Where does the electron go? The nature of ortho/para and meta group directing in electrophilic aromatic substitution

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

Liu, Shubin, E-mail: shubin@email.unc.edu

Electrophilic aromatic substitution as one of the most fundamental chemical processes is affected by atoms or groups already attached to the aromatic ring. The groups that promote substitution at the ortho/para or meta positions are, respectively, called ortho/para and meta directing groups, which are often characterized by their capability to donate electrons to or withdraw electrons from the ring. Though resonance and inductive effects have been employed in textbooks to explain this phenomenon, no satisfactory quantitative interpretation is available in the literature. Here, based on the theoretical framework we recently established in density functional reactivity theory (DFRT), where electrophilicity andmore » nucleophilicity are simultaneously quantified by the Hirshfeld charge, the nature of ortho/para and meta group directing is systematically investigated for a total of 85 systems. We find that regioselectivity of electrophilic attacks is determined by the Hirshfeld charge distribution on the aromatic ring. Ortho/para directing groups have most negative charges on the ortho/para positions, while meta directing groups often possess the largest negative charge on the meta position. Our results do not support that ortho/para directing groups are electron donors and meta directing groups are electron acceptors. Most neutral species we studied here are electron withdrawal in nature. Anionic systems are always electron donors. There are also electron donors serving as meta directing groups. We predicted ortho/para and meta group directing behaviors for a list of groups whose regioselectivity is previously unknown. In addition, strong linear correlations between the Hirshfeld charge and the highest occupied molecular orbital have been observed, providing the first link between the frontier molecular orbital theory and DFRT.« less

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

Adhesion signals of phospholipid vesicles at an electrified interface.

PubMed

DeNardis, Nadica Ivošević; Žutić, Vera; Svetličić, Vesna; Frkanec, Ruža

2012-09-01

General adhesion behavior of phospholipid vesicles was examined in a wide range of potentials at the mercury electrode by recording time-resolved adhesion signals. It was demonstrated that adhesion-based detection is sensitive to polar headgroups in phospholipid vesicles. We identified a narrow potential window around the point of zero charge of the electrode where the interaction of polar headgroups of phosphatidylcholine vesicles with the substrate is manifested in the form of bidirectional signals. The bidirectional signal is composed of the charge flow due to the nonspecific interaction of vesicle adhesion and spreading and of the charge flow due to a specific interaction of the negatively charged electrode and the most exposed positively charged choline headgroups. These signals are expected to appear only when the electrode surface charge density is less than the surface charge density of the choline groups at the contact interface. In comparison, for the negatively charged phosphatidylserine vesicles, we identified the potential window at the mercury electrode where charge compensation takes place, and bidirectional signals were not detected.

[Sorption properties of various polysaccharide matrixes to Lactobacillus plantarum 8RA-3 bacteria].

PubMed

Bondarenko, V M; Larionov, I V; Rybal'chenko, O V; Potokin, I L; Ryzhankova, A V

2011-01-01

Study of sorption properties of various spherical polysaccharide matrixes designated as Spherocell to probiotic Lactobacillus plantarum 8RA-3 bacteria. Industrial strain of L. plantarum 8PA-3 was used. The process of immobilization of lactobacilli on 3 variants of spherical sorbents was studied. The first sorbent - neutral, composed of nonpolar cellulose matrix with ("0") charge, the second--DEAE obtained by modification of cellulose by diethylaminoethyl groups with positive ("+") charge and the third--CM (carboxymethyl) with negative ("-") charge. Cellulose matrixes were designated by us by the term Spherocell. Immobilization of bacterial cells on Spherocell was performed by addition of suspension containing 1.0 x 10(9) CFU/ml. The effect of bacterial immobilization was evaluated by CFU/ ml titration and by electron microscopy. The dependence on matrix charge of adsorption immobilization on sorbent granules of lactobacilli cells was shown. At certain equal parameters (granule size, surface characteristics, charge value) the positively charged matrix sorbed 3-10 times more cells than neutral and 20-25 times more than negatively charged matrix. Each 100-180 microm Spherocell DEAE particle could sorb more than 1000 viable bacterial cells. Positively charged polysaccharide matrix Spherocell DEAE obtained by modification of cellulose by diethylaminoethyl groups is promising for creation of immobilized probiotic preparations.

Intermolecular Interaction between Phosphatidylcholine and Sulfobetaine Lipid: A Combination of Lipids with Antiparallel Arranged Headgroup Charge.

PubMed

Aikawa, Tatsuo; Yokota, Keisuke; Kondo, Takeshi; Yuasa, Makoto

2016-10-05

Intermolecular interactions between lipid molecules are important when designing lipid bilayer interfaces, which have many biomedical applications such as in drug delivery vehicles and biosensors. Phosphatidylcholine, a naturally occurring lipid, is the most common lipid found in organisms. Its chemical structure has a negatively charged phosphate linkage, adjacent to an ester linkage in a glycerol moiety, and a positively charged choline group, placed at the terminus of the molecule. Recently, several types of synthetic lipids that have headgroups with the opposite charge to that of phosphatidylcholine have emerged; that is, a positively charged ammonium group is present adjacent to the ester linkage in their glycerol moiety and a negatively charged group is placed at their terminus. These types of lipids constitute a new class of soft material. The aim of this study was to determine how such lipids, with antiparallel arranged headgroup charge, interact with naturally occurring phosphatidylcholines. We synthesized 1,2-dipalmitoyl-sn-glycero-3-sulfobetaine (DPSB) to represent a reversed-head lipid; 1,2-dipalmitoyl-sn-glycero-3-phosphatidylcholine (DPPC) was used to represent a naturally occurring phospholipid. The intermolecular interaction between these lipids was investigated using surface pressure-area (π-A) isotherms of the lipid monolayer at the air/water interface. We found that the extrapolated area and excess free energy of the mixed monolayer deviated negatively when compared with the ideal values from additivity. Moreover, differential scanning calorimetry of the lipid mixture in aqueous dispersion showed that the gel-to-liquid crystal transition temperature increased compared with that of each pure lipid composition. These results clearly indicate that DPSB preferably interacts with DPPC in the mixture. We believe that the attraction between the oppositely charged headgroups of these lipids reinforces the intermolecular interaction. Our results provide insight into the intermolecular interaction between phospholipids and reversed-head lipids, which may prove useful for the design of lipid-based materials in the future.

Electrostatic interactions play an essential role in the binding of oleic acid with α-lactalbumin in the HAMLET-like complex: a study using charge-specific chemical modifications.

PubMed

Xie, Yongjing; Min, Soyoung; Harte, Níal P; Kirk, Hannah; O'Brien, John E; Voorheis, H Paul; Svanborg, Catharina; Hun Mok, K

2013-01-01

Human α-lactalbumin made lethal to tumor cells (HAMLET) and its analogs are partially unfolded protein-oleic acid (OA) complexes that exhibit selective tumoricidal activity normally absent in the native protein itself. To understand the nature of the interaction between protein and OA moieties, charge-specific chemical modifications of lysine side chains involving citraconylation, acetylation, and guanidination were employed and the biophysical and biological properties were probed. Upon converting the original positively-charged lysine residues to negatively-charged citraconyl or neutral acetyl groups, the binding of OA to protein was eliminated, as were any cytotoxic activities towards osteosarcoma cells. Retention of the positive charges by converting lysine residues to homoarginine groups (guanidination); however, yielded unchanged binding of OA to protein and identical tumoricidal activity to that displayed by the wild-type α-lactalbumin-oleic acid complex. With the addition of OA, the wild-type and guanidinated α-lactalbumin proteins underwent substantial conformational changes, such as partial unfolding, loss of tertiary structure, but retention of secondary structure. In contrast, no significant conformational changes were observed in the citraconylated and acetylated α-lactalbumins, most likely because of the absence of OA binding. These results suggest that electrostatic interactions between the positively-charged basic groups on α-lactalbumin and the negatively-charged carboxylate groups on OA molecules play an essential role in the binding of OA to α-lactalbumin and that these interactions appear to be as important as hydrophobic interactions. Copyright © 2012 Wiley Periodicals, Inc.

On the solvation structure of dimethylsulfoxide/water around the phosphatidylcholine head group in solution

NASA Astrophysics Data System (ADS)

Dabkowska, Aleksandra P.; Foglia, Fabrizia; Lawrence, M. Jayne; Lorenz, Christian D.; McLain, Sylvia E.

2011-12-01

The solution structure of the phosphocholine (PC) head group in 1,2-dipropionyl-sn-glycero-3-phosphocholine (C3-PC) in 30 mol. % dimethylsulfoxide (DMSO)-water solutions has been determined by using neutron diffraction enhanced with isotopic substitution in combination with computer simulation techniques. By investigating the atomic scale hydration structure around the PC head group, a unique description of the displacement of water molecules by DMSO molecules is detailed around various locations of the head group. Specifically, DMSO molecules were found to be the most prevalent around the onium portion of the head group, with the dipoles of the DMSO molecules being aligned where the negatively charged oxygen can interact strongly with the positively charged lipid group. The phosphate group is also partially dehydrated by the presence of the DMSO molecules. However, around this group the bulkier positive end of the DMSO dipole is interacting with negatively charged groups of the lipid head group, the DMSO layer shows no obvious ordering as it cannot form hydrogen bonds with the oxygen atoms in the PO4 group such as water molecules can. Interestingly, DMSO-water contacts have also increased in the presence of the lipid molecule relative to DMSO-water contacts observed in pure DMSO/water solutions at similar concentrations.

Intracellular sorting of differently charged chitosan derivatives and chitosan-based nanoparticles

NASA Astrophysics Data System (ADS)

Zubareva, A. A.; Shcherbinina, T. S.; Varlamov, V. P.; Svirshchevskaya, E. V.

2015-04-01

Chitosan (Chi) is a biodegradable nontoxic polycation with multiple reactive groups that is easily used to obtain derivatives with a desired charge and hydrophobic properties. The aim of this work was to study the intracellular traffic of positively charged hexanoyl-chitosan (HC) or HC-based nanoparticles (HCNPs) and negatively charged succinoyl-chitosan (SC) and SCNPs in epithelial and macrophage cell lines. By using flow cytometry we demonstrated that positively charged HC adhered to cell membranes quicker and more efficiently than negatively charged SC or NPs. However confocal studies showed that SC and SCNPs penetrated cells much more efficiently than HC while HCNPs did not enter the epithelial cells. Macrophages also phagocyted better negatively charged material but were able to engulf both HC and HCNPs. Upon entering the cells, SC and SCNPs were co-localized with endosomes and lysosomes while HC was found in mitochondria and, to a lesser extent, in lysosomes of epithelial cells. Macrophages, RAW264.7, more efficiently transported all Chi samples to the lysosomal compartment while some positively charged material was still found in mitochondria. Incubation of Chi derivatives and ChiNPs at pH specific to mitochondria (8.0) and lysosomes (4.5) demonstrated the neutralization of Chi charge. We concluded that epithelial cells and, to a lesser extent, macrophages sort charged material to the organelles neutralizing Chi charge.

Comparing Positively and Negatively Charged Distonic Radical Ions in Phenylperoxyl Forming Reactions.

PubMed

Williams, Peggy E; Marshall, David L; Poad, Berwyck L J; Narreddula, Venkateswara R; Kirk, Benjamin B; Trevitt, Adam J; Blanksby, Stephen J

2018-06-04

In the gas phase, arylperoxyl forming reactions play a significant role in low-temperature combustion and atmospheric processing of volatile organic compounds. We have previously demonstrated the application of charge-tagged phenyl radicals to explore the outcomes of these reactions using ion trap mass spectrometry. Here, we present a side-by-side comparison of rates and product distributions from the reaction of positively and negatively charge tagged phenyl radicals with dioxygen. The negatively charged distonic radical ions are found to react with significantly greater efficiency than their positively charged analogues. The product distributions of the anion reactions favor products of phenylperoxyl radical decomposition (e.g., phenoxyl radicals and cyclopentadienone), while the comparable fixed-charge cations yield the stabilized phenylperoxyl radical. Electronic structure calculations rationalize these differences as arising from the influence of the charged moiety on the energetics of rate-determining transition states and reaction intermediates within the phenylperoxyl reaction manifold and predict that this influence could extend to intra-molecular charge-radical separations of up to 14.5 Å. Experimental observations of reactions of the novel 4-(1-carboxylatoadamantyl)phenyl radical anion confirm that the influence of the charge on both rate and product distribution can be modulated by increasing the rigidly imposed separation between charge and radical sites. These findings provide a generalizable framework for predicting the influence of charged groups on polarizable radicals in gas phase distonic radical ions. Graphical Abstract.

Comparing Positively and Negatively Charged Distonic Radical Ions in Phenylperoxyl Forming Reactions

NASA Astrophysics Data System (ADS)

Williams, Peggy E.; Marshall, David L.; Poad, Berwyck L. J.; Narreddula, Venkateswara R.; Kirk, Benjamin B.; Trevitt, Adam J.; Blanksby, Stephen J.

2018-06-01

In the gas phase, arylperoxyl forming reactions play a significant role in low-temperature combustion and atmospheric processing of volatile organic compounds. We have previously demonstrated the application of charge-tagged phenyl radicals to explore the outcomes of these reactions using ion trap mass spectrometry. Here, we present a side-by-side comparison of rates and product distributions from the reaction of positively and negatively charge tagged phenyl radicals with dioxygen. The negatively charged distonic radical ions are found to react with significantly greater efficiency than their positively charged analogues. The product distributions of the anion reactions favor products of phenylperoxyl radical decomposition (e.g., phenoxyl radicals and cyclopentadienone), while the comparable fixed-charge cations yield the stabilized phenylperoxyl radical. Electronic structure calculations rationalize these differences as arising from the influence of the charged moiety on the energetics of rate-determining transition states and reaction intermediates within the phenylperoxyl reaction manifold and predict that this influence could extend to intra-molecular charge-radical separations of up to 14.5 Å. Experimental observations of reactions of the novel 4-(1-carboxylatoadamantyl)phenyl radical anion confirm that the influence of the charge on both rate and product distribution can be modulated by increasing the rigidly imposed separation between charge and radical sites. These findings provide a generalizable framework for predicting the influence of charged groups on polarizable radicals in gas phase distonic radical ions.

Phosphatidic acid in neuronal development: a node for membrane and cytoskeleton rearrangements.

PubMed

Ammar, Mohamed-Raafet; Kassas, Nawal; Bader, Marie-France; Vitale, Nicolas

2014-12-01

Phosphatidic acid (PA) is the simplest phospholipid naturally existing in all-living organisms. It constitutes only a minor fraction of the total cell lipids but has attracted considerable attention being both a lipid second messenger and a modulator of membrane shape. The pleiotropic functions of PA are the direct consequence of its very simple chemical structure consisting of only two acyl chains linked by ester bonds to two adjacent hydroxyl groups of glycerol, whose remaining hydroxyl group is esterified with a phosphomonoester group. Hence the small phosphate head group of PA gives it the shape of a cone providing flexibility and negative curvatures in the context of a lipid bilayer. In addition, the negatively charged phosphomonoester headgroup of PA is unique because it can potentially carry one or two negative charges playing a role in the recruitment of positively charged molecules to biomembranes. In consequence, PA has been proposed to play various key cellular functions. In the brain, a fine balance between cell growth, migration and differentiation, and cell death is required to sculpt the nervous system during development. In this review, we will summarize the various functions that have been proposed for PA in neuronal development. Copyright © 2014 Elsevier Masson SAS. All rights reserved.

Quantifying reactivity for electrophilic aromatic substitution reactions with Hirshfeld charge.

PubMed

Liu, Shubin

2015-03-26

An electrophilic aromatic substitution is a process where one atom or group on an aromatic ring is replaced by an incoming electrophile. The reactivity and regioselectivity of this category of reactions is significantly impacted by the group that is already attached to the aromatic ring. Groups promoting substitution at the ortho/para and meta position are called ortho/para and meta directing groups, respectively. Earlier, we have shown that regioselectivity of the electrophilic aromatic substitution is dictated by the nucleophilicity of the substituted aromatic ring, which is proportional to the Hirshfeld charge on the regioselective site. Ortho/para directing groups have the largest negative charge values at the ortho/para positions, whereas meta directing groups often have the largest negative charge value at the meta position. The electron donation or acceptance feature of a substitution group is irrelevant to the regioselectivity. In this contribution, we extend our previous study by quantifying the reactivity for this kind of reactions. To that end, we examine the transition-state structure and activation energy of an identity reaction for a series of monosubstituted-benzene molecules reacting with hydrogen fluoride using BF3 as the catalyst in the gas phase. A total of 18 substitution groups will be considered, nine of which are ortho/para directing and the other nine groups meta directing. From this study, we found that the barrier height of these reactions strongly correlates with the Hirshfeld charge on the regioselective site for both ortho/para and meta directing groups, with the correlation coefficient R(2) both better than 0.96. We also discovered a less accurate correlation between the barrier height and HOMO energy. These results reconfirm the validity and effectiveness of employing the Hirshfeld charge as a reliable descriptor of both reactivity and regioselectivity for this vastly important category of chemical transformations.

Protein charge distribution in proteomes and its impact on translation

PubMed Central

Requião, Rodrigo D.; Fernandes, Luiza; de Souza, Henrique José Araujo; Rossetto, Silvana; Domitrovic, Tatiana

2017-01-01

As proteins are synthesized, the nascent polypeptide must pass through a negatively charged exit tunnel. During this stage, positively charged stretches can interact with the ribosome walls and slow the translation. Therefore, charged polypeptides may be important factors that affect protein expression. To determine the frequency and distribution of positively and negatively charged stretches in different proteomes, the net charge was calculated for every 30 consecutive amino acid residues, which corresponds to the length of the ribosome exit tunnel. The following annotated and reviewed proteins in the UniProt database (Swiss-Prot) were analyzed: 551,705 proteins from different organisms and a total of 180 million protein segments. We observed that there were more negative than positive stretches and that super-charged positive sequences (i.e., net charges ≥ 14) were underrepresented in the proteomes. Overall, the proteins were more positively charged at their N-termini and C-termini, and this feature was present in most organisms and subcellular localizations. To investigate whether the N-terminal charges affect the elongation rates, previously published ribosomal profiling data obtained from S. cerevisiae, without translation-interfering drugs, were analyzed. We observed a nonlinear effect of the charge on the ribosome occupancy in which values ≥ +5 and ≤ -6 showed increased and reduced ribosome densities, respectively. These groups also showed different distributions across 80S monosomes and polysomes. Basic polypeptides are more common within short proteins that are translated by monosomes, whereas negative stretches are more abundant in polysome-translated proteins. These findings suggest that the nascent peptide charge impacts translation and can be one of the factors that regulate translation efficiency and protein expression. PMID:28531225

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

Biasing hydrogen bond donating host systems towards chemical warfare agent recognition.

PubMed

Hiscock, Jennifer R; Wells, Neil J; Ede, Jayne A; Gale, Philip A; Sambrook, Mark R

2016-10-12

A series of neutral ditopic and negatively charged, monotopic host molecules have been evaluated for their ability to bind chloride and dihydrogen phosphate anions, and neutral organophosphorus species dimethyl methylphosphonate (DMMP), pinacolyl methylphosphonate (PMP) and the chemical warfare agent (CWA) pinacolyl methylphosphonofluoridate (GD, soman) in organic solvent via hydrogen bonding. Urea, thiourea and boronic acid groups are shown to bind anions and neutral guests through the formation of hydrogen bonds, with the urea and thiourea groups typically exhibiting higher affinity interactions. The introduction of a negative charge on the host structure is shown to decrease anion affinity, whilst still allowing for high stability host-GD complex formation. Importantly, the affinity of the host for the neutral CWA GD is greater than for anionic guests, thus demonstrating the potential for selectivity reversal based on charge repulsion.

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.

Preparation and chromatographic evaluation of zwitterionic stationary phases with controllable ratio of positively and negatively charged groups.

PubMed

Cheng, Xiao-Dong; Hao, Yan-Hong; Peng, Xi-Tian; Yuan, Bi-Feng; Shi, Zhi-Guo; Feng, Yu-Qi

2015-08-15

The present study described the preparation and application of zwitterionic stationary phases (ACS) with controllable ratio of positively charged tertiary amine groups and negatively charged carboxyl groups. Various parameters, including water content, pH values and ionic strength of the mobile phase, were investigated to study the chromatographic characteristics of ACS columns. The prepared ACS columns demonstrated a mix-mode retention mechanism composed of surface adsorption, partitioning and electrostatic interactions. The elemental analysis of different batches of the ACS phases demonstrated good reproducibility of the preparation strategy. Additionally, various categories of compounds, including nucleosides, water-soluble vitamins, benzoic acid derivatives and basic compounds were successively employed to evaluate the separation selectivity of the prepared ACS stationary phases. These ACS phases exhibited entirely different selectivity and retention behavior from each other for various polar analytes, demonstrating the excellent application potential in the analysis of polar compounds in HILIC. Copyright © 2015 Elsevier B.V. All rights reserved.

Electrokinetic Response of Charge-Selective Nanostructured Polymeric Membranes

NASA Astrophysics Data System (ADS)

Schiffbauer, Jarrod; Li, Diya; Gao, Feng; Phillip, William; Chang, Hsueh-Chia

2017-11-01

Nanostructured polymeric membranes, with a tunable pore size and ease of surface molecular functionalization, are a promising material for separations, filtration, and sensing applications. Recently, such membranes have been fabricated wherein the ion selectivity is imparted by self-assembled functional groups through a two-step process. Amine groups are used to provide a positive surface charge and acid groups are used to yield a negative charge. The membranes can be fabricated as either singly-charged or patterned/mosaic membranes, where there are alternating regions of amine- lined or acid-lined pores. We demonstrate that such membranes, in addition to having many features in common with other charge selective membranes (i.e. AMX or Nafion), display a unique single-membrane rectification behavior. This is due to the asymmetric distribution of charged functional groups during the fabrication process. We demonstrate this rectification effect using both dc current-voltage characteristics as well as dc-biased electrical impedance spectroscopy. Furthermore, surface charge changes due to dc concentration polarization and generation of localized pH shifts are monitored using electrical impedance spectroscopy. (formerly at University of Notre Dame).

Functionally charged nanosize particles differentially activate BV2 microglia.

EPA Science Inventory

The effect of particle surface charge on the biological activation of immortalized mouse microglia (BV2) was examined. Nanosize (860-950 nm) spherical polystyrene microparticles (SPM) were coated with carboxyl (COOH-) or dimethyl amino (CH3)2-N- groups to give a net negative or p...

Through-Space Charge Interaction Substituent Effects in Molecular Catalysis Leading to the Design of the Most Efficient Catalyst of CO2-to-CO Electrochemical Conversion.

PubMed

Azcarate, Iban; Costentin, Cyrille; Robert, Marc; Savéant, Jean-Michel

2016-12-28

The starting point of this study of through-space substituent effects on the catalysis of the electrochemical CO 2 -to-CO conversion by iron(0) tetraphenylporphyrins is the linear free energy correlation between through-structure electronic effects and the iron(I/0) standard potential that we established separately. The introduction of four positively charged trimethylanilinium groups at the para positions of the tetraphenylporphyrin (TPP) phenyls results in an important positive deviation from the correlation and a parallel improvement of the catalytic Tafel plot. The assignment of this catalysis boosting effect to the Coulombic interaction of these positive charges with the negative charge borne by the initial Fe 0 -CO 2 adduct is confirmed by the negative deviation observed when the four positive charges are replaced by four negative charges borne by sulfonate groups also installed in the para positions of the TPP phenyls. The climax of this strategy of catalysis boosting by means of Coulombic stabilization of the initial Fe 0 -CO 2 adduct is reached when four positively charged trimethylanilinium groups are introduced at the ortho positions of the TPP phenyls. The addition of a large concentration of a weak acid-phenol-helps by cleaving one of the C-O bonds of CO 2 . The efficiency of the resulting catalyst is unprecedented, as can be judged by the catalytic Tafel plot benchmarking with all presently available catalysts of the electrochemical CO 2 -to-CO conversion. The maximal turnover frequency (TOF) is as high as 10 6 s -1 and is reached at an overpotential of only 220 mV; the extrapolated TOF at zero overpotential is larger than 300 s -1 . This catalyst leads to a highly selective formation of CO (practically 100%) in spite of the presence of a high concentration of phenol, which could have favored H 2 evolution. It is also very stable, showing no significant alteration after more than 80 h of electrolysis.

Fractionation and characterization of natural organic matter from certain rivers and soils by free-flow electrophoresis

USGS Publications Warehouse

Leenheer, J.A.; Malcolm, R.L.

1973-01-01

Soluble river organic matter and soil fulvic acids from a variety of environments were compared by examining the free-flow electrophoretic fractionation curves of organic carbon, color, and polysaccharides. Significant amounts of virtually colorless organic material were found in both the soil and the river preparations. Polysaccharides comprised 20-75 percent of the colorless material in the soil fulvic acids but only 3.2-7.0 percent of the colorless material in the river preparations. A significant amount of polysaccharides was complexed with organic materials having negative charges. Amounts of polysaccharides were greater in the Fairbanks soil from Alaska than in the soils from North Carolina or Iowa, and they were greater in the Tahquamenon River in Michigan than in the two rivers in Florida; this suggests that polysaccharide degradation is slower in cooler environments. For all of the organic preparations which were fractionated, the intensity of the yellow color increased as the charge on the organic anion increased. Highly colored, negatively charged organic material was found to be present in greater amounts in the subsurface spodic soil horizon of the Lakewood and Fairbanks soils than in the surface mollic horizon of the Macksburg soil. Infrared spectroscopy and elemental analysis of four pooled fractions of the Fairbanks fulvic acid indicated increasing aromatic character with increasing negative charge. An increase in the carboxyl content with negative charge suggests the carboxyl group as the primary source of the negative charge.

A Sliding-Mode Triboelectric Nanogenerator with Chemical Group Grated Structure by Shadow Mask Reactive Ion Etching.

PubMed

Shang, Wanyu; Gu, Guang Qin; Yang, Feng; Zhao, Lei; Cheng, Gang; Du, Zu-Liang; Wang, Zhong Lin

2017-09-26

The sliding-mode triboelectric nanogenerator (S-TENG) with grated structure has important applications in energy harvest and active sensors; however its concavo-convex structure leads to large frictional resistance and abrasion. Here, we developed a S-TENG with a chemical group grated structure (S-TENG-CGG), in which the triboelectric layer's triboelectric potential has a positive-negative alternating charged structure. The triboelectric layer of the S-TENG-CGG was fabricated through a reactive ion etching process with a metal shadow mask with grated structure. In the etched region, the nylon film, originally positively charged as in friction with stainless steel, gained opposite triboelectric potential and became negatively charged because of the change of surface functional groups. The output signals of the S-TENG-CGG are alternating and the frequency is determined by both the segment numbers and the moving speed. The applications of the S-TENG-CGG in the charging capacitor and driving calculator are demonstrated. In the S-TENG-CGG, since there is no concavo-convex structure, the frictional resistance and abrasion are largely reduced, which enhances its performances in better stability and longer working time.

Structural Analysis of Charge Discrimination in the Binding of Inhibitors to Human Carbonic Anhydrases I and II

PubMed Central

Srivastava, D. K.; Jude, Kevin M.; Banerjee, Abir L.; Haldar, Manas; Manokaran, Sumathra; Kooren, Joel; Mallik, Sanku; Christianson, David W.

2008-01-01

Despite the similarity in the active site pockets of carbonic anhydrase (CA) isozymes I and II, the binding affinities of benzenesulfonamide inhibitors are invariably higher with CA II as compared to CA I. To explore the structural basis of this molecular recognition phenomenon, we have designed and synthesized simple benzenesulfonamide inhibitors substituted at the para position with positively-charged, negatively-charged, and neutral functional groups, and we have determined the affinities and X-ray crystal structures of their enzyme complexes. The para-substituents are designed to bind in the midsection of the 15 Å deep active site cleft, where interactions with enzyme residues and solvent molecules are possible. We find that a para-substituted positively-charged amino group is more poorly tolerated in the active site of CA I compared with CA II. In contrast, a para-substituted negatively-charged carboxylate substituent is tolerated equally well in the active sites of both CA isozymes. Notably, enzyme-inhibitor affinity increases upon neutralization of inhibitor charged groups by amidation or esterification. These results inform the design of short molecular linkers connecting the benzenesulfonamide group and a para-substituted tail group in “two-prong” CA inhibitors: an optimal linker segment will be electronically neutral, yet capable of engaging in at least some hydrogen bond interactions with protein residues and/or solvent. Microcalorimetric data reveal that inhibitor binding to CA I is enthalpically less favorable and entropically more favorable than inhibitor binding to CA II. This contrasting behavior may arise in part from differences in active site desolvation and the conformational entropy of inhibitor binding to each isozyme active site. PMID:17407288

The influence of PAMAM dendrimers surface groups on their interaction with porcine pepsin.

PubMed

Ciolkowski, Michal; Rozanek, Monika; Bryszewska, Maria; Klajnert, Barbara

2013-10-01

In this study the ability of three polyamidoamine (PAMAM) dendrimers with different surface charge (positive, neutral and negative) to interact with a negatively charged protein (porcine pepsin) was examined. It was shown that the dendrimer with a positively charged surface (G4 PAMAM-NH2), as well as the dendrimer with a neutral surface (G4 PAMAM-OH), were able to inhibit enzymatic activity of pepsin. It was also found that these dendrimers act as mixed partially non-competitive pepsin inhibitors. The negatively charged dendrimer (G3.5 PAMAM-COOH) was not able to inhibit the enzymatic activity of pepsin, probably due to the electrostatic repulsion between this dendrimer and the protein. No correlation between changes in enzymatic activity of pepsin and alterations in CD spectrum of the protein was observed. It indicates that the interactions between dendrimers and porcine pepsin are complex, multidirectional and not dependent only on disturbances of the secondary structure. © 2013.

Effect of surface charge on the colloidal stability and in vitro uptake of carboxymethyl dextran-coated iron oxide nanoparticles

PubMed Central

Ayala, Vanessa; Herrera, Adriana P.; Latorre-Esteves, Magda; Torres-Lugo, Madeline

2013-01-01

Nanoparticle physicochemical properties such as surface charge are considered to play an important role in cellular uptake and particle–cell interactions. In order to systematically evaluate the role of surface charge on the uptake of iron oxide nanoparticles, we prepared carboxymethyl-substituted dextrans with different degrees of substitution, ranging from 38 to 5 groups per chain, and reacted them using carbodiimide chemistry with amine–silane-coated iron oxide nanoparticles with narrow size distributions in the range of 33–45 nm. Surface charge of carboxymethyl-substituted dextran-coated nano-particles ranged from −50 to 5 mV as determined by zeta potential measurements, and was dependent on the number of carboxymethyl groups incorporated in the dextran chains. Nanoparticles were incubated with CaCo-2 human colon cancer cells. Nanoparticle–cell interactions were observed by confocal laser scanning microscopy and uptake was quantified by elemental analysis using inductively coupled plasma mass spectroscopy. Mechanisms of internalization were inferred using pharmacological inhibitors for fluid-phase, clathrin-mediated, and caveola-mediated endocytosis. Results showed increased uptake for nanoparticles with greater negative charge. Internalization patterns suggest that uptake of the most negatively charged particles occurs via non-specific interactions. PMID:24470787

The role of negatively charged lipids in lysosomal phospholipase A2 function

PubMed Central

Abe, Akira; Shayman, James A.

2009-01-01

Lysosomal phospholipase A2 (LPLA2) is characterized by increased activity toward zwitterionic phospholipid liposomes containing negatively charged lipids under acidic conditions. The effect of anionic lipids on LPLA2 activity was investigated. Mouse LPLA2 activity was assayed as C2-ceramide transacylation. Sulfatide incorporated into liposomes enhanced LPLA2 activity under acidic conditions and was weakened by NaCl or increased pH. Amiodarone, a cationic amphiphilic drug, reduced LPLA2 activity. LPLA2 exhibited esterase activity when p-nitro-phenylbutyrate (pNPB) was used as a substrate. Unlike the phospholipase A2 activity, the esterase activity was detected over wide pH range and not inhibited by NaCl or amiodarone. Presteady-state kinetics using pNPB were consistent with the formation of an acyl-enzyme intermediate. C2-ceramide was an acceptor for the acyl group of the acyl-enzyme but was not available as the acyl group acceptor when dispersed in liposomes containing amiodarone. Cosedimentation of LPLA2 with liposomes was enhanced in the presence of sulfatide and was reduced by raising NaCl, amiodarone, or pH in the reaction mixture. LPLA2 adsorption to negatively charged lipid membrane surfaces through an electrostatic attraction, therefore, enhances LPLA2 enzyme activity toward insoluble substrates. Thus, anionic lipids present within lipid membranes enhance the rate of phospholipid hydrolysis by LPLA2 at lipid-water interfaces.—Abe, A., and J. A. Shayman. The role of negatively charged lipids in lysosomal phospholipase A2 function. PMID:19321879

On-bead combinatorial synthesis and imaging of europium(III)-based paraCEST agents aids in identification of chemical features that enhance CEST sensitivity.

PubMed

Singh, Jaspal; Rustagi, Vineeta; Zhang, Shanrong; Sherry, A Dean; Udugamasooriya, D Gomika

2017-08-01

The rate of water exchange between the inner sphere of a paramagnetic ion and bulk water is an important parameter in determining the magnitude of the chemical exchange saturation transfer signal from paramagnetic CEST agents (paraCEST). This is governed by various geometric, steric and ligand field factors created by macrocyclic ligands surrounding the paramagnetic metal ion. Our previous on-bead combinatorial studies of di-peptoid-europium(III)-1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA)-tetraamide complexes revealed that negatively charged groups in the immediate vicinity of the metal center strongly enhances the CEST signal. Here, we report a solid phase synthesis and on-bead imaging of 76 new DOTA derivatives that are developed by coupling with a single residue onto each of the three arms of a DOTA-tetraamide scaffold attached to resin beads. This single residue predominantly carries negatively charged groups blended with various physico-chemical characteristics. We found that non-bulky negatively charged groups are best suited at the immediate vicinity of the metal ion, while positive, bulky and halogen containing moieties suppress the CEST signal. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

Analysis of the interaction between Bacillus coagulans and Bacillus thuringiensis S-layers and calcium ions by XRD, light microscopy, and FTIR.

PubMed

Babolmorad, Ghazal; Emtiazi, Giti; Emamzadeh, Rahman

2014-05-01

S-layer is a self-assemble regularly crystalline surface that covers major cell wall component of many bacteria and archaea and exhibits a high metal-binding capacity. We have studied the effect of the calcium ions and type of solid support (glass or mica) on the structure of the S-layers from Bacillus coagulans HN-68 and Bacillus thuringiensis MH14 upon simple methods based on light microscopy and AFM. Furthermore, the Fourier transform infrared spectroscopy (FTIR) study is indicated that the calcium-S-layer interaction occurred mainly through the carboxylate groups of the side chains of aspartic acid (Asp) and glutamic acid (Glu) and nitrogen atoms of Lys, Asn, and histidine (His) amino acids and N-H groups of the peptide backbone. Studied FTIR revealed that inner faces of S-layer are mainly negative, and outer faces of S-layer are mainly positive. Probably, calcium ions with positive charges bound to the carboxyl groups of Glu and Asp. Accordingly, calcium ions are anchored in the space between the inner faces of S-layer with negative charge and the surface of mica with negative charge. This leads to regular arrangement of the S-layer subunits.

