954

Polyelectrolyte adsorption onto like-charged surfaces mediated by trivalent counterions: A Monte Carlo simulation study

NASA Astrophysics Data System (ADS)

Luque-Caballero, Germán; Martín-Molina, Alberto; Quesada-Pérez, Manuel

2014-05-01

Both experiments and theory have evidenced that multivalent cations can mediate the interaction between negatively charged polyelectrolytes and like-charged objects, such as anionic lipoplexes (DNA-cation-anionic liposome complexes). In this paper, we use Monte Carlo simulations to study the electrostatic interaction responsible for the trivalent-counterion-mediated adsorption of polyelectrolytes onto a like-charged planar surface. The evaluation of the Helmholtz free energy allows us to characterize both the magnitude and the range of the interaction as a function of the polyelectrolyte charge, surface charge density, [3:1] electrolyte concentration, and cation size. Both polyelectrolyte and surface charge favor the adsorption. It should be stressed, however, that the adsorption will be negligible if the surface charge density does not exceed a threshold value. The effect of the [3:1] electrolyte concentration has also been analyzed. In certain range of concentrations, the counterion-mediated attraction seems to be independent of this parameter, whereas very high concentrations of salt weaken the adsorption. If the trivalent cation diameter is doubled the adsorption moderates due to the excluded volume effects. The analysis of the integrated charge density and ionic distributions suggests that a delicate balance between charge inversion and screening effects governs the polyelectrolyte adsorption onto like-charged surfaces mediated by trivalent cations.

Charge renormalization and inversion of a highly charged lipid bilayer: effects of dielectric discontinuities and charge correlations.

PubMed

Taheri-Araghi, Sattar; Ha, Bae-Yeun

2005-08-01

We reexamine the problem of charge renormalization and inversion of a highly charged surface of a low dielectric constant immersed in ionic solutions. To be specific, we consider an asymmetrically charged lipid bilayer, in which only one layer is negatively charged. In particular, we study how dielectric discontinuities and charge correlations (among lipid charges and condensed counterions) influence the effective charge of the surface. When counterions are monovalent (e.g., Na+), our mean-field approach implies that dielectric discontinuities can enhance counterion condensation. A simple scaling picture shows how the effects of dielectric discontinuities and surface-charge distributions are intertwined: Dielectric discontinuities diminish condensation if the backbone charge is uniformly smeared out while counterions are localized in space; they can, however, enhance condensation when the backbone charge is discrete. In the presence of asymmetric salts such as CaCl2 , we find that the correlation effect, treated at the Gaussian level, is more pronounced when the surface has a lower dielectric constant, inverting the sign of the charge at a smaller value of Ca2+ concentration.

Ion association at discretely-charged dielectric interfaces: Giant charge inversion [Dielectric response controlled ion association at physically heterogeneous surfaces: Giant charge reversal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Zhi -Yong; Wu, Jianzhong

2017-07-11

Giant charge reversal has been identified for the first time by Monte Carlo simulation for a discretely charged surface in contact with a trivalent electrolyte solution. It takes place regardless of the surface charge density under study and the monovalent salt. In stark contrast to earlier predictions based on the 2-dimensional Wigner crystal model to describe strong correlation of counterions at the macroion surface, we find that giant charge reversal reflects an intricate interplay of ionic volume effects, electrostatic correlations, surface charge heterogeneity, and the dielectric response of the confined fluids. While the novel phenomenon is yet to be confirmedmore » with experiment, the simulation results appear in excellent agreement with a wide range of existing observations in the subregime of charge inversion. Lastly, our findings may have far-reaching implications to understanding complex electrochemical phenomena entailing ionic fluids under dielectric confinements.« less

Triboelectric, Corona, and Induction Charging of Insulators as a Function of Pressure

NASA Technical Reports Server (NTRS)

Hogue, Michael D.; Mucciolo, Eduardo R.; Calle, Carlos I.

2006-01-01

Theoretical and experimental research has been performed that shows that the surface charge on an insulator after triboelectric charging with another insulator is rapidly dissipated with lowered atmospheric pressure. This pressure discharge is consistent with surface ions being evaporated off the surface once their vapor pressure is attained. In this paper we will report on the results of three different charging techniques (triboelectric, corona, and induction) performed on selected polymers with varying atmospheric pressure. This data will show that ion exchange between the polymer samples is the mechanism responsible for most of the surface charge on the polymer surfaces.

Impact of thermal annealing on wettability and antifouling characteristics of alginate poly-l-lysine polyelectrolyte multilayer films.

PubMed

Diamanti, Eleftheria; Muzzio, Nicolas; Gregurec, Danijela; Irigoyen, Joseba; Pasquale, Miguel; Azzaroni, Omar; Brinkmann, Martin; Moya, Sergio Enrique

2016-09-01

Polyelectrolyte multilayers (PEMs) of poly-l-lysine (PLL) and alginic acid sodium salt (Alg) are fabricated applying the layer by layer technique and annealed at a constant temperature; 37, 50 and 80°C, for 72h. Atomic force microscopy reveals changes in the topography of the PEM, which is changing from a fibrillar to a smooth surface. Advancing contact angle in water varies from 36° before annealing to 93°, 77° and 95° after annealing at 37, 50 and 80°C, respectively. Surface energy changes after annealing were calculated from contact angle measurements performed with organic solvents. Quartz crystal microbalance with dissipation, contact angle and fluorescence spectroscopy measurements show a significant decrease in the adsorption of the bovine serum albumin protein to the PEMs after annealing. Changes in the physical properties of the PEMs are interpreted as a result of the reorganization of the polyelectrolytes in the PEMs from a layered structure into complexes where the interaction of polycations and polyanions is enhanced. This work proposes a simple method to endow bio-PEMs with antifouling characteristics and tune their wettability. Copyright © 2016 Elsevier B.V. All rights reserved.

Modulating the fixed charge density in silicon nitride films while monitoring the surface recombination velocity by photoluminescence imaging

NASA Astrophysics Data System (ADS)

Bazilchuk, Molly; Haug, Halvard; Marstein, Erik Stensrud

2015-04-01

Several important semiconductor devices such as solar cells and photodetectors may be fabricated based on surface inversion layer junctions induced by fixed charge in a dielectric layer. Inversion layer junctions can easily be fabricated by depositing layers with a high density of fixed charge on a semiconducting substrate. Increasing the fixed charge improves such devices; for instance, the efficiency of a solar cell can be substantially increased by reducing the surface recombination velocity, which is a function of the fixed charge density. Methods for increasing the charge density are therefore of interest. In this work, the fixed charge density in silicon nitride layers deposited by plasma enhanced chemical vapor deposition is increased to very high values above 1 × 1013 cm-2 after the application of an external voltage to a gate electrode. The effect of the fixed charge density on the surface recombination velocity was experimentally observed using the combination of capacitance-voltage characterization and photoluminescence imaging, showing a significant reduction in the surface recombination velocity for increasing charge density. The surface recombination velocity vs. charge density data was analyzed using a numerical device model, which indicated the presence of a sub-surface damage region formed during deposition of the layers. Finally, we have demonstrated that the aluminum electrodes used for charge injection may be chemically removed in phosphoric acid without loss of the underlying charge. The injected charge was shown to be stable for a prolonged time period, leading us to propose charge injection in silicon nitride films by application of soaking voltage as a viable method for fabricating inversion layer devices.

The development of non-toxic ionic-crosslinked chitosan-based microspheres as carriers for the controlled release of silk sericin.

PubMed

Aramwit, Pornanong; Ekasit, Sanong; Yamdech, Rungnapha

2015-10-01

Silk sericin is recently shown to possess various biological activities for biomedical applications. While various sericin carriers were developed for drug delivery system, very few researches considered sericin as a bioactive molecule itself. In this study, sericin incorporated in the chitosan-based microspheres was introduced as a bioactive molecule and bioactive carrier at the same time. The chitosan/sericin (CH/SS) microspheres at different composition (80/20, 70/30, 60/40, and 50/50) were successfully fabricated using anhydroustri-polyphosphate (TPP) as a polyanionic crosslinker. The microspheres with an average size of 1-4 μm and narrow size distribution were obtained. From FT-IR spectra, the presence of both chitosan and sericin in the microspheres confirmed the occurrence of ionic interaction that crosslink them within the microspheres. We also found that the CH/SS microspheres prepared at 50/50 could encapsulate sericin at the highest percentage (37.28%) and release sericin in the most sustained behavior, possibly due to the strong ionic interaction of the positively charged chitosan and the negatively charged sericin. On the other hand, the composition of CH/SS had no effect on the degradation rate of microspheres. All microspheres continuously degraded and remained around 20% after 14 days of enzymatic degradation. This explained that the ionic crosslinkings between chitosan and sericin could be demolished by the enzyme and hydrolysis. Furthermore, we have verified that all CH/SS microspheres at any concentrations showed non-toxicity to L929 mouse fibroblast cells. Therefore, we suggested that the non-toxic ionic-crosslinked CH/SS microspheres could be incorporated in wound dressing material to achieve the sustained release of sericin for accelerated wound healing.

Effect of Divalent Cation Removal on the Structure of Gram-Negative Bacterial Outer Membrane Models

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clifton, Luke A.; Skoda, Maximilian W. A.; Le Brun, Anton P.

The Gram-negative bacterial outer membrane (GNB-OM) is asymmetric in its lipid composition with a phospholipid-rich inner leaflet and an outer leaflet predominantly composed of lipopolysaccharides (LPS). LPS are polyanionic molecules, with numerous phosphate groups present in the lipid A and core oligosaccharide regions. The repulsive forces due to accumulation of the negative charges are screened and bridged by the divalent cations (Mg 2+ and Ca 2+) that are known to be crucial for the integrity of the bacterial OM. Indeed, chelation of divalent cations is a well-established method to permeabilize Gram-negative bacteria such as Escherichia coli. Here, we use X-raymore » and neutron reflectivity (XRR and NR, respectively) techniques to examine the role of calcium ions in the stability of a model GNB-OM. Using XRR we show that Ca 2+ binds to the core region of the rough mutant LPS (RaLPS) films, producing more ordered structures in comparison to divalent cation free monolayers. Using recently developed solid-supported models of the GNB-OM, we study the effect of calcium removal on the asymmetry of DPPC:RaLPS bilayers. We show that without the charge screening effect of divalent cations, the LPS is forced to overcome the thermodynamically unfavorable energy barrier and flip across the hydrophobic bilayer to minimize the repulsive electrostatic forces, resulting in about 20% mixing of LPS and DPPC between the inner and outer bilayer leaflets. These results reveal for the first time the molecular details behind the well-known mechanism of outer membrane stabilization by divalent cations. This confirms the relevance of the asymmetric models for future studies of outer membrane stability and antibiotic penetration.« less

Synthetic and Biopolymer Gels - Similarities and Difference.

NASA Astrophysics Data System (ADS)

Horkay, Ferenc

2006-03-01

Ion exchange plays a central role in a variety of physiological processes, such as nerve excitation, muscle contraction and cell locomotion. Hydrogels can be used as model systems for identifying fundamental chemical and physical interactions that govern structure formation, phase transition, etc. in biopolymer systems. Polyelectrolyte gels are particularly well-suited to study ion-polymer interactions because their structure and physical-chemical properties (charge density, crosslink density, etc) can be carefully controlled. They are sensitive to different external stimuli such as temperature, ionic composition and pH. Surprisingly few investigations have been made on polyelectrolyte gels in salt solutions containing both monovalent and multivalent cations. We have developed an experimental approach that combines small angle neutron scattering and osmotic swelling pressure measurements. The osmotic pressure exerted on a macroscopic scale is a consequence of changes occurring at a molecular level. The intensity of the neutron scattering signal, which provides structural information as a function of spatial resolution, is directly related to the osmotic pressure. We have found a striking similarity in the scattering and osmotic behavior of polyacrylic acid gels and DNA gels swollen in nearly physiological salt solutions. Addition of calcium ions to both systems causes a sudden volume change. This volume transition, which occurs when the majority of the sodium counterions are replaced by calcium ions, is reversible. Such reversibility implies that the calcium ions are not strongly bound by the polyanion, but are free to move along the polymer chain, which allows these ions to form temporary bridges between negative charges on adjacent chains. Mechanical measurements reveal that the elastic modulus is practically unchanged in the calcium-containing gels, i.e., ion bridging is qualitatively different from covalent crosslinks.

Effect of Divalent Cation Removal on the Structure of Gram-Negative Bacterial Outer Membrane Models

DOE PAGES

Clifton, Luke A.; Skoda, Maximilian W. A.; Le Brun, Anton P.; ...

2014-12-09

The Gram-negative bacterial outer membrane (GNB-OM) is asymmetric in its lipid composition with a phospholipid-rich inner leaflet and an outer leaflet predominantly composed of lipopolysaccharides (LPS). LPS are polyanionic molecules, with numerous phosphate groups present in the lipid A and core oligosaccharide regions. The repulsive forces due to accumulation of the negative charges are screened and bridged by the divalent cations (Mg 2+ and Ca 2+) that are known to be crucial for the integrity of the bacterial OM. Indeed, chelation of divalent cations is a well-established method to permeabilize Gram-negative bacteria such as Escherichia coli. Here, we use X-raymore » and neutron reflectivity (XRR and NR, respectively) techniques to examine the role of calcium ions in the stability of a model GNB-OM. Using XRR we show that Ca 2+ binds to the core region of the rough mutant LPS (RaLPS) films, producing more ordered structures in comparison to divalent cation free monolayers. Using recently developed solid-supported models of the GNB-OM, we study the effect of calcium removal on the asymmetry of DPPC:RaLPS bilayers. We show that without the charge screening effect of divalent cations, the LPS is forced to overcome the thermodynamically unfavorable energy barrier and flip across the hydrophobic bilayer to minimize the repulsive electrostatic forces, resulting in about 20% mixing of LPS and DPPC between the inner and outer bilayer leaflets. These results reveal for the first time the molecular details behind the well-known mechanism of outer membrane stabilization by divalent cations. This confirms the relevance of the asymmetric models for future studies of outer membrane stability and antibiotic penetration.« less

Effect of Divalent Cation Removal on the Structure of Gram-Negative Bacterial Outer Membrane Models

PubMed Central

2014-01-01

The Gram-negative bacterial outer membrane (GNB-OM) is asymmetric in its lipid composition with a phospholipid-rich inner leaflet and an outer leaflet predominantly composed of lipopolysaccharides (LPS). LPS are polyanionic molecules, with numerous phosphate groups present in the lipid A and core oligosaccharide regions. The repulsive forces due to accumulation of the negative charges are screened and bridged by the divalent cations (Mg2+ and Ca2+) that are known to be crucial for the integrity of the bacterial OM. Indeed, chelation of divalent cations is a well-established method to permeabilize Gram-negative bacteria such as Escherichia coli. Here, we use X-ray and neutron reflectivity (XRR and NR, respectively) techniques to examine the role of calcium ions in the stability of a model GNB-OM. Using XRR we show that Ca2+ binds to the core region of the rough mutant LPS (RaLPS) films, producing more ordered structures in comparison to divalent cation free monolayers. Using recently developed solid-supported models of the GNB-OM, we study the effect of calcium removal on the asymmetry of DPPC:RaLPS bilayers. We show that without the charge screening effect of divalent cations, the LPS is forced to overcome the thermodynamically unfavorable energy barrier and flip across the hydrophobic bilayer to minimize the repulsive electrostatic forces, resulting in about 20% mixing of LPS and DPPC between the inner and outer bilayer leaflets. These results reveal for the first time the molecular details behind the well-known mechanism of outer membrane stabilization by divalent cations. This confirms the relevance of the asymmetric models for future studies of outer membrane stability and antibiotic penetration. PMID:25489959

Electric Double-Layer Interaction between Dissimilar Charge-Conserved Conducting Plates.

PubMed

Chan, Derek Y C

2015-09-15

Small metallic particles used in forming nanostructured to impart novel optical, catalytic, or tribo-rheological can be modeled as conducting particles with equipotential surfaces that carry a net surface charge. The value of the surface potential will vary with the separation between interacting particles, and in the absence of charge-transfer or electrochemical reactions across the particle surface, the total charge of each particle must also remain constant. These two physical conditions require the electrostatic boundary condition for metallic nanoparticles to satisfy an equipotential whole-of-particle charge conservation constraint that has not been studied previously. This constraint gives rise to a global charge conserved constant potential boundary condition that results in multibody effects in the electric double-layer interaction that are either absent or are very small in the familiar constant potential or constant charge or surface electrochemical equilibrium condition.

Bacterial attachment to RO membranes surface-modified by concentration-polarization-enhanced graft polymerization.

PubMed

Bernstein, Roy; Belfer, Sofia; Freger, Viatcheslav

2011-07-15

Concentration polarization-enhanced radical graft polymerization, a facile surface modification technique, was examined as an approach to reduce bacterial deposition onto RO membranes and thus contribute to mitigation of biofouling. For this purpose an RO membrane ESPA-1 was surface-grafted with a zwitterionic and negatively and positively charged monomers. The low monomer concentrations and low degrees of grafting employed in modifications moderately reduced flux (by 20-40%) and did not affect salt rejection, yet produced substantial changes in surface chemistry, charge and hydrophilicity. The propensity to bacterial attachment of original and modified membranes was assessed using bacterial deposition tests carried out in a parallel plate flow setup using a fluorescent strain of Pseudomonas fluorescens. Compared to unmodified ESPA-1 the deposition (mass transfer) coefficient was significantly increased for modification with the positively charged monomer. On the other hand, a substantial reduction in bacterial deposition rates was observed for membranes modified with zwitterionic monomer and, still more, with very hydrophilic negatively charged monomers. This trend is well explained by the effects of surface charge (as measured by ζ-potential) and hydrophilicity (contact angle). It also well correlated with force distance measurements by AFM using surrogate spherical probes with a negative surface charge mimicking the bacterial surface. The positively charged surface showed a strong hysteresis with a large adhesion force, which was weaker for unmodified ESPA-1 and still weaker for zwitterionic surface, while negatively charged surface showed a long-range repulsion and negligible hysteresis. These results demonstrate the potential of using the proposed surface- modification approach for varying surface characteristics, charge and hydrophilicity, and thus minimizing bacterial deposition and potentially reducing propensity biofouling.

Charging of moving surfaces by corona discharges sustained in air

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Jun-Chieh, E-mail: junchwan@umich.edu; Kushner, Mark J., E-mail: mjkush@umich.edu; Zhang, Daihua, E-mail: dhzhang@tju.edu.cn

Atmospheric pressure corona discharges are used in electrophotographic (EP) printing technologies for charging imaging surfaces such as photoconductors. A typical corona discharge consists of a wire (or wire array) biased with a few hundred volts of dc plus a few kV of ac voltage. An electric discharge is produced around the corona wire from which electrons drift towards and charge the underlying dielectric surface. The surface charging reduces the voltage drop across the gap between the corona wire and the dielectric surface, which then terminates the discharge, as in a dielectric barrier discharge. In printing applications, this underlying surface ismore » continuously moving throughout the charging process. For example, previously charged surfaces, which had reduced the local electric field and terminated the local discharge, are translated out of the field of view and are replaced with uncharged surface. The uncharged surface produces a rebound in the electric field in the vicinity of the corona wire which in turn results in re-ignition of the discharge. The discharge, so reignited, is then asymmetric. We found that in the idealized corona charging system we investigated, a negatively dc biased corona blade with a dielectric covered ground electrode, the discharge is initially sustained by electron impact ionization from the bulk plasma and then dominated by ionization from sheath accelerated secondary electrons. Depending on the speed of the underlying surface, the periodic re-ignition of the discharge can produce an oscillatory charging pattern on the moving surface.« less

Adsorption of insulin peptide on charged single-walled carbon nanotubes: significant role of ordered water molecules.

PubMed

Shen, Jia-Wei; Wu, Tao; Wang, Qi; Kang, Yu; Chen, Xin

2009-06-02

Ordered hydration shells: The more ordered hydration shells outside the charged CNT surfaces prevent more compact adsorption of the peptide in the charged CNT systems [picture: see text], but peptide binding strengths on the charged CNT surfaces are stronger due to the electrostatic interaction.Studies of adsorption dynamics and stability for peptides/proteins on single-walled carbon nanotubes (SWNTs) are of great importance for a better understanding of the properties and nature of nanotube-based biosystems. Herein, the dynamics and mechanism of the adsorption of the insulin chain B peptide on different charged SWNTs are investigated by explicit solvent molecular dynamics simulations. The results show that all types of surfaces effectively attract the model peptide. Water molecules play a significant role in peptide adsorption on the surfaces of charged carbon nanotubes (CNTs). Compared to peptide adsorption on neutral CNT surfaces, the more ordered hydration shells outside the tube prevent more compact adsorption of the peptide in charged CNT systems. This shield effect leads to a smaller conformational change and van der Waals interaction between the peptide and surfaces, but peptide binding strengths on charged CNT surfaces are stronger than those on the neutral CNT surface due to the strong electrostatic interaction. The result of these simulations implies the possibility of improving the binding strength of peptides/proteins on CNT surfaces, as well as keeping the integrity of the peptide/protein conformation in peptide/protein-CNT complexes by charging the CNTs.

Effect of surface charge density on the affinity of oxide nanoparticles for the vapor-water interface.

PubMed

Brown, Matthew A; Duyckaerts, Nicolas; Redondo, Amaia Beloqui; Jordan, Inga; Nolting, Frithjof; Kleibert, Armin; Ammann, Markus; Wörner, Hans Jakob; van Bokhoven, Jeroen A; Abbas, Zareen

2013-04-23

Using in-situ X-ray photoelectron spectroscopy at the vapor-water interface, the affinity of nanometer-sized silica colloids to adsorb at the interface is shown to depend on colloid surface charge density. In aqueous suspensions at pH 10 corrected Debye-Hückel theory for surface complexation calculations predict that smaller silica colloids have increased negative surface charge density that originates from enhanced screening of deprotonated silanol groups (≡Si-O(-)) by counterions in the condensed ion layer. The increased negative surface charge density results in an electrostatic repulsion from the vapor-water interface that is seen to a lesser extent for larger particles that have a reduced charge density in the XPS measurements. We compare the results and interpretation of the in-situ XPS and corrected Debye-Hückel theory for surface complexation calculations with traditional surface tension measurements. Our results show that controlling the surface charge density of colloid particles can regulate their adsorption to the interface between two dielectrics.

The effect of surface charge, negative and bipolar ionization on the deposition of airborne bacteria.

PubMed

Meschke, S; Smith, B D; Yost, M; Miksch, R R; Gefter, P; Gehlke, S; Halpin, H A

2009-04-01

A series of experiments were conducted to evaluate the effect of surface charge and air ionization on the deposition of airborne bacteria. The interaction between surface electrostatic potential and the deposition of airborne bacteria in an indoor environment was investigated using settle plates charged with electric potentials of 0, +/-2.5kV and +/-5kV. Results showed that bacterial deposition on the plates increased proportionally with increased potential to over twice the gravitational sedimentation rate at +5kV. Experiments were repeated under similar conditions in the presence of either negative or bipolar air ionization. Bipolar air ionization resulted in reduction of bacterial deposition onto the charged surfaces to levels nearly equal to gravitational sedimentation. In contrast, diffusion charging appears to have occurred during negative air ionization, resulting in an even greater deposition onto the oppositely charged surface than observed without ionization. Static charges on fomitic surfaces may attract bacteria resulting in deposition in excess of that expected by gravitational sedimentation or simple diffusion. Implementation of bipolar ionization may result in reduction of bacterial deposition. Fomitic surfaces are important vehicles for the transmission of infectious organisms. This study has demonstrated a simple strategy for minimizing charge related deposition of bacteria on surfaces.

The role of electrostatic charge in the adhesion of spherical particles onto planar surfaces in atmospheric systems

DOE PAGES

Kweon, Hyojin; Yiacoumi, Sotira Z.; Tsouris, Costas

2015-06-19

In this study, the influence of electrostatic charge on the adhesive force between spherical particles and planar surfaces in atmospheric systems was studied using atomic force microscopy. Electrical bias was applied to modify the surface charge, and it was found that application of a stronger positive bias to a particle induces a stronger total adhesive force. The sensitivity of the system to changes in the bias depended on the surface charge density. For larger-size particles, the contribution of the electrostatic force decreased, and the capillary force became the major contributor to the total adhesive force. The influence of water adsorptionmore » on the total adhesive force and, specifically, on the contribution of the electrostatic force depended on the hydrophobicity of interacting surfaces. For a hydrophilic surface, water adsorption either attenuated the surface charge or screened the effect of surface potential. An excessive amount of adsorbed water provided a path to surface charge leakage, which might cancel out the electrostatic force, leading to a reduction in the adhesive force. Theoretically calculated forces were comparable with measured adhesive forces except for mica which has a highly localized surface potential. The results of this study provide information on the behavior of charged colloidal particles in atmospheric systems.« less

Altering surface charge nonuniformity on individual colloidal particles.

PubMed

Feick, Jason D; Chukwumah, Nkiru; Noel, Alexandra E; Velegol, Darrell

2004-04-13

Charge nonuniformity (sigmazeta) was altered on individual polystyrene latex particles and measured using the novel experimental technique of rotational electrophoresis. It has recently been shown that unaltered sulfated latices often have significant charge nonuniformity (sigmazeta = 100 mV) on individual particles. Here it is shown that anionic polyelectrolytes and surfactants reduce the native charge nonuniformity on negatively charged particles by 80% (sigmazeta = 20 mV), even while leaving the average surface charge density almost unchanged. Reduction of charge uniformity occurs as large domains of nonuniformity are minimized, giving a more random distribution of charge on individual particle surfaces. Targeted reduction of charge nonuniformity opens new opportunities for the dispersion of nanoparticles and the oriented assembly of particles.

Mechanism of the free charge carrier generation in the dielectric breakdown

NASA Astrophysics Data System (ADS)

Rahim, N. A. A.; Ranom, R.; Zainuddin, H.

2017-12-01

Many studies have been conducted to investigate the effect of environmental, mechanical and electrical stresses on insulator. However, studies on physical process of discharge phenomenon, leading to the breakdown of the insulator surface are lacking and difficult to comprehend. Therefore, this paper analysed charge carrier generation mechanism that can cause free charge carrier generation, leading toward surface discharge development. Besides, this paper developed a model of surface discharge based on the charge generation mechanism on the outdoor insulator. Nernst’s Planck theory was used in order to model the behaviour of the charge carriers while Poisson’s equation was used to determine the distribution of electric field on insulator surface. In the modelling of surface discharge on the outdoor insulator, electric field dependent molecular ionization was used as the charge generation mechanism. A mathematical model of the surface discharge was solved using method of line technique (MOL). The result from the mathematical model showed that the behaviour of net space charge density was correlated with the electric field distribution.

Collisional charging of individual submillimeter particles: Using ultrasonic levitation to initiate and track charge transfer

NASA Astrophysics Data System (ADS)

Lee, Victor; James, Nicole M.; Waitukaitis, Scott R.; Jaeger, Heinrich M.

2018-03-01

Electrostatic charging of insulating fine particles can be responsible for numerous phenomena ranging from lightning in volcanic plumes to dust explosions. However, even basic aspects of how fine particles become charged are still unclear. Studying particle charging is challenging because it usually involves the complexities associated with many-particle collisions. To address these issues, we introduce a method based on acoustic levitation, which makes it possible to initiate sequences of repeated collisions of a single submillimeter particle with a flat plate, and to precisely measure the particle charge in situ after each collision. We show that collisional charge transfer between insulators is dependent on the hydrophobicity of the contacting surfaces. We use glass, which we modify by attaching nonpolar molecules to the particle, the plate, or both. We find that hydrophilic surfaces develop significant positive charges after contacting hydrophobic surfaces. Moreover, we demonstrate that charging between a hydrophilic and a hydrophobic surface is suppressed in an acidic environment and enhanced in a basic one. Application of an electric field during each collision is found to modify the charge transfer, again depending on surface hydrophobicity. We discuss these results within the context of contact charging due to ion transfer, and we show that they lend strong support to O H- ions as the charge carriers.

Manual and Flow-Injection Detection/Quantification of Polyquaterniums via Fully Reversible Polyion-Sensitive Polymeric Membrane-Based Ion-Selective Electrodes.

PubMed

Ferguson, Stephen A; Meyerhoff, Mark E

2017-10-27

The detection of four different polyquaterniums (PQs) using a fully reversible potentiometric polyion sensor in three different detection modes is described. The polyion sensing "pulstrodes" serve as the detector for direct dose-response experiments, beaker titrations, and in a flow-injection analysis (FIA) system. Direct polycation response toward PQ-2, PQ-6, PQ-10, and poly(2-methacryloxyethyltrimethylammonium) chloride (PMETAC) yields characteristic information about each PQ species (e.g., relative charge densities, etc.) via syringe pump addition of each PQ species to a background electrolyte solution. Quantitative titrations are performed using a syringe pump to deliver heparin as the polyanion titrant to quantify all four PQs at μg/mL levels. Both the direct and indirect methods incorporate the use of a three-electrode system including counter, double junction reference, and working electrodes. The working electrode possesses a plasticized poly(vinyl chloride) (PVC) membrane containing the neutral lipophilic salt of dinonylnaphthalenesulfonate (DNNS - ) tridodecylmethylammonium (TDMA + ). Further, the titration method is shown to be useful to quantify PQ-6 levels in recreational swimming pool water collected in Ann Arbor, MI. Finally, a FIA system equipped with a pulstrode detector is used to demonstrate the ability to potentially quantify PQ levels via a more streamlined and semiautomated testing platform.

A Combined Model of Charging of the Surface and Bulk of a Dielectric Target by Electrons with the Energies 10-30 keV

NASA Astrophysics Data System (ADS)

Zykov, V. M.; Neiman, D. A.

2018-04-01

A physico-mathematical model of the processes of radiation-induced charging of dielectric materials with open surfaces, irradiated with monoenergetic electrons in the energy range 10-30 keV, is described. The model takes into account the relationship between the processes of surface and bulk charging for the given conditions of the experimental design, which accounts for the effect of anomalously long charging of dielectrics after the incident energy of primary electrons during charging is reduced to below the second critical energy for the secondary electronic emission coefficient. The initial fast phase of charging a high-resistivity dielectric material (Al2O3) is investigated. It is shown that as the incident electron energy is approaching the second critical energy during charging, the secondary electronic emission is partially suppressed due to negative charging of the open surface of the dielectric and formation of a near-surface inversion electrical field retarding the electronic emission yield.

Ion association at discretely-charged dielectric interfaces: Giant charge inversion

NASA Astrophysics Data System (ADS)

Wang, Zhi-Yong; Wu, Jianzhong

2017-07-01

Giant charge reversal has been identified for the first time by Monte Carlo simulation for a discretely charged surface in contact with a trivalent electrolyte solution. It takes place regardless of the surface charge density under study and the monovalent salt. In stark contrast to earlier predictions based on the 2-dimensional Wigner crystal model to describe strong correlation of counterions at the macroion surface, we find that giant charge reversal reflects an intricate interplay of ionic volume effects, electrostatic correlations, surface charge heterogeneity, and the dielectric response of the confined fluids. While the novel phenomenon is yet to be confirmed with experiment, the simulation results appear in excellent agreement with a wide range of existing observations in the subregime of charge inversion. Our findings may have far-reaching implications to understanding complex electrochemical phenomena entailing ionic fluids under dielectric confinements.

VARIABLE CHARGE SOILS: MINERALOGY AND CHEMISTRY

DOE Office of Scientific and Technical Information (OSTI.GOV)

Van Ranst, Eric; Qafoku, Nikolla; Noble, Andrew

2016-09-19

Soils rich in particles with amphoteric surface properties in the Oxisols, Ultisols, Alfisols, Spodosols and Andisols orders (1) are considered to be variable charge soils (2) (Table 1). The term “variable charge” is used to describe organic and inorganic soil constituents with reactive surface groups whose charge varies with pH and ionic concentration and composition of the soil solution. Such groups are the surface carboxyl, phenolic and amino functional groups of organic materials in soils, and surface hydroxyl groups of Fe and Al oxides, allophane and imogolite. The hydroxyl surface groups are also present on edges of some phyllosilicate mineralsmore » such as kaolinite, mica, and hydroxyl-interlayered vermiculite. The variable charge is developed on the surface groups as a result of adsorption or desorption of ions that are constituents of the solid phase, i.e., H+, and the adsorption or desorption of solid-unlike ions that are not constituents of the solid phase. Highly weathered soils and subsoils (e.g., Oxisols and some Ultisols, Alfisols and Andisols) may undergo isoelectric weathering and reach a “zero net charge” stage during their development. They usually have a slightly acidic to acidic soil solution pH, which is close to either the point of zero net charge (PZNC) (3) or the point of zero salt effect (PZSE) (3). They are characterized by high abundances of minerals with a point of zero net proton charge (PZNPC) (3) at neutral and slightly basic pHs; the most important being Fe and Al oxides and allophane. Under acidic conditions, the surfaces of these minerals are net positively charged. In contrast, the surfaces of permanent charge phyllosilicates are negatively charged regardless of ambient conditions. Variable charge soils therefore, are heterogeneous charge systems.« less

Water organization between oppositely charged surfaces: Implications for protein sliding along DNA a)

NASA Astrophysics Data System (ADS)

Marcovitz, Amir; Naftaly, Aviv; Levy, Yaakov

2015-02-01

Water molecules are abundant in protein-DNA interfaces, especially in their nonspecific complexes. In this study, we investigated the organization and energetics of the interfacial water by simplifying the geometries of the proteins and the DNA to represent them as two equally and oppositely charged planar surfaces immersed in water. We found that the potential of mean force for bringing the two parallel surfaces into close proximity comprises energetic barriers whose properties strongly depend on the charge density of the surfaces. We demonstrated how the organization of the water molecules into discretized layers and the corresponding energetic barriers to dehydration can be modulated by the charge density on the surfaces, salt, and the structure of the surfaces. The 1-2 layers of ordered water are tightly bound to the charged surfaces representing the nonspecific protein-DNA complex. This suggests that water might mediate one-dimensional diffusion of proteins along DNA (sliding) by screening attractive electrostatic interactions between the positively charged molecular surface on the protein and the negatively charged DNA backbone and, in doing so, reduce intermolecular friction in a manner that smoothens the energetic landscape for sliding, and facilitates the 1D diffusion of the protein.

Characterizing the effects of regolith surface roughness on photoemission from surfaces in space

NASA Astrophysics Data System (ADS)

Dove, A.; Horanyi, M.; Wang, X.

2017-12-01

Surfaces of airless bodies and spacecraft in space are exposed to a variety of charging environments. A balance of currents due to plasma bombardment, photoemission, electron and ion emission and collection, and secondary electron emission determines the surface's charge. Photoelectron emission is the dominant charging process on sunlit surfaces in the inner solar system due to the intense solar UV radiation. This can result in a net positive surface potential, with a cloud of photoelectrons immediately above the surface, called the photoelectron sheath. Conversely, the unlit side of the body will charge negatively due the collection of the fast-moving solar wind electrons. The interaction of charged dust grains with these positively and negatively charged surfaces, and within the photoelectron and plasma sheaths may explain the occurrence of dust lofting, levitation and transport above the lunar surface. The surface potential of exposed objects is also dependent on the material properties of their surfaces. Composition and particle size primarily affect the quantum efficiency of photoelectron generation; however, surface roughness can also control the charging process. In order to characterize these effects, we have conducted laboratory experiments to examine the role of surface roughness in generating photoelectrons in dedicated laboratory experiments using solid and dusty surfaces of the same composition (CeO2), and initial comparisons with JSC-1 lunar simulant. Using Langmuir probe measurements, we explore the measured potentials above insulating surfaces exposed to UV and an electric field, and we show that the photoemission current from a dusty surface is largely reduced due to its higher surface roughness, which causes a significant fraction of the emitted photoelectrons to be re-absorbed within the surface. We will discuss these results in context of similar situations on planetary surfaces.

Space and surface charge behavior analysis of charge-eliminated polymer films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oda, Tetsuji; Takashima, Kazunori; Ichiyama, Shinichiro

1995-12-31

Charge behavior of corona-charged or charge eliminated polymer films being dipped in the city water were studied. They were polytetrafluoroethylene (PTFE teflon{trademark}), polypropylene (PP), low density or high density polyethylene (LDPE or HDPE) thin films which are as grown (native) or plasma-processed. The plasma processing at low pressure was tested as antistatic processing. Charge elimination was done by being dipped in alcohol or city water. TSDC analysis and surface charge profile measurement were done for both charged and charge eliminated polymer films. Surface charge density of plasma processed polymer films just after corona charging is roughly the same as thatmore » of an original film. There is little difference between surface charge density profile of a native film and that of a plasma processed film. A large hetero current peak of TSDC was observed at room temperature for a processed film. It was found that the hetero peak disappears after charge elimination process. A pressure pulse wave method by using a pulse-driven piezoelectric PVDF polymer film as a piezoelectric actuator was newly developed to observe real space charge distribution. A little difference of internal space charge distribution between the plasma processed film and the native one after corona charging is found.« less

Ordered adsorption of coagulation factor XII on negatively charged polymer surfaces probed by sum frequency generation vibrational spectroscopy.

PubMed

Chen, Xiaoyun; Wang, Jie; Paszti, Zoltan; Wang, Fulin; Schrauben, Joel N; Tarabara, Volodymyr V; Schmaier, Alvin H; Chen, Zhan

2007-05-01

Electrostatic interactions between negatively charged polymer surfaces and factor XII (FXII), a blood coagulation factor, were investigated by sum frequency generation (SFG) vibrational spectroscopy, supplemented by several analytical techniques including attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), quartz crystal microbalance (QCM), zeta-potential measurement, and chromogenic assay. A series of sulfonated polystyrenes (sPS) with different sulfonation levels were synthesized as model surfaces with different surface charge densities. SFG spectra collected from FXII adsorbed onto PS and sPS surfaces with different surface charge densities showed remarkable differences in spectral features and especially in spectral intensity. Chromogenic assay experiments showed that highly charged sPS surfaces induced FXII autoactivation. ATR-FTIR and QCM results indicated that adsorption amounts on the PS and sPS surfaces were similar even though the surface charge densities were different. No significant conformational change was observed from FXII adsorbed onto surfaces studied. Using theoretical calculations, the possible contribution from the third-order nonlinear optical effect induced by the surface electric field was evaluated, and it was found to be unable to yield the SFG signal enhancement observed. Therefore it was concluded that the adsorbed FXII orientation and ordering were the main reasons for the remarkable SFG amide I signal increase on sPS surfaces. These investigations indicate that negatively charged surfaces facilitate or induce FXII autoactivation on the molecular level by imposing specific orientation and ordering on the adsorbed protein molecules.

Experimental and Theoretical Investigations of Glass Surface Charging Phenomena

NASA Astrophysics Data System (ADS)

Agnello, Gabriel

Charging behavior of multi-component display-type (i.e. low alkali) glass surfaces has been studied using a combination of experimental and theoretical methods. Data obtained by way of a Rolling Sphere Test (RST), streaming/zeta potential and surface energy measurements from commercially available display glass surfaces (Corning EAGLE XGRTM and Lotus(TM) XT) suggest that charge accumulation is highly dependent on surface treatment (chemical and/or physical modification) and measurement environment, presumably through reactionary mechanisms at the surface with atmospheric moisture. It has been hypothesized that water dissociation, along with the corresponding hydroxylation of the glass surface, are important processes related to charging in glass-metal contact systems. Classical Molecular Dynamics (MD) simulations, in conjunction with various laboratory based measurements (RST, a newly developed ElectroStatic Gauge (ESG) and Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS)) on simpler Calcium AluminoSilicate (CAS) glass surfaces were used to further explore these phenomena. Analysis of simulated high-silica content (≥50%) (CAS) glass structures suggest that controlled variation of bulk chemistry can directly affect surface defect concentrations, such as non-bridging oxygen (NBO), which can be suitable high-energy sites for hydrolysis-type reactions to occur. Calculated NBO surface concentrations correlate well with charge based measurements on laboratory fabricated CAS surfaces. The data suggest that a directional/polar shift in contact-charge transfer occurs at low silica content (≤50%) where the highest concentrations of NBOs are observed. Surface charging sensitivity with respect to NBO concentration decreases as the relative humidity of the measurement environment increases; which should be expected as the highly reactive sites are progressively covered by liquid water layers. DRIFTS analysis of CAS powders expand on this analysis showing a gradual increase in molecular water absorption at the surface in samples containing ≥60% silica, and an abrupt decrease in those with ≤60% silica. This behavior is very likely related to the aforementioned charge polarity shift (negative (-) to positive (+)) in low silica containing glasses, leading to the conclusion that structural defect mediated charge accumulation and/or transfer are likely to be important mechanisms related to the contact charging of glass surfaces.

Direct measurement of sub-Debye-length attraction between oppositely charged surfaces.

PubMed

Kampf, Nir; Ben-Yaakov, Dan; Andelman, David; Safran, S A; Klein, Jacob

2009-09-11

Using a surface force balance with fast video analysis, we have measured directly the attractive forces between oppositely charged solid surfaces (charge densities sigma(+), sigma(-)) across water over the entire range of interaction, in particular, at surface separations D below the Debye screening length lambda(S). At very low salt concentration we find a long-ranged attraction between the surfaces (onset ca. 100 nm), whose variation at D

Mesoporous LiFeBO3/C hollow spheres for improved stability lithium-ion battery cathodes

NASA Astrophysics Data System (ADS)

Chen, Zhongxue; Cao, Liufei; Chen, Liang; Zhou, Haihui; Zheng, Chunman; Xie, Kai; Kuang, Yafei

2015-12-01

Polyanionic compounds are regarded as one of the most promising cathode materials for the next generation lithium-ion batteries due to their abundant resource and thermal stability. LiFeBO3 has a relatively higher capacity than olivine LiFePO4, however, moisture sensitivity and low conductivity hinder its further development. Here, we design and synthesize mesoporous LiFeBO3/C (LFB/C) hollow spheres to enhance its structural stability and electric conductivity, two LiFeBO3/C electrodes with different carbon content are prepared and tested. The experimental results show that mesoporous LiFeBO3/C hollow spheres with higher carbon content exhibit superior lithium storage capacity, cycling stability and rate capability. Particularly, the LFB/C electrode with higher carbon content demonstrates good structural stability, which can maintain its original crystal structure and Li storage properties even after three months of air exposure at room temperature. The exceptional structural stability and electrochemical performance may justify their potential use as high-performance cathode materials for advanced lithium-ion batteries. In addition, the synthesis strategy demonstrated herein is simple and versatile for the fabrication of other polyanionic cathode materials with mesoporous hollow spherical structure.

Fabrication and properties of light-emitting diodes based on self-assembled multilayers of poly(phenylene vinylene)

NASA Astrophysics Data System (ADS)

Fou, A. C.; Onitsuka, O.; Ferreira, M.; Rubner, M. F.; Hsieh, B. R.

1996-05-01

Light-emitting diodes have been fabricated from self-assembled multilayers of poly(p-phenylene vinylene) (PPV) and two different polyanions; polystyrene sulfonic acid (SPS) and polymethacrylic acid (PMA). The type of polyanion used to assemble the multilayer thin films was found to dramatically influence the behavior and performance of devices fabricated with indium tin oxide and aluminum electrodes. Light-emitting devices fabricated from PMA/PPV multilayers were found to exhibit luminance levels in the range of 20-60 cd/m2, a thickness dependent turn-on voltage and classical rectifying behavior with rectification ratios greater than 105. In sharp contrast, the devices based on SPS/PPV exhibited near symmetric current-voltage curves, thickness independent turn-on voltages and much lower luminance levels. The significant difference in device behavior observed between these two systems is primarily due to a doping effect induced either chemically or electrochemically by the sulfonic acid groups of SPS. It was also found that the performance of these devices depends on the type of layer that is in contact with the Al top electrode thereby making it possible to manipulate device efficiency at the molecular level.

Mapping surface charge density of lipid bilayers by quantitative surface conductivity microscopy

PubMed Central

Klausen, Lasse Hyldgaard; Fuhs, Thomas; Dong, Mingdong

2016-01-01

Local surface charge density of lipid membranes influences membrane–protein interactions leading to distinct functions in all living cells, and it is a vital parameter in understanding membrane-binding mechanisms, liposome design and drug delivery. Despite the significance, no method has so far been capable of mapping surface charge densities under physiologically relevant conditions. Here, we use a scanning nanopipette setup (scanning ion-conductance microscope) combined with a novel algorithm to investigate the surface conductivity near supported lipid bilayers, and we present a new approach, quantitative surface conductivity microscopy (QSCM), capable of mapping surface charge density with high-quantitative precision and nanoscale resolution. The method is validated through an extensive theoretical analysis of the ionic current at the nanopipette tip, and we demonstrate the capacity of QSCM by mapping the surface charge density of model cationic, anionic and zwitterionic lipids with results accurately matching theoretical values. PMID:27561322

Mapping surface charge density of lipid bilayers by quantitative surface conductivity microscopy

NASA Astrophysics Data System (ADS)

Klausen, Lasse Hyldgaard; Fuhs, Thomas; Dong, Mingdong

2016-08-01

Local surface charge density of lipid membranes influences membrane-protein interactions leading to distinct functions in all living cells, and it is a vital parameter in understanding membrane-binding mechanisms, liposome design and drug delivery. Despite the significance, no method has so far been capable of mapping surface charge densities under physiologically relevant conditions. Here, we use a scanning nanopipette setup (scanning ion-conductance microscope) combined with a novel algorithm to investigate the surface conductivity near supported lipid bilayers, and we present a new approach, quantitative surface conductivity microscopy (QSCM), capable of mapping surface charge density with high-quantitative precision and nanoscale resolution. The method is validated through an extensive theoretical analysis of the ionic current at the nanopipette tip, and we demonstrate the capacity of QSCM by mapping the surface charge density of model cationic, anionic and zwitterionic lipids with results accurately matching theoretical values.

Mapping surface charge density of lipid bilayers by quantitative surface conductivity microscopy.

PubMed

Klausen, Lasse Hyldgaard; Fuhs, Thomas; Dong, Mingdong

2016-08-26

Local surface charge density of lipid membranes influences membrane-protein interactions leading to distinct functions in all living cells, and it is a vital parameter in understanding membrane-binding mechanisms, liposome design and drug delivery. Despite the significance, no method has so far been capable of mapping surface charge densities under physiologically relevant conditions. Here, we use a scanning nanopipette setup (scanning ion-conductance microscope) combined with a novel algorithm to investigate the surface conductivity near supported lipid bilayers, and we present a new approach, quantitative surface conductivity microscopy (QSCM), capable of mapping surface charge density with high-quantitative precision and nanoscale resolution. The method is validated through an extensive theoretical analysis of the ionic current at the nanopipette tip, and we demonstrate the capacity of QSCM by mapping the surface charge density of model cationic, anionic and zwitterionic lipids with results accurately matching theoretical values.

Surface charges for gravity and electromagnetism in the first order formalism

NASA Astrophysics Data System (ADS)

Frodden, Ernesto; Hidalgo, Diego

2018-02-01

A new derivation of surface charges for 3  +  1 gravity coupled to electromagnetism is obtained. Gravity theory is written in the tetrad-connection variables. The general derivation starts from the Lagrangian, and uses the covariant symplectic formalism in the language of forms. For gauge theories, surface charges disentangle physical from gauge symmetries through the use of Noether identities and the exactness symmetry condition. The surface charges are quasilocal, explicitly coordinate independent, gauge invariant and background independent. For a black hole family solution, the surface charge conservation implies the first law of black hole mechanics. As a check, we show the first law for an electrically charged, rotating black hole with an asymptotically constant curvature (the Kerr–Newman (anti-)de Sitter family). The charges, including the would-be mass term appearing in the first law, are quasilocal. No reference to the asymptotic structure of the spacetime nor the boundary conditions is required and therefore topological terms do not play a rôle. Finally, surface charge formulae for Lovelock gravity coupled to electromagnetism are exhibited, generalizing the one derived in a recent work by Barnich et al Proc. Workshop ‘ About Various Kinds of Interactions’ in honour of Philippe Spindel (4–5 June 2015, Mons, Belgium) C15-06-04 (2016 (arXiv:1611.01777 [gr-qc])). The two different symplectic methods to define surface charges are compared and shown equivalent.

The molecular basis of memory. Part 2: chemistry of the tripartite mechanism.

PubMed

Marx, Gerard; Gilon, Chaim

2013-06-19

We propose a tripartite mechanism to describe the processing of cognitive information (cog-info), comprising the (1) neuron, (2) surrounding neural extracellular matrix (nECM), and (3) numerous "trace" metals distributed therein. The neuron is encased in a polyanionic nECM lattice doped with metals (>10), wherein it processes (computes) and stores cog-info. Each [nECM:metal] complex is the molecular correlate of a cognitive unit of information (cuinfo), similar to a computer "bit". These are induced/sensed by the neuron via surface iontophoretic and electroelastic (piezoelectric) sensors. The generic cuinfo are used by neurons to biochemically encode and store cog-info in a rapid, energy efficient, but computationally expansive manner. Here, we describe chemical reactions involved in various processes that underline the tripartite mechanism. In addition, we present novel iconographic representations of various types of cuinfo resulting from"tagging" and cross-linking reactions, essential for the indexing cuinfo for organized retrieval and storage of memory.

Exploring the Effect of Surface Functionality on the Self-Assembly of Polyoxopalladate Macroions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Haso, Fadi; Yang, Peng; Gao, Yunyi

2015-05-12

The solution behavior of the two polyoxo-13-palladates(II) ([Pd(II) 13 As(V) 8 O34 (OH)6 ](8-) and [Pd(II) 13 (As(V) Ph)8 O32 ](6-) ) was studied in detail. We discovered that the countercation-mediated attraction is the driving force for their self-assembly into larger architectures. However, the presence of phenyl groups in the periphery of [Pd(II) 13 (As(V) Ph)8 O32 ](6-) results in an enhanced attraction among these polyanions through hydrophobic interactions, which leads to completely different trends of assembly size for these two very similar clusters when decreasing solvent polarity. An increase of assembly size with increasing solvent polarity was observed formore » [Pd(II) 13 (As(V) Ph)8 O32 ](6-) , whereas for [Pd(II) 13 As (V) 8 O34 (OH)6 ](8-) it was the opposite, due to the absence of hydrophobic interactions.« less

Direct Observation of Charge Transfer at a MgO(111) Surface

NASA Astrophysics Data System (ADS)

Subramanian, A.; Marks, L. D.; Warschkow, O.; Ellis, D. E.

2004-01-01

Transmission electron diffraction (TED) combined with direct methods have been used to study the √(3)×√(3)R30° reconstruction on the polar (111) surface of MgO and refine the valence charge distribution. The surface is nonstoichiometric and is terminated by a single magnesium atom. A charge-compensating electron hole is localized in the next oxygen layer and there is a nominal charge transfer from the oxygen atoms to the top magnesium atom. The partial charges that we obtain for the surface atoms are in reasonable agreement with empirical bond-valence estimations.

Ionic content and permeability of polyelectrolyte multilayers and complexes

NASA Astrophysics Data System (ADS)

Ghostine, Ramy A.

Ultrathin films of polyelectrolyte multilayers (PEMUs) are built by the alternating deposition of oppositely charged polymers from aqueous solutions onto a clean substrate. The most used protocol to fabricate this type of films is called the Layer-by-Layer assembly technique. The type of polyelectrolytes, the buildup conditions, and the post-assembly treatments can be modified in order to control both the chemical and physical properties of multilayers. In recent years, multilayers have been used in commercially available products, corrosion protection, biocompatible surfaces, hydrophobic and hydrophilic coatings and chromatographic applications. Their robustness and stability make polyelectrolyte multilayer thin films good candidates for a series of other applications such as cell growth control, ion exchange membranes, drug delivery, sensors and electronics. In this dissertation, the permeability of polyelectrolyte multilayers made from poly(diallyldimethylammonium chloride) (PDADMAC) and sodium poly(4-styrene sulfonate) (NaPSS) is discussed in details. The permeability was studied by measuring the flux of redox active ions across a PEMU coated electrode. The effect of temperature, salt type and concentration was studied and it was determined that the flux of ions increases with temperature and salt concentration, and the permeability of ions strongly depends on the type of salt ions present in solution. The membrane concentration of the redox active ion was also calculated using attenuated total reflectance Fourier transform infra red spectroscopy. In another part of this dissertation, the ionic content of PEMUs was investigated by using radioactive counterions to track the ratio of positive to negative polymer repeat units. It was found that the accepted model of charge overcompensation for each layer is incorrect. In fact, overcompensation at the surface occurs only on the addition of the polycation, whereas the polyanion merely compensates the polycation. After the assembly of about a dozen layers, positive sites begin to accrue in the multilayer. The buildup mechanism is highly asymmetric with respect to the layer number, thus a new model profile for PEMU was employed. The critical impact of asymmetric growth on various properties of multilayers is also discussed. Thickness change, surface roughness, mechanical properties and ionic content of PEMUs were also studied in another part of this dissertation. The effect of salt annealing on these properties was investigated by the use of radiolabeling technique and atomic force microscopy. It was determined that salt annealing causes the polymer mobility in the multilayer to increase, reducing the amount of extrinsic charges and decreasing the surface roughness of the multilayer. The incorporation of 2nd generation fibroblast growth factor was studied in another chapter of this dissertation. FGF-1 is an important protein used in the wound healing process. The addition of FGF into films of PEMU was successful after modifying the ionic content of these films. It was shown that treating PSS terminated PEMU films with 10 mM PSS at high salt concentration would remove all positive extrinsic charges from the multilayer and add extra PSS chains in the bulk of the film. The addition of extra PSS depends on the salt concentration used during the PSS treatment. The highest amount of incorporated FGF was 58 mug cm-2. The release of FGF in phosphate buffer saline solution was also tracked for 30 days period. A total of 13 mug cm-2 of FGF were released from (PDADMA/PSS) 10 when treated with PSS at 1.5 M NaCl. Doping constants and diffusion coefficients for an extruded, stoichiometric, dense polyelectrolyte complex, exPEC, were determined for a Hofmeister series of anions in the last part of this dissertation. Both parameters describe the extent and speed to which a complex may be doped, where they followed a Hofmeister ordering and covered a wide range of response. Doping and undoping kinetics of polyelectrolyte complexes of PDADMA and PSS were also investigated using conductivity and radioactivity techniques. Tracer diffusion of radiolabeled Na+, compared with coupled diffusion of NaCl, revealed slightly faster diffusion of Na+ compared to Cl- withing the PEC.

The surface charge of trypanosomatids.

PubMed

Souto-Padrón, Thaïs

2002-12-01

The surface charge of trypanosomatids was evaluated by means of the binding of cationic particles, as visualized by electron microscopy and by direct measurements of the electrophoretic mobility of cells. The results obtained indicate that most of the trypanosomatids exhibit a negatively charged surface whose value is species specific and varies according to the developmental stages. Sialic acids associated with glycoproteins, glycolipids and phosphate groups are the major components responsible for the net negative surface charge of the trypanosomatids.

Miniaturized ultrafine particle sizer and monitor

NASA Technical Reports Server (NTRS)

Qi, Chaolong (Inventor); Chen, Da-Ren (Inventor)

2011-01-01

An apparatus for measuring particle size distribution includes a charging device and a precipitator. The charging device includes a corona that generates charged ions in response to a first applied voltage, and a charger body that generates a low energy electrical field in response to a second applied voltage in order to channel the charged ions out of the charging device. The corona tip and the charger body are arranged relative to each other to direct a flow of particles through the low energy electrical field in a direction parallel to a direction in which the charged ions are channeled out of the charging device. The precipitator receives the plurality of particles from the charging device, and includes a disk having a top surface and an opposite bottom surface, wherein a predetermined voltage is applied to the top surface and the bottom surface to precipitate the plurality of particles.

Method of adhesion between an oxide layer and a metal layer

DOEpatents

Jennison, Dwight R.; Bogicevic, Alexander; Kelber, Jeffry A.; Chambers, Scott A.

2004-09-14

A method of controlling the wetting characteristics and increasing the adhesion between a metal and an oxide layer. By introducing a negatively-charged species to the surface of an oxide layer, layer-by-layer growth of metal deposited onto the oxide surface is promoted, increasing the adhesion strength of the metal-oxide interface. The negatively-charged species can either be deposited onto the oxide surface or a compound can be deposited that dissociates on, or reacts with, the surface to form the negatively-charged species. The deposited metal adatoms can thereby bond laterally to the negatively-charged species as well as vertically to the oxide surface as well as react with the negatively charged species, be oxidized, and incorporated on or into the surface of the oxide.

Method and system for treating an interior surface of a workpiece using a charged particle beam

DOEpatents

Swenson, David Richard

2007-05-23

A method and system of treating an interior surface on an internal cavity of a workpiece using a charged particle beam. A beam deflector surface of a beam deflector is placed within the internal cavity of the workpiece and is used to redirect the charged particle beam toward the interior surface to treat the interior surface.

Five inorganic–organic hybrids based on Keggin polyanion [SiMo{sub 12}O{sub 40}]{sup 4−}: From 0D to 2D network

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Xiao-Yang, E-mail: yangyangyu0103@sohu.com; Jilin Institute of Chemical Technology, Jilin City, Jilin 132022; Cui, Xiao-Bing

2014-01-15

Five new inorganic–organic hybrids based on 4,4′-bipyridine and Keggin-type polyoxometalate [SiMo{sub 12}O{sub 40}]{sup 4−}, (SiMo{sub 12}O{sub 40})(H{sub 2}bipy){sub 2}·2H{sub 2}O (1), [Cu(Hbipy){sub 4}(HSiMo{sub 12}O{sub 40})(SiMo{sub 12}O{sub 40})](H{sub 2}bipy){sub 0.5}·7H{sub 2}O (2), [Cu{sub 2}(Hbipy){sub 6}(bipy)(SiMo{sub 12}O{sub 40}){sub 3}](Hbipy){sub 2}·6H{sub 2}O (3), [Cu(bipy){sub 2}(SiMo{sub 12}O{sub 40})](H{sub 2}bipy)·2H{sub 2}O (4) and [Cu{sub 2}(bipy){sub 4}(H{sub 2}O){sub 4}](SiMo{sub 12}O{sub 40})·13H{sub 2}O (5) (bipy=4,4′-bipyridine), have been hydrothermally synthesized. 1 consists of H{sub 2}bipy{sup 2+} and [SiMo{sub 12}O{sub 40}]{sup 4−} units. In 2, two [SiMo{sub 12}O{sub 40}]{sup 4−} are bridged by [Cu(Hbipy){sub 4}]{sup 6+} to form a [Cu(Hbipy){sub 4}(SiMo{sub 12}O{sub 40}){sub 2}]{sup 2−} dimmer. In 3, [SiMo{submore » 12}O{sub 40}]{sup 4−} polyanions acting as bidentated bridging ligands and monodentated auxiliary ligands connect [Cu{sub 2}(Hbipy){sub 6}(bipy)]{sup 8+} units into a 1D zigzag chain. In 4, [SiMo{sub 12}O{sub 40}]{sup 4−} polyanions bridge neighboring 1D [Cu(bipy){sub 2}]{sup 2+} double chains into a 2D extended layer. In 5, [SiMo{sub 12}O{sub 40}]{sup 4−} polyanions acting as templates site alternately upon the grids from both sides of the square grid [Cu{sub 2}(bipy){sub 4}(H{sub 2}O){sub 4}]{sup 4+} layer. In addition, the electrochemical behaviors of 1, 3 and 4 and the photocatalysis property of 1 have been investigated. - Graphical abstract: Five new compounds based on [SiMo{sub 12}O{sub 40}]{sup 4−} have been successfully generated. [SiMo{sub 12}O{sub 40}]{sup 4−} anions play different roles in the structures of the five compounds. Display Omitted - Highlights: • Five new compounds based on [SiMo{sub 12}O{sub 40}]{sup 4−} have been generated. • [SiMo{sub 12}O{sub 40}]{sup 4−} anions play different roles in the five structures. • The electrochemical behaviors of 1, 3 and 4 have been investigated. • The photocatalysis property of 1 has been investigated.« less

Determination of molecular configuration by debye length modulation.

PubMed

Vacic, Aleksandar; Criscione, Jason M; Rajan, Nitin K; Stern, Eric; Fahmy, Tarek M; Reed, Mark A

2011-09-07

Silicon nanowire field effect transistors (FETs) have emerged as ultrasensitive, label-free biodetectors that operate by sensing bound surface charge. However, the ionic strength of the environment (i.e., the Debye length of the solution) dictates the effective magnitude of the surface charge. Here, we show that control of the Debye length determines the spatial extent of sensed bound surface charge on the sensor. We apply this technique to different methods of antibody immobilization, demonstrating different effective distances of induced charge from the sensor surface.

Mapping the surface charge distribution of amyloid fibril

NASA Astrophysics Data System (ADS)

Lee, Gyudo; Lee, Wonseok; Lee, Hyungbeen; Woo Lee, Sang; Sung Yoon, Dae; Eom, Kilho; Kwon, Taeyun

2012-07-01

It is of high importance to measure and map the surface charge distribution of amyloids, since electrostatic interaction between amyloidogenic proteins and biomolecules plays a vital role in amyloidogenesis. In this work, we have measured and mapped the surface charge distributions of amyloids (i.e., β-lactoglobulin fibril) using Kelvin probe force microscopy. It is shown that the surface charge distribution is highly dependent on the conformation of amyloids (e.g., the helical pitch of amyloid fibrils) as well as the pH of a solvent.

Charging Characteristics of an Insulating Hollow Cylinder in Vacuum

NASA Astrophysics Data System (ADS)

Yamamoto, Osamu; Hayashi, Hirotaka; Wadahama, Toshihiko; Takeda, Daisuke; Hamada, Shoji; Ohsawa, Yasuharu

This paper deals with charging characteristics of the inner surface of an insulating hollow cylinder in vacuum. We conducted measurements of electric field strength near the triple points on cathode by using an electrostatic probe. Also we conducted a computer simulation of charging based on the Secondary Electron Emission Avalanche (SEEA) mechanism. These results are compared with those obtained previously for solid cylinders. As a result, we have clarified that hollow cylinders acquire surface charge which is larger than that of solid cylinders. We have also found that charge controlling effect by roughening the inner surface, which have been proved effective to depress charging on the surface of solid cylinders in our previous studies, is limited for hollow cylinders.

Relating Silica Scaling in Reverse Osmosis to Membrane Surface Properties.

PubMed

Tong, Tiezheng; Zhao, Song; Boo, Chanhee; Hashmi, Sara M; Elimelech, Menachem

2017-04-18

We investigated the relationship between membrane surface properties and silica scaling in reverse osmosis (RO). The effects of membrane hydrophilicity, free energy for heterogeneous nucleation, and surface charge on silica scaling were examined by comparing thin-film composite polyamide membranes grafted with a variety of polymers. Results show that the rate of silica scaling was independent of both membrane hydrophilicity and free energy for heterogeneous nucleation. In contrast, membrane surface charge demonstrated a strong correlation with the extent of silica scaling (R 2 > 0.95, p < 0.001). Positively charged membranes significantly facilitated silica scaling, whereas a more negative membrane surface charge led to reduced scaling. This observation suggests that deposition of negatively charged silica species on the membrane surface plays a critical role in silica scale formation. Our findings provide fundamental insights into the mechanisms governing silica scaling in reverse osmosis and highlight the potential of membrane surface modification as a strategy to reduce silica scaling.

Molecular dynamics investigation of the ionic liquid/enzyme interface: application to engineering enzyme surface charge.

PubMed

Burney, Patrick R; Nordwald, Erik M; Hickman, Katie; Kaar, Joel L; Pfaendtner, Jim

2015-04-01

Molecular simulations of the enzymes Candida rugosa lipase and Bos taurus α-chymotrypsin in aqueous ionic liquids 1-butyl-3-methylimidazolium chloride and 1-ethyl-3-methylimidazolium ethyl sulfate were used to study the change in enzyme-solvent interactions induced by modification of the enzyme surface charge. The enzymes were altered by randomly mutating lysine surface residues to glutamate, effectively decreasing the net surface charge by two for each mutation. These mutations resemble succinylation of the enzyme by chemical modification, which has been shown to enhance the stability of both enzymes in ILs. After establishing that the enzymes were stable on the simulated time scales, we focused the analysis on the organization of the ionic liquid substituents about the enzyme surface. Calculated solvent charge densities show that for both enzymes and in both solvents that changing positively charged residues to negative charge does indeed increase the charge density of the solvent near the enzyme surface. The radial distribution of IL constituents with respect to the enzyme reveals decreased interactions with the anion are prevalent in the modified systems when compared to the wild type, which is largely accompanied by an increase in cation contact. Additionally, the radial dependence of the charge density and ion distribution indicates that the effect of altering enzyme charge is confined to short range (≤1 nm) ordering of the IL. Ultimately, these results, which are consistent with that from prior experiments, provide molecular insight into the effect of enzyme surface charge on enzyme stability in ILs. © 2015 Wiley Periodicals, Inc.

Competitive Adsorption and Ordered Packing of Counterions near Highly Charged Surfaces: From Mean-Field Theory to Monte Carlo Simulations

PubMed Central

Wen, Jiayi; Zhou, Shenggao; Xu, Zhenli; Li, Bo

2013-01-01

Competitive adsorption of counterions of multiple species to charged surfaces is studied by a size-effect included mean-field theory and Monte Carlo (MC) simulations. The mean-field electrostatic free-energy functional of ionic concentrations, constrained by Poisson’s equation, is numerically minimized by an augmented Lagrangian multiplier method. Unrestricted primitive models and canonical ensemble MC simulations with the Metropolis criterion are used to predict the ionic distributions around a charged surface. It is found that, for a low surface charge density, the adsorption of ions with a higher valence is preferable, agreeing with existing studies. For a highly charged surface, both of the mean-field theory and MC simulations demonstrate that the counterions bind tightly around the charged surface, resulting in a stratification of counterions of different species. The competition between mixed entropy and electrostatic energetics leads to a compromise that the ionic species with a higher valence-to-volume ratio has a larger probability to form the first layer of stratification. In particular, the MC simulations confirm the crucial role of ionic valence-to-volume ratios in the competitive adsorption to charged surfaces that had been previously predicted by the mean-field theory. The charge inversion for ionic systems with salt is predicted by the MC simulations but not by the mean-field theory. This work provides a better understanding of competitive adsorption of counterions to charged surfaces and calls for further studies on the ionic size effect with application to large-scale biomolecular modeling. PMID:22680474

Competitive adsorption and ordered packing of counterions near highly charged surfaces: From mean-field theory to Monte Carlo simulations.

PubMed

Wen, Jiayi; Zhou, Shenggao; Xu, Zhenli; Li, Bo

2012-04-01

Competitive adsorption of counterions of multiple species to charged surfaces is studied by a size-effect-included mean-field theory and Monte Carlo (MC) simulations. The mean-field electrostatic free-energy functional of ionic concentrations, constrained by Poisson's equation, is numerically minimized by an augmented Lagrangian multiplier method. Unrestricted primitive models and canonical ensemble MC simulations with the Metropolis criterion are used to predict the ionic distributions around a charged surface. It is found that, for a low surface charge density, the adsorption of ions with a higher valence is preferable, agreeing with existing studies. For a highly charged surface, both the mean-field theory and the MC simulations demonstrate that the counterions bind tightly around the charged surface, resulting in a stratification of counterions of different species. The competition between mixed entropy and electrostatic energetics leads to a compromise that the ionic species with a higher valence-to-volume ratio has a larger probability to form the first layer of stratification. In particular, the MC simulations confirm the crucial role of ionic valence-to-volume ratios in the competitive adsorption to charged surfaces that had been previously predicted by the mean-field theory. The charge inversion for ionic systems with salt is predicted by the MC simulations but not by the mean-field theory. This work provides a better understanding of competitive adsorption of counterions to charged surfaces and calls for further studies on the ionic size effect with application to large-scale biomolecular modeling.

Battery Power Management in Heavy-duty HEVs based on the Estimated Critical Surface Charge

DTIC Science & Technology

2011-03-01

health prospects without any penalty on fuel efficiency. Keywords: Lithium - ion battery ; power management; critical surface charge; Lithium-ion...fuel efficiency. 15. SUBJECT TERMS Lithium - ion battery ; power management; critical surface charge; Lithium-ion concentration; estimation; extended...Di Domenico, D., Fiengo, G., and Stefanopoulou, A. (2008) ’ Lithium - ion battery state of charge estimation with a kalman filter based on a

Aggregation and charging of sulfate and amidine latex particles in the presence of oxyanions.

PubMed

Sugimoto, Takuya; Cao, Tianchi; Szilagyi, Istvan; Borkovec, Michal; Trefalt, Gregor

2018-08-15

Electrophoretic mobility and time resolved light scattering are used to measure the effect on charging and aggregation of amidine and sulfate latex particles of different oxyanions namely, phosphate, arsenate, sulfate, and selenate. In the case of negatively charged sulfate latex particles oxyanions represent the coions, while they represent counterions in the case of the positively charged amidine latex. Repulsive interaction between the sulfate latex surface and the coions results in weak ion specific effects on the charging and aggregation. On the other hand the interaction of oxyanions with the amidine latex surface is highly specific. The monovalent dihydrogen phosphate ion strongly adsorbs to the positively charged surface and reverses the charge of the particle. This charge reversal leads also to the restabilization of the amidine latex suspension at the intermediate phosphate concentrations. In the case of dihydrogen arsenate the adsorption to amidine latex surface is weaker and no charge reversal and restabilization occurs. Similar differences are seen between the sulfate and selenate analogues, where selenate adsorbs more strongly to the surface as compared to the sulfate ion and invokes charge reversal. The present results indicate that ion specificity is much more pronounced in the case of counterions. Copyright © 2018 Elsevier Inc. All rights reserved.

Role of protein surface charge in monellin sweetness.

PubMed

Xue, Wei-Feng; Szczepankiewicz, Olga; Thulin, Eva; Linse, Sara; Carey, Jannette

2009-03-01

A small number of proteins have the unusual property of tasting intensely sweet. Despite many studies aimed at identifying their sweet taste determinants, the molecular basis of protein sweetness is not fully understood. Recent mutational studies of monellin have implicated positively charged residues in sweetness. In the present work, the effect of overall net charge was investigated using the complementary approach of negative charge alterations. Multiple substitutions of Asp/Asn and Glu/Gln residues radically altered the surface charge of single-chain monellin by removing six negative charges or adding four negative charges. Biophysical characterization using circular dichroism, fluorescence, and two-dimensional NMR demonstrates that the native fold of monellin is preserved in the variant proteins under physiological solution conditions although their stability toward chemical denaturation is altered. A human taste test was employed to determine the sweetness detection threshold of the variants. Removal of negative charges preserves monellin sweetness, whereas added negative charge has a large negative impact on sweetness. Meta-analysis of published charge variants of monellin and other sweet proteins reveals a general trend toward increasing sweetness with increasing positive net charge. Structural mapping of monellin variants identifies a hydrophobic surface predicted to face the receptor where introduced positive or negative charge reduces sweetness, and a polar surface where charges modulate long-range electrostatic complementarity.

Fibronectin module FN(III)9 adsorption at contrasting solid model surfaces studied by atomistic molecular dynamics.

PubMed

Kubiak-Ossowska, Karina; Mulheran, Paul A; Nowak, Wieslaw

2014-08-21

The mechanism of human fibronectin adhesion synergy region (known as integrin binding region) in repeat 9 (FN(III)9) domain adsorption at pH 7 onto various and contrasting model surfaces has been studied using atomistic molecular dynamics simulations. We use an ionic model to mimic mica surface charge density but without a long-range electric field above the surface, a silica model with a long-range electric field similar to that found experimentally, and an Au {111} model with no partial charges or electric field. A detailed description of the adsorption processes and the contrasts between the various model surfaces is provided. In the case of our model silica surface with a long-range electrostatic field, the adsorption is rapid and primarily driven by electrostatics. Because it is negatively charged (-1e), FN(III)9 readily adsorbs to a positively charged surface. However, due to its partial charge distribution, FN(III)9 can also adsorb to the negatively charged mica model because of the absence of a long-range repulsive electric field. The protein dipole moment dictates its contrasting orientation at these surfaces, and the anchoring residues have opposite charges to the surface. Adsorption on the model Au {111} surface is possible, but less specific, and various protein regions might be involved in the interactions with the surface. Despite strongly influencing the protein mobility, adsorption at these model surfaces does not require wholesale FN(III)9 conformational changes, which suggests that the biological activity of the adsorbed protein might be preserved.

Suppression of surface charge accumulation on Al{sub 2}O{sub 3}-filled epoxy resin insulator under dc voltage by direct fluorination

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Boya; Zhang, Guixin, E-mail: guixin@mail.tsinghua.edu.cn; Li, Chuanyang

2015-12-15

Surface charge accumulation on insulators under high dc voltage is a major factor that may lead to the reduction of insulation levels in gas insulated devices. In this paper, disc insulators made of Al{sub 2}O{sub 3}-filled epoxy resin were surface fluorinated using a F{sub 2}/N{sub 2} mixture (12.5% F{sub 2}) at 50 °C and 0.1 MPa for different durations of 15 min, 30 min and 60 min. A dc voltage was applied to the insulator for 30 min and the charge density on its surface was measured by an electrostatic probe. The results revealed significant lower surface charge densities on themore » fluorinated insulators in comparison with the original one. Surface conductivity measurements indicated a higher surface conductivity by over three orders of magnitude after fluorination, which would allow the charges to transfer along the surface and thus may suppress their accumulation. Further, attenuated total reflection infrared analysis and surface morphology observations of the samples revealed that the introduction of fluoride groups altered the surface physicochemical properties. These structure changes, especially the physical defects reduced the depth of charge traps in the surface layer, which was verified by the measurement of energy distributions of the electron and hole traps based on the isothermal current theory. The results in this paper demonstrate that fluorination can be a promising and effective method to suppress surface charge accumulation on epoxy insulators in gas insulated devices.« less

Charge heterogeneity of surfaces: mapping and effects on surface forces.

PubMed

Drelich, Jaroslaw; Wang, Yu U

2011-07-11

The DLVO theory treats the total interaction force between two surfaces in a liquid medium as an arithmetic sum of two components: Lifshitz-van der Waals and electric double layer forces. Despite the success of the DLVO model developed for homogeneous surfaces, a vast majority of surfaces of particles and materials in technological systems are of a heterogeneous nature with a mosaic structure composed of microscopic and sub-microscopic domains of different surface characteristics. In such systems, the heterogeneity of the surface can be more important than the average surface character. Attractions can be stronger, by orders of magnitude, than would be expected from the classical mean-field DLVO model when area-averaged surface charge or potential is employed. Heterogeneity also introduces anisotropy of interactions into colloidal systems, vastly ignored in the past. To detect surface heterogeneities, analytical tools which provide accurate and spatially resolved information about material surface chemistry and potential - particularly at microscopic and sub-microscopic resolutions - are needed. Atomic force microscopy (AFM) offers the opportunity to locally probe not only changes in material surface characteristic but also charges of heterogeneous surfaces through measurements of force-distance curves in electrolyte solutions. Both diffuse-layer charge densities and potentials can be calculated by fitting the experimental data with a DLVO theoretical model. The surface charge characteristics of the heterogeneous substrate as recorded by AFM allow the charge variation to be mapped. Based on the obtained information, computer modeling and simulation can be performed to study the interactions among an ensemble of heterogeneous particles and their collective motions. In this paper, the diffuse-layer charge mapping by the AFM technique is briefly reviewed, and a new Diffuse Interface Field Approach to colloid modeling and simulation is briefly discussed. Copyright © 2011 Elsevier B.V. All rights reserved.

The impact of nano-coating on surface charge accumulation of epoxy resin insulator: characteristic and mechanism

NASA Astrophysics Data System (ADS)

Qi, Bo; Gao, Chunjia; Lv, Yuzhen; Li, Chengrong; Tu, Youping; Xiong, Jun

2018-06-01

The flashover phenomenon of the insulator is the main cause for insulating failure of GIS/GIL, and one of the most critical impacting factors is the accumulation of surface charge. The common methods to restrain the surface charge accumulation are reviewed in this paper. Through the reasonable comparison and analysis of these methods, nano-coatings for the insulator were selected as a way to restrain the surface charge accumulation. Based on this, six nano-coated epoxy resin samples with different concentrations of P25-TiO2 nanoparticles were produced. A high precision 3D surface charge measurement system was developed in this paper with a spatial resolution of 4.0 mm2 and a charge resolution of 0.01 µC (m2 · mV)‑1. The experimental results for the epoxy resin sample showed that with the concentration of nanoparticles of the coating material increasing, the surface charge density tended to first decrease and then increase. In the sample coated with 0.5% concentration of nanoparticles, the suppression effect is the optimum, leading to a 63.8% reduction of charge density under DC voltage. The application test for actual nano-coated GIS/GIL basin insulator indicated that the maximum suppression degree for the charge density under DC voltage could reach 48.3%, while it could reach 22.2% for switching impulse voltage and 12.5% for AC context. The control mechanism of nano-coatings on charge accumulation was proposed based on the analysis for surface morphology features and traps characteristics; the shallow traps dominate in the migration of charges while the deep traps operate on the charge accumulation. With the concentration of nanoparticles in nano-coating material mounting up, the density of shallow traps continuously increases, while for deep traps, it first decreases and then increases. For the sample with 0.5% concentration of nanoparticles coated, the competition between shallow traps and deep traps comes to the most balanced state, producing the most significant suppression impact on surface charge accumulation.

Enhanced cell uptake via non-covalent decollation of a single-walled carbon nanotube-DNA hybrid with polyethylene glycol-grafted poly(l-lysine) labeled with an Alexa-dye and its efficient uptake in a cancer cell

NASA Astrophysics Data System (ADS)

Fujigaya, Tsuyohiko; Yamamoto, Yuki; Kano, Arihiro; Maruyama, Atsushi; Nakashima, Naotoshi

2011-10-01

The use of single-walled carbon nanotubes (SWNTs) for biomedical applications is a promising approach due to their unique outer optical stimuli response properties, such as a photothermal response triggered by near-IR laser irradiation. The challenging task in order to realize such applications is to render the SWNTs biocompatible. For this purpose, the stable and homogeneous functionalization of the SWNTs with a molecule carrying a biocompatible group is very important. Here, we describe the design and synthesis of a polyanionic SWNT/DNA hybrid combined with a cationic poly(l-lysine) grafted by polyethylene glycol (PLL-g-PEG) to provide a supramolecular SWNT assembly. A titration experiment revealed that the assembly undergoes an approximately 1 : 1 reaction of the SWNT/DNA with PLL-g-PEG. We also found that SWNT/DNA is coated with PLL-g-PEG very homogeneously that avoids the non-specific binding of proteins on the SWNT surface. The experiment using the obtained supramolecular hybrid was carried out in vitro and a dramatic enhancement in the cell uptake efficiency compared to that of the SWNT/DNA hybrid without PLL-g-PEG was found.The use of single-walled carbon nanotubes (SWNTs) for biomedical applications is a promising approach due to their unique outer optical stimuli response properties, such as a photothermal response triggered by near-IR laser irradiation. The challenging task in order to realize such applications is to render the SWNTs biocompatible. For this purpose, the stable and homogeneous functionalization of the SWNTs with a molecule carrying a biocompatible group is very important. Here, we describe the design and synthesis of a polyanionic SWNT/DNA hybrid combined with a cationic poly(l-lysine) grafted by polyethylene glycol (PLL-g-PEG) to provide a supramolecular SWNT assembly. A titration experiment revealed that the assembly undergoes an approximately 1 : 1 reaction of the SWNT/DNA with PLL-g-PEG. We also found that SWNT/DNA is coated with PLL-g-PEG very homogeneously that avoids the non-specific binding of proteins on the SWNT surface. The experiment using the obtained supramolecular hybrid was carried out in vitro and a dramatic enhancement in the cell uptake efficiency compared to that of the SWNT/DNA hybrid without PLL-g-PEG was found. Electronic supplementary information (ESI) available: Additional absorption spectra, DLS plots and PL spectra. See DOI: 10.1039/c1nr10635j

Secondary Structures of Ubiquitin Ions Soft-Landed onto Self-Assembled Monolayer Surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Qichi; Laskin, Julia

2016-06-09

The secondary structures of multiply charged ubiquitin ions soft-landed onto self-assembled monolayer (SAM) surfaces were studied using in situ infrared reflection-absorption spectroscopy (IRRAS). Two charge states of ubiquitin, 5+ and 13+, were mass selected separately from a mixture of different charge states produced by electrospray ionization (ESI). The low 5+ charge state represents a native-like folded state of ubiquitin, while the high 13+ charge state assumes an extended, almost linear conformation. Each of the two charge states was soft-landed onto a CH 3- and COOH-terminated SAM of alkylthiols on gold (HSAM and COOH-SAM). HSAM is a hydrophobic surface known tomore » stabilize helical conformations of soft-landed protonated peptides, whereas COOH-SAM is a hydrophilic surface that preferentially stabilizes β-sheet conformations. IRRAS spectra of the soft-landed ubiquitin ions were acquired as a function of time during and after ion soft-landing. Similar to smaller peptide ions, helical conformations of ubiquitin are found to be more abundant on HSAM, while the relative abundance of β-sheet conformations increases on COOH-SAM. The initial charge state of ubiquitin also has a pronounced effect on its conformation on the surface. Specifically, on both surfaces, a higher relative abundance of helical conformations and lower relative abundance of β-sheet conformations is observed for the 13+ charge state compared to the 5+ charge state. Time-resolved experiments indicate that the α-helical band in the spectrum of the 13+ charge state slowly increases with time on the HSAM surface and decreases in the spectrum of the 13+ charge state on COOH-SAM. These results further support the preference of the hydrophobic HSAM surface toward helical conformations and demonstrate that soft-landed protein ions may undergo slow conformational changes during and after deposition.« less

The study of surface wetting, nanobubbles and boundary slip with an applied voltage: A review

PubMed Central

Pan, Yunlu; Zhao, Xuezeng

2014-01-01

Summary The drag of fluid flow at the solid–liquid interface in the micro/nanoscale is an important issue in micro/nanofluidic systems. Drag depends on the surface wetting, nanobubbles, surface charge and boundary slip. Some researchers have focused on the relationship between these interface properties. In this review, the influence of an applied voltage on the surface wettability, nanobubbles, surface charge density and slip length are discussed. The contact angle (CA) and contact angle hysteresis (CAH) of a droplet of deionized (DI) water on a hydrophobic polystyrene (PS) surface were measured with applied direct current (DC) and alternating current (AC) voltages. The nanobubbles in DI water and three kinds of saline solution on a PS surface were imaged when a voltage was applied. The influence of the surface charge density on the nanobubbles was analyzed. Then the slip length and the electrostatic force on the probe were measured on an octadecyltrichlorosilane (OTS) surface with applied voltage. The influence of the surface charge on the boundary slip and drag of fluid flow has been discussed. Finally, the influence of the applied voltage on the surface wetting, nanobubbles, surface charge, boundary slip and the drag of liquid flow are summarized. With a smaller surface charge density which could be achieved by applying a voltage on the surface, larger and fewer nanobubbles, a larger slip length and a smaller drag of liquid flow could be found. PMID:25161839

The study of surface wetting, nanobubbles and boundary slip with an applied voltage: A review.

PubMed

Pan, Yunlu; Bhushan, Bharat; Zhao, Xuezeng

2014-01-01

The drag of fluid flow at the solid-liquid interface in the micro/nanoscale is an important issue in micro/nanofluidic systems. Drag depends on the surface wetting, nanobubbles, surface charge and boundary slip. Some researchers have focused on the relationship between these interface properties. In this review, the influence of an applied voltage on the surface wettability, nanobubbles, surface charge density and slip length are discussed. The contact angle (CA) and contact angle hysteresis (CAH) of a droplet of deionized (DI) water on a hydrophobic polystyrene (PS) surface were measured with applied direct current (DC) and alternating current (AC) voltages. The nanobubbles in DI water and three kinds of saline solution on a PS surface were imaged when a voltage was applied. The influence of the surface charge density on the nanobubbles was analyzed. Then the slip length and the electrostatic force on the probe were measured on an octadecyltrichlorosilane (OTS) surface with applied voltage. The influence of the surface charge on the boundary slip and drag of fluid flow has been discussed. Finally, the influence of the applied voltage on the surface wetting, nanobubbles, surface charge, boundary slip and the drag of liquid flow are summarized. With a smaller surface charge density which could be achieved by applying a voltage on the surface, larger and fewer nanobubbles, a larger slip length and a smaller drag of liquid flow could be found.

Profiling charge complementarity and selectivity for binding at the protein surface.

PubMed

Sulea, Traian; Purisima, Enrico O

2003-05-01

A novel analysis and representation of the protein surface in terms of electrostatic binding complementarity and selectivity is presented. The charge optimization methodology is applied in a probe-based approach that simulates the binding process to the target protein. The molecular surface is color coded according to calculated optimal charge or according to charge selectivity, i.e., the binding cost of deviating from the optimal charge. The optimal charge profile depends on both the protein shape and charge distribution whereas the charge selectivity profile depends only on protein shape. High selectivity is concentrated in well-shaped concave pockets, whereas solvent-exposed convex regions are not charge selective. This suggests the synergy of charge and shape selectivity hot spots toward molecular selection and recognition, as well as the asymmetry of charge selectivity at the binding interface of biomolecular systems. The charge complementarity and selectivity profiles map relevant electrostatic properties in a readily interpretable way and encode information that is quite different from that visualized in the standard electrostatic potential map of unbound proteins.

A New Kinetic Simulation Model with Self-Consistent Calculation of Regolith Layer Charging for Moon-Plasma Interactions

NASA Astrophysics Data System (ADS)

Han, D.; Wang, J.

2015-12-01

The moon-plasma interactions and the resulting surface charging have been subjects of extensive recent investigations. While many particle-in-cell (PIC) based simulation models have been developed, all existing PIC simulation models treat the surface of the Moon as a boundary condition to the plasma flow. In such models, the surface of the Moon is typically limited to simple geometry configurations, the surface floating potential is calculated from a simplified current balance condition, and the electric field inside the regolith layer cannot be resolved. This paper presents a new full particle PIC model to simulate local scale plasma flow and surface charging. A major feature of this new model is that the surface is treated as an "interface" between two mediums rather than a boundary, and the simulation domain includes not only the plasma but also the regolith layer and the bedrock underneath it. There are no limitations on the surface shape. An immersed-finite-element field solver is applied which calculates the regolith surface floating potential and the electric field inside the regolith layer directly from local charge deposition. The material property of the regolith layer is also explicitly included in simulation. This new model is capable of providing a self-consistent solution to the plasma flow field, lunar surface charging, the electric field inside the regolith layer and the bedrock for realistic surface terrain. This new model is applied to simulate lunar surface-plasma interactions and surface charging under various ambient plasma conditions. The focus is on the lunar terminator region, where the combined effects from the low sun elevation angle and the localized plasma wake generated by plasma flow over a rugged terrain can generate strongly differentially charged surfaces and complex dust dynamics. We discuss the effects of the regolith properties and regolith layer charging on the plasma flow field, dust levitation, and dust transport.

Acceleration of osteogenesis by using barium titanate piezoelectric ceramic as an implant material

NASA Astrophysics Data System (ADS)

Furuya, K.; Morita, Y.; Tanaka, K.; Katayama, T.; Nakamachi, E.

2011-04-01

As bone has piezoelectric properties, it is expected that activity of bone cells and bone formation can be accelerated by applying piezoelectric ceramics to implants. Since lead ions, included in ordinary piezoelectric ceramics, are harmful, a barium titanate (BTO) ceramic, which is a lead-free piezoelectric ceramic, was used in this study. The purpose of this study was to investigate piezoelectric effects of surface charge of BTO on cell differentiation under dynamic loading in vitro. Rat bone marrow cells seeded on surfaces of BTO ceramics were cultured in culture medium supplemented with dexamethasone, β-glycerophosphate and ascorbic acid while a dynamic load was applied to the BTO ceramics. After 10 days of cultivation, the cell layer and synthesized matrix on the BTO surfaces were scraped off, and then DNA content, alkaline phosphtase (ALP) activity and calcium content were measured, to evaluate osteogenic differentiation. ALP activity on the charged BTO surface was slightly higher than that on the non-charged BTO surface. The amount of calcium on the charged BTO surface was also higher than that on the non-charged BTO surface. These results showed that the electric charged BTO surface accelerated osteogenesis.

Adsorption of hydrophobin on different self-assembled monolayers: the role of the hydrophobic dipole and the electric dipole.