Interactions between charged nanoparticles and giant vesicles fabricated from inverted-headgroup lipids

NASA Astrophysics Data System (ADS)

Wang, Lu; Malmstadt, Noah

2017-10-01

The surface chemistry of the cell membrane plays an important role in how cells interact with particulate species. These interactions are dictated in large part by lipid headgroup charge. To investigate the nature of electrostatic interactions between lipid bilayers and nanoparticles in solution, we studied nanoparticles interacting with the zwitterionic lipid 1,2-dioleoyl-glycero-3-phosphocholine (DOPC), and its inverted-headgroup analog DOCP. These interactions were investigated by fabricating giant unilamellar vesicles (GUVs) with DOPC lipids and DOCP lipids respectively, and introducing nanoparticles to suspensions of both. GUVs displayed various deformational modes depending on the charge and size of the nanoparticles as well as the compositions of the GUVs. The differences in the responses of the two lipid species illuminate how the phosphate and choline groups on the lipid interact with charged nanoparticles. This study suggests that the phosphate group dominates the lipid-nanoparticle electrostatic interaction. We speculate that the formation of water clathrate structures around the choline group inhibits interactions between negatively charged nanoparticles and the positively charged choline.

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.

Modeling the Acid-Base Properties of Montmorillonite Edge Surfaces.

PubMed

Tournassat, Christophe; Davis, James A; Chiaberge, Christophe; Grangeon, Sylvain; Bourg, Ian C

2016-12-20

The surface reactivity of clay minerals remains challenging to characterize because of a duality of adsorption surfaces and mechanisms that does not exist in the case of simple oxide surfaces: edge surfaces of clay minerals have a variable proton surface charge arising from hydroxyl functional groups, whereas basal surfaces have a permanent negative charge arising from isomorphic substitutions. Hence, the relationship between surface charge and surface potential on edge surfaces cannot be described using the Gouy-Chapman relation, because of a spillover of negative electrostatic potential from the basal surface onto the edge surface. While surface complexation models can be modified to account for these features, a predictive fit of experimental data was not possible until recently, because of uncertainty regarding the densities and intrinsic pK a values of edge functional groups. Here, we reexamine this problem in light of new knowledge on intrinsic pK a values obtained over the past decade using ab initio molecular dynamics simulations, and we propose a new formalism to describe edge functional groups. Our simulation results yield reasonable predictions of the best available experimental acid-base titration data.

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

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

Sentinel lymph node intraoperative imprint cytology in patients with breast cancer-costly or cost effective?

PubMed

Kamiński, Jan P; Case, Doug; Howard-McNatt, Marissa; Geisinger, Kim R; Levine, Edward A

2010-11-01

Sentinel lymph node (SLN) biopsy is now standard of care for breast cancer patients. Intraoperative imprint cytology (IIC) provides results to the surgeon, which may lead to a lymphadenectomy under the same anesthetic when it is positive for metastases. Thus, a positive IIC can spare the patient a second operation and the charges associated with it. The aim of this study is to assess the cost effectiveness of IIC in breast cancer patients. This study evaluated 98 patients who underwent a SLN biopsy between July 2008 and May 2009. The patients were divided into 1 of 3 groups based on the results of IIC and permanent sections: (1) true-negative (TN) IIC, (2) true-positive (TP) IIC, and (3) false-negative (FN) IIC. Total charges for each patient were extracted retrospectively, and nonparametric tests assessed differences in the charges between the three groups. The median total charges per patient for each population were the following: (1) $14,764.62, (2) $19,025.89, and (3) $29,750.64 (P < 0.05). A difference of more than $10,000 exists in total charges per patient between the node-positive population who did not benefit from IIC (FN) and the node-positive population who did benefit from IIC (TP). IIC is a cost-effective evaluation of breast cancer patients. The difference in total charges between the FN and TP groups outweighs the cost of the IIC. In addition to the reduced costs incurred by the patient and the hospital, IIC spares the patient the psychological and physical stress of a second operation.

Positive and negative ion mode ESI-MS and MS/MS for studying drug-DNA complexes

NASA Astrophysics Data System (ADS)

Rosu, Frédéric; Pirotte, Sophie; Pauw, Edwin De; Gabelica, Valérie

2006-07-01

We report systematic investigation of duplex DNA complexes with minor groove binders (Hoechsts 33258 and 33342, netropsin and DAPI) and intercalators (daunomycin, doxorubicin, actinomycin D, ethidium, cryptolepine, neocryptolepine, m-Amsacrine, proflavine, ellipticine and mitoxantrone) by ESI-MS and ESI-MS/MS in the negative ion mode and in the positive ion mode. The apparent solution phase equilibrium binding constants can be determined by measuring relative intensities in the ESI-MS spectrum. While negative ion mode gives reliable results, positive ion mode gives a systematic underestimation of the binding constants and even a complete suppression of the complexes for intercalators lacking functional groups capable of interacting in the grooves. In the second part of the paper we systematically compare MS/MS fragmentation channels and breakdown curves in the positive and the negative modes, and discuss the possible uses and caveats of MS/MS in drug-DNA complexes. In the negative mode, the drugs can be separated in three groups: (1) those that leave the complex with no net charge; (2) those that leave the complex with a negative charge; and (3) those that remain attached on the strands upon dissociation of the duplex due to their positive charge. In the positive ion mode, all complexes fragment via the loss of protonated drug. Information on the stabilization of the complex by drug-DNA noncovalent interactions can be obtained straightforwardly only in the case of neutral drug loss. In all other cases, proton affinity (in the positive ion mode), gas-phase basicity (in the negative ion mode) and coulombic repulsion are the major factors influencing the fragmentation channel and the dissociation kinetics.

Penetration and release studies of positively and negatively charged nanoemulsions--is there a benefit of the positive charge?

PubMed

Baspinar, Yücel; Borchert, Hans-Hubert

2012-07-01

The surface of all tissues, including the stratum corneum, carries a negative charge. Following that fact it is assumed that a positively charged topical formulation could lead to an enhanced penetration because of an increased interaction with the negative charge of the membrane. The intention of this study is to prove an enhanced penetration of a positively charged nanoemulsion compared to a negatively charged nanoemulsion, both containing prednicarbate. The release and penetration of these nanoemulsions, produced with the high pressure homogenization method, were investigated. Regarding these results reveals that the release of the negatively charged formulation is higher compared to the positively charged nanoemulsion, while the penetration of the positively charged nanoemulsion is enhanced compared to the negatively charged formulation. The results of the investigated positively charged nanoemulsion containing prednicarbate show that its topical use could be advantageous for the therapy of atopic dermatitis, especially regarding phytosphingosine, which was responsible for the positive charge. Copyright © 2012 Elsevier B.V. All rights reserved.

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

The influence of ligand charge and length on the assembly of Brome mosaic virus derived virus-like particles with magnetic core

NASA Astrophysics Data System (ADS)

Mieloch, Adam A.; Krecisz, Monika; Rybka, Jakub D.; Strugała, Aleksander; Krupiński, Michał; Urbanowicz, Anna; Kozak, Maciej; Skalski, Bohdan; Figlerowicz, Marek; Giersig, Michael

2018-03-01

Virus-like particles (VLPs) have sparked a great interest in the field of nanobiotechnology and nanomedicine. The introduction of superparamagnetic nanoparticles (SPIONs) as a core, provides potential use of VLPs in the hyperthermia therapy, MRI contrast agents and magnetically-powered delivery agents. Magnetite NPs also provide a significant improvement in terms of VLPs stability. Moreover employing viral structural proteins as self-assembling units has opened a new paths for targeted therapy, drug delivery systems, vaccines design, and many more. In many cases, the self-assembly of a virus strongly depends on electrostatic interactions between positively charged groups of the capsid proteins and negatively charged nucleic acid. This phenomenon imposes the negative net charge as a key requirement for the core nanoparticle. In our experiments, Brome mosaic virus (BMV) capsid proteins isolated from infected plants Hordeum vulgare were used. Superparamagnetic iron oxide nanoparticles (Fe3O4) with 15 nm in diameter were synthesized by thermal decomposition and functionalized with COOH-PEG-PL polymer or dihexadecylphosphate (DHP) in order to provide water solubility and negative charge required for the assembly. Nanoparticles were characterized by Transmission Electron Microscopy (TEM), Dynamic Light Scattering (DLS), Zeta Potential, Fourier Transformed Infrared Spectroscopy (FTIR) and Superconducting Quantum Interference Device (SQUID) magnetometry. TEM and DLS study were conducted to verify VLPs creation. This study demonstrates that the increase of negative surface charge is not a sufficient factor determining successful assembly. Additional steric interactions provided by longer ligands are crucial for the assembly of BMV SPION VLPs and may enhance the colloidal stability.

Reagent Anions for Charge Inversion of Polypeptide/Protein Cations in the Gas Phase

PubMed Central

He, Min; Emory, Joshua F.; McLuckey, Scott A.

2005-01-01

Various reagent anions capable of converting polypeptide cations to anions via ion/ion reactions have been investigated. The major charge inversion reaction channels include multiple proton transfer and adduct formation. Dianions composed of sulfonate groups as the negative charge carriers show essentially exclusive adduct formation in converting protonated peptides and proteins to anions. Dianions composed of carboxylate groups, on the other hand, show far more charge inversion via multiple proton transfer, with the degree of adduct formation dependent upon both the size of the polypeptide and the spacings between carboxylate groups in the dianion. More highly charged carboxylate-containing anions, such as those derived from carboxylate-terminated polyamidoamine half-generation dendrimers show charge inversion to give anion charges as high in magnitude as −4, with the degree of adduct formation being inversely related to dendrimer generation. All observations can be interpreted on the basis of charge inversion taking place via a long-lived chemical complex. The lifetime of this complex is related to the strengths and numbers of the interactions of the reactants in the complex. Calculations with model systems are fully consistent with sulfonate groups giving rise to more stable complexes. The kinetic stability of the complex can also be affected by the presence of electrostatic repulsion if it is multiply charged. In general, this situation destabilizes the complex and reduces the likelihood for observation of adducts. The findings highlight the characteristics of multiply charged anions that play roles in determining the nature of charge inversion products associated with protonated peptides and proteins. PMID:15889906

Correlation between octanol/water and liposome/water distribution coefficients and drug absorption of a set of pharmacologically active compounds.

PubMed

Esteves, Freddy; Moutinho, Carla; Matos, Carla

2013-06-01

Absorption and consequent therapeutic action are key issues in the development of new drugs by the pharmaceutical industry. In this sense, different models can be used to simulate biological membranes to predict the absorption of a drug. This work compared the octanol/water and the liposome/water models. The parameters used to relate the two models were the distribution coefficients between liposomes and water and octanol and water and the fraction of drug orally absorbed. For this study, 66 drugs were collected from literature sources and divided into four groups according to charge and ionization degree: neutral; positively charged; negatively charged; and partially ionized/zwitterionic. The results show a satisfactory linear correlation between the octanol and liposome systems for the neutral (R²= 0.9324) and partially ionized compounds (R²= 0.9367), contrary to the positive (R²= 0.4684) and negatively charged compounds (R²= 0.1487). In the case of neutral drugs, results were similar in both models because of the high fraction orally absorbed. However, for the charged drugs (positively, negatively, and partially ionized/zwitterionic), the liposomal model has a more-appropriate correlation with absorption than the octanol model. These results show that the neutral compounds only interact with membranes through hydrophobic bonds, whereas charged drugs favor electrostatic interactions established with the liposomes. With this work, we concluded that liposomes may be a more-appropriate biomembrane model than octanol for charged compounds.

Avoidance of an electric field by insects: Fundamental biological phenomenon for an electrostatic pest-exclusion strategy

NASA Astrophysics Data System (ADS)

Matsuda, Y.; Nonomura, T.; Kakutani, K.; Kimbara, J.; Osamura, K.; Kusakari, S.; Toyoda, H.

2015-10-01

An electric field screen is a physical device used to exclude pest insects from greenhouses and warehouses to protect crop production and storage. The screen consists of iron insulated conductor wires (ICWs) arrayed in parallel and linked to each other, an electrostatic DC voltage generator used to supply a negative charge to the ICWs, and an earthed stainless net placed on one side of the ICW layer. The ICW was negatively charged to polarize the earthed net to create a positive charge on the ICW side surface, and an electric field formed between the opposite charges of the ICW and earthed net. The current study focused on the ability of the screen to repel insects reaching the screen net. This repulsion was a result of the insect's behaviour, i.e., the insects were deterred from entering the electric field of the screen. In fact, when the screen was negatively charged with the appropriate voltages, the insects placed their antennae inside the screen and then flew away without entering. Obviously, the insects recognized the electric field using their antennae and thereby avoided entering. Using a wide range of insects and spiders belonging to different taxonomic groups, we confirmed that the avoidance response to the electric field was common in these animals.

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.

A PDDA/poly(2,6-pyridinedicarboxylic acid)-CNTs composite film DNA electrochemical sensor and its application for the detection of specific sequences related to PAT gene and NOS gene.

PubMed

Yang, Tao; Zhang, Wei; Du, Meng; Jiao, Kui

2008-05-30

2,6-Pyridinedicarboxylic acid (PDC) was electropolymerized on the glassy carbon electrode (GCE) surface combined with carboxylic group-functionalized single-walled carbon nanotubes (SWNTs) by cyclic voltammetry (CV) to form PDC-SWNTs composite film, which was rich in negatively charged carboxylic group. Then, poly(diallyldimethyl ammonium chloride) (PDDA), a linear cationic polyelectrolyte, was electrostatically adsorbed on the PDC-SWNTs/GCE surface. DNA probes with negatively charged phosphate group at the 5' end were immobilized on the PDDA/PDC-SWNTs/GCE due to the strong electrostatic attraction between PDDA and phosphate group of DNA. It has been found that modification of the electrode with PDC-SWNTs film has enhanced the effective electrode surface area and electron-transfer ability, in addition to providing negatively charged groups for the electrostatic assembly of cationic polyelectrolyte. PDDA plays a key role in the attachment of DNA probes to the PDC-SWNTs composite film and acts as a bridge to connect DNA with PDC-SWNTs film. The cathodic peak current of methylene blue (MB), an electroactive label, decreased obviously after the hybridization of DNA probe (ssDNA) with the complementary DNA (cDNA). This peak current change was used to monitor the recognition of the specific sequences related to PAT gene in the transgenic corn and the polymerase chain reaction (PCR) amplification of NOS gene from the sample of transgenic soybean with satisfactory results. Under optimal conditions, the dynamic detection range of the sensor to PAT gene target sequence was from 1.0x10(-11) to 1.0x10(-6) mol/L with the detection limit of 2.6x10(-12) mol/L.

Stabilization of enzymes in ionic liquids via modification of enzyme charge.

PubMed

Nordwald, Erik M; Kaar, Joel L

2013-09-01

Due to the propensity of ionic liquids (ILs) to inactivate enzymes, the development of strategies to improve enzyme utility in these solvents is critical to fully exploit ILs for biocatalysis. We have developed a strategy to broadly improve enzyme utility in ILs based on elucidating the effect of charge modifications on the function of enzymes in IL environments. Results of stability studies in aqueous-IL mixtures indicated a clear connection between the ratio of enzyme-containing positive-to-negative sites and enzyme stability in ILs. Stability studies of the effect of [BMIM][Cl] and [EMIM][EtSO4 ] on chymotrypsin specifically found an optimum ratio of positively-charged amine-to-negatively-charged acid groups (0.39). At this ratio, the half-life of chymotrypsin was increased 1.6- and 4.3-fold relative to wild-type chymotrypsin in [BMIM][Cl] and [EMIM][EtSO4 ], respectively. The half-lives of lipase and papain were similarly increased as much as 4.0 and 2.4-fold, respectively, in [BMIM][Cl] by modifying the ratio of positive-to-negative sites of each enzyme. More generally, the results of stability studies found that modifications that reduce the ratio of enzyme-containing positive-to-negative sites improve enzyme stability in ILs. Understanding the impact of charge modification on enzyme stability in ILs may ultimately be exploited to rationally engineer enzymes for improved function in IL environments. Copyright © 2013 Wiley Periodicals, Inc.

The 4-pyridylmethyl ester as a protecting group for glutamic and aspartic acids: 'flipping' peptide charge states for characterization by positive ion mode ESI-MS.

PubMed

Garapati, Sriramya; Burns, Colin S

2014-03-01

Use of the 4-pyridylmethyl ester group for side-chain protection of glutamic acid residues in solid-phase peptide synthesis enables switching of the charge state of a peptide from negative to positive, thus making detection by positive ion mode ESI-MS possible. The pyridylmethyl ester moiety is readily removed from peptides in high yield by hydrogenation. Combining the 4-pyridylmethyl ester protecting group with benzyl ester protection reduces the number of the former needed to produce a net positive charge and allows for purification by RP HPLC. This protecting group is useful in the synthesis of highly acidic peptide sequences, which are often beset by problems with purification by standard RP HPLC and characterization by ESI-MS. Copyright © 2014 European Peptide Society and John Wiley & Sons, Ltd.

Design of anticoagulant surfaces based on cellulose nanocrystals.

PubMed

Ehmann, Heike M A; Mohan, Tamilselvan; Koshanskaya, Maria; Scheicher, Sylvia; Breitwieser, Doris; Ribitsch, Volker; Stana-Kleinschek, Karin; Spirk, Stefan

2014-11-07

The anticoagulant activity of surfaces decorated with cellulose nanocrystals (CNCs) prepared via sulfuric acid hydrolysis, is explored. Such surfaces bear a high amount of negatively charged sulfate groups, which mimic the naturally occurring anticoagulant heparin in terms of charge density. It is demonstrated that CNC decorated surfaces significantly enhance the coagulation times of blood plasma and whole blood as proven by QCM-D and simple clotting tests.

An analysis of five negative sprite-parent discharges and their associated thunderstorm charge structures

NASA Astrophysics Data System (ADS)

Boggs, Levi D.; Liu, Ningyu; Splitt, Michael; Lazarus, Steven; Glenn, Chad; Rassoul, Hamid; Cummer, Steven A.

2016-01-01

In this study we analyze the discharge morphologies of five confirmed negative sprite-parent discharges and the associated charge structures of the thunderstorms that produced them. The negative sprite-parent lightning took place in two thunderstorms that were associated with a tropical disturbance in east central and south Florida. The first thunderstorm, which moved onshore in east central Florida, produced four of the five negative sprite-parent discharges within a period of 17 min, as it made landfall from the Atlantic Ocean. These negative sprite-parents were composed of bolt-from-the-blue (BFB), hybrid intracloud-negative cloud-to-ground (IC-NCG), and multicell IC-NCGs discharges. The second thunderstorm, which occurred inland over south Florida, produced a negative sprite-parent that was a probable hybrid IC-NCG discharge and two negative gigantic jets (GJs). Weakened upper positive charge with very large midlevel negative charge was inferred for both convective cells that initiated the negative-sprite-parent discharges. Our study suggests tall, intense convective systems with high wind shear at the middle to upper regions of the cloud accompanied by low cloud-to-ground (CG) flash rates promote these charge structures. The excess amount of midlevel negative charge results in these CG discharges transferring much more charge to ground than typical negative CG discharges. We find that BFB discharges prefer an asymmetrical charge structure that brings the negative leader exiting the upper positive charge region closer to the lateral positive screening charge layer. This may be the main factor in determining whether a negative leader exiting the upper positive region of the thundercloud forms a BFB or GJ.

Nitrogen-doped partially reduced graphene oxide rewritable nonvolatile memory.

PubMed

Seo, Sohyeon; Yoon, Yeoheung; Lee, Junghyun; Park, Younghun; Lee, Hyoyoung

2013-04-23

As memory materials, two-dimensional (2D) carbon materials such as graphene oxide (GO)-based materials have attracted attention due to a variety of advantageous attributes, including their solution-processability and their potential for highly scalable device fabrication for transistor-based memory and cross-bar memory arrays. In spite of this, the use of GO-based materials has been limited, primarily due to uncontrollable oxygen functional groups. To induce the stable memory effect by ionic charges of a negatively charged carboxylic acid group of partially reduced graphene oxide (PrGO), a positively charged pyridinium N that served as a counterion to the negatively charged carboxylic acid was carefully introduced on the PrGO framework. Partially reduced N-doped graphene oxide (PrGODMF) in dimethylformamide (DMF) behaved as a semiconducting nonvolatile memory material. Its optical energy band gap was 1.7-2.1 eV and contained a sp2 C═C framework with 45-50% oxygen-functionalized carbon density and 3% doped nitrogen atoms. In particular, rewritable nonvolatile memory characteristics were dependent on the proportion of pyridinum N, and as the proportion of pyridinium N atom decreased, the PrGODMF film lost memory behavior. Polarization of charged PrGODMF containing pyridinium N and carboxylic acid under an electric field produced N-doped PrGODMF memory effects that followed voltage-driven rewrite-read-erase-read processes.

An Analysis of Two Thunderstorms Producing Five Negative Sprites on 12 September 2014

NASA Astrophysics Data System (ADS)

Boggs, L.; Liu, N.; Splitt, M. E.; Lazarus, S. M.; Cummer, S. A.; Rassoul, H.

2015-12-01

We present a detailed analysis of the thunderstorms and the parent lightning discharge morphologies of five confirmed negative sprites taking place in two different thunderstorms. These two thunderstorms took place in east-central and south Florida on 12 September 2014. We utilized several lightning location networks, remote magnetic field measurements, dual polarization radar, and balloon borne soundings in our analysis. Each parent discharge was immediately preceded by intra-cloud (IC) discharges between the mid-level negative and upper positive charge regions. This either allowed a second upward negative leader to escape the upper positive charge region, or encouraged a downward negative leader to be initiated and connect with ground. The discharges found in this study support the findings of Lu et al., 2012 [JGR,117, D04212, 2012] that negative sprite-parent lightning consists primarily of hybrid intra-cloud negative cloud-to-ground (IC-NCG) and bolt-from-the-blue (BFB) lightning. Our work finds these unique discharges form in thunderstorms that have an excess of mid-level negative charge and weakened upper positive charge. Due to this charge structure, these unusual discharges transfer more charge to the ground than typical negative cloud-to-ground discharges. Our study suggests that the key difference separating bolt-from-the-blue and gigantic jet discharges is an asymmetric charge structure. This acts to bring the negative leader exiting the thundercloud closer to the lateral positive screening layer, encouraging the negative leader to turn towards ground. This investigation reveals IC discharges that involve multiple convective cells and come to ground as a negative CG discharge, a breed of hybrid IC-NCG discharges, also transfer more negative charge to ground than typical negative CG discharges and are able to initiate negative sprites. From this work, the charge structures mentioned above resulted from tall, intense convective cells with low CG flash rates with high wind shear in the mid to upper regions of the cloud. This acted to create a large reservoir of mid-level negative charge and create a general asymmetry to the charge structure. The wind shear in the upper regions also acted to weaken the upper positive charge by turbulent mixing with the upper negative screening charge layer.

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.

Halogeno-substituted 2-aminobenzoic acid derivatives for negative ion fragmentation studies of N-linked carbohydrates.

PubMed

Harvey, David J

2005-01-01

Negative ion electrospray mass spectra of high-mannose N-linked glycans derivatised with 2-aminobenzoic acids and ionised from solutions containing ammonium hydroxide gave prominent [M-H](-) ions accompanied by weaker [M-2H](2-) ions. Fragmentation of both types of ions gave prominent singly charged glycosidic cleavage ions containing the derivatised reducing terminus and ions from the non-reducing terminus that appeared to be products of cross-ring cleavages. Differentiation of these two groups of ions was conveniently achieved in a single spectrum by use of chloro- or bromo-substituted benzoic acids in order to label ions containing the derivative with an atom with a distinctive isotope pattern. Fragmentation of the doubly charged ions gave more abundant fragments, both singly and doubly charged, than did fragmentation of the singly charged ions, but information of chain branching was masked by the appearance of prominent ions produced by internal cleavages. Copyright (c) 2005 John Wiley & Sons, Ltd.

Electrochemical Grafting of Graphene Nano Platelets with Aryl Diazonium Salts.

PubMed

Qiu, Zhipeng; Yu, Jun; Yan, Peng; Wang, Zhijie; Wan, Qijin; Yang, Nianjun

2016-10-26

To vary interfacial properties, electrochemical grafting of graphene nano platelets (GNP) with 3,5-dichlorophenyl diazonium tetrafluoroborate (aryl-Cl) and 4-nitrobenzene diazonium tetrafluoroborate (aryl-NO 2 ) was realized in a potentiodynamic mode. The covalently bonded aryl layers on GNP were characterized using atomic force microscopy and X-ray photoelectron spectroscopy. Electrochemical conversion of aryl-NO 2 into aryl-NH 2 was conducted. The voltammetric and impedance behavior of negatively and positively charged redox probes (Fe(CN) 6 3-/4- and Ru(NH 3 ) 6 2+/3+ ) on three kinds of aryl layers grafted on GNP reveal that their interfacial properties are determined by the charge states of redox probes and reactive terminal groups (-Cl, -NO 2 , -NH 2 ) in aryl layers. On aryl-Cl and aryl-NH 2 garted GNP, selective and sensitive monitoring of positively charged lead ions as well as negatively charged nitrite and sulfite ions was achieved, respectively. Such a grafting procedure is thus a perfect way to design and control interfacial properties of graphene.

Hydroxyapatite formation on graphene oxide modified with amino acids: arginine versus glutamic acid

PubMed Central

Tavafoghi, M.; Brodusch, N.; Gauvin, R.; Cerruti, M.

2016-01-01

Hydroxyapatite (HA, Ca5(PO4)3OH) is the main inorganic component of hard tissues, such as bone and dentine. HA nucleation involves a set of negatively charged phosphorylated proteins known as non-collagenous proteins (NCPs). These proteins attract Ca2+ and PO43− ions and increase the local supersaturation to a level required for HA precipitation. Polar and charged amino acids (AAs) are highly expressed in NCPs, and seem to be responsible for the mineralizing effect of NCPs; however, the individual effect of these AAs on HA mineralization is still unclear. In this work, we investigate the effect of a negatively charged (Glu) and positively charged (Arg) AA bound to carboxylated graphene oxide (CGO) on HA mineralization in simulated body fluids (SBF). Our results show that Arg induces HA precipitation faster and in larger amounts than Glu. We attribute this to the higher stability of the complexes formed between Arg and Ca2+ and PO43− ions, and also to the fact that Arg exposes both carboxyl and amino groups on the surface. These can electrostatically attract both Ca2+ and PO43− ions, thus increasing local supersaturation more than Glu, which exposes carboxyl groups only. PMID:26791001

Hydroxyapatite formation on graphene oxide modified with amino acids: arginine versus glutamic acid.

PubMed

Tavafoghi, M; Brodusch, N; Gauvin, R; Cerruti, M

2016-01-01

Hydroxyapatite (HA, Ca5(PO4)3OH) is the main inorganic component of hard tissues, such as bone and dentine. HA nucleation involves a set of negatively charged phosphorylated proteins known as non-collagenous proteins (NCPs). These proteins attract Ca(2+) and PO4(3-) ions and increase the local supersaturation to a level required for HA precipitation. Polar and charged amino acids (AAs) are highly expressed in NCPs, and seem to be responsible for the mineralizing effect of NCPs; however, the individual effect of these AAs on HA mineralization is still unclear. In this work, we investigate the effect of a negatively charged (Glu) and positively charged (Arg) AA bound to carboxylated graphene oxide (CGO) on HA mineralization in simulated body fluids (SBF). Our results show that Arg induces HA precipitation faster and in larger amounts than Glu. We attribute this to the higher stability of the complexes formed between Arg and Ca(2+) and PO4(3-) ions, and also to the fact that Arg exposes both carboxyl and amino groups on the surface. These can electrostatically attract both Ca(2+) and PO4(3-) ions, thus increasing local supersaturation more than Glu, which exposes carboxyl groups only. © 2016 The Author(s).

Metal nanoparticles triggered persistent negative photoconductivity in silk protein hydrogels

NASA Astrophysics Data System (ADS)

Gogurla, Narendar; Sinha, Arun K.; Naskar, Deboki; Kundu, Subhas C.; Ray, Samit K.

2016-03-01

Silk protein is a natural biopolymer with intriguing properties, which are attractive for next generation bio-integrated electronic and photonic devices. Here, we demonstrate the negative photoconductive response of Bombyx mori silk protein fibroin hydrogels, triggered by Au nanoparticles. The room temperature electrical conductivity of Au-silk hydrogels is found to be enhanced with the incorporation of Au nanoparticles over the control sample, due to the increased charge transporting networks within the hydrogel. Au-silk lateral photoconductor devices show a unique negative photoconductive response under an illumination of 325 nm, with excitation energy higher than the characteristic metal plasmon resonance band. The enhanced photoconductance yield in the hydrogels over the silk protein is attributed to the photo-oxidation of amino groups in the β-pleated sheets of the silk around the Au nanoparticles followed by the breaking of charge transport networks. The Au-silk nanocomposite does not show any photoresponse under visible illumination because of the localization of excited charges in Au nanoparticles. The negative photoconductive response of hybrid Au-silk under UV illumination may pave the way towards the utilization of silk for future bio-photonic devices using metal nanoparticle platforms.

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.

Observation of Iron Specific Interaction with a Charge Neutral Phospholipid

NASA Astrophysics Data System (ADS)

Wang, Wenjie; Zhang, Honghu; Feng, Shuren; San Emeterio, Josue; Kuzmenko, Ivan; Nilsen-Hamilton, Marit; Mallapragada, Surya; Vaknin, David

2015-03-01

Using surface sensitive X-ray scattering and spectroscopic techniques we show that phosphatidyl choline (PC) head groups attract positively charged iron ions and complexes even at pH values that are lower than 3. DPPC (1,2-dipalmitoyl-sn-glycero-3-phosphocholine) is a zwitterionic lipid typically used as a model system for cell membranes. Within a large pH range (3 -11), it carries a negative charge on the phosphate group and a positive charge on the quaternary ammonium cation, thus appears charge neutral. Further lowering the pH, i.e. adding a proton to the phosphate group, results in a positively charged headgroup. Surprisingly, we detect significant enrichment of iron at the interface of the DPPC monolayer and the aqueous subphase with the pH maintained at 3 or even lower. With a supposedly charge neutral or even positive surface, the observation of surface bound, charge positive iron ions or iron hydroxides is counter-intuitive and suggests iron-specific interaction with the phospholipid headgroup, which is not governed by electrostatic interaction. The effect of the integration of Mms6, a membrane protein that promotes the formation of magnetic nanocrystals, into the DPPC monolayer will also be discussed. Research supported by the U.S. Department of Energy under Contract No. DE-AC02-07CH11358 and DE-AC02-06CH11357.

Interactions of human hemoglobin with charged ligand-functionalized iron oxide nanoparticles and effect of counterions

NASA Astrophysics Data System (ADS)

Ghosh, Goutam; Panicker, Lata

2014-12-01

Human hemoglobin is an important metalloprotein. It has tetrameric structure with each subunit containing a `heme' group which carries oxygen and carbon dioxide in blood. In this work, we have investigated the interactions of human hemoglobin (Hb) with charged ligand-functionalized iron oxide nanoparticles and the effect of counterions, in aqueous medium. Several techniques like DLS and ζ-potential measurements, UV-vis, fluorescence, and CD spectroscopy have been used to characterize the interaction. The nanoparticle size was measured to be in the range of 20-30 nm. Our results indicated the binding of Hb with both positively as well as negatively charged ligand-functionalized iron oxide nanoparticles in neutral aqueous medium which was driven by the electrostatic and the hydrophobic interactions. The electrostatic binding interaction was not seen in phosphate buffer at pH 7.4. We have also observed that the `heme' groups of Hb remained unaffected on binding with charged nanoparticles, suggesting the utility of the charged ligand-functionalized nanoparticles 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.

Modulating protein behaviors on responsive surface by external electric fields: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Xie, Yun; Pan, Yufang; Zhang, Rong; Liang, Ying; Li, Zhanchao

2015-01-01

Molecular dynamics simulations were employed to investigate the modulation of protein behaviors on the electrically responsive zwitterionic phosphorylcholine self-assembled monolayers (PC-SAMs). Results show that PC-SAMs could sensitively respond to the applied electric fields and exhibit three states with different charge distributions, namely both the negatively charged phosphate groups and the positively charged choline groups are exposed to the solution in the absence of electric fields (state 1), phosphate groups exposed in the presence of positive electric fields (state 2), and choline groups exposed in the presence of negative electric fields (state 3). Under state 1, the adsorption of Cyt c on the PC-SAM is reversible and the orientations of Cyt c are randomly distributed. Under state 2, the adsorption of Cyt c is enhanced due to the electrostatic attractions between the exposed phosphate groups and the positively charged protein; when adsorbed on the PC-SAMs, Cyt c tends to adopt the orientation with the heme plane perpendicular to the surface plane, and the percentage of this orientation increases as the field strength rises up. Under state 3, the adsorption of Cyt c is retarded because of the electrostatic repulsions between the exposed choline groups and the protein; however, if the gaps between PC chains are large enough, Cyt c could insert into the PC-SAM and access the phosphate groups after overcoming a slight energy barrier. Under three states, the basic backbone structures of Cyt c are well kept within the simulation time since the conformation of Cyt c is mainly affected by the surface-generated electric fields, whose strengths are modulated by the external electric fields and are not strong enough to deform protein. The results indicate the possibility of regulating protein behaviors, including promoting or retarding protein adsorption and regulating protein orientations, on responsive surfaces by applying electric fields on the surfaces without worrying protein deformation, which may be helpful in the applications of protein separation and controlled drug delivery.

Is the negative glow plasma of a direct current glow discharge negatively charged?

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

Bogdanov, E. A.; Saifutdinov, A. I.; Demidov, V. I., E-mail: Vladimir.Demidov@mail.wvu.edu

A classic problem in gas discharge physics is discussed: what is the sign of charge density in the negative glow region of a glow discharge? It is shown that traditional interpretations in text-books on gas discharge physics that states a negative charge of the negative glow plasma are based on analogies with a simple one-dimensional model of discharge. Because the real glow discharges with a positive column are always two-dimensional, the transversal (radial) term in divergence with the electric field can provide a non-monotonic axial profile of charge density in the plasma, while maintaining a positive sign. The numerical calculationmore » of glow discharge is presented, showing a positive space charge in the negative glow under conditions, where a one-dimensional model of the discharge would predict a negative space charge.« less

Space charge characteristics of fluorinated polyethylene: Different effects of fluorine and oxygen

NASA Astrophysics Data System (ADS)

Zhao, Ni; Nie, Yongjie; Li, Shengtao

2018-04-01

Direct fluorination are proved having obvious effect on space charge characteristics of polyethylene. It is believed that fluorine has a positive effect on suppressing space charge injection while oxygen impurity has a negative effect. However, the mechanism for the opposite effect of fluorine and oxygen is still not clear. In this paper, the different effects of fluorine and oxygen on space charge characteristics of fluorinated low density polyethylene (LDPE) are investigated on the basis of dielectric property, chemical constitutes and trap performance of surface fluorinated layers. The results show that direct fluorination has obvious effect on chemical constitutes and dielectric properties of surface fluorinated layer. Introduced fluorine is the main factor for suppressing charge injection from the electrodes, because it seriously changes the chemical constitutes and further the trap properties of the surface fluorinated layer. While introduction of oxygen results in heterocharges and makes space charge distribution complex, due to the ionization of generated small groups like C=O containing groups. Moreover, direct fluorination will result in cleavage of some LDPE molecules whatever there is oxygen impurity or not.

New Horizons in C-F Activation by Main Group Electrophiles

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

Ozerov, Oleg V.

2016-02-13

This technical report describes progress on the DOE sponsored project "New Horizons in C-F Activation by Main Group Electrophiles" during the period of 09/15/2010 – 08/31/2015. The main goal of this project was to develop improved catalysts for conversion of carbon-fluorine bonds in potentially harmful compounds. The approach involved combining of a highly reactive positively charged main-group compound with a highly unreactive negatively charged species (anions) as a way to access potent catalysts for carbon-fluorine bond activation. This report details progress made in improving synthetic pathways to a variety of new anions with improved properties and analysis of their potentialmore » in catalysis.« less

Negative emotions can attenuate the influence of beliefs on logical reasoning.

PubMed

Goel, Vinod; Vartanian, Oshin

2011-01-01

Although the influence of beliefs on logical reasoning is well documented, how emotions modulate the effect of beliefs during reasoning remains unexamined. We instructed participants to reason about syllogisms involving neutral or emotionally charged content. We also manipulated the consistency of beliefs with logical validity. When content was neutral, participants exhibited the belief-bias effect observed in previous studies of reasoning. In contrast, when confronted with emotionally charged content participants were less likely to be influenced by their beliefs. Our results suggest that under certain conditions negative emotions can attenuate the influence of beliefs during logical reasoning. Drawing on the affect infusion model, we attribute this effect to a more vigilant, systematic scrutiny of beliefs in the presence of negative emotions. © 2010 Psychology Press, an imprint of the Taylor & Francis Group, an Informa business

Thunderstorm Charge Structures Producing Negative Gigantic Jets

NASA Astrophysics Data System (ADS)

Boggs, L.; Liu, N.; Riousset, J. A.; Shi, F.; Rassoul, H.

2016-12-01

Here we present observational and modeling results that provide insight into thunderstorm charge structures that produce gigantic jet discharges. The observational results include data from four different thunderstorms producing 9 negative gigantic jets from 2010 to 2014. We used radar, very high frequency (VHF) and low frequency (LF) lightning data to analyze the storm characteristics, charge structures, and lightning activity when the gigantic jets emerged from the parent thunderstorms. A detailed investigation of the evolution of one of the charge structures by analyzing the VHF data is also presented. The newly found charge structure obtained from the observations was analyzed with fractal modeling and compared with previous fractal modeling studies [Krehbiel et al., Nat. Geosci., 1, 233-237, 2008; Riousset et al., JGR, 115, A00E10, 2010] of gigantic jet discharges. Our work finds that for normal polarity thunderstorms, gigantic jet charge structures feature a narrow upper positive charge region over a wide middle negative charge region. There also likely exists a `ring' of negative screening charge located around the perimeter of the upper positive charge. This is different from previously thought charge structures of the storms producing gigantic jets, which had a very wide upper positive charge region over a wide middle negative charge region, with a very small negative screening layer covering the cloud top. The newly found charge structure results in leader discharge trees in the fractal simulations that closely match the parent flashes of gigantic jets inside and outside the thundercloud. The previously used charge structures, while vital to the understanding of gigantic jet initiation and the role of charge imbalances inside the cloud, do not produce leader discharge trees that agree with observed gigantic jet discharges.Finally, the newly discovered gigantic jet charge structures are formed near the end of a convective pulse [Meyer et al., JGR, 118, 2013; Lazarus et al., JGR, 120, 8469-8490, 2015] that pushes the negative screening charge radially outward and causes mixing around the updraft.

Development and testing of a high cycle life 30 A-h sealed AgO-Zn battery

NASA Technical Reports Server (NTRS)

Bogner, R. S.

1972-01-01

A two-phase program was initiated to investigate design parameters and technology to develop an improved AgO-Zn battery. The basic performance goal was 100 charge/discharge cycles (22 h/2 h) at 50 percent depth of discharge following a six-month period of charged stand at room temperature. Phase 1, cell evaluation, involved testing 70 cells in five-cell groups. The major design variables were active material ratios, electrolyte concentrations, separator systems, and negative plate shape. Phase 1 testing showed that cycle life could be improved 10 percent to 20 percent by using greater ratios of zinc to silver oxide and higher electrolyte concentrations. Wedge-shaped negatives increased cycle life by nearly 100 percent. Phase 2 battery evaluation, which was initiated before the Phase 1 results were known completely, involved evaluation of six designs as 19-cell batteries. Only one battery exceeded 100 cycles following nine months charged stand.

Genetics Home Reference: SLC4A1-associated distal renal tubular acidosis

MedlinePlus

... exchanger 1 (AE1) protein, which transports negatively charged atoms (anions) across cell membranes. Specifically, AE1 exchanges negatively charged atoms of chlorine (chloride ions) for negatively charged bicarbonate ...

Direct analysis of samples under ambient condition by high-voltage-assisted laser desorption ionization mass spectrometry in both positive and negative ion mode.

PubMed

Ren, Xinxin; Liu, Jia; Zhang, Chengsen; Luo, Hai

2013-03-15

With the rapid development of ambient mass spectrometry, the hybrid laser-based ambient ionization methods which can generate multiply charged ions of large biomolecules and also characterize small molecules with good signal-to-noise in both positive and negative ion modes are of particular interest. An ambient ionization method termed high-voltage-assisted laser desorption ionization (HALDI) is developed, in which a 1064 nm laser is used to desorb various liquid samples from the sample target biased at a high potential without the need for an organic matrix. The pre-charged liquid samples are desorbed by the laser to form small charged droplets which may undergo an electrospray-like ionization process to produce multiply charged ions of large biomolecules. Various samples including proteins, oligonucleotides (ODNs), drugs, whole milk and chicken eggs have been analyzed by HALDI-MS in both positive and negative ion mode with little or no sample preparation. In addition, HALDI can generate intense signals with better signal-to-noise in negative ion mode than laser desorption spay post-ionization (LDSPI) from the same samples, such as ODNs and some carboxylic-group-containing small drug molecules. HALDI-MS can directly analyze a variety of liquid samples including proteins, ODNs, pharmaceuticals and biological fluids in both positive and negative ion mode without the use of an organic matrix. This technique may be further developed into a useful tool for rapid analysis in many different fields such as pharmaceutical, food, and biological sciences. Copyright © 2013 John Wiley & Sons, Ltd.

The Synthesis of Beta-Peptides Containing Guanidino Groups

NASA Technical Reports Server (NTRS)

Wen, Ke; Han, Hyunsoo; Hoffman, Timothy Z.; Janda, Kim D.; Orgel, Leslie E.

2003-01-01

The synthesis of the beta-peptide 1 by the postsynthetic modification of the corresponding amino-containing peptide 3 is described. The potential of 1 to act as a template for the ligation of complementary negatively-charged peptides is discussed.

Electron detachment of the hydrogen-bonded amino acid side-chain guanine complexes

NASA Astrophysics Data System (ADS)

Wang, Jing; Gu, Jiande; Leszczynski, Jerzy

2007-07-01

The photoelectron spectra of the hydrogen-bonded amino acid side-chain-guanine complexes has been studied at the partial third order (P3) self-energy approximation of the electron propagator theory. The correlation between the vertical electron detachment energy and the charge distributions on the guanine moiety reveals that the vertical electron detachment energy (VDE) increases as the positive charge distribution on the guanine increases. The low VDE values determined for the negatively charged complexes of the guanine-side-chain-group of Asp/Glu suggest that the influence of the H-bonded anionic groups on the VDE of guanine could be more important than that of the anionic backbone structure. The even lower vertical electron detachment energy for guanine is thus can be expected in the H-bonded protein-DNA systems.

Cassini observations of carbon-based anions in Titan's ionosphere

NASA Astrophysics Data System (ADS)

Desai, Ravindra; Lewis, Gethyn; Waite, J. Hunter; Kataria, Dhiren; Wellbrock, Anne; Jones, Geraint; Coates, Andrew

2016-07-01

Cassini observations of Titan's ionosphere revealed an atmosphere rich in positively and negatively charged ions and organic molecules. The detection of large quantities of negatively charged ions was particularly surprising and adds Titan to the growing list of locations where anion chemistry has been observed to play an important role. In this study we present updated analysis on these negatively charged ions through an enhanced understanding of the Cassini CAPS Electron Spectrometer (CAPS-ELS) instrument response. The ionisation of Titan's dominant atmospheric constituent, N2, by the HeII Solar line, results in an observable photoelectron population at 24.1eV which we use to correct for differential spacecraft charging. Correcting for further energy-angle signatures within this dataset, we use an updated fitting procedure to show how the ELS mass spectrum, previously grouped into broad mass ranges, can be resolved into specific peaks at multiples of carbon-based anion species up to over 100amu/q. These peaks are shown to be ubiquitous within Titan's upper atmosphere and reminiscent of carbon-based anions identified in dense molecular clouds beyond our Solar System. It is thus shown how the moon Titan in the Outer Solar System can be used as an analogue to study these even more remote and exotic astrophysical environments.

A quantitative study of nanoparticle skin penetration with interactive segmentation.

PubMed

Lee, Onseok; Lee, See Hyun; Jeong, Sang Hoon; Kim, Jaeyoung; Ryu, Hwa Jung; Oh, Chilhwan; Son, Sang Wook

2016-10-01

In the last decade, the application of nanotechnology techniques has expanded within diverse areas such as pharmacology, medicine, and optical science. Despite such wide-ranging possibilities for implementation into practice, the mechanisms behind nanoparticle skin absorption remain unknown. Moreover, the main mode of investigation has been qualitative analysis. Using interactive segmentation, this study suggests a method of objectively and quantitatively analyzing the mechanisms underlying the skin absorption of nanoparticles. Silica nanoparticles (SNPs) were assessed using transmission electron microscopy and applied to the human skin equivalent model. Captured fluorescence images of this model were used to evaluate degrees of skin penetration. These images underwent interactive segmentation and image processing in addition to statistical quantitative analyses of calculated image parameters including the mean, integrated density, skewness, kurtosis, and area fraction. In images from both groups, the distribution area and intensity of fluorescent silica gradually increased in proportion to time. Since statistical significance was achieved after 2 days in the negative charge group and after 4 days in the positive charge group, there is a periodic difference. Furthermore, the quantity of silica per unit area showed a dramatic change after 6 days in the negative charge group. Although this quantitative result is identical to results obtained by qualitative assessment, it is meaningful in that it was proven by statistical analysis with quantitation by using image processing. The present study suggests that the surface charge of SNPs could play an important role in the percutaneous absorption of NPs. These findings can help achieve a better understanding of the percutaneous transport of NPs. In addition, these results provide important guidance for the design of NPs for biomedical applications.

Numerical renormalization group method for entanglement negativity at finite temperature

NASA Astrophysics Data System (ADS)

Shim, Jeongmin; Sim, H.-S.; Lee, Seung-Sup B.

2018-04-01

We develop a numerical method to compute the negativity, an entanglement measure for mixed states, between the impurity and the bath in quantum impurity systems at finite temperature. We construct a thermal density matrix by using the numerical renormalization group (NRG), and evaluate the negativity by implementing the NRG approximation that reduces computational cost exponentially. We apply the method to the single-impurity Kondo model and the single-impurity Anderson model. In the Kondo model, the negativity exhibits a power-law scaling at temperature much lower than the Kondo temperature and a sudden death at high temperature. In the Anderson model, the charge fluctuation of the impurity contributes to the negativity even at zero temperature when the on-site Coulomb repulsion of the impurity is finite, while at low temperature the negativity between the impurity spin and the bath exhibits the same power-law scaling behavior as in the Kondo model.

Polarization of gold in nanopores leads to ion current rectification

DOE PAGES

Yang, Crystal; Hinkle, Preston; Menestrina, Justin; ...

2016-10-03

Biomimetic nanopores with rectifying properties are relevant components of ionic switches, ionic circuits, and biological sensors. Rectification indicates that currents for voltages of one polarity are higher than currents for voltages of the opposite polarity. Ion current rectification requires the presence of surface charges on the pore walls, achieved either by the attachment of charged groups or in multielectrode systems by applying voltage to integrated gate electrodes. Here we present a simpler concept for introducing surface charges via polarization of a thin layer of Au present at one entrance of a silicon nitride nanopore. In an electric field applied bymore » two electrodes placed in bulk solution on both sides of the membrane, the Au layer polarizes such that excess positive charge locally concentrates at one end and negative charge concentrates at the other end. Consequently, a junction is formed between zones with enhanced anion and cation concentrations in the solution adjacent to the Au layer. This bipolar double layer together with enhanced cation concentration in a negatively charged silicon nitride nanopore leads to voltage-controlled surface-charge patterns and ion current rectification. The experimental findings are supported by numerical modeling that confirm modulation of ionic concentrations by the Au layer and ion current rectification even in low-aspect ratio nanopores. Lastly, our findings enable a new strategy for creating ionic circuits with diodes and transistors.« less

Non-equilibrium character of resistive switching and negative differential resistance in Ga-doped Cr2O3 system

NASA Astrophysics Data System (ADS)

Bhowmik, R. N.; Siva, K. Venkata

2018-07-01

The samples of Ga-doped Cr2O3 system in rhombohedral crystal structure with space group R 3 bar C were prepared by chemical co-precipitation route and annealing at 800 °C. The current-voltage (I-V) curves exhibited many unique non-linear properties, e.g., hysteresis loop, resistive switching, and negative differential resistance (NDR). In this work, we report non-equilibrium properties of resistive switching and NDR phenomena. The non-equilibrium I-V characteristics were confirmed by repetiting measurement and time relaxation of current. The charge conduction process was understood by analysing the I-V curves using electrode-limited and bulk-limited charge conduction mechanisms, which were proposed for metal electrode/metal oxide/metal electrode structure. The I-V curves in the NDR regime and at higher bias voltage regime in our samples did not obey Fowler-Nordheim equation, which was proposed for charge tunneling mechanism in many thin film junctions. The non-equilibrium I-V phenomena were explained by considering the competitions between the injection of charge carriers from metal electrode to metal oxide, the charge flow through bulk material mediated by trapping/de-trapping and recombination of charge carriers at the defect sites of ions, the space charge effects at the junctions of electrodes and metal oxides, and finally, the out flow of electrons from metal oxide to metal electrode.

Surface Oxide Net Charge of a Titanium Alloy ; Modulation of Fibronectin-Activated Attachment and Spreading of Osteogenic Cells

PubMed Central

Rapuano, Bruce E.; MacDonald, Daniel E.

2010-01-01

In the current study, we have altered the surface oxide properties of a Ti6Al4V alloy using heat treatment or radiofrequency glow discharge (RFGD) in order to evaluate the relationship between the physico-chemical and biological properties of the alloy's surface oxide. The effects of surface pretreatments on the attachment of cells from two osteogenic cell lines (MG63 and MC3T3) and a mesenchymal stem cell line (C3H10T1/2) to fibronectin adsorbed to the alloy were measured. Both heat and RFGD pretreatments produced a several-fold increase in the number of cells that attached to fibronectin adsorbed to the alloy (0.001 and 10 nM FN) for each cell line tested. An antibody (HFN7.1) directed against the central integrin binding domain of fibronectin produced a 65-70% inhibition of cell attachment to fibronectin-coated disks, incdicating that cell attachment to the metal discs was dependent on fibronectin binding to cell integrin receptors. Both treatments also accelerated the cell spreading response manifested by extensive flattening and an increase in mean cellular area. The treatment-induced increases in the cell attachment activity of adsorbed fibronectin were correlated with previously demonstrated increases in Ti6Al4V oxide negative net surface charge at physiological pH produced by both heat and RFGD pretreatments. Since neither treatment increased the adsorption mass of fibronectin, these findings suggest that negatively charged surface oxide functional groups in Ti6Al4V can modulate fibronectin's integrin receptor activity by altering the adsorbed protein's conformation. Our results further suggest that negatively charged functional groups in the surface oxide can play a prominent role in the osseointegration of metallic implant materials. PMID:20884181

Sorption of pharmaceuticals to soil organic matter in a constructed wetland by electrostatic interaction.

PubMed

Park, Jongkwan; Cho, Kyung Hwa; Lee, Eunkyung; Lee, Sungyun; Cho, Jaeweon

2018-09-01

There is a growing interest in the removal of pharmaceuticals from wastewater because pharmaceuticals have potential ecotoxicological effects. Among several removal mechanisms, the sorption of pharmaceuticals to sediment organic matter is an important mechanism related to the mobility of pharmaceuticals. This study investigated the sorption of pharmaceuticals to soil organic matter (SOM) by electrostatic interactions. SOM located on the surface of soil/sediment generally has a negative charge because of the functional groups present (i.e., carboxylic and phenolic groups). Thus, the electrical characteristics of SOM can induce electrical attraction with positively charged chemical compounds. In this study, SOM was extracted from soils under different aquatic plants (Acorus and Typha) in a constructed wetland in Korea. Experiments were carried out with the following three pharmaceuticals with different electrical characteristics at pH 7: atenolol (positive charge; pKa 9.5), carbamazepine (neutral; no pKa), and ibuprofen (negative charge; pKa 4.9). The SOM in the Acorus pond had a higher hydrophobicity and electrical charge density than that in the Typha pond. Regarding the sorption efficiency between SOM and charged pharmaceuticals, atenolol showed highest sorption efficiency (~60%), followed by carbamazepine (~40%) and ibuprofen (<~30%). In addition, the removal efficiency of the targeted pharmaceuticals in the constructed wetland was estimated by comparing the concentrations of the pharmaceuticals at sampling points with flowing water. The results showed that the removal efficiency of atenolol and carbamazepine was almost 50%, whereas that of ibuprofen was only ~10%. A comparison of the results of lab-scale and field experiments showed that electrostatic interaction is one of the major pharmaceutical removal mechanisms in a constructed wetland. Copyright © 2018 Elsevier B.V. All rights reserved.

Theoretical interpretation of Warburg's impedance in unsupported electrolytic cells.

PubMed

Barbero, G

2017-12-13

We discuss the origin of Warburg's impedance in unsupported electrolytic cells containing only one group of positive and one group of negative ions. Our analysis is based on the Poisson-Nernst-Planck model, where the generation-recombination phenomenon is neglected. We show that to observe Warburg-like impedance the diffusion coefficient of the positive ions has to differ from that of the negative ones, and furthermore the electrodes have to be not blocking. We assume that the non-blocking properties of the electrodes can be described by means of an Ohmic model, where the charge exchange between the cell and the external circuit is described by means of an electrode conductivity. For simplicity we consider a symmetric cell. However, our analysis can be easily generalized to more complicated situations, where the cell is not symmetric and the charge exchange is described by the Chang-Jaffe model, or by a linearized version of the Butler-Volmer equation. Our analysis allows justification of the expression for Warburg's impedance proposed previously by several groups, based on wrong assumptions.

Glycobiology of the cell surface: Its debt to cell electrophoresis 1940-65.

PubMed

Cook, Geoffrey M W

2016-06-01

This Review describes how in the period 1940-1959 cell electrophoresis (in the earlier literature often referred to as 'microelectrophoresis') was used to explore the surface chemistry of cells. Using the erythrocyte as a suitable model for the study of biological membranes, the early investigators were agreed on the presence of negatively charged groups at the surface of this cell. The contemporary dogma was that these were phosphate groups associated with phospholipids. Work in the 1960s, particularly on changes in the electrokinetic properties of erythrocytes following treatment with proteolytic enzymes, lead to the realization that the negatively charged groups at the red cell surface are predominantly due to sialic acids carried on glycoproteins. It quickly became apparent from cell electrophoresis that sialic acids have a ubiquitous presence on the surface of animal cells. This finding required that any complete model of the plasma membrane must include glycosylated molecules at the cell periphery, thus laying the foundations for the field termed 'Glycobiology of the Cell Surface'. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Observation and analysis of electrical structure change and diversity in thunderstorms on the Qinghai-Tibet Plateau

NASA Astrophysics Data System (ADS)

Li, Yajun; Zhang, Guangshu; Wang, Yanhui; Wu, Bin; Li, Jing

2017-09-01

A comprehensive observation on thunderstorms was conducted in the Qinghai area by using a very high frequency three-dimensional lightning mapping system and Doppler radar. The spatio-temporal evolution of the charge structure of the isolated thunderstorm was analyzed according to the developing process of thunderstorm, and the reasons for the change in charge structure diversity were studied. During the initial developing and mature stages of the thunderstorm, the charge structure was a steady negative dipole polarity, i.e., the negative charge region was above the positive charge region. Furthermore, the total number of flashes was lower during these two stages. During the thunderstorm's dissipation stage, the charge structure was varied and complicated, with a positive dipole, negative dipole, and a tripole charge structure changing and coexisting during this stage. This charge structure diversity was primarily caused by the collision and merging of two local thunderstorm cells, leading to a charge rearrangement and distribution and the formation of a new charge structure. The frequency of the negative cloud-to-ground and intracloud flashes increased sharply in the dissipation stage, reaching a maximum value. The increase in frequency of negative cloud-to-ground was mainly caused by the lower positive charge weakening during the dissipation stage. In addition, the relationship between charging regions and temperature layers was analyzed by combining sounding temperature data with the theory of a non-inductive charging mechanism.

Electrochemical storage cell containing a substituted anisole or di-anisole redox shuttle additive for overcharge protection and suitable for use in liquid organic and solid polymer electrolytes

DOEpatents

Kerr, John B.; Tian, Minmin

2000-01-01

A electrochemical cell is described comprising an anode, a cathode, a solid polymer electrolyte, and a redox shuttle additive to protect the cell against overcharging and a redox shuttle additive to protect the cell against overcharging selected from the group consisting of: (a) a substituted anisole having the general formula (in an uncharged state): ##STR1## where R.sub.1 is selected from the group consisting of H, OCH.sub.3, OCH.sub.2 CH.sub.3, and OCH.sub.2 phenyl, and R.sub.2 is selected from the group consisting of OCH.sub.3, OCH.sub.2 CH.sub.3, OCH.sub.2 phenyl, and O.sup.- Li.sup.+ ; and (b) a di-anisole compound having the general formula (in an uncharged state): ##STR2## where R is selected from the group consisting of -OCH.sub.3 and -CH.sub.3, m is either 1 or 0, n is either 1 or 0, and X is selected from the group consisting of -OCH.sub.3 (methoxy) or its lithium salt --O.sup.- Li.sup.+. The lithium salt of the di-anisole is the preferred form of the redox shuttle additive because the shuttle anion will then initially have a single negative charge, it loses two electrons when it is oxidized at the cathode, and then moves toward the anode as a single positively charged species where it is then reduced to a single negatively charged species by gaining back two electrons.

The influence of clinician emotion on decisions in child and adolescent eating disorder treatment: a survey of self and others.

PubMed

Lafrance Robinson, Adele; Kosmerly, Stacey

2015-01-01

Eating disorder clinicians from various disciplines participated in one of two surveys: the "self" group (n = 143) completed a survey assessing the negative influence of emotions on their own clinical decisions, while the "other" group (n = 145) completed a parallel version of the survey that assessed their perceptions of the negative influence of emotion in their colleagues. Both groups endorsed this phenomenon to some degree, although differences in reporting were noted between groups. The perceived negative influence of emotion with regards to specific treatment decisions fell within three categories: decisions regarding food and weight, decisions regarding the involvement of the family in treatment, and decisions related to autonomy and control. Decisions regarding the involvement of the family were perceived to be the most emotionally charged, in particular the involvement of a critical or dismissive parent.

Surface-binding through polyfunction groups of Rhodamine B on composite surface and its high performance photodegradation

NASA Astrophysics Data System (ADS)

Wan, Yiqun; Wang, Xiaofen; Gu, Yun; Guo, Lan; Xu, Zhaodi

2016-03-01

A kind of novel composite ZnS/In(OH)3/In2S3 is synthesized using zinc oxide nanoplates as zinc raw material during hydrothermal process. Although the obtained samples are composited of ZnS and In(OH)3 and In2S3 phase, the samples possess different structure, morphology and optical absorption property depending on molar ratio of raw materials. Zeta potential analysis indicates different surface electrical property since various content and particle size of the phases. The equilibrium adsorption study confirms the composite ZnS/In(OH)3/In2S3 with surface negative charge is good adsorbent for Rhodamine B (Rh B) dye. In addition, the degradation of Rh B over the samples with surface negative charge under visible light (λ ≥ 420 nm) is more effective than the samples with surface positive charge. The samples before and after adsorbing Rh B molecule are examined by FTIR spectra and Zetasizer. It is found that the three function groups of Rh B molecule, especially carboxyl group anchors to surface of the sample through electrostatic adsorption, coordination and hydrogen-bond. It contributes to rapid transformation of photogenerated electron to conduction band of In(OH)3 and suppresses the recombination of photogenerated carrier. The possible adsorption modes of Rh B are discussed on the basis of the experiment results.

Intermetallic negative electrodes for non-aqueous lithium cells and batteries

DOEpatents

Thackeray, Michael M.; Vaughey, John T.; Johnson, Christopher S.; Fransson, Linda M.; Edstrom, Ester Kristina; Henriksen, Gary

2004-05-04

A method of operating an electrochemical cell is disclosed. The cell has an intermetallic negative electrode of Cu.sub.6-x M.sub.x Sn.sub.5, wherein x is .ltoreq.3 and M is one or more metals including Si and a positive electrode containing Li in which Li is shuttled between the positive electrode and the negative electrode during charge and discharge to form a lithiated intermetallic negative electrode during charge. The voltage of the electrochemical cell is controlled during the charge portion of the charge-discharge cycles so that the potential of the lithiated intermetallic negative electrode in the fully charged electrochemical cell is less than 0.2 V but greater than 0 V versus metallic lithium.

Substituent effects on photosensitized splitting of thymine cyclobutane dimer by an attached indole.

PubMed

Tang, Wenjian; Zhou, Hongmei; Wang, Jing; Pan, Chunxiao; Shi, Jingbo; Song, Qinhua

2012-12-21

In chromophore-containing cyclobutane pyrimidine dimer (CPD) model systems, solvent effects on the splitting efficiency may depend on the length of the linker, the molecular conformation, and the oxidation potential of the donor. To further explore the relationship between chromophore structure and splitting efficiency, we prepared a series of substituted indole-T< >T model compounds 2 a-2 g and measured their splitting quantum yields in various solvents. Two reverse solvent effects were observed: an increase in splitting efficiency in solvents of lower polarity for models 2 a-2 d with an electron-donating group (EDG), and vice versa for models 2 e-2 g with an electron-withdrawing group (EWG). According to the Hammett equation, the negative value of the slope of the Hammett plot indicates that the indole moiety during the T< >T-splitting reaction loses negative charge, and the larger negative value implies that the repair reaction is more sensitive to substituent effects in low-polarity solvents. The EDGs of the models 2 a-2 d can delocalize the charge-separated state, and low-polarity solvents make it more stable, which leads to higher splitting efficiency in low-polarity solvents. Conversely, the EWGs of models 2 e-2 g favor destabilization of the charge-separated state, and high-polarity solvents decrease the destabilization and hence lead to more efficient splitting in high-polarity solvents. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polarization spectroscopy of positive and negative trions in an InAs quantum dot

NASA Astrophysics Data System (ADS)

Ware, Morgan E.; Bracker, Allan S.; Stinaff, Eric; Gammon, Daniel; Gershoni, David; Korenev, Vladimir L.

2005-02-01

Using polarization-sensitive photoluminescence and photoluminescence excitation spectroscopy, we study single InAs/GaAs self-assembled quantum dots. The dots were embedded in an n-type, Schottky diode structure allowing for control of the charge state. We present here the exciton, singly charged exciton (positive and negative trions), and the twice negatively charged exciton. For non-resonant excitation below the wetting layer, we observed a large degree of polarization memory from the radiative recombination of both the positive and negative trions. In excitation spectra, through the p-shell, we have found several sharp resonances in the emission from the s-shell recombination of the dot in all charged states. Some of these excitation resonances exhibit strong coulomb shifts upon addition of charges into the quantum dot. One particular resonance of the negatively charged trion was found to exhibit a fine structure doublet under circular polarization. This observation is explained in terms of resonant absorption into the triplet states of the negative trion.

The Antimicrobial Mechanism of Action of Epsilon-Poly-l-Lysine

PubMed Central

Hyldgaard, Morten; Mygind, Tina; Vad, Brian S.; Stenvang, Marcel; Otzen, Daniel E.

2014-01-01

Epsilon-poly-l-lysine (ε-PL) is a natural antimicrobial cationic peptide which is generally regarded as safe (GRAS) as a food preservative. Although its antimicrobial activity is well documented, its mechanism of action is only vaguely described. The aim of this study was to clarify ε-PL's mechanism of action using Escherichia coli and Listeria innocua as model organisms. We examined ε-PL's effect on cell morphology and membrane integrity and used an array of E. coli deletion mutants to study how specific outer membrane components affected the action of ε-PL. We furthermore studied its interaction with lipid bilayers using membrane models. In vitro cell studies indicated that divalent cations and the heptose I and II phosphate groups in the lipopolysaccharide layer of E. coli are critical for ε-PL's binding efficiency. ε-PL removed the lipopolysaccharide layer and affected cell morphology of E. coli, while L. innocua underwent minor morphological changes. Propidium iodide staining showed that ε-PL permeabilized the cytoplasmic membrane in both species, indicating the membrane as the site of attack. We compared the interaction with neutral or negatively charged membrane systems and showed that the interaction with ε-PL relied on negative charges on the membrane. Suspended membrane vesicles were disrupted by ε-PL, and a detergent-like disruption of E. coli membrane was confirmed by atomic force microscopy imaging of supported lipid bilayers. We hypothesize that ε-PL destabilizes membranes in a carpet-like mechanism by interacting with negatively charged phospholipid head groups, which displace divalent cations and enforce a negative curvature folding on membranes that leads to formation of vesicles/micelles. PMID:25304506

The antimicrobial mechanism of action of epsilon-poly-l-lysine.

PubMed

Hyldgaard, Morten; Mygind, Tina; Vad, Brian S; Stenvang, Marcel; Otzen, Daniel E; Meyer, Rikke L

2014-12-01

Epsilon-poly-l-lysine (ε-PL) is a natural antimicrobial cationic peptide which is generally regarded as safe (GRAS) as a food preservative. Although its antimicrobial activity is well documented, its mechanism of action is only vaguely described. The aim of this study was to clarify ε-PL's mechanism of action using Escherichia coli and Listeria innocua as model organisms. We examined ε-PL's effect on cell morphology and membrane integrity and used an array of E. coli deletion mutants to study how specific outer membrane components affected the action of ε-PL. We furthermore studied its interaction with lipid bilayers using membrane models. In vitro cell studies indicated that divalent cations and the heptose I and II phosphate groups in the lipopolysaccharide layer of E. coli are critical for ε-PL's binding efficiency. ε-PL removed the lipopolysaccharide layer and affected cell morphology of E. coli, while L. innocua underwent minor morphological changes. Propidium iodide staining showed that ε-PL permeabilized the cytoplasmic membrane in both species, indicating the membrane as the site of attack. We compared the interaction with neutral or negatively charged membrane systems and showed that the interaction with ε-PL relied on negative charges on the membrane. Suspended membrane vesicles were disrupted by ε-PL, and a detergent-like disruption of E. coli membrane was confirmed by atomic force microscopy imaging of supported lipid bilayers. We hypothesize that ε-PL destabilizes membranes in a carpet-like mechanism by interacting with negatively charged phospholipid head groups, which displace divalent cations and enforce a negative curvature folding on membranes that leads to formation of vesicles/micelles. Copyright © 2014, American Society for Microbiology. All Rights Reserved.

Evaluation of newly synthesized and commercially available charged cyclomaltooligosaccharides (cyclodextrins) for capillary electrokinetic chromatography.

PubMed

Culha, Mustafa; Schell, Fred M; Fox, Shannon; Green, Thomas; Betts, Thomas; Sepaniak, Michael J

2004-01-22

A highly new charged cyclodextrin (CD) derivatives, (6-O-carboxymethyl-2,3-di-O-methyl)cyclomaltoheptaoses (CDM-beta-CDs), was synthesized and characterized as anionic reagents for capillary electrophoresis (CE) in an electrokinetic chromatography mode of separation. Substitution with dimethyl groups at the secondary hydroxyl sites of the CD is aimed at influencing the magnitude and selectivity of analyte-CD interactions, while substitution by carboxymethyl groups at the primary hydroxyl sites provides for high charge and electrophoretic mobility. Full regioselective methylation at the secondary hydroxyl sites was achieved in this work, while substitution at the primary hydroxyl sites generated a mixture of multiply charged products. The separation performance of CDM-beta-CD was evaluated using a variety of analyte mixtures. The results obtained from commercially available negatively charged cyclodextrins, heptakis(2,3-di-O-methyl-6-O-sulfo)cyclomaltoheptaose (HDMS-beta-CD) and O-(carboxymethyl)cyclomaltoheptaose (CM-beta-CD) with an average degree of substitution one (DS 1), were compared to CDM-beta-CD using a sample composed of eight positional isomers of dihydroxynaphthalene. Four hydroxylated polychlorobiphenyl derivatives, a group of chiral and isomeric catchecins, and chiral binaphthyl compounds were also separated with CDM-beta-CD. The effect of adding neutral beta-cyclodextrin (beta-CD) into the running buffer containing charged cyclodextrins was investigated and provided evidence of significant inter-CD interactions. Under certain running buffer conditions, the charged cyclodextrins also appear to adsorb to the capillary walls to various degrees.

Negative differential mobility for negative carriers as revealed by space charge measurements on crosslinked polyethylene insulated model cables

NASA Astrophysics Data System (ADS)

Teyssedre, G.; Vu, T. T. N.; Laurent, C.