PubMed

Peng, Chunwang; Liu, Jie; Zhao, Daohui; Zhou, Jian

2014-09-30

In this work, the adsorptions of hydrophobin (HFBI) on four different self-assembled monolayers (SAMs) (i.e., CH3-SAM, OH-SAM, COOH-SAM, and NH2-SAM) were investigated by parallel tempering Monte Carlo and molecular dynamics simulations. Simulation results indicate that the orientation of HFBI adsorbed on neutral surfaces is dominated by a hydrophobic dipole. HFBI adsorbs on the hydrophobic CH3-SAM through its hydrophobic patch and adopts a nearly vertical hydrophobic dipole relative to the surface, while it is nearly horizontal when adsorbed on the hydrophilic OH-SAM. For charged SAM surfaces, HFBI adopts a nearly vertical electric dipole relative to the surface. HFBI has the narrowest orientation distribution on the CH3-SAM, and thus can form an ordered monolayer and reverse the wettability of the surface. For HFBI adsorption on charged SAMs, the adsorption strength weakens as the surface charge density increases. Compared with those on other SAMs, a larger area of the hydrophobic patch is exposed to the solution when HFBI adsorbs on the NH2-SAM. This leads to an increase of the hydrophobicity of the surface, which is consistent with the experimental results. The binding of HFBI to the CH3-SAM is mainly through hydrophobic interactions, while it is mediated through a hydration water layer near the surface for the OH-SAM. For the charged SAM surfaces, the adsorption is mainly induced by electrostatic interactions between the charged surfaces and the oppositely charged residues. The effect of a hydrophobic dipole on protein adsorption onto hydrophobic surfaces is similar to that of an electric dipole for charged surfaces. Therefore, the hydrophobic dipole may be applied to predict the probable orientations of protein adsorbed on hydrophobic surfaces.

Determination of Protein Surface Hydration by Systematic Charge Mutations

NASA Astrophysics Data System (ADS)

Yang, Jin; Jia, Menghui; Qin, Yangzhong; Wang, Dihao; Pan, Haifeng; Wang, Lijuan; Xu, Jianhua; Zhong, Dongping; Dongping Zhong Collaboration; Jianhua Xu Collaboration

Protein surface hydration is critical to its structural stability, flexibility, dynamics and function. Recent observations of surface solvation on picosecond time scales have evoked debate on the origin of such relatively slow motions, from hydration water or protein charged sidechains, especially with molecular dynamics simulations. Here, we used a unique nuclease with a single tryptophan as a local probe and systematically mutated neighboring three charged residues to differentiate the contributions from hydration water and charged sidechains. By mutations of alternative one and two and all three charged residues, we observed slight increases in the total tryptophan Stokes shifts with less neighboring charged residue(s) and found insensitivity of charged sidechains to the relaxation patterns. The dynamics is correlated with hydration water relaxation with the slowest time in a dense charged environment and the fastest time at a hydrophobic site. On such picosecond time scales, the protein surface motion is restricted. The total Stokes shifts are dominantly from hydration water relaxation and the slow dynamics is from water-driven relaxation, coupled with local protein fluctuations.

Phosphorus solubility of agricultural soils: a surface charge and phosphorus-31 NMR speciation study

USDA-ARS?s Scientific Manuscript database

We investigated ten soils from six states in United States to determine the relationship between potentiometric titration derived soil surface charge and Phosphorus-31 (P) nuclear magnetic resonance (NMR) speciation with the concentration of water-extractable P (WEP). The surface charge value at the...

Charge gradient microscopy

DOEpatents

Roelofs, Andreas; Hong, Seungbum

2018-02-06

A method for rapid imaging of a material specimen includes positioning a tip to contact the material specimen, and applying a force to a surface of the material specimen via the tip. In addition, the method includes moving the tip across the surface of the material specimen while removing electrical charge therefrom, generating a signal produced by contact between the tip and the surface, and detecting, based on the data, the removed electrical charge induced through the tip during movement of the tip across the surface. The method further includes measuring the detected electrical charge.

Variable Charge Soils: Mineralogy and Chemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qafoku, Nik; Van Ranst, Eric; Noble, Andrew

2003-11-01

Soils rich in particles with amphoteric surface properties in the Oxisols, Ultisols, Alfisols, Spodosols and Andisols orders (1) are considered variable charge soils (2). The term “variable charge” is used to describe organic and inorganic soil constituents with reactive surface groups whose charge varies with pH, ionic concentration and composition of the soil solution. Such groups are the surface carboxyl, phenolic and amino functional groups of organic materials in soils, and surface hydroxyl groups of Fe and Al oxides, allophane and imogolite. The hydroxyl surface groups are also present on edges of some phyllosilicate minerals such as kaolinite, mica, andmore » hydroxyl-interlayered vermiculite. The variable charge is developed on the surface groups as a result of adsorption or desorption of ions that are constituents of the solid phase, i.e., H+, and the adsorption or desorption of solid-unlike ions that are not constituents of the solid. Highly weathered soils usually undergo isoeletric weathering and reach a “zero net charge” stage during their development. They have a slightly acidic to acidic soil solution pH, which is close to either point of zero net charge (PZNC) (3) or point of zero salt effect (PZSE) (3). They are characterized by high abundances of minerals with a point of zero net proton charge (PZNPC) (3) at neutral and slightly basic pHs; the most important being Fe and Al oxides and allophane. Under acidic conditions, the surfaces of these minerals are net positively charged. In contrast, the surfaces of permanent charge phyllosilicates are negatively charged regardless of ambient conditions. Variable charge soils therefore, are heterogeneous charge systems. The coexistence and interactions of oppositely charged surfaces or particles confers a different pattern of physical and chemical behavior on the soil, relatively to a homogeneously charged system of temperate regions. In some variable charge soils (Oxisols and some Ultisols developed on ferromagnesian-rich parent materials) the surfaces of phyllosilicates are coated to a lesser or greater extent by amorphous or crystalline, oppositely charged nanoparticles of Fe and Al oxides. These coatings exhibit a high reactive surface area and help cementing larger particles with one another. As a result of these electrostatic interactions, stable microaggregates that are difficult to disperse are formed in variable charge soils. Most of highly weathered soils have reached the “advanced stage” of Jackson-Sherman weathering sequence that is characterized by the removal of Na, K, Ca, Mg, and Fe(II), the presence of Fe and Al polymers, and very dilute soil solutions with an ionic strength (IS) of less than 1 mmol L-1. The inter-penetration or overlapping of the diffuse double layers on oppositely charged surfaces may occur in these dilute systems. These diffuse layer interactions may affect the magnitude of the effective charge, i.e., the counter-ion charge (4). In addition, salt adsorption, which is defined as the simultaneous adsorption in equivalent amounts of the cation and anion of an electrolyte with no net release of other ions into the soil solution, appears to be a common phenomenon in these soils. They act as cation- and anion-exchangers and as salt-sorbers. The magnitude of salt adsorption depends strongly on initial IS in the soil solution and the presence in appreciable amounts of oppositely charged surfaces. Among the authors that have made illustrious contributions towards a better understanding of these fascinating soil systems are S. Matson, R.K. Schofield, van Olphen, M.E. Sumner, G.W. Thomas, G.P. Gillman, G. Uehara, B.K.G. Theng, K. Wada, N.J. Barrow, J.W. Bowden, R.J. Hunter and G. Sposito. This entry is mainly based on publications by these authors.« less

Effect of Surfaces on Amyloid Fibril Formation

PubMed Central

Moores, Bradley; Drolle, Elizabeth; Attwood, Simon J.; Simons, Janet; Leonenko, Zoya

2011-01-01

Using atomic force microscopy (AFM) we investigated the interaction of amyloid beta (Aβ) (1–42) peptide with chemically modified surfaces in order to better understand the mechanism of amyloid toxicity, which involves interaction of amyloid with cell membrane surfaces. We compared the structure and density of Aβ fibrils on positively and negatively charged as well as hydrophobic chemically-modified surfaces at physiologically relevant conditions. We report that due to the complex distribution of charge and hydrophobicity amyloid oligomers bind to all types of surfaces investigated (CH3, COOH, and NH2) although the charge and hydrophobicity of surfaces affected the structure and size of amyloid deposits as well as surface coverage. Hydrophobic surfaces promote formation of spherical amorphous clusters, while charged surfaces promote protofibril formation. We used the nonlinear Poisson-Boltzmann equation (PBE) approach to analyze the electrostatic interactions of amyloid monomers and oligomers with modified surfaces to complement our AFM data. PMID:22016789

Parallel tempering Monte Carlo simulations of lysozyme orientation on charged surfaces

NASA Astrophysics Data System (ADS)

Xie, Yun; Zhou, Jian; Jiang, Shaoyi

2010-02-01

In this work, the parallel tempering Monte Carlo (PTMC) algorithm is applied to accurately and efficiently identify the global-minimum-energy orientation of a protein adsorbed on a surface in a single simulation. When applying the PTMC method to simulate lysozyme orientation on charged surfaces, it is found that lysozyme could easily be adsorbed on negatively charged surfaces with "side-on" and "back-on" orientations. When driven by dominant electrostatic interactions, lysozyme tends to be adsorbed on negatively charged surfaces with the side-on orientation for which the active site of lysozyme faces sideways. The side-on orientation agrees well with the experimental results where the adsorbed orientation of lysozyme is determined by electrostatic interactions. As the contribution from van der Waals interactions gradually dominates, the back-on orientation becomes the preferred one. For this orientation, the active site of lysozyme faces outward, which conforms to the experimental results where the orientation of adsorbed lysozyme is co-determined by electrostatic interactions and van der Waals interactions. It is also found that despite of its net positive charge, lysozyme could be adsorbed on positively charged surfaces with both "end-on" and back-on orientations owing to the nonuniform charge distribution over lysozyme surface and the screening effect from ions in solution. The PTMC simulation method provides a way to determine the preferred orientation of proteins on surfaces for biosensor and biomaterial applications.

Effect of electrical polarization of hydroxyapatite ceramics on new bone formation.

PubMed

Itoh, S; Nakamura, S; Kobayashi, T; Shinomiya, K; Yamashita, K; Itoh, S

2006-03-01

Large surface charges can be induced on hydroxyapatite (HAp) ceramics by proton transport polarization, but this does not affect beta-tricalcium phosphate (TCP) because of its low polarizability. We wished to examine differences in osteogenic cell activity and new bone growth between positively or negatively surface-charged HAp and HAp/TCP plates using a calvarial bone defect model. In the first group of rats, test pieces were placed with their positively charged surfaces face down on the dura mater. In the second group, test pieces were placed with their negatively charged surfaces face down on the dura mater. A third group received noncharged test pieces. Histological examination, including enzymatic staining for osteoblasts and osteoclasts, was carried out. While no bone formation was observed at the pericranium, direct bone formation on the cranial bone debris and new bone growth expanded from the margins of the sites of injury to bridge across both the positively and negatively charged surfaces of HAp and HAp/TCP plates occurred. Electrical polarization of implanted plates, including positive charge, led to enhanced osteoblast activity, though decreased osteoclast activity was seen on the positively charged plate surface. Thus, polarization of HAp ceramics may modulate new bone formation and resorption.

PALS and SPM/EFM investigation of charged nanoporous electret films

NASA Astrophysics Data System (ADS)

Chiang, Dar-Ming; Liu, Wen-Liang; Chen, Jen-Luan; Susuki, Ryoichi

2005-08-01

The electret properties of nanoporous Teflon-FEP films, fabricated by the super-critical fluids method and charged by the corona method at room temperature, are investigated. PALS and SAXS are applied first to examine the charge characteristics of a free volume of electret materials. The topography and surface charges of electret materials are determined by scanning probe microscopy and electric field microscopy, respectively. The experimental results reveal that the interior surface areas of the pores of the electret materials influence the retention and stability of charge. Initial and aged surface charge was increased by factors of two and ten, with and without nanoporous Teflon-FEP films, respectively.

Solar Wind Access to Lunar Polar Craters: Feedback Between Surface Charging and Plasma Expansion

NASA Technical Reports Server (NTRS)

Zimmerman, M. I.; Farrell, W. M.; Stubbs, T. J.; Halekas, J. S.; Jackson, T. L.

2011-01-01

Determining the plasma environment within permanently shadowed lunar craters is critical to understanding local processes such as surface charging, electrostatic dust transport, volatile sequestration, and space weathering. In order to investigate the nature of this plasma environment, the first two-dimensional kinetic simulations of solar wind expansion into a lunar crater with a self-consistent plasma-surface interaction have been undertaken. The present results reveal how the plasma expansion into a crater couples with the electrically-charged lunar surface to produce a quasi-steady wake structure. In particular, there is a negative feedback between surface charging and ambipolar wake potential that allows an equilibrium to be achieved, with secondary electron emission strongly moderating the process. A range of secondary electron yields is explored, and two distinct limits are highlighted in which either surface charging or ambipoiar expansion is responsible for determining the overall wake structure.

Microelectrophoretic study of calcium oxalate monohydrate in macromolecular solutions

NASA Technical Reports Server (NTRS)

Curreri, P. A.; Onoda, G. Y., Jr.; Finlayson, B.

1987-01-01

Electrophoretic mobilities were measured for calcium oxalate monohydrate (COM) in solutions containing macromolecules. Two mucopolysaccharides (sodium heparin and chondroitin sulfate) and two proteins (positively charged lysozyme and negatively charged bovine serum albumin) were studied as adsorbates. The effects of pH, calcium oxalate surface charge (varied by calcium or oxalate ion activity), and citrate concentration were investigated. All four macromolecules showed evidence for adsorption. The macromolecule concentrations needed for reversing the surface charge indicated that the mucopolysaccharides have greater affinity for the COM surface than the proteins. Citrate ions at high concentrations appear to compete effectively with the negative protein for surface sites but show no evidence for competing with the positively charged protein.

Structural charge site influence on the interlayer hydration of expandable three-sheet clay minerals

USGS Publications Warehouse

Kerns, Raymond L.; Mankin, Charles J.

1968-01-01

Previous investigations have demonstrated the influences of interlayer cation composition, relative humidity, temperature, and magnitude of interlayer surface charge on the interlayer hydration of montmorillonites and vermiculites. It has been suggested that the sites of layer charge deficiencies may also have an influence upon the amount of hydration that can take place in the interlayers of expandable clay minerals. If the interlayer cation-to-layer bonds are considered as ideally electrostatic, the magnitude of the forces resisting expansion may be expressed as a form of Coulomb's law. If this effect is significant, expandable structures in which the charge-deficiency sites are predominantly in the tetrahedral sheet should have less pronounced swelling properties than should structures possessing charge deficiencies located primarily in the octahedral sheet.Three samples that differed in location of layer charge sites were selected for study. An important selection criterion was a non-correlation between tetrahedral charge sites and high surface-charge density, and between octahedral charge sites and low surface-charge density.The effects of differences in interlayer cation composition were eliminated by saturating portions of each sample with the same cations. Equilibrium (001) d values at controlled constant humidities were used as a measure of the relative degree of interlayer hydration.Although no correlation could be made between the degree of interlayer hydration and total surface-charge density, the investigation does not eliminate total surface-charge density as being significant to the swelling properties of three-sheet clay-mineral structures. The results do indicate a correlation between more intense expandability and predominance of charge deficiencies in the octahedral sheet. Conversely, less intense swelling behavior is associated with predominantly tetrahedral charge deficiencies.

The role of surface charge on the uptake and biocompatibility of hydroxyapatite nanoparticles with osteoblast cells

PubMed Central

Chen, Liang; Mccrate, Joseph M.; Lee, James C-M.; Li, Hao

2011-01-01

The objective of this study is to evaluate the effect of hydroxyapatite (HAP) nanoparticles with different surface charges on the cellular uptake behavior and in vitro cell viability and proliferation of MC3T3-E1 cell lines (osteoblast). The nanoparticles surface charge was varied by the surface modification with two carboxylic acids: 12-aminododecanoic acid (positive) and dodecanedioic acid (negative). The untreated HAP nanoparticles and dodecanoic acid modified HAP nanoparticles (neutral) were used as the control. X-ray diffraction (XRD) revealed that surface modifications by the three carboxylic acids did not change the crystal structure of HAP nanoparticles; Fourier transform infrared spectroscopy (FTIR) confirmed the adsorption and binding of the carboxylic acids on HAP nanoparticle surface; and zeta potential measurement confirmed that the chemicals successfully modified the surface charge of HAP nanoparticles in water based solution. Transmission electron microscopy (TEM) images showed that positively charged, negatively charged and untreated HAP nanoparticles, with similar size and shape, all penetrated into the cells and cells had more uptake of HAP nanoparticles with positive charge compared to those with negative charge, which might be attributed to the attractive or repulsive interaction between the negatively charged cell membrane and positively/negatively charged HAP nanoparticles. The neutral HAP nanoparticles could not penetrate cell membrane due to the larger size. MTT assay and LDH assay results indicated that as compared with the polystyrene control, greater cell viability and cell proliferation were measured on MC3T3-E1 cells treated with the three kinds of the HAP nanoparticles (neutral, positive, and untreated), among which positively charged HAP nanoparticles shows strongest improvement for cell viability and cell proliferation. In summary, the surface charge of HAP nanoparticles can be modified to influence the cellular uptake of HAP nanoparticles and the different uptake also influence the behavior of cells. These in-vitro results may also provide useful information for investigations of HAP nanoparticles applications in the gene delivery and intracellular drug delivery. PMID:21289408

Charge Retention by Monodisperse Gold Clusters on Surfaces Prepared Using Soft Landing of Mass Selected Ions

NASA Astrophysics Data System (ADS)

Johnson, Grant; Priest, Thomas; Laskin, Julia

2012-02-01

Monodisperse gold clusters have been prepared on surfaces in different charge states through soft landing of mass-selected ions. Gold clusters were synthesized in methanol solution by reduction of a gold precursor with a weak reducing agent in the presence of a diphosphine capping ligand. Electrospray ionization was used to introduce the clusters into the gas-phase and mass-selection was employed to isolate a single ionic cluster species which was delivered to surfaces at well controlled kinetic energies. Using in-situ time of flight secondary ion mass spectrometry (SIMS) it is demonstrated that the cluster retains its 3+ charge state when soft landed onto the surface of a fluorinated self assembled monolayer on gold. In contrast, when deposited onto carboxylic acid terminated and conventional alkyl thiol surfaces on gold the clusters exhibit larger relative abundances of the 2+ and 1+ charge states, respectively. The kinetics of charge reduction on the surface have been investigated using in-situ Fourier Transform Ion Cyclotron Resonance SIMS. It is shown that an extremely slow interfacial charge reduction occurs on the fluorinated monolayer surface while an almost instantaneous neutralization takes place on the surface of the alkyl thiol monolayer. Our results demonstrate that the size and charge state of small gold clusters on surfaces, both of which exert a dramatic influence on their chemical and physical properties, may be tuned through soft landing of mass-selected ions onto selected substrates.

A Spacecraft Charging Capability for SXTF.

DTIC Science & Technology

1979-01-17

surfaces can charge up. ’Iiiis differential charging of satellite surfaces can cause vacutum sparks , and dielectric breakdowns, and wi 11 effect the S...times required to reach steady charge state in the spacecraft internal dielectrics upon electron irradiation. In space , typical times (order of magni...WORDS (Continue on reverse side it necessary end Identify by block nunmber) Spacecraft charging Dielectric breakdown SGEMP Electron accelerators

Precise control of surface electrostatic forces on polymer brush layers with opposite charges for resistance to protein adsorption.

PubMed

Sakata, Sho; Inoue, Yuuki; Ishihara, Kazuhiko

2016-10-01

Various molecular interaction forces are generated during protein adsorption process on material surfaces. Thus, it is necessary to control them to suppress protein adsorption and the subsequent cell and tissue responses. A series of binary copolymer brush layers were prepared via surface-initiated atom transfer radical polymerization, by mixing the cationic monomer unit and anionic monomer unit randomly in various ratios. Surface characterization revealed that the constructed copolymer brush layers exhibited an uniform super-hydrophilic nature and different surface potentials. The strength of the electrostatic interaction forces operating on these mixed-charge copolymer brush surfaces was evaluated quantitatively using force-versus-distance (f-d) curve measurements by atomic force microscopy (AFM) and probes modified by negatively charged carboxyl groups or positively charged amino groups. The electrostatic interaction forces were determined based on the charge ratios of the copolymer brush layers. Notably, the surface containing equivalent cationic/anionic monomer units hardly interacted with both the charged groups. Furthermore, the protein adsorption force and the protein adsorption mass on these surfaces were examined by AFM f-d curve measurement and surface plasmon resonance measurement, respectively. To clarify the influence of the electrostatic interaction on the protein adsorption behavior on the surface, three kinds of proteins having negative, positive, and relatively neutral net charges under physiological conditions were used in this study. We quantitatively demonstrated that the amount of adsorbed proteins on the surfaces would have a strong correlation with the strength of surface-protein interaction forces, and that the strength of surface-protein interaction forces would be determined from the combination between the properties of the electrostatic interaction forces on the surfaces and the charge properties of the proteins. Especially, the copolymer brush surface composed of equivalent cationic/anionic monomer units exhibited no significant interaction forces, and dramatically suppressed the adsorption of proteins regardless of their charge properties. We conclude that the established methodology could elucidate relationship between the protein adsorption behavior and molecular interaction, especially the electrostatic interaction forces, and demonstrated that the suppression of the electrostatic interactions with the ionic functional groups would be important for the development of new polymeric biomaterials with a high repellency of protein adsorption. Copyright © 2016 Elsevier Ltd. All rights reserved.

The role of interfacial water layer in atmospherically relevant charge separation

NASA Astrophysics Data System (ADS)

Bhattacharyya, Indrani

Charge separation at interfaces is important in various atmospheric processes, such as thunderstorms, lightning, and sand storms. It also plays a key role in several industrial processes, including ink-jet printing and electrostatic separation. Surprisingly, little is known about the underlying physics of these charging phenomena. Since thin films of water are ubiquitous, they may play a role in these charge separation processes. This talk will focus on the experimental investigation of the role of a water adlayer in interfacial charging, with relevance to meteorologically important phenomena, such as atmospheric charging due to wave actions on oceans and sand storms. An ocean wave generates thousands of bubbles, which upon bursting produce numerous large jet droplets and small film droplets that are charged. In the 1960s, Blanchard showed that the jet droplets are positively charged. However, the charge on the film droplets was not known. We designed an experiment to exclusively measure the charge on film droplets generated by bubble bursting on pure water and aqueous salt solution surfaces. We measured their charge to be negative and proposed a model where a slight excess of hydroxide ions in the interfacial water layer is responsible for generating these negatively charged droplets. The findings from this research led to a better understanding of the ionic disposition at the air-water interface. Sand particles in a wind-blown sand layer, or 'saltation' layer, become charged due to collisions, so much so, that it can cause lightning. Silica, being hydrophilic, is coated with a water layer even under low-humidity conditions. To investigate the importance of this water adlayer in charging the silica surfaces, we performed experiments to measure the charge on silica surfaces due to contact and collision processes. In case of contact charging, the maximum charge separation occurred at an optimum relative humidity. On the contrary, in collisional charging process, no humidity effect was observed. We proposed an ion transfer mechanism in case of contact charging. However, an electron transfer mechanism explained the collisional charging process. The effects of temperature, surface roughness, and chemical nature of surface were also studied for both contact and collisional charging processes.

Polyelectrolytes tethered to a free surface

NASA Astrophysics Data System (ADS)

Dubreuil, F.; Guenoun, P.

Several attempts have been already carried out in order to tether charged chains by an end at a free fluctuating surface. We review here most of these attempts and focus on how close the physics of charged brushes can be investigated by such an approach. We first describe results about films of charged-neutral diblock copolymers spread at the surface of water. Results can be mostly rationalized in terms of charged brushes although additional structurations and fluctuations of the interface can be observed. The latter deformations are also observed when adsorbed layers of charged-neutral diblock copolymers are considered. At last, we examine how free suspended films of charged-neutral diblock copolymers can be viewed as two opposing charged brushes, both in terms of thickness and pressure.

Depletion region surface effects in electron beam induced current measurements.

PubMed

Haney, Paul M; Yoon, Heayoung P; Gaury, Benoit; Zhitenev, Nikolai B

2016-09-07

Electron beam induced current (EBIC) is a powerful characterization technique which offers the high spatial resolution needed to study polycrystalline solar cells. Current models of EBIC assume that excitations in the p - n junction depletion region result in perfect charge collection efficiency. However we find that in CdTe and Si samples prepared by focused ion beam (FIB) milling, there is a reduced and nonuniform EBIC lineshape for excitations in the depletion region. Motivated by this, we present a model of the EBIC response for excitations in the depletion region which includes the effects of surface recombination from both charge-neutral and charged surfaces. For neutral surfaces we present a simple analytical formula which describes the numerical data well, while the charged surface response depends qualitatively on the location of the surface Fermi level relative to the bulk Fermi level. We find the experimental data on FIB-prepared Si solar cells is most consistent with a charged surface, and discuss the implications for EBIC experiments on polycrystalline materials.

Significance of surface charge and shell material of superparamagnetic iron oxide nanoparticle (SPION) based core/shell nanoparticles on the composition of the protein corona.

PubMed

Sakulkhu, Usawadee; Mahmoudi, Morteza; Maurizi, Lionel; Coullerez, Geraldine; Hofmann-Amtenbrink, Margarethe; Vries, Marcel; Motazacker, Mahdi; Rezaee, Farhad; Hofmann, Heinrich

2015-02-01

As nanoparticles (NPs) are increasingly used in many applications their safety and efficient applications in nanomedicine have become concerns. Protein coronas on nanomaterials' surfaces can influence how the cell "recognizes" nanoparticles, as well as the in vitro and in vivo NPs' behaviors. The SuperParamagnetic Iron Oxide Nanoparticle (SPION) is one of the most prominent agents because of its superparamagnetic properties, which is useful for separation applications. To mimic surface properties of different types of NPs, a core-shell SPION library was prepared by coating with different surfaces: polyvinyl alcohol polymer (PVA) (positive, neutral and negative), SiO2 (positive and negative), titanium dioxide and metal gold. The SPIONs with different surfaces were incubated at a fixed serum : nanoparticle surface ratio, magnetically trapped and washed. The tightly bound proteins were quantified and identified. The surface charge has a great impact on protein adsorption, especially on PVA and silica where proteins preferred binding to the neutral and positively charged surfaces. The importance of surface material on protein adsorption was also revealed by preferential binding on TiO2 and gold coated SPION, even negatively charged. There is no correlation between the protein net charge and the nanoparticle surface charge on protein binding, nor direct correlation between the serum proteins' concentration and the proteins detected in the coronas.

Determination of the surface charge density and temperature dependence of purple membrane by electric force microscopy.

PubMed

Du, Huiwen; Li, Denghua; Wang, Yibing; Wang, Chenxuan; Zhang, Dongdong; Yang, Yan-lian; Wang, Chen

2013-08-29

We report here the measurement of the temperature-dependent surface charge density of purple membrane (PM) by using electrostatic force microscopy (EFM). The surface charge density was measured to be 3.4 × 10(5) e/cm(2) at room temperature and reaches the minimum at around 52 °C. The initial decrease of the surface charge density could be attributed to the reduced dipole alignment because of the thermally induced protein mobility in PM. The increase of charge density at higher temperature could be ascribed to the weakened interaction between proteins and the lipids, which leads to the exposure of the charged amino acids. This work could be a benefit to the direct assessment of the structural stability and electric properties of biological membranes at the nanoscale.

Surface-Charge-Based Micro-Models--A Solid Foundation for Learning about Direct Current Circuits

ERIC Educational Resources Information Center

Hirvonen, P. E.

2007-01-01

This study explores how the use of a surface-charge-based instructional approach affects introductory university level students' understanding of direct current (dc) circuits. The introduced teaching intervention includes electrostatics, surface-charge-based micro-models that explain the existence of an electric field inside the current-carrying…

Modulating interactions between ligand-coated nanoparticles and phase-separated lipid bilayers by varying the ligand density and the surface charge.

PubMed

Chen, Xiaojie; Tieleman, D Peter; Liang, Qing

2018-02-01

The interactions between nanoparticles and lipid bilayers are critical in applications of nanoparticles in nanomedicine, cell imaging, toxicology, and elsewhere. Here, we investigate the interactions between nanoparticles coated with neutral and/or charged ligands and phase-separated lipid bilayers using coarse-grained molecular dynamics simulation. Both penetration and adsorption processes as well as the final distribution of the nanoparticles can be readily modulated by varying the ligand density and the surface charge of the nanoparticles. Completely hydrophobic (neutral) nanoparticles with larger size initially preferentially penetrate into the liquid-disordered region of the lipid bilayer and finally transfer into the liquid-ordered region; partially hydrophilic nanoparticles with low or moderate surface charge tend to either distribute in the liquid-disordered region or be adsorbed on the surface of the lipid bilayer, while strongly hydrophilic nanoparticles with high surface charge always reside on the surface of the lipid bilayer. Interactions of the nanoparticles with the lipid bilayers are affected by the surface charge of nanoparticles, hydrophobic mismatch, bending of the ligands, and the packing state of the lipids. Insight in these factors can be used to improve the efficiency of designing nanoparticles for specific applications.

Modulation of Silica Nanoparticle Uptake into Human Osteoblast Cells by Variation of the Ratio of Amino and Sulfonate Surface Groups: Effects of Serum

PubMed Central

2015-01-01

To study the importance of the surface charge for cellular uptake of silica nanoparticles (NPs), we synthesized five different single- or multifunctionalized fluorescent silica NPs (FFSNPs) by introducing various ratios of amino and sulfonate groups into their surface. The zeta potential values of these FFSNPs were customized from highly positive to highly negative, while other physicochemical properties remained almost constant. Irrespective of the original surface charge, serum proteins adsorbed onto the surface, neutralized the zeta potential values, and prevented the aggregation of the tailor-made FFSNPs. Depending on the surface charge and on the absence or presence of serum, two opposite trends were found concerning the cellular uptake of FFSNPs. In the absence of serum, positively charged NPs were more strongly accumulated by human osteoblast (HOB) cells than negatively charged NPs. In contrast, in serum-containing medium, anionic FFSNPs were internalized by HOB cells more strongly, despite the similar size and surface charge of all types of protein-covered FFSNPs. Thus, at physiological condition, when the presence of proteins is inevitable, sulfonate-functionalized silica NPs are the favorite choice to achieve a desired high rate of NP internalization. PMID:26030456

Increasing binding density of yeast cells by control of surface charge with allylamine grafting to ion modified polymer surfaces.

PubMed

Tran, Clara T H; Kondyurin, Alexey; Chrzanowski, Wojciech; Bilek, Marcela M M; McKenzie, David R

2014-10-01

Plasma immersion ion implantation (PIII) treatment of polymers creates a biointerface capable of direct covalent immobilization of biomolecules. The immobilization of protein molecules is achieved by covalent bonds formed between embedded radicals on the treated surface and amino acid side chains and cells can be immobilized through cell-wall proteins. The attachment density of negatively charged entities on a PIII treated surface is inhibited by its negative surface charge at neutral pH. To reduce the negative charge of PIII treated surfaces in phosphate buffer (pH 7.4, 11mM), we develop an effective approach of grafting allylamine monomers onto the treated surface. The results reveal reactions between allylamine and radicals on the PIII treated surface. One of these triggers polymerization, increasing the number of amine groups grafted. As a consequence, the PIII treated polystyrene surface after allylamine exposure becomes more hydrophobic and less negatively charged in phosphate buffer. Using yeast cells as an example, we have shown a significant improvement (6-15 times) of cell density immobilized on the PIII treated surface after exposure to allylamine. Copyright © 2014 Elsevier B.V. All rights reserved.

Numerical modelling of needle-grid electrodes for negative surface corona charging system

NASA Astrophysics Data System (ADS)

Zhuang, Y.; Chen, G.; Rotaru, M.

2011-08-01

Surface potential decay measurement is a simple and low cost tool to examine electrical properties of insulation materials. During the corona charging stage, a needle-grid electrodes system is often used to achieve uniform charge distribution on the surface of the sample. In this paper, a model using COMSOL Multiphysics has been developed to simulate the gas discharge. A well-known hydrodynamic drift-diffusion model was used. The model consists of a set of continuity equations accounting for the movement, generation and loss of charge carriers (electrons, positive and negative ions) coupled with Poisson's equation to take into account the effect of space and surface charges on the electric field. Four models with the grid electrode in different positions and several mesh sizes are compared with a model that only has the needle electrode. The results for impulse current and surface charge density on the sample clearly show the effect of the extra grid electrode with various positions.

Protein interactions with layers of TiO2 nanotube and nanopore arrays: Morphology and surface charge influence.

PubMed

Kulkarni, Mukta; Mazare, Anca; Park, Jung; Gongadze, Ekaterina; Killian, Manuela Sonja; Kralj, Slavko; von der Mark, Klaus; Iglič, Aleš; Schmuki, Patrik

2016-11-01

In the present work we investigate the key factors involved in the interaction of small-sized charged proteins with TiO 2 nanostructures, i.e. albumin (negatively charged), histone (positively charged). We examine anodic nanotubes with specific morphology (simultaneous control over diameter and length, e.g. diameter - 15, 50 or 100nm, length - 250nm up to 10μm) and nanopores. The nanostructures surface area has a direct influence on the amount of bound protein, nonetheless the protein physical properties as electric charge and size (in relation to nanotopography and biomaterial's electric charge) are crucial too. The highest quantity of adsorbed protein is registered for histone, for 100nm diameter nanotubes (10μm length) while higher values are registered for 15nm diameter nanotubes when normalizing protein adsorption to nanostructures' surface unit area (evaluated from dye desorption measurements) - consistent with theoretical considerations. The proteins presence on the nanostructures is evaluated by XPS and ToF-SIMS; additionally, we qualitatively assess their presence along the nanostructures length by ToF-SIMS depth profiles, with decreasing concentration towards the bottom. Surface nanostructuring of titanium biomedical devices with TiO 2 nanotubes was shown to significantly influence the adhesion, proliferation and differentiation of mesenchymal stem cells (and other cells too). A high level of control over the nanoscale topography and over the surface area of such 1D nanostructures enables a direct influence on protein adhesion. Herein, we investigate and show how the nanostructure morphology (nanotube diameter and length) influences the interactions with small-sized charged proteins, using as model proteins bovine serum albumin (negatively charged) and histone (positively charged). We show that the protein charge strongly influences their adhesion to the TiO 2 nanostructures. Protein adhesion is quantified by ELISA measurements and determination of the nanostructures' total surface area. We use a quantitative surface charge model to describe charge interactions and obtain an increased magnitude of the surface charge density at the top edges of the nanotubes. In addition, we track the proteins presence on and inside the nanostructures. We believe that these aspects are crucial for applications where the incorporation of active molecules such as proteins, drugs, growth factors, etc., into nanotubes is desired. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Surface transport processes in charged porous media

DOE PAGES

Gabitto, Jorge; Tsouris, Costas

2017-03-03

Surface transport processes are important in chemistry, colloidal sciences, engineering, biology, and geophysics. Natural or externally produced charges on surfaces create electrical double layers (EDLs) at the solid-liquid interface. The existence of the EDLs produces several complex processes including bulk and surface transport of ions. In this work, a model is presented to simulate bulk and transport processes in homogeneous porous media comprising big pores. It is based on a theory for capacitive charging by ideally polarizable porous electrodes without Faradaic reactions or specific adsorption of ions. A volume averaging technique is used to derive the averaged transport equations inmore » the limit of thin electrical double layers. Description of the EDL between the electrolyte solution and the charged wall is accomplished using the Gouy-Chapman-Stern (GCS) model. The surface transport terms enter into the average equations due to the use of boundary conditions for diffuse interfaces. Two extra surface transports terms appear in the closed average equations. One is a surface diffusion term equivalent to the transport process in non-charged porous media. The second surface transport term is a migration term unique to charged porous media. The effective bulk and transport parameters for isotropic porous media are calculated solving the corresponding closure problems.« less

Dust Grain Charge above the Lunar terminator

NASA Astrophysics Data System (ADS)

Vaverka, Jakub; Richterova, Ivana; Nemecek, Zdenek; Safrankova, Jana; Pavlu, Jiri; Vysinka, Marek

Interaction of a lunar surface with the solar wind and magnetosphere leads to its charging by several processes as photoemission, a collection of primary particles, and secondary electron emission. Nevertheless, charging of the lunar surface is complicated by a shielding of solar light and solar wind ions by hills, craters, and boulders that can locally influence the surface potential. Moreover, a presence of a plasma wake can strongly affect this potential at the night side of the Moon. A typical surface potential varies from slightly positive (dayside) to negative values of the order of several hundred volts (night side). An electric field above the charged surface can lead to a levitation of dust grains as it has been observed by several spacecraft and by astronauts during Apollo missions. Although charging and transport of dust grains above the lunar surface are in the center of interest for many years, these phenomena are not still completely understood. We present calculation of an equilibrium potential of dust grains above the lunar surface. We focus on a terminator area during the Earth’s plasma sheet crossing. We use the secondary electron emission model for dust grains which takes into account an influence of the grain size, material, and surface roughness and findings from laboratory experiments with charging of lunar dust simulants by an electron beam.

Surface transport processes in charged porous media

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gabitto, Jorge; Tsouris, Costas

Surface transport processes are important in chemistry, colloidal sciences, engineering, biology, and geophysics. Natural or externally produced charges on surfaces create electrical double layers (EDLs) at the solid-liquid interface. The existence of the EDLs produces several complex processes including bulk and surface transport of ions. In this work, a model is presented to simulate bulk and transport processes in homogeneous porous media comprising big pores. It is based on a theory for capacitive charging by ideally polarizable porous electrodes without Faradaic reactions or specific adsorption of ions. A volume averaging technique is used to derive the averaged transport equations inmore » the limit of thin electrical double layers. Description of the EDL between the electrolyte solution and the charged wall is accomplished using the Gouy-Chapman-Stern (GCS) model. The surface transport terms enter into the average equations due to the use of boundary conditions for diffuse interfaces. Two extra surface transports terms appear in the closed average equations. One is a surface diffusion term equivalent to the transport process in non-charged porous media. The second surface transport term is a migration term unique to charged porous media. The effective bulk and transport parameters for isotropic porous media are calculated solving the corresponding closure problems.« less

Profiling Charge Complementarity and Selectivity for Binding at the Protein Surface

PubMed Central

Sulea, Traian; Purisima, Enrico O.

2003-01-01

A novel analysis and representation of the protein surface in terms of electrostatic binding complementarity and selectivity is presented. The charge optimization methodology is applied in a probe-based approach that simulates the binding process to the target protein. The molecular surface is color coded according to calculated optimal charge or according to charge selectivity, i.e., the binding cost of deviating from the optimal charge. The optimal charge profile depends on both the protein shape and charge distribution whereas the charge selectivity profile depends only on protein shape. High selectivity is concentrated in well-shaped concave pockets, whereas solvent-exposed convex regions are not charge selective. This suggests the synergy of charge and shape selectivity hot spots toward molecular selection and recognition, as well as the asymmetry of charge selectivity at the binding interface of biomolecular systems. The charge complementarity and selectivity profiles map relevant electrostatic properties in a readily interpretable way and encode information that is quite different from that visualized in the standard electrostatic potential map of unbound proteins. PMID:12719221

Deionization and desalination using electrostatic ion pumping

DOEpatents

Bourcier, William L.; Aines, Roger D.; Haslam, Jeffery J.; Schaldach, Charlene M.; O& #x27; Brien, Kevin C.; Cussler, Edward

2013-06-11

The present invention provides a new method and apparatus/system for purifying ionic solutions, such as, for example, desalinating water, using engineered charged surfaces to sorb ions from such solutions. Surface charge is applied externally, and is synchronized with oscillatory fluid movements between substantially parallel charged plates. Ions are held in place during fluid movement in one direction (because they are held in the electrical double layer), and released for transport during fluid movement in the opposite direction by removing the applied electric field. In this way the ions, such as salt, are "ratcheted" across the charged surface from the feed side to the concentrate side. The process itself is very simple and involves only pumps, charged surfaces, and manifolds for fluid collection.

Deionization and desalination using electrostatic ion pumping

DOEpatents

Bourcier, William L [Livermore, CA; Aines, Roger D [Livermore, CA; Haslam, Jeffery J [Livermore, CA; Schaldach, Charlene M [Pleasanton, CA; O'Brien, Kevin C [San Ramon, CA; Cussler, Edward [Edina, MN

2011-07-19

The present invention provides a new method and apparatus/system for purifying ionic solutions, such as, for example, desalinating water, using engineered charged surfaces to sorb ions from such solutions. Surface charge is applied externally, and is synchronized with oscillatory fluid movements between substantially parallel charged plates. Ions are held in place during fluid movement in one direction (because they are held in the electrical double layer), and released for transport during fluid movement in the opposite direction by removing the applied electric field. In this way the ions, such as salt, are "ratcheted" across the charged surface from the feed side to the concentrate side. The process itself is very simple and involves only pumps, charged surfaces, and manifolds for fluid collection.

A switchable polymer layer: Chain folding in end-charged polymer brushes

NASA Astrophysics Data System (ADS)

Heine, David; Wu, David T.

2001-03-01

We use a self-consistent field approximation to model the configurations of end-charged homopolymer and block copolymer brushes in response to an external electric field due to charges on the grafting surface. By varying the charge density on the grafting surface, we can cause the chains either to extend outward, greatly increasing the brush height, or to loop back to the grafting surface. We show that such a copolymer brush can present one block at the exposed surface in the extended state and present the other block in the retracted state. This occurs for both a solvated brush and a dry brush. We also compare these results to those of a modified Alexander-de Gennes model for the end-charged homopolymer brush.

Complexation of ferric oxide particles with pectins of different charge density.

PubMed

Milkova, Viktoria; Kamburova, Kamelia; Petkanchin, Ivana; Radeva, Tsetska

2008-09-02

The effect of polyelectrolyte charge density on the electrical properties and stability of suspensions of oppositely charged oxide particles is followed by means of electro-optics and electrophoresis. Variations in the electro-optical effect and the electrophoretic mobility are examined at conditions where fully ionized pectins of different charge density adsorb onto particles with ionizable surfaces. The charge neutralization point coincides with the maximum of particle aggregation in all suspensions. We find that the concentration of polyelectrolyte, needed to neutralize the particle charge, decreases with increasing charge density of the pectin. The most highly charged pectin presents an exception to this order, which is explained with a reduction of the effective charge density of this pectin due to condensation of counterions. The presence of condensed counterions, remaining bound to the pectin during its adsorption on the particle surface, is proved by investigation of the frequency behavior of the electro-optical effect at charge reversal of the particle surface.

Photodynamic Molecular Beacons: An Image-Guided Therapeutic Approach to Breast Cancer Vertebral Metastases

DTIC Science & Technology

2011-03-01

pyropheophorbide carboxylic acid succinimidyl ester (Pyro- NHS) was prepared according to a published procedure (18). Other chemicals were obtained from Aldrich...2) a polycation and a polyanion attached to each end of the linker, forming a “zipper” structure via electrostatic attraction, (3) pyropheophorbide as...is achievable by simply switching D to a fluorescent photosensitizer, such as pyropheophorbide . The ZMBs will then possess novel targeting

Hyaluronan Tumor Cell Interactions in Prostate Cancer Growth and Survival

DTIC Science & Technology

2009-12-01

is a high molecular weight polyanionic polysaccharide that is increased in more advanced prostate cancers. Tumor cell interaction with this... polysaccharide by specific receptors CD44 and RHAMM promote tumor growth, survival and invasion. Work during the last funding period have further defined the... polysaccharide to its cognate receptors. These peptides inhibit tumor growth both in vitro and in vivo and the residues important for the activity

A fluorophosphate-based inverse Keggin structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fielden, John; Quasdorf, Kyle; Cronin, Leroy

An unusual PFO(3)(2-)-templated "inverse Keggin" polyanion, [Mo(12)O(46)(PF)(4)](4-), has been isolated from the degradation reaction of an {Mo(132)}-type Keplerate to [PMo(12)O(40)](3-) by [Cu(MeCN)(4)](PF(6)) in acetonitrile. (31)P-NMR studies suggest a structure-directing role for [Cu(MeCN)(4)](+) in the formation of the highly unusual all-inorganic inverse Keggin structure.

A fluorophosphate-based inverse Keggin structure.