2015-12-01

Among features observed in polyethylene materials under relatively high field, space charge packets, consisting in a pulse of net charge that remains in the form of a pulse as it crosses the insulation, are repeatedly observed but without complete theory explaining their formation and propagation. Positive charge packets are more often reported, and the models based on negative differential mobility(NDM) for the transport of holes could account for some charge packets phenomenology. Conversely, NDM for electrons transport has never been reported so far. The present contribution reports space charge measurements by pulsed electroacoustic method on miniature cables that are model of HVDC cables. The measurements were realized at room temperature or with a temperature gradient of 10 °C through the insulation under DC fields on the order 30-60 kV/mm. Space charge results reveal systematic occurrence of a negative front of charges generated at the inner electrode that moves toward the outer electrode at the beginning of the polarization step. It is observed that the transit time of the front of negative charge increases, and therefore the mobility decreases, with the applied voltage. Further, the estimated mobility, in the range 10-14-10-13 m2 V-1 s-1 for the present results, increases when the temperature increases for the same condition of applied voltage. The features substantiate the hypothesis of negative differential mobility used for modelling space charge packets.

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.

Retrieval of charge mobility from apparent charge packet movements in LDPE thin films

NASA Astrophysics Data System (ADS)

Meng, Jia; Zhang, Yewen; Holé, Stéphane; Zheng, Feihu; An, Zhenlian

2017-03-01

The charge packet phenomenon observed in polyethylene materials has been reported extensively during the last decades. To explain its movement, Negative Differential Mobility (NDM) theory is a competitive model among several proposed mechanisms. However, as a key concept of this theory, a sufficiently acute relationship between charge mobility and electric field has never been reported until now, which makes it hard to precisely describe the migration of charge packets with this theory. Based on the substantial negative-charge packet observations with a sufficiently by wide electric field range from 15 kV/mm to 50 kV/mm, the present contribution successfully retrieved the negative-charge mobility from the apparent charge packet movements, which reveals a much closer relationship between the NDM theory and charge packet migrations. Back simulations of charge packets with the retrieved charge mobility offer a good agreement with the experimental data.

Interaction Between Cyanine Dye IR-783 and Polystyrene Nanoparticles in Solution.

PubMed

Zhang, Yunzhi; Xu, Hui; Casabianca, Leah B

2018-05-17

The interactions between small molecule drugs or dyes and nanoparticles are important to the use of nanoparticles in medicine. Noncovalent adsorption of dyes on nanoparticle surfaces is also important to the development of nanoparticle dual-use imaging contrast agents. In the present work, solution-state NMR is used to examine the noncovalent interaction between a near-infrared cyanine dye and the surface of polystyrene nanoparticles in solution. Using 1D proton NMR, we can approximate the number of dye molecules that associate with each nanoparticle for different sized nanoparticles. Saturation-Transfer Difference (STD)-NMR was also used to show that protons near the positively-charged nitrogen in the dye are more strongly associated with the negatively-charged nanoparticle surface than protons near the negatively-charged sulfate groups of the dye. The methods described here can be used to study similar drug or dye molecules interacting with the surface of organic nanoparticles. This article is protected by copyright. All rights reserved.

Amine-Rich Organic Thin Films for Cell Culture: Possible Electrostatic Effects in Cell-Surface Interactions

NASA Astrophysics Data System (ADS)

Wertheimer, Michael R.; St-Georges-Robillard, Amélie; Lerouge, Sophie; Mwale, Fackson; Elkin, Bentsian; Oehr, Christian; Wirges, Werner; Gerhard, Reimund

2012-11-01

In recent communications from these laboratories, we observed that amine-rich thin organic layers are very efficient surfaces for the adhesion of mammalian cells. We prepare such deposits by plasma polymerization at low pressure, atmospheric pressure, or by vacuum-ultraviolet photo-polymerization. More recently, we have also investigated a commercially available material, Parylene diX AM. In this article we first briefly introduce literature relating to electrostatic interactions between cells, proteins, and charged surfaces. We then present certain selected cell-response results that pertain to applications in orthopedic and cardiovascular medicine: we discuss the influence of surface properties on the observed behaviors of two particular cell lines, human U937 monocytes, and Chinese hamster ovary cells. Particular emphasis is placed on possible electrostatic attractive forces due to positively charged R-NH3+ groups and negatively charged proteins and cells, respectively. Experiments carried out with electrets, polymers with high positive or negative surface potentials are added for comparison.

Optimization of microelectrophoresis to select highly negatively charged sperm.

PubMed

Simon, Luke; Murphy, Kristin; Aston, Kenneth I; Emery, Benjamin R; Hotaling, James M; Carrell, Douglas T

2016-06-01

The sperm membrane undergoes extensive surface remodeling as it matures in the epididymis. During this process, the sperm is encapsulated in an extensive glycocalyx layer, which provides the membrane with its characteristic negative electrostatic charge. In this study, we develop a method of microelectrophoresis and standardize the protocol to isolate sperm with high negative membrane charge. Under an electric field, the percentage of positively charged sperm (PCS), negatively charged sperm (NCS), and neutrally charged sperm was determined for each ejaculate prior to and following density gradient centrifugation (DGC), and evaluated for sperm DNA damage, and histone retention. Subsequently, PCS, NCS, and neutrally charged sperm were selected using an ICSI needle and directly analyzed for DNA damage. When raw semen was analyzed using microelectrophoresis, 94 % were NCS. In contrast, DGC completely or partially stripped the negative membrane charge from sperm resulting PCS and neutrally charged sperm, while the charged sperm populations are increased with an increase in electrophoretic current. Following DGC, high sperm DNA damage and abnormal histone retention were inversely correlated with percentage NCS and directly correlated with percentage PCS. NCS exhibited significantly lower DNA damage when compared with control (P < 0.05) and PCS (P < 0.05). When the charged sperm population was corrected for neutrally charged sperm, sperm DNA damage was strongly associated with NCS at a lower electrophoretic current. The results suggest that selection of NCS at lower current may be an important biomarker to select healthy sperm for assisted reproductive treatment.

Organic Reaction Mechanisms in the Sixth Form Part 2.

ERIC Educational Resources Information Center

Simpson, Peter

1989-01-01

Presents the mechanistic ideas underlying reactions between nucleophiles and carbonyl compounds as well as some popular misconceptions. Relates reactions of carboxylic acid derivatives to those of aldehydes and ketones. Discusses leaving group ability and the ability of carbonyl oxygen to accept a negative charge. (Author/MVL)

Charging of dust grains in a plasma with negative ions

NASA Astrophysics Data System (ADS)

Kim, Su-Hyun; Merlino, Robert L.

2006-05-01

The effect of negative ions on the charging of dust particles in a plasma is investigated experimentally. A plasma containing a very low percentage of electrons is formed in a single-ended SF6 is admitted into the vacuum system. The relatively cold (Te≈0.2eV ) readily attach to SF6 molecules to form SF6- negative ions. Calculations of the dust charge indicate that for electrons, negative ions, and positive ions of comparable temperatures, the charge (or surface potential) of the dust can be positive if the positive ion mass is smaller than the negative ion mass and if ɛ, the ratio of the electron to positive ion density, is sufficiently small. The K+ positive ions (mass 39amu) and SF6- negative ions (mass 146amu), and also utilizes a rotating cylinder to dispense dust into the plasma column. Analysis of the current-voltage characteristics of a Langmuir probe in the dusty plasma shows evidence for the reduction in the (magnitude) of the negative dust charge and the transition to positively charged dust as the relative concentration of the residual electrons is reduced. Some remarks are offered concerning experiments that could become possible in a dusty plasma with positive grains.

Devices that can identify positive vs. negative charge

NASA Astrophysics Data System (ADS)

Lincoln, James

2017-10-01

When your clothes come out of the dryer, covered with static, do you know whether they are positively or negatively charged? In this article, I discuss a variety of devices that can determine sign of the charge on an insulator or conductor. Purposefully, none of these methods utilize comparison with a known charge. Some of these ideas have been previously published, and I am extending them, but many are original. These demonstrations provide students and teachers with an opportunity to contrast the actual flow of charge with conventional current and to compare the behavior of positive and negative charges with what we expect from protons and electrons.

[Clinical study and pathological examination on the treatment of deep partial thickness burn wound with negative charge aerosol].

PubMed

Li, Tian-zeng; Xu, Ying-bin; Hu, Xiao-gen; Shen, Rui; Peng, Xiao-dong; Wu, Wei-jiang; Luo, Lan; Dai, Xin-ming; Zou, Yong-tong; Qi, Shao-hai; Wu, Li-ping; Xie, Ju-lin; Deng, Xiao-xin; Chen, E; Zhang, Hui-Zhen

2005-08-01

To investigate the effect of negative charge aerosol (NCA) on the treatment of burn wound. Patients with superficial or deep partial thickness burn only were enrolled in the study, and they were randomly divided into trial group (T, including 180 cases of superficial thickness burn and 100 cases of deep partial thickness burn), control group (C, including 30 cases with superficial thickness burn and 30 with deep partial thickness burn), and self control group (SC, including 10 cases with superficial thickness burn and 10 with deep partial thickness burn). The patients in T and SC groups were treated with NCA for 1.5 hours, 1-2 times a day, from 6 postburn hour (PBH) to 2 postburn day (PBD), while those in C group received conventional treatment. For those in SC group, some of the wounds were covered with sterile schissel, while other wounds without schissel covering. The general changes in the wounds during NCA treatment were observed, and bacterial culture before and after NCA treatment was performed. The healing time was recorded and the blood biochemical parameters were determined. Rat model with deep partial thickness scald was established, and the rats were also divided into T and C groups, and received treatment as in human. Tissue samples were harvested from the wounds of rats in the 2 groups before and 1, 2, 3 weeks after treatment for pathological examination. There was no infection and little exudation in the patients in T group. No bacteria were found in the wound before and after NCA treatment. The healing time of the wounds of patients with superficial and deep partial thickness burn in T group was 6.3 +/- 1.6 d and 15.1 +/- 3.1 d, respectively, which was obviously shorter than those in C group (11.3 +/- 1.4 d and 21.2 +/- 1.4 d, P < 0.01). In SC group, the healing time of those with sterile schissel coverage was also significantly shorter than those without covering (P < 0.01). There was no obvious change in the liver and kidney functions and blood biochemical parameters among the patients. Pathological examination showed that the skin structure was almost recovered in the rats in T group 3 weeks after treatment, while those in C group was not. Negative charge aerosol is safe and effective in promoting wound healing of the patients with partial thickness burns.

Negative differential mobility for negative carriers as revealed by space charge measurements on crosslinked polyethylene insulated model cables

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

Teyssedre, G., E-mail: gilbert.teyssedre@laplace.univ-tlse.fr; Laurent, C.; CNRS, LAPLACE, F-31062 Toulouse

Among features observed in polyethylene materials under relatively high field, space charge packets, consisting in a pulse of net charge that remains in the form of a pulse as it crosses the insulation, are repeatedly observed but without complete theory explaining their formation and propagation. Positive charge packets are more often reported, and the models based on negative differential mobility(NDM) for the transport of holes could account for some charge packets phenomenology. Conversely, NDM for electrons transport has never been reported so far. The present contribution reports space charge measurements by pulsed electroacoustic method on miniature cables that are modelmore » of HVDC cables. The measurements were realized at room temperature or with a temperature gradient of 10 °C through the insulation under DC fields on the order 30–60 kV/mm. Space charge results reveal systematic occurrence of a negative front of charges generated at the inner electrode that moves toward the outer electrode at the beginning of the polarization step. It is observed that the transit time of the front of negative charge increases, and therefore the mobility decreases, with the applied voltage. Further, the estimated mobility, in the range 10{sup −14}–10{sup −13} m{sup 2} V{sup −1} s{sup −1} for the present results, increases when the temperature increases for the same condition of applied voltage. The features substantiate the hypothesis of negative differential mobility used for modelling space charge packets.« less

Ion-source modeling and improved performance of the CAMS high-intensity Cs-sputter ion source

NASA Astrophysics Data System (ADS)

Brown, T. A.; Roberts, M. L.; Southon, J. R.

2000-10-01

The interior of the high-intensity Cs-sputter source used in routine operations at the Center for Accelerator Mass Spectrometry (CAMS) has been computer modeled using the program NEDLab, with the aim of improving negative ion output. Space charge effects on ion trajectories within the source were modeled through a successive iteration process involving the calculation of ion trajectories through Poisson-equation-determined electric fields, followed by calculation of modified electric fields incorporating the charge distribution from the previously calculated ion trajectories. The program has several additional features that are useful in ion source modeling: (1) averaging of space charge distributions over successive iterations to suppress instabilities, (2) Child's Law modeling of space charge limited ion emission from surfaces, and (3) emission of particular ion groups with a thermal energy distribution and at randomized angles. The results of the modeling effort indicated that significant modification of the interior geometry of the source would double Cs + ion production from our spherical ionizer and produce a significant increase in negative ion output from the source. The results of the implementation of the new geometry were found to be consistent with the model results.

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).

Bactericidal action mechanism of negatively charged food grade clove oil nanoemulsions.

PubMed

Majeed, Hamid; Liu, Fei; Hategekimana, Joseph; Sharif, Hafiz Rizwan; Qi, Jing; Ali, Barkat; Bian, Yuan-Yuan; Ma, Jianguo; Yokoyama, Wallace; Zhong, Fang

2016-04-15

Clove oil (CO) anionic nanoemulsions were prepared with varying ratios of CO to canola oil (CA), emulsified and stabilized with purity gum ultra (PGU), a newly developed succinylated waxy maize starch. Interfacial tension measurements showed that CO acted as a co-surfactant and there was a gradual decrease in interfacial tension which favored the formation of small droplet sizes on homogenization until a critical limit (5:5% v/v CO:CA) was reached. Antimicrobial activity of the negatively charged CO nanoemulsion was determined against Gram positive GPB (Listeria monocytogenes and Staphylococcus aureus) and Gram negative GNB (Escherichia coli) bacterial strains using minimum inhibitory concentration (MIC) and a time kill dynamic method. Negatively charged PGU emulsified CO nanoemulsion showed prolonged antibacterial activities against Gram positive bacterial strains. We concluded that negatively charged CO nanoemulsion droplets self-assemble with GPB cell membrane, and facilitated interaction with cellular components of bacteria. Moreover, no electrostatic interaction existed between negatively charged droplets and the GPB membrane. Copyright © 2015 Elsevier Ltd. All rights reserved.

Natural dyeing and UV protection of plasma treated cotton

NASA Astrophysics Data System (ADS)

Gorjanc, Marija; Mozetič, Miran; Vesel, Alenka; Zaplotnik, Rok

2018-03-01

Raw cotton fabrics have been exposed to low-pressure non-equilibrium gaseous plasma to improve the adsorption of natural dyes as well as ultraviolet (UV) protection factor. Plasma created in a glass tube by an electrodeless radiofrequency (RF) discharge was created either in oxygen or ammonia at the pressure of 50 Pa to stimulate formation of oxygen and nitrogen groups, respectively. The type and concentration of functional groups was determined by X-ray photoelectron spectroscopy (XPS) and morphological modifications by scanning electron microscopy (SEM). The colour yield for curcumin dye was improved significantly for samples treated with ammonia plasma what was explained by bonding of the dye to surface of amino groups. Contrary, the yield decreased when oxygen plasma treatment was applied due to the negatively charged surface that repels the negatively charged dye molecules. The effect was even more pronounced when using green tea extract as the colouring agent. The colour difference between the untreated and ammonia plasma treated sample increased linearly with plasma treatment time reaching the factor of 3.5 for treatment time of 300 s. The ultraviolet protection factor (UPF) was over 50 indicating excellent protection due to improved adsorption of the dye on the ammonia plasma treated samples.

Physicochemical Properties of Cartilage in the Light of Ion Exchange Theory

PubMed Central

Maroudas, Alice

1968-01-01

Ion exchange theory has been applied to articular cartilage. Relationships were derived between permeability, diffusivity, electrical conductivity, and streaming potential. Systematic measurements were undertaken on these properties. Experimental techniques are described and data tabulated. Theoretical correlations were found to hold within the experimental error. The concentration of fixed negatively-charged groups in cartilage was shown to be the most important parameter. Fixed charge density was found to increase with distance from the articular surface and this variation was reflected in the other properties. PMID:5699797

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

Stereotypes of the elderly in U.S. television commercials from the 1950s to the 1990s.

PubMed

Miller, Darryl W; Leyell, Teresita S; Mazachek, Juliann

2004-01-01

Critics have charged that American advertisers have often portrayed the elderly with negative stereotypes. These negative portrayals, they suggest, not only offend elderly consumers but also contribute to ageism. This study examined whether American advertisers have indeed used a great deal of negative stereotyping of the elderly, as the critics have suggested. Employing a concept of stereotypes found in cognitive psychology, the authors examined trends in the portrayal of the elderly in television commercials produced in the United States from the 1950s through the 1990s. Results of the study do not support the contentions of the critics. Very little negative stereotyping was discovered. Analysis indicated trends in the appearance of several positive stereotypes, and differences in the stereotyping of gender groups and age segments within the elderly group. Results are interpreted from both marketing and social science perspectives.

Inferential false memories of events: negative consequences protect from distortions when the events are free from further elaboration.

PubMed

Mirandola, Chiara; Toffalini, Enrico; Grassano, Massimo; Cornoldi, Cesare; Melinder, Annika

2014-01-01

The present experiment was conducted to investigate whether negative emotionally charged and arousing content of to-be-remembered scripted material would affect propensity towards memory distortions. We further investigated whether elaboration of the studied material through free recall would affect the magnitude of memory errors. In this study participants saw eight scripts. Each of the scripts included an effect of an action, the cause of which was not presented. Effects were either negatively emotional or neutral. Participants were assigned to either a yes/no recognition test group (recognition), or to a recall and yes/no recognition test group (elaboration + recognition). Results showed that participants in the recognition group produced fewer memory errors in the emotional condition. Conversely, elaboration + recognition participants had lower accuracy and produced more emotional memory errors than the other group, suggesting a mediating role of semantic elaboration on the generation of false memories. The role of emotions and semantic elaboration on the generation of false memories is discussed.

Neutrally Charged Gas/Liquid Interface by a Catanionic Langmuir Monolayer

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

Vaknin, David; Bu, Wei

Surface-sensitive synchrotron X-ray scattering and spectroscopic experiments were performed to explore the characteristics of Langmuir monolayers of oppositely charged mixed amphiphiles. A premixed (molar 1:1 stearic acid/stearylamine) solution was spread as a monolayer at the gas/liquid interface on pure water and on mono- and divalent salt solutions, revealing that the negatively charged carboxyl groups and positively charged amine groups are miscible into one another and tend to bond together to form a nearly neutral surface. Similar control experiments on pure stearic acid (SA) and stearylamine (ST) were also conducted for comparison. Due to the strong bonding, hexagonal structures in smallmore » domains with acyl-chains normal to the liquid surface are formed at zero surface pressures, that is, at molecular areas much larger than those of the densely packed acyl chains. In-plane X-ray diffraction indicates that the catanionic surface is highly ordered and modifies the structure of the water surface and thus can serve as a model system for interactions of an amino acid template with solutes.« less

Niosomal carriers enhance oral bioavailability of carvedilol: effects of bile salt-enriched vesicles and carrier surface charge.

PubMed

Arzani, Gelareh; Haeri, Azadeh; Daeihamed, Marjan; Bakhtiari-Kaboutaraki, Hamid; Dadashzadeh, Simin

2015-01-01

Carvedilol (CRV) is an antihypertensive drug with both alpha and beta receptor blocking activity used to preclude angina and cardiac arrhythmias. To overcome the low, variable oral bioavailability of CRV, niosomal formulations were prepared and characterized: plain niosomes (without bile salts), bile salt-enriched niosomes (bilosomes containing various percentages of sodium cholate or sodium taurocholate), and charged niosomes (negative, containing dicetyl phosphate and positive, containing hexadecyl trimethyl ammonium bromide). All formulations were characterized in terms of encapsulation efficiency, size, zeta potential, release profile, stability, and morphology. Various formulations were administered orally to ten groups of Wistar rats (n=6 per group). The plasma levels of CRV were measured by a validated high-performance liquid chromatography (HPLC) method and pharmacokinetic properties of different formulations were characterized. Contribution of lymphatic transport to the oral bioavailability of niosomes was also investigated using a chylomicron flow-blocking approach. Of the bile salt-enriched vesicles examined, bilosomes containing 20% sodium cholate (F2) and 30% sodium taurocholate (F5) appeared to give the greatest enhancement of intestinal absorption. The relative bioavailability of F2 and F5 formulations to the suspension was estimated to be 1.84 and 1.64, respectively. With regard to charged niosomes, the peak plasma concentrations (Cmax) of CRV for positively (F7) and negatively charged formulations (F10) were approximately 2.3- and 1.7-fold higher than after a suspension. Bioavailability studies also revealed a significant increase in extent of drug absorption from charged vesicles. Tissue histology revealed no signs of inflammation or damage. The study proved that the type and concentration of bile salts as well as carrier surface charge had great influences on oral bioavailability of niosomes. Blocking the lymphatic absorption pathway significantly reduced oral bioavailability of CRV niosomes. Overall twofold enhancement in bioavailability in comparison with drug suspension confers the potential of niosomes as suitable carriers for improved oral delivery of CRV.

Aberration of a negative ion beam caused by space charge effect.

PubMed

Miyamoto, K; Wada, S; Hatayama, A

2010-02-01

Aberrations are inevitable when the charged particle beams are extracted, accelerated, transmitted, and focused with electrostatic and magnetic fields. In this study, we investigate the aberration of a negative ion accelerator for a neutral beam injector theoretically, especially the spherical aberration caused by the negative ion beam expansion due to the space charge effect. The negative ion current density profiles with the spherical aberration are compared with those without the spherical aberration. It is found that the negative ion current density profiles in a log scale are tailed due to the spherical aberration.

Solvent dielectric effect and side chain mutation on the structural stability of Burkholderia cepacia lipase active site: a quantum mechanical/molecular mechanics study.

PubMed

Tahan, A; Monajjemi, M

2011-12-01

Quantum mechanical and molecular dynamics methods were used to analyze the structure and stability of neutral and zwitterionic configurations of the extracted active site sequence from a Burkholderia cepacia lipase, histidyl-seryl-glutamin (His86-Ser87-Gln88) and its mutated form, histidyl-cysteyl-glutamin (His86-Cys87-Gln88) in vacuum and different solvents. The effects of solvent dielectric constant, explicit and implicit water molecules and side chain mutation on the structure and stability of this sequence in both neutral and zwitterionic forms are represented. The quantum mechanics computations represent that the relative stability of zwitterionic and neutral configurations depends on the solvent structure and its dielectric constant. Therefore, in vacuum and the considered non-polar solvents, the neutral form of the interested sequences is more stable than the zwitterionic form, while their zwitterionic form is more stable than the neutral form in the aqueous solution and the investigated polar solvents in most cases. However, on the potential energy surfaces calculated, there is a barrier to proton transfer from the positively charged ammonium group to the negatively charged carboxylat group or from the ammonium group to the adjacent carbonyl oxygen and or from side chain oxygen and sulfur to negatively charged carboxylat group. Molecular dynamics simulations (MD) were also performed by using periodic boundary conditions for the zwitterionic configuration of the hydrated molecules in a box of water molecules. The obtained results demonstrated that the presence of explicit water molecules provides the more compact structures of the studied molecules. These simulations also indicated that side chain mutation and replacement of sulfur with oxygen leads to reduction of molecular flexibility and packing.

Recombination energy for negatively charged excitons inside type-II core/shell spherical quantum dots

NASA Astrophysics Data System (ADS)

Chafai, A.; Essaoudi, I.; Ainane, A.; Dujardin, F.; Ahuja, R.

2018-07-01

The recombination energy of isolated neutral exciton and that of isolated negatively charged exciton inside a type-II core/shell spherical quantum dot are studied. Our investigation considers the charge-carriers effective mass discontinuity at the surface contact between the core and shell materials. Although our model omits the effect of the surface polarization, the dielectric-constant mismatch at the nanodot boundaries was taken into account. In order to achieve the exciton and negative trion energies, we proceed by a variational calculation in the framework of the envelope approximation. Our results reveal a strong correlation between the nanodot morphology and the energy spectrum of the neutral and negatively charged exciton.

Charge mobility retrieval approach from apparent charge packet movements based on the negative differential resistance theory.

PubMed

Meng, Jia; Zhang, Yewen; Holé, Stéphane; Zheng, Feihu; An, Zhenlian

2018-04-12

Space charge migration characteristics play an important role in the evaluation of polymer insulation performance. However, an accurate description of charge carrier mobility in several typical insulating polymers such as polyethylene, polypropylene is currently not available. Recently, with the observation of a series of negative charge packet movements associated with the negative differential resistance characteristic of charge mobility in LDPE films, the extraction of charge mobility from the apparent charge packet movement has been attempted using appropriate methods. Based on the previous report of the successful derivation of charge mobility from experimental results using numerical methods, the present research improves the derivation accuracy and describes the details of the charge mobility derivation procedure. Back simulation results under several typical polarizing fields using the derived charge mobility are exhibited. The results indicate that both the NDR theory and the simulation models for the polyethylene materials are reasonable. A significant migration velocity difference between the charge carrier and the charge packet is observed. Back simulations of the charge packet under several typical polarizing fields using the obtained E-v curve show good agreement with the experimental results. The charge packet shapes during the migrations were also found to vary with the polarizing field.

ESI-MS of Cucurbituril Complexes Under Negative Polarity.

PubMed

Rodrigues, Maria A A; Mendes, Débora C; Ramamurthy, Vaidhyanathan; Da Silva, José P

2017-11-01

Electrospray ionization mass spectrometry (ESI-MS) is a powerful tool to study host-guest supramolecular interactions. ESI-MS can be used for detailed gas-phase reactivity studies, to clarify the structure, or simply to verify the formation of complexes. Depending on the structure of the host and of the guest, negative and/or positive ESI are used. Here we report the unexpected formation of host-guest complexes between cucurbit[n]urils (n = 7, 8, CB[n]) and amine, styryl pyridine, and styryl pyridine dimer cations, under negative ESI. Non-complexed CB[n] form double charged halide (Br - , Cl - , F - ) adducts. Under negative ESI, halide ions interact with CB[n] outer surface hydrogen atoms. One to one host-guest complexes (1:1) of CB[n] with positive charged guests were also observed as single and double charged ions under negative ESI. The positive charge of guests is neutralized by ion-pairing with halide anions. Depending on the number of positive charges guests retain in the gas phase, one or two additional halide ions are required for neutralization. Complexes 1:2 of CB[8] with styryl pyridines retain two halide ions in the gas phase, one per guest. Styryl pyridine dimers form 1:1 complexes possessing a single extra halide ion and therefore a single positive charge. Negative ESI is sensitive to small structural differences between complexes, distinguishing between 1:2 complexes of styryl pyridine-CB[8] and corresponding 1:1 complexes with the dimer. Negative ESI gives simpler spectra than positive ESI and allows the determination of guest charge state of CB[n] complexes in the gas phase. Graphical Abstract ᅟ.

Oblique Interaction of Dust-ion Acoustic Solitons with Superthermal Electrons in a Magnetized Plasma

NASA Astrophysics Data System (ADS)

Parveen, Shahida; Mahmood, Shahzad; Adnan, Muhammad; Qamar, Anisa

2018-01-01

The oblique interaction between two dust-ion acoustic (DIA) solitons travelling in the opposite direction, in a collisionless magnetized plasma composed of dynamic ions, static dust (positive/negative) charged particles and interialess kappa distributed electrons is investigated. By employing extended Poincaré-Lighthill-Kuo (PLK) method, Korteweg-de Vries (KdV) equations are derived for the right and left moving low amplitude DIA solitons. Their trajectories and corresponding phase shifts before and after their interaction are also obtained. It is found that in negatively charged dusty plasma above the critical dust charged to ion density ratio the positive polarity pulse is formed, while below the critical dust charged density ratio the negative polarity pulse of DIA soliton exist. However it is found that only positive polarity pulse of DIA solitons exist for the positively charged dust particles case in a magnetized nonthermal plasma. The nonlinearity coefficient in the KdV equation vanishes for the negatively charged dusty plasma case for a particular set of parameters. Therefore, at critical plasma density composition for negatively charged dust particles case, the modified Korteweg-de Vries (mKdV) equations having cubic nonlinearity coefficient of the DIA solitons, and their corresponding phase shifts are derived for the left and right moving solitons. The effects of the system parameters including the obliqueness of solitons propagation with respect to magnetic field direction, superthermality of electrons and concentration of positively/negatively static dust charged particles on the phase shifts of the colliding solitons are also discussed and presented numerically. The results are applicable to space magnetized dusty plasma regimes.

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

Towards chiral distributions of dopants in microporous frameworks: helicoidal supramolecular arrangement of (1R,2S)-ephedrine and transfer of chirality.

PubMed

Gómez-Hortigüela, Luis; Álvaro-Muñoz, Teresa; Bernardo-Maestro, Beatriz; Pérez-Pariente, Joaquín

2015-01-07

A molecular-mechanics computational study is performed in order to analyze the arrangement of (1R,2S)-(-)-ephedrine molecules within the 12-MR channels of the AFI aluminophosphate microporous framework and the influence on the spatial distribution of dopants embedded in the tetrahedral network. Results showed that ephedrine molecules arrange exclusively as dimers by π-π stacking of the aromatic rings within the AFI channels. Interestingly, the asymmetric nature of ephedrine and the presence of H-bond-forming groups (NH2 and OH) involve a preferential orientation where consecutive dimers within the channels are rotated by an angle of +30°; this is driven by the establishment of inter-dimer H-bonds. This preferential orientation leads to the development of a supramolecular enantiomerically-pure helicoidal (chiral) arrangement of ephedrine dimers. In addition, the computational results demonstrate that the particular molecular structure of ephedrine imparts a strong trend to attract negative charges to the vicinity of the NH2(+) positively-charged groups. Hence divalent dopants such as Mg, whose replacement by trivalent Al in the aluminophosphate network involves the generation of a negative charge, will tend to locate close to the NH2(+) molecular groups, suggesting that an imprinting of the organic arrangement to the spatial distribution of dopants would be feasible. Combined with the trend of ephedrine to arrange in a helicoidal fashion, an enantiomerically-pure helicoidal distribution of dopants would be expected, thus inducing a new type of chirality in microporous materials.

A novel blood-pooling MR contrast agent: Carboxymethyl-diethylaminoethyl dextran magnetite.

PubMed

Sonoda, Akinaga; Nitta, Norihisa; Tsuchiya, Keiko; Nitta-Seko, Ayumi; Ohta, Shinichi; Otani, Hideji; Murata, Kiyoshi

2016-12-01

Gadofosveset trisodium is available as a prolonged pooling vascular contrast agent for magnetic resonance imaging. As gadolinium (Gd)-based agents may increase the risk for nephrogenic systemic fibrosis in patients with severe renal insufficiency, the present study synthesized carboxymethyl-diethylaminoethyl dextran magnetite (CMEADM) particles as a blood-pooling, non-Gd‑based contrast agent. CMEADM particles carry a negative or positive charge due to the binding of amino and carboxyl groups to the hydroxyl group of dextran. The present study evaluated whether the degree of charge alters the blood‑pooling time. The evaluation was performed by injecting four groups of three Japanese white rabbits each with CMEADM‑, CMEADM2‑, CMEADM+ (surface charges: ‑10.4, ‑41.0 and +9.6 mV, respectively) or with ultrasmall superparamagnetic iron oxide (USPIO; ‑11.5 mV). The relative signal intensity (SIrel) of each was calculated using the following formula: SIrel = (SI post‑contrast ‑ SI pre‑contrast / SI pre‑contrast) x 100. Following injection with the CMEADMs, but not with USPIO, the in vivo pooling time was prolonged to >300 min. No significant differences were attributable to the electric charge among the CMEADM‑, CMEADM2‑ or and CMEADM+ particles when analyzed with analysis of variance and Tukey's HSD test. Taken together, all three differently‑charged CMEADM2 particles exhibited prolonged vascular enhancing effects, compared with the USPIO. The degree of charge of the contrast agents used in the present study did not result in alteration of the prolonged blood pooling time.

Molecular dynamics simulations of pyrrolidinium and imidazolium ionic liquids at graphene interfaces.

PubMed

Begić, Srđan; Jónsson, Erlendur; Chen, Fangfang; Forsyth, Maria

2017-11-15

Understanding the electrode-electrolyte interface is essential in the battery research as the ion transport and ion structures at the interface most likely affect the performance of a battery. Here we investigate interfacial structures of three ionic liquids: 1-ethyl-3-methylimidazolium dicyanamide ([C 2 mim][dca]), 1-butyl-3-methylimidazolium dicyanamide ([C 4 mim][dca]) and N-butyl-N-methylpyrrolidinium dicyanamide ([C 4 myr][dca]) at a charged and uncharged graphene interface using molecular dynamics simulations. We find that these ionic liquids (ILs) behave differently both in the bulk phase and near a graphene interface and we find that this difference is apparent in all types of analyses performed here. First, a partial density analysis in the direction perpendicular to the surface of the electrodes, which, in the cases near a negatively charged graphene, reveals that the pyrrolidinium system is generally more layered than the imidazolium systems. Second, a 2D topographic structure analysis of the IL species in the inner layer near a negatively charged graphene surface, which reveals that the pyrrolidinium system exhibits a quasi-hexagonal surface configuration of the cations, while the imidazolium systems show linearly arranged groups of cations. Third, a 3D orientation-preference analysis of cation rings near the negative graphene electrode, which shows that the pyrrolidinium rings prefer to lie parallel to the electrode surface while the imidazolium rings prefer to stand on the electrode surface at high tilt angles. Extending the imidazolium alkyl chain was found to reduce the number of imidazoliums that can link up into linearly arranged groups in the inner layer 2D structures. Our results support earlier experimental findings and indicate that the interfacial nanostructures may have a significant influence on the electrochemical performance of IL-based batteries.

Positively-charged reduced graphene oxide as an adhesion promoter for preparing a highly-stable silver nanowire film

NASA Astrophysics Data System (ADS)

Sun, Qijun; Lee, Seong Jun; Kang, Hyungseok; Gim, Yuseong; Park, Ho Seok; Cho, Jeong Ho

2015-04-01

An ultrathin conductive adhesion promoter using positively charged reduced graphene oxide (rGO-NH3+) has been demonstrated for preparing highly stable silver nanowire transparent conductive electrodes (AgNW TCEs). The adhesion promoter rGO-NH3+, spray coated between the substrate and AgNWs, significantly enhances the chemical and mechanical stabilities of the AgNW TCEs. Besides, the ultrathin thickness of the rGO-NH3+ ensures excellent optical transparency and mechanical flexibility for TCEs. The AgNW films prepared using the adhesion promoter are extremely stable under harsh conditions, including ultrasonication in a variety of solvents, 3M Scotch tape detachment test, mechanical bending up to 0.3% strain, or fatigue over 1000 cycles. The greatly enhanced adhesion force is attributed to the ionic interactions between the positively charged protonated amine groups in rGO-NH3+ and the negatively charged hydroxo- and oxo-groups on the AgNWs. The positively charged GO-NH3+ and commercial polycationic polymer (poly allylamine hydrochloride) are also prepared as adhesion promoters for comparison with rGO-NH3+. Notably, the closely packed hexagonal atomic structure of rGO offers better barrier properties to water permeation and demonstrates promising utility in durable waterproof electronics. This work offers a simple method to prepare high-quality TCEs and is believed to have great potential application in flexible waterproof electronics.An ultrathin conductive adhesion promoter using positively charged reduced graphene oxide (rGO-NH3+) has been demonstrated for preparing highly stable silver nanowire transparent conductive electrodes (AgNW TCEs). The adhesion promoter rGO-NH3+, spray coated between the substrate and AgNWs, significantly enhances the chemical and mechanical stabilities of the AgNW TCEs. Besides, the ultrathin thickness of the rGO-NH3+ ensures excellent optical transparency and mechanical flexibility for TCEs. The AgNW films prepared using the adhesion promoter are extremely stable under harsh conditions, including ultrasonication in a variety of solvents, 3M Scotch tape detachment test, mechanical bending up to 0.3% strain, or fatigue over 1000 cycles. The greatly enhanced adhesion force is attributed to the ionic interactions between the positively charged protonated amine groups in rGO-NH3+ and the negatively charged hydroxo- and oxo-groups on the AgNWs. The positively charged GO-NH3+ and commercial polycationic polymer (poly allylamine hydrochloride) are also prepared as adhesion promoters for comparison with rGO-NH3+. Notably, the closely packed hexagonal atomic structure of rGO offers better barrier properties to water permeation and demonstrates promising utility in durable waterproof electronics. This work offers a simple method to prepare high-quality TCEs and is believed to have great potential application in flexible waterproof electronics. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr00777a

Pulsed field sample neutralization

DOEpatents

Appelhans, Anthony D.; Dahl, David A.; Delmore, James E.

1990-01-01

An apparatus and method for alternating voltage and for varying the rate of extraction during the extraction of secondary particles, resulting in periods when either positive ions, or negative ions and electrons are extracted at varying rates. Using voltage with alternating charge during successive periods to extract particles from materials which accumulate charge opposite that being extracted causes accumulation of surface charge of opposite sign. Charge accumulation can then be adjusted to a ratio which maintains a balance of positive and negative charge emission, thus maintaining the charge neutrality of the sample.

A pH-tunable nanofluidic diode with a broad range of rectifying properties.

PubMed

Ali, Mubarak; Ramirez, Patricio; Mafé, Salvador; Neumann, Reinhard; Ensinger, Wolfgang

2009-03-24

The use of fixed charge nanopores in practical applications requires tuning externally the electrostatic interaction between the charged groups and the ionic permeants in order to allow integrating a variety of functions on the same nanostructure. We design, produce, and characterize, theoretically and experimentally, a single-track amphoteric nanopore functionalized with lysine and histidine chains whose positive and negative charges are very sensitive to the external pH. This nanofluidic diode with amphoteric chains attached to the pore surface allows for a broad set of rectification properties supported by a single nanodevice. A definite plus is to functionalize these groups on a conical nanopore with well-defined, controlled structural asymmetry which gives virtually every rectification characteristic that may be required in practical applications. Nanometerscaled amphoteric pores are of general interest because of the potential applications in drug delivery systems, ion-exchange membranes for separation of biomacromolecules, antifouling materials with reduced molecular adsorption, and biochemical sensors.

Mobile charge, soft breakdown, and self-healing in hydrogen silsesquioxane based intermetal dielectric

NASA Astrophysics Data System (ADS)

Devine, R. A. B.

2002-09-01

The electrical characteristics of hydrogen silsesquioxane based flowable oxide (FOxregistered) films proposed for interconnect isolation applications have been studied. It is demonstrated that negative and positive charges exist in the as-made, cured films with densities of 0.95 x1012 and 1.5 x1012 cm-2, respectively for thicknesses of 114 nm. The negative charges can be removed from the films by application of modest electric fields (positive or negative, approx1.75 MV cm-1). The positive charge can be similarly displaced but not removed from the film; this results in time dependent relaxation and redistribution of the positive charge if the films are left unbiased. Time dependent irreversible evolution of the leakage current under positive and negative bias (approx3 MV cm-1) shows a slow breakdown phenomena. An unusual self-healing effect is evidenced in these films.

Electronically conductive polymer binder for lithium-ion battery electrode

DOEpatents

Liu, Gao; Xun, Shidi; Battaglia, Vincent S.; Zheng, Honghe

2017-05-16

A family of carboxylic acid group containing fluorene/fluorenon copolymers is disclosed as binders of silicon particles in the fabrication of negative electrodes for use with lithium ion batteries. These binders enable the use of silicon as an electrode material as they significantly improve the cycle-ability of silicon by preventing electrode degradation over time. In particular, these polymers, which become conductive on first charge, bind to the silicon particles of the electrode, are flexible so as to better accommodate the expansion and contraction of the electrode during charge/discharge, and being conductive promote the flow battery current.

Electronically conductive polymer binder for lithium-ion battery electrode

DOEpatents

Liu, Gao; Xun, Shidi; Battaglia, Vincent S; Zheng, Honghe

2014-10-07

A family of carboxylic acid group containing fluorene/fluorenon copolymers is disclosed as binders of silicon particles in the fabrication of negative electrodes for use with lithium ion batteries. These binders enable the use of silicon as an electrode material as they significantly improve the cycle-ability of silicon by preventing electrode degradation over time. In particular, these polymers, which become conductive on first charge, bind to the silicon particles of the electrode, are flexible so as to better accommodate the expansion and contraction of the electrode during charge/discharge, and being conductive promote the flow battery current.

Stabilized thallium bromide radiation detectors and methods of making the same

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

Leao, Cedric Rocha; Lordi, Vincenzo

According to one embodiment, a crystal includes thallium bromide (TlBr), one or more positively charged dopants, and one or more negatively charged dopants. According to another embodiment, a system includes a monolithic crystal including thallium bromide (TlBr), one or more positively charged dopants, and one or more negatively charged dopants; and a detector configured to detect a signal response of the crystal.

Influence of liposome charge on the association of liposomes with Kupffer cells in vitro. Effects of divalent cations and competition with latex particles.

PubMed

Dijkstra, J; van Galen, M; Scherphof, G

1985-03-14

We studied the interaction of large unilamellar liposomes carrying different surface charges with rat Kupffer cells in maintenance culture. In addition to 14C-labeled phosphatidylcholine, all liposome preparations contained either 3H-labeled inulin or 125I-labeled bovine serum albumin as a non-degradable or a degradable aqueous space marker, respectively. With vesicles carrying no net charge, intracellular processing of internalized liposomes caused nearly complete release of protein label into the medium in acid-soluble form, while phospholipid label was predominantly retained by the cells, only about one third being released. The presence of the lysosomotropic agent, ammonia, inhibited the release of both labels from the cells. At 4 degrees C, the association and degradation of the vesicles were strongly reduced. These results are very similar to what we reported on negatively charged liposomes (Dijkstra, J., Van Galen, W.J.M., Hulstaert, C.E., Kalicharan, D., Roerdink, F.H. and Scherphof, G.L. (1984) Exp. Cell Res. 150, 161-176). The interaction of both types of vesicles apparently proceeds by adsorption to the cell surface followed by virtually complete internalization by endocytosis. Similar experiments with positively charged vesicles indicated that only about half of the liposomes were taken up by the endocytic route, the other half remaining adsorbed to the cell-surface. Attachment of all types of liposomes to the cells was strongly dependent on the presence of divalent cations; Ca2+ appeared to be required for optimal binding. Neutral liposomes only slightly competed with the uptake of negatively charged vesicles, both at 4 degrees and 37 degrees C, whereas negatively charged small unilamellar vesicles and negatively charged latex beads were found to compete very effectively with the large negatively charged liposomes. Neutral vesicles competed effectively for uptake with positively charged ones. These results suggest that neutral and positively charged liposomes are largely bound by the same cell-surface binding sites, while negatively charged vesicles attach mainly to other binding sites.

Formation of stable inverse sheath in ion–ion plasma by strong negative ion emission

NASA Astrophysics Data System (ADS)

Zhang, Zhe; Wu, Bang; Yang, Shali; Zhang, Ya; Chen, Dezhi; Fan, Mingwu; Jiang, Wei

2018-06-01

The effect of strong charged particle emission on plasma–wall interactions is a classical, yet unresolved question in plasma physics. Previous studies on secondary electron emission have shown that with different emission coefficients, there are classical, space-charge-limited, and inverse sheaths. In this letter, we demonstrate that a stable ion–ion inverse sheath and ion–ion plasma are formed with strong surface emission of negative ions. The continuous space-charge-limited to inverse ion–ion sheath transition is observed, and the plasma near the surface consequently transforms into pure ion–ion plasma. The results may explain the long-puzzled experimental observation that the density of negative ions depends on only charge not mass in negative ion sources.

Electrostatic plasma lens for focusing negatively charged particle beams.

PubMed

Goncharov, A A; Dobrovolskiy, A M; Dunets, S M; Litovko, I V; Gushenets, V I; Oks, E M

2012-02-01

We describe the current status of ongoing research and development of the electrostatic plasma lens for focusing and manipulating intense negatively charged particle beams, electrons, and negative ions. The physical principle of this kind of plasma lens is based on magnetic isolation electrons providing creation of a dynamical positive space charge cloud in shortly restricted volume propagating beam. Here, the new results of experimental investigations and computer simulations of wide-aperture, intense electron beam focusing by plasma lens with positive space charge cloud produced due to the cylindrical anode layer accelerator creating a positive ion stream towards an axis system is presented.

Meaning and consequence of the coexistence of competitive hydrogen bond/salt forms on the dissociation orientation of non-covalent complexes.

PubMed

Darii, Ekaterina; Alves, Sandra; Gimbert, Yves; Perret, Alain; Tabet, Jean-Claude

2017-03-15

Non-covalent complexes (NCC) between hexose monophosphates (HexP) and arginine (R) were analyzed using ESI MS and MS/MS in negative mode under different (hard, HC and soft, SC) desolvation conditions. High resolution mass spectrometry (HRMS) revealed the presence of different ionic species, namely, homo- and heteromultimers of R and HexP. Deprotonated heterodimers and corresponding sodiated species were enhanced under HC likely due to a decrease in available charge number associated with the reduction of H + /Na + exchange. The quantum calculations showed that the formation of covalent systems is very little exothermic, therefore, such systems are disfavored. Desolvation dependent CID spectra of deprotonated [(HexP+R)‒H] - complexes demonstrated that they can exist within the hydrogen bond (HB) and salt bridge (SB) forms, yielding either NCC separation or covalent bond cleavages, respectively. Although HB forms are the main species, they cannot survive under HC; therefore, the minor SB forms became detectable. Energy-resolved mass spectrometry (ERMS) experiments revealed diagnostic fragment ions from both SB and HB forms, providing evidence that these isomeric forms are inconvertible. SB formation should result from the ionic interactions of highly acidic group of HexP with strongly basic guanidine group of arginine and thus requires an arginine zwitterion (ZW) form. This was confirmed by quantum calculations. Ion-ion interactions are significantly affected by the presence of sodium cation as demonstrated by the fragmentation patterns of sodiated complex species. Regarding CID data, only SB between protonated amino group of R and deprotonated phosphate group of HexP could be suggested, but the primary amine is not enough basic then, the SB must be fleeting. Nevertheless, the observation of the covalent bond cleavages suggests the presence of structures with a free negative charge able to induce fragmentations. Indeed, according to quantum calculations, solvated salt (SS) systems involving Na + /COO - salt solvated by neutral phosphate and negative charge on sugar ring are preferentially formed. Copyright © 2016 Elsevier B.V. All rights reserved.

The influence of space charge shielding on dielectric multipactor

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

Chang, C.; Liu, G. Z.; Tang, C. X.

2009-05-15

A model of space charge influenced by multipactor electrons and plasma has been established. The positive space charge potential/field for vacuum dielectric multipactor is analytically studied. After considering the plasma, the positive space charge field is further shielded, and multipactor saturates at higher surface accumulated field, compared with that for only considering multipactor electrons. The negative space charge potential/field for dielectric breakdown at high pressure is analyzed. It is found that the negative potential can be nonmonotonously varied, forming a minimum potential well.

Effect of silica nanoparticles with variable size and surface functionalization on human endothelial cell viability and angiogenic activity

NASA Astrophysics Data System (ADS)

Guarnieri, Daniela; Malvindi, Maria Ada; Belli, Valentina; Pompa, Pier Paolo; Netti, Paolo

2014-02-01

Silica nanoparticles could be promising delivery vehicles for drug targeting or gene therapy. However, few studies have been undertaken to determine the biological behavior effects of silica nanoparticles on primary endothelial cells. Here we investigated uptake, cytotoxicity and angiogenic properties of silica nanoparticle with positive and negative surface charge and sizes ranging from 25 to 115 nm in primary human umbilical vein endothelial cells. Dynamic light scattering measurements and nanoparticle tracking analysis were used to estimate the dispersion status of nanoparticles in cell culture media, which was a key aspect to understand the results of the in vitro cellular uptake experiments. Nanoparticles were taken up by primary endothelial cells in a size-dependent manner according to their degree of agglomeration occurring after transfer in cell culture media. Functionalization of the particle surface with positively charged groups enhanced the in vitro cellular uptake, compared to negatively charged nanoparticles. However, this effect was contrasted by the tendency of particles to form agglomerates, leading to lower internalization efficiency. Silica nanoparticle uptake did not affect cell viability and cell membrane integrity. More interestingly, positively and negatively charged 25 nm nanoparticles did not influence capillary-like tube formation and angiogenic sprouting, compared to controls. Considering the increasing interest in nanomaterials for several biomedical applications, a careful study of nanoparticle-endothelial cells interactions is of high relevance to assess possible risks associated to silica nanoparticle exposure and their possible applications in nanomedicine as safe and effective nanocarriers for vascular transport of therapeutic agents.

Binding of cationic pentapeptides with modified side chain lengths to negatively charged lipid membranes: Complex interplay of electrostatic and hydrophobic interactions.

PubMed

Hoernke, Maria; Schwieger, Christian; Kerth, Andreas; Blume, Alfred

2012-07-01

Basic amino acids play a key role in the binding of membrane associated proteins to negatively charged membranes. However, side chains of basic amino acids like lysine do not only provide a positive charge, but also a flexible hydrocarbon spacer that enables hydrophobic interactions. We studied the influence of hydrophobic contributions to the binding by varying the side chain length of pentapeptides with ammonium groups starting with lysine to lysine analogs with shorter side chains, namely omithine (Orn), alpha, gamma-diaminobutyric acid (Dab) and alpha, beta-diaminopropionic acid (Dap). The binding to negatively charged phosphatidylglycerol (PG) membranes was investigated by calorimetry, FT-infrared spectroscopy (FT-IR) and monolayer techniques. The binding was influenced by counteracting and sometimes compensating contributions. The influence of the bound peptides on the lipid phase behavior depends on the length of the peptide side chains. Isothermal titration calorimetry (ITC) experiments showed exothermic and endothermic effects compensating to a different extent as a function of side chain length. The increase in lipid phase transition temperature was more significant for peptides with shorter side chains. FTIR-spectroscopy revealed changes in hydration of the lipid bilayer interface after peptide binding. Using monolayer techniques, the contributions of electrostatic and hydrophobic effects could clearly be observed. Peptides with short side chains induced a pronounced decrease in surface pressure of PG monolayers whereas peptides with additional hydrophobic interactions decreased the surface pressure much less or even lead to an increase, indicating insertion of the hydrophobic part of the side chain into the lipid monolayer.

New dimensions for wound strings: The modular transformation of geometry to topology

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

McGreevy, John; Silverstein, Eva; Starr, David

2007-02-15

We show, using a theorem of Milnor and Margulis, that string theory on compact negatively curved spaces grows new effective dimensions as the space shrinks, generalizing and contextualizing the results in E. Silverstein, Phys. Rev. D 73, 086004 (2006).. Milnor's theorem relates negative sectional curvature on a compact Riemannian manifold to exponential growth of its fundamental group, which translates in string theory to a higher effective central charge arising from winding strings. This exponential density of winding modes is related by modular invariance to the infrared small perturbation spectrum. Using self-consistent approximations valid at large radius, we analyze this correspondencemore » explicitly in a broad set of time-dependent solutions, finding precise agreement between the effective central charge and the corresponding infrared small perturbation spectrum. This indicates a basic relation between geometry, topology, and dimensionality in string theory.« less

Binding of carboxylate and trimethylammonium salts to octa-acid and TEMOA deep-cavity cavitands

NASA Astrophysics Data System (ADS)

Sullivan, Matthew R.; Sokkalingam, Punidha; Nguyen, Thong; Donahue, James P.; Gibb, Bruce C.

2017-01-01

In participation of the fifth statistical assessment of modeling of proteins and ligands (SAMPL5), the strength of association of six guests ( 3- 8) to two hosts ( 1 and 2) were measured by 1H NMR and ITC. Each host possessed a unique and well-defined binding pocket, whilst the wide array of amphiphilic guests possessed binding moieties that included: a terminal alkyne, nitro-arene, alkyl halide and cyano-arene groups. Solubilizing head groups for the guests included both positively charged trimethylammonium and negatively charged carboxylate functionality. Measured association constants ( K a ) covered five orders of magnitude, ranging from 56 M-1 for guest 6 binding with host 2 up to 7.43 × 106 M-1 for guest 6 binding to host 1.

Large-area fabrication of patterned ZnO-nanowire arrays using light stamping lithography.

PubMed

Hwang, Jae K; Cho, Sangho; Seo, Eun K; Myoung, Jae M; Sung, Myung M

2009-12-01

We demonstrate selective adsorption and alignment of ZnO nanowires on patterned poly(dimethylsiloxane) (PDMS) thin layers with (aminopropyl)siloxane self-assembled monolayers (SAMs). Light stamping lithography (LSL) was used to prepare patterned PDMS thin layers as neutral passivation regions on Si substrates. (3-Aminopropyl)triethoxysilane-based SAMs were selectively formed only on regions exposing the silanol groups of the Si substrates. The patterned positively charged amino groups define and direct the selective adsorption of ZnO nanowires with negative surface charges in the protic solvent. This procedure can be adopted in automated printing machines that generate patterned ZnO-nanowire arrays on large-area substrates. To demonstrate its usefulness, the LSL method was applied to prepare ZnO-nanowire transistor arrays on 4-in. Si wafers.

Excitation of Kelvin Helmholtz instability by an ion beam in a plasma with negatively charged dust grains

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

Rani, Kavita; Sharma, Suresh C.

2015-02-15

An ion beam propagating through a magnetized dusty plasma drives Kelvin Helmholtz Instability (KHI) via Cerenkov interaction. The frequency of the unstable wave increases with the relative density of negatively charged dust grains. It is observed that the beam has stabilizing effect on the growth rate of KHI for low shear parameter, but for high shear parameter, the instability is destabilized with relative density of negatively charged dust grains.

Application of Artificial Thunderstorm Cells for the Investigation of Lightning Initiation Problems between a Thundercloud and the Ground

NASA Astrophysics Data System (ADS)

Temnikov, A. G.; Chernensky, L. L.; Orlov, A. V.; Lysov, N. Y.; Zhuravkova, D. S.; Belova, O. S.; Gerastenok, T. K.

2017-12-01

The results of the experimental application of artificial thunderstorm cells of negative and positive polarities for the investigation of the lightning initiation problems between the thundercloud and the ground using model hydrometeor arrays are presented. Possible options of the initiation and development of a discharge between the charged cloud and the ground in the presence of model hydrometeors are established. It is experimentally shown that groups of large hydrometeors of various shapes significantly increase the probability of channel discharge initiation between the artificial thunderstorm cell and the ground, especially in the case of positive polarity of the cloud. The authors assume that large hail arrays in the thundercloud can initiate the preliminary breakdown stage in the lower part of the thundercloud or initiate and stimulate the propagation of positive lightning from its upper part. A significant effect of the shape of model hydrometeors and the way they are grouped on the processes of initiation and stimulation of the channel discharge propagation in the artificial thunderstorm cell of negative or positive polarity-ground gap is experimentally established. It is found that, in the case of negative polarity of a charged cloud, the group of conductive cylindrical hydrometeors connected by a dielectric string more effectively initiates the channel discharge between the artificial thunderstorm cell and the ground. In the case of positive polarity of the artificial thunderstorm cell, the best effect of the channel discharge initiation is achieved for model hydrometeors grouped together by the dielectric tape. The obtained results can be used in the development of the method for the directed artificial lightning initiation between the thundercloud and the ground.

Tribological Properties of Nanodiamonds in Aqueous Suspensions: Effect of the Surface Charge

NASA Astrophysics Data System (ADS)

Krim, J.; Liu, Zijian; Leininger, D. A.; Kooviland, A.; Smirnov, A. I.; Shendarova, O.; Brenner, D. W.

The presence of granular nanoparticulates, be they wear particles created naturally by frictional rubbing at a geological fault line or products introduced as lubricant additives, can dramatically alter friction at solid-liquid interfaces. Given the complexity of such systems, understanding system properties at a fundamental level is particularly challenging. The Quartz Crystal Microbalance (QCM) is an ideal tool for studies of material-liquid-nanoparticulate interfaces. We have employed it here to study the uptake and nanotribological properties of positively and negatively charged 5-15 nm diameter nanodiamonds dispersed in water[1] in the both the presence and absence of a macroscopic contact with the QCM electrode. The nanodiamonds were found to impact tribological performance at both nanometer and macroscopic scales. The tribological effects were highly sensitive to the sign of the charge: negatively (positively) charged particles were more weakly (strongly) bound and reduced (increased) frictional drag at the solid-liquid interface. For the macroscopic contacts, negatively charged nanodiamonds appeared to be displaced from the contact, while the positively charged ones were not. Overall, the negatively charged nanodiamonds were more stable in an aqueous dispersion for extended time periods. Work supported by NSF and DOE.

Effects of adhesions of amorphous Fe and Al hydroxides on surface charge and adsorption of K+ and Cd2+ on rice roots.

PubMed

Liu, Zhao-Dong; Wang, Hai-Cui; Zhou, Qin; Xu, Ren-Kou

2017-11-01

Iron (Fe) and aluminum (Al) hydroxides in variable charge soils attached to rice roots may affect surface-charge properties and subsequently the adsorption and uptake of nutrients and toxic metals by the roots. Adhesion of amorphous Fe and Al hydroxides onto rice roots and their effects on zeta potential of roots and adsorption of potassium (K + ) and cadmium (Cd 2+ ) by roots were investigated. Rice roots adsorbed more Al hydroxide than Fe hydroxide because of the greater positive charge on Al hydroxide. Adhesion of Fe and Al hydroxides decreased the negative charge on rice roots, and a greater effect of the Al hydroxide. Consequently, adhesion of Fe and Al hydroxides reduced the K + and Cd 2+ adsorption by rice roots. The results of attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) and desorption of K + and Cd 2+ from rice roots indicated that physical masking by Fe and Al hydroxides and diffuse-layer overlapping between the positively-charged hydroxides and negatively-charged roots were responsible for the reduction of negative charge on roots induced by adhesion of the hydroxides. Therefore, the interaction between Fe and Al hydroxides and rice roots reduced negative charge on roots and thus inhibited their adsorption of nutrient and toxic cations. Copyright © 2017 Elsevier Inc. All rights reserved.

Positive zeta potential of a negatively charged semi-permeable plasma membrane

NASA Astrophysics Data System (ADS)

Sinha, Shayandev; Jing, Haoyuan; Das, Siddhartha

2017-08-01

The negative charge of the plasma membrane (PM) severely affects the nature of moieties that may enter or leave the cells and controls a large number of ion-interaction-mediated intracellular and extracellular events. In this letter, we report our discovery of a most fascinating scenario, where one interface (e.g., membrane-cytosol interface) of the negatively charged PM shows a positive surface (or ζ) potential, while the other interface (e.g., membrane-electrolyte interface) still shows a negative ζ potential. Therefore, we encounter a completely unexpected situation where an interface (e.g., membrane-cytosol interface) that has a negative surface charge density demonstrates a positive ζ potential. We establish that the attainment of such a property by the membrane can be ascribed to an interplay of the nature of the membrane semi-permeability and the electrostatics of the electric double layer established on either side of the charged membrane. We anticipate that such a membrane property can lead to such capabilities of the cell (in terms of accepting or releasing certain kinds of moieties as well regulating cellular signaling) that was hitherto inconceivable.

Nuclear magnetic resonance studies of the interaction of general anesthetics with 1,2-dihexadecyl-sn-glycero-3-phosphorylcholine bilayer.

PubMed Central

Shieh, D D; Ueda, I; Lin, H; Eyring, H

1976-01-01

Sonicated 1,2-dihexadecyl-sn-glycero-3-phosphorylcholine forms liposomes. Studies by Fourier transform proton magnetic resonance of the interaction of these bilayers with some general anesthetics, i.e., chloroform, halothane, methoxyflurane, and enflurane, show that the addition of a general anesthetic to the liposomes and raising the temperature have a similar effect in cuasing the fluidization of the bilayer. General anesthetics act on the hydrophilic site (choline group) in clinical concentrations and then diffuse into the hydrophobic region with the addition of larger amount of anesthetics. There is evidence that the lecithin choline groups are involved in the interaction with protein and that the general anesthetics change the conformation of some polypeptides and proteins. We conclude that the general anesthetics, by increasing the motion of positively charged choline groups and negatively charged groups in protein, weaken the Coulomb-type interaction and cause the liprotein conformational changes. PMID:1069285

Effect of incorporation of nitrogen atoms in Al2O3 gate dielectric of wide-bandgap-semiconductor MOSFET on gate leakage current and negative fixed charge

NASA Astrophysics Data System (ADS)

Kojima, Eiji; Chokawa, Kenta; Shirakawa, Hiroki; Araidai, Masaaki; Hosoi, Takuji; Watanabe, Heiji; Shiraishi, Kenji

2018-06-01

We performed first-principle calculations to investigate the effect of incorporation of N atoms into Al2O3 gate dielectrics. Our calculations show that the defect levels generated by VO in Al2O3 are the origin of the stress-induced gate leakage current and that VOVAl complexes in Al2O3 cause negative fixed charge. We revealed that the incorporation of N atoms into Al2O3 eliminates the VO defect levels, reducing the stress-induced gate leakage current. Moreover, this suppresses the formation of negatively charged VOVAl complexes. Therefore, AlON can reduce both stress-induced gate leakage current and negative fixed charge in wide-bandgap-semiconductor MOSFETs.

DNA-binding and oxidative properties of cationic phthalocyanines and their dimeric complexes with anionic phthalocyanines covalently linked to oligonucleotides.

PubMed

Kuznetsova, A A; Lukyanets, E A; Solovyeva, L I; Knorre, D G; Fedorova, O S

2008-12-01

Design of chemically modified oligonucleotides for regulation of gene expression has attracted considerable attention over the past decades. One actively pursued approach involves antisense or antigene oligonucleotide constructs carrying reactive groups, many of these based on transition metal complexes. The complexes of Fe(II) and Co(II) with phthalocyanines are extremely good catalysts of oxidation of organic compounds with molecular oxygen and hydrogen peroxide. The binding of positively charged Fe(II) and Co(II) phthalocyanines with single- and double-stranded DNA was investigated. It was shown that these phthalocyanines interact with nucleic acids through an outside binding mode. The site-directed modification of single-stranded DNA by O2 and H2O2 in the presence of dimeric complexes of negatively and positively charged Fe(II) and Co(II) phthalocyanines was investigated. These complexes were formed directly on single-stranded DNA through interaction between negatively charged phthalocyanine in conjugate and positively charged phthalocyanine in solution. The resulting oppositely charged phthalocyanine complexes showed significant increase of catalytic activity compared with monomeric forms of phthalocyanines Fe(II) and Co(II). These complexes catalyzed the DNA oxidation with high efficacy and led to direct DNA strand cleavage. It was determined that oxidation of DNA by molecular oxygen catalyzed by complex of Fe(II)-phthalocyanines proceeds with higher rate than in the case of Co(II)-phthalocyanines but the latter led to a greater extent of target DNA modification.

Effect of charge and molecular weight on the functionality of gelatin carriers for corneal endothelial cell therapy.

PubMed

Lai, Jui-Yang; Lu, Pei-Lin; Chen, Ko-Hua; Tabata, Yasuhiko; Hsiue, Ging-Ho

2006-06-01

Cell transplantation strategies usually involve the use of supporting carrier materials because of the soft and fragile nature of these grafts. In this work, a cell-adhesive gelatin hydrogel carrier was fabricated to deliver cultivated human corneal endothelial cell (HCEC) sheets, which were harvested from thermo-responsive poly(N-isopropylacrylamide) (PNIPAAm)-grafted culture surfaces. The carrier disks, consisting of gelatins with a different isoelectric point (IEP = 5.0 and 9.0) and a molecular weight (MW) ranging from 3 to 100 kDa, were subjected to 16.6 kGy gamma irradiation for sterilization. The effect of IEP and MW of the raw gelatins (i.e., before irradiation) on the functionality of sterilized disks was studied by determinations of mechanical property, water content, dissolution degree, and cytocompatibility. Irrespective of the IEP of raw gelatin, hydrogel disks prepared with high MW (100 kDa) exhibited a greater tensile strength, lower water content, and slower dissolution rate than those made of low MW gelatin (8 and 3 kDa). From the investigation of cellular responses to the disks, the negatively charged gelatin (IEP = 5.0) groups were more cytocompatible when compared with their positively charged counterparts (IEP = 9.0) at the same MW (100 kDa). Additionally, in the negatively charged gelatin groups, only a slight increase in pro-inflammatory cytokine expression was observed with increasing MW of gelatin from 3 to 100 kDa. It is concluded that the gamma-sterilized hydrogel disks made from raw gelatins (IEP = 5.0, MW = 100 kDa) with appropriate dissolution degree and acceptable cytocompatibility are capable of providing stable mechanical support, making these carriers promising candidates for intraocular delivery of cultivated HCEC sheets.

Superposition Principle in Auger Recombination of Charged and Neutral Multicarrier States in Semiconductor Quantum Dots

DOE PAGES

Wu, Kaifeng; Lim, Jaehoon; Klimov, Victor I.

2017-07-19

Application of colloidal semiconductor quantum dots (QDs) in optical and optoelectronic devices is often complicated by unintentional generation of extra charges, which opens fast nonradiative Auger recombination pathways whereby the recombination energy of an exciton is quickly transferred to the extra carrier(s) and ultimately dissipated as heat. Previous studies of Auger recombination have primarily focused on neutral and, more recently, negatively charged multicarrier states. Auger dynamics of positively charged species remains more poorly explored due to difficulties in creating, stabilizing, and detecting excess holes in the QDs. Here we apply photochemical doping to prepare both negatively and positively charged CdSe/CdSmore » QDs with two distinct core/shell interfacial profiles (“sharp” versus “smooth”). Using neutral and charged QD samples we evaluate Auger lifetimes of biexcitons, negative and positive trions (an exciton with an extra electron or a hole, respectively), and multiply negatively charged excitons. Using these measurements, we demonstrate that Auger decay of both neutral and charged multicarrier states can be presented as a superposition of independent elementary three-particle Auger events. As one of the manifestations of the superposition principle, we observe that the biexciton Auger decay rate can be presented as a sum of the Auger rates for independent negative and positive trion pathways. Furthermore, by comparing the measurements on the QDs with the “sharp” versus “smooth” interfaces, we also find that while affecting the absolute values of Auger lifetimes, manipulation of the shape of the confinement potential does not lead to violation of the superposition principle, which still allows us to accurately predict the biexciton Auger lifetimes based on the measured negative and positive trion dynamics. Our findings indicate considerable robustness of the superposition principle as applied to Auger decay of charged and neutral multicarrier states, suggesting its generality to quantum-confined nanocrystals of arbitrary compositions and complexities.« less

Superposition Principle in Auger Recombination of Charged and Neutral Multicarrier States in Semiconductor Quantum Dots.

PubMed

Wu, Kaifeng; Lim, Jaehoon; Klimov, Victor I

2017-08-22

Application of colloidal semiconductor quantum dots (QDs) in optical and optoelectronic devices is often complicated by unintentional generation of extra charges, which opens fast nonradiative Auger recombination pathways whereby the recombination energy of an exciton is quickly transferred to the extra carrier(s) and ultimately dissipated as heat. Previous studies of Auger recombination have primarily focused on neutral and, more recently, negatively charged multicarrier states. Auger dynamics of positively charged species remains more poorly explored due to difficulties in creating, stabilizing, and detecting excess holes in the QDs. Here we apply photochemical doping to prepare both negatively and positively charged CdSe/CdS QDs with two distinct core/shell interfacial profiles ("sharp" versus "smooth"). Using neutral and charged QD samples we evaluate Auger lifetimes of biexcitons, negative and positive trions (an exciton with an extra electron or a hole, respectively), and multiply negatively charged excitons. Using these measurements, we demonstrate that Auger decay of both neutral and charged multicarrier states can be presented as a superposition of independent elementary three-particle Auger events. As one of the manifestations of the superposition principle, we observe that the biexciton Auger decay rate can be presented as a sum of the Auger rates for independent negative and positive trion pathways. By comparing the measurements on the QDs with the "sharp" versus "smooth" interfaces, we also find that while affecting the absolute values of Auger lifetimes, manipulation of the shape of the confinement potential does not lead to violation of the superposition principle, which still allows us to accurately predict the biexciton Auger lifetimes based on the measured negative and positive trion dynamics. These findings indicate considerable robustness of the superposition principle as applied to Auger decay of charged and neutral multicarrier states, suggesting its generality to quantum-confined nanocrystals of arbitrary compositions and complexities.

Comment on 'The effect of liquid water on thunderstorm charging' by C.P.R. Saunders et al

NASA Technical Reports Server (NTRS)

Williams, Earle; Zhang, Renyi

1993-01-01

This paper is a comment on the claims made in the paper by Saunders et al. (1991), which reports on a laboratory simulation of ice particle charging in thunderstorms, concerning the microphysical condition of riming ice particles and the conditions for sublimation and negative charging in thunderclouds. It is argued that the interpretation of Saunders is contrary to the findings of Williams et al. (1991), which support the hypothesis that sublimating graupel charge negatively (in collision with smaller ice particles) and graupel in deposition charge positively. Based on microphysical calculations as well as observations in thunderclouds, it is concluded that, while sublimation of the rimer surface and negative charging do not appear to account for the laboratory observations reported by Saunders et al., these authors do not have sufficient evidence for rejecting the sublimation hypothesis presented by Williams et al. (1991) for thunderstorms.