PubMed

Fielden, John; Quasdorf, Kyle; Cronin, Leroy; Kögerler, Paul

2012-09-07

An unusual PFO(3)(2-)-templated "inverse Keggin" polyanion, [Mo(12)O(46)(PF)(4)](4-), has been isolated from the degradation reaction of an {Mo(132)}-type Keplerate to [PMo(12)O(40)](3-) by [Cu(MeCN)(4)](PF(6)) in acetonitrile. (31)P-NMR studies suggest a structure-directing role for [Cu(MeCN)(4)](+) in the formation of the highly unusual all-inorganic inverse Keggin structure.

Corrigendum to "The effect of gradient boracic polyanion-doping on structure, morphology, and cycling performance of Ni-rich LiNi0.8Co0.15Al0.05O2 cathode material" [J. Power Sources 374 (2018) 1-11

NASA Astrophysics Data System (ADS)

Chen, Tao; Li, Xiang; Wang, Hao; Yan, Xinxiu; Wang, Lei; Deng, Bangwei; Ge, Wujie; Qu, Meizhen

2018-07-01

The authors regret that the author's second address was incorrect. It has been amended from 'Graduate university of Chinese Academy of Sciences, Beijing 100039, PR China' to 'University of Chinese Academy of Sciences, Beijing 100049, PR China'.

Intracrystalline site preference of hydrogen isotopes in borax

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pradhananga, T.M.; Matsuo, S.

1985-01-03

The total hydrogen involved in borax synthesized at 25/sup 0/C in aqueous solution is enriched in deuterium by 5.3% compared with the mother liquor. There is no change in the value of the D/H fractionation factor between the hydrogen in borax and those in the mother liquor with changes in the degree of supersaturation. The fractionation factor changes slightly with a change in the crystallization temperature of borax in the range from 5 to 25/sup 0/C. The D/H ratio in the different sites of borax was estimated by a fractional dehydration technique. The results show that hydrogen atoms of themore » polyanionic group (B/sub 4/O/sub 5/(OH)/sub 4/) are much more enriched in deuterium than those of the cationic group (Na/sub 2/ x 8H/sub 2/O). The delta D values, referred to the mother liquor from which the borax was crystallized, for the cationic group (site A) and the polyanionic group (site B) are -35 +/- 3 and 167 +/- 13%, respectively based on the fractional dehydration results obtained at -21/sup 0/C. At -21/sup 0/C, isotopic exchange between different sites during dehydration is assumed not to occur. The mechanism for dehydration of borax is discussed. 48 references, 8 figures, 3 tables.« less

In Situ Tracking Kinetic Pathways of Li+/Na+ Substitution during Ion-Exchange Synthesis of LixNa1.5-xVOPO4F0.5.

PubMed

Park, Young-Uk; Bai, Jianming; Wang, Liping; Yoon, Gabin; Zhang, Wei; Kim, Hyungsub; Lee, Seongsu; Kim, Sung-Wook; Looney, J Patrick; Kang, Kisuk; Wang, Feng

2017-09-13

Ion exchange is a ubiquitous phenomenon central to wide industrial applications, ranging from traditional (bio)chemical separation to the emerging chimie douce synthesis of materials with metastable structure for batteries and other energy applications. The exchange process is complex, involving substitution and transport of different ions under non-equilibrium conditions, and thus difficult to probe, leaving a gap in mechanistic understanding of kinetic exchange pathways toward final products. Herein, we report in situ tracking kinetic pathways of Li + /Na + substitution during solvothermal ion-exchange synthesis of Li x Na 1.5-x VOPO 4 F 0.5 (0 ≤ x ≤ 1.5), a promising multi-Li polyanionic cathode for batteries. The real-time observation, corroborated by first-principles calculations, reveals a selective replacement of Na + by Li + , leading to peculiar Na + /Li + /vacancy orderings in the intermediates. Contradicting the traditional belief of facile topotactic substitution via solid solution reaction, an abrupt two-phase transformation occurs and predominantly governs the kinetics of ion exchange and transport in the 1D polyanionic framework, consequently leading to significant difference of Li stoichiometry and electrochemical properties in the exchanged products. The findings may help to pave the way for rational design of ion exchange synthesis for making new materials.

Kinetics of optically excited charge carriers at the GaN surface: Influence of catalytic Pt nanostructures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Winnerl, Andrea, E-mail: andrea.winnerl@wsi.tum.de; Pereira, Rui N.; Stutzmann, Martin

2015-10-21

In this work, we use GaN with different deposited Pt nanostructures as a controllable model system to investigate the kinetics of photo-generated charge carriers in hybrid photocatalysts. We combine conductance and contact potential difference measurements to investigate the influence of Pt on the processes involved in the capture and decay of photo-generated charge carriers at and close to the GaN surface. We found that in the presence of Pt nanostructures the photo-excitation processes are similar to those found in Pt free GaN. However, in GaN with Pt nanostructures, photo-generated holes are preferentially trapped in surface states of the GaN coveredmore » with Pt and/or in electronic states of the Pt and lead to an accumulation of positive charge there, whereas negative charge is accumulated in localized states in a shallow defect band of the GaN covered with Pt. This preferential accumulation of photo-generated electrons close to the surface is responsible for a dramatic acceleration of the turn-off charge transfer kinetics and a stronger dependence of the surface photovoltage on light intensity when compared to a Pt free GaN surface. Our study shows that in hybrid photocatalysts, the metal nanostructures induce a spatially inhomogeneous surface band bending of the semiconductor that promotes a lateral drift of photogenerated charges towards the catalytic nanostructures.« less

Mediating electrostatic binding of 1-butyl-3-methylimidazolium chloride to enzyme surfaces improves conformational stability.

PubMed

Nordwald, Erik M; Kaar, Joel L

2013-08-01

We have recently developed a general approach to improve the utility of enzymes in ionic liquids (ILs) via tuning of the ratio of enzyme-containing positive to negative surface charges. In this work, the impact of enzyme surface charge ratio on the biophysical interaction of 1-butyl-3-methylimidazolium chloride ([BMIM][Cl]) with chymotrypsin and lipase was investigated to understand this approach at the molecular level. Results of fluorescence quenching assays indicated that the extent of binding of the [BMIM] cation decreased (7- and 3.5-fold for chymotrypsin and lipase, respectively) as a function of increasing ratio of positive to negative surface charges. Conformational stability assays further showed a close correlation between thermodynamic stabilization and enzyme surface charge ratio as well as [BMIM] binding. As evidence of this correlation, succinylation and acetylation resulted in the stabilization of chymotrypsin in 10% (v/v) [BMIM][Cl] by 17.0 and 6.6 kJ/mol, respectively, while cationization destabilized chymotrypsin by 3.6 kJ/mol. Combined, these results indicate that altering the surface charge ratio mediates the organization of IL molecules, namely, [BMIM] and [Cl], around the enzymes. Preferential exclusion of [Cl], in particular, via lowering of the ratio of positive to negative surface charges, correlated with increased enzyme stability. Accordingly, these results more broadly provide insight into the mechanism of stabilization in ILs via charge modification.

Effect of Atomic Oxygen Exposure on Surface Resistivity Change of Spacecraft Insulator Material

NASA Astrophysics Data System (ADS)

Mundari, Noor Danish Ahrar; Khan, Arifur Rahman; Chiga, Masaru; Okumura, Teppei; Masui, Hirokazu; Iwata, Minoru; Toyoda, Kazuhiro; Cho, Mengu

Spacecraft surface charging can lead to arcing and a loss of electricity generation capability in solar panels or even loss of a satellite. The charging problem may be further aggravated by atomic oxygen (AO) exposure in Low Earth orbits, which modifies the surface of materials like polyimide, Teflon, anti-reflective coatings, cover glass etc, used on satellite surfaces, affecting materials properties, such as resistivity, secondary electron emissivity and photo emission, which govern the charging behavior. These properties are crucial input parameters for spacecraft charging analysis. To study the AO exposure effect on charging governing properties, an atomic oxygen exposure facility based on laser detonation of oxygen was built. The facility produces AO with a peak velocity value around 10-12km/s and a higher flux than that existing in orbit. After exposing the polyimide test material to the equivalent of 10 years of AO fluence at an altitude of 700-800 km, surface charging properties like surface resistivity and volume resistivity were measured. The measurement was performed in a vacuum using the charge storage decay method at room temperature, which is considered the most appropriate for measuring resistivity for space applications. The results show that the surface resistivity increases and the volume resistivity remains almost the same for the AO exposure fluence of 5.4×1018 atoms cm-2.

Surface charge sensing by altering the phase transition in VO2

NASA Astrophysics Data System (ADS)

Kumar, S.; Esfandyarpour, R.; Davis, R.; Nishi, Y.

2014-08-01

Detection of surface charges has various applications in medicine, electronics, biotechnology, etc. The source of surface charge induction may range from simple charge-polarized molecules like water to complicated proteins. It was recently discovered that surface charge accumulation can alter the temperature at which VO2 undergoes a Mott transition. Here, we deposited polar molecules onto the surface of two-terminal thin-film VO2 lateral devices and monitored the joule-heating-driven Mott transition, or conductance switching. We observed that the power required to induce the conductance switching reduced upon treatment with polar molecules and, using in-situ blackbody-emission direct measurement of local temperature, we show that this reduction in power was accompanied by reduction in the Mott transition temperature. Further evidence suggested that this effect has specificity to the nature of the species used to induce surface charges. Using x-ray absorption spectroscopy, we also show that there is no detectable change in oxidation state of vanadium or structural phase in the bulk of the 40 nm VO2 thin-film even as the phase transition temperature is reduced by up to 20 K by the polar molecules. The ability to alter the phase transition parameters by depositing polar molecules suggests a potential application in sensing surface charges of different origins and this set of results also highlights interesting aspects of the phase transition in VO2.

Atomistic Molecular Dynamics Simulations of Charged Latex Particle Surfaces in Aqueous Solution.

PubMed

Li, Zifeng; Van Dyk, Antony K; Fitzwater, Susan J; Fichthorn, Kristen A; Milner, Scott T

2016-01-19

Charged particles in aqueous suspension form an electrical double layer at their surfaces, which plays a key role in suspension properties. For example, binder particles in latex paint remain suspended in the can because of repulsive forces between overlapping double layers. Existing models of the double layer assume sharp interfaces bearing fixed uniform charge, and so cannot describe aqueous binder particle surfaces, which are soft and diffuse, and bear mobile charge from ionic surfactants as well as grafted multivalent oligomers. To treat this industrially important system, we use atomistic molecular dynamics simulations to investigate a structurally realistic model of commercial binder particle surfaces, informed by extensive characterization of particle synthesis and surface properties. We determine the interfacial profiles of polymer, water, bound and free ions, from which the charge density and electrostatic potential can be calculated. We extend the traditional definitions of the inner and outer Helmholtz planes to our diffuse interfaces. Beyond the Stern layer, the simulated electrostatic potential is well described by the Poisson-Boltzmann equation. The potential at the outer Helmholtz plane compares well to the experimental zeta potential. We compare particle surfaces bearing two types of charge groups, ionic surfactant and multivalent oligomers, with and without added salt. Although the bare charge density of a surface bearing multivalent oligomers is much higher than that of a surfactant-bearing surface at realistic coverage, greater counterion condensation leads to similar zeta potentials for the two systems.

Host-guest chemistry of dendrimer-drug complexes. 2. Effects of molecular properties of guests and surface functionalities of dendrimers.

PubMed

Hu, Jingjing; Cheng, Yiyun; Wu, Qinglin; Zhao, Libo; Xu, Tongwen

2009-08-06

The host-guest chemistry of dendrimer-drug complexes is investigated by NMR techniques, including (1)H NMR and 2D-NOESY studies. The effects of molecular properties of drug molecules (protonation ability and spatial steric hindrance of charged groups) and surface functionalities of dendrimers (positively charged amine groups and negatively charged carboxylate groups) on the host-guest interactions are discussed. Different interaction mechanisms between dendrimers and drug molecules are proposed on the basis of NMR results. Primary amine- and secondary amine-containing drugs preferentially bind to negatively charged dendrimers by strong electrostatic interactions, whereas tertiary amine and quaternary ammonium-containing drugs have weak binding ability with dendrimers due to relatively low protonation ability of the tertiary amine group and serious steric hindrance of the quaternary ammonium group. Positively charged drugs locate only on the surface of negatively charged dendrimers, whereas negatively charged drugs locate both on the surface and in the interior cavities of positively charged dendrimers. The host-guest chemistry of dendrimer-drug complexes is promising for the development of new drug delivery systems.

Effect of surface charge alteration on stability of L-asparaginase II from Escherichia sp.

PubMed

Vidya, Jalaja; Ushasree, Mrudula Vasudevan; Pandey, Ashok

2014-03-05

Escherichia coli L-asparaginases have great significance in the treatment of leukemia. Consequently, there is considerable interest in engineering this enzyme for improving its stability. In this work, the effect of surface charge on the stability of the enzyme l-asparaginase II was studied by site-directed mutagenesis of the cloned ansB gene from Escherichia sp. Replacement of two positively charged residues (K139 and K207) on the surface loops with neutral and reverse charges resulted in altered thermo stability in designed variants. Neutral charge substitutions (K139A and K207A) retained greater tolerance and stability followed by negative charge substitutions (K139D and K207D) compared to control mutant K139R and wild enzyme. From the results, it was concluded that the optimization of surface charge contributed much to the thermal properties of proteins without affecting the structure. Copyright © 2013 Elsevier Inc. All rights reserved.

Analysis of microscopic parameters of surface charging in polymer caused by defocused electron beam irradiation.

PubMed

Liu, Jing; Zhang, Hai-Bo

2014-12-01

The relationship between microscopic parameters and polymer charging caused by defocused electron beam irradiation is investigated using a dynamic scattering-transport model. The dynamic charging process of an irradiated polymer using a defocused 30 keV electron beam is conducted. In this study, the space charge distribution with a 30 keV non-penetrating e-beam is negative and supported by some existing experimental data. The internal potential is negative, but relatively high near the surface, and it decreases to a maximum negative value at z=6 μm and finally tend to 0 at the bottom of film. The leakage current and the surface potential behave similarly, and the secondary electron and leakage currents follow the charging equilibrium condition. The surface potential decreases with increasing beam current density, trap concentration, capture cross section, film thickness and electron-hole recombination rate, but with decreasing electron mobility and electron energy. The total charge density increases with increasing beam current density, trap concentration, capture cross section, film thickness and electron-hole recombination rate, but with decreasing electron mobility and electron energy. This study shows a comprehensive analysis of microscopic factors of surface charging characteristics in an electron-based surface microscopy and analysis. Copyright © 2014 Elsevier Ltd. All rights reserved.

The role of surface charge density in cationic liposome-promoted dendritic cell maturation and vaccine-induced immune responses

NASA Astrophysics Data System (ADS)

Ma, Yifan; Zhuang, Yan; Xie, Xiaofang; Wang, Ce; Wang, Fei; Zhou, Dongmei; Zeng, Jianqiang; Cai, Lintao

2011-05-01

Cationic liposomes have emerged as a novel adjuvant and antigen delivery system to enhance vaccine efficacy. However, the role of surface charge density in cationic liposome-regulated immune responses has not yet been elucidated. In the present study, we prepared a series of DOTAP/DOPC cationic liposomes with different surface densities by incorporating varying amounts of DOPC (a neutral lipid) into DOTAP (a cationic lipid). The results showed that DOTAP/DOPC cationic liposome-regulated immune responses relied on the surface charge density, and might occur through ROS signaling. The liposomes with a relatively high charge density, such as DOTAP/DOPC 5 : 0 and 4 : 1 liposomes, potently enhanced dendritic cell maturation, ROS generaion, antigen uptake, as well as the production of OVA-specific IgG2a and IFN-γ. In contrast, low-charge liposomes, such as DOTAP/DOPC 1 : 4 liposome, failed to promote immune responses even at high concentrations, confirming that the immunoregulatory effect of cationic liposomes is mostly attributable to their surface charge density. Moreover, the DOTAP/DOPC 1 : 4 liposome suppressed anti-OVA antibody responses in vivo. Overall, maintaining an appropriate surface charge is crucial for optimizing the adjuvant effect of cationic liposomes and enhancing the efficacy of liposome-based vaccines.

Effect of plasma-induced surface charging on catalytic processes: application to CO2 activation

NASA Astrophysics Data System (ADS)

Bal, Kristof M.; Huygh, Stijn; Bogaerts, Annemie; Neyts, Erik C.

2018-02-01

Understanding the nature and effect of the multitude of plasma-surface interactions in plasma catalysis is a crucial requirement for further process development and improvement. A particularly intriguing and rather unique property of a plasma-catalytic setup is the ability of the plasma to modify the electronic structure, and hence chemical properties, of the catalyst through charging, i.e. the absorption of excess electrons. In this work, we develop a quantum chemical model based on density functional theory to study excess negative surface charges in a heterogeneous catalyst exposed to a plasma. This method is specifically applied to investigate plasma-catalytic CO2 activation on supported M/Al2O3 (M = Ti, Ni, Cu) single atom catalysts. We find that (1) the presence of a negative surface charge dramatically improves the reductive power of the catalyst, strongly promoting the splitting of CO2 to CO and oxygen, and (2) the relative activity of the investigated transition metals is also changed upon charging, suggesting that controlled surface charging is a powerful additional parameter to tune catalyst activity and selectivity. These results strongly point to plasma-induced surface charging of the catalyst as an important factor contributing to the plasma-catalyst synergistic effects frequently reported for plasma catalysis.

Charge reversal at a planar boundary between two dielectrics.

PubMed

Wang, Zhi-Yong

2016-01-01

Despite the ubiquitous character and relevance of the electric double layer in the entire realm of interface and colloid science, very little is known of the effect that surface heterogeneity exerts on the underlying mechanisms of ion adsorption. Herein, computer simulations offer a perspective that, in sharp contrast to the homogeneously charged surface, discrete groups promote multivalent counterion binding, leading to charge reversal but possibly having not a sign change of the electrophoretic mobility. Counterintuitively, the introduction of dielectric images yields a significantly greater accumulation of counterions, which further facilitates the magnitude of charge reversal. The reported results are very sensitive to both the degree of ion hydration and the representation of surface charges. Our findings shed light on the mechanism for charge reversal over a broad range of coupling regimes operating the adsorption of counterions through surface group bridging attraction with their own images and provide opportunities for experimental studies and theoretical development.

Charge reversal at a planar boundary between two dielectrics

NASA Astrophysics Data System (ADS)

Wang, Zhi-Yong

2016-01-01

Despite the ubiquitous character and relevance of the electric double layer in the entire realm of interface and colloid science, very little is known of the effect that surface heterogeneity exerts on the underlying mechanisms of ion adsorption. Herein, computer simulations offer a perspective that, in sharp contrast to the homogeneously charged surface, discrete groups promote multivalent counterion binding, leading to charge reversal but possibly having not a sign change of the electrophoretic mobility. Counterintuitively, the introduction of dielectric images yields a significantly greater accumulation of counterions, which further facilitates the magnitude of charge reversal. The reported results are very sensitive to both the degree of ion hydration and the representation of surface charges. Our findings shed light on the mechanism for charge reversal over a broad range of coupling regimes operating the adsorption of counterions through surface group bridging attraction with their own images and provide opportunities for experimental studies and theoretical development.

Electrostatic thin film chemical and biological sensor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prelas, Mark A.; Ghosh, Tushar K.; Tompson, Jr., Robert V.

A chemical and biological agent sensor includes an electrostatic thin film supported by a substrate. The film includes an electrostatic charged surface to attract predetermined biological and chemical agents of interest. A charge collector associated with said electrostatic thin film collects charge associated with surface defects in the electrostatic film induced by the predetermined biological and chemical agents of interest. A preferred sensing system includes a charge based deep level transient spectroscopy system to read out charges from the film and match responses to data sets regarding the agents of interest. A method for sensing biological and chemical agents includesmore » providing a thin sensing film having a predetermined electrostatic charge. The film is exposed to an environment suspected of containing the biological and chemical agents. Quantum surface effects on the film are measured. Biological and/or chemical agents can be detected, identified and quantified based on the measured quantum surface effects.« less

Biochemical Study of Anti-Inflammatory Proteins vCCI and vMIP-II

DTIC Science & Technology

2014-07-17

protein ), where we showed that vCCI is able to bind so many different chemokines due to its general negatively charged surface , allowing it to bind...sample of these competition curves. Our conclusion from the data in Table 1 and Figure 1 is that the negatively charged surface of vCCI allows it to...Similar to our mutagenesis results, the overall data indicate that vCCI uses a negatively charged surface to bind positive charges on the chemokine

SPM observation of nano-dots induced by slow highly charged ions

NASA Astrophysics Data System (ADS)

Nakamura, Nobuyuki; Terada, Masashi; Nakai, Yoichi; Kanai, Yasuyuki; Ohtani, Shunsuke; Komaki, Ken-ichiro; Yamazaki, Yasunori

2005-05-01

We have observed nano-dots on a highly oriented pyrolytic graphite (HOPG) surface produced by highly charged ion impacts with a scanning probe microscope. In order to clarify the role of potential and kinetic energies in surface modification, we have measured the kinetic energy and incident ion charge dependences of the dot size. The results showed that the potential energy or the incident ion charge has strong influence on the surface modification rather than the kinetic energy.

Electrostatic dust transport on the surfaces of airless bodies

NASA Astrophysics Data System (ADS)

Wang, X.; Schwan, J.; Hsu, H. W.; Horanyi, M.

2015-12-01

The surfaces of airless bodies are charged due to the exposure to solar wind plasma and UV radiation. Dust particles on the regolith of these surfaces can become charged, and may move and even get lofted due to electrostatic force. Electrostatic dust transport has been a long-standing problem that may be related to many observed phenomena on the surfaces of airless planetary bodies, including the lunar horizon glow, the dust ponds on asteroid Eros, the spokes in Saturn's rings, and more recently, the collection of dust particles ejected off Comet 67P, observed by Rosetta. In order to resolve these puzzles, a handful of laboratory experiments have been performed in the past and demonstrated that dust indeed moves and lifts from surfaces exposed to plasma. However, the exact mechanisms for the mobilization of dust particles still remain a mystery. Current charging models, including the so-called "shared charge model" and the charge fluctuation theory, will be discussed. It is found that neither of these models can explain the results from either laboratory experiments or in-situ observations. Recently, single dust trajectories were captured with our new dust experiments, enabling novel micro-scale investigations. The particles' initial launch speeds and size distributions are analyzed, and a new so-called "patched charge model" is proposed to explain our findings. We identify the role of plasma micro-cavities that are formed in-between neighboring dust particles. The emitted secondary or photo- electrons are proposed to be absorbed inside the micro-cavities, resulting in significant charge accumulation on the exposed patches of the surfaces of neighboring particles. The resulting enhanced Coulomb force (repulsion) between particles is likely the dominant force to mobilize and lift them off the surface. The role of other properties, including surface morphology, cohesion and photoelectron charging, will also be discussed.

Influence of charge and flexibility on smectic phase formation in filamentous virus suspensions

NASA Astrophysics Data System (ADS)

Purdy, Kirstin R.; Fraden, Seth

2007-07-01

We present experimental measurements of the cholesteric-smectic phase transition of suspensions of charged semiflexible rods as a function of rod flexibility and surface charge. The rod particles consist of the bacteriophage M13 and closely related mutants, which are structurally identical to M13, but vary either in contour length and therefore ratio of persistence length to contour length, or surface charge. Surface charge is altered in two ways; by changing solution pH and by comparing M13 with fd virus, a virus which differs from M13 only by the substitution of a single charged amino acid for a neutral one per viral coat protein. Phase diagrams are measured as a function of particle length, particle charge, and ionic strength. The experimental results are compared with existing theoretical predictions for the phase behavior of flexible rods and charged rods.

Influence of radioactivity on surface charging and aggregation kinetics of particles in the atmosphere.

PubMed

Kim, Yong-Ha; Yiacoumi, Sotira; Lee, Ida; McFarlane, Joanna; Tsouris, Costas

2014-01-01

Radioactivity can influence surface interactions, but its effects on particle aggregation kinetics have not been included in transport modeling of radioactive particles. In this research, experimental and theoretical studies have been performed to investigate the influence of radioactivity on surface charging and aggregation kinetics of radioactive particles in the atmosphere. Radioactivity-induced charging mechanisms have been investigated at the microscopic level, and heterogeneous surface potential caused by radioactivity is reported. The radioactivity-induced surface charging is highly influenced by several parameters, such as rate and type of radioactive decay. A population balance model, including interparticle forces, has been employed to study the effects of radioactivity on particle aggregation kinetics in air. It has been found that radioactivity can hinder aggregation of particles because of similar surface charging caused by the decay process. Experimental and theoretical studies provide useful insights into the understanding of transport characteristics of radioactive particles emitted from severe nuclear events, such as the recent accident of Fukushima or deliberate explosions of radiological devices.

The role of charged surface residues in the binding ability of small hubs in protein-protein interaction networks

PubMed Central

Patil, Ashwini; Nakamura, Haruki

2007-01-01

Hubs are highly connected proteins in a protein-protein interaction network. Previous work has implicated disordered domains and high surface charge as the properties significant in the ability of hubs to bind multiple proteins. While conformational flexibility of disordered domains plays an important role in the binding ability of large hubs, high surface charge is the dominant property in small hubs. In this study, we further investigate the role of the high surface charge in the binding ability of small hubs in the absence of disordered domains. Using multipole expansion, we find that the charges are highly distributed over the hub surfaces. Residue enrichment studies show that the charged residues in hubs are more prevalent on the exposed surface, with the exception of Arg, which is predominantly found at the interface, as compared to non-hubs. This suggests that the charged residues act primarily from the exposed surface rather than the interface to affect the binding ability of small hubs. They do this through (i) enhanced intra-molecular electrostatic interactions to lower the desolvation penalty, (ii) indirect long – range intermolecular interactions with charged residues on the partner proteins for better complementarity and electrostatic steering, and (iii) increased solubility for enhanced diffusion-controlled rate of binding. Along with Arg, we also find a high prevalence of polar residues Tyr, Gln and His and the hydrophobic residue Met at the interfaces of hubs, all of which have the ability to form multiple types of interactions, indicating that the interfaces of hubs are optimized to participate in multiple interactions. PMID:27857564

The role of charged surface residues in the binding ability of small hubs in protein-protein interaction networks.

PubMed

Patil, Ashwini; Nakamura, Haruki

2007-01-01

Hubs are highly connected proteins in a protein-protein interaction network. Previous work has implicated disordered domains and high surface charge as the properties significant in the ability of hubs to bind multiple proteins. While conformational flexibility of disordered domains plays an important role in the binding ability of large hubs, high surface charge is the dominant property in small hubs. In this study, we further investigate the role of the high surface charge in the binding ability of small hubs in the absence of disordered domains. Using multipole expansion, we find that the charges are highly distributed over the hub surfaces. Residue enrichment studies show that the charged residues in hubs are more prevalent on the exposed surface, with the exception of Arg, which is predominantly found at the interface, as compared to non-hubs. This suggests that the charged residues act primarily from the exposed surface rather than the interface to affect the binding ability of small hubs. They do this through (i) enhanced intra-molecular electrostatic interactions to lower the desolvation penalty, (ii) indirect long - range intermolecular interactions with charged residues on the partner proteins for better complementarity and electrostatic steering, and (iii) increased solubility for enhanced diffusion-controlled rate of binding. Along with Arg, we also find a high prevalence of polar residues Tyr, Gln and His and the hydrophobic residue Met at the interfaces of hubs, all of which have the ability to form multiple types of interactions, indicating that the interfaces of hubs are optimized to participate in multiple interactions.

Characterization of the APLF FHA–XRCC1 phosphopeptide interaction and its structural and functional implications

PubMed Central

Kim, Kyungmin; Pedersen, Lars C.; Kirby, Thomas W.; DeRose, Eugene F.

2017-01-01

Abstract Aprataxin and PNKP-like factor (APLF) is a DNA repair factor containing a forkhead-associated (FHA) domain that supports binding to the phosphorylated FHA domain binding motifs (FBMs) in XRCC1 and XRCC4. We have characterized the interaction of the APLF FHA domain with phosphorylated XRCC1 peptides using crystallographic, NMR, and fluorescence polarization studies. The FHA–FBM interactions exhibit significant pH dependence in the physiological range as a consequence of the atypically high pK values of the phosphoserine and phosphothreonine residues and the preference for a dianionic charge state of FHA-bound pThr. These high pK values are characteristic of the polyanionic peptides typically produced by CK2 phosphorylation. Binding affinity is greatly enhanced by residues flanking the crystallographically-defined recognition motif, apparently as a consequence of non-specific electrostatic interactions, supporting the role of XRCC1 in nuclear cotransport of APLF. The FHA domain-dependent interaction of XRCC1 with APLF joins repair scaffolds that support single-strand break repair and non-homologous end joining (NHEJ). It is suggested that for double-strand DNA breaks that have initially formed a complex with PARP1 and its binding partner XRCC1, this interaction acts as a backup attempt to intercept the more error-prone alternative NHEJ repair pathway by recruiting Ku and associated NHEJ factors. PMID:29059378

Microwave-Assisted Synthesis of Silver Vanadium Phosphorus Oxide, Ag 2VO 2PO 4 : Crystallite Size Control and Impact on Electrochemistry

DOE PAGES

Huang, Jianping; Marschilok, Amy C.; Takeuchi, Esther S.; ...

2016-03-07

We study silver vanadium phosphorus oxide, Ag 2VO 2PO 4, that is a promising cathode material for Li batteries due in part to its large capacity and high current capability. Herein, a new synthesis of Ag 2VO 2PO 4 based on microwave heating is presented, where the reaction time is reduced by approximately 100× relative to other reported methods, and the crystallite size is controlled via synthesis temperature, showing a linear correlation of crystallite size with temperature. Notably, under galvanostatic reduction, the Ag 2VO 2PO 4 sample with the smallest crystallite size delivers the highest capacity and shows the highestmore » loaded voltage. Further, pulse discharge tests show a significant resistance decrease during the initial discharge coincident with the formation of Ag metal. Thus, the magnitude of the resistance decrease observed during pulse tests depends on the Ag 2VO 2PO 4 crystallite size, with the largest resistance decrease observed for the smallest crystallite size. Additional electrochemical measurements indicate a quasi-reversible redox reaction involving Li + insertion/deinsertion, with capacity fade due to structural changes associated with the discharge/charge process. In summary, this work demonstrates a faster synthetic approach for bimetallic polyanionic materials which also provides the opportunity for tuning of electrochemical properties through control of material physical properties such as crystallite size.« less

Novel ionically crosslinked casein nanoparticles for flutamide delivery: formulation, characterization, and in vivo pharmacokinetics

PubMed Central

Elzoghby, Ahmed O; Helmy, Maged W; Samy, Wael M; Elgindy, Nazik A

2013-01-01

A novel particulate delivery matrix based on ionically crosslinked casein (CAS) nanoparticles was developed for controlled release of the poorly soluble anticancer drug flutamide (FLT). Nanoparticles were fabricated via oil-in-water emulsification then stabilized by ionic crosslinking of the positively charged CAS molecules below their isoelectric point, with the polyanionic crosslinker sodium tripolyphosphate. With the optimal preparation conditions, the drug loading and incorporation efficiency achieved were 8.73% and 64.55%, respectively. The nanoparticles exhibited a spherical shape with a size below 100 nm and a positive zeta potential (+7.54 to +17.3 mV). FLT was molecularly dispersed inside the nanoparticle protein matrix, as revealed by thermal analysis. The biodegradability of CAS nanoparticles in trypsin solution could be easily modulated by varying the sodium tripolyphosphate crosslinking density. A sustained release of FLT from CAS nanoparticles for up to 4 days was observed, depending on the crosslinking density. After intravenous administration of FLT-CAS nanoparticles into rats, CAS nanoparticles exhibited a longer circulation time and a markedly delayed blood clearance of FLT, with the half-life of FLT extended from 0.88 hours to 14.64 hours, compared with drug cosolvent. The results offer a promising method for tailoring biodegradable, drug-loaded CAS nanoparticles as controlled, long-circulating drug delivery systems of hydrophobic anticancer drugs in aqueous vehicles. PMID:23658490

Preparation and structure of Na2Ag5Fe3(P2O7)4 -Ag metal composite: Insights on electrochemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yiman; Marschilok, Amy C.; Takeuchi, Esther S.

ABSTRACT Ag 7Fe 3(P 2O 7) 4is a 3D structured material which has been recently studied as a possible cathode material for lithium batteries. Notably, Na 7Fe 3(P 2O 7) 4is reported to be a fast-ion conductor, yet poor electrical conductor. Here, partial replacement of Na +for Ag +yielded Na 2Ag 5Fe 3(P 2O 7) 4pyrophosphate framework where the formation of Ag metal is proposed to increase the intrinsic low electrical conductivity of this polyanion electrode. Specifically, the Ag 5Na 2Fe 3(P 2O 7) 4-Ag composite is synthesized via chemical reduction of Ag 7Fe 3(P 2O 7) 4using NaBH 4.more » The occupancy of Ag +and Na +in each site was determined via Rietveld analysis of the diffraction pattern. Electrochemistry of the Ag 5Na 2Fe 3(P 2O 7) 4-Ag metal composite was explored with voltammetry and galvanostatic charge/discharge cycling. The Ag 5Na 2Fe 3(P 2O 7) 4-Ag metal composite electrodes displayed good rate capability assisted by the presence of Ag metal from the chemical reduction and in-situ electrochemical formation of a Ag conductive network.« less

The effect of charging rate on the graphite electrode of commercial lithium-ion cells: A post-mortem study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Somerville, L.; Bareno, J.; Trask, S.

Increased charging rates negatively affect the lifetime of lithium-ion cells by increasing cell resistance and reducing capacity. This work is a post-mortem study of 18650 cells subjected to charge rates of 0.7-, 2-, 4-, and 6-C. For cells charged at 0.7-C to 4-C, this performance degradation is primarily related to surface film thickness with no observable change in surface film chemical composition. However, at charge rates of 6-C, the chemical composition of the surface film changes significantly, suggesting that this change is the reason for the sharper increase in cell resistance compared to the lower charge rates. In addition, wemore » found that surface film formation was not uniform across the electrode. Surface film was thicker and chemically different along the central band of the electrode “jelly roll”. This result is most likely attributable to an increase in temperature that results from non-uniform electrode wetting during manufacture. As a result, this non-uniform change further resulted in active material delamination from the current collector owing to chemical changes to the binder for the cell charged at 6-C.« less

The effect of charging rate on the graphite electrode of commercial lithium-ion cells: A post-mortem study

DOE PAGES

Somerville, L.; Bareno, J.; Trask, S.; ...

2016-10-22

Increased charging rates negatively affect the lifetime of lithium-ion cells by increasing cell resistance and reducing capacity. This work is a post-mortem study of 18650 cells subjected to charge rates of 0.7-, 2-, 4-, and 6-C. For cells charged at 0.7-C to 4-C, this performance degradation is primarily related to surface film thickness with no observable change in surface film chemical composition. However, at charge rates of 6-C, the chemical composition of the surface film changes significantly, suggesting that this change is the reason for the sharper increase in cell resistance compared to the lower charge rates. In addition, wemore » found that surface film formation was not uniform across the electrode. Surface film was thicker and chemically different along the central band of the electrode “jelly roll”. This result is most likely attributable to an increase in temperature that results from non-uniform electrode wetting during manufacture. As a result, this non-uniform change further resulted in active material delamination from the current collector owing to chemical changes to the binder for the cell charged at 6-C.« less

[Sorption of microorganisms by fiber materials].

PubMed

Nikovskaia, G N; Gordienko, A S; Globa, L I

1986-01-01

Candida guilliermondii and Escherichia coli cells were adsorbed on glass and basalt fibres with a similar specific surface, but with a different charge. The quantity of adsorbed microorganisms did not depend on the type and charge of a fibre surface. However, cells were adsorbed faster and more firmly on positively charged and uncharged fibres than on negatively charged fibres.

Charge collection kinetics on ferroelectric polymer surface using charge gradient microscopy

DOE PAGES

Choi, Yoon-Young; Tong, Sheng; Ducharme, Stephen P.; ...

2016-05-03

Here, a charge gradient microscopy (CGM) probe was used to collect surface screening charges on poly(vinylidene fluoride-trifluoroethylene) [P(VDF-TrFE)] thin films. These charges are naturally formed on unscreened ferroelectric domains in ambient condition. The CGM data were used to map the local electric current originating from the collected surface charges on the poled ferroelectric domains in the P(VDF-TrFE) thin films. Both the direction and amount of the collected current were controlled by changing the polarity and area of the poled domains. The endurance of charge collection by rubbing the CGM tip on the polymer film was limited to 20 scan cycles,more » after which the current reduced to almost zero. This degradation was attributed to the increase of the chemical bonding strength between the external screening charges and the polarization charges. Once this degradation mechanism is mitigated, the CGM technique can be applied to efficient energy harvesting devices using polymer ferroelectrics.« less

Surface Assisted Transient Displacement Charge Technique. II. Effect of Gases on Photoinduced Charge Transfer in Self-Assembled Monolayers

PubMed Central

Krasnoslobodtsev, Alexey V.; Smirnov, Sergei N.

2008-01-01

Surface assisted photoinduced transient displacement charge (SPTDC) technique was used to study charge transfer in self-assembled monolayers of 7-diethylaminocoumarin covalently linked to oxide surface in atmosphere of different gases. The dipole signal was found to be opposite to that in solution and dependent on the nature of gas and its pressure. The results were explained by collision-induced relaxation that impedes uninhibited tilting of molecules onto the surface. Collisions with paramagnetic oxygen induce intersystem crossing to long-lived triplet dipolar states of coumarin with the rate close to the half of that for the collision rate. PMID:16956285

Role of Surface Charge Density in Nanoparticle-templated Assembly of Bromovirus Protein Cages

PubMed Central

Daniel, Marie-Christine; Tsvetkova, Irina B.; Quinkert, Zachary T.; Murali, Ayaluru; De, Mrinmoy; Rotello, Vincent M.; Kao, C. Cheng; Dragnea, Bogdan

2010-01-01

Self-assembling icosahedral protein cages have potencially useful physical and chemical characteristics for a variety of nanotechnology applications, ranging from therapeutic or diagnostic vectors to building blocks for hierarchical materials. For application-specific functional control of protein cage assemblies, a deeper understanding of the interaction between the protein cage and its payload is necessary. Protein-cage encapsulated nanoparticles, with their well-defined surface chemistry, allow for systematic control over key parameters of encapsulation such as the surface charge, hydrophobicity, and size. Independent control over these variables allows experimental testing of different assembly mechanism models. Previous studies done with Brome mosaic virus capsids and negatively-charged gold nanoparticles indicated that the result of the self-assembly process depends on the diameter of the particle. However, in these experiments, the surface-ligand density was maintained at saturation levels, while the total charge and the radius of curvature remained coupled variables, making the interpretation of the observed dependence on the core size difficult. The current work furnishes evidence of a critical surface charge density for assembly through an analysis aimed at decoupling the surface charge the core size. PMID:20575505

In Vitro Biocompatibility of Si Alloyed Multi-Principal Element Carbide Coatings

PubMed Central

Vladescu, Alina; Titorencu, Irina; Dekhtyar, Yuri; Jinga, Victor; Pruna, Vasile; Balaceanu, Mihai; Dinu, Mihaela; Pana, Iulian; Vendina, Viktorija

2016-01-01

In the current study, we have examined the possibility to improve the biocompatibility of the (TiZrNbTaHf)C through replacement of either Ti or Ta by Si. The coatings were deposited on Si and 316L stainless steel substrates by magnetron sputtering in an Ar+CH4 mixed atmosphere and were examined for elemental composition, chemical bonds, surface topography, surface electrical charge and biocompatible characteristics. The net surface charge was evaluated at nano and macroscopic scale by measuring the electrical potential and work function, respectively. The biocompatible tests comprised determination of cell viability and cell attachment to the coated surface. The deposited coatings had C/(metal+Si) ratios close to unity, while a mixture of metallic carbide, free-carbon and oxidized species formed on the film surface. The coatings’ surfaces were smooth and no influence of surface roughness on electrical charge or biocompatibility was found. The biocompatible characteristics correlated well with the electrical potential/work function, suggesting a significant role of surface charge in improving biocompatibility, particularly cell attachment to coating's surface. Replacement of either Ti or Ta by Si in the (TiZrNbTaHf)C coating led to an enhanced surface electrical charge, as well as to superior biocompatible properties, with best results for the (TiZrNbSiHf)C coating. PMID:27571361

Enhanced flashover strength in polyethylene nanodielectrics by secondary electron emission modification

NASA Astrophysics Data System (ADS)

Wang, Weiwang; Li, Shengtao; Min, Daomin

2016-04-01

This work studies the correlation between secondary electron emission (SEE) characteristics and impulse surface flashover in polyethylene nanodielectrics both theoretically and experimentally, and illustrates the enhancement of flashover voltage in low-density polyethylene (LDPE) through incorporating Al2O3 nanoparticles. SEE characteristics play key roles in surface charging and gas desorption during surface flashover. This work demonstrates that the presence of Al2O3 nanoparticles decreases the SEE coefficient of LDPE and enhances the impact energy at the equilibrium state of surface charging. These changes can be explained by the increase of surface roughness and of surface ionization energy, and the strong interaction between nanoparticles and the polymer dielectric matrix. The surface charge and flashover voltage are calculated according to the secondary electron emission avalanche (SEEA) model, which reveals that the positive surface charges are reduced near the cathode triple point, while the presence of more nanoparticles in high loading samples enhances the gas desorption. Consequently, the surface flashover performance of LDPE/Al2O3 nanodielectrics is improved.

Coverage Dependent Charge Reduction of Cationic Gold Clusters on Surfaces Prepared Using Soft Landing of Mass-selected Ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, Grant E.; Priest, Thomas A.; Laskin, Julia

2012-11-29

The ionic charge state of monodisperse cationic gold clusters on surfaces may be controlled by selecting the coverage of mass-selected ions soft landed onto a substrate. Polydisperse diphosphine-capped gold clusters were synthesized in solution by reduction of chloro(triphenylphosphine)gold(I) with borane tert-butylamine in the presence of 1,3-bis(diphenylphosphino)propane. The polydisperse gold clusters were introduced into the gas phase by electrospray ionization and mass selection was employed to select a multiply charged cationic cluster species (Au11L53+, m/z = 1409, L = 1,3-bis(diphenylphosphino)propane) which was delivered to the surfaces of four different self-assembled monolayers on gold (SAMs) at coverages of 1011 and 1012 clusters/mm2.more » Employing the spatial profiling capabilities of in-situ time-of-flight secondary ion mass spectrometry (TOF-SIMS) it is shown that, in addition to the chemical functionality of the monolayer (as demonstrated previously: ACS Nano, 2012, 6, 573) the coverage of cationic gold clusters on the surface may be used to control the distribution of ionic charge states of the soft-landed multiply charged clusters. In the case of a 1H,1H,2H,2H-perfluorodecanethiol SAM (FSAM) almost complete retention of charge by the deposited Au11L53+ clusters was observed at a lower coverage of 1011 clusters/mm2. In contrast, at a higher coverage of 1012 clusters/mm2, pronounced reduction of charge to Au11L52+ and Au11L5+ was observed on the FSAM. When soft landed onto 16- and 11-mercaptohexadecanoic acid surfaces on gold (16,11-COOH-SAMs), the mass-selected Au11L53+ clusters exhibited partial reduction of charge to Au11L52+ at lower coverage and additional reduction of charge to both Au11L52+ and Au11L5+ at higher coverage. The reduction of charge was found to be more pronounced on the surface of the shorter (thinner) C11 than the longer (thicker) C16-COOH-SAM. On the surface of the 1-dodecanethiol (HSAM) monolayer, the most abundant charge state was found to be Au11L52+ at lower coverage and Au11L5+ at higher coverage, respectively. A coverage-dependent electron tunneling mechanism is proposed to account for the observed reduction of charge of mass-selected multiply charged gold clusters soft landed on SAMs. The results demonstrate that one of the critical parameters that influence the chemical and physical properties of supported metal clusters, ionic charge state, may be controlled by selecting the coverage of charged species soft landed onto surfaces.« less

Effects of O 2 and N 2/H 2 plasma treatments on the neuronal cell growth on single-walled carbon nanotube paper scaffolds

NASA Astrophysics Data System (ADS)

Yoon, Ok Ja; Lee, Hyun Jung; Jang, Yeong Mi; Kim, Hyun Woo; Lee, Won Bok; Kim, Sung Su; Lee, Nae-Eung

2011-08-01

The O 2 and N 2/H 2 plasma treatments of single-walled carbon nanotube (SWCNT) papers as scaffolds for enhanced neuronal cell growth were conducted to functionalize their surfaces with different functional groups and to roughen their surfaces. To evaluate the effects of the surface roughness and functionalization modifications of the SWCNT papers, we investigated the neuronal morphology, mitochondrial membrane potential, and acetylcholine/acetylcholinesterase levels of human neuroblastoma during SH-SY5Y cell growth on the treated SWCNT papers. Our results demonstrated that the plasma-chemical functionalization caused changes in the surface charge states with functional groups with negative and positive charges and then the increased surface roughness enhanced neuronal cell adhesion, mitochondrial membrane potential, and the level of neurotransmitter in vitro. The cell adhesion and mitochondrial membrane potential on the negatively charged SWCNT papers were improved more than on the positively charged SWCNT papers. Also, measurements of the neurotransmitter level showed an enhanced acetylcholine level on the negatively charged SWCNT papers compared to the positively charged SWCNT papers.