Electrostatic Power Generation from Negatively Charged, Simulated Lunar Regolith

NASA Technical Reports Server (NTRS)

Choi, Sang H.; King, Glen C.; Kim, Hyun-Jung; Park, Yeonjoon

2010-01-01

Research was conducted to develop an electrostatic power generator for future lunar missions that facilitate the utilization of lunar resources. The lunar surface is known to be negatively charged from the constant bombardment of electrons and protons from the solar wind. The resulting negative electrostatic charge on the dust particles, in the lunar vacuum, causes them to repel each other minimizing the potential. The result is a layer of suspended dust about one meter above the lunar surface. This phenomenon was observed by both Clementine and Surveyor spacecrafts. During the Apollo 17 lunar landing, the charged dust was a major hindrance, as it was attracted to the astronauts' spacesuits, equipment, and the lunar buggies. The dust accumulated on the spacesuits caused reduced visibility for the astronauts, and was unavoidably transported inside the spacecraft where it caused breathing irritation [1]. In the lunar vacuum, the maximum charge on the particles can be extremely high. An article in the journal "Nature", titled "Moon too static for astronauts?" (Feb 2, 2007) estimates that the lunar surface is charged with up to several thousand volts [2]. The electrostatic power generator was devised to alleviate the hazardous effects of negatively charged lunar soil by neutralizing the charged particles through capacitive coupling and thereby simultaneously harnessing power through electric charging [3]. The amount of power generated or collected is dependent on the areal coverage of the device and hovering speed over the lunar soil surface. A thin-film array of capacitors can be continuously charged and sequentially discharged using a time-differentiated trigger discharge process to produce a pulse train of discharge for DC mode output. By controlling the pulse interval, the DC mode power can be modulated for powering devices and equipment. In conjunction with a power storage system, the electrostatic power generator can be a power source for a lunar rover or other systems. The negatively charged lunar soil would also be neutralized mitigating some of the adverse effects resulting from lunar dust.

On the Control of the Fixed Charge Densities in Al2O3-Based Silicon Surface Passivation Schemes.

PubMed

Simon, Daniel K; Jordan, Paul M; Mikolajick, Thomas; Dirnstorfer, Ingo

2015-12-30

A controlled field-effect passivation by a well-defined density of fixed charges is crucial for modern solar cell surface passivation schemes. Al2O3 nanolayers grown by atomic layer deposition contain negative fixed charges. Electrical measurements on slant-etched layers reveal that these charges are located within a 1 nm distance to the interface with the Si substrate. When inserting additional interface layers, the fixed charge density can be continuously adjusted from 3.5 × 10(12) cm(-2) (negative polarity) to 0.0 and up to 4.0 × 10(12) cm(-2) (positive polarity). A HfO2 interface layer of one or more monolayers reduces the negative fixed charges in Al2O3 to zero. The role of HfO2 is described as an inert spacer controlling the distance between Al2O3 and the Si substrate. It is suggested that this spacer alters the nonstoichiometric initial Al2O3 growth regime, which is responsible for the charge formation. On the basis of this charge-free HfO2/Al2O3 stack, negative or positive fixed charges can be formed by introducing additional thin Al2O3 or SiO2 layers between the Si substrate and this HfO2/Al2O3 capping layer. All stacks provide very good passivation of the silicon surface. The measured effective carrier lifetimes are between 1 and 30 ms. This charge control in Al2O3 nanolayers allows the construction of zero-fixed-charge passivation layers as well as layers with tailored fixed charge densities for future solar cell concepts and other field-effect based devices.

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.

NOVA SCIENCE UNIT 15, FUNDAMENTAL PARTICLES 4.

ERIC Educational Resources Information Center

1964

THE PRINCIPLES OF ATOMIC STRUCTURE WHICH ARE STRESSED ARE THAT ATOMS ARE MADE UP OF A NUCLEUS WITH A POSITIVE CHARGE, SURROUNDED BY ELECTRONS WITH A NEGATIVE CHARGE, AND THAT THERE IS NO CHANGE IN THE ATOM WHEN THE POSITIVE AND NEGATIVE CHARGES ARE EQUAL. EXPERIMENTS ILLUSTRATE THAT CURRENT ELECTRICITY IS ACTUALLY ELECTRONS IN MOTION, THAT THERE…

Borophene as a Promising Material for Charge-Modulated Switchable CO2 Capture.

PubMed

Tan, Xin; Tahini, Hassan A; Smith, Sean C

2017-06-14

Ideal carbon dioxide (CO 2 ) capture materials for practical applications should bind CO 2 molecules neither too weakly to limit good loading kinetics nor too strongly to limit facile release. Although charge-modulated switchable CO 2 capture has been proposed to be a controllable, highly selective, and reversible CO 2 capture strategy, the development of a practical gas-adsorbent material remains a great challenge. In this study, by means of density functional theory (DFT) calculations, we have examined the possibility of conductive borophene nanosheets as promising sorbent materials for charge-modulated switchable CO 2 capture. Our results reveal that the binding strength of CO 2 molecules on negatively charged borophene can be significantly enhanced by injecting extra electrons into the adsorbent. At saturation CO 2 capture coverage, the negatively charged borophene achieves CO 2 capture capacities up to 6.73 × 10 14 cm -2 . In contrast to the other CO 2 capture methods, the CO 2 capture/release processes on negatively charged borophene are reversible with fast kinetics and can be easily controlled via switching on/off the charges carried by borophene nanosheets. Moreover, these negatively charged borophene nanosheets are highly selective for separating CO 2 from mixtures with CH 4 , H 2 , and/or N 2 . This theoretical exploration will provide helpful guidance for identifying experimentally feasible, controllable, highly selective, and high-capacity CO 2 capture materials with ideal thermodynamics and reversibility.

Mechanisms of Polyelectrolyte Enhanced Surfactant Adsorption at the Air-Water Interface

PubMed Central

Stenger, Patrick C.; Palazoglu, Omer A.; Zasadzinski, Joseph A.

2009-01-01

Chitosan, a naturally occurring cationic polyelectrolyte, restores the adsorption of the clinical lung surfactant Survanta to the air-water interface in the presence of albumin at much lower concentrations than uncharged polymers such as polyethylene glycol. This is consistent with the positively charged chitosan forming ion pairs with negative charges on the albumin and lung surfactant particles, reducing the net charge in the double-layer, and decreasing the electrostatic energy barrier to adsorption to the air-water interface. However, chitosan, like other polyelectrolytes, cannot perfectly match the charge distribution on the surfactant, which leads to patches of positive and negative charge at net neutrality. Increasing the chitosan concentration further leads to a reduction in the rate of surfactant adsorption consistent with an over-compensation of the negative charge on the surfactant and albumin surfaces, which creates a new repulsive electrostatic potential between the now cationic surfaces. This charge neutralization followed by charge inversion explains the window of polyelectrolyte concentration that enhances surfactant adsorption; the same physical mechanism is observed in flocculation and re-stabilization of anionic colloids by chitosan and in alternate layer deposition of anionic and cationic polyelectrolytes on charged colloids. PMID:19366599

Mechanisms of polyelectrolyte enhanced surfactant adsorption at the air-water interface.

PubMed

Stenger, Patrick C; Palazoglu, Omer A; Zasadzinski, Joseph A

2009-05-01

Chitosan, a naturally occurring cationic polyelectrolyte, restores the adsorption of the clinical lung surfactant Survanta to the air-water interface in the presence of albumin at much lower concentrations than uncharged polymers such as polyethylene glycol. This is consistent with the positively charged chitosan forming ion pairs with negative charges on the albumin and lung surfactant particles, reducing the net charge in the double-layer, and decreasing the electrostatic energy barrier to adsorption to the air-water interface. However, chitosan, like other polyelectrolytes, cannot perfectly match the charge distribution on the surfactant, which leads to patches of positive and negative charge at net neutrality. Increasing the chitosan concentration further leads to a reduction in the rate of surfactant adsorption consistent with an over-compensation of the negative charge on the surfactant and albumin surfaces, which creates a new repulsive electrostatic potential between the now cationic surfaces. This charge neutralization followed by charge inversion explains the window of polyelectrolyte concentration that enhances surfactant adsorption; the same physical mechanism is observed in flocculation and re-stabilization of anionic colloids by chitosan and in alternate layer deposition of anionic and cationic polyelectrolytes on charged colloids.

Phosphonium carbosilane dendrimers - interaction with a simple biological membrane model.

PubMed

Wrobel, Dominika; Kubikova, Radka; Müllerová, Monika; Strašák, Tomas; RůŽička, Květoslav; Fulem, Michal; Maly, Jan

2018-05-30

The influence of three generations of five different phosphonium carbosilane dendrimers and one ammonium carbosilane dendrimer as a reference (PMe3, PBu3, P(Et2)2(CH2)3OH, PPh3, P(MeOPh)3 and NMe3, peripheral functional groups) on dimyristoylphosphatidylcholine (DMPC) or a lipid mixture dimyristoylphosphatidylcholine/dimyristoylphosphatidylglycerol (DMPC/DMPG) of liposomes was studied by fluorescence polarization measurements and differential scanning calorimetry. All types of dendrimers interacted with neutral as well as negatively charged liposomes, but the strength and observed influence were different. Concentration, type of peripheral functional group modification and dendrimer generation were the main factors influencing the interaction. Generally, weak interactions as well as destabilization of the lipid membranes at low concentrations, regardless of liposome type, were observed in the case of DmPMe3, DmNMe3, DmPBu3 and DmP(Et2)2(CH2)3OH. Dendrimers with PPh3 and P(MeOPh)3 peripheral functional groups interacted much more strongly and increased the rigidity of liposomes. Electrostatic interactions, the hydrophobicity of substituents and charge shielding on the peripheral phosphonium group are important factors in the interaction. We suggest that, among the other types of dendrimers, the dendrimer with the P(MeOPh)3 peripheral functional group is a highly promising candidate for the design of a drug delivery system due to its positive charge, efficient interaction with lipidic membranes and low cytotoxicity.

Plasmon modes supported by left-handed material slab waveguide with conducting interfaces

NASA Astrophysics Data System (ADS)

Taya, Sofyan A.

2018-07-01

Theoretical analysis of left-handed material core layer waveguide in the presence of interface free charge layers is presented. The thickness of the interface charge layer can be neglected compared with the incident wavelength. The tangential component of the magnetic field is no longer continuous due to the conducting interfaces. The non-homogeneous boundary conditions are solved and the corresponding dispersion relation is found. The dispersion properties are studied. The proposed structure is found to support even as well as odd plasmon modes. Moreover, the structure shows abnormal dispersion property of decreasing the effective index with the increase of the frequency which means negative group velocity.

Structure and stability of complexes of agmatine with some functional receptor residues of proteins

NASA Astrophysics Data System (ADS)

Remko, Milan; Broer, Ria; Remková, Anna; Van Duijnen, Piet Th.

2017-04-01

The paper reports the results of a theoretical study of the conformational behavior and basicity of biogenic amine agmatine. The complexes modelling of agmatine - protein interaction are also under scrutiny of our investigation using the Becke3LYP and B97D levels of the density functional theory. The relative stabilities (Gibbs energies) of individual complexes are by both DFT methods described equally. Hydration has a dramatic effect on the hydrogen bonded complexes studied. The pairing acidic carboxylate group with different agmatine species resulted in charged hydrogen bond complexes containing negatively charged acetate species acting as proton acceptors.

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.

Triboelectricity: macroscopic charge patterns formed by self-arraying ions on polymer surfaces.

PubMed

Burgo, Thiago A L; Ducati, Telma R D; Francisco, Kelly R; Clinckspoor, Karl J; Galembeck, Fernando; Galembeck, Sergio E

2012-05-15

Tribocharged polymers display macroscopically patterned positive and negative domains, verifying the fractal geometry of electrostatic mosaics previously detected by electric probe microscopy. Excess charge on contacting polyethylene (PE) and polytetrafluoroethylene (PTFE) follows the triboelectric series but with one caveat: net charge is the arithmetic sum of patterned positive and negative charges, as opposed to the usual assumption of uniform but opposite signal charging on each surface. Extraction with n-hexane preferentially removes positive charges from PTFE, while 1,1-difluoroethane and ethanol largely remove both positive and negative charges. Using suitable analytical techniques (electron energy-loss spectral imaging, infrared microspectrophotometry and carbonization/colorimetry) and theoretical calculations, the positive species were identified as hydrocarbocations and the negative species were identified as fluorocarbanions. A comprehensive model is presented for PTFE tribocharging with PE: mechanochemical chain homolytic rupture is followed by electron transfer from hydrocarbon free radicals to the more electronegative fluorocarbon radicals. Polymer ions self-assemble according to Flory-Huggins theory, thus forming the experimentally observed macroscopic patterns. These results show that tribocharging can only be understood by considering the complex chemical events triggered by mechanical action, coupled to well-established physicochemical concepts. Patterned polymers can be cut and mounted to make macroscopic electrets and multipoles.

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.

VHF lightning mapping observations of a triggered lightning flash

NASA Astrophysics Data System (ADS)

Edens, H. E.; Eack, K. B.; Eastvedt, E. M.; Trueblood, J. J.; Winn, W. P.; Krehbiel, P. R.; Aulich, G. D.; Hunyady, S. J.; Murray, W. C.; Rison, W.; Behnke, S. A.; Thomas, R. J.

2012-10-01

On 3 August 2010 an extensive lightning flash was triggered over Langmuir Laboratory in New Mexico. The upward positive leader propagated into the storm's midlevel negative charge region, extending over a horizontal area of 13 × 13 km and 7.5 km altitude. The storm had a normal-polarity tripolar charge structure with upper positive charge over midlevel negative charge. Lightning Mapping Array (LMA) observations were used to estimate positive leader velocities along various branches, which were in the range of 1-3 × 104 m s-1, slower than in other studies. The upward positive leader initiated at 3.4 km altitude, but was mapped only above 4.0 km altitude after the onset of retrograde negative breakdown, indicating a change in leader propagation and VHF emissions. The observations suggest that both positive and negative breakdown produce VHF emissions that can be located by time-of-arrival systems, and that not all VHF emissions occurring along positive leader channels are associated with retrograde negative breakdown.

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

In situ measurements and radar observations of a severe storm - Electricity, kinematics, and precipitation

NASA Technical Reports Server (NTRS)

Byrne, G. J.; Few, A. A.; Stewart, M. F.; Conrad, A. C.; Torczon, R. L.

1987-01-01

Electric field measurements made inside a multicell severe storm in Oklahoma in 1983 with a balloon-borne instrument are presented. The properties of the electric charge regions, such as altitude, thickness, and charge concentrations, are studied. These measurements are analzyed with meteorological measurements of temperature and humidity, and balloon tracking and radar observations. The relation between the electric charge structure and the precipitation and kinematic features of the storm is examined. The data reveal that the cell exhibits a bipolar charge structure with negative charge below positive charge. The average charge concentrations of the two regions are estimated as -1.2 and 0.15 nC/cu m, respectively; the upper positive charge is about 6 km in vertical extent, and the lower negative charge is less than 1 km in vertical extent.

Positively versus negatively charged moral emotion expectancies in adolescence: the role of situational context and the developing moral self.

PubMed

Krettenauer, Tobias; Johnston, Megan

2011-09-01

The study analyses adolescents' positively charged versus negatively charged moral emotion expectancies. Two hundred and five students (M= 14.83 years, SD= 2.21) participated in an interview depicting various situations in which a moral norm was either regarded or transgressed. Emotion expectancies were assessed for specific emotions (pride, guilt) as well as for overall strength and valence. In addition, self-importance of moral values was measured by a questionnaire. Results revealed that positively charged emotion expectancies were more pronounced in contexts of prosocial action than in the context of moral transgressions, whereas the opposite was true for negatively charged emotions. At the same time, expectations of guilt and pride were substantially related to the self-importance of moral values. ©2010 The British Psychological Society.

Charge rearrangement deduced from nearby electric field measurements of an intracloud flash with K‒changes

NASA Astrophysics Data System (ADS)

Hager, William W.; Feng, Wei

2013-09-01

An intracloud flash near Langmuir Laboratory is analyzed to determine the net rearrangement of charge. The analysis employed data from a balloon borne electric field sensor, or Esonde, that was within a few hundred meters of the lightning channel, data from a similar Esonde on a mountain about 6.4 km from the balloon, and data from the New Mexico Institute of Mining and Technology Lightning Mapping Array (LMA). The recovery of the charge transport required the solution of Poisson's equation over the mountainous terrain surrounding Langmuir Laboratory and the solution of a vastly under‒determined system of equations. The charge movement is analyzed using a new smooth charge transport model that incorporates constraints in the least squares fitting process through the use of penalty terms to smooth the charge movement and prevent data overfitting. The electric field measurements were consistent with about 26% of the negative charge being transported to the end of the channel, 36% deposited along the channel in the positive region, 8% deposited near the start of the channel in the positive region, and 30% deposited in another positive region several kilometers beneath the main channel. The transport of negative charge to a lower positive region occurred during the K‒processes when some negative charge was also deposited along the main channel in the upper positive region. Hence, the charge transport process during the K‒processes amounted to a tripolar charge rearrangement where the charge from the negative region was transported to two distinct positive regions, the positive region along the main channel and a lower positive region beneath the main channel. High altitude, widely scattered LMA sources beyond the end of the main channel could indicate the existence of streamers which transported the end‒of‒channel charge into the surrounding volume. Although the LMA showed the development of two upper channels, the charge transport analysis showed that measurable charge transport only occurred on one of the channels. The channel that did not transport charge was missing the high altitude, widely scattered LMA sources seen at the end of the channel that carried charge.

Zeta Sperm Selection Improves Pregnancy Rate and Alters Sex Ratio in Male Factor Infertility Patients: A Double-Blind, Randomized Clinical Trial

PubMed Central

Nasr Esfahani, Mohammad Hossein; Deemeh, Mohammad Reza; Tavalaee, Marziyeh; Sekhavati, Mohammad Hadi; Gourabi, Hamid

2016-01-01

Background Selection of sperm for intra-cytoplasmic sperm injection (ICSI) is usually considered as the ultimate technique to alleviate male-factor infertility. In routine ICSI, selection is based on morphology and viability which does not necessarily preclude the chance injection of DNA-damaged or apoptotic sperm into the oocyte. Sperm with high negative surface electrical charge, named “Zeta potential”, are mature and more likely to have intact chromatin. In addition, X-bearing spermatozoa carry more negative charge. Therefore, we aimed to compare the clinical outcomes of Zeta procedure with routine sperm selection in infertile men candidate for ICSI. Materials and Methods From a total of 203 ICSI cycles studied, 101 cycles were allocated to density gradient centrifugation (DGC)/Zeta group and the remaining 102 were included in the DGC group in this prospective study. Clinical outcomes were com- pared between the two groups. The ratios of Xand Y bearing sperm were assessed by fluorescence in situ hybridization (FISH) and quantitative polymerase chain reaction (qPCR) methods in 17 independent semen samples. Results In the present double-blind randomized clinical trial, a significant increase in top quality embryos and pregnancy rate were observed in DGC/Zeta group compared to DGC group. Moreover, sex ratio (XY/XX) at birth significantly was lower in the DGC/Zeta group compared to DGC group despite similar ratio of X/Y bearings sper- matozoa following Zeta selection. Conclusion Zeta method not only improves the percentage of top embryo quality and pregnancy outcome but also alters the sex ratio compared to the conventional DGC method, despite no significant change in the ratio of Xand Ybearing sperm population (Registration number: IRCT201108047223N1). PMID:27441060

Characteristic study of head-on collision of dust-ion acoustic solitons of opposite polarity with kappa distributed electrons

NASA Astrophysics Data System (ADS)

Parveen, Shahida; Mahmood, Shahzad; Adnan, Muhammad; Qamar, Anisa

2016-09-01

The head on collision between two dust ion acoustic (DIA) solitary waves, propagating in opposite directions, is studied in an unmagnetized plasma constituting adiabatic ions, static dust charged (positively/negatively) grains, and non-inertial kappa distributed electrons. In the linear limit, the dispersion relation of the dust ion acoustic (DIA) solitary wave is obtained using the Fourier analysis. For studying characteristic head-on collision of DIA solitons, the extended Poincaré-Lighthill-Kuo method is employed to obtain Korteweg-de Vries (KdV) equations with quadratic nonlinearities and investigated the phase shifts in their trajectories after the interaction. It is revealed that only compressive solitary waves can exist for the positive dust charged concentrations while for negative dust charge concentrations both the compressive and rarefactive solitons can propagate in such dusty plasma. It is found that for specific sets of plasma parameters, the coefficient of nonlinearity disappears in the KdV equation for the negative dust charged grains. Therefore, the modified Korteweg-de Vries (mKdV) equations with cubic nonlinearity coefficient, and their corresponding phase shift and trajectories, are also derived for negative dust charged grains plasma at critical composition. The effects of different plasma parameters such as superthermality, concentration of positively/negatively static dust charged grains, and ion to electron temperature ratio on the colliding soliton profiles and their corresponding phase shifts are parametrically examined.

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

Wu, Kaifeng; Lim, Jaehoon; Klimov, Victor I.

Application of colloidal semiconductor quantum dots (QDs) in optical and optoelectronic devices is often complicated by unintentional generation of extra charges, which opens fast nonradiative Auger recombination pathways whereby the recombination energy of an exciton is quickly transferred to the extra carrier(s) and ultimately dissipated as heat. Previous studies of Auger recombination have primarily focused on neutral and, more recently, negatively charged multicarrier states. Auger dynamics of positively charged species remains more poorly explored due to difficulties in creating, stabilizing, and detecting excess holes in the QDs. Here we apply photochemical doping to prepare both negatively and positively charged CdSe/CdSmore » QDs with two distinct core/shell interfacial profiles (“sharp” versus “smooth”). Using neutral and charged QD samples we evaluate Auger lifetimes of biexcitons, negative and positive trions (an exciton with an extra electron or a hole, respectively), and multiply negatively charged excitons. Using these measurements, we demonstrate that Auger decay of both neutral and charged multicarrier states can be presented as a superposition of independent elementary three-particle Auger events. As one of the manifestations of the superposition principle, we observe that the biexciton Auger decay rate can be presented as a sum of the Auger rates for independent negative and positive trion pathways. Furthermore, by comparing the measurements on the QDs with the “sharp” versus “smooth” interfaces, we also find that while affecting the absolute values of Auger lifetimes, manipulation of the shape of the confinement potential does not lead to violation of the superposition principle, which still allows us to accurately predict the biexciton Auger lifetimes based on the measured negative and positive trion dynamics. Our findings indicate considerable robustness of the superposition principle as applied to Auger decay of charged and neutral multicarrier states, suggesting its generality to quantum-confined nanocrystals of arbitrary compositions and complexities.« less

A Unified Model of Cloud-to-Ground Lightning Stroke

NASA Astrophysics Data System (ADS)

Nag, A.; Rakov, V. A.

2014-12-01

The first stroke in a cloud-to-ground lightning discharge is thought to follow (or be initiated by) the preliminary breakdown process which often produces a train of relatively large microsecond-scale electric field pulses. This process is poorly understood and rarely modeled. Each lightning stroke is composed of a downward leader process and an upward return-stroke process, which are usually modeled separately. We present a unified engineering model for computing the electric field produced by a sequence of preliminary breakdown, stepped leader, and return stroke processes, serving to transport negative charge to ground. We assume that a negatively-charged channel extends downward in a stepped fashion through the relatively-high-field region between the main negative and lower positive charge centers and then through the relatively-low-field region below the lower positive charge center. A relatively-high-field region is also assumed to exist near ground. The preliminary breakdown pulse train is assumed to be generated when the negatively-charged channel interacts with the lower positive charge region. At each step, an equivalent current source is activated at the lower extremity of the channel, resulting in a step current wave that propagates upward along the channel. The leader deposits net negative charge onto the channel. Once the stepped leader attaches to ground (upward connecting leader is presently neglected), an upward-propagating return stroke is initiated, which neutralizes the charge deposited by the leader along the channel. We examine the effect of various model parameters, such as step length and current propagation speed, on model-predicted electric fields. We also compare the computed fields with pertinent measurements available in the literature.

Carbon nanotubes' surface chemistry determines their potency as vaccine nanocarriers in vitro and in vivo

PubMed Central

Hassan, Hatem A.F.M.; Smyth, Lesley; Rubio, Noelia; Ratnasothy, Kulachelvy; Wang, Julie T.-W.; Bansal, Sukhvinder S.; Summers, Huw D.; Diebold, Sandra S.; Lombardi, Giovanna; Al-Jamal, Khuloud T.

2016-01-01

Carbon nanotubes (CNTs) have shown marked capabilities in enhancing antigen delivery to antigen presenting cells. However, proper understanding of how altering the physical properties of CNTs may influence antigen uptake by antigen presenting cells, such as dendritic cells (DCs), has not been established yet. We hypothesized that altering the physical properties of multi-walled CNTs (MWNTs)-antigen conjugates, e.g. length and surface charge, can affect the internalization of MWNT-antigen by DCs, hence the induced immune response potency. For this purpose, pristine MWNTs (p-MWNTs) were exposed to various chemical reactions to modify their physical properties then conjugated to ovalbumin (OVA), a model antigen. The yielded MWNTs-OVA conjugates were long MWNT-OVA (~ 386 nm), bearing net positive charge (5.8 mV), or short MWNTs-OVA (~ 122 nm) of increasing negative charges (− 23.4, − 35.8 or − 39 mV). Compared to the short MWNTs-OVA bearing high negative charges, short MWNT-OVA with the lowest negative charge demonstrated better cellular uptake and OVA-specific immune response both in vitro and in vivo. However, long positively-charged MWNT-OVA showed limited cellular uptake and OVA specific immune response in contrast to short MWNT-OVA displaying the least negative charge. We suggest that reduction in charge negativity of MWNT-antigen conjugate enhances cellular uptake and thus the elicited immune response intensity. Nevertheless, length of MWNT-antigen conjugate might also affect the cellular uptake and immune response potency; highlighting the importance of physical properties as a consideration in designing a MWNT-based vaccine delivery system. PMID:26802552

Interactions of microbicide nanoparticles with a simulated vaginal fluid.

PubMed

das Neves, José; Rocha, Cristina M R; Gonçalves, Maria Pilar; Carrier, Rebecca L; Amiji, Mansoor; Bahia, Maria Fernanda; Sarmento, Bruno

2012-11-05

The interaction with cervicovaginal mucus presents the potential to impact the performance of drug nanocarriers. These systems must migrate through this biological fluid in order to deliver their drug payload to the underlying mucosal surface. We studied the ability of dapivirine-loaded polycaprolactone (PCL)-based nanoparticles (NPs) to interact with a simulated vaginal fluid (SVF) incorporating mucin. Different surface modifiers were used to produce NPs with either negative (poloxamer 338 NF and sodium lauryl sulfate) or positive (cetyltrimethylammonium bromide) surface charge. Studies were performed using the mucin particle method, rheological measurements, and real-time multiple particle tracking. Results showed that SVF presented rheological properties similar to those of human cervicovaginal mucus. Analysis of NP transport indicated mild interactions with mucin and low adhesive potential. In general, negatively charged NPs underwent subdiffusive transport in SVF, i.e., hindered as compared to their diffusion in water, but faster than for positively charged NPs. These differences were increased when the pH of SVF was changed from 4.2 to 7.0. Diffusivity was 50- and 172-fold lower in SVF at pH 4.2 than in water for negatively charged and positively charged NPs, respectively. At pH 7.0, this decrease was around 20- and 385-fold, respectively. The estimated times required to cross a layer of SVF were equal to or lower than 1.7 h for negatively charged NPs, while for positively charged NPs these values were equal to or higher than 7 h. Overall, our results suggest that negatively charged PCL NPs may be suitable to be used as carriers in order to deliver dapivirine and potentially other antiretroviral drugs to the cervicovaginal mucosal lining. Also, they further reinforce the importance in characterizing the interactions of nanosystems with mucus fluids or surrogates when considering mucosal drug delivery.

Peptide structure: Its effect on penetration into human hair.

PubMed

Silva, Carla J S M; Vasconcelos, Andreia; Cavaco-Paulo, Artur

2007-01-01

The influence of the peptide structure on its penetration inside hair was studied, together with the effect of hair bleaching (oxidation). For that reason, the outcome of positioning a charged sequence (KAKAK) either at the N or C terminal on hair penetration has been studied for peptides with 17 residues each. It was observed that the penetration of these peptides into hair was driven by electrostatic interactions, where the position of the charged group at the peptide structure was of major importance. The penetration was only achieved for damaged hair due to its higher negative charge at the membrane surface. It was also observed that the peptides were able to restore the original tensile strength of bleached hair. Consequently, the knowledge of hair surface properties is of extreme importance when designing peptides directed for hair treatment.

Detecting negative ions on board small satellites

NASA Astrophysics Data System (ADS)

Lepri, S. T.; Raines, J. M.; Gilbert, J. A.; Cutler, J.; Panning, M.; Zurbuchen, T. H.

2017-04-01

Recent measurements near comets, planets, and their satellites have shown that heavy ions, energetic neutral atoms, molecular ions, and charged dust contain a wealth of information about the origin, evolution, and interaction of celestial bodies with their space environment. Using highly sensitive plasma instruments, positively charged heavy ions have been used to trace exospheric and surface composition of comets, planets, and satellites as well as the composition of interplanetary and interstellar dust. While positive ions dominate throughout the heliosphere, negative ions are also produced from surface interactions. In fact, laboratory experiments have shown that oxygen released from rocky surfaces is mostly negatively charged. Negative ions and negatively charged nanograins have been detected with plasma electron analyzers in several different environments (e.g., by Cassini and Rosetta), though more extensive studies have been challenging without instrumentation dedicated to negative ions. We discuss an adaptation of the Fast Imaging Plasma Spectrometer (FIPS) flown on MErcury Surface, Space ENvironment, GEochemistry and Ranging (MESSENGER) for the measurement of negatively charged particles. MESSENGER/FIPS successfully measured the plasma environment of Mercury from 2011 until 2015, when the mission ended, and has been used to map multiple ion species (H+ through Na+ and beyond) throughout Mercury's space environment. Modifications to the existing instrument design fits within a 3U CubeSat volume and would provide a low mass, low power instrument, ideal for future CubeSat or distributed sensor missions seeking, for the first time, to characterize the contribution of negative particles in the heliospheric plasmas near the planets, moons, comets, and other sources.

Bactericidal activity of partially oxidized nanodiamonds.

PubMed

Wehling, Julia; Dringen, Ralf; Zare, Richard N; Maas, Michael; Rezwan, Kurosch

2014-06-24

Nanodiamonds are a class of carbon-based nanoparticles that are rapidly gaining attention, particularly for biomedical applications, i.e., as drug carriers, for bioimaging, or as implant coatings. Nanodiamonds have generally been considered biocompatible with a broad variety of eukaryotic cells. We show that, depending on their surface composition, nanodiamonds kill Gram-positive and -negative bacteria rapidly and efficiently. We investigated six different types of nanodiamonds exhibiting diverse oxygen-containing surface groups that were created using standard pretreatment methods for forming nanodiamond dispersions. Our experiments suggest that the antibacterial activity of nanodiamond is linked to the presence of partially oxidized and negatively charged surfaces, specifically those containing acid anhydride groups. Furthermore, proteins were found to control the bactericidal properties of nanodiamonds by covering these surface groups, which explains the previously reported biocompatibility of nanodiamonds. Our findings describe the discovery of an exciting property of partially oxidized nanodiamonds as a potent antibacterial agent.

Modulating the line shape of magnetoconductance by varying the charge injection in polymer light-emitting diodes

NASA Astrophysics Data System (ADS)

Chitraningrum, Nidya; Chu, Ting-Yi; Huang, Ping-Tsung; Wen, Ten-Chin; Guo, Tzung-Fang

2018-02-01

We fabricate the phenyl-substituted poly(p-phenylene vinylene) copolymer (super yellow, SY-PPV)-based polymer light-emitting diodes (PLEDs) with different device architectures to modulate the injection of opposite charge carriers and investigate the corresponding magnetoconductance (MC) responses. At the first glance, we find that all PLEDs exhibit the positive MC responses. By applying the mathematical analysis to fit the curves with two empirical equations of a non-Lorentzian and a Lorentzian function, we are able to extract the hidden negative MC component from the positive MC curve. We attribute the growth of the negative MC component to the reduced interaction of the triplet excitons with charges to generate the free charge carriers as modulated by the applied magnetic field, known as the triplet exciton-charge reaction, by analyzing MC responses for PLEDs of the charge-unbalanced and hole-blocking device configurations. The negative MC component causes the broadening of the line shape in MC curves.

Novel synthetic analogues of avian β-defensin-12: the role of charge, hydrophobicity, and disulfide bridges in biological functions.

PubMed

Yang, Ming; Zhang, Chunye; Zhang, Michael Z; Zhang, Shuping

2017-02-23

Avian β-defensins (AvBD) possess broad-spectrum antimicrobial, LPS neutralizing and chemotactic properties. AvBD-12 is a chemoattractant for avian immune cells and mammalian dendritic cells (JAWSII) - a unique feature that is relevant to the applications of AvBDs as chemotherapeutic agents in mammalian hosts. To identify the structural components essential to various biological functions, we have designed and evaluated seven AvBD analogues. In the first group of analogues, the three conserved disulfide bridges were eliminated by replacing cysteines with alanine and serine residues, peptide hydrophobicity and charge were increased by changing negatively charged amino acid residues to hydrophobic (AvBD-12A1) or positively charged residues (AvBD-12A2 and AvBD-12A3). All three analogues in this group showed improved antimicrobial activity, though AvBD-12A3, with a net positive charge of +9, hydrophobicity of 40% and a predicted CCR2 binding domain, was the most potent antimicrobial peptide. AvBD-12A3 also retained more than 50% of wild type chemotactic activity. In the second group of analogues (AvBD-12A4 to AvBD-12A6), one to three disulfide bridges were removed via substitution of cysteines with isosteric amino acids. Their antimicrobial activity was compromised and chemotactic activity abolished. The third type of analogue was a hybrid that had the backbone of AvBD-12 and positively charged amino acid residues AvBD-6. The antimicrobial and chemotactic activities of the hybrid resembled that of AvBD-6 and AvBD-12, respectively. While the net positive charge and charge distribution have a dominating effect on the antimicrobial potency of AvBDs, the three conserved disulfide bridges are essential to the chemotactic property and the maximum antimicrobial activity. Analogue AvBD-12A3 with a high net positive charge, a moderate degree of hydrophobicity and a CCR2-binding domain can serve as a template for the design of novel antimicrobial peptides with chemotactic property and salt resistance.

pH-dependence of pesticide adsorption by wheat-residue-derived black carbon.

PubMed

Yang, Yaning; Chun, Yuan; Sheng, Guangyao; Huang, Minsheng

2004-08-03

The potential of black carbon as an adsorbent for pesticides in soils may be strongly influenced by the properties of the adsorbent and pesticides and by the environmental conditions. This study evaluated the effect of pH on the adsorption of diuron, bromoxynil, and ametryne by a wheat (Triticum aestivum L.) residue derived black carbon (WC) as compared to a commercial activated carbon (AC). The pH drift method indicated that WC had a point of zero charge of 4.2, much lower than that of 7.8 for AC. The density of oxygen-containing surface functional groups, measured by the Boehm titration, on WC was 5.4 times higher than that on AC, resulting in a pesticide adsorption by WC being 30-50% of that by AC, due to the blockage of WC surface by the waters associated with the functional groups. A small decrease (5.5%/unit pH) in diuron adsorption by WC with increase in pH resulted from increased deprotonation of surface functional groups at higher pH values. A much larger decrease (14-21%/unit pH) in bromoxynil adsorption by WC with increase in pH resulted from the deprotonation of both the adsorbate and surface functional groups of the adsorbent. The deprotonation reduced the adsorptive interaction between bromoxynil and the neutral carbon surface and increased the electrical repulsion between the negatively charged WC surface and bromoxynil anions. Deprotonation of ametryne with increase in pH over the low pH range increased its fraction of molecular form and thus adsorption on WC by 15%/unit pH. Further increase in pH resulted in a 20%/unit pH decrease in ametryne adsorption by WC due primarily to the development of a negative charge on the surface of WC. The pH-dependent adsorption of pesticides by black carbon may significantly influence their environmental fate in soils.

Negative charge emission due to excimer laser bombardment of sodium trisilicate glass

NASA Astrophysics Data System (ADS)

Langford, S. C.; Jensen, L. C.; Dickinson, J. T.; Pederson, L. R.

1990-10-01

We describe measurements of negative charge emission accompanying irradiation of sodium trisilicate glass (Na2Oṡ3SiO2) with 248-nm excimer laser light at fluences on the order of 2 J/cm2 per pulse, i.e., at the threshold for ablative etching of the glass surface. The negative charge emission consists of a very prompt photoelectron burst coincident with the laser pulse, followed by a much slower plume of electrons and negative ions traveling with a high density cloud of positive ions, previously identified as primarily Na+. Using combinations of E and B fields in conjunction with time-of-flight methods, the negative ions were successfully separated from the plume and tentatively identified as O-, Si-, NaO-, and perhaps NaSi-. These negative species are probably formed by gas phase collisions in the near-surface region which result in electron attachment.

Negatively Charged Lipid Membranes Promote a Disorder-Order Transition in the Yersinia YscU Protein

PubMed Central

Weise, Christoph F.; Login, Frédéric H.; Ho, Oanh; Gröbner, Gerhard; Wolf-Watz, Hans; Wolf-Watz, Magnus

2014-01-01

The inner membrane of Gram-negative bacteria is negatively charged, rendering positively charged cytoplasmic proteins in close proximity likely candidates for protein-membrane interactions. YscU is a Yersinia pseudotuberculosis type III secretion system protein crucial for bacterial pathogenesis. The protein contains a highly conserved positively charged linker sequence that separates membrane-spanning and cytoplasmic (YscUC) domains. Although disordered in solution, inspection of the primary sequence of the linker reveals that positively charged residues are separated with a typical helical periodicity. Here, we demonstrate that the linker sequence of YscU undergoes a largely electrostatically driven coil-to-helix transition upon binding to negatively charged membrane interfaces. Using membrane-mimicking sodium dodecyl sulfate micelles, an NMR derived structural model reveals the induction of three helical segments in the linker. The overall linker placement in sodium dodecyl sulfate micelles was identified by NMR experiments including paramagnetic relaxation enhancements. Partitioning of individual residues agrees with their hydrophobicity and supports an interfacial positioning of the helices. Replacement of positively charged linker residues with alanine resulted in YscUC variants displaying attenuated membrane-binding affinities, suggesting that the membrane interaction depends on positive charges within the linker. In vivo experiments with bacteria expressing these YscU replacements resulted in phenotypes displaying significantly reduced effector protein secretion levels. Taken together, our data identify a previously unknown membrane-interacting surface of YscUC that, when perturbed by mutations, disrupts the function of the pathogenic machinery in Yersinia. PMID:25418176

Negatively charged lipid membranes promote a disorder-order transition in the Yersinia YscU protein.

PubMed

Weise, Christoph F; Login, Frédéric H; Ho, Oanh; Gröbner, Gerhard; Wolf-Watz, Hans; Wolf-Watz, Magnus

2014-10-21

The inner membrane of Gram-negative bacteria is negatively charged, rendering positively charged cytoplasmic proteins in close proximity likely candidates for protein-membrane interactions. YscU is a Yersinia pseudotuberculosis type III secretion system protein crucial for bacterial pathogenesis. The protein contains a highly conserved positively charged linker sequence that separates membrane-spanning and cytoplasmic (YscUC) domains. Although disordered in solution, inspection of the primary sequence of the linker reveals that positively charged residues are separated with a typical helical periodicity. Here, we demonstrate that the linker sequence of YscU undergoes a largely electrostatically driven coil-to-helix transition upon binding to negatively charged membrane interfaces. Using membrane-mimicking sodium dodecyl sulfate micelles, an NMR derived structural model reveals the induction of three helical segments in the linker. The overall linker placement in sodium dodecyl sulfate micelles was identified by NMR experiments including paramagnetic relaxation enhancements. Partitioning of individual residues agrees with their hydrophobicity and supports an interfacial positioning of the helices. Replacement of positively charged linker residues with alanine resulted in YscUC variants displaying attenuated membrane-binding affinities, suggesting that the membrane interaction depends on positive charges within the linker. In vivo experiments with bacteria expressing these YscU replacements resulted in phenotypes displaying significantly reduced effector protein secretion levels. Taken together, our data identify a previously unknown membrane-interacting surface of YscUC that, when perturbed by mutations, disrupts the function of the pathogenic machinery in Yersinia.

Instrumentation for Studies of Electron Emission and Charging From Insulators

NASA Technical Reports Server (NTRS)

Thomson, C. D.; Zavyalov, V.; Dennison, J. R.

2004-01-01

Making measurements of electron emission properties of insulators is difficult since insulators can charge either negatively or positively under charge particle bombardment. In addition, high incident energies or high fluences can result in modification of a material s conductivity, bulk and surface charge profile, structural makeup through bond breaking and defect creation, and emission properties. We discuss here some of the charging difficulties associated with making insulator-yield measurements and review the methods used in previous studies of electron emission from insulators. We present work undertaken by our group to make consistent and accurate measurements of the electron/ion yield properties for numerous thin-film and thick insulator materials using innovative instrumentation and techniques. We also summarize some of the necessary instrumentation developed for this purpose including fast response, low-noise, high-sensitivity ammeters; signal isolation and interface to standard computer data acquisition apparatus using opto-isolation, sample-and-hold, and boxcar integration techniques; computer control, automation and timing using Labview software; a multiple sample carousel; a pulsed, compact, low-energy, charge neutralization electron flood gun; and pulsed visible and UV light neutralization sources. This work is supported through funding from the NASA Space Environments and Effects Program and the NASA Graduate Research Fellowship Program.

Coacervates of lactotransferrin and β- or κ-casein: structure determined using SAXS.

PubMed

de Kruif, C G Kees; Pedersen, JanSkov; Huppertz, Thom; Anema, Skelte G

2013-08-20

Lactotransferrin (LF) is a large globular protein in milk with immune-regulatory and bactericidal properties. At pH 6.5, LF (M = 78 kDa) carries a net (calculated) charge of +21. β-Casein (BCN) and κ-casein (KCN) are part of the casein micelle complex in milk. Both BCN and KCN are amphiphillic proteins with a molar mass of 24 and 19 kDa and carry net charges of -14 and -4, respectively. Both BCN and KCN form soap-like micelles, with 40 and 65 monomers, respectively. The net negative charges are located in the corona of the micelles. On mixing LF with the caseins, coacervates are formed. We analyzed the structure of these coarcervates using SAXS. It was found that LF binds to the corona of the micellar structures, at the charge neutrality point. BCN/LF and KCN/LF ratios at the charge neutrality point were found to be ~1.2 and ~5, respectively. We think that the findings are relevant for the protection mechanism of globular proteins in bodily fluids where unstructured proteins are abundant (saliva). The complexes will prevent docking of enzymes on specific charged groups on the globular protein.

Effects of Particle Hydrophobicity, Surface Charge, Media pH Value and Complexation with Human Serum Albumin on Drug Release Behavior of Mitoxantrone-Loaded Pullulan Nanoparticles

PubMed Central

Tao, Xiaojun; Jin, Shu; Wu, Dehong; Ling, Kai; Yuan, Liming; Lin, Pingfa; Xie, Yongchao; Yang, Xiaoping

2015-01-01

We prepared two types of cholesterol hydrophobically modified pullulan nanoparticles (CHP) and carboxyethyl hydrophobically modified pullulan nanoparticles (CHCP) substituted with various degrees of cholesterol, including 3.11, 6.03, 6.91 and 3.46 per polymer, and named CHP−3.11, CHP−6.03, CHP−6.91 and CHCP−3.46. Dynamic laser light scattering (DLS) showed that the pullulan nanoparticles were 80–120 nm depending on the degree of cholesterol substitution. The mean size of CHCP nanoparticles was about 160 nm, with zeta potential −19.9 mV, larger than CHP because of the carboxyethyl group. A greater degree of cholesterol substitution conferred greater nanoparticle hydrophobicity. Drug-loading efficiency depended on nanoparticle hydrophobicity, that is, nanoparticles with the greatest degree of cholesterol substitution (6.91) showed the most drug encapsulation efficiency (90.2%). The amount of drug loading increased and that of drug release decreased with enhanced nanoparticle hydrophobicity. Nanoparticle surface-negative charge disturbed the amount of drug loading and drug release, for an opposite effect relative to nanoparticle hydrophobicity. The drug release in pullulan nanoparticles was higher pH 4.0 than pH 6.8 media. However, the changed drug release amount was not larger for negative-surface nanoparticles than CHP nanoparticles in the acid release media. Drug release of pullulan nanoparticles was further slowed with human serum albumin complexation and was little affected by nanoparticle hydrophobicity and surface negative charge. PMID:28344259

Some modification of cellulose nanocrystals for functional Pickering emulsions

PubMed Central

Saidane, Dorra; Perrin, Emilie; Cherhal, Fanch; Guellec, Florian

2016-01-01

Cellulose nanocrystals (CNCs) are negatively charged colloidal particles well known to form highly stable surfactant-free Pickering emulsions. These particles can vary in surface charge density depending on their preparation by acid hydrolysis or applying post-treatments. CNCs with three different surface charge densities were prepared corresponding to 0.08, 0.16 and 0.64 e nm−2, respectively. Post-treatment might also increase the surface charge density. The well-known TEMPO-mediated oxidation substitutes C6-hydroxyl groups by C6-carboxyl groups on the surface. We report that these different modified CNCs lead to stable oil-in-water emulsions. TEMPO-oxidized CNC might be the basis of further modifications. It is shown that they can, for example, lead to hydrophobic CNCs with a simple method using quaternary ammonium salts that allow producing inverse water-in-oil emulsions. Different from CNC modification before emulsification, modification can be carried out on the droplets after emulsification. This way allows preparing functional capsules according to the layer-by-layer process. As a result, it is demonstrated here the large range of use of these biobased rod-like nanoparticles, extending therefore their potential use to highly sophisticated formulations. This article is part of the themed issue ‘Soft interfacial materials: from fundamentals to formulation’. PMID:27298429

Nonequilibrium Kondo effect by the equilibrium numerical renormalization group method: The hybrid Anderson model subject to a finite spin bias

NASA Astrophysics Data System (ADS)

Fang, Tie-Feng; Guo, Ai-Min; Sun, Qing-Feng

2018-06-01

We investigate Kondo correlations in a quantum dot with normal and superconducting electrodes, where a spin bias voltage is applied across the device and the local interaction U is either attractive or repulsive. When the spin current is blockaded in the large-gap regime, this nonequilibrium strongly correlated problem maps into an equilibrium model solvable by the numerical renormalization group method. The Kondo spectra with characteristic splitting due to the nonequilibrium spin accumulation are thus obtained at high precision. It is shown that while the bias-induced decoherence of the spin Kondo effect is partially compensated by the superconductivity, the charge Kondo effect is enhanced out of equilibrium and undergoes an additional splitting by the superconducting proximity effect, yielding four Kondo peaks in the local spectral density. In the charge Kondo regime, we find a universal scaling of charge conductance in this hybrid device under different spin biases. The universal conductance as a function of the coupling to the superconducting lead is peaked at and hence directly measures the Kondo temperature. Our results are of direct relevance to recent experiments realizing a negative-U charge Kondo effect in hybrid oxide quantum dots [Nat. Commun. 8, 395 (2017), 10.1038/s41467-017-00495-7].

Establishment of a Charge Reversal Derivatization Strategy to Improve the Ionization Efficiency of Limaprost and Investigation of the Fragmentation Patterns of Limaprost Derivatives Via Exclusive Neutral Loss and Survival Yield Method

NASA Astrophysics Data System (ADS)

Sun, Dong; Meng, Xiangjun; Ren, Tianming; Fawcett, John Paul; Wang, Hualu; Gu, Jingkai

2018-04-01

Sensitivity is generally an issue in bioassays of prostaglandins and their synthetic analogs due to their extremely low concentration in vivo. To improve the ionization efficiency of limaprost, an oral prostaglandin E1 (PGE1) synthetic analog, we investigated a charge reversal derivatization strategy in electrospray ionization mass spectrometry (ESI-MS). We established that the cholamine derivative exhibits much greater signal intensity in the positive-ion mode compared with limaprost in the negative ion mode. Collision-induced dissociation (CID) involved exclusive neutral mass loss and positive charge migration to form stable cationic product ions with the positive charge on the limaprost residue rather than on the modifying group. This has the effect of maintaining the efficiency and specificity of multiple reaction monitoring (MRM) and avoiding cross talk. CID fragmentation patterns of other limaprost derivatives allowed us to relate the dissociation tendency of different neutral leaving groups to an internal energy distribution scale based on the survival yield method. Knowledge of the energy involved in the production of stabilized positive ions will potentially assist the selection of suitable derivatization reagents for the analysis of a wide variety of lipid acids. [Figure not available: see fulltext.

Influences of Probe’s Morphology for Metal Ion Detection Based on Light-Addressable Potentiometric Sensors

PubMed Central

Shao, Chen; Zhou, Shuang; Yin, Xuebo; Gu, Yajun; Jia, Yunfang

2016-01-01

The sensing mechanism of binding Hg2+ into thymine-thymine (T-T) mismatched base pairs was introduced into a light-addressable potentiometric sensor (LAPS) with anti-Hg2+ aptamer as the sensing units. Three kinds of T-rich single-strand DNA (ssDNA) chains with different spacer lengths, from 0 to 12 –CH2 groups, were designed to investigate surface charge and morphological effects on the LAPS’ output. First, by comparing the responding of LAPS modified with three kinds of ssDNA, it was found that the best performance for Hg2+ sensing was exhibited by the probe without –CH2 groups. The detection limit of Hg2+ ion was 1 ppt under the optimal condition. Second, the cooperative effects of surface charge and morphology on the output were observed by the controlled experiments. The two effects were the negative charge balanced by metal cations and the morphological changing caused by the formation of T-Hg2+-T structure. In conclusion, not only the influences of the aptamer probe’s morphology and surface charge was investigated on the platform of LAPS, but also sensing Hg2+ ions was achieved for the first time by the presented aptamer LAPS. PMID:27187412

Tandem mass spectrometry characteristics of polyester anions and cations formed by electrospray ionization.

PubMed

Arnould, Mark A; Buehner, Rita W; Wesdemiotis, Chrys; Vargas, Rafael

2005-01-01

Electrospray ionization of polyesters composed of isophthalic acid and neopentyl glycol produces carboxylate anions in negative mode and mainly sodium ion adducts in positive mode. A tandem mass spectrometry (MS/MS) study of these ions in a quadrupole ion trap shows that the collisionally activated dissociation pathways of the anions are simpler than those of the corresponding cations. Charge-remote fragmentations predominate in both cases, but the spectra obtained in negative mode are devoid of the complicating cation exchange observed in positive mode. MS/MS of the Na(+) adducts gives rise to a greater number of fragments but not necessarily more structural information. In either positive or negative mode, polyester oligomers with different end groups fragment by similar mechanisms. The observed fragments are consistent with rearrangements initiated by the end groups. Single-stage ESI mass spectra also are more complex in positive mode because of extensive H/Na substitutions; this is also true for matrix-assisted laser desorption ionization (MALDI) mass spectra. Hence, formation and analysis of anions might be the method of choice for determining block length, end group structure and copolymer sequence, provided the polyester contains at least one carboxylic acid end group that is ionizable to anions.

Protein corona affects the relaxivity and MRI contrast efficiency of magnetic nanoparticles

NASA Astrophysics Data System (ADS)

Amiri, Houshang; Bordonali, Lorenzo; Lascialfari, Alessandro; Wan, Sha; Monopoli, Marco P.; Lynch, Iseult; Laurent, Sophie; Mahmoudi, Morteza

2013-08-01

Magnetic nanoparticles (NPs) are increasingly being considered for use in biomedical applications such as biosensors, imaging contrast agents and drug delivery vehicles. In a biological fluid, proteins associate in a preferential manner with NPs. The small sizes and high curvature angles of NPs influence the types and amounts of proteins present on their surfaces. This differential display of proteins bound to the surface of NPs can influence the tissue distribution, cellular uptake and biological effects of NPs. To date, the effects of adsorption of a protein corona (PC) on the magnetic properties of NPs have not been considered, despite the fact that some of their potential applications require their use in human blood. Here, to investigate the effects of a PC (using fetal bovine serum) on the MRI contrast efficiency of superparamagnetic iron oxide NPs (SPIONs), we have synthesized two series of SPIONs with variation in the thickness and functional groups (i.e. surface charges) of the dextran surface coating. We have observed that different physico-chemical characteristics of the dextran coatings on the SPIONs lead to the formation of PCs of different compositions. 1H relaxometry was used to obtain the longitudinal, r1, and transverse, r2, relaxivities of the SPIONs without and with a PC, as a function of the Larmor frequency. The transverse relaxivity, which determines the efficiency of negative contrast agents (CAs), is very much dependent on the functional group and the surface charge of the SPIONs' coating. The presence of the PC did not alter the relaxivity of plain SPIONs, while it slightly increased the relaxivity of the negatively charged SPIONs and dramatically decreased the relaxivity of the positively charged ones, which was coupled with particle agglomeration in the presence of the proteins. To confirm the effect of the PC on the MRI contrast efficiency, in vitro MRI experiments at ν = 8.5 MHz were performed using a low-field MRI scanner. The MRI contrasts, produced by different samples, were fully in agreement with the relaxometry findings.Magnetic nanoparticles (NPs) are increasingly being considered for use in biomedical applications such as biosensors, imaging contrast agents and drug delivery vehicles. In a biological fluid, proteins associate in a preferential manner with NPs. The small sizes and high curvature angles of NPs influence the types and amounts of proteins present on their surfaces. This differential display of proteins bound to the surface of NPs can influence the tissue distribution, cellular uptake and biological effects of NPs. To date, the effects of adsorption of a protein corona (PC) on the magnetic properties of NPs have not been considered, despite the fact that some of their potential applications require their use in human blood. Here, to investigate the effects of a PC (using fetal bovine serum) on the MRI contrast efficiency of superparamagnetic iron oxide NPs (SPIONs), we have synthesized two series of SPIONs with variation in the thickness and functional groups (i.e. surface charges) of the dextran surface coating. We have observed that different physico-chemical characteristics of the dextran coatings on the SPIONs lead to the formation of PCs of different compositions. 1H relaxometry was used to obtain the longitudinal, r1, and transverse, r2, relaxivities of the SPIONs without and with a PC, as a function of the Larmor frequency. The transverse relaxivity, which determines the efficiency of negative contrast agents (CAs), is very much dependent on the functional group and the surface charge of the SPIONs' coating. The presence of the PC did not alter the relaxivity of plain SPIONs, while it slightly increased the relaxivity of the negatively charged SPIONs and dramatically decreased the relaxivity of the positively charged ones, which was coupled with particle agglomeration in the presence of the proteins. To confirm the effect of the PC on the MRI contrast efficiency, in vitro MRI experiments at ν = 8.5 MHz were performed using a low-field MRI scanner. The MRI contrasts, produced by different samples, were fully in agreement with the relaxometry findings. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr00345k

Sialoglycoproteins in morphological distinct stages of Mucor polymorphosporus and their influence on phagocytosis by human blood phagocytes.

PubMed

Almeida, Catia Amancio; de Campos-Takaki, Galba Maria; Portela, Maristela Barbosa; Travassos, Luiz R; Alviano, Celuta Sales; Alviano, Daniela Sales

2013-10-01

The possible role of sialic acids in host cells-fungi interaction and their association with glycoproteins were evaluated using a clinical isolate of the dimorphic fungus Mucor polymorphosporus. Lectin-binding assays with spores and yeast cells denoted the presence of surface sialoglycoconjugates containing 2,3- and 2,6-linked sialylglycosyl groups. Western blotting with peroxidase-labeled Limulus polyphemus agglutinin revealed the occurrence of different sialoglycoprotein types in both cell lysates and cell wall protein extracts of mycelia, spores, and yeasts of M. polymorphosporus. Sialic acids contributed to the surface negative charge of spores and yeast forms as evaluated by adherence to a cationic substrate. Sialidase-treated spores were less resistant to phagocytosis by human neutrophils and monocytes from healthy individuals than control (untreated) fungal suspensions. The results suggest that sialic acids are terminal units of various glycoproteins of M. polymorphosporus, contributing to negative charge of yeasts and spore cells and protecting infectious propagules from destruction by host cells.

Kinetic stability and membrane structure of liposomes during in vitro infant intestinal digestion: Effect of cholesterol and lactoferrin.

PubMed

Liu, Weilin; Wei, Fuqiang; Ye, Aiqian; Tian, Mengmeng; Han, Jianzhong

2017-09-01

The effects of cholesterol and lactoferrin on the kinetic stability and membrane structural integrity of negatively charged liposomes under in vitro infant intestinal digestion conditions were elucidated using dynamic light scattering, pH-stat titration, Fourier transform infrared spectroscopy, and pyrene steady state fluorescence probes. The liposomes had a smaller particle diameter, a wider size distribution, and a greater negative charge after digestion. The incorporation of cholesterol into the phospholipid bilayers resulted in a more ordered conformation in the aliphatic tail region and reduced micropolarity, indicating that cholesterol can improve the structural stability of liposomal membranes against intestinal environmental stress. Lactoferrin coverage facilitated the release of free fatty acids and increased the microfluidity of the bilayers, reducing the structural integrity of the liposomes. This study provides useful information on the design of liposomes and other microcapsules with improved and controlled release properties during digestion for particular groups of people. Copyright © 2017 Elsevier Ltd. All rights reserved.

Protein Charge and Mass Contribute to the Spatio-temporal Dynamics of Protein-Protein Interactions in a Minimal Proteome

PubMed Central

Xu, Yu; Wang, Hong; Nussinov, Ruth; Ma, Buyong

2013-01-01

We constructed and simulated a ‘minimal proteome’ model using Langevin dynamics. It contains 206 essential protein types which were compiled from the literature. For comparison, we generated six proteomes with randomized concentrations. We found that the net charges and molecular weights of the proteins in the minimal genome are not random. The net charge of a protein decreases linearly with molecular weight, with small proteins being mostly positively charged and large proteins negatively charged. The protein copy numbers in the minimal genome have the tendency to maximize the number of protein-protein interactions in the network. Negatively charged proteins which tend to have larger sizes can provide large collision cross-section allowing them to interact with other proteins; on the other hand, the smaller positively charged proteins could have higher diffusion speed and are more likely to collide with other proteins. Proteomes with random charge/mass populations form less stable clusters than those with experimental protein copy numbers. Our study suggests that ‘proper’ populations of negatively and positively charged proteins are important for maintaining a protein-protein interaction network in a proteome. It is interesting to note that the minimal genome model based on the charge and mass of E. Coli may have a larger protein-protein interaction network than that based on the lower organism M. pneumoniae. PMID:23420643

An analytic expression for the sheath criterion in magnetized plasmas with multi-charged ion species

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

Hatami, M. M., E-mail: m-hatami@kntu.ac.ir

2015-04-15

The generalized Bohm criterion in magnetized multi-component plasmas consisting of multi-charged positive and negative ion species and electrons is analytically investigated by using the hydrodynamic model. It is assumed that the electrons and negative ion density distributions are the Boltzmann distribution with different temperatures and the positive ions enter into the sheath region obliquely. Our results show that the positive and negative ion temperatures, the orientation of the applied magnetic field and the charge number of positive and negative ions strongly affect the Bohm criterion in these multi-component plasmas. To determine the validity of our derived generalized Bohm criterion, itmore » reduced to some familiar physical condition and it is shown that monotonically reduction of the positive ion density distribution leading to the sheath formation occurs only when entrance velocity of ion into the sheath satisfies the obtained Bohm criterion. Also, as a practical application of the obtained Bohm criterion, effects of the ionic temperature and concentration as well as magnetic field on the behavior of the charged particle density distributions and so the sheath thickness of a magnetized plasma consisting of electrons and singly charged positive and negative ion species are studied numerically.« less

Preparation of poly(β-L-malic acid)-based charge-conversional nanoconjugates for tumor-specific uptake and cellular delivery.

PubMed

Zhou, Qing; Yang, Tiehong; Qiao, Youbei; Guo, Songyan; Zhu, Lin; Wu, Hong

2015-01-01

In this study, a multifunctional poly(β-L-malic acid)-based nanoconjugate with a pH-dependent charge conversional characteristic was developed for tumor-specific drug delivery. The short branched polyethylenimine-modified poly(β-L-malic acid) (PEPM) was first synthesized. Then, the fragment HAb18 F(ab')2 and 2,3-dimethylmaleic anhydride were covalently attached to the PEPM to form the nanoconjugate, HDPEPM. In this nanoconjugate, the 2,3-dimethylmaleic anhydride, the shielding group, could shield the positive charge of the conjugate at pH 7.4, while it was selectively hydrolyzed in the tumor extracellular space (pH 6.8) to expose the previously-shielded positive charge. To study the anticancer activity, the anticancer drug, doxorubicin, was covalently attached to the nanoconjugate. The doxorubicin-loaded HDPEPM nanoconjugate was able to efficiently undergo a quick charge conversion from -11.62 mV to 9.04 mV in response to the tumor extracellular pH. The electrostatic interaction between the positively charged HDPEPM nanoconjugates and the negatively charged cell membrane significantly enhanced their cellular uptake, resulting in the enhanced anticancer activity. Also, the tumor targetability of the nanoconjugates could be further improved via the fragment HAb18 F(ab')2 ligand-receptor-mediated tumor cell-specific endocytosis.

Influence of the size and charge of gold nanoclusters on complexation with siRNA: a molecular dynamics simulation study.

PubMed

Mudedla, Sathish Kumar; Azhagiya Singam, Ettayapuram Ramaprasad; Balamurugan, Kanagasabai; Subramanian, Venkatesan

2015-11-11

The complexation of small interfering RNA (siRNA) with positively charged gold nanoclusters has been studied in the present investigation with the help of classical molecular dynamics and steered molecular dynamics simulations accompanied by free energy calculations. The results show that gold nanoclusters form a stable complex with siRNA. The wrapping of siRNA around the gold nanocluster depends on the size and charge on the surface of the gold cluster. The binding pattern of the gold nanocluster with siRNA is also influenced by the presence of another cluster. The interaction between the positively charged amines in the gold nanocluster and the negatively charged phosphate group in the siRNA is responsible for the formation of complexes. The binding free energy value increases with the size of the gold cluster and the number of positive charges present on the surface of the gold nanocluster. The results reveal that the binding energy of small gold nanoclusters increases in the presence of another gold nanocluster while the binding of large gold nanoclusters decreases due to the introduction of another gold nanocluster. Overall, the findings have clearly demonstrated the effect of size and charge of gold nanoclusters on their interaction pattern with siRNA.

Synthesis and Characterization of Positively Charged Pentacationic [60]Fullerene Monoadducts for Antimicrobial Photodynamic Inactivation

PubMed Central

Thota, Sammaiah; Wang, Min; Jeon, Seaho; Maragani, Satyanarayana; Hamblin, Michael R.; Chiang, Long Y.

2012-01-01

We designed and synthesized two analogous pentacationic [60]fullerenyl monoadducts, C60(>ME1N6+C3) (1) and C60(>ME3N6+C3) (2), with variation of the methoxyethyleneglycol length. Each of these derivatives bears a well-defined number of cationic charges aimed to enhance and control their ability to target pathogenic Gram-positive and Gram-negative bacterial cells for allowing photodynamic inactivation. The synthesis was achieved by the use of a common synthon of pentacationic N,N’,N,N,N,N-hexapropyl-hexa(aminoethyl)amine arm (C3N6+) having six attached propyl groups, instead of methyl or ethyl groups, to provide a well-balanced hydrophobicity–hydrophilicity character of pentacationic precursor intermediates and better compatibility with the highly hydrophobic C60 cage moiety. We demonstrated two plausible synthetic routes for the preparation of 1 and 2 with the product characterization via various spectroscopic methods. PMID:22565476

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.

Water-soluble fullerene (C60) derivatives as nonviral gene-delivery vectors.

PubMed

Sitharaman, Balaji; Zakharian, Tatiana Y; Saraf, Anita; Misra, Preeti; Ashcroft, Jared; Pan, Su; Pham, Quynh P; Mikos, Antonios G; Wilson, Lon J; Engler, David A

2008-01-01

A new class of water-soluble C60 transfecting agents has been prepared using Hirsch-Bingel chemistry and assessed for their ability to act as gene-delivery vectors in vitro. In an effort to elucidate the relationship between the hydrophobicity of the fullerene core, the hydrophilicity of the water-solubilizing groups, and the overall charge state of the C60 vectors in gene delivery and expression, several different C60 derivatives were synthesized to yield either positively charged, negatively charged, or neutral chemical functionalities under physiological conditions. These fullerene derivatives were then tested for their ability to transfect cells grown in culture with DNA carrying the green fluorescent protein (GFP) reporter gene. Statistically significant expression of GFP was observed for all forms of the C60 derivatives when used as DNA vectors and compared to the ability of naked DNA alone to transfect cells. However, efficient in vitro transfection was only achieved with the two positively charged C60 derivatives, namely, an octa-amino derivatized C60 and a dodeca-amino derivatized C60 vector. All C60 vectors showed an increase in toxicity in a dose-dependent manner. Increased levels of cellular toxicity were observed for positively charged C60 vectors relative to the negatively charged and neutral vectors. Structural analyses using dynamic light scattering and optical microscopy offered further insights into possible correlations between the various derivatized C60 compounds, the C60 vector/DNA complexes, their physical attributes (aggregation, charge) and their transfection efficiencies. Recently, similar Gd@C60-based compounds have demonstrated potential as advanced contrast agents for magnetic resonance imaging (MRI). Thus, the successful demonstration of intracellular DNA uptake, intracellular transport, and gene expression from DNA using C60 vectors suggests the possibility of developing analogous Gd@C60-based vectors to serve simultaneously as both therapeutic and diagnostic agents.

Electron Emission Properties of Insulator Materials Pertinent to the International Space Station

NASA Technical Reports Server (NTRS)

Thomson, C. D.; Zavyalov, V.; Dennison, J. R.; Corbridge, Jodie

2004-01-01

We present the results of our measurements of the electron emission properties of selected insulating and conducting materials used on the International Space Station (ISS). Utah State University (USU) has performed measurements of the electron-, ion-, and photon-induced electron emission properties of conductors for a few years, and has recently extended our capabilities to measure electron yields of insulators, allowing us to significantly expand current spacecraft material charging databases. These ISS materials data are used here to illustrate our various insulator measurement techniques that include: i) Studies of electron-induced secondary and backscattered electron yield curves using pulsed, low current electron beams to minimize deleterious affects of insulator charging. ii) Comparison of several methods used to determine the insulator 1st and 2nd crossover energies. These incident electron energies induce unity total yield at the transition between yields greater than and less than one with either negative or positive charging, respectively. The crossover energies are very important in determining both the polarity and magnitude of spacecraft surface potentials. iii) Evolution of electron emission energy spectra as a function of insulator charging used to determine the surface potential of insulators. iv) Surface potential evolution as a function of pulsed-electron fluence to determine how quickly insulators charge, and how this can affect subsequent electron yields. v) Critical incident electron energies resulting in electrical breakdown of insulator materials and the effect of breakdown on subsequent emission, charging and conduction. vi) Charge-neutralization techniques such as low-energy electron flooding and UV light irradiation to dissipate both positive and negative surface potentials during yield measurements. Specific ISS materials being tested at USU include chromic and sulfuric anodized aluminum, RTV-silicone solar array adhesives, solar cell cover glasses, Kapton, and gold. Further details of the USU testing facilities, the instrumentation used for insulator measurements, and the NASA/SEE Charge Collector materials database are provided in other Spacecraft Charging Conference presentations (Dennison, 2003b). The work presented was supported in part by the NASA Space Environments and Effects (SEE) Program, the Boeing Corporation, and a NASA Graduate Fellowship. Samples were supplied by Boeing, the Environmental Effects Group at Marshall Space Flight Center, and Sheldahl, Inc.

Hydrogels with Modulated Ionic Load for Mammalian Cell Harvesting with Reduced Bacterial Adhesion.

PubMed

Gallardo, Alberto; Martínez-Campos, Enrique; García, Carolina; Cortajarena, Aitziber L; Rodríguez-Hernández, Juan

2017-05-08

In this manuscript, we describe the fabrication of hydrogel supports for mammalian cell handling that can simultaneously prevent materials from microbial contamination and therefore allow storage in aqueous media. For that purpose, hydrogels based on the antifouling polymer polyvinylpyrrolidone (PVP) were functionalized with different ionic groups (anionic, cationic, or two types of zwitterions). In order to prevent bacterial adhesion in the long-term, we took advantage of the synergistic effect of inherently antifouling PVP and additional antifouling moieties incorporated within the hydrogel structure. We evaluated, in a separated series of experiments, both the capability of the materials to act as supports for the growth of mammalian cell monolayers for transplantation (using C-166-GFP endothelial cell line), as well their antifouling properties against Staphylococcus aureus, were studied. All of the hydrogels are structurally pseudodouble networks with high swelling (around 90%) and similar mechanical properties (in the low range for hydrogel materials with Young modulus below 1250 kPa). With some differences, all the charged hydrogels were capable of hosting mouse endothelial cell line C166-GFP to confluence, as well as a monolayer detachment and transplantation through simple mechanical agitation. On the contrary, the uncharged hydrogel was not capable to detach a full monolayer for transplantation. Bacterial adhesion and proliferation was highly sensitive to the functionality (type of charge and density). In particular, we evidenced that monomers bearing zwitterionic sulfobetaine groups, those negatively charged as well as "electro neutral" hydrogels fabricated from stoichiometric amounts of positive and negative units, exhibit excellent antifouling properties both at initial adhesion times and during longer periods up to 72 h.