Proton transfer to charged platinum electrodes. A molecular dynamics trajectory study.

PubMed

Wilhelm, Florian; Schmickler, Wolfgang; Spohr, Eckhard

2010-05-05

A recently developed empirical valence bond (EVB) model for proton transfer on Pt(111) electrodes (Wilhelm et al 2008 J. Phys. Chem. C 112 10814) has been applied in molecular dynamics (MD) simulations of a water film in contact with a charged Pt surface. A total of seven negative surface charge densities σ between -7.5 and -18.9 µC cm(-2) were investigated. For each value of σ, between 30 and 84 initial conditions of a solvated proton within a water slab were sampled, and the trajectories were integrated until discharge of a proton occurred on the charged surfaces. We have calculated the mean rates for discharge and for adsorption of solvated protons within the adsorbed water layer in contact with the metal electrode as a function of surface charge density. For the less negative values of σ we observe a Tafel-like exponential increase of discharge rate with decreasing σ. At the more negative values this exponential increase levels off and the discharge process is apparently transport limited. Mechanistically, the Tafel regime corresponds to a stepwise proton transfer: first, a proton is transferred from the bulk into the contact water layer, which is followed by transfer of a proton to the charged surface and concomitant discharge. At the more negative surface charge densities the proton transfer into the contact water layer and the transfer of another proton to the surface and its discharge occur almost simultaneously.

Effect of dipolar fields, surface termination, and surface orientation on photochemical reactions on transition metal oxides

NASA Astrophysics Data System (ADS)

Giocondi, Jennifer Lynn

Experiments have been conducted to determine the effects of dipolar fields, surface termination, and surface orientation on the photochemical reactivity of several transition metal oxides. These compounds include BaTiO3, SrTiO3, BaTi4O9, Sr2Nb2O 7, and Sr2Ta2O7 which were studied as polycrystalline ceramics, single crystals, micron-sized faceted particles, or some combination of these forms. The reduction of Ag+ from an aqueous AgNO3 solution (Ag0 product) and the oxidation of Pb2+ from an aqueous lead acetate solution (PbO 2 product) were selected as probe reactions because they leave insoluble products on the oxide surfaces. The reactivity of ferroelectric BaTiO3 was dominated by the effect of dipolar fields on the transport of photogenerated charge carriers. Silver was reduced on domains with a positive surface charge while lead was oxidized on domains with a negative surface charge. This reactivity implies that the dipolar field in individual domains drives photogenerated charge carriers to oppositely charged surfaces. This reaction mechanism results in a physical separation of the photogenerated charge carriers and the locations of the oxidation and reduction half reactions on the catalyst surface. Experiments performed on polycrystalline ceramics, single crystals, and micron-sized particles all showed this domain specific reactivity. SrTiO3 has the ideal cubic perovskite structure from which the tetragonally distorted ferroelectric BaTiO3 phase is derived. Polished and annealed surfaces of randomly oriented grain surfaces were bound by some combination of the following three planes: {110}, {111}, and a complex facet inclined approximately 24° from {100}. Surfaces with the complex {100} facet were found to be the most active for Ag reduction. Single crystal studies also showed that the nonpolar (100) surface is the most reactive and that the composition of the termination layer does not influence this reaction. However, the polar (111) and (110) surfaces had a non-uniform distribution of reaction products. For these orientations, the location of the reduction and oxidation reactions is determined by the chemical and charge terminations of the different terraces or facets. The reactivity for silver reduction on the faceted particles is ranked as (100) > (111) > (110) while the (100) surface was least reactive for lead oxidation. Overall, these results show that the photochemical reactivity of SrTiO3 is anisotropic and that on polar surfaces, dipolar fields arising from charged surface domains influence the transport of photogenerated charge carriers and promote spatially selective oxidation and reduction reactions. (Abstract shortened by UMI.)

Applying simulation model to uniform field space charge distribution measurements by the PEA method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Y.; Salama, M.M.A.

1996-12-31

Signals measured under uniform fields by the Pulsed Electroacoustic (PEA) method have been processed by the deconvolution procedure to obtain space charge distributions since 1988. To simplify data processing, a direct method has been proposed recently in which the deconvolution is eliminated. However, the surface charge cannot be represented well by the method because the surface charge has a bandwidth being from zero to infinity. The bandwidth of the charge distribution must be much narrower than the bandwidths of the PEA system transfer function in order to apply the direct method properly. When surface charges can not be distinguished frommore » space charge distributions, the accuracy and the resolution of the obtained space charge distributions decrease. To overcome this difficulty a simulation model is therefore proposed. This paper shows their attempts to apply the simulation model to obtain space charge distributions under plane-plane electrode configurations. Due to the page limitation for the paper, the charge distribution originated by the simulation model is compared to that obtained by the direct method with a set of simulated signals.« less

Control of single-electron charging of metallic nanoparticles onto amorphous silicon surface.

PubMed

Weis, Martin; Gmucová, Katarína; Nádazdy, Vojtech; Capek, Ignác; Satka, Alexander; Kopáni, Martin; Cirák, Július; Majková, Eva

2008-11-01

Sequential single-electron charging of iron oxide nanoparticles encapsulated in oleic acid/oleyl amine envelope and deposited by the Langmuir-Blodgett technique onto Pt electrode covered with undoped hydrogenated amorphous silicon film is reported. Single-electron charging (so-called quantized double-layer charging) of nanoparticles is detected by cyclic voltammetry as current peaks and the charging effect can be switched on/off by the electric field in the surface region induced by the excess of negative/positive charged defect states in the amorphous silicon layer. The particular charge states in amorphous silicon are created by the simultaneous application of a suitable bias voltage and illumination before the measurement. The influence of charged states on the electric field in the surface region is evaluated by the finite element method. The single-electron charging is analyzed by the standard quantized double layer model as well as two weak-link junctions model. Both approaches are in accordance with experiment and confirm single-electron charging by tunnelling process at room temperature. This experiment illustrates the possibility of the creation of a voltage-controlled capacitor for nanotechnology.

Electrification of particulate entrained fluid flows-Mechanisms, applications, and numerical methodology

NASA Astrophysics Data System (ADS)

Wei, Wei; Gu, Zhaolin

2015-10-01

Particulates in natural and industrial flows have two basic forms: liquid (droplet) and solid (particle). Droplets would be charged in the presence of the applied electric field (e.g. electrospray). Similar to the droplet charging, particles can also be charged under the external electric field (e.g. electrostatic precipitator), while in the absence of external electric field, tribo-electrostatic charging is almost unavoidable in gas-solid two-phase flows due to the consecutive particle contacts (e.g. electrostatic in fluidized bed or wind-blown sand). The particle charging may be beneficial, or detrimental. Although electrostatics in particulate entrained fluid flow systems have been so widely used and concerned, the mechanisms of particulate charging are still lack of a thorough understanding. The motivation of this review is to explore a clear understanding of particulate charging and movement of charged particulate in two-phase flows, by summarizing the electrification mechanisms, physical models of particulate charging, and methods of charging/charged particulate entrained fluid flow simulations. Two effective methods can make droplets charged in industrial applications: corona charging and induction charging. The droplet charge to mass ratio by corona charging is more than induction discharge. The particle charging through collisions could be attributed to electron transfer, ion transfer, material transfer, and/or aqueous ion shift on particle surfaces. The charges on charged particulate surface can be measured, nevertheless, the charging process in nature or industry is difficult to monitor. The simulation method might build a bridge of investigating from the charging process to finally charged state on particulate surface in particulate entrained fluid flows. The methodology combining the interface tracking under the action of the applied electric with the fluid flow governing equations is applicable to the study of electrohydrodynamics problems. The charge distribution and mechanical behaviors of liquid surface can be predicted by using this method. The methodology combining particle charging model with Computational Fluid Dynamics (CFD) and Discrete element method (DEM) is applicable to study the particle charging/charged processes in gas-solid two phase flows, the influence factors of particle charging, such as gas-particle interaction, contact force, contact area, and various velocities, are described systematically. This review would explore a clear understanding of the particulate charging and provide theoretical references to control and utilize the charging/charged particulate entrained fluid system.

Charge Retention by Organometallic Dications on Self-Assembled Monolayer Surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Laskin, Julia; Wang, Peng

2014-05-15

Charge retention by mass-selected ruthenium trisbipyridine dications, or Ru(bpy)32+, soft-landed onto self-assembled monolayer (SAM) surfaces of 1H, 1H, 2H, 2H-perfluorodecane-1-thiol (FSAM), 11-mercaptoundecanoic acid (COOH-SAM), and 11-amino-1-undecanethiol (HSAM) on gold was examined using in situ time-resolved secondary ion mass spectrometry in a Fourier transform ion cyclotron resonance apparatus (FT-ICR SIMS). FT-ICR SIMS analysis was performed during ion soft-landing and for 8–15 hours after the ion beam was switched off. Our results demonstrate efficient retention of the doubly charged precursor ion on the FSAM and COOH-SAM surfaces manifested by the abundant Ru(bpy)32+ ions in the SIMS spectra. In contrast, only the singlymore » charged Ru(bpy)3+ and Ru(bpy)2+ ions were observed on HSAM, indicating rapid loss of at least one charge by the deposited dications. The signal of Ru(bpy)32+ on COOH-SAM remained almost constant for more than 8 hours after the end of ion soft-landing, while a relatively fast decay followed by a plateau region was observed on the FSAM surface. However, we found that SIMS analysis of Ru(bpy)32+ ions soft-landed onto FSAM is complicated by facile ion-molecule reactivity occurring either on the surface or in the SIMS plume, making it difficult to accurately measure the charge reduction kinetics. Efficient retention of the doubly charged Ru(bpy)32+ ions on COOH-SAM is remarkably different from facile neutralization of protonated peptides deposited onto this surface reported in previous studies. Our results indicate different mechanisms of charge reduction of protonated molecules and permanent ions, such as Ru(bpy)32+, on SAM surfaces. Thus, we propose that proton loss is the major charge reduction channel for the protonated species, while electron transfer through the insulating SAM is responsible for the charge loss by permanent ions. Fundamental understanding of charge reduction phenomena is essential for controlled preparation of catalytically active substrates using ion soft-landing.« less

Characterization of triboelectrically charged particles deposited on dielectric surfaces

NASA Astrophysics Data System (ADS)

Nesterov, A.; Löffler, F.; Cheng, Yun-Chien; Torralba, G.; König, K.; Hausmann, M.; Lindenstruth, V.; Stadler, V.; Bischoff, F. R.; Breitling, F.

2010-04-01

A device for the measurement of q/m-values and charge degradation of triboelectrically charged particles deposited on a surface was developed. The setup is based on the integration of currents, which are induced in a Faraday cage by insertion of a solid support covered with charged particles. The conductivity of different particle supports was taken into account. The 'blow-off' method, in which the particles are first deposited, and then blown off using an air stream, can be used for characterization of triboelectric properties of particles relative to different surfaces.

Dust Grain Charge in the Lunar Environment

NASA Astrophysics Data System (ADS)

Vaverka, Jakub; Richterova, Ivana; Vysinka, Marek; Pavlu, Jiri; Safrankova, Jana; Nemecek, Zdenek

2014-05-01

Interaction of a lunar surface with solar wind and magnetosphere plasmas leads to it charging by several processes as photoemission, a collection of primary particles and secondary electron emission. Nevertheless, charging of the lunar surface is complicated by a presence of crustal magnetic anomalies with can generate a "mini-magnetosphere" capable for more or less complete shielding the surface. On the other hand, shielding of solar light and plasma particles by rocks and craters can also locally influence the surface potential as well as a presence of a plasma wake strongly changes this potential at the night side of the Moon. A typical surface potential varies from slightly positive (dayside) to negative values of the order of several hundred of volts (night side). At the night side, negative potentials can reach -4 kV during solar energetic particle (SEP) events. Recent measurements of the surface potential by Lunar Prospector and Artemis spacecraft have shown surprisingly high negative dayside surface potentials (-500 V) during the magnetotail crossings as well as the positive surface potential higher than 100 V. One possible explanation is its non-monotonic profile above a surface where the potential minimum is formed by the space charge. Dust grains presented in this complicated environment are also charged by similar processes as the lunar surface. A strong dependence of the secondary electron yield on the grain size can significantly influence dust charging mainly in the Earth's plasma sheet where an equilibrium grain potential can by different than the surface potential and can reach even the opposite sign. This process can lead to levitation of dust above a surface observed by the Surveyor spacecraft.

Development of Charge to Mass Ratio Microdetector for Future Mars Mission

NASA Technical Reports Server (NTRS)

Chen, Yuan-Lian Albert

2003-01-01

The Mars environment comprises a dry, cold and low air pressure atmosphere with low gravity (0.38g) and high resistivity soil. The global dust storms that cover a large portion of Mars are observed often from Earth. This environment provides an ideal condition for turboelectric charging. The extremely dry conditions on the Martian surface have raised concerns that electrostatic charge buildup will not be dissipated easily. If turboelectrically generated charge cannot be dissipated or avoided, then dust will accumulate on charged surfaces and electrostatic discharge may cause hazards for future exploration missions. The low surface on Mars helps to prolong the charge decay on the dust particles and soil. To better understanding the physics of Martian charged dust particles is essential to future Mars missions. We research and design two sensors, velocity/charge sensor and PZT momentum sensors, to measure the velocity distribution, charge distribution and mass distribution of Martian wed dust particles. These sensors are fabricated at NASA Kenney Space Center, Electrostatic and Surface Physics Laboratory. The sensors are calibrated. The momentum sensor is capable to measure 45 pan size particles. The designed detector is very simple, robust, without moving parts, and does not require a high voltage power supply. Two sensors are combined to form the Dust Microdetector - CHAL.

The Review on the Charge Distribution on the Conductor Surface

ERIC Educational Resources Information Center

Matehkolaee, M. Jafari; Asrami, A. Naderi

2013-01-01

In this paper we have a full review on the surface charge density at disordered conductor surfaces. Basically, reading text books does not resolve ambiguities in this field. As far as is possible, we have tried to the concepts easier to turn. In fact we will answer two questions. One of them is that why do charges tend to go where the curvature is…

On the dependence of charge density on surface curvature of an isolated conductor

NASA Astrophysics Data System (ADS)

Bhattacharya, Kolahal

2016-03-01

A study of the relation between the electrostatic charge density at a point on a conducting surface and the curvature of the surface (at that point) is presented. Two major papers in the scientific literature on this topic are reviewed and the apparent discrepancy between them is resolved. Hence, a step is taken towards obtaining a general analytic formula for relating the charge density with surface curvature of conductors. The merit of this formula and its limitations are discussed.

Charging of particles on a surface

NASA Astrophysics Data System (ADS)

Heijmans, Lucas; Nijdam, Sander

2016-09-01

This contribution focusses on the seemingly easy problem of the charging of micrometer sized particles on a substrate in a plasma. This seems trivial, because much is known about both the charging of surfaces near a plasma and of particles in the plasma bulk. The problem, however, becomes much more complicated when the particle is on the substrate surface. The charging currents to the particle are then highly altered by the substrate plasma sheath. Currently there is no consensus in literature about the resulting particle charge. We shall present both experimental measurements and numerical simulations of the charge on these particles. The experimental results are acquired by measuring the particle acceleration in an external electric field. For the simulations we have used our specially developed model. We shall compare these results to other estimates found in literature.

Enhanced electrohydrodynamic force generation in a two-stroke cycle dielectric-barrier-discharge plasma actuator

NASA Astrophysics Data System (ADS)

Sato, Shintaro; Takahashi, Masayuki; Ohnishi, Naofumi

2017-05-01

An approach for electrohydrodynamic (EHD) force production is proposed with a focus on a charge cycle on a dielectric surface. The cycle, consisting of positive-charging and neutralizing strokes, is completely different from the conventional methodology, which involves a negative-charging stroke, in that the dielectric surface charge is constantly positive. The two-stroke charge cycle is realized by applying a DC voltage combined with repetitive pulses. Simulation results indicate that the negative pulse eliminates the surface charge accumulated during constant voltage phase, resulting in repetitive EHD force generation. The time-averaged EHD force increases almost linearly with increasing repetitive pulse frequency and becomes one order of magnitude larger than that driven by the sinusoidal voltage, which has the same peak-to-peak voltage.

Simulation study of spheroidal dust gains charging: Applicable to dust grain alignment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zahed, H.; Sobhanian, S.; Mahmoodi, J.

2006-09-15

The charging process of nonspherical dust grains in an unmagnetized plasma as well as in the presence of a magnetic field is studied. It is shown that unlike the spherical dust grain, due to nonhomogeneity of charge distribution on the spheroidal dust surface, the resultant electric forces on electrons and ions are different. This process produces some surface charge density gradient on the nonspherical grain surface. Effects of a magnetic field and other plasma parameters on the properties of the dust particulate are studied. It has been shown that the alignment direction could be changed or even reversed with themore » magnetic field and plasma parameters. Finally, the charge distribution on the spheroidal grain surface is studied for different ambient parameters including plasma temperature, neutral collision frequency, and the magnitude of the magnetic field.« less

Model simulations of the adsorption of statherin to solid surfaces: Effects of surface charge and hydrophobicity

NASA Astrophysics Data System (ADS)

Skepö, M.

2008-11-01

The structural properties of the salivary protein statherin upon adsorption have been examined using a coarse-grained model and Monte Carlo simulation. A simple model system with focus on electrostatic interactions and short-ranged attractions among the uncharged amino acids has been used. To mimic hydrophobically modified surfaces, an extra short-ranged interaction was implemented between the amino acids and the surface. It has been shown that the adsorption and the thickness of the adsorbed layer are determined by (i) the affinity for the surface, i.e., denser layer with an extrashort-ranged potential, and (ii) the distribution of the charges along the chain. If all the amino acids have a high affinity for the surface, the protein adsorbs in a train conformation, if the surface is negatively charged the protein adsorbs in a tail-train conformation, whereas if the surface is positively charged the protein adsorbs in a loop conformation. The latter gives rise to a more confined adsorbed layer.

In situ mineralization of hydroxyapatite on electrospun chitosan-based nanofibrous scaffolds.

PubMed

Yang, Dongzhi; Jin, Yu; Zhou, Yingshan; Ma, Guiping; Chen, Xiangmei; Lu, Fengmin; Nie, Jun

2008-03-10

A biocomposite of hydroxyapatite (HAp) with electrospun nanofibrous scaffolds was prepared by using chitosan/polyvinyl alcohol (CS/PVA) and N-carboxyethyl chitosan/PVA (CECS/PVA) electrospun membranes as organic matrix, and HAp was formed in supersaturated CaCl2 and KH2PO4 solution. The influences of carboxylic acid groups in CECS/PVA fibrous scaffold and polyanionic additive poly(acrylic acid) (PAA) in the incubation solution on the crystal distribution of the HAp were investigated. Field-emission scanning electron microscopy (FE-SEM), energy-dispersive spectroscopy (EDS), wide-angle X-ray diffraction (WAXD), and Fourier transform infrared (FTIR) were used to characterize the morphology and structure of the deposited mineral phase on the scaffolds. It was found that addition of PAA to the mineral solution and use of matrix with carboxylic acid groups promoted mineral growth and distribution of HAp. MTT testing and SEM imaging from mouse fibroblast (L929) cell culture revealed the attachment and growth of mouse fibroblast on the surface of biocomposite scaffold, and that the cell morphology and viability were satisfactory for the composite to be used in bioapplications.

Current insights into the laboratory diagnosis of HIT.

PubMed

Bakchoul, T; Zöllner, H; Greinacher, A

2014-06-01

Heparin-induced thrombocytopenia (HIT) is an adverse drug reaction and prothrombotic disorder caused by immunization against platelet factor 4 (PF4) after complex formation with heparin or other polyanions. After antibody binding to PF4/heparin complexes, HIT antibodies are capable of intravascular platelet activation by cross-linking Fc gamma receptor IIa (FcγRIIa) on the platelet surface leading to a platelet count decrease and/or thrombosis. In contrast to most other immune-mediated disorders, the currently available laboratory tests for anti-PF4/heparin antibodies show a high sensitivity also for clinically irrelevant antibodies. This makes the diagnosis of HIT challenging and bears the risk to substantially overdiagnose HIT. The strength of the antigen assays for HIT is in ruling out HIT when the test is negative. Functional assays have a higher specificity for clinically relevant antibodies, but they are restricted to specialized laboratories. Currently, a Bayesian approach combining the clinical likelihood estimation for HIT with laboratory tests is the most appropriate approach to diagnose HIT. In this review, we give an overview on currently available diagnostic procedures and discuss their limitations. © 2014 John Wiley & Sons Ltd.

Charge Storage, Conductivity and Charge Profiles of Insulators as Related to Spacecraft Charging

NASA Technical Reports Server (NTRS)

Dennison, J. R.; Swaminathan, Prasanna; Frederickson, A. R.

2004-01-01

Dissipation of charges built up near the surface of insulators due to space environment interaction is central to understanding spacecraft charging. Conductivity of insulating materials is key to determine how accumulated charge will distribute across the spacecraft and how rapidly charge imbalance will dissipate. To understand these processes requires knowledge of how charge is deposited within the insulator, the mechanisms for charge trapping and charge transport within the insulator, and how the profile of trapped charge affects the transport and emission of charges from insulators. One must consider generation of mobile electrons and holes, their trapping, thermal de-trapping, mobility and recombination. Conductivity is more appropriately measured for spacecraft charging applications as the "decay" of charge deposited on the surface of an insulator, rather than by flow of current across two electrodes around the sample. We have found that conductivity determined from charge storage decay methods is 102 to 104 smaller than values obtained from classical ASTM and IEC methods for a variety of thin film insulating samples. For typical spacecraft charging conditions, classical conductivity predicts decay times on the order of minutes to hours (less than typical orbit periods); however, the higher charge storage conductivities predict decay times on the order of weeks to months leading to accumulation of charge with subsequent orbits. We found experimental evidence that penetration profiles of radiation and light are exceedingly important, and that internal electric fields due to charge profiles and high-field conduction by trapped electrons must be considered for space applications. We have also studied whether the decay constants depend on incident voltage and flux or on internal charge distributions and electric fields; light-activated discharge of surface charge to distinguish among differing charge trapping centers; and radiation-induced conductivity. Our experiments also show that "Malter" electron emission occurs for hours after turning off the electron beam. This Malter emission similar to emission due to negative electron affinity in semiconductors is a result of the prior radiation or optical excitations of valence electrons and their slow drift among traps towards the surface where they are subsequently emitted. This work is supported through funding from the NASA Space Environments and Effects Program.

Investigations of charged particle motion on the surfaces of dusty, airless solar system bodies (Invited)

NASA Astrophysics Data System (ADS)

Dove, A.; Colwell, J. E.

2013-12-01

Dynamic charging conditions exist on the dusty surfaces of planetary bodies such as the Moon, asteroids, and the moons of Mars. On these so-called 'airless bodies', the motions of dust particles above the surface become complex due to grain-grain and grain-plasma interactions. For example, tribocharging and other charge transfer processes can occur due to relative dust grain movements, and charged dust grains immersed in plasma interact with local electromagnetic forces. This is thought to lead to effects such as the lunar 'horizon glow,' (Rennilson and Criswell, 1974, The Moon, 10) and potential dusty 'fountains' above the lunar surface (Stubbs et al., 2006, Adv. Sp. Res., 37). Regolith grains can be mobilized by impacts or other mechanical disturbances, or simply by the Coulomb force acting on grains. Previous work has increased our theoretical understanding of the behavior of charged particles in these low-gravity environments (i.e. Poppe and Horanyi, 2010, JGR, A115; Colwell et al., 2007, Rev. Geophys., 45 (and references therein)). Experimental work has also analyzed grain surface charging due to plasma or tribocharging (Sickafoose et al., 2001, JGR, 106) and the motion of grains on surfaces in the presence of an electric field (Wang et al., 2009, JGR, 114). Occasionally, there is disagreement between theoretical predictions and observations. We present the results of new laboratory experiments aimed at understanding particle charging and the dynamics of charged particles on the surfaces of airless bodies. In the initial experiments, we analyze the motion of particles in the presence of an electric field in vacuum, either in a bell-jar or in a 0.75-second microgravity drop tower experiment box. Prior to motion, particles may be charged due to triboelectric effects, plasma interactions, or a combination of the two. Motion is induced by shaking or by low-velocity impacts in order to simulate the natural motion of slow-moving objects on regolith surfaces, or induced motion such as that due to a spacecraft. The resulting particle dynamics are tracked using high-speed, high-resolution video. Future exploration on or near the surfaces of airless bodies will certainly experience complications arising from these dusty environments, where particles may contaminate or interfere with the operation of almost any mechanical equipment. By exploring the dynamic behavior of charged particles in these environments, we can work towards solutions that will enable exploration.

Differential photoelectric charging of nonconducting surfaces in space. [on sunlit strip

NASA Technical Reports Server (NTRS)

Pelizzari, M. A.; Criswell, D. R.

1978-01-01

The photoelectric charging caused by an infinitely long strip of sunlight across a nonconducting plane is studied by use of a model which contains an electrical cutoff radius, and the results of numerical calculations are presented. The model simulates charging of a sunlit area with dimensions equal to the strip's width, exposed to a plasma with a comparatively large Debye length. Uniform potential is quickly established on a uniformly sunlit strip as a result of charge redistribution by low-energy photoelectrons. The results are in accord with a theoretical surface conductivity derived for photoelectron sheaths above highly charged sunlit areas. The surface potential, which drops sharply across the sunlight-shadow boundary, is discussed.

On the theoretical description of weakly charged surfaces.

PubMed

Wang, Rui; Wang, Zhen-Gang

2015-03-14

It is widely accepted that the Poisson-Boltzmann (PB) theory provides a valid description for charged surfaces in the so-called weak coupling limit. Here, we show that the image charge repulsion creates a depletion boundary layer that cannot be captured by a regular perturbation approach. The correct weak-coupling theory must include the self-energy of the ion due to the image charge interaction. The image force qualitatively alters the double layer structure and properties, and gives rise to many non-PB effects, such as nonmonotonic dependence of the surface energy on concentration and charge inversion. In the presence of dielectric discontinuity, there is no limiting condition for which the PB theory is valid.

Dynamics of charges and solitons

NASA Astrophysics Data System (ADS)

Barros, Manuel; Ferrández, Ángel; Garay, Óscar J.

2018-02-01

We first show that trajectories traced by charges moving in rotational magnetic fields are, basically, the non-parallel geodesics of surfaces of revolution with coincident axis. Thus, people living in a surface of revolution are not able to sense the magnetic Hall effect induced by the surrounding magnetic field and perceive charges as influenced, exclusively, by the gravity action on the surface of revolution. Secondly, the extended Hasimoto transformations are introduced and then used to identify trajectories of charges moving through a Killing rotational magnetic field in terms of non-circular elastic curves. As a consequence, we see that in this case charges evolve along trajectories which are obtained as extended Hasimoto transforms of solitons of the filament equation.

Charged plate in asymmetric electrolytes: One-loop renormalization of surface charge density and Debye length due to ionic correlations.

PubMed

Ding, Mingnan; Lu, Bing-Sui; Xing, Xiangjun

2016-10-01

Self-consistent field theory (SCFT) is used to study the mean potential near a charged plate inside a m:-n electrolyte. A perturbation series is developed in terms of g=4πκb, where band1/κ are Bjerrum length and bare Debye length, respectively. To the zeroth order, we obtain the nonlinear Poisson-Boltzmann theory. For asymmetric electrolytes (m≠n), the first order (one-loop) correction to mean potential contains a secular term, which indicates the breakdown of the regular perturbation method. Using a renormalizaton group transformation, we remove the secular term and obtain a globally well-behaved one-loop approximation with a renormalized Debye length and a renormalized surface charge density. Furthermore, we find that if the counterions are multivalent, the surface charge density is renormalized substantially downwards and may undergo a change of sign, if the bare surface charge density is sufficiently large. Our results agrees with large MC simulation even when the density of electrolytes is relatively high.

Coarse-grained modeling of proline rich protein 1 (PRP-1) in bulk solution and adsorbed to a negatively charged surface.

PubMed

Skepö, Marie; Linse, Per; Arnebrant, Thomas

2006-06-22

Structural properties of the acidic proline rich protein PRP-1 of salivary origin in bulk solution and adsorbed onto a negatively charged surface have been studied by Monte Carlo simulations. A simple model system with focus on electrostatic interactions and short-ranged attractions among the uncharged amino acids has been used. In addition to PRP-1, some mutants were considered to assess the role of the interactions in the systems. Contrary to polyelectrolytes, the protein has a compact structure in salt-free bulk solutions, whereas at high salt concentration the protein becomes more extended. The protein adsorbs to a negatively charged surface, although its net charge is negative. The adsorbed protein displays an extended structure, which becomes more compact upon addition of salt. Hence, the conformational response upon salt addition in the adsorbed state is the opposite as compared to that in bulk solution. The conformational behavior of PRP-1 in bulk solution and at charged surfaces as well as its propensity to adsorb to surfaces with the same net charge are rationalized by the block polyampholytic character of the protein. The presence of a triad of positively charged amino acids in the C-terminal was found to be important for the adsorption of the protein.

Cellulose nanocrystals with tunable surface charge for nanomedicine

NASA Astrophysics Data System (ADS)

Hosseinidoust, Zeinab; Alam, Md Nur; Sim, Goeun; Tufenkji, Nathalie; van de Ven, Theo G. M.

2015-10-01

Crystalline nanoparticles of cellulose exhibit attractive properties as nanoscale carriers for bioactive molecules in nanobiotechnology and nanomedicine. For applications in imaging and drug delivery, surface charge is one of the most important factors affecting the performance of nanocarriers. However, current methods of preparation offer little flexibility for controlling the surface charge of cellulose nanocrystals, leading to compromised colloidal stability under physiological conditions. We report a synthesis method that results in nanocrystals with remarkably high carboxyl content (6.6 mmol g-1) and offers continuous control over surface charge without any adjustment to the reaction conditions. Six fractions of nanocrystals with various surface carboxyl contents were synthesized from a single sample of softwood pulp with carboxyl contents varying from 6.6 to 1.7 mmol g-1 and were fully characterized. The proposed method resulted in highly stable colloidal nanocrystals that did not aggregate when exposed to high salt concentrations or serum-containing media. Interactions of these fractions with four different tissue cell lines were investigated over a wide range of concentrations (50-300 μg mL-1). Darkfield hyperspectral imaging and confocal microscopy confirmed the uptake of nanocrystals by selected cell lines without any evidence of membrane damage or change in cell density; however a charge-dependent decrease in mitochondrial activity was observed for charge contents higher than 3.9 mmol g-1. A high surface carboxyl content allowed for facile conjugation of fluorophores to the nanocrystals without compromising colloidal stability. The cellular uptake of fluoresceinamine-conjugated nanocrystals exhibited a time-dose dependent relationship and increased significantly with doubling of the surface charge.Crystalline nanoparticles of cellulose exhibit attractive properties as nanoscale carriers for bioactive molecules in nanobiotechnology and nanomedicine. For applications in imaging and drug delivery, surface charge is one of the most important factors affecting the performance of nanocarriers. However, current methods of preparation offer little flexibility for controlling the surface charge of cellulose nanocrystals, leading to compromised colloidal stability under physiological conditions. We report a synthesis method that results in nanocrystals with remarkably high carboxyl content (6.6 mmol g-1) and offers continuous control over surface charge without any adjustment to the reaction conditions. Six fractions of nanocrystals with various surface carboxyl contents were synthesized from a single sample of softwood pulp with carboxyl contents varying from 6.6 to 1.7 mmol g-1 and were fully characterized. The proposed method resulted in highly stable colloidal nanocrystals that did not aggregate when exposed to high salt concentrations or serum-containing media. Interactions of these fractions with four different tissue cell lines were investigated over a wide range of concentrations (50-300 μg mL-1). Darkfield hyperspectral imaging and confocal microscopy confirmed the uptake of nanocrystals by selected cell lines without any evidence of membrane damage or change in cell density; however a charge-dependent decrease in mitochondrial activity was observed for charge contents higher than 3.9 mmol g-1. A high surface carboxyl content allowed for facile conjugation of fluorophores to the nanocrystals without compromising colloidal stability. The cellular uptake of fluoresceinamine-conjugated nanocrystals exhibited a time-dose dependent relationship and increased significantly with doubling of the surface charge. Electronic supplementary information (ESI) available: Additional results are presented in the ESI in Fig. S1 through S4. See DOI: 10.1039/c5nr02506k

Surface correlation effects in two-band strongly correlated slabs.

PubMed

Esfahani, D Nasr; Covaci, L; Peeters, F M

2014-02-19

Using an extension of the Gutzwiller approximation for an inhomogeneous system, we study the two-band Hubbard model with unequal band widths for a slab geometry. The aim is to investigate the mutual effect of individual bands on the spatial distribution of quasi-particle weight and charge density, especially near the surface of the slab. The main effect of the difference in band width is the presence of two different length scales corresponding to the quasi-particle profile of each band. This is enhanced in the vicinity of the critical interaction of the narrow band where an orbitally selective Mott transition occurs and a surface dead layer forms for the narrow band. For the doped case, two different regimes of charge transfer between the surface and the bulk of the slab are revealed. The charge transfer from surface/center to center/surface depends on both the doping level and the average relative charge accumulated in each band. Such effects could also be of importance when describing the accumulation of charges at the interface between structures made of multi-band strongly correlated materials.

Surface Charge and Hydrophobicity of Endospores of Bacillus anthracis and Related Species in Aqueous Solution

EPA Science Inventory

The surface properties of microorganisms play an important role in attachment and detachment in the environment. The change in surface charge can effect coagulation, disinfection, adhesion to surfaces, uptake of chemicals, and environmental transport. In aqueous solution, cell s...

Convective transport of electric charge within the planetary boundary layer

NASA Astrophysics Data System (ADS)

Nicoll, Keri; Harrison, Giles; Silva, Hugo; Silgado, Rui; Melgao, Marta

2017-04-01

Turbulent and convective processes within the planetary boundary layer are responsible for the transport of moisture, momentum and particulate matter, but are also of major importance in determining the electrical charge structure of the lower atmosphere. This paper presents rare experimental measurements of vertical profiles of charge measured during fair weather conditions by specially instrumented radiosonde balloons over Alqueva, Portugal during the summer of 2014. Space charge was measured directly using a sensitive electrometer, rather than the conventional method of deriving it from electric field measurements. The high frequency of balloon flights enabled the diurnal variation in the vertical profile of charge within the boundary layer to be examined in detail, with much smaller levels of charge (up to 20pC m-3) observed during stable night time periods than during the day. Following sunrise, the evolution of the charge profile was much more complex, showing a dependence on lofting of surface aerosol due to daytime convection. This produced charge up to 92pC m-3 up to 500m above the surface. The diurnal variation in the integrated column of charge above the measurement site was also found to track closely with the diurnal variation in near surface charge as measured by an electric field mill at the same site, confirming the importance of the link between surface charge generation processes and aloft. Co-located lidar backscatter measurements were also made during the measurement campaign and will be discussed here in the context of the effect of aerosol on the vertical charge profile.

Piezoelectric modulation of surface voltage in GaN and AlGaN/GaN: charge screening effects and 2DEG

NASA Astrophysics Data System (ADS)

Wilson, Marshall; Schrayer, Bret; Savtchouk, Alexandre; Hillard, Bob; Lagowski, Jacek

2017-02-01

Surface voltage response to pulses of piezoelectric polarization is measured with a Kelvin-probe providing a unique means for investigation of the dynamics of polarization induced sheet charge and 2DEG. Combined with biasing of the surface with a corona-deposited charge from accumulation to deep depletion and corresponding non-contact C-V type characterization, the technique identifies surface band bending and interface traps as key factors that affect the magnitude and time decay of piezoelectric polarization. For 2DEG structures, surface potential pinning is observed when the 2DEG is fully populated. Pinning is released by negative corona charging to fully deplete the 2DEG. These results are consistent with the role of surface states. Presently demonstrated polarization modulation and wafer scale measurements shall impact the in-depth characterization and fundamental understanding of AlGaN/GaN 2DEG structures.

Bounding Extreme Spacecraft Charging in the Lunar Environment

NASA Technical Reports Server (NTRS)

Minow, Joseph I.; Parker, Linda N.

2008-01-01

Robotic and manned spacecraft from the Apollo era demonstrated that the lunar surface in daylight will charge to positive potentials of a few tens of volts because the photoelectron current dominates the charging process. In contrast, potentials of the lunar surface in darkness which were predicted to be on the order of a hundred volts negative in the Apollo era have been shown more recently to reach values of a few hundred volts negative with extremes on the order of a few kilovolts. The recent measurements of night time lunar surface potentials are based on electron beams in the Lunar Prospector Electron Reflectometer data sets interpreted as evidence for secondary electrons generated on the lunar surface accelerated through a plasma sheath from a negatively charged lunar surface. The spacecraft potential was not evaluated in these observations and therefore represents a lower limit to the magnitude of the lunar negative surface potential. This paper will describe a method for obtaining bounds on the magnitude of lunar surface potentials from spacecraft measurements in low lunar orbit based on estimates of the spacecraft potential. We first use Nascap-2k surface charging analyses to evaluate potentials of spacecraft in low lunar orbit and then include the potential drops between the ambient space environment and the spacecraft to the potential drop between the lunar surface and the ambient space environment to estimate the lunar surface potential from the satellite measurements.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Laskin, Julia; Johnson, Grant E.; Prabhakaran, Venkateshkumar

Immobilization of complex molecules and clusters on supports plays an important role in a variety of disciplines including materials science, catalysis and biochemistry. In particular, deposition of clusters on surfaces has attracted considerable attention due to their non-scalable, highly size-dependent properties. The ability to precisely control the composition and morphology of clusters and small nanoparticles on surfaces is crucial for the development of next generation materials with rationally tailored properties. Soft- and reactive landing of ions onto solid or liquid surfaces introduces unprecedented selectivity into surface modification by completely eliminating the effect of solvent and sample contamination on the qualitymore » of the film. The ability to select the mass-to-charge ratio of the precursor ion, its kinetic energy and charge state along with precise control of the size, shape and position of the ion beam on the deposition target makes soft-landing an attractive approach for surface modification. High-purity uniform thin films on surfaces generated using mass-selected ion deposition facilitate understanding of critical interfacial phenomena relevant to catalysis, energy generation and storage, and materials science. Our efforts have been directed toward understanding charge retention by soft-landed metal and metal-oxide cluster ions, which may affect both their structure and reactivity. Specifically, we have examined the effect of the surface on charge retention by both positively and negatively charged cluster ions. We found that the electronic properties of the surface play an important role in charge retention by cluster cations. Meanwhile, the electron binding energy is a key factor determining charge retention by cluster anions. These findings provide the scientific foundation for the rational design of interfaces for advanced catalysts and energy storage devices. Further optimization of electrode-electrolyte interfaces for applications in energy storage and electrocatalysis may be achieved by understanding and controlling the properties of soft-landed cluster ions.« less

Investigation of surface charge density on solid-liquid interfaces by modulating the electrical double layer.

PubMed

Moon, Jong Kyun; Song, Myung Won; Pak, Hyuk Kyu

2015-05-20

A solid surface in contact with water or aqueous solution usually carries specific electric charges. These surface charges attract counter ions from the liquid side. Since the geometry of opposite charge distribution parallel to the solid-liquid interface is similar to that of a capacitor, it is called an electrical double layer capacitor (EDLC). Therefore, there is an electrical potential difference across an EDLC in equilibrium. When a liquid bridge is formed between two conducting plates, the system behaves as two serially connected EDLCs. In this work, we propose a new method for investigating the surface charge density on solid-liquid interfaces. By mechanically modulating the electrical double layers and simultaneously applying a dc bias voltage across the plates, an ac electric current can be generated. By measuring the voltage drop across a load resistor as a function of bias voltage, we can study the surface charge density on solid-liquid interfaces. Our experimental results agree very well with the simple equivalent electrical circuit model proposed here. Furthermore, using this method, one can determine the polarity of the adsorbed state on the solid surface depending on the material used. We expect this method to aid in the study of electrical phenomena on solid-liquid interfaces.

Study of space charge layer in silver bromide microcrystals by means of ultraviolet photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Tani, Tadaaki; Inami, Yoshiyasu

2000-09-01

Ultraviolet photoelectron spectroscopy has been successfully used to measure the heights of the tops of the valence bands of the surfaces of AgBr layers on Ag substrates for the verification of the space charge layer model. According to this model, the positive space charge layer (composed of negative charges with excess negative kink sites on the surface and corresponding positive charges with interstitial silver ions in the interior) is formed in silver halides, causing the difference in the electronic energy levels between their surface and interior. The depression of the positive space charge layer of AgBr caused by such adsorbates as photographic stabilizers and antifoggants was estimated from the decrease in the ionic conductivity of cubic AgBr microcrystals by the adsorbates. It was confirmed by the decrease in the heights of the tops of the valence bands of the surfaces of AgBr layers caused by the adsorbates in the presence of thin gelatin membranes on their surfaces. This result provided the explanation for the fact that the adsorbates increased the number of the microcrystals which formed latent image centers on the surface and decreased the number of the microcrystals, which formed latent image centers in the interior.

Crystallization of calcium oxalates is controlled by molecular hydrophilicity and specific polyanion-crystal interactions.

PubMed

Grohe, Bernd; Taller, Adam; Vincent, Peter L; Tieu, Long D; Rogers, Kem A; Heiss, Alexander; Sørensen, Esben S; Mittler, Silvia; Goldberg, Harvey A; Hunter, Graeme K

2009-10-06

To gain more insight into protein structure-function relationships that govern ectopic biomineralization processes in kidney stone formation, we have studied the ability of urinary proteins (Tamm-Horsfall protein, osteopontin (OPN), prothrombin fragment 1 (PTF1), bikunin, lysozyme, albumin, fetuin-A), and model compounds (a bikunin fragment, recombinant-, milk-, bone osteopontin, poly-L-aspartic acid (poly asp), poly-L-glutamic acid (poly glu)) in modulating precipitation reactions of kidney stone-related calcium oxalate mono- and dihydrates (COM, COD). Combining scanning confocal microscopy and fluorescence imaging, we determined the crystal faces of COM with which these polypeptides interact; using scanning electron microscopy, we characterized their effects on crystal habits and precipitated volumes. Our findings demonstrate that polypeptide adsorption to COM crystals is dictated first by the polypeptide's affinity for the crystal followed by its preference for a crystal face: basic and relatively hydrophobic macromolecules show no adsorption, while acidic and more hydrophilic polypeptides adsorb either nonspecifically to all faces of COM or preferentially to {100}/{121} edges and {100} faces. However, investigating calcium oxalates grown in the presence of these polypeptides showed that some acidic proteins that adsorb to crystals do not affect crystallization, even if present in excess of physiological concentrations. These proteins (albumin, bikunin, PTF1, recombinant OPN) have estimated total hydrophilicities from 200 to 850 kJ/mol and net negative charges from -9 to -35, perhaps representing a "window" in which proteins adsorb and coat urinary crystals (support of excretion) without affecting crystallization. Strongest effects on crystallization were observed for polypeptides that are either highly hydrophilic (>950 kJ/mol) and highly carboxylated (poly asp, poly glu), or else highly hydrophilic and highly phosphorylated (native OPN isoforms), suggesting that highly hydrophilic proteins strongly affect precipitation processes in the urinary tract. Therefore, the level of hydrophilicity and net charge is a critical factor in the ability of polypeptides to affect crystallization and to regulate biomineralization processes.

Instrumentation and Methodology Development for Mars Mission

NASA Technical Reports Server (NTRS)

Chen, Yuan-Liang Albert

2002-01-01

The Mars environment comprises a dry, cold and low air pressure atmosphere with low gravity (0.38g) and high resistivity soil. The global dust storms that cover a large portion of Mars were observed often from Earth. This environment provides an idea condition for triboelectric charging. The extremely dry conditions on the Martian surface have raised concerns that electrostatic charge buildup will not be dissipated easily. If triboelectrically generated charge cannot be dissipated or avoided, then dust will accumulate on charged surfaces and electrostatic discharge may cause hazards for future exploration missions. The low surface temperature on Mars helps to prolong the charge decay on the dust particles and soil. To better understand the physics of Martian charged dust particles is essential to future Mars missions. We research and design two sensors, velocity/charge sensor and PZT momentum sensors, to detect the velocity distribution, charge distribution and mass distribution of Martian charged dust particles. These sensors are fabricated at NASA Kenney Space Center, Electromagnetic Physics Testbed. The sensors will be tested and calibrated for simulated Mars atmosphere condition with JSC MARS-1 Martian Regolith simulant in this NASA laboratory.

The role of electrostatic interactions in protease surface diffusion and the consequence for interfacial biocatalysis.

PubMed

Feller, Bob E; Kellis, James T; Cascão-Pereira, Luis G; Robertson, Channing R; Frank, Curtis W

2010-12-21

This study examines the influence of electrostatic interactions on enzyme surface diffusion and the contribution of diffusion to interfacial biocatalysis. Surface diffusion, adsorption, and reaction were investigated on an immobilized bovine serum albumin (BSA) multilayer substrate over a range of solution ionic strength values. Interfacial charge of the enzyme and substrate surface was maintained by performing the measurements at a fixed pH; therefore, electrostatic interactions were manipulated by changing the ionic strength. The interfacial processes were investigated using a combination of techniques: fluorescence recovery after photobleaching, surface plasmon resonance, and surface plasmon fluorescence spectroscopy. We used an enzyme charge ladder with a net charge ranging from -2 to +4 with respect to the parent to systematically probe the contribution of electrostatics in interfacial enzyme biocatalysis on a charged substrate. The correlation between reaction rate and adsorption was determined for each charge variant within the ladder, each of which displayed a maximum rate at an intermediate surface concentration. Both the maximum reaction rate and adsorption value at which this maximum rate occurs increased in magnitude for the more positive variants. In addition, the specific enzyme activity increased as the level of adsorption decreased, and for the lowest adsorption values, the specific enzyme activity was enhanced compared to the trend at higher surface concentrations. At a fixed level of adsorption, the specific enzyme activity increased with positive enzyme charge; however, this effect offers diminishing returns as the enzyme becomes more highly charged. We examined the effect of electrostatic interactions on surface diffusion. As the binding affinity was reduced by increasing the solution ionic strength, thus weakening electrostatic interaction, the rate of surface diffusion increased considerably. The enhancement in specific activity achieved at the lowest adsorption values is explained by the substantial rise in surface diffusion at high ionic strength due to decreased interactions with the surface. Overall, knowledge of the electrostatic interactions can be used to control surface parameters such as surface concentration and surface diffusion, which intimately correlate with surface biocatalysis. We propose that the maximum reaction rate results from a balance between adsorption and surface diffusion. The above finding suggests enzyme engineering and process design strategies for improving interfacial biocatalysis in industrial, pharmaceutical, and food applications.

Silver nanoparticles as a key feature of a plasma polymer composite layer in mitigation of charge injection into polyethylene under dc stress

NASA Astrophysics Data System (ADS)

Milliere, L.; Maskasheva, K.; Laurent, C.; Despax, B.; Boudou, L.; Teyssedre, G.

2016-01-01

The aim of this work is to limit charge injection from a semi-conducting electrode into low density polyethylene (LDPE) under dc field by tailoring the polymer surface using a silver nanoparticles-containing layer. The layer is composed of a plane of silver nanoparticles embedded in a semi-insulating organosilicon matrix deposited on the polyethylene surface by a plasma process. Size, density and surface coverage of the nanoparticles are controlled through the plasma process. Space charge distribution in 300 μm thick LDPE samples is measured by the pulsed-electroacoustic technique following a short term (step-wise voltage increase up to 50 kV mm-1, 20 min in duration each, followed by a polarity inversion) and a longer term (up to 12 h under 40 kV mm-1) protocols for voltage application. A comparative study of space charge distribution between a reference polyethylene sample and the tailored samples is presented. It is shown that the barrier effect depends on the size distribution and the surface area covered by the nanoparticles: 15 nm (average size) silver nanoparticles with a high surface density but still not percolating form an efficient barrier layer that suppress charge injection. It is worthy to note that charge injection is detected for samples tailored with (i) percolating nanoparticles embedded in organosilicon layer; (ii) with organosilicon layer only, without nanoparticles and (iii) with smaller size silver particles (<10 nm) embedded in organosilicon layer. The amount of injected charges in the tailored samples increases gradually in the samples ranking given above. The mechanism of charge injection mitigation is discussed on the basis of complementary experiments carried out on the nanocomposite layer such as surface potential measurements. The ability of silver clusters to stabilize electrical charges close to the electrode thereby counterbalancing the applied field appears to be a key factor in explaining the charge injection mitigation effect.

The Thomas-Fermi model in the theory of systems of charged particles above the surface of liquid dielectrics

NASA Astrophysics Data System (ADS)

Lytvtnenko, D. M.; Slyusarenko, Yu. V.; Kirdin, A. I.

2012-10-01

A consistent theory of equilibrium states of same sign charges above the surface of liquid dielectric film located on solid substrate in the presence of external attracting constant electric field is proposed. The approach to the development of the theory is based on the Thomas-Fermi model generalized to the systems under consideration and on the variational principle. The using of self-consistent field model allows formulating a theory containing no adjustable constants. In the framework of the variational principle we obtain the self-consistency equations for the parameters describing the system: the distribution function of charges above the liquid dielectric surface, the electrostatic field potentials in all regions of the system and the surface profile of the liquid dielectric. The self-consistency equations are used to describe the phase transition associated with the formation of spatially periodic structures in the system of charges on liquid dielectric surface. Assuming the non-degeneracy of the gas of charges above the surface of liquid dielectric film the solutions of the self-consistency equations near the critical point are obtained. In the case of the symmetric phase we obtain the expressions for the potentials and electric fields in all regions of the studied system. The distribution of the charges above the surface of liquid dielectric film for the symmetric phase is derived. The system parameters of the phase transition to nonsymmetric phase - the states with a spatially periodic ordering are obtained. We derive the expression determining the period of two-dimensional lattice as a function of physical parameters of the problem - the temperature, the external attractive electric field, the number of electrons per unit of the flat surface area of the liquid dielectric, the density of the dielectric, its surface tension and permittivity, and the permittivity of the solid substrate. The possibility of generalizing the developed theory in the case of degenerate gas of like-charged particles above the liquid dielectric surface is discussed.

Surface functionalization of dopamine coated iron oxide nanoparticles for various surface functionalities

NASA Astrophysics Data System (ADS)

Sherwood, Jennifer; Xu, Yaolin; Lovas, Kira; Qin, Ying; Bao, Yuping

2017-04-01

We present effective conjugation of four small molecules (glutathione, cysteine, lysine, and Tris(hydroxymethyl)aminomethane) onto dopamine-coated iron oxide nanoparticles. Conjugation of these molecules could improve the surface functionality of nanoparticles for more neutral surface charge at physiological pH and potentially reduce non-specific adsorption of proteins to nanoparticles surfaces. The success of conjugation was evaluated with dynamic light scattering by measuring the surface charge changes and Fourier transform infrared spectroscopy for surface chemistry analysis. The stability of dopamine-coated nanoparticles and the ability of conjugated nanoparticles to reduce the formation of protein corona were evaluated by measuring the size and charge of the nanoparticles in biological medium. This facile conjugation method opens up possibilities for attaching various surface functionalities onto iron oxide nanoparticle surfaces for biomedical applications.

Enhanced flashover strength in polyethylene nanodielectrics by secondary electron emission modification

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Weiwang; Li, Shengtao, E-mail: sli@xjtu.edu.cn; Min, Daomin

2016-04-15

This work studies the correlation between secondary electron emission (SEE) characteristics and impulse surface flashover in polyethylene nanodielectrics both theoretically and experimentally, and illustrates the enhancement of flashover voltage in low-density polyethylene (LDPE) through incorporating Al{sub 2}O{sub 3} nanoparticles. SEE characteristics play key roles in surface charging and gas desorption during surface flashover. This work demonstrates that the presence of Al{sub 2}O{sub 3} nanoparticles decreases the SEE coefficient of LDPE and enhances the impact energy at the equilibrium state of surface charging. These changes can be explained by the increase of surface roughness and of surface ionization energy, and themore » strong interaction between nanoparticles and the polymer dielectric matrix. The surface charge and flashover voltage are calculated according to the secondary electron emission avalanche (SEEA) model, which reveals that the positive surface charges are reduced near the cathode triple point, while the presence of more nanoparticles in high loading samples enhances the gas desorption. Consequently, the surface flashover performance of LDPE/Al{sub 2}O{sub 3} nanodielectrics is improved.« less

In situ measurement of surface potential developed on MgO thin film surface under ion irradiation using ion scattering spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nagatomi, T.; Kuwayama, T.; Takai, Y.

2009-11-15

The application of ion scattering spectroscopy (ISS) to the in situ measurement of the surface potential developed on an insulator surface under positive ion irradiation was investigated. The ISS spectra measured for a MgO film of 600 nm thickness on a Si substrate by the irradiation of 950 eV He{sup +} ions revealed that the surface is positively charged by approximately 180 V. For accurate measurement of the surface potential, a correction to take into account the angular deflection of primary ions induced by the high surface potential is required. The dependence of the surface potential on the sample temperaturemore » revealed that no charging is induced above 700 deg. C, indicating that accumulated charges can be removed by heating to 700 deg. C. From the measurement of the ion-induced secondary electron yield using a collector electrode located in front of the sample surface, the surface potential and ion-induced secondary electron yield were found to be strongly affected by the experimental setup. Secondary electrons produced by the impact of slow positive secondary ions, the maximum energy of which corresponds to the surface potential, play an important role when the bias voltage applied to the collector electrode is positively high for the present experimental setup. The surface potential developed on the surface of MgO films of 600 and 200 nm thickness was measured in situ, revealing that the amount of accumulated charges and the time required to attain the steady state of charging are slightly dependent on the beam current of primary ions and strongly dependent on the thickness of the MgO film. The present results confirmed that the application of ISS has high potential for investigating charging phenomena and the secondary electron emission from insulator surfaces under positive ion irradiation.« less

Ferrocene Containing Copolymers with Improved Electrostatic Dissipation Properties for Advanced Applications

NASA Technical Reports Server (NTRS)

Smith, T. M.; Nelson, G. L.

2005-01-01

Electrostatic dissipative polymers are used for a variety of functions. Typical methods utilized to transform electrically insulating polymers into either charge dissipative or conductive materials involve incorporating a conductive filler, conductive polymer, oxidizing the surface using plasma, or incorporating surfactants that act as surface wetting agents. Another approach is to synthesize a block copolymer that is expected to result in better electrical properties with minimal impacts to physical, fire, and thermal properties. One such block that can be added into the main chain of polymers is a diol terminated ferrocene oligomer, which is expected to impart electrostatic dissipative properties into the host polymer while concurrently improving the overall fire properties. Previous work with polyurethanes incorporating a ferrocene oligomer into the main chain resulted in much improved fire retardancy. In dealing with electrostatic dissipative materials the important questions are: how easily does the material charge and how quickly can the charge move to ground. One normally describes the materials conductivity, but conductivity only measures the fastest path for an electron not the slowest path. The slowest path is the one of interest, since it is left on the surface and thus can cause discharges. In order to assess ease of charging and decay times corona charge dissipation measurements can accurately assess these properties by introducing a charge on the surface of the material then measuring the surface voltage and the amount of charge deposited. The charge decay curve then will give an indication of a materials electrostatic dissipation properties. Normally, triboelectric testing can be performed, but results vary. Corona charge dissipation results are more repeatable.

Self-consistent simulation of radio frequency multipactor on micro-grooved dielectric surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cai, Libing; Wang, Jianguo, E-mail: wanguiuc@mail.xjtu.edu.cn; Northwest Institute of Nuclear Technology, Xi'an, Shaanxi 710024

2015-02-07

The multipactor plays a key role in the surface breakdown on the feed dielectric window irradiated by high power microwave. To study the suppression of multipactor, a 2D electrostatic PIC-MCC simulation code was developed. The space charge field, including surface deposited charge and multipactor electron charge field, is obtained by solving 2D Poisson's equation in time. Therefore, the simulation is self-consistent and does not require presetting a fixed space charge field. By using this code, the self-consistent simulation of the RF multipactor on the periodic micro-grooved dielectric surface is realized. The 2D space distributions of the multipactor electrons and spacemore » charge field are presented. From the simulation results, it can be found that only half slopes have multipactor discharge when the slope angle exceeds a certain value, and the groove presents a pronounced suppression effect on the multipactor.« less

Hydrolysis-controlled protein adsorption and antifouling behaviors of mixed charged self-assembled monolayer: A molecular simulation study.

PubMed

Liu, Jie; Zhou, Jian

2016-08-01

Understanding the mechanism of the antimicrobial and antifouling properties of mixed charged materials is of great significance. The interactions between human gamma fibrinogen (γFg) and mixed carboxylic methyl ether-terminated (COOCH3-) and trimethylamino-terminated (N(CH3)3(+)-) SAMs and the influence of hydrolysis were studied by molecular simulations. After hydrolysis, the mixed SAMs exhibit behaviors from antimicrobial to antifouling, since the COOCH3-thiols were translated into carboxylic acid (COO(-)-) terminated thiols, which carried a net charge of -1 e. Simulation results showed that the main differences between COOCH3-/N(CH3)3(+)-SAM and COO(-)-/N(CH3)3(+)-SAM are the charged property and the hydration layer above the surface. γFg could stably adsorb on the positively-charged COOCH3-/N(CH3)3(+)-SAM. The adsorption behavior is mainly induced by the strong electrostatic attraction. There is a single hydration layer bound to the surface, which is related to the N(CH3)3(+) groups. The van der Waals repulsion between γFg and the single hydration layer are not strong enough to compensate the strong electrostatic attraction. After hydrolysis, the positively-charged SAM was transferred to a neutral mixed charged surface, the electrostatic attraction between γFg and the surface disappears. Meanwhile, the SAM surface is covered by double hydration layers, which is induced by the N(CH3)3(+) and COO(-) groups; water molecules around COO(-) groups are obviously denser than that around N(CH3)3(+) groups. With the combined contribution from double hydration layers and the vanishment of electrostatic attraction, γFg is forced to desorb from the surface. After hydrolysis, the internal structure of mixed SAM appears more ordered due to the electrostatic interactions between charged groups on the top of SAMs. The antimicrobial and antifouling materials are of great importance in many biological applications. The strong hydration property of surfaces and the interactions between proteins and surfaces play a key role in resisting protein adsorption. The mixed SAMs, constructed from a 1:1 combination of COOCH3- and N(CH3)3(+)-terminated thiols, can induce protein adsorption mainly through the electrostatic interaction. When the COOCH3-terminated thiols were hydrolyzed to negatively charged COO(-)-terminated thiols, the mixed-charged SAMs switched from antimicrobial to antifouling. Due to the strong hydration property of the mixed charged SAMs, the adsorbed γFg moved away from the surface. Understanding the interactions between protein and mixed-charged SAMs in the atomistic level is important for the practical design and development of new antimicrobial and antifouling materials. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

NASCAP modelling computations on large optics spacecraft in geosynchronous substorm environments

NASA Technical Reports Server (NTRS)

Stevens, N. J.; Purvis, C. K.

1980-01-01

Satellites in geosynchronous orbits have been found to be charged to significant negative voltages during encounters with geomagnetic substorms. When satellite surfaces are charged, there is a probability of enhanced contamination from charged particles attracted back to the satellite by electrostatic forces. This could be particularly disturbing to large satellites using sensitive optical systems. In this study the NASA Charging Analyzer Program (NASCAP) is used to evaluate qualitatively the possibility of such enhanced contamination on a conceptual version of a large satellite. The evaluation is made by computing surface voltages on the satellite due to encounters with substorm environments and then computing charged-particle trajectories in the electric fields around the satellite. Particular attention is paid to the possibility of contaminants reaching a mirror surface inside a dielectric tube because this mirror represents a shielded optical surface in the satellite model used. Deposition of low energy charged particles from other parts of the spacecraft onto the mirror was found to be possible in the assumed moderate substorm environment condition. In the assumed severe substorm environment condition, however, voltage build up on the inside and edges of the dielectric tube in which the mirror is located prevents contaminants from reaching the mirror surface.

Extremely large nonsaturating magnetoresistance and ultrahigh mobility due to topological surface states in the metallic Bi2Te3 topological insulator

NASA Astrophysics Data System (ADS)

Shrestha, K.; Chou, M.; Graf, D.; Yang, H. D.; Lorenz, B.; Chu, C. W.

2017-05-01

Weak antilocalization (WAL) effects in Bi2Te3 single crystals have been investigated at high and low bulk charge-carrier concentrations. At low charge-carrier density the WAL curves scale with the normal component of the magnetic field, demonstrating the dominance of topological surface states in magnetoconductivity. At high charge-carrier density the WAL curves scale with neither the applied field nor its normal component, implying a mixture of bulk and surface conduction. WAL due to topological surface states shows no dependence on the nature (electrons or holes) of the bulk charge carriers. The observations of an extremely large nonsaturating magnetoresistance and ultrahigh mobility in the samples with lower carrier density further support the presence of surface states. The physical parameters characterizing the WAL effects are calculated using the Hikami-Larkin-Nagaoka formula. At high charge-carrier concentrations, there is a greater number of conduction channels and a decrease in the phase coherence length compared to low charge-carrier concentrations. The extremely large magnetoresistance and high mobility of topological insulators have great technological value and can be exploited in magnetoelectric sensors and memory devices.

Dangerous liaisons: anion-induced protonation in phosphate-polyamine interactions and their implications for the charge states of biologically relevant surfaces.

PubMed

Laucirica, Gregorio; Marmisollé, Waldemar A; Azzaroni, Omar

2017-03-22

Although not always considered a preponderant interaction, amine-phosphate interactions are omnipresent in multiple chemical and biological systems. This study aims to answer questions that are still pending about their nature and consequences. We focus on the description of the charge state as surface charges constitute directing agents of the interaction of amine groups with either natural or synthetic counterparts. Our results allow us to quantitatively determine the relative affinities of HPO 4 2- and H 2 PO 4 - from the analysis of the influence of phosphates on the zeta-potential of amino-functionalized surfaces in a broad pH range. We show that phosphate anions enhance the protonation of amino groups and, conversely, charged amines induce further proton dissociation of phosphates, yielding a complex dependence of the surface effective charge on the pH and phosphate concentration. We also demonstrate that phosphate-amine interaction is specific and the modulation of surface charge occurs in the physiological phosphate concentration range, emphasizing its biochemical and biotechnological relevance and the importance of considering this veiled association in both in vivo and in vitro studies.

Mechanical Removal and Rescreening of Local Screening Charges on Ferroelectric Surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tong, Sheng; Park, Woon Ik; Choi, YoonYoung

2015-01-20

We report the kinetics of screening charge removal and rescreening on periodically poled lithium niobate using charge-gradient microscopy and electrostatic force microscopy (EFM). A minimum pressure needs to be applied to initiate mechanical screening charge removal, and increasing the pressure leads to further removal of charge until a threshold is reached when all screening charges are removed. We fit all rescreening EFM contrast curves under various pressures into a universal exponential decay. The findings imply that we can control the screening degree of ferroelectric surfaces by mechanical means without affecting the polarization underneath.

Mechanical Removal and Rescreening of Local Screening Charges at Ferroelectric Surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tong, Sheng; Park, Woon Ik; Choi, Yoon-Young

2015-01-20

In this paper, we report the kinetics of screening charge removal and rescreening on periodically poled lithium niobate using charge-gradient microscopy and electrostatic force microscopy (EFM). A minimum pressure needs to be applied to initiate mechanical screening charge removal, and increasing the pressure leads to further removal of charge until a threshold is reached when all screening charges are removed. We fit all rescreening EFM contrast curves under various pressures into a universal exponential decay. Finally, the findings imply that we can control the screening degree of ferroelectric surfaces by mechanical means without affecting the polarization underneath.

Field observations of the electrostatic charges of blowing snow in Hokkaido, Japan

NASA Astrophysics Data System (ADS)

Omiya, S.; Sato, A.

2011-12-01

An electrostatic charge of blowing snow may be a contributing factor in the formation of a snow drift and a snow cornice, and changing of the trajectory of own motion. However, detailed electrification characteristics of blowing snow are not known as there are few reports of charge measurements. We carried out field observations of the electrostatic charges of blowing snow in Tobetsu, Hokkaido, Japan in the mid winter of 2011. An anemovane and a thermohygrometer were used for the meteorological observation. Charge-to-mass ratios of blowing snow were obtained by a Faraday-cage, an electrometer and an electric balance. In this observation period, the air temperature during the blowing snow event was -6.5 to -0.5 degree Celsius. The measured charges in this observation were consistent with the previous studies in sign, which is negative, but they were smaller than the previous one. In most cases, the measured values increased with the temperature decrease, which corresponds with previous studies. However, some results contradicted the tendency, and the maximum value was obtained on the day of the highest air temperature of -0.5 degree Celsius. This discrepancy may be explained from the difference of the snow surface condition on observation day. The day when the maximum value was obtained, the snow surface was covered with old snow, and hard. On the other hand, in many other cases, the snow surface was covered with the fresh snow, and soft. Blowing snow particles on the hard surface can travel longer distance than on the soft one. Therefore, it can be surmised that the hard surface makes the blowing snow particles accumulate a lot of negative charges due to a large number of collisions to the surface. This can be supported by the results of the wind tunnel experiments by Omiya and Sato (2011). By this field observation, it was newly suggested that the electrostatic charge of blowing snow are influenced greatly by the difference of the snow surface condition. REFERENCE: Omiya and Sato,(2010):An electrostatic charge measurement of blowing snow particles focusing on collision frequency to the snow surface. AGU Abstract Database, 2010 Fall Meeting.

Regioselective Sequential Modification of Chitosan via Azide-Alkyne Click Reaction: Synthesis, Characterization, and Antimicrobial Activity of Chitosan Derivatives and Nanoparticles

PubMed Central

Sarwar, Atif; Katas, Haliza; Samsudin, Siti Noradila; Zin, Noraziah Mohamad

2015-01-01

Recently, the attention of researchers has been drawn toward the synthesis of chitosan derivatives and their nanoparticles with enhanced antimicrobial activities. In this study, chitosan derivatives with different azides and alkyne groups were synthesized using click chemistry, and these were further transformed into nanoparticles by using the ionotropic gelation method. A series of chitosan derivatives was successfully synthesized by regioselective modification of chitosan via an azide-alkyne click reaction. The amino moieties of chitosan were protected during derivatization by pthaloylation and subsequently unblocked at the end to restore their functionality. Nanoparticles of synthesized derivatives were fabricated by ionic gelation to form complexes of polyanionic penta-sodium tripolyphosphate (TPP) and cationic chitosan derivatives. Particle size analysis showed that nanoparticle size ranged from 181.03 ± 12.73 nm to 236.50 ± 14.32 nm and had narrow polydispersity index and positive surface charge. The derivatives and corresponding nanoparticles were evaluated in vitro for antibacterial and antifungal activities against three gram-positive and gram-negative bacteria and three fungal strains, respectively. The minimum inhibitory concentration (MIC) of all derivatives ranged from 31.3 to 250 µg/mL for bacteria and 188 to1500 µg/mL for fungi and was lower than that of native chitosan. The nanoparticles with MIC ranging from 1.56 to 25 µg/mLfor bacteria and 94 to 750 µg/mL for fungi exhibited higher activity than the chitosan derivatives. Chitosan O-(1-methylbenzene) triazolyl carbamate and chitosan O-(1-methyl phenyl sulfide) triazolyl carbamate were the most active against the tested bacterial and fungal strains. The hemolytic assay on erythrocytes and cell viability test on two different cell lines (Chinese hamster lung fibroblast cells V79 and Human hepatic cell line WRL68) demonstrated the safety; suggesting that these derivatives could be used in future medical applications. Chitosan derivatives with triazole functionality, synthesized by Huisgen 1,3-dipolar cycloaddition, and their nanoparticles showed significant enhancement in antibacterial and antifungal activities in comparison to those associated with native, non-altered chitosan. PMID:25928293

Influence of Protamine Functionalization on the Colloidal Stability of 1D and 2D Titanium Oxide Nanostructures.

PubMed

Rouster, Paul; Pavlovic, Marko; Horváth, Endre; Forró, László; Dey, Sandwip K; Szilagyi, Istvan

2017-09-26

The colloidal stability of titanium oxide nanosheets (TNS) and nanowires (TiONW) was studied in the presence of protamine (natural polyelectrolyte) in aqueous dispersions, where the nanostructures possessed negative net charge, and the protamine was positively charged. Regardless of their shape, similar charging and aggregation behaviors were observed for both TNS and TiONW. Electrophoretic experiments performed at different protamine loadings revealed that the adsorption of protamine led to charge neutralization and charge inversion depending on the polyelectrolyte dose applied. Light scattering measurements indicated unstable dispersions once the surface charge was close to zero or slow aggregation below and above the charge neutralization point with negatively or positively charged nanostructures, respectively. These stability regimes were confirmed by the electron microscopy images taken at different polyelectrolyte loadings. The protamine dose and salt-dependent colloidal stability confirmed the presence of DLVO-type interparticle forces, and no experimental evidence was found for additional interactions (e.g., patch-charge, hydrophobic, or steric forces), which are usually present in similar polyelectrolyte-particle systems. These findings indicate that the polyelectrolyte adsorbs on the TNS and TiONW surfaces in a flat and extended conformation giving rise to the absence of surface heterogeneities. Therefore, protamine is an excellent biocompatible candidate to form smooth surfaces, for instance in multilayers composed of polyelectrolytes and particles to be used in biomedical applications.

Recovery curves of the surface electric field after lightning discharges occurring between the positive charge pocket and negative charge centre in a thundercloud

NASA Astrophysics Data System (ADS)

Pawar, S. D.; Kamra, A. K.

2002-12-01

Surface observations of the electric field recovery curves of the lightning discharges occurring between the positive charge pocket and negative main charge centre in an overhead thundercloud are reported. Such recovery curves are observed to have an additional step of very slow field-change observed at an after-discharge value of electric field equal to 5-6 kV m-1. The behavior of recovery curves is explained in terms of the coronae charge and the relative efficiencies of the charge generating processes responsible for growth of positive charge pocket and main negative charge centre in the thundercloud. The charging currents responsible for the growth of charge in positive charge pockets is computed to be 2-4 times larger than that for the growth of the main negative charge. However, the charge destroyed in such a discharge is found to be comparable to that in a discharge between the main charge centres of the thundercloud.

A Self-Assembling Protein Hydrogel Technology for Enzyme Incorporation onto Electrodes in Biofuel Cells

DTIC Science & Technology

2015-10-26

amount of the product J and the unreacted N/C in the same lane. Figure 2. Crystal structure of Tip1-Tip1lig ( PDB code: 3IDW). (A...stability (able to retain its trimeric quaternary structure in solutions after boiling in SDS buffer). We reasoned that its very strong...109, 10 is a flexible polyanionic linker and was incorporated as the midblock for water retention. Mixing of the two protein block copolymers

A novel method for producing microspheres with semipermeable polymer membranes

NASA Technical Reports Server (NTRS)

Lin, K. C.; Wang, Taylor G.

1992-01-01

A new and systematic approach for producing polymer microspheres has been demonstrated. The membrane of the microsphere is formed by immersing the polyanionic droplet into a collapsing annular sheet, which is made of another polycation polymer solution. This method minimizes the impact force during the time when the chemical reaction takes place, hence eliminating the shortcomings of the current encapsulation techniques. The results of this study show the feasibility of this method for mass production of microcapsules.

A Closer Look at Solar Wind Sputtering of Lunar Surface Materials

NASA Technical Reports Server (NTRS)

Barghouty, A. F.; Adams, J. H., Jr.; Meyer, F.; Mansur, L.; Reinhold, C.

2008-01-01

Solar-wind induced potential sputtering of the lunar surface may be a more efficient erosive mechanism than the "standard" kinetic (or physical) sputtering. This is partly based on new but limited laboratory measurements which show marked enhancements in the sputter yields of slow-moving, highly-charged ions impacting oxides. The enhancements seen in the laboratory can be orders of magnitude for some surfaces and highly charged incident ions, but seem to depend very sensitively on the properties of the impacted surface in addition to the fluence, energy and charge of the impacting ion. For oxides, potential sputtering yields are markedly enhanced and sputtered species, especially hydrogen and light ions, show marked dependence on both charge and dose.

Time and voltage dependences of nanoscale dielectric constant modulation on indium tin oxide films

NASA Astrophysics Data System (ADS)

Li, Liang; Hao, Haoyue; Zhao, Hua

2017-01-01

The modulation of indium tin oxide (ITO) films through surface charge accumulation plays an important role in many different applications. In order to elaborately study the modulation, we measured the dielectric constant of the modulated layer through examining the excitation of surface plasmon polaritons. Charges were pumped on the surfaces of ITO films through applying high voltage in appropriate directions. Experiments unveiled that the dielectric constant of the modulated layer had large variation along with the nanoscale charge accumulation. Corresponding numerical results were worked out through combining Drude model and Mayadas-Shatzkes model. Based on the above results, we deduced the time and voltage dependences of accumulated charge density, which revealed a long-time charge accumulation process.

In Situ Tracking Kinetic Pathways of Li + /Na + Substitution during Ion-Exchange Synthesis of Li xNa 1.5–x VOPO 4 F 0.5

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, Young-Uk; Bai, Jianming; Wang, Liping

Ion exchange is a ubiquitous phenomenon central to wide industrial applications, ranging from traditional (bio)chemical separation to the emerging chimie douce synthesis of materials for batteries and other energy applications. The exchange process is complex, involving substitution and transport of different ions under non-equilibrium conditions, and thus difficult to probe, leaving a gap in mechanistic understanding of kinetic exchange pathways toward final products. Herein, we report in situ tracking kinetic pathways of Li +/Na + substitution during solvothermal ion-exchange synthesis of Li xNa 1.5-xVOPO 4F 0.5 (0 ≤ x ≤ 1.5), a promising multi-Li polyanionic cathode for batteries. The real-timemore » observation, corroborated by first-principles calculations, reveals a selective replacement of Na + by Li +, leading to peculiar Na +/Li +/vacancy orderings in the intermediates. Contradicting the traditional belief of facile topotactic substitution via solid solution reaction, an abrupt two-phase transformation occurs and predominantly governs the kinetics of ion exchange and transport in the 1D polyanionic framework, consequently leading to significant difference of Li stoichiometry and electrochemical properties in the exchanged products. The findings may help to pave the way for rational design of ion exchange synthesis for making new materials.« less

Reaction enthalpy from the binding of multivalent cations to anionic polyelectrolytes in dilute solutions

NASA Astrophysics Data System (ADS)

Hansch, Markus; Kaub, Hans Peter; Deck, Sascha; Carl, Nico; Huber, Klaus

2018-03-01

Dilute solutions of sodium poly(styrene sulfonate) (NaPSS) in the presence of Al3+, Ca2+, and Ba2+ were analysed by means of isothermal titration calorimetry (ITC) in order to investigate the heat effect of bond formation between those cations and the anionic SO3- residues of NaPSS. The selection of the cations was guided by the solution behavior of the corresponding PSS salts from a preceding study [M. Hansch et al., J. Chem. Phys. 148(1), 014901 (2018)], where bonds between Ba2+ and anionic PSS showed an increasing solubility with decreasing temperature and Al3+ exhibited the inverse trend. Unlike to Al3+ and Ba2+, Ca2+ is expected to behave as a purely electrostatically interacting bivalent cation and was thus included in the present study. Results from ITC satisfactorily succeeded to explain the temperature-dependent solution behavior of the salts with Al3+ and Ba2+ and confirmed the non-specific behavior of Ca2+. Additional ITC experiments with salts of Ca2+ and Ba2+ and sodium poly(acrylate) complemented the results on PSS by data from a chemically different polyanion. Availability of these joint sets of polyanion-cation combinations not only offers the chance to identify common features and subtle differences in the solution behavior of polyelectrolytes in the presence of multi-valent cations but also points to a new class of responsive materials.

In Situ Tracking Kinetic Pathways of Li + /Na + Substitution during Ion-Exchange Synthesis of Li xNa 1.5–x VOPO 4 F 0.5

DOE PAGES

Park, Young-Uk; Bai, Jianming; Wang, Liping; ...

2017-08-29

Ion exchange is a ubiquitous phenomenon central to wide industrial applications, ranging from traditional (bio)chemical separation to the emerging chimie douce synthesis of materials for batteries and other energy applications. The exchange process is complex, involving substitution and transport of different ions under non-equilibrium conditions, and thus difficult to probe, leaving a gap in mechanistic understanding of kinetic exchange pathways toward final products. Herein, we report in situ tracking kinetic pathways of Li +/Na + substitution during solvothermal ion-exchange synthesis of Li xNa 1.5-xVOPO 4F 0.5 (0 ≤ x ≤ 1.5), a promising multi-Li polyanionic cathode for batteries. The real-timemore » observation, corroborated by first-principles calculations, reveals a selective replacement of Na + by Li +, leading to peculiar Na +/Li +/vacancy orderings in the intermediates. Contradicting the traditional belief of facile topotactic substitution via solid solution reaction, an abrupt two-phase transformation occurs and predominantly governs the kinetics of ion exchange and transport in the 1D polyanionic framework, consequently leading to significant difference of Li stoichiometry and electrochemical properties in the exchanged products. The findings may help to pave the way for rational design of ion exchange synthesis for making new materials.« less

The molecular basis of the solution properties of hyaluronan investigated by confocal fluorescence recovery after photobleaching.

PubMed Central

Gribbon, P; Heng, B C; Hardingham, T E

1999-01-01

Hyaluronan (HA) is a highly hydrated polyanion, which is a network-forming and space-filling component in the extracellular matrix of animal tissues. Confocal fluorescence recovery after photobleaching (confocal-FRAP) was used to investigate intramolecular hydrogen bonding and electrostatic interactions in hyaluronan solutions. Self and tracer lateral diffusion coefficients within hyaluronan solutions were measured over a wide range of concentrations (c), with varying electrolyte and at neutral and alkaline pH. The free diffusion coefficient of fluoresceinamine-labeled HA of 500 kDa in PBS was 7.9 x 10(-8) cm(2) s(-1) and of 830 kDa HA was 5.6 x 10(-8) cm(2) s(-1). Reductions in self- and tracer-diffusion with c followed a stretched exponential model. Electrolyte-induced polyanion coil contraction and destiffening resulted in a 2.8-fold increase in self-diffusion between 0 and 100 mM NaCl. Disruption of hydrogen bonds by strong alkali (0.5 M NaOH) resulted in further larger increases in self- and tracer-diffusion coefficients, consistent with a more dynamic and permeable network. Concentrated hyaluronan solution properties were attributed to hydrodynamic and entanglement interactions between domains. There was no evidence of chain-chain associations. At physiological electrolyte concentration and pH, the greatest contribution to the intrinsic stiffness of hyaluronan appeared to be due to hydrogen bonds between adjacent saccharides. PMID:10512840

Synthesis, anion exchange, and delamination of Co-Al layered double hydroxide: assembly of the exfoliated nanosheet/polyanion composite films and magneto-optical studies.

PubMed

Liu, Zhaoping; Ma, Renzhi; Osada, Minoru; Iyi, Nobuo; Ebina, Yasuo; Takada, Kazunori; Sasaki, Takayoshi

2006-04-12

This paper describes a systematic study on the synthesis, anion exchange, and delamination of Co-Al layered double hydroxide (LDH), with the aim of achieving fabrication and clarifying the properties of LDH nanosheet/polyanion composite films. Co-Al-CO3 LDH hexagonal platelets of 4 mum in lateral size were synthesized by the urea method under optimized reaction conditions. The as-prepared CO3(2-)-LDH was converted to Cl- -LDH by treating with a NaCl-HCl mixed solution, retaining its high crystallinity and hexagonal platelike morphology. LDHs intercalated with a variety of anions (such as NO3-, ClO4-, acetate, lactate, dodecyl sulfate, and oleate) were further prepared from Cl- -LDH via an anion-exchange process employing corresponding salts. Exchanged products in various anion forms were found to show different delamination behaviors in formamide. Among them, best results were observed for NO3- -LDH in terms of the exfoliating degree and the quality of the exfoliated nanosheets. The delamination gave a pink transparent suspension containing well-defined nanosheets with lateral sizes of up to 2 microm. The resulting nanosheets were assembled layer-by-layer with an anionic polymer, poly(sodium styrene 4-sulfonate) (PSS), onto quartz glass substrates to produce composite films. Magnetic circular dichroism (MCD) measurements revealed that the assembled multilayer films exhibited an interesting magneto-optical response.

Photocurrent generation in SnO2 thin film by surface charged chemisorption O ions

NASA Astrophysics Data System (ADS)

Lee, Po-Ming; Liao, Ching-Han; Lin, Chia-Hua; Liu, Cheng-Yi

2018-06-01

We report a photocurrent generation mechanism in the SnO2 thin film surface layer by the charged chemisorption O ions on the SnO2 thin film surface induced by O2-annealing. A critical build-in electric field in the SnO2 surface layer resulted from the charged O ions on SnO2 surface prolongs the lifetime and reduces the recombination probability of the photo-excited electron-hole pairs by UV-laser irradiation (266 nm) in the SnO2 surface layer, which is the key for the photocurrent generation in the SnO2 thin film surface layer. The critical lifetime of prolonged photo-excited electron-hole pair is calculated to be 8.3 ms.

Hydration of excess electrons trapped in charge pockets on molecular surfaces

NASA Astrophysics Data System (ADS)

Jalbout, Abraham F.; Del Castillo, R.; Adamowicz, Ludwik

2007-01-01

In this work we strive to design a novel electron trap located on a molecular surface. The process of electron trapping involves hydration of the trapped electron. Previous calculations on surface electron trapping revealed that clusters of OH groups can form stable hydrogen-bonded networks on one side of a hydrocarbon surface (i.e. cyclohexane sheets), while the hydrogen atoms on the opposite side of the surface form pockets of positive charge that can attract extra negative charge. The excess electron density on such surfaces can be further stabilized by interactions with water molecules. Our calculations show that these anionic systems are stable with respect to vertical electron detachment (VDE).

Design of asymmetric particles containing a charged interior and a neutral surface charge: comparative study on in vivo circulation of polyelectrolyte microgels.

PubMed

Chen, Kai; Xu, Jing; Luft, J Christopher; Tian, Shaomin; Raval, Jay S; DeSimone, Joseph M

2014-07-16

Lowering the modulus of hydrogel particles could enable them to bypass in vivo physical barriers that would otherwise filter particles with similar size but higher modulus. Incorporation of electrolyte moieties into the polymer network of hydrogel particles to increase the swelling ratio is a straightforward and quite efficient way to decrease the modulus. In addition, charged groups in hydrogel particles can also help secure cargoes. However, the distribution of charged groups on the surface of a particle can accelerate the clearance of particles. Herein, we developed a method to synthesize highly swollen microgels of precise size with near-neutral surface charge while retaining interior charged groups. A strategy was employed to enable a particle to be highly cross-linked with very small mesh size, and subsequently PEGylated to quench the exterior amines only without affecting the internal amines. Acidic degradation of the cross-linker allows for swelling of the particles to microgels with a desired size and deformability. The microgels fabricated demonstrated extended circulation in vivo compared to their counterparts with a charged surface, and could potentially be utilized in in vivo applications including as oxygen carriers or nucleic acid scavengers.

Work Function of Oxide Ultrathin Films on the Ag(100) Surface.

PubMed

Sementa, Luca; Barcaro, Giovanni; Negreiros, Fabio R; Thomas, Iorwerth O; Netzer, Falko P; Ferrari, Anna Maria; Fortunelli, Alessandro

2012-02-14

Theoretical calculations of the work function of monolayer (ML) and bilayer (BL) oxide films on the Ag(100) surface are reported and analyzed as a function of the nature of the oxide for first-row transition metals. The contributions due to charge compression, charge transfer and rumpling are singled out. It is found that the presence of empty d-orbitals in the oxide metal can entail a charge flow from the Ag(100) surface to the oxide film which counteracts the decrease in the work function due to charge compression. This flow can also depend on the thickness of the film and be reduced in passing from ML to BL systems. A regular trend is observed along first-row transition metals, exhibiting a maximum for CuO, in which the charge flow to the oxide is so strong as to reverse the direction of rumpling. A simple protocol to estimate separately the contribution due to charge compression is discussed, and the difference between the work function of the bare metal surface and a Pauling-like electronegativity of the free oxide slabs is used as a descriptor quantity to predict the direction of charge transfer.

Effect of Ca2+ ion concentration on adsorption of poly(carboxylate ether)-based (PCE) superplasticizer on mica.

PubMed

Wu, Bo; Chun, Byong-Wa; Gu, Le; Kuhl, Tonya L

2018-05-09

Poly(carboxylate ether)-based (PCE) superplasticizers consist of a carboxylic acid backbone and grafted poly(ethylene glycol) (PEG) side chains. Ca 2+ ion bridging mechanism is commonly purported to control PCE's adsorption on negatively charged cement particle surfaces in cement suspension, thus PCE was expected to adsorb on negatively charged surfaces in synthetic pore solutions via Ca 2+ /COO - interactions. Adsorption behaviors of a commercial PCE on negatively charged mica were studied in aqueous electrolyte solutions by a surface forces apparatus. Direct force measurements indicated that the PCE adsorbed onto mica from 0.1 M K 2 SO 4 due to K + ion chelation by the ether oxygen units CH 2 CH 2 O on the PEG chains, but surprisingly did not adsorb from either 0.1 M K 2 SO 4 with saturated Ca(OH) 2 or 0.1 M Ca(NO 3 ) 2 . The adsorption in K 2 SO 4 was weak, enabling the adsorbed PCE layers to be squeezed out under modest compression. Upon separating the surfaces, the PCE immediately achieved an identical re-adsorption. In high-calcium conditions, the PCE was highly positively charged due to Ca 2+ ion chelation by PEG chains and backbone carboxylic groups COO - , and mica also underwent charge reversal due to electrostatic adsorption/binding of Ca 2+ ions. Consequently, the interaction between mica and PCE was electrostatically repulsive and no PCE adsorption occurred. These findings can be explained by the complex interplay of ion chelation by PEG chains, electrostatic binding and screening interactions with charged surfaces in the presence of monovalent and divalent counterions, and ultimately charge reversal of both the charged surfaces and polyelectrolyte in high divalent ion conditions. Copyright © 2018 Elsevier Inc. All rights reserved.

Nanoscale charge transfer and diffusion at the MoS2/SiO2 interface by atomic force microscopy: contact injection versus triboelectrification.

PubMed

Xu, Rui; Ye, Shili; Xu, Kunqi; Lei, Le; Hussain, Sabir; Zheng, Zhiyue; Pang, Fei; Xing, Shuya; Liu, Xinmeng; Ji, Wei; Cheng, Zhihai

2018-08-31

Understanding the process of charge generation, transfer, and diffusion between two-dimensional (2D) materials and their supporting substrates is very important for potential applications of 2D materials. Compared with the systematic studies of triboelectric charging in a bulk sample, a fundamental understanding of the triboelectrification of the 2D material/insulator system is rather limited. Here, the charge transfer and diffusion of both the SiO 2 surface and MoS 2 /SiO 2 interface through contact electrification and frictional electrification are investigated systematically in situ by scanning Kelvin probe microscopy and dual-harmonic electrostatic force microscopy. Different from the simple static charge transfer between SiO 2 and the PtSi alloy atomic force microscope (AFM) tip, the charge transfer between the tip and the MoS 2 /SiO 2 system is complicated. Triboelectric charges, generated by contact or frictional electrification with the AFM tip, are trapped at the MoS 2 /SiO 2 interface and act as floating gates. The local charge discharge processes can be obtained by monitoring the surface potential. The charge decay time (τ) of the MoS 2 /SiO 2 interface is one (or two) orders of magnitude larger than the decay time τ of the SiO 2 surface. This work facilitates an understanding of the triboelectric and de-electrification of the interface between 2D materials and substrates. In addition to the charge transfer and diffusion, we demonstrate the nanopatterns of surface and interfacial charges, which have great potential for the application of self-assembly of charged nanostructures.

Entropic effects in the electric double layer of model colloids with size-asymmetric monovalent ions

NASA Astrophysics Data System (ADS)

Guerrero-García, Guillermo Iván; González-Tovar, Enrique; Olvera de la Cruz, Mónica

2011-08-01

The structure of the electric double layer of charged nanoparticles and colloids in monovalent salts is crucial to determine their thermodynamics, solubility, and polyion adsorption. In this work, we explore the double layer structure and the possibility of charge reversal in relation to the size of both counterions and coions. We examine systems with various size-ratios between counterions and coions (ion size asymmetries) as well as different total ion volume fractions. Using Monte Carlo simulations and integral equations of a primitive-model electric double layer, we determine the highest charge neutralization and electrostatic screening near the electrified surface. Specifically, for two binary monovalent electrolytes with the same counterion properties but differing only in the coion's size surrounding a charged nanoparticle, the one with largest coion size is found to have the largest charge neutralization and screening. That is, in size-asymmetric double layers with a given counterion's size the excluded volume of the coions dictates the adsorption of the ionic charge close to the colloidal surface for monovalent salts. Furthermore, we demonstrate that charge reversal can occur at low surface charge densities, given a large enough total ion concentration, for systems of monovalent salts in a wide range of ion size asymmetries. In addition, we find a non-monotonic behavior for the corresponding maximum charge reversal, as a function of the colloidal bare charge. We also find that the reversal effect disappears for binary salts with large-size counterions and small-size coions at high surface charge densities. Lastly, we observe a good agreement between results from both Monte Carlo simulations and the integral equation theory across different colloidal charge densities and 1:1-elec-trolytes with different ion sizes.

Probing surface charge potentials of clay basal planes and edges by direct force measurements.

PubMed

Zhao, Hongying; Bhattacharjee, Subir; Chow, Ross; Wallace, Dean; Masliyah, Jacob H; Xu, Zhenghe

2008-11-18

The dispersion and gelation of clay suspensions have major impact on a number of industries, such as ceramic and composite materials processing, paper making, cement production, and consumer product formulation. To fundamentally understand controlling mechanisms of clay dispersion and gelation, it is necessary to study anisotropic surface charge properties and colloidal interactions of clay particles. In this study, a colloidal probe technique was employed to study the interaction forces between a silica probe and clay basal plane/edge surfaces. A muscovite mica was used as a representative of 2:1 phyllosilicate clay minerals. The muscovite basal plane was prepared by cleavage, while the edge surface was obtained by a microtome cutting technique. Direct force measurements demonstrated the anisotropic surface charge properties of the basal plane and edge surface. For the basal plane, the long-range forces were monotonically repulsive within pH 6-10 and the measured forces were pH-independent, thereby confirming that clay basal planes have permanent surface charge from isomorphic substitution of lattice elements. The measured interaction forces were fitted well with the classical DLVO theory. The surface potentials of muscovite basal plane derived from the measured force profiles were in good agreement with those reported in the literature. In the case of edge surfaces, the measured forces were monotonically repulsive at pH 10, decreasing with pH, and changed to be attractive at pH 5.6, strongly suggesting that the charge on the clay edge surfaces is pH-dependent. The measured force profiles could not be reasonably fitted with the classical DLVO theory, even with very small surface potential values, unless the surface roughness was considered. The surface element integration (SEI) method was used to calculate the DLVO forces to account for the surface roughness. The surface potentials of the muscovite edges were derived by fitting the measured force profiles with the surface element integrated DLVO model. The point of zero charge of the muscovite edge surface was estimated to be pH 7-8.

The Influence of Particle Charge on Heterogeneous Reaction Rate Coefficients

NASA Technical Reports Server (NTRS)

Aikin, A. C.; Pesnell, W. D.

2000-01-01

The effects of particle charge on heterogeneous reaction rates are presented. Many atmospheric particles, whether liquid or solid are charged. This surface charge causes a redistribution of charge within a liquid particle and as a consequence a perturbation in the gaseous uptake coefficient. The amount of perturbation is proportional to the external potential and the square of the ratio of debye length in the liquid to the particle radius. Previous modeling has shown how surface charge affects the uptake coefficient of charged aerosols. This effect is now included in the heterogeneous reaction rate of an aerosol ensemble. Extension of this analysis to ice particles will be discussed and examples presented.

Group IV nanocrystals with ion-exchangeable surface ligands and methods of making the same

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wheeler, Lance M.; Nichols, Asa W.; Chernomordik, Boris D.

Methods are described that include reacting a starting nanocrystal that includes a starting nanocrystal core and a covalently bound surface species to create an ion-exchangeable (IE) nanocrystal that includes a surface charge and a first ion-exchangeable (IE) surface ligand ionically bound to the surface charge, where the starting nanocrystal core includes a group IV element.

Single ion induced surface nanostructures: a comparison between slow highly charged and swift heavy ions.

PubMed

Aumayr, Friedrich; Facsko, Stefan; El-Said, Ayman S; Trautmann, Christina; Schleberger, Marika

2011-10-05

This topical review focuses on recent advances in the understanding of the formation of surface nanostructures, an intriguing phenomenon in ion-surface interaction due to the impact of individual ions. In many solid targets, swift heavy ions produce narrow cylindrical tracks accompanied by the formation of a surface nanostructure. More recently, a similar nanometric surface effect has been revealed for the impact of individual, very slow but highly charged ions. While swift ions transfer their large kinetic energy to the target via ionization and electronic excitation processes (electronic stopping), slow highly charged ions produce surface structures due to potential energy deposited at the top surface layers. Despite the differences in primary excitation, the similarity between the nanostructures is striking and strongly points to a common mechanism related to the energy transfer from the electronic to the lattice system of the target. A comparison of surface structures induced by swift heavy ions and slow highly charged ions provides a valuable insight to better understand the formation mechanisms. © 2011 IOP Publishing Ltd

The influence of size and charge of chitosan/polyglutamic acid hollow spheres on cellular internalization, viability and blood compatibility.

PubMed

Dash, Biraja C; Réthoré, Gildas; Monaghan, Michael; Fitzgerald, Kathleen; Gallagher, William; Pandit, Abhay

2010-11-01

Polymeric hollow spheres can be tailored as efficient carriers of various therapeutic molecules due to their tunable properties. However, the entry of these synthetic vehicles into cells, their cell viability and blood compatibility depend on their physical and chemical properties e.g. size, surface charge. Herein, we report the effect of size and surface charge on cell viability and cellular internalization behaviour and their effect on various blood components using chitosan/polyglutamic acid hollow spheres as a model system. Negatively charged chitosan/polyglutamic acid hollow spheres of various sizes 100, 300, 500 and 1000 nm were fabricated using a template based method and covalently surface modified using linear polyethylene glycol and methoxyethanol amine to create a gradient of surface charge from negative to neutrally charged spheres respectively. The results here suggest that both size and surface charge have a significant influence on the sphere's behaviour, most prominently on haemolysis, platelet activation, plasma recalcification time, cell viability and internalization over time. Additionally, cellular internalization behaviour and viability was found to vary with different cell types. These results are in agreement with those of inorganic spheres and liposomes, and can serve as guidelines for tailoring polymeric solid spheres for specific desired applications in biological and pharmaceutical fields, including the design of nanometer to submicron-sized delivery vehicles. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

An environmentally benign dual action antimicrobial: quaternized chitosan/sodium alga acid multilayer films and silver nanoparticles decorated on magnetic nanoparticles.

PubMed

Jin, Feng; Xiang, Qian; Chen, Xiaoqin; Peng, Xuefeng; Xing, Xiaodong

2016-10-01

There is an urgent need to develop a puissant and environmentally benign antibacterial composite that act via multiple mechanisms to make response to the potentially daunting complexity of the microbial population and microbial antibiotic resistance. In this work, a facile and green approach, layer-by-layer self-assembly technology was applied to assemble polycation quaternized chitosan (QAC) and polyanion sodium alga acid onto magnetic nanoparticles (MNPs). Then silver nanoparticles (AgNPs) with stable and narrow-sized distribution in the range of 25-35 nm were immobilized on the surface of MNPs with L-ascorbic acid as reducing agent and organic multilayers as stabilizer. Through above modification on MNPs, we expected to achieve a green dual antibacterial and recyclable composite via the combined antibacterial action of QAC and AgNPs. Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, transmission electron microscopy, zeta potentials, and dynamic light scattering were employed to confirm the success of the surface functionalization. Silver ion release process was detected by inductively coupled plasma mass spectrometry. Furthermore, the antibacterial properties of the biomaterials against Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus were studied. The modified MNPs exhibited rapid, efficient, and long-lasting biocidal abilities against E. coli and S. aureus. The magnetic antibacterial composite still showed excellent antibacterial efficiency during five exposure/collection/recycle procedures.

Human mesenchymal stem cell osteoblast differentiation, ECM deposition, and biomineralization on PAH/PAA polyelectrolyte multilayers.

PubMed

Pattabhi, Sudhakara Rao; Lehaf, Ali M; Schlenoff, Joseph B; Keller, Thomas C S

2015-05-01

Polyelectrolyte multilayer (PEMU) coatings built layer by layer with alternating pairs of polyelectrolytes can be tuned to improve cell interactions with surfaces and may be useful as biocompatible coatings to improve fixation between implants and tissues. Here, we show that human mesenchymal stromal cells (hMSCs) induced with bone differentiation medium (BDM) to become osteoblasts biomineralize crosslinked PEMUs built with the polycation poly(allylamine hydrochloride) (PAH) and the polyanion poly(acrylic acid) (PAA). Degrees of hMSC osteoblast differentiation and surface biomineralization on the smooth PAH-terminated PEMUs (PAH-PEMUs) and microstructured PAA-terminated PEMUs (PAA-PEMUs) reflect differences in cell-deposited extracellular matrix (ECM). BDM-induced hMSCs expressed higher levels of the early osteoblast differentiation marker alkaline phosphatase and collagen 1 (COL1) sooner on PAA-PEMUs than on PAH-PEMUs. Cells on both types of PEMUs proceeded to express the later stage osteoblast differentiation marker bone sialoprotein (BSP), but the BDM-induced cells organized a more amorphous Collagen I and denser BSP localization on PAA-PEMUs than on PAH-PEMUs. These ECM properties correlated with greater biomineralization on the PAA-PEMUs than on PAH-PEMUs. Together, these results confirm the suitability of PAH/PAA PEMUs as a substrate for hMSC osteogenesis and highlight the importance of substrate effects on ECM organization and BSP presentation on biomineralization. © 2014 Wiley Periodicals, Inc.

Catalytic Micromotors Moving Near Polyelectrolyte-Modified Substrates: The Roles of Surface Charges, Morphology, and Released Ions.

PubMed

Wei, Mengshi; Zhou, Chao; Tang, Jinyao; Wang, Wei

2018-01-24

Synthetic microswimmers, or micromotors, are finding potential uses in a wide range of applications, most of which involve boundaries. However, subtle yet important effects beyond physical confinement on the motor dynamics remain less understood. In this letter, glass substrates were functionalized with positively and negatively charged polyelectrolytes, and the dynamics of micromotors moving close to the modified surfaces was examined. Using acoustic levitation and numerical simulation, we reveal how the speed of a chemically propelled micromotor slows down significantly near a polyelectrolyte-modified surface by the combined effects of surface charges, surface morphology, and ions released from the films.

Effect of solid surface charge on the binding behaviour of a metal-binding peptide

PubMed Central

Donatan, Senem; Sarikaya, Mehmet; Tamerler, Candan; Urgen, Mustafa

2012-01-01

Over the last decade, solid-binding peptides have been increasingly used as molecular building blocks coupling bio- and nanotechnology. Despite considerable research being invested in this field, the effects of many surface-related parameters that define the binding of peptide to solids are still unknown. In the quest to control biological molecules at solid interfaces and, thereby, tailoring the binding characteristics of the peptides, the use of surface charge of the solid surface may probably play an important role, which then can be used as a potential tuning parameter of peptide adsorption. Here, we report quantitative investigation on the viscoelastic properties and binding kinetics of an engineered gold-binding peptide, 3RGBP1, adsorbed onto the gold surface at different surface charge densities. The experiments were performed in aqueous solutions using an electrochemical dissipative quartz crystal microbalance system. Hydrodynamic mass, hydration state and surface coverage of the adsorbed peptide films were determined as a function of surface charge density of the gold metal substrate. Under each charged condition, binding of 3rGBP1 displayed quantitative differences in terms of adsorbed peptide amount, surface coverage ratio and hydration state. Based on the intrinsically disordered structure of the peptide, we propose a possible mechanism for binding of the peptide that can be used for tuning surface adsorption in further studies. Controlled alteration of peptide binding on solid surfaces, as shown here, may provide novel methods for surface functionalization used for bioenabled processing and fabrication of future micro- and nanodevices. PMID:22491974

The study of the dynamics of erythrocytes under the influence of an external electric field

NASA Astrophysics Data System (ADS)

Mamaeva, Sargylana N.; Maksimov, Georgy V.; Antonov, Stepan R.

2017-11-01

A mathematical model is considered for the determination of the surface charge of an erythrocyte with its shape approximated by a surface of revolution of the second order, and the investigation of the dynamics of erythrocytes under the influence of an external electric field. In the first part of this work, the electrical surface charge of the erythrocyte of the patient was calculated with the assumption that the change in the shape and size of the red blood cells leads to stabilization of the electric field, providing a normal electrostatic repulsion. In the second part of the work, the research results of dynamics of changes in the morphology of erythrocytes under the influence of an external electric field depending on the values of their surface charge and resistance of blood plasma is presented. In the course of the work, the dependence of the surface charge of red blood cells from their shape and size is presented. The determination of the relationship between the value of the charge field and the surface of erythrocytes in norm and in pathology is shown. The dependence of the velocity of the erythrocytes on the characteristics of the external electric field, surface charge of the erythrocyte and properties of the medium is obtained. The results of this study can be applied indirectly to diagnose diseases and to develop recommendations for experimental studies of hemodynamics under the influence of various external physical factors.

Rover wheel charging on the lunar surface

NASA Astrophysics Data System (ADS)

Jackson, Telana L.; Farrell, William M.; Zimmerman, Michael I.

2015-03-01

The environment at the Moon is dynamic, with highly variable solar wind plasma conditions at the lunar dayside, terminator, and night side regions. Moving objects such as rover wheels will charge due to contact electrification with the surface, but the degree of charging is controlled by the local plasma environment. Using a dynamic charging model of a wheel, it is demonstrated herein that moving tires will tribocharge substantially when venturing into plasma-current starved regions such as polar craters or the lunar nightside. The surface regolith distribution and the overall effect on charge accumulation of grains cohesively sticking to the rover tire has been incorporated into the model. It is shown that dust sticking can limit the overall charge accumulated on the system. However charge dissipation times are greatly increased in shadowed regions and can present a potential hazard to astronauts and electrical systems performing extra-vehicular activities. We show that dissipation times change with wheel composition and overall system tribocharging is dependent upon wheel velocity.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Chunya; Skelton, Adam A.; Chen, Mingjun

Here the binding of a negatively charged residue, aspartic acid (Asp) in tripeptide arginine-glycine-aspartic acid, onto a negatively charged hydroxylated rutile (110) surface in aqueous solution, containing divalent (Mg 2+, Ca 2+, or Sr 2+) or monovalent (Na +, K +, or Rb +) cations, was studied by molecular dynamics (MD) simulations. The results indicate that ionic radii and charges will significantly affect the hydration, adsorption geometry, and distance of cations from the rutile surface, thereby regulating the Asp/rutile binding mode. The adsorption strength of monovalent cations on the rutile surface in the order Na + > K + >more » Rb + shows a “reverse” lyotropic trend, while the divalent cations on the same surface exhibit a “regular” lyotropic behavior with decreasing crystallographic radii (the adsorption strength of divalent cations: Sr 2+ > Ca 2+ > Mg 2+). The Asp side chain in NaCl, KCl, and RbCl solutions remains stably H-bonded to the surface hydroxyls and the inner-sphere adsorbed compensating monovalent cations act as a bridge between the COO – group and the rutile, helping to “trap” the negatively charged Asp side chain on the negatively charged surface. In contrast, the mediating divalent cations actively participate in linking the COO– group to the rutile surface; thus the Asp side chain can remain stably on the rutile (110) surface, even if it is not involved in any hydrogen bonds with the surface hydroxyls. Inner- and outer-sphere geometries are all possible mediation modes for divalent cations in bridging the peptide to the rutile surface.« less

Ground Simulations of Near-Surface Plasma Field and Charging at the Lunar Terminator

NASA Astrophysics Data System (ADS)

Polansky, J.; Ding, N.; Wang, J.; Craven, P.; Schneider, T.; Vaughn, J.

2012-12-01

Charging in the lunar terminator region is the most complex and is still not well understood. In this region, the surface potential is sensitively influenced by both solar illumination and plasma flow. The combined effects from localized shadow generated by low sun elevation angles and localized wake generated by plasma flow over the rugged terrain can generate strongly differentially charged surfaces. Few models currently exist that can accurately resolve the combined effects of plasma flow and solar illumination over realistic lunar terminator topographies. This paper presents an experimental investigation of lunar surface charging at the terminator region in simulated plasma environments in a vacuum chamber. The solar wind plasma flow is simulated using an electron bombardment gridded Argon ion source. An electrostatic Langmuir probe, nude Faraday probes, a floating emissive probe, and retarding potential analyzer are used to quantify the plasma flow field. Surface potentials of both conducting and dielectric materials immersed in the plasma flow are measured with a Trek surface potential probe. The conducting material surface potential will simultaneously be measured with a high impedance voltmeter to calibrate the Trek probe. Measurement results will be presented for flat surfaces and objects-on-surface for various angles of attack of the plasma flow. The implications on the generation of localized plasma wake and surface charging at the lunar terminator will be discussed. (This research is supported by the NASA Lunar Advanced Science and Exploration Research program.)

Holographic charged Rényi entropies

NASA Astrophysics Data System (ADS)

Belin, Alexandre; Hung, Ling-Yan; Maloney, Alexander; Matsuura, Shunji; Myers, Robert C.; Sierens, Todd

2013-12-01

We construct a new class of entanglement measures by extending the usual definition of Rényi entropy to include a chemical potential. These charged Rényi entropies measure the degree of entanglement in different charge sectors of the theory and are given by Euclidean path integrals with the insertion of a Wilson line encircling the entangling surface. We compute these entropies for a spherical entangling surface in CFT's with holographic duals, where they are related to entropies of charged black holes with hyperbolic horizons. We also compute charged Rényi entropies in free field theories.

An Investigation of Low Earth Orbit Internal Charging

NASA Technical Reports Server (NTRS)

NeergaardParker, Linda; Minow, Joseph I.; Willis, Emily M.

2014-01-01

Low Earth orbit is usually considered a relatively benign environment for internal charging threats due to the low flux of penetrating electrons with energies of a few MeV that are encountered over an orbit. There are configurations, however, where insulators and ungrounded conductors used on the outside of a spacecraft hull may charge when exposed to much lower energy electrons of some 100's keV in a process that is better characterized as internal charging than surface charging. For example, the minimal radiation shielding afforded by thin thermal control materials such as metalized polymer sheets (e.g., aluminized Kapton or Mylar) and multilayer insulation may allow electrons of 100's of keV to charge underlying materials. Yet these same thermal control materials protect the underlying insulators and ungrounded conductors from surface charging currents due to electrons and ions at energies less than a few keV as well as suppress the photoemission, secondary electron, and backscattered electron processes associated with surface charging. We investigate the conditions required for this low Earth orbit "internal charging" to occur and evaluate the environments for which the process may be a threat to spacecraft. First, we describe a simple one-dimensional internal charging model that is used to compute the charge accumulation on materials under thin shielding. Only the electron flux that penetrates exposed surface shielding material is considered and we treat the charge balance in underlying insulation as a parallel plate capacitor accumulating charge from the penetrating electron flux and losing charge due to conduction to a ground plane. Charge dissipation due to conduction can be neglected to consider the effects of charging an ungrounded conductor. In both cases, the potential and electric field is computed as a function of time. An additional charge loss process is introduced due to an electrostatic discharge current when the electric field reaches a prescribed breakdown strength. For simplicity, the amount of charge lost in the discharge is treated as a random percentage of the total charge between a set maximum and minimum amount so a user can consider partial discharges of insulating materials (small loss of charge) or arcing from a conductor (large loss of charge). We apply the model to electron flux measurements from the NOAA-19 spacecraft to demonstrate that charging can reach levels where electrostatic discharges occur and estimate the magnitude of the discharge.

Charge effects on the hindered transport of macromolecules across the endothelial surface glycocalyx layer.

PubMed

Sugihara-Seki, Masako; Akinaga, Takeshi; O-Tani, Hideyuki

2012-01-01

A fluid mechanical and electrostatic model for the transport of solute molecules across the vascular endothelial surface glycocalyx layer (EGL) was developed to study the charge effect on the diffusive and convective transport of the solutes. The solute was assumed to be a spherical particle with a constant surface charge density, and the EGL was represented as an array of periodically arranged circular cylinders of like charge, with a constant surface charge density. By combining the fluid mechanical analyses for the flow around a solute suspended in an electrolyte solution and the electrostatic analyses for the free energy of the interaction between the solute and cylinders based on a mean field theory, we estimated the transport coefficients of the solute across the EGL. Both of diffusive and convective transports are reduced compared to those for an uncharged system, due to the stronger exclusion of the solute that results from the repulsive electrostatic interaction. The model prediction for the reflection coefficient for serum albumin agreed well with experimental observations if the charge density in the EGL is ranged from approximately -10 to -30 mEq/l.

Model for thickness dependence of radiation charging in MOS structures

NASA Technical Reports Server (NTRS)

Viswanathan, C. R.; Maserjian, J.

1976-01-01

The model considers charge buildup in MOS structures due to hole trapping in the oxide and the creation of sheet charge at the silicon interface. The contribution of hole trapping causes the flatband voltage to increase with thickness in a manner in which square and cube dependences are limiting cases. Experimental measurements on samples covering a 200 - 1000 A range of oxide thickness are consistent with the model, using independently obtained values of hole-trapping parameters. An important finding of our experimental results is that a negative interface charge contribution due to surface states created during irradiation compensates most of the positive charge in the oxide at flatband. The tendency of the surface states to 'track' the positive charge buildup in the oxide, for all thicknesses, applies both in creation during irradiation and in annihilation during annealing. An explanation is proposed based on the common defect origin of hole traps and potential surface states.

Adsorption properties of subtropical and tropical variable charge soils: Implications from climate change and biochar amendment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Ren-Kou; Qafoku, Nikolla; Van Ranst, Eric

2016-01-25

This review paper attempts to summarize the progress made in research efforts conducted over the last years to study the surface chemical properties of the tropical and subtropical soils, usually called variable charge soils, and the way they response to different management practices. The paper is composed of an introductory section that provides a brief discussion on the surface chemical properties of these soils, and five other review sections. The focus of these sections is on the evolution of surface chemical properties during the development of the variable charge properties (second section), interactions between oppositely charged particles and the resultingmore » effects on the soil properties and especially on soil acidity (third section), the surface effects of low molecular weight organic acids sorbed to mineral surfaces and the chemical behavior of aluminum (fourth section), and the crop straw derived biochar induced changes of the surface chemical properties of these soils (fifth section). A discussion on the effect of climate change variables on the properties of the variable charge soils is included at the end of this review paper (sixth section).« less

Influence of surface charge on the rate, extent, and structure of adsorbed Bovine Serum Albumin to gold electrodes.

PubMed

Beykal, Burcu; Herzberg, Moshe; Oren, Yoram; Mauter, Meagan S

2015-12-15

The objective of this work is to investigate the rate, extent, and structure of amphoteric proteins with charged solid surfaces over a range of applied potentials and surface charges. We use Electrochemical Quartz Crystal Microbalance with Dissipation Monitoring (E-QCM-D) to investigate the adsorption of amphoteric Bovine Serum Albumin (BSA) to a gold electrode while systematically varying the surface charge on the adsorbate and adsorbent by manipulating pH and applied potential, respectively. We also perform cyclic voltammetry-E-QCM-D on an adsorbed layer of BSA to elucidate conformational changes in response to varied applied potentials. We confirm previous results demonstrating that increasing magnitude of applied potential on the gold electrode is positively correlated with increasing mass adsorption when the protein and the surface are oppositely charged. On the other hand, we find that the rate of BSA adsorption is not governed by simple electrostatics, but instead depends on solution pH, an observation not well documented in the literature. Cyclic voltammetry with simultaneous E-QCM-D measurements suggest that BSA protein undergoes a conformational change as the surface potential varies. Copyright © 2015 Elsevier Inc. All rights reserved.

On charging of snow particles in blizzard

NASA Technical Reports Server (NTRS)

Shio, Hisashi

1991-01-01

The causes of the charge polarity on the blizzard, which consisted of fractured snow crystals and ice particles, were investigated. As a result, the charging phenomena showed that the characteristics of the blizzard are as follows: (1) In the case of the blizzard with snowfall, the fractured snow particles drifting near the surface of snow field (lower area: height 0.3 m) had positive charge, while those drifting at higher area (height 2 m) from the surface of snow field had negative charge. However, during the series of blizzards two kinds of particles positively and negatively charged were collected in equal amounts in a Faraday Cage. It may be considered that snow crystals with electrically neutral properties were separated into two kinds of snow flakes (charged positively and negatively) by destruction of the snow crystals. (2) In the case of the blizzard which consisted of irregularly formed ice drops (generated by peeling off the hardened snow field), the charge polarity of these ice drops salting over the snow field was particularly controlled by the crystallographic characteristics of the surface of the snow field hardened by the powerful wind pressure.

Hamiltonian surface charges using external sources

DOE Office of Scientific and Technical Information (OSTI.GOV)

Troessaert, Cédric, E-mail: troessaert@cecs.cl

2016-05-15

In this work, we interpret part of the boundary conditions as external sources in order to partially solve the integrability problem present in the computation of surface charges associated to gauge symmetries in the hamiltonian formalism. We start by describing the hamiltonian structure of external symmetries preserving the action up to a transformation of the external sources of the theory. We then extend these results to the computation of surface charges for field theories with non-trivial boundary conditions.

Molecular Self-Assembly and Interfacial Engineering for Highly Efficient Organic Field Effect Transistors and Solar Cells

DTIC Science & Technology

2012-09-23

balance between disordered SAMs to promote large pentacene grains and thick SAMs to aid in physically buffering the charge carriers in pentacene from...to 0.76 µF/cm2), and enhanced pentacene OFET device performance such as higher charge carrier mobility, current on/off ratio, and lower threshold...surface charge trap • Tuning of surface energy • Control of surface group orientation SAM/MO ultrathin dielectric: • Low-voltage operation

On the Applicability of DLVO Theory to the Prediction of Clay Colloids Stability.

PubMed

Missana; Adell

2000-10-01

The stability behavior of Na-montmorillonite colloids has been studied by combining the analysis of their surface charge properties and time-resolved dynamic light scattering experiments. The chemical surface model for several types of clays, including montmorillonite, has to take into account the double surface charge contribution due to their permanent structural charge and to their pH-dependent charge, which is developed at the edge sites, therefore, these stability studies were carried out as a function of both ionic strength and pH. DLVO theory is largely applied for the prediction of the stability of many colloidal systems, including the natural ones. This work shows that the stability behavior of Na-montmorillonite colloids cannot be satisfactorily reproduced by DLVO theory, using the surface parameters experimentally obtained. Particularly, this theory is unable to explain their pH-dependent stability behavior caused by the small charge at the edge sites. Based on these results, a literature review of DLVO stability prediction of clay colloids was performed. It confirmed that this theory is not capable of taking into account the double contribution to the total surface charge and, at the same time, pointed out the main uncertainties related to the appropriate use of the input parameters for the calculation as, for example, the Hamaker constant or the surface potential. Copyright 2000 Academic Press.

Surface charge effects in protein adsorption on nanodiamonds

NASA Astrophysics Data System (ADS)

Aramesh, M.; Shimoni, O.; Ostrikov, K.; Prawer, S.; Cervenka, J.

2015-03-01

Understanding the interaction of proteins with charged diamond nanoparticles is of fundamental importance for diverse biomedical applications. Here we present a thorough study of protein binding, adsorption kinetics and structure on strongly positively (hydrogen-terminated) and negatively (oxygen-terminated) charged nanodiamond particles using a quartz crystal microbalance by dissipation and infrared spectroscopy. By using two model proteins (bovine serum albumin and lysozyme) of different properties (charge, molecular weight and rigidity), the main driving mechanism responsible for the protein binding to the charged nanoparticles was identified. Electrostatic interactions were found to dominate the protein adsorption dynamics, attachment and conformation. We developed a simple electrostatic model that can qualitatively explain the observed adsorption behaviour based on charge-induced pH modifications near the charged nanoparticle surfaces. Under neutral conditions, the local pH around the positively and negatively charged nanodiamonds becomes very high (11-12) and low (1-3) respectively, which has a profound impact on the protein charge, hydration and affinity to the nanodiamonds. Small proteins (lysozyme) were found to form multilayers with significant conformational changes to screen the surface charge, while larger proteins (albumin) formed monolayers with minor conformational changes. The findings of this study provide a step forward toward understanding and eventually predicting nanoparticle interactions with biofluids.Understanding the interaction of proteins with charged diamond nanoparticles is of fundamental importance for diverse biomedical applications. Here we present a thorough study of protein binding, adsorption kinetics and structure on strongly positively (hydrogen-terminated) and negatively (oxygen-terminated) charged nanodiamond particles using a quartz crystal microbalance by dissipation and infrared spectroscopy. By using two model proteins (bovine serum albumin and lysozyme) of different properties (charge, molecular weight and rigidity), the main driving mechanism responsible for the protein binding to the charged nanoparticles was identified. Electrostatic interactions were found to dominate the protein adsorption dynamics, attachment and conformation. We developed a simple electrostatic model that can qualitatively explain the observed adsorption behaviour based on charge-induced pH modifications near the charged nanoparticle surfaces. Under neutral conditions, the local pH around the positively and negatively charged nanodiamonds becomes very high (11-12) and low (1-3) respectively, which has a profound impact on the protein charge, hydration and affinity to the nanodiamonds. Small proteins (lysozyme) were found to form multilayers with significant conformational changes to screen the surface charge, while larger proteins (albumin) formed monolayers with minor conformational changes. The findings of this study provide a step forward toward understanding and eventually predicting nanoparticle interactions with biofluids. Electronic supplementary information (ESI) available: The FTIR spectrum of nanodiamonds, QCM-D profiles of 50 nm nanodiamond adsorption on silica surfaces, QCM-D profiles of protein desorption after rinsing with water (rinsing experiment) and the full FTIR spectrum of proteins before and after adsorption on ND particles. See DOI: 10.1039/c5nr00250h

Surface potential-governed cellular osteogenic differentiation on ferroelectric polyvinylidene fluoride trifluoroethylene films.

PubMed

Tang, Bolin; Zhang, Bo; Zhuang, Junjun; Wang, Qi; Dong, Lingqing; Cheng, Kui; Weng, Wenjian

2018-07-01

Surface potential of biomaterials can dramatically influence cellular osteogenic differentiation. In this work, a wide range of surface potential on ferroelectric polyvinylidene fluoride trifluoroethylene (P(VDF-TrFE)) films was designed to get insight into the interfacial interaction of cell-charged surface. The P(VDF-TrFE) films poled by contact electric poling at various electric fields obtained well stabilized surface potential, with wide range from -3 to 915 mV. The osteogenic differentiation level of cells cultured on the films was strongly dependent on surface potential and reached the optimum at 391 mV in this system. Binding specificity assay indicated that surface potential could effectively govern the binding state of the adsorbed fibronectin (FN) with integrin. Molecular dynamic (MD) simulation further revealed that surface potential brought a significant difference in the relative distance between RGD and synergy PHSRN sites of adsorbed FN, resulting in a distinct integrin-FN binding state. These results suggest that the full binding of integrin α5β1 with both RGD and PHSRN sites of FN possesses a strong ability to activate osteogenic signaling pathway. This work sheds light on the underlying mechanism of osteogenic differentiation behavior on charged material surfaces, and also provides a guidance for designing a reasonable charged surface to enhance osteogenic differentiation. The ferroelectric P(VDF-TrFE) films with steady and a wide range of surface potential were designed to understand underlying mechanism of cell-charged surface interaction. The results showed that the charged surface well favored upregulation of osteogenic differentiation of MC3T3-E1 cells, and more importantly, a highest level occurred on the film with a moderate surface potential. Experiments and molecular dynamics simulation demonstrated that the surface potential could govern fibronectin conformation and then the integrin-fibronectin binding. We propose that a full binding state of integrin α5β1 with fibronectin induces effective activation of integrin-mediated FAK/ERK signaling pathway to upregulate cellular osteogenic differentiation. This work provides a guidance for designing a reasonable charged surface to enhance osteogenic differentiation. Copyright © 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Surface Oxide Net Charge of a Titanium Alloy; Comparison Between Effects of Treatment With Heat or Radiofrequency Plasma Glow Discharge

PubMed Central

MacDonald, Daniel E.; Rapuano, Bruce E.; Schniepp, Hannes C.

2010-01-01

In the current study, we have compared the effects of heat and radiofrequency plasma glow discharge (RFGD) treatment of a Ti6Al4V alloy on the physico-chemical properties of the alloy’s surface oxide. Titanium alloy (Ti6Al4V) disks were passivated alone, heated to 600 °C, or RFGD plasma treated in pure oxygen. RFGD treatment did not alter the roughness, topography, elemental composition or thickness of the alloy’s surface oxide layer. In contrast, heat treatment altered oxide topography by creating a pattern of oxide elevations approximately 50–100 nm in diameter. These nanostructures exhibited a three-fold increase in roughness compared to untreated surfaces when RMS roughness was calculated after applying a spatial high-pass filter with a 200 nm cutoff wavelength. Heat treatment also produced a surface enrichment in aluminum and vanadium oxides. Both RFGD and heat treatment produced similar increases in oxide wettability. Atomic force microscopy (AFM) measurements of metal surface oxide net charge signified by a long range force of attraction to or repulsion from a (negatively charged) silicon nitride AFM probe were also obtained for all three experimental groups. Force measurements showed that the RFGD-treated Ti6Al4V samples demonstrated a higher net positive surface charge at pH values below 6 and a higher net negative surface charge at physiological pH (pH values between 7 and 8) compared to control and heat-treated samples These findings suggest that RFGD treatment of metallic implant materials can be used to study the role of negatively charged surface oxide functional groups in protein bioactivity, osteogenic cell behavior and osseointegration independently of oxide topography. PMID:20880672

LUNAR SURFACE AND DUST GRAIN POTENTIALS DURING THE EARTH’S MAGNETOSPHERE CROSSING

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vaverka, J.; Richterová, I.; Pavlu, J.

2016-07-10

Interaction between the lunar surface and the solar UV radiation and surrounding plasma environment leads to its charging by different processes like photoemission, collection of charged particles, or secondary electron emission (SEE). Whereas the photoemission depends only on the angle between the surface and direction to the Sun and varies only slowly, plasma parameters can change rapidly as the Moon orbits around the Earth. This paper presents numerical simulations of one Moon pass through the magnetospheric tail including the real plasma parameters measured by THEMIS as an input. The calculations are concentrated on different charges of the lunar surface itselfmore » and a dust grain lifted above this surface. Our estimations show that (1) the SEE leads to a positive charging of parts of the lunar surface even in the magnetosphere, where a high negative potential is expected; (2) the SEE is generally more important for isolated dust grains than for the lunar surface covered by these grains; and (3) the time constant of charging of dust grains depends on their diameter being of the order of hours for sub-micrometer grains. In view of these results, we discuss the conditions under which and the areas where a levitation of the lifted dust grains could be observed.« less

Liouville master equation for multielectron dynamics: Neutralization of highly charged ions near a LiF surface

NASA Astrophysics Data System (ADS)

Wirtz, Ludger; Reinhold, Carlos O.; Lemell, Christoph; Burgdörfer, Joachim

2003-01-01

We present a simulation of the neutralization of highly charged ions in front of a lithium fluoride surface including the close-collision regime above the surface. The present approach employs a Monte Carlo solution of the Liouville master equation for the joint probability density of the ionic motion and the electronic population of the projectile and the target surface. It includes single as well as double particle-hole (de)excitation processes and incorporates electron correlation effects through the conditional dynamics of population strings. The input in terms of elementary one- and two-electron transfer rates is determined from classical trajectory Monte Carlo calculations as well as quantum-mechanical Auger calculations. For slow projectiles and normal incidence, the ionic motion depends sensitively on the interplay between image acceleration towards the surface and repulsion by an ensemble of positive hole charges in the surface (“trampoline effect”). For Ne10+ we find that image acceleration is dominant and no collective backscattering high above the surface takes place. For grazing incidence, our simulation delineates the pathways to complete neutralization. In accordance with recent experimental observations, most ions are reflected as neutral or even as singly charged negative particles, irrespective of the charge state of the incoming ions.

FY04 LDRD Final Report: Interaction of Viruses with Membranes and Soil Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schaldach, C M

2005-02-08

The influence of ionic strength on the electrostatic interaction of viruses with environmentally relevant surfaces was determined for three viruses, MS2, Q{beta} and Norwalk. The environmental surface is modeled as charged Gouy-Chapman plane with and without a finite atomistic region (patch) of opposite charge. The virus is modeled as a particle comprised of ionizable amino acid residues in a shell surrounding a spherical RNA core of negative charge, these charges being compensated for by a Coulomb screening due to intercalated ions. Surface potential calculations for each of the viruses show excellent agreement with electrophoretic mobility and zeta potential measurements asmore » a function of pH. The results indicate that the electrostatic interaction between the virus and the planar surface, mitigated by the ionic strength of the solute, is dependent upon the spatial distribution of the amino acid residues in the different viruses. Specifically, the order of interaction energies with the patch (MS2 greatest at 5 mM; Norwalk greatest at 20 mM) is dependent upon the ionic strength of the fluid as a direct result of the viral coat amino acid distributions. We have developed an atomistic-scale method of calculation of the binding energy of viruses to surfaces including electrostatic, van der Waals, electron-overlap repulsion, surface charge polarization (images), and hydrophobic effects. The surface is treated as a Gouy-Chapman plane allowing inclusion of pH and ionic strength effects on the electrostatic potential at each amino acid charge. Van der Waals parameters are obtained from the DREIDING force field and from Hamaker constant measurements. We applied this method to the calculation of the Cowpea Mosaic Virus (CPMV), a negatively charged virus at a pH of 7.0, and find that the viral-gold surface interaction is very long range for both signs of surface potential, a result due to the electrostatic forces. For a negative (Au) surface potential of -0.05 volts, a nearly 4 eV barrier must be overcome to reach 1 nm from the surface.« less

Role of surface charge and oxidative stress in cytotoxicity of organic monolayer-coated silicon nanoparticles towards macrophage NR8383 cells

PubMed Central

2010-01-01

Background Surface charge and oxidative stress are often hypothesized to be important factors in cytotoxicity of nanoparticles. However, the role of these factors is not well understood. Hence, the aim of this study was to systematically investigate the role of surface charge, oxidative stress and possible involvement of mitochondria in the production of intracellular reactive oxygen species (ROS) upon exposure of rat macrophage NR8383 cells to silicon nanoparticles. For this aim highly monodisperse (size 1.6 ± 0.2 nm) and well-characterized Si core nanoparticles (Si NP) were used with a surface charge that depends on the specific covalently bound organic monolayers: positively charged Si NP-NH2, neutral Si NP-N3 and negatively charged Si NP-COOH. Results Positively charged Si NP-NH2 proved to be more cytotoxic in terms of reducing mitochondrial metabolic activity and effects on phagocytosis than neutral Si NP-N3, while negatively charged Si NP-COOH showed very little or no cytotoxicity. Si NP-NH2 produced the highest level of intracellular ROS, followed by Si NP-N3 and Si NP-COOH; the latter did not induce any intracellular ROS production. A similar trend in ROS production was observed in incubations with an isolated mitochondrial fraction from rat liver tissue in the presence of Si NP. Finally, vitamin E and vitamin C induced protection against the cytotoxicity of the Si NP-NH2 and Si NP-N3, corroborating the role of oxidative stress in the mechanism underlying the cytotoxicity of these Si NP. Conclusion Surface charge of Si-core nanoparticles plays an important role in determining their cytotoxicity. Production of intracellular ROS, with probable involvement of mitochondria, is an important mechanism for this cytotoxicity. PMID:20831820

Field-induced charge transport at the surface of pentacene single crystals: A method to study charge dynamics of two-dimensional electron systems in organic crystals

NASA Astrophysics Data System (ADS)

Takeya, J.; Goldmann, C.; Haas, S.; Pernstich, K. P.; Ketterer, B.; Batlogg, B.

2003-11-01

A method has been developed to inject mobile charges at the surface of organic molecular crystals, and the dc transport of field-induced holes has been measured at the surface of pentacene single crystals. To minimize damage to the soft and fragile surface, the crystals are attached to a prefabricated substrate which incorporates a gate dielectric (SiO2) and four probe pads. The surface mobility of the pentacene crystals ranges from 0.1 to 0.5 cm2/V s and is nearly temperature independent above ˜150 K, while it becomes thermally activated at lower temperatures when the induced charges become localized. Ruling out the influence of electric contacts and crystal grain boundaries, the results contribute to the microscopic understanding of trapping and detrapping mechanisms in organic molecular crystals.

Nanotoxicological and teratogenic effects: A linkage between dendrimer surface charge and zebrafish developmental stages.

PubMed

Calienni, Maria Natalia; Feas, Daniela Agustina; Igartúa, Daniela Edith; Chiaramoni, Nadia Silvia; Alonso, Silvia Del Valle; Prieto, Maria Jimena

2017-12-15

This article reports novel results about nanotoxicological and teratogenic effects of the PAMAM dendrimers DG4 and DG4.5 in zebrafish (Danio rerio). Zebrafish embryos and larvae were used as a rapid, high-throughput, cost-effective whole-animal model. The objective was to provide a more comprehensive and predictive developmental toxicity screening of DG4 and DG4.5 and test the influence of their surface charge. Nanotoxicological and teratogenic effects were assessed at developmental, morphological, cardiac, neurological and hepatic level. The effect of surface charge was determined in both larvae and embryos. DG4 with positive surface charge was more toxic than DG4.5 with negative surface charge. DG4 and DG4.5 induced teratogenic effects in larvae, whereas DG4 also induced lethal effects in both zebrafish embryos and larvae. However, larvae were less sensitive than embryos to the lethal effects of DG4. The platform of assays proposed and data obtained may contribute to the characterization of hazards and differential effects of these nanoparticles. Copyright © 2017 Elsevier Inc. All rights reserved.

Dependence of Lunar Surface Charging on Solar Wind Plasma Conditions and Solar Irradiation

NASA Technical Reports Server (NTRS)

Stubbs, T. J.; Farrell, W. M.; Halekas, J. S.; Burchill, J. K.; Collier, M. R.; Zimmerman, M. I.; Vondrak, R. R.; Delory, G. T.; Pfaff, R. F.

2014-01-01

The surface of the Moon is electrically charged by exposure to solar radiation on its dayside, as well as by the continuous flux of charged particles from the various plasma environments that surround it. An electric potential develops between the lunar surface and ambient plasma, which manifests itself in a near-surface plasma sheath with a scale height of order the Debye length. This study investigates surface charging on the lunar dayside and near-terminator regions in the solar wind, for which the dominant current sources are usually from the pohotoemission of electrons, J(sub p), and the collection of plasma electrons J(sub e) and ions J(sub i). These currents are dependent on the following six parameters: plasma concentration n(sub 0), electron temperature T(sub e), ion temperature T(sub i), bulk flow velocity V, photoemission current at normal incidence J(sub P0), and photo electron temperature T(sub p). Using a numerical model, derived from a set of eleven basic assumptions, the influence of these six parameters on surface charging - characterized by the equilibrium surface potential, Debye length, and surface electric field - is investigated as a function of solar zenith angle. Overall, T(sub e) is the most important parameter, especially near the terminator, while J(sub P0) and T(sub p) dominate over most of the dayside.

Selective binding of proteins on functional nanoparticles via reverse charge parity model: an in vitro study

NASA Astrophysics Data System (ADS)

Ghosh, Goutam; Panicker, Lata; Barick, K. C.

2014-03-01

The conformation of proteins absorbed on nanoparticles surface plays a crucial role in applications of nanoparticles in biomedicine. The surface protein conformation depends on several factors, namely, nature of protein-nanoparticles interaction, chemical composition of the surface of nanoparticles etc. A model of the electrostatic binding of proteins on charged surface nanoparticles has been proposed earlier (Ghosh et al 2013 Colloids Surf. B 103 267). Also, the irreversible denaturation of the protein conformation due to binding of counterions was reported. In this paper, we have used this model, involving reverse charge parity, to show selective binding of proteins on charged surface iron oxide nanoparticles (IONPs). IONPs were surface functionalized with cetylpyridinium chloride (CPC), cetyl(trimethyl)ammonium bromide (CTAB) and cetylpyridinium iodide (CPI). The effect of counterions (Cl-, Br- and I-) on protein conformation has also been investigated. Several proteins such as α-lactalbumin (ALA), β-lactoglobulin (BLG), ovalbumin (OVA), bovin serum albumin (BSA) and HEWL were chosen for this investigation.

Electromagnetic Field Redistribution in Metal Nanoparticle on Graphene.

PubMed

Li, Keke; Liu, Anping; Wei, Dapeng; Yu, Keke; Sun, Xiaonan; Yan, Sheng; Huang, Yingzhou

2018-04-25

Benefiting from the induced image charge on metal film, the light energy is confined on a film surface under metal nanoparticle dimer, which is called electromagnetic field redistribution. In this work, electromagnetic field distribution of metal nanoparticle monomer or dimer on graphene is investigated through finite-difference time-domain method. The results point out that the electromagnetic field (EM) redistribution occurs in this nanoparticle/graphene hybrid system at infrared region where light energy could also be confined on a monolayer graphene surface. Surface charge distribution was analyzed using finite element analysis, and surface-enhanced Raman spectrum (SERS) was utilized to verify this phenomenon. Furthermore, the data about dielectric nanoparticle on monolayer graphene demonstrate this EM redistribution is attributed to strong coupling between light-excited surface charge on monolayer graphene and graphene plasmon-induced image charge on dielectric nanoparticle surface. Our work extends the knowledge of monolayer graphene plasmon, which has a wide range of applications in monolayer graphene-related film.

Enhanced charging kinetics of porous electrodes: surface conduction as a short-circuit mechanism.

PubMed

Mirzadeh, Mohammad; Gibou, Frederic; Squires, Todd M

2014-08-29

We use direct numerical simulations of the Poisson-Nernst-Planck equations to study the charging kinetics of porous electrodes and to evaluate the predictive capabilities of effective circuit models, both linear and nonlinear. The classic transmission line theory of de Levie holds for general electrode morphologies, but only at low applied potentials. Charging dynamics are slowed appreciably at high potentials, yet not as significantly as predicted by the nonlinear transmission line model of Biesheuvel and Bazant. We identify surface conduction as a mechanism which can effectively "short circuit" the high-resistance electrolyte in the bulk of the pores, thus accelerating the charging dynamics and boosting power densities. Notably, the boost in power density holds only for electrode morphologies with continuous conducting surfaces in the charging direction.

Interfaces Charged by a Nonionic Surfactant.

PubMed

Lee, Joohyung; Zhou, Zhang-Lin; Behrens, Sven Holger

2018-05-24

Highly hydrophobic, water-insoluble nonionic surfactants are often considered irrelevant to the ionization of interfaces at which they adsorb, despite observations that suggest otherwise. In the present study, we provide unambiguous evidence for the participation of a water-insoluble surfactant in interfacial ionization by conducting electrophoresis experiments for surfactant-stabilized nonpolar oil droplets in aqueous continuous phase. It was found that the surfactant with amine headgroup positively charged the surface of oil suspended in aqueous continuous phase (oil/water interface), which is consistent with its basic nature. In nonpolar oil continuous phase, the same surfactant positively charged the surface of solid silica (solid/oil interface) which is often considered acidic. The latter observation is exactly opposite to what the traditional acid-base mechanism of surface charging would predict, most clearly suggesting the possibility for another charging mechanism.

Anomalous mobility of highly charged particles in pores

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qiu, Yinghua; Yang, Crystal; Hinkle, Preston

2015-07-16

Single micropores in resistive-pulse technique were used to understand a complex dependence of particle mobility on its surface charge density. We show that the mobility of highly charged carboxylated particles decreases with the increase of the solution pH due to an interplay of three effects: (i) ion condensation, (ii) formation of an asymmetric electrical double layer around the particle, and (iii) electroosmotic flow induced by the charges on the pore walls and the particle surfaces. The results are important for applying resistive-pulse technique to determine surface charge density and zeta potential of the particles. As a result, the experiments alsomore » indicate the presence of condensed ions, which contribute to the measured current if a sufficiently high electric field is applied across the pore.« less

Charged drop dynamics experiment using an electrostatic-acoustic hybrid system

NASA Technical Reports Server (NTRS)

Rhim, W. K.; Chung, S. K.; Trinh, E. H.; Elleman, D. D.

1987-01-01

The design and the performance of an electrostatic-acoustic hybrid system and its application to a charge drop rotation experiment are presented. This system can levitate a charged drop electrostatically and induce drop rotation or oscillation by imposing an acoustic torque or an oscillating acoustic pressure. Using this system, the equilibrium shapes and stability of a rotating charged drop were experimentally investigated. A 3 mm size water drop was rotated as a rigid body and its gyrostatic equilibrium shapes were observed. Families of axisymmetric shapes, two-lobed shapes, and eventual fissioning have been observed. With the assumption of 'effective surface tension' in which the surface charge simply modified the surface tension of neutral liquid, the results agree exceptionally well with the Brown and Scriven's (1980) prediction for uncharged drops.

Maximum Frictional Charge Generation on Polymer Surfaces

NASA Astrophysics Data System (ADS)

Calle, Carlos; Groop, Ellen; Mantovani, James; Buehler, Martin

2001-03-01

The maximum amount of charge that a given surface area can hold is limited by the surrounding environmental conditions such as the atmospheric composition, pressure, humidity, and temperature. Above this charge density limit, the surface will discharge to the atmosphere or to a nearby conductive surface that is at a different electric potential. We have performed experiments using the MECA Electrometer, a flight instrument developed jointly by the Jet Propulsion Laboratory and NASA Kennedy Space Center to study the electrostatic properties of the Martian soil. The electrometer contains five types of polymers: fiberglass/epoxy, polycarbonate (Lexan), polytetraflouroethylene (Teflon), Rulon J, and polymethylmethacrylate (PMMA, Lucite). We repeatedly rubbed the polymers with another material until each polymer's charge saturation was determined. We will discuss the correlation of our data with the triboelectric series.

Surface Tension Mediated Under-Water Adhesion of Rigid Spheres on Soft, Charged Surfaces

NASA Astrophysics Data System (ADS)

Sinha, Shayandev; Das, Siddhartha

2015-11-01

Understanding the phenomenon of surface-tension-mediated under-water adhesion is necessary for studying a plethora of physiological and technical phenomena, such as the uptake of bacteria or nanoparticle by cells, attachment of virus on bacterial surfaces, biofouling on large ocean vessels and marine devices, etc. This adhesion phenomenon becomes highly non-trivial in case the soft surface where the adhesion occurs is also charged. Here we propose a theory for analyzing such an under-water adhesion of a rigid sphere on a soft, charged surface, represented by a grafted polyelectrolyte layer (PEL). We develop a model based on the minimization of free energy that, in addition to considering the elastic and the surface-tension-mediated adhesion energies, also accounts for the PEL electric double layer (EDL) induced electrostatic energies. We show that in the presence of surface charges, adhesion gets enhanced. This can be explained by the fact that the increase in the elastic energy is better balanced by the lowering of the EDL energy associated with the adhesion process. The entire behaviour is further dictated by the surface tension components that govern the adhesion energy.

Concurrent application of charge using a novel circuit prevents heat-related coagulum formation during radiofrequency ablation.

PubMed

Lim, Bernard; Venkatachalam, Kalpathi L; Jahangir, Arshad; Johnson, Susan B; Asirvatham, Samuel J

2008-08-01

Thromboembolism resulting from coagulum formation on the catheter and electrode surfaces is a serious complication with radiofrequency ablation procedures for heart rhythm disorders. Why coagulum occurs despite therapeutic heparinization is unclear. In this report, we demonstrate a novel approach to minimize coagulum formation based on the electromolecular characteristics of fibrinogen. Atomic force microscopy was used to establish that fibrinogen deposited on surfaces underwent conformational changes that resulted in spontaneous clot formation. We then immersed ablation catheters that were uncharged, negatively, or positively charged in heparinized blood for 30 minutes and noted the extent of clot formation. In separate experiments, ablation catheters were sutured to the ventricle of an excised porcine heart immersed in whole, heparinized blood and radiofrequency ablation performed for 5 minutes with and without charge delivered to the catheter tips. Electron microscopy of the catheter tips showed surface coverage of fibrin clot of the catheter to be 33.8% for negatively charged catheters, compared with 84.7% (P = 0.01) in noncharged catheters. There was no significant difference in surface coverage of fibrin clot between positively charged catheters (93.8%) and noncharged catheters (84.7%, P = ns). In contrast, the thickness of surface clot coverage for positively charged catheters was 87.5%, compared with 28.45% (P= 0.03) for noncharged catheters and 11.25% (P = 0.03) for negatively charged catheters, compared with noncharged catheters. We describe a novel method of placing negative charge on electrodes during ablation that reduced coagulum formation. This may decrease thromboembolism-related complications with radiofrequency ablation procedures.

Interaction between like-charged polyelectrolyte-colloid complexes in electrolyte solutions: a Monte Carlo simulation study in the Debye-Hückel approximation.

PubMed

Truzzolillo, D; Bordi, F; Sciortino, F; Sennato, S

2010-07-14

We study the effective interaction between differently charged polyelectrolyte-colloid complexes in electrolyte solutions via Monte Carlo simulations. These complexes are formed when short and flexible polyelectrolyte chains adsorb onto oppositely charged colloidal spheres, dispersed in an electrolyte solution. In our simulations the bending energy between adjacent monomers is small compared to the electrostatic energy, and the chains, once adsorbed, do not exchange with the solution, although they rearrange on the particles surface to accommodate further adsorbing chains or due to the electrostatic interaction with neighbor complexes. Rather unexpectedly, when two interacting particles approach each other, the rearrangement of the surface charge distribution invariably produces antiparallel dipolar doublets that invert their orientation at the isoelectric point. These findings clearly rule out a contribution of dipole-dipole interactions to the observed attractive interaction between the complexes, pointing out that such suspensions cannot be considered dipolar fluids. On varying the ionic strength of the electrolyte, we find that a screening length kappa(-1), short compared with the size of the colloidal particles, is required in order to observe the attraction between like-charged complexes due to the nonuniform distribution of the electric charge on their surface ("patch attraction"). On the other hand, by changing the polyelectrolyte/particle charge ratio xi(s), the interaction between like-charged polyelectrolyte-decorated particles, at short separations, evolves from purely repulsive to strongly attractive. Hence, the effective interaction between the complexes is characterized by a potential barrier, whose height depends on the net charge and on the nonuniformity of their surface charge distribution.

Surface-charge-dependent cell localization and cytotoxicity of cerium oxide nanoparticles.

PubMed

Asati, Atul; Santra, Santimukul; Kaittanis, Charalambos; Perez, J Manuel

2010-09-28

Cerium oxide nanoparticles (nanoceria) have shown great potential as antioxidant and radioprotective agents for applications in cancer therapy. Recently, various polymer-coated nanoceria preparations have been developed to improve their aqueous solubility and allow for surface functionalization of these nanoparticles. However, the interaction of polymer-coated nanoceria with cells, their uptake mechanism, and subcellular localization are poorly understood. Herein, we engineered polymer-coated cerium oxide nanoparticles with different surface charges (positive, negative, and neutral) and studied their internalization and toxicity in normal and cancer cell lines. The results showed that nanoceria with a positive or neutral charge enters most of the cell lines studied, while nanoceria with a negative charge internalizes mostly in the cancer cell lines. Moreover, upon entry into the cells, nanoceria is localized to different cell compartments (e.g., cytoplasm and lysosomes) depending on the nanoparticle's surface charge. The internalization and subcellular localization of nanoceria plays a key role in the nanoparticles' cytotoxicity profile, exhibiting significant toxicity when they localize in the lysosomes of the cancer cells. In contrast, minimal toxicity is observed when they localize into the cytoplasm or do not enter the cells. Taken together, these results indicate that the differential surface-charge-dependent localization of nanoceria in normal and cancer cells plays a critical role in the nanoparticles' toxicity profile.

Long-range interaction between heterogeneously charged membranes.

PubMed

Jho, Y S; Brewster, R; Safran, S A; Pincus, P A

2011-04-19

Despite their neutrality, surfaces or membranes with equal amounts of positive and negative charge can exhibit long-range electrostatic interactions if the surface charge is heterogeneous; this can happen when the surface charges form finite-size domain structures. These domains can be formed in lipid membranes where the balance of the different ranges of strong but short-ranged hydrophobic interactions and longer-ranged electrostatic repulsion result in a finite, stable domain size. If the domain size is large enough, oppositely charged domains in two opposing surfaces or membranes can be strongly correlated by the electrostatic interactions; these correlations give rise to an attractive interaction of the two membranes or surfaces over separations on the order of the domain size. We use numerical simulations to demonstrate the existence of strong attractions at separations of tens of nanometers. Large line tensions result in larger domains but also increase the charge density within the domain. This promotes correlations and, as a result, increases the intermembrane attraction. On the other hand, increasing the salt concentration increases both the domain size and degree of domain anticorrelation, but the interactions are ultimately reduced due to increased screening. The result is a decrease in the net attraction as salt concentration is increased. © 2011 American Chemical Society

Surface charge effects in protein adsorption on nanodiamonds.

PubMed

Aramesh, M; Shimoni, O; Ostrikov, K; Prawer, S; Cervenka, J

2015-03-19

Understanding the interaction of proteins with charged diamond nanoparticles is of fundamental importance for diverse biomedical applications. Here we present a thorough study of protein binding, adsorption kinetics and structure on strongly positively (hydrogen-terminated) and negatively (oxygen-terminated) charged nanodiamond particles using a quartz crystal microbalance by dissipation and infrared spectroscopy. By using two model proteins (bovine serum albumin and lysozyme) of different properties (charge, molecular weight and rigidity), the main driving mechanism responsible for the protein binding to the charged nanoparticles was identified. Electrostatic interactions were found to dominate the protein adsorption dynamics, attachment and conformation. We developed a simple electrostatic model that can qualitatively explain the observed adsorption behaviour based on charge-induced pH modifications near the charged nanoparticle surfaces. Under neutral conditions, the local pH around the positively and negatively charged nanodiamonds becomes very high (11-12) and low (1-3) respectively, which has a profound impact on the protein charge, hydration and affinity to the nanodiamonds. Small proteins (lysozyme) were found to form multilayers with significant conformational changes to screen the surface charge, while larger proteins (albumin) formed monolayers with minor conformational changes. The findings of this study provide a step forward toward understanding and eventually predicting nanoparticle interactions with biofluids.

Adsorption of weak polyelectrolytes on charged nanoparticles. Impact of salt valency, pH, and nanoparticle charge density. Monte Carlo simulations.

PubMed

Carnal, Fabrice; Stoll, Serge

2011-10-27

Complex formation between a weak flexible polyelectrolyte chain and one positively charged nanoparticle in presence of explicit counterions and salt particles is investigated using Monte Carlo simulations. The influence of parameters such as the nanoparticle surface charge density, salt valency, and solution property such as the pH on the chain protonation/deprotonation process and monomer adsorption at the nanoparticle surface are systematically investigated. It is shown that the nanoparticle presence significantly modifies chain acid/base and polyelectrolyte conformational properties. The importance of the attractive electrostatic interactions between the chain and the nanoparticle clearly promotes the chain deprotonation leading, at high pH and nanoparticle charge density, to fully wrapped polyelectrolyte at the nanoparticle surface. When the nanoparticle bare charge is overcompensated by the polyelectrolyte charges, counterions and salt particles condense at the surface of the polyelectrolyte-nanoparticle complex to compensate for the excess of charges providing from the adsorbed polyelectrolyte chain. It is also shown that the complex formation is significantly affected by the salt valency. Indeed, with the presence of trivalent salt cations, competition is observed between the nanoparticle and the trivalent cations. As a result, the amount of adsorbed monomers is less important than in the monovalent and divalent case and chain conformations are different due to the collapse of polyelectrolyte segments around trivalent cations out of the nanoparticle adsorption layer.

The effect of surface charge of glycerol monooleate-based nanoparticles on the round window membrane permeability and cochlear distribution.

PubMed

Liu, Hongzhuo; Chen, Shichao; Zhou, Yanyan; Che, Xin; Bao, Zhihong; Li, Sanming; Xu, Jinghua

2013-11-01

The aim of this study is to elucidate the impact of surface charge of glycerol monooleate-based nanoparticles (NPs) on the cellular uptake and its distribution in the cochlea. These NPs are modified using varied concentration of anionic or cationic lipid. Upon dilution, these lipid mixtures self-assemble to form a series of cubic NPs with various surface charges, but with similar particle size. Positively charged NPs exhibited dose-dependent cytotoxicities against L929 cells proportional to the concentration of cationic lipid; whereas negatively charged NPs did not show obvious cytotoxic properties as compared to unmodified NPs. Meanwhile, confocal microscopy and flow cytometry results suggested that NPs with high positive surface charge were taken up more efficiently by L929 cells. The permeability of round window membrane (RWM) was high for highly positively charged NPs, which is likely due to their highly cellular uptake efficiency and consequently high concentration gradient between RWM and cochlear fluid. More importantly, 1,2-dioleoyl-3-trimethylammonium-propane (DOTAP) modified NPs greatly facilitated broadly distribution in cochlea, favoring the treatment of hearing loss of low frequencies. Taken together, these findings about charge-dependent of NPs on RWM permeability and cochlear distribution could serve as guideline in the rational design of NP for drug and gene delivery to inner ear.

Supercharging of the Lunar Surface by Solar Wind Halo Electrons

NASA Astrophysics Data System (ADS)

Stubbs, T. J.; Farrell, W. M.; Collier, M. R.; Halekas, J. S.; Delory, G. T.; Holland, M. P.; Vondrak, R. R.

2007-12-01

Lunar surface potentials can reach several kilovolts negative during Solar Energetic Particle (SEPs) events, as indicated by recent analysis of data from the Lunar Prospector Electron Reflectometer (LP/ER). The lunar surface- plasma interactions that result in such extreme surface potentials are poorly characterized and understood. Extreme lunar surface charging, and the associated electrostatic discharges and transport of charged dust, will likely present significant hazards to future human explorers. This is of particular concern near the terminator and polar regions, such as the South Pole/Aiken Basin site planned for NASA's manned outpost. It is the flux of electrons from the ambient plasma that charges the surface of the Moon to negative potentials. In the solar wind, the electron temperature is typically ~10 eV which tends to charge the lunar surface to ~100 V negative in shadow. However, during space weather events the solar wind electrons are often better described by the sum of two Maxwellian distributions, referred to as the "core" and "halo" components. The core electrons are relatively cool and dense (e.g., ~10 eV and ~10/cc), whereas the halo electrons are hot and tenuous (e.g., ~100 eV and ~0.1/cc). Despite, the tenuous nature of the halo electrons, our surface charging model - using core and halo electron data derived from the Solar Wind Experiment (SWE) aboard the Wind spacrcraft - predicts that they are capable of "supercharging" the lunar surface to kilovolt potentials during space weather events, which could explain the LP/ER observations.

Over-limiting Current and Control of Dendritic Growth by Surface Conduction in Nanopores

PubMed Central

Han, Ji-Hyung; Khoo, Edwin; Bai, Peng; Bazant, Martin Z.

2014-01-01

Understanding over-limiting current (faster than diffusion) is a long-standing challenge in electrochemistry with applications in desalination and energy storage. Known mechanisms involve either chemical or hydrodynamic instabilities in unconfined electrolytes. Here, it is shown that over-limiting current can be sustained by surface conduction in nanopores, without any such instabilities, and used to control dendritic growth during electrodeposition. Copper electrodeposits are grown in anodized aluminum oxide membranes with polyelectrolyte coatings to modify the surface charge. At low currents, uniform electroplating occurs, unaffected by surface modification due to thin electric double layers, but the morphology changes dramatically above the limiting current. With negative surface charge, growth is enhanced along the nanopore surfaces, forming surface dendrites and nanotubes behind a deionization shock. With positive surface charge, dendrites avoid the surfaces and are either guided along the nanopore centers or blocked from penetrating the membrane. PMID:25394685

Depletion region surface effects in electron beam induced current measurements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Haney, Paul M.; Zhitenev, Nikolai B.; Yoon, Heayoung P.

2016-09-07

Electron beam induced current (EBIC) is a powerful characterization technique which offers the high spatial resolution needed to study polycrystalline solar cells. Current models of EBIC assume that excitations in the p-n junction depletion region result in perfect charge collection efficiency. However, we find that in CdTe and Si samples prepared by focused ion beam (FIB) milling, there is a reduced and nonuniform EBIC lineshape for excitations in the depletion region. Motivated by this, we present a model of the EBIC response for excitations in the depletion region which includes the effects of surface recombination from both charge-neutral and chargedmore » surfaces. For neutral surfaces, we present a simple analytical formula which describes the numerical data well, while the charged surface response depends qualitatively on the location of the surface Fermi level relative to the bulk Fermi level. We find that the experimental data on FIB-prepared Si solar cells are most consistent with a charged surface and discuss the implications for EBIC experiments on polycrystalline materials.« less

Aromaticity and Antiaromaticity in Zintl Clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Zhong -Ming; Liu, Chao; Popov, Ivan Aleksandrovich

Originally, the concepts of aromaticity and antiaromaticity were introduced to explain the stability and reactivity of unsaturated organic compounds. Since then, they have been extended to other species with delocalized electrons including various saturated systems, organometallic compounds, and even inorganic clusters and molecules. In this study, we focus on the most recent progress of using these concepts to guide experimental synthesis and rationalize geometrical and electronic structures of a particular family of polyanions composed of Group 14 and 15 elements, namely Zintl clusters.

Thermometric titration in investigation of the formation of polyanions of molybdenum(VI), tungsten(VI), vanadium(V), and chromium (VI)-I: comparison of thermometric and potentiometric titration curves.

PubMed

Kiba, N; Takeuchi, T

1973-09-01

A new twin-cell thermometric titrator has been devised and used for thermometric titration of solutions of sodium molybdate, sodium tungstate, sodium orthovanadate, ammonium metavanadate, and potassium chromate with perchloric acid. The thermometric titration curves were compared with corresponding pH-titration curves for elucidation of the reactions occurring in the titrations. Thermometric titrimetric methods have been developed for the determination of tungsten, vanadium and chromium.

Co5In(BTC)4[B2O4(OH)]2: the first MOF material constructed by borate polyanions and carboxylate mixed ligands.

PubMed

Li, Sa-Ying; Liu, Zhi-Hong

2016-01-07

A novel heterometallic organic-inorganic hybrid MOF material, Co5In(BTC)4[B2O4(OH)]2, has been synthesized under ionothermal conditions. Its structure is characterized as a 3D open framework constructed by the Co2.5In0.5[B2O4(OH)] cluster and the 1,3,5-benzenetricarboxylate ligand. Furthermore, its fluorescent and adsorption properties have also been studied.

Aromaticity and Antiaromaticity in Zintl Clusters

DOE PAGES

Sun, Zhong -Ming; Liu, Chao; Popov, Ivan Aleksandrovich; ...

2018-05-18

Originally, the concepts of aromaticity and antiaromaticity were introduced to explain the stability and reactivity of unsaturated organic compounds. Since then, they have been extended to other species with delocalized electrons including various saturated systems, organometallic compounds, and even inorganic clusters and molecules. In this study, we focus on the most recent progress of using these concepts to guide experimental synthesis and rationalize geometrical and electronic structures of a particular family of polyanions composed of Group 14 and 15 elements, namely Zintl clusters.

Image method for induced surface charge from many-body system of dielectric spheres

NASA Astrophysics Data System (ADS)

Qin, Jian; de Pablo, Juan J.; Freed, Karl F.

2016-09-01

Charged dielectric spheres embedded in a dielectric medium provide the simplest model for many-body systems of polarizable ions and charged colloidal particles. We provide a multiple scattering formulation for the total electrostatic energy for such systems and demonstrate that the polarization energy can be rapidly evaluated by an image method that generalizes the image methods for conducting spheres. Individual contributions to the total electrostatic energy are ordered according to the number of polarized surfaces involved, and each additional surface polarization reduces the energy by a factor of (a/R)3ɛ, where a is the sphere radius, R the average inter-sphere separation, and ɛ the relevant dielectric mismatch at the interface. Explicit expressions are provided for both the energy and the forces acting on individual spheres, which can be readily implemented in Monte Carlo and molecular dynamics simulations of polarizable charged spheres, thereby avoiding costly computational techniques that introduce a surface charge distribution that requires numerical solution.

IImage method for induced surface charge from many-body system of dielectric spheres

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qin, Jian; de Pablo, Juan J.; Freed, Karl F.

2016-09-28

Charged dielectric spheres embedded in a dielectric medium provide the simplest model for many-body systems of polarizable ions and charged colloidal particles. We provide a multiple scattering formulation for the total electrostatic energy for such systems and demonstrate that the polarization energy can be rapidly evaluated by an image method that generalizes the image methods for conducting spheres. Individual contributions to the total electrostatic energy are ordered according to the number of polarized surfaces involved, and each additional surface polarization reduces the energy by a factor of (a/R)(3) epsilon, where a is the sphere radius, R the average inter-sphere separation,more » and. the relevant dielectric mismatch at the interface. Explicit expressions are provided for both the energy and the forces acting on individual spheres, which can be readily implemented in Monte Carlo and molecular dynamics simulations of polarizable charged spheres, thereby avoiding costly computational techniques that introduce a surface charge distribution that requires numerical solution.« less

Charge Dynamics in near-Surface, Variable-Density Ensembles of Nitrogen-Vacancy Centers in Diamond.

PubMed

Dhomkar, Siddharth; Jayakumar, Harishankar; Zangara, Pablo R; Meriles, Carlos A

2018-06-13

Although the spin properties of superficial shallow nitrogen-vacancy (NV) centers have been the subject of extensive scrutiny, considerably less attention has been devoted to studying the dynamics of NV charge conversion near the diamond surface. Using multicolor confocal microscopy, here we show that near-surface point defects arising from high-density ion implantation dramatically increase the ionization and recombination rates of shallow NVs compared to those in bulk diamond. Further, we find that these rates grow linearly, not quadratically, with laser intensity, indicative of single-photon processes enabled by NV state mixing with other defect states. Accompanying these findings, we observe NV ionization and recombination in the dark, likely the result of charge transfer to neighboring traps. Despite the altered charge dynamics, we show that one can imprint rewritable, long-lasting patterns of charged-initialized, near-surface NVs over large areas, an ability that could be exploited for electrochemical biosensing or to optically store digital data sets with subdiffraction resolution.

Engineering and Probing Topological Properties of Dirac Semimetal Films by Asymmetric Charge Transfer.

PubMed

Villanova, John W; Barnes, Edwin; Park, Kyungwha

2017-02-08

Dirac semimetals (DSMs) have topologically robust three-dimensional Dirac (doubled Weyl) nodes with Fermi-arc states. In heterostructures involving DSMs, charge transfer occurs at the interfaces, which can be used to probe and control their bulk and surface topological properties through surface-bulk connectivity. Here we demonstrate that despite a band gap in DSM films, asymmetric charge transfer at the surface enables one to accurately identify locations of the Dirac-node projections from gapless band crossings and to examine and engineer properties of the topological Fermi-arc surface states connecting the projections, by simulating adatom-adsorbed DSM films using a first-principles method with an effective model. The positions of the Dirac-node projections are insensitive to charge transfer amount or slab thickness except for extremely thin films. By varying the amount of charge transfer, unique spin textures near the projections and a separation between the Fermi-arc states change, which can be observed by gating without adatoms.

Effects of surface charges of gold nanoclusters on long-term in vivo biodistribution, toxicity, and cancer radiation therapy.

PubMed

Wang, Jun-Ying; Chen, Jie; Yang, Jiang; Wang, Hao; Shen, Xiu; Sun, Yuan-Ming; Guo, Meili; Zhang, Xiao-Dong

2016-01-01

Gold nanoclusters (Au NCs) have exhibited great advantages in medical diagnostics and therapies due to their efficient renal clearance and high tumor uptake. The in vivo effects of the surface chemistry of Au NCs are important for the development of both nanobiological interfaces and potential clinical contrast reagents, but these properties are yet to be fully investigated. In this study, we prepared glutathione-protected Au NCs of a similar hydrodynamic size but with three different surface charges: positive, negative, and neutral. Their in vivo biodistribution, excretion, and toxicity were investigated over a 90-day period, and tumor uptake and potential application to radiation therapy were also evaluated. The results showed that the surface charge greatly influenced pharmacokinetics, particularly renal excretion and accumulation in kidney, liver, spleen, and testis. Negatively charged Au NCs displayed lower excretion and increased tumor uptake, indicating a potential for NC-based therapeutics, whereas positively charged clusters caused transient side effects on the peripheral blood system.

Evidences for dry deintercalation in layered compounds upon controlled surface charging in x-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Feldman, Y.; Zak, A.; Tenne, R.; Cohen, H.

2003-09-01

Pronounced surface diffusion is observed during x-ray photoelectron spectroscopy measurements of 2H platelets and inorganic fullerene-like (IF) MS2 (M=W,Mo) powders, intercalated with alkaline (A=K,Na) elements. Using controlled surface charging the intercalants migrate towards the surface, where they oxidize. This dry deintercalation is controllable via external charging parameters, yet showing that internal chemical and structural parameters play an important role in the process. Diffusion rates out of 2H matrixes are generally higher than in corresponding IF samples. Clear differences are also found between Mo and W-based systems. Application of this approach into surface modification and processing is proposed.

Controlling Ionic Transport for Device Design in Synthetic Nanopores

NASA Astrophysics Data System (ADS)

Kalman, Eric Boyd

Polymer nanopores present a number of behaviors not seen in microscale systems, such as ion current rectification, ionic selectivity, size exclusion and potential dependent ion concentrations in and near the pore. The existence of these effects stems from the small size of nanopores with respect to the characteristic length scales of surface interactions at the interface between the nanopore surface and the solution within it. The large surface-to-volume ratio due to the nanoscale geometry of a nanopore, as well as similarity in scale between geometry and interaction demands the solution interact with the nanopore walls. As surfaces in solution almost always carry residual charge, these surface forces are primarily the electrostatic interactions between the charge groups on the pore surface and the ions in solution. These interactions may be used by the experimentalist to control ionic transport through synthetic nanopores, and use them as a template for the construction of devices. In this research, we present our work on creating a number of ionic analogs to seminal electronic devices, specifically diodes, and transistors, by controlling ionic transport through the electrostatic interactions between a single synthetic nanopore and ions. Control is achieved by "doping" the effective charge carrier concentration in specific regions of the nanopore through manipulation of the pore's surface charge. This manipulation occurs through two mechanisms: chemical modification of the surface charge and electrostatic manipulation of the local internal nanopore potential using a gate electrode. Additionally, the innate selectivity of the charged nanopores walls allows for the separation of charges in solution. This well-known effect, which spawns measureable quantities, the streaming potential and current, has been used to create nanoscale water desalination membranes. We attempt to create a device using membranes with large nanopore densities for the desalination of water which should theoretically outperform currently available devices, as through our previous work we have developed techniques allowing for transport manipulation not current accessible in traditional membrane motifs.

Field effect sensors for PCR applications

NASA Astrophysics Data System (ADS)

Taing, Meng-Houit; Sweatman, Denis R.

2004-03-01

The use of field effect sensors for biological and chemical sensing is widely employed due to its ability to make detections based on charge and surface potential. Because proteins and DNA almost always carry a charge [1], silicon can be used to micro fabricate such a sensor. The EIS structure (Electrolyte on Insulator on Silicon) provides a novel, label-free and simple to fabricate way to make a field effect DNA detection sensor. The sensor responds to fluctuating capacitance caused by a depletion layer thickness change at the surface of the silicon substrate through DNA adsorption onto the dielectric oxide/PLL (Poly-L-Lysine) surface. As DNA molecules diffuse to the sensor surface, they are bound to their complimentary capture probes deposited on the surface. The negative charge exhibited by the DNA forces negative charge carriers in the substrate to move away from the surface. This causes an n-type depletion layer substrate to thicken and a p-type to thin. The depletion layer thickness can be measured by its capacitance using an LCR meter. This experiment is conducted using the ConVolt (constant voltage) approach. Nucleic acids are amplified by an on chip PCR (Polymerase Chain Reaction) system and then fed into the sensor. The low ionic solution strength will ensure that counter-ions do not affect the sensor measurements. The sensor surface contains capture probes that bind to the pathogen. The types of pathogens we"ll be detecting include salmonella, campylobacter and E.Coli DNA. They are held onto the sensor surface by the positively charged Poly-L-Lysine layer. The electrolyte is biased through a pseudo-reference electrode. Pseudo reference electrodes are usually made from metals such as Platinum or Silver. The problem associated with "floating" biasing electrodes is they cannot provide stable biasing potentials [2]. They drift due to surface charging effects and trapped charges on the surface. To eliminate this, a differential system consisting of 2 sensors that share a common pseudo-reference electrode is used to cancel out this effect. This paper will look at a differential system for multi-arrayed biosensors fabricated on silicon.

Charging properties of cassiterite (alfa-SnO2) surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rosenqvist, Jorgen K; Machesky, Michael L.; Vlcek, L.

The acid-base properties of cassiterite (alfa-SnO2) surfaces at 10 50 C were studied using potentiometric titrations of powder suspensions in aqueous NaCl and RbCl media. The proton sorption isotherms exhibited common intersection points in the pH-range 4.0 to 4.5 at all conditions and the magnitude of charging was similar but not identical in NaCl and RbCl. The hydrogen bonding configuration at the oxide-water interface, obtained from classical Molecular Dynamics (MD) simulations, was analyzed in detail and the results were explicitly incorporated in calculations of protonation constants for the reactive surface sites using the revised MUSIC model. The calculations indicated thatmore » the terminal SnOH2 group is more acidic than the bridging Sn2OH group, with protonation constants (log KH) of 3.60 and 5.13 at 25 C, respectively. This is contrary to the situation on the isostructural alfa-TiO2 (rutile), apparently due to the difference in electronegativity between Ti and Sn. MD simulations and speciation calculations indicated considerable differences in the speciation of Na+ and Rb+, despite the similarities in overall charging. Adsorbed sodium ions are almost exclusively found in bidentate surface complexes, while adsorbed rubidium ions form comparable amounts of bidentate and tetradentate complexes. Also, the distribution of adsorbed Na+ between the different complexes shows a considerable dependence on surface charge density (pH), while the distribution of adsorbed Rb+ is almost independent of pH. A Surface Complexation Model (SCM) capable of accurately describing both the measured surface charge and the MD predicted speciation of adsorbed Na+/Rb+ was formulated. According to the SCM, the deprotonated terminal group (SnOH-0.40) and the protonated bridging group (Sn2OH+0.36) dominate the surface speciation over the entire pH-range (2.7 10), illustrating the ability of positively and negatively charged surface groups to coexist. Complexation of the medium cations increases significantly with increasing negative surface charge and at pH 10 roughly 40 percent of the terminal sites are predicted to form cation complexes, while anion complexation is minor throughout the studied pH-range.« less

Measurement of surface charges on the dielectric film based on field mills under the HVDC corona wire

NASA Astrophysics Data System (ADS)

Donglai, WANG; Tiebing, LU; Yuan, WANG; Bo, CHEN; Xuebao, LI

2018-05-01

The ion flow field on the ground is one of the significant parameters used to evaluate the electromagnetic environment of high voltage direct current (HVDC) power lines. HVDC lines may cross the greenhouses due to the restricted transmission corridors. Under the condition of ion flow field, the dielectric films on the greenhouses will be charged, and the electric fields in the greenhouses may exceed the limit value. Field mills are widely used to measure the ground-level direct current electric fields under the HVDC power lines. In this paper, the charge inversion method is applied to calculate the surface charges on the dielectric film according to the measured ground-level electric fields. The advantages of hiding the field mill probes in the ground are studied. The charge inversion algorithm is optimized in order to decrease the impact of measurement errors. Based on the experimental results, the surface charge distribution on a piece of quadrate dielectric film under a HVDC corona wire is studied. The enhanced effect of dielectric film on ground-level electric field is obviously weakened with the increase of film height. Compared with the total electric field strengths, the normal components of film-free electric fields at the corresponding film-placed positions have a higher effect on surface charge accumulation.

Effect of laundry surfactants on surface charge and colloidal stability of silver nanoparticles.

PubMed

Skoglund, Sara; Lowe, Troy A; Hedberg, Jonas; Blomberg, Eva; Wallinder, Inger Odnevall; Wold, Susanna; Lundin, Maria

2013-07-16

The stability of silver nanoparticles (Ag NPs) potentially released from clothing during a laundry cycle and their interactions with laundry-relevant surfactants [anionic (LAS), cationic (DTAC), and nonionic (Berol)] have been investigated. Surface interactions between Ag NPs and surfactants influence their speciation and stability. In the absence of surfactants as well as in the presence of LAS, the negatively charged Ag NPs were stable in solution for more than 1 day. At low DTAC concentrations (≤1 mM), DTAC-Ag NP interactions resulted in charge neutralization and formation of agglomerates. The surface charge of the particles became positive at higher concentrations due to a bilayer type formation of DTAC that prevents from agglomeration due to repulsive electrostatic forces between the positively charged colloids. The adsorption of Berol was enhanced when above its critical micelle concentration (cmc). This resulted in a surface charge close to zero and subsequent agglomeration. Extended DLVO theory calculations were in compliance with observed findings. The stability of the Ag NPs was shown to depend on the charge and concentration of the adsorbed surfactants. Such knowledge is important as it may influence the subsequent transport of Ag NPs through different chemical transients and thus their potential bioavailability and toxicity.

Nanotribology of charged polymer brushes

NASA Astrophysics Data System (ADS)

Klein, Jacob

Polymers at surfaces, whose modern understanding may be traced back to early work by Sam Edwards1, have become a paradigm for modification of surface properties, both as steric stabilizers and as remarkable boundary lubricants2. Charged polymer brushes are of particular interest, with both technological implications and especially biological relevance where most macromolecules are charged. In the context of biolubrication, relevant in areas from dry eye syndrome to osteoarthritis, charged polymer surface phases and their complexes with other macromolecules may play a central role. The hydration lubrication paradigm, where tenaciously-held yet fluid hydration shells surrounding ions or zwitterions serve as highly-efficient friction-reducing elements, has been invoked to understand the excellent lubrication provided both by ionized3 and by zwitterionic4 brushes. In this talk we describe recent advances in our understanding of the nanotribology of such charged brush systems. We consider interactions between charged end-grafted polymers, and how one may disentangle the steric from the electrostatic surface forces5. We examine the limits of lubrication by ionized brushes, both synthetic and of biological origins, and how highly-hydrated zwitterionic chains may provide extremely effective boundary lubrication6. Finally we describe how the lubrication of articular cartilage in the major joints, a tribosystem presenting some of the greatest challenges and opportunities, may be understood in terms of a supramolecular synergy between charged surface-attached polymers and zwitterionic groups7. Work supported by European Research Council (HydrationLube), Israel Science Foundation (ISF), Petroleum Research Fund of the American Chemical Society, ISF-NSF China Joint Program.

Dynamics of two-dimensional monolayer water confined in hydrophobic and charged environments.

PubMed

Kumar, Pradeep; Han, Sungho

2012-09-21

We perform molecular dynamics simulations to study the effect of charged surfaces on the intermediate and long time dynamics of water in nanoconfinements. Here, we use the transferable interaction potential with five points (TIP5P) model of a water molecule confined in both hydrophobic and charged surfaces. For a single molecular layer of water between the surfaces, we find that the temperature dependence of the lateral diffusion constant of water up to very high temperatures remains Arrhenius with a high activation energy. In case of charged surfaces, however, the dynamics of water in the intermediate time regime is drastically modified presumably due to the transient coupling of dipoles of water molecules with electric field fluctuations induced by charges on the confining surfaces. Specifically, the lateral mean square displacements display a distinct super-diffusive behavior at intermediate time scale, defined as the time scale between ballistic and diffusive regimes. This change in the intermediate time-scale dynamics in the charged confinement leads to the enhancement of long-time dynamics as reflected in increasing diffusion constant. We introduce a simple model for a possible explanation of the super-diffusive behavior and find it to be in good agreement with our simulation results. Furthermore, we find that confinement and the surface polarity enhance the low frequency vibration in confinement compared to bulk water. By introducing a new effective length scale of coupling between translational and orientational motions, we find that the length scale increases with the increasing strength of the surface polarity. Further, we calculate the correlation between the diffusion constant and the excess entropy and find a disordering effect of polar surfaces on the structure of water. Finally, we find that the empirical relation between the diffusion constant and the excess entropy holds for a monolayer of water in nanoconfinement.

Experimental validation of a numerical model predicting the charging characteristics of Teflon and Kapton under electron beam irradiation

NASA Technical Reports Server (NTRS)

Hazelton, R. C.; Yadlowsky, E. J.; Churchill, R. J.; Parker, L. W.; Sellers, B.

1981-01-01

The effect differential charging of spacecraft thermal control surfaces is assessed by studying the dynamics of the charging process. A program to experimentally validate a computer model of the charging process was established. Time resolved measurements of the surface potential were obtained for samples of Kapton and Teflon irradiated with a monoenergetic electron beam. Results indicate that the computer model and experimental measurements agree well and that for Teflon, secondary emission is the governing factor. Experimental data indicate that bulk conductivities play a significant role in the charging of Kapton.

The study of surface acoustic wave charge transfer device

NASA Technical Reports Server (NTRS)

Papanicolaou, N.; Lin, H. C.

1978-01-01

A surface acoustic wave-charge transfer device, consisting of an n-type silicon substrate, a thermally grown silicon dioxide layer, and a sputtered film of piezoelectric zinc oxide is proposed as a means of circumventing problems associated with charge-coupled device (CCD) applications in memory, signal processing, and imaging. The proposed device creates traveling longitudinal electric fields in the silicon and replaces the multiphase clocks in CCD's. The traveling electric fields create potential wells which carry along charges stored there. These charges may be injected into the wells by light or by using a p-n junction as in conventional CCD's.

Novel Approach to Evaluation of Charging on Semiconductor Surface by Noncontact, Electrode-Free Capacitance/Voltage Measurement

NASA Astrophysics Data System (ADS)

Hirae, Sadao; Kohno, Motohiro; Okada, Hiroshi; Matsubara, Hideaki; Nakatani, Ikuyoshi; Kusuda, Tatsufumi; Sakai, Takamasa

1994-04-01

This paper describes a novel approach to the quantitative characterization of semiconductor surface charging caused by plasma exposures and ion implantations. The problems in conventional evaluation of charging are also discussed. Following the discussions above, the necessity of unified criteria is suggested for efficient development of systems or processes without charging damage. Hence, the charging saturation voltage between a top oxide surface and substrate, V s, and the charging density per unit area per second, ρ0, should be taken as criteria of charging behavior, which effectively represent the charging characteristics of both processes. The unified criteria can be obtained from the exposure time dependence of a net charging density on the thick field oxide. In order to determine V s and ρ0, the analysis using the C-V curve measured in a noncontact method with the metal-air-insulator-semiconductor (MAIS) technique is employed. The total space-charge density in oxide and its centroid can be determined at the same time by analyzing the flat-band voltage (V fb) of the MAIS capacitor as a function of the air gap. The net charge density can be obtained by analyzing the difference between the total space-charge density in oxide before and after charging. Finally, it is shown that charge damage of the large area metal-oxide-semiconductor (MOS) capacitor can be estimated from both V s and ρ0 which are obtained from results for a thick field oxide implanted with As+ and exposed to oxygen plasma.