Electronically conductive polymer binder for lithium-ion battery electrode

DOEpatents

Liu, Gao; Xun, Shidi; Battaglia, Vincent S.; Zheng, Honghe; Wu, Mingyan

2015-07-07

A family of carboxylic acid groups containing fluorene/fluorenon copolymers is disclosed as binders of silicon particles in the fabrication of negative electrodes for use with lithium ion batteries. Triethyleneoxide side chains provide improved adhesion to materials such as, graphite, silicon, silicon alloy, tin, tin alloy. These binders enable the use of silicon as an electrode material as they significantly improve the cycle-ability of silicon by preventing electrode degradation over time. In particular, these polymers, which become conductive on first charge, bind to the silicon particles of the electrode, are flexible so as to better accommodate the expansion and contraction of the electrode during charge/discharge, and being conductive promote the flow battery current.

Electronically conductive polymer binder for lithium-ion battery electrode

DOEpatents

Liu, Gao; Battaglia, Vincent S.; Park, Sang -Jae

2015-10-06

A family of carboxylic acid groups containing fluorene/fluorenon copolymers is disclosed as binders of silicon particles in the fabrication of negative electrodes for use with lithium ion batteries. Triethyleneoxide side chains provide improved adhesion to materials such as, graphite, silicon, silicon alloy, tin, tin alloy. These binders enable the use of silicon as an electrode material as they significantly improve the cycle-ability of silicon by preventing electrode degradation over time. In particular, these polymers, which become conductive on first charge, bind to the silicon particles of the electrode, are flexible so as to better accommodate the expansion and contraction of the electrode during charge/discharge, and being conductive promote the flow battery current.

Electronically conductive polymer binder for lithium-ion battery electrode

DOEpatents

Liu, Gao; Xun, Shidi; Battaglia, Vincent S.; Zheng, Honghe; Wu, Mingyan

2017-08-01

A family of carboxylic acid groups containing fluorene/fluorenon copolymers is disclosed as binders of silicon particles in the fabrication of negative electrodes for use with lithium ion batteries. Triethyleneoxide side chains provide improved adhesion to materials such as, graphite, silicon, silicon alloy, tin, tin alloy. These binders enable the use of silicon as an electrode material as they significantly improve the cycle-ability of silicon by preventing electrode degradation over time. In particular, these polymers, which become conductive on first charge, bind to the silicon particles of the electrode, are flexible so as to better accommodate the expansion and contraction of the electrode during charge/discharge, and being conductive promote the flow battery current.

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

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.

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.

Rational Design of Multilayer Collagen Nanosheets with Compositional and Structural Control.

PubMed

Jiang, Tao; Vail, Owen A; Jiang, Zhigang; Zuo, Xiaobing; Conticello, Vincent P

2015-06-24

Two collagen-mimetic peptides, CP(+) and CP(-), are reported in which the sequences comprise a multiblock architecture having positively charged N-terminal (Pro-Arg-Gly)3 and negatively charged C-terminal (Glu-Hyp-Gly)3 triad extensions, respectively. CP(+) rapidly self-associates into positively charged nanosheets based on a monolayer structure. In contrast, CP(-) self-assembles to form negatively charged monolayer nanosheets at a much slower rate, which can be accelerated in the presence of calcium(II) ion. A 2:1 mixture of unassociated CP(-) peptide with preformed CP(+) nanosheets generates structurally defined triple-layer nanosheets in which two CP(-) monolayers have formed on the identical surfaces of the CP(+) nanosheet template. Experimental data from electrostatic force microscopy (EFM) image analysis, zeta potential measurements, and charged nanoparticle binding assays support a negative surface charge state for the triple-layer nanosheets, which is the reverse of the positive surface charge state observed for the CP(+) monolayer nanosheets. The electrostatic complementarity between the CP(+) and CP(-) triple helical cohesive ends at the layer interfaces promotes a (CP(-)/CP(+)/CP(-)) compositional gradient along the z-direction of the nanosheet. This structurally informed approach represents an attractive strategy for the fabrication of two-dimensional nanostructures with compositional control.

Electrical structure in two thunderstorm anvil clouds

NASA Technical Reports Server (NTRS)

Marshall, Thomas C.; Rust, W. David; Winn, William P.; Gilbert, Kenneth E.

1989-01-01

Electrical structures in two thunderstorm anvil clouds (or 'anvils'), one in New Mexico, the other in Oklahoma, were investigated, using measurements of electric field by balloon-carried instruments and a one-dimensional model to calculate the time and spatial variations of electrical parameters in the clear air below the anvil. The electric field soundings through the two thunderstorm anvils showed similar charge structures; namely, negatively charged screening layers on the top and the bottom surfaces, a layer of positive charge in the interior, and one or two layers of zero charge. It is suggested that the positive charge originated in the main positive charge region normally found at high altitudes in the core of thunderclouds, and the negatively charged layers probably formed as screening layers, resulting from the discontinuity in the electrical conductivity at the cloud boundaries.

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.

Influence of natural organic matter on equilibrium adsorption of neutral and charged pharmaceuticals onto activated carbon.

PubMed

de Ridder, D J; Verliefde, A R D; Heijman, S G J; Verberk, J Q J C; Rietveld, L C; van der Aa, L T J; Amy, G L; van Dijk, J C

2011-01-01

Natural organic matter (NOM) can influence pharmaceutical adsorption onto granular activated carbon (GAC) by direct adsorption competition and pore blocking. However, in the literature there is limited information on which of these mechanisms is more important and how this is related to NOM and pharmaceutical properties. Adsorption batch experiments were carried out in ultrapure, waste- and surface water and fresh and NOM preloaded GAC was used. Twenty-one pharmaceuticals were selected with varying hydrophobicity and with neutral, negative or positive charge. The influence of NOM competition and pore blocking could not be separated. However, while reduction in surface area was similar for both preloaded GACs, up to 50% lower pharmaceutical removal was observed on wastewater preloaded GAC. This was attributed to higher hydrophobicity of wastewater NOM, indicating that NOM competition may influence pharmaceutical removal more than pore blocking. Preloaded GAC was negatively charged, which influenced removal of charged pharmaceuticals significantly. At a GAC dose of 6.7 mg/L, negatively charged pharmaceuticals were removed for 0-58%, while removal of positively charged pharmaceuticals was between 32-98%. Charge effects were more pronounced in ultrapure water, as it contained no ions to shield the surface charge. Solutes with higher log D could compete better with NOM, resulting in higher removal.

International Aerospace and Ground Conference on Lightning and Static Electricity Held in Dayton, Ohio on 24-26 June 1986

DTIC Science & Technology

1986-10-01

developed by the AEH Group has the advantages: of compactness which makes it easily transportable; computer controlled acquisi- tion, signal processing...be available to a negatively charged aircraft. The experimental arrangement attempts to simulate the streamer propagation and growth in a quasi ...separate foam configurations: the operational configuration of non - conductive foam and a second configuration which contained an experimental

Presence of negative charge on the basal planes of New York talc.

PubMed

Burdukova, E; Becker, M; Bradshaw, D J; Laskowski, J S

2007-11-01

Potentiometric titration measurements as well as rheological measurements of talc aqueous suspensions indicate that the behavior of the New York talc particles is consistent with the presence of a negative charge on their basal planes. The possibility of the presence of a negative electrical charge on the basal planes of talc particles is analyzed in this paper. Samples of New York talc were studied using electron microprobe analysis and dehydration techniques and the exact chemical formula of New York talc was determined. It was found that there exists a deficiency of protons in the tetrahedral layers of talc, resulting from substitution of Si(4+) ions with Al(3+) and Ti(3+) ions. The comparison of the level of substitution of Si(4+) ions with ions of a lower valency was found to be of a similar order of magnitude as that found in other talc deposits. This strongly points to the presence of a negative charge on the talc basal planes.

Electrochemical energy storage devices comprising self-compensating polymers

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

Johnson, Paul; Bautista-Martinez, Jose Antonio; Friesen, Cody

The disclosed technology relates generally to devices comprising conductive polymers and more particularly to electrochemical devices comprising self-compensating conductive polymers. In one aspect, electrochemical energy storage device comprises a negative electrode comprising an active material including a redox-active polymer. The device additionally comprises a positive electrode comprising an active material including a redox-active polymer. The device further comprises an electrolyte material interposed between the negative electrode and positive electrode and configured to conduct mobile counterions therethrough between the negative electrode and positive electrode. At least one of the negative electrode redox-active polymer and the positive electrode redox-active polymer comprises amore » zwitterionic polymer unit configured to reversibly switch between a zwitterionic state in which the zwitterionic polymer unit has first and second charge centers having opposite charge states that compensate each other, and a non-zwitterionic state in which the zwitterionic polymer unit has one of the first and second charge centers whose charge state is compensated by mobile counterions.« less

Poly(zwitterionic liquids) functionalized polypyrrole/graphene oxide nanosheets for electrochemically detecting dopamine at low concentration.

PubMed

Mao, Hui; Liang, Jiachen; Ji, Chunguang; Zhang, Haifeng; Pei, Qi; Zhang, Yuyang; Zhang, Yu; Hisaeda, Yoshio; Song, Xi-Ming

2016-08-01

Poly(3-(1-vinylimidazolium-3-yl)propane-1-sulfonate) (PVIPS), a novel kind of poly(zwitterionic liquids) (PZILs) containing both imidazolium cation and sulfonate anion, was successfully modified on the surface of polypyrrole/graphene oxide nanosheets (PPy/GO) by covalent bonding. The obtained novel PZILs functionalized PPy/GO nanosheets (PVIPS/PPy/GO) modified glassy carbon electrode (GCE) presented the excellent electrochemical catalytic activity towards dopamine (DA) with high stability, sensitivity, selectivity and wide linear range (40-1220nM), especially having a lower detection limit (17.3nM). The excellent analytical performance is attributed to the strongly negative charges on the surface of modified GCE in aqueous solution, which is different from conventional poly(ionic liquids) modified GCE. DA cations could be quickly enriched on the electrode surface by electrostatic interaction in solution due to the existence of SO3(-) groups with negative charge at the end of pendant groups in zwitterionic PVIPS, resulting in a change of the electrons transmission mode in the oxidation of DA, that is, from a typical diffusion-controlled process at conventional poly(1-vinyl-3-ethylimidazole bromide) (PVEIB)/PPy/GO modified GCE to a typical surface-controlled process. Copyright © 2016 Elsevier B.V. All rights reserved.

Important parameters affecting the cell voltage of aqueous electrical double-layer capacitors

NASA Astrophysics Data System (ADS)

Wu, Tzu-Ho; Hsu, Chun-Tsung; Hu, Chi-Chang; Hardwick, Laurence J.

2013-11-01

This study discusses and demonstrates how the open-circuit potential and charges stored in the working potential window on positive and negative electrodes affect the cell voltage of carbon-based electrical double-layer capacitors (EDLCs) in aqueous electrolytes. An EDLC consisting of two activated carbon electrodes is employed as the model system for identifying these key parameters although the potential window of water decomposition can be simply determined by voltammetric methods. First, the capacitive performances of an EDLC with the same charge on positive and negative electrodes are evaluated by cyclic voltammetric, charge-discharge, electrochemical impedance spectroscopic (EIS) analyses, and inductance-capacitance-resistance meter (LCR meter). The principles for obtaining the highest acceptable cell voltage of such symmetric ECs with excellent reversibility and capacitor-like behaviour are proposed. Aqueous charge-balanced EDLCs can be operated as high as 2.0 V with high energy efficiency (about 90%) and only 4% capacitance loss after the 600-cycle stability checking. The necessity of charge balance (but not capacitance balance) for positive and negative electrodes is substantiated from the lower acceptable cell voltage of charge-unbalanced EDLCs.

Hindered Diffusion in Polymeric Solutions Studied by Fluorescence Correlation Spectroscopy

PubMed Central

Zustiak, Silviya P.; Nossal, Ralph; Sackett, Dan L.

2011-01-01

Diffusion of molecules in the crowded and charged interior of the cell has long been of interest for understanding cellular processes. Here, we introduce a model system of hindered diffusion that includes both crowding and binding. In particular, we obtained the diffusivity of the positively charged protein, ribonuclease A (RNase), in solutions of dextrans of various charges (binding) and concentrations (crowding), as well as combinations of both, in a buffer of physiological ionic strength. Using fluorescence correlation spectroscopy, we observed that the diffusivity of RNase was unaffected by the presence of positively charged or neutral dextrans in the dilute regime but was affected by crowding at higher polymer concentrations. Conversely, protein diffusivity was significantly reduced by negatively charged dextrans, even at 0.4 μM (0.02% w/v) dextran. The diffusivity of RNase decreased with increasing concentrations of negative dextran, and the amount of bound RNase increased until it reached a plateau of ∼80% bound RNase. High salt concentrations were used to establish the electrostatic nature of the binding. Binding of RNase to the negatively charged dextrans was further confirmed by ultrafiltration. PMID:21723836

Effect of a Dual Charge on the DNA-Conjugated Redox Probe on DNA Sensing by Short Hairpin Beacons Tethered to Gold Electrodes.

PubMed

Kékedy-Nagy, László; Shipovskov, Stepan; Ferapontova, Elena E

2016-08-16

Charges of redox species can critically affect both the interfacial state of DNA and electrochemistry of DNA-conjugated redox labels and, as a result, the electroanalytical performance of those systems. Here, we show that the kinetics of electron transfer (ET) between the gold electrode and methylene blue (MB) label conjugated to a double-stranded (ds) DNA tethered to gold strongly depend on the charge of the MB molecule, and that affects the performance of genosensors exploiting MB-labeled hairpin DNA beacons. Positively charged MB binds to dsDNA via electrostatic and intercalative/groove binding, and this binding allows the DNA-mediated electrochemistry of MB intercalated into the duplex and, as a result, a complex mode of the electrochemical signal change upon hairpin hybridization to the target DNA, dominated by the "on-off" signal change mode at nanomolar levels of the analyzed DNA. When MB bears an additional carboxylic group, the negative charge provided by this group prevents intimate interactions between MB and DNA, and then the ET in duplexes is limited by the diffusion of the MB-conjugated dsDNA (the phenomenon first shown in Farjami , E. ; Clima , L. ; Gothelf , K. ; Ferapontova , E. E. Anal. Chem. 2011 , 83 , 1594 ) providing the robust "off-on" nanomolar DNA sensing. Those results can be extended to other intercalating redox probes and are of strategic importance for design and development of electrochemical hybridization sensors exploiting DNA nanoswitchable architectures.

Magnetic circular dichroism of UCl 6– in the ligand-to-metal charge-transfer spectral region

DOE PAGES

Gendron, Frederic; Fleischauer, Valerie R.; Duignan, Thomas J.; ...

2017-06-23

Here, we present a combined ab initio theoretical and experimental study of the magnetic circular dichroism (MCD) spectrum of the octahedral UCl 6- complex ion in the UV-Vis spectral region. The ground state is an orbitally non-degenerate doublet E 5/2u and the MCD is a $C$-term spectrum caused by spin–orbit coupling. Calculations of the electronic spectrum at various levels of theory indicate that differential dynamic electron correlation has a strong influence on the energies of the dipole-allowed transitions and the envelope of the MCD spectrum. The experimentally observed bands are assigned to dipole-allowed ligand-to-metal charge transfer into the 5f shell,more » and 5f to 6d transitions. Charge transfer excitations into the U 6d shell appear at much higher energies. The MCD-allowed transitions can be assigned via their signs of the $C$-terms: Under O h double group symmetry, E 5/2u → E 5/2g transitions have negative $C$-terms whereas E 5/2u → F 3/2g transitions have positive $C$-terms if the ground state g-factor is negative, as it is the case for UCl 6-.« less

Learning from Synthetic Models of Extracellular Matrix; Differential Binding of Wild Type and Amyloidogenic Human Apolipoprotein A-I to Hydrogels Formed from Molecules Having Charges Similar to Those Found in Natural GAGs.

PubMed

Rosú, Silvana A; Toledo, Leandro; Urbano, Bruno F; Sanchez, Susana A; Calabrese, Graciela C; Tricerri, M Alejandra

2017-08-01

Among other components of the extracellular matrix (ECM), glycoproteins and glycosaminoglycans (GAGs) have been strongly associated to the retention or misfolding of different proteins inducing the formation of deposits in amyloid diseases. The composition of these molecules is highly diverse and a key issue seems to be the equilibrium between physiological and pathological events. In order to have a model in which the composition of the matrix could be finely controlled, we designed and synthesized crosslinked hydrophilic polymers, the so-called hydrogels varying the amounts of negative charges and hydroxyl groups that are prevalent in GAGs. We checked and compared by fluorescence techniques the binding of human apolipoprotein A-I and a natural mutant involved in amyloidosis to the hydrogel scaffolds. Our results indicate that both proteins are highly retained as long as the negative charge increases, and in addition it was shown that the mutant is more retained than the Wt, indicating that the retention of specific proteins in the ECM could be part of the pathogenicity. These results show the importance of the use of these polymers as a model to get deep insight into the studies of proteins within macromolecules.

A painful link between the TRPV1 channel and lysophosphatidic acid.

PubMed

Morales-Lázaro, Sara L; Rosenbaum, Tamara

2015-03-15

The Transient Receptor Potential Vanilloid 1 (TRPV1) ion channel is expressed mainly by sensory neurons that detect noxious stimuli from the environment such as high temperatures and pungent compounds (such as allicin and capsaicin) and has been extensively linked to painful and inflammatory processes. This extraordinary protein also responds to endogenous stimuli among which we find molecules of a lipidic nature. We recently described that lysophosphatidic acid (LPA), a bioactive lysophospholipid linked to the generation and maintenance of pain, can directly activate TRPV1 and produce pain by binding to the channels' C-terminal region, specifically to residue K710. In an effort to further understand how activation of TRPV1 is achieved by this negatively-charged lipid, we used several synthetic and naturally-occurring lipids to determine the structural requirements that need to be met by these charged lipids in order to produce the activation of TRPV1. In this review, we detail the findings obtained by other research groups and our own on the field of TRPV1-regulation by negatively-charged lipids and discuss the possible therapeutic relevance of these findings on the basis of the role of TRPV1 in pathophysiological processes. Copyright © 2014 Elsevier Inc. All rights reserved.

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.

Polymers incorporating covalently attached organoimido polyoxometalates

DOEpatents

Maatta, Eric A.; Moore, Aaron R.

2004-03-16

New polyoxometalate compounds and polymers comprising recurring monomers of those compounds are provided. The compounds are formed by replacing at least one oxide of the starting polyoxometalate with an organoimido (NR) group bonded to the polyoxometalate via a triple bond to the nitrogen atom. The R of the (NR) group comprises a reactive functional group which renders the compound readily polymerizable, alone or with other monomers (e.g., divinylbenzene), to form the inventive polymers. Additionally, a countercation (e.g., bis(tetra-n-butylammonium)) can be mixed with the polyoxometalate compounds in order to neutralize the negative charge thereof as well as to make those compounds more soluble in organic solvents.

Differential effects of DEAE negative mode chromatography and gel-filtration chromatography on the charge status of Helicobacter pylori neutrophil-activating protein

PubMed Central

Pan, Timothy; Tzeng, Huey-Fen

2017-01-01

Helicobacter pylori neutrophil-activating protein (HP-NAP) is involved in H. pylori-associated gastric inflammation. HP-NAP is also a vaccine candidate, a possible drug target, and a potential diagnostic marker for H. pylori-associated diseases. Previously, we purified recombinant HP-NAP by one-step diethylaminoethyl (DEAE) negative mode chromatography by collecting the unbound fraction at pH 8.0 at 4°C. It remains unclear why HP-NAP does not bind to DEAE resins at the pH above its isoelectric point during the purification. To investigate how pH affects the surface net charge of HP-NAP and its binding to DEAE resins during the purification, recombinant HP-NAP expressed in Escherichia coli was subjected to DEAE negative mode chromatography at pH ranging from 7.0 to 9.0 at 25°C and the surface charge of purified HP-NAP was determined by capillary electrophoresis. A minimal amount of HP-NAP was detected in the elution fraction of DEAE Sepharose resin at pH 8.5, whereas recombinant HP-NAP was detected in the elution fraction of DEAE Sephadex resin only at pH 7.0 and 8.0. The purified recombinant HP-NAP obtained from the unbound fractions was not able to bind to DEAE resins at pH 7.0 to 9.0. In addition, the surface charge of the purified HP-NAP was neutral at pH 7.0 to 8.0 and was either neutral or slightly negative at pH 8.5 and 9.0. However, recombinant HP-NAP purified from gel-filtration chromatography was able to bind to DEAE Sepharose resin at pH 7.0 to 9.0 and DEAE Sephadex resin at pH 7.0. At pH 8.5 and 9.0, only the negatively charged species of HP-NAP were found. Thus, recombinant HP-NAP with different charge status can be differentially purified by DEAE negative mode chromatography and gel-filtration chromatography. Furthermore, the charge distribution on the surface of HP-NAP, the presence of impure proteins, and the overall net charge of the resins all affect the binding of HP-NAP to DEAE resins during the negative purification. PMID:28328957

Differential effects of DEAE negative mode chromatography and gel-filtration chromatography on the charge status of Helicobacter pylori neutrophil-activating protein.

PubMed

Hong, Zhi-Wei; Yang, Yu-Chi; Pan, Timothy; Tzeng, Huey-Fen; Fu, Hua-Wen

2017-01-01

Helicobacter pylori neutrophil-activating protein (HP-NAP) is involved in H. pylori-associated gastric inflammation. HP-NAP is also a vaccine candidate, a possible drug target, and a potential diagnostic marker for H. pylori-associated diseases. Previously, we purified recombinant HP-NAP by one-step diethylaminoethyl (DEAE) negative mode chromatography by collecting the unbound fraction at pH 8.0 at 4°C. It remains unclear why HP-NAP does not bind to DEAE resins at the pH above its isoelectric point during the purification. To investigate how pH affects the surface net charge of HP-NAP and its binding to DEAE resins during the purification, recombinant HP-NAP expressed in Escherichia coli was subjected to DEAE negative mode chromatography at pH ranging from 7.0 to 9.0 at 25°C and the surface charge of purified HP-NAP was determined by capillary electrophoresis. A minimal amount of HP-NAP was detected in the elution fraction of DEAE Sepharose resin at pH 8.5, whereas recombinant HP-NAP was detected in the elution fraction of DEAE Sephadex resin only at pH 7.0 and 8.0. The purified recombinant HP-NAP obtained from the unbound fractions was not able to bind to DEAE resins at pH 7.0 to 9.0. In addition, the surface charge of the purified HP-NAP was neutral at pH 7.0 to 8.0 and was either neutral or slightly negative at pH 8.5 and 9.0. However, recombinant HP-NAP purified from gel-filtration chromatography was able to bind to DEAE Sepharose resin at pH 7.0 to 9.0 and DEAE Sephadex resin at pH 7.0. At pH 8.5 and 9.0, only the negatively charged species of HP-NAP were found. Thus, recombinant HP-NAP with different charge status can be differentially purified by DEAE negative mode chromatography and gel-filtration chromatography. Furthermore, the charge distribution on the surface of HP-NAP, the presence of impure proteins, and the overall net charge of the resins all affect the binding of HP-NAP to DEAE resins during the negative purification.

Polyelectrolyte-assisted preparation of gold nanocluster-doped silica particles with high incorporation efficiency and improved stability

NASA Astrophysics Data System (ADS)

Wang, Haonan; Huang, Zhenzhen; Guo, Zilong; Yang, Wensheng

2017-07-01

In this paper, we reported an approach for efficient incorporation of glutathione-capped gold nanoclusters (GSH-Au NCs) into silica particles with the assistance of a polyelectrolyte, poly-diallyldimethyl-ammoniumchloride (PDDA). In this approach, the negatively charged GSH-Au NCs were firstly mixed with the positively charged PDDA to form PDDA-Au NC complexes. Then, the complexes were added into a pre-hydrolyzed Stöber system to get the Au NCs-doped silica particles. With increased ratio of PDDA in the complexes, the negative charges on surface of the Au NCs were neutralized gradually and finally reversed to positive in presence of excess PDDA, which facilitated the incorporation of the Au NCs into the negatively charged silica matrix. Under the optimal amount of PDDA in the complexes, the incorporation efficiency of Au NCs could be as high as 88%. After being incorporated into the silica matrix, the Au NCs become much robust against pH and heavy metal ions attributed to the protection effect of silica and PDDA. This approach was also extendable to highly efficient incorporation of other negatively charged metal nanoclusters, such as bovine serum albumin-capped Cu nanoclusters, into silica matrix.

Functionalized nanoparticle interactions with polymeric membranes

PubMed Central

Ladner, D.A.; Steele, M.; Weir, A.; Hristovski, K.; Westerhoff, P.

2011-01-01

A series of experiments was performed to measure the retention of a class of functionalized nanoparticles (NPs) onporous (microfiltration and ultrafiltration) membranes. The findings impact engineered water and wastewater treatment using membrane technology, characterization and analytical schemes for NP detection, and the use of NPs in waste treatment scenarios. The NPs studied were composed of silver, titanium dioxide, and gold; had organic coatings to yield either positive or negative surface charge; and were between 2 and 10 nm in diameter. NP solutions were applied to polymeric membranes composed of different materials and pore sizes (ranging from ~2 nm [3 kDa molecular weight cutoff] to 0.2 μm). Greater than 99% rejection was observed of positively charged NPs by negatively charged membranes even though pore diameters were up to 20 times the NP diameter; thus, sorption caused rejection. Negatively charged NPs were less well rejected, but behavior was dependant not only on surface functionality but on NP core material (Ag, TiO2, or Au). NP rejection depended more upon NP properties than membrane properties; all of the negatively charged polymeric membranes behaved similarly. The NP-membrane interaction behavior fell into four categories, which are defined and described here. PMID:22177020

High-energy e- /e+ spectrometer via coherent interaction in a bent crystal

NASA Astrophysics Data System (ADS)

Bagli, Enrico; Guidi, Vincenzo; Howard, Alexander

2018-01-01

We propose a novel spectrometer based on the crystal channeling effect capable of discriminating between positive and negative particles well beyond the TeV energy scale. The atomic order of a crystalline structure generates an electrostatic field built up by all the atoms in the crystals, which confines charged particle trajectories between neighbouring atomic planes. Through such an interaction in a tiny curved crystal, the same dynamical action on the highest energy particles as that of a huge superconducting magnet is achieved. Depending on the charge sign, points of equilibrium of the oscillatory motion under channeling lie between or on atomic planes for positive and negative particles, respectively, forcing positive particles to stably oscillate far from the planes, while negative ones repeatedly cross them. The different interaction rate with atomic planes causes a tremendous discrepancy between the deflection efficiency of positive and negative particles under channeling. We suggest the use of interactions between charged particles and oriented bent crystals as a novel non-cryogenic passive charge spectrometer to aid the search for dark matter in the Universe in satellite-borne experiment. The limited angular acceptance makes this technique particularly suited for directional local sources of energetic charged particles.

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.

How Native and Alien Metal Cations Bind ATP: Implications for Lithium as a Therapeutic Agent

NASA Astrophysics Data System (ADS)

Dudev, Todor; Grauffel, Cédric; Lim, Carmay

2017-02-01

Adenosine triphosphate (ATP), the major energy currency of the cell, exists in solution mostly as ATP-Mg. Recent experiments suggest that Mg2+ interacts with the highly charged ATP triphosphate group and Li+ can co-bind with the native Mg2+ to form ATP-Mg-Li and modulate the neuronal purine receptor response. However, it is unclear how the negatively charged ATP triphosphate group binds Mg2+ and Li+ (i.e. which phosphate group(s) bind Mg2+/Li+) and how the ATP solution conformation depends on the type of metal cation and the metal-binding mode. Here, we reveal the preferred ATP-binding mode of Mg2+/Li+ alone and combined: Mg2+ prefers to bind ATP tridentately to each of the three phosphate groups, but Li+ prefers to bind bidentately to the terminal two phosphates. We show that the solution ATP conformation depends on the cation and its binding site/mode, but it does not change significantly when Li+ binds to Mg2+-loaded ATP. Hence, ATP-Mg-Li, like Mg2+-ATP, can fit in the ATP-binding site of the host enzyme/receptor, activating specific signaling pathways.

Bias-induced conformational switching of supramolecular networks of trimesic acid at the solid-liquid interface

NASA Astrophysics Data System (ADS)

Ubink, J.; Enache, M.; Stöhr, M.

2018-05-01

Using the tip of a scanning tunneling microscope, an electric field-induced reversible phase transition between two planar porous structures ("chickenwire" and "flower") of trimesic acid was accomplished at the nonanoic acid/highly oriented pyrolytic graphite interface. The chickenwire structure was exclusively observed for negative sample bias, while for positive sample bias only the more densely packed flower structure was found. We suggest that the slightly negatively charged carboxyl groups of the trimesic acid molecule are the determining factor for this observation: their adsorption behavior varies with the sample bias and is thus responsible for the switching behavior.

Stepped electrophoresis for movement and concentration of DNA

DOEpatents

Miles, Robin R.; Wang, Amy Wei-Yun; Mariella, Jr., Raymond P.

2005-03-15

A fluidic channel patterned with a series of thin-film electrodes makes it possible to move and concentrate DNA in a fluid passing through the fluidic channel. The DNA has an inherent negative charge and by applying a voltage between adjacent electrodes the DNA is caused to move. By using a series of electrodes, when one electrode voltage or charge is made negative with respect to adjacent electrodes, the DNA is repelled away from this electrode and attached to a positive charged electrode of the series. By sequentially making the next electrode of the series negative, the DNA can be moved to and concentrated over the remaining positive electrodes.

Neutralization by a Corona Discharge Ionizer in Nitrogen Atmosphere

NASA Astrophysics Data System (ADS)

Ikeuchi, Toru; Takahashi, Kazunori; Ohkubo, Takahiro; Fujiwara, Tamiya

An electrostatic neutralization of multilayer-loading silicon wafers is demonstrated using a corona discharge ionizer in nitrogen atmosphere, where ac and dc voltages are applied to two needle electrodes for generation of the negative- and positive-charged particles, respectively. We observe a surface potential of the silicon wafer decreases from ±1kV to ±20V within three seconds. Moreover, the density profiles of the charged particles generated by the electrodes are experimentally and theoretically investigated in nitrogen and air atmospheres. Our results show the possibility that the negative-charged particles contributing to the electrostatic neutralization are electrons and negative ions in nitrogen and air atmospheres, respectively.

Analysis of heparin oligosaccharides by capillary electrophoresis-negative-ion electrospray ionization mass spectrometry.

PubMed

Lin, Lei; Liu, Xinyue; Zhang, Fuming; Chi, Lianli; Amster, I Jonathan; Leach, Franklyn E; Xia, Qiangwei; Linhardt, Robert J

2017-01-01

Most hyphenated analytical approaches that rely on liquid chromatography-MS require relatively long separation times, produce incomplete resolution of oligosaccharide mixtures, use eluents that are incompatible with electrospray ionization, or require oligosaccharide derivatization. Here we demonstrate the analysis of heparin oligosaccharides, including disaccharides, ultralow molecular weight heparin, and a low molecular weight heparin, using a novel electrokinetic pump-based CE-MS coupling eletrospray ion source. Reverse polarity CE separation and negative-mode electrospray ionization were optimized using a volatile methanolic ammonium acetate electrolyte and sheath fluid. The online CE hyphenated negative-ion electrospray ionization MS on an LTQ Orbitrap mass spectrometer was useful in disaccharide compositional analysis and bottom-up and top-down analysis of low molecular weight heparin. The application of this CE-MS method to ultralow molecular heparin suggests that a charge state distribution and the low level of sulfate group loss that is achieved make this method useful for online tandem MS analysis of heparins. Graphical abstract Most hyphenated analytical approaches that rely on liquid chromatography-MS require relatively long separation times, produce incomplete resolution of oligosaccharide mixtures, use eluents that are incompatible with electrospray ionization, or require oligosaccharide derivatization. Here we demonstrate the analysis of heparin oligosaccharides, including disaccharides, ultralow molecular weight heparin, and a low molecular weight heparin, using a novel electrokinetic pump-based CE-MS coupling eletrospray ion source. Reverse polarity CE separation and negative-mode electrospray ionization were optimized using a volatile methanolic ammonium acetate electrolyte and sheath fluid. The online CE hyphenated negative-ion electrospray ionization MS on an LTQ Orbitrap mass spectrometer was useful in disaccharide compositional analysis and bottom-up and top-down analysis of low molecular weight heparin. The application of this CE-MS method to ultralow molecular heparin suggests that a charge state distribution and the low level of sulfate group loss that is achieved make this method useful for online tandem MS analysis of heparins.

Charge density distribution and the electrostatic moments of CTPB in the active site of p300 enzyme: a DFT and charge density study.

PubMed

Devipriya, B; Kumaradhas, P

2013-10-21

A molecular docking and charge density analysis have been carried out to understand the conformational change, charge distribution and electrostatic properties of N-(4-chloro-3-trifluoromethyl-phenyl)-2-ethoxy-6-pentadecyl-benzamide (CTPB) in the active site of p300. The nearest neighbors, shortest intermolecular contacts between CTPB-p300 and the lowest binding energy of CTPB have been analyzed from the docking analysis. Further, a charge density analysis has been carried out for the molecule in gas phase and for the corresponding molecule lifted from the active site of p300. Due to the intermolecular interaction between CTPB and the amino acids of active site, the conformation of the CTPB has been significantly altered (particularly the pentadecyl chain). CTPB forms strong interaction with the amino acid residues Tyr1397 and Trp1436 at the distance 2.12 and 2.72Å, respectively. However, the long pentadecyl alkyl chain of CTPB produces a barrier and reducing the chance of forming hydrogen bonding with p300. The electron density ρbcp(r) of the polar bonds (C-O, C-N, C-F and C-Cl) of CTPB are increased when it present in the active site. The dipole moment of CTPB in the active site is significantly less (5.73D) when compared with the gas phase (8.16D) form. In the gas phase structure, a large region of negative electrostatic potential (ESP) is found at the vicinity of O(2) and CF3 group, which is less around the O(1) atom. Whereas, in the active site, the negative ESP around the CF3 group is decreased and increased at the O(1) and O(2)-atoms. The ESP modifications of CTPB in the active site are mainly attributed to the effect of intermolecular interaction. The gas phase and active site study insights the molecular flexibility and the electrostatic properties of CTPB in the active site. © 2013 Elsevier Ltd. All rights reserved.

Maintenance of coat protein N-terminal net charge and not primary sequence is essential for zucchini yellow mosaic virus systemic infectivity.

PubMed

Kimalov, Boaz; Gal-On, Amit; Stav, Ran; Belausov, Eduard; Arazi, Tzahi

2004-11-01

Zucchini yellow mosaic virus (ZYMV) surface exposed coat protein (CP) N-terminal domain (Nt) is 43 aa long and contains an equal number of positively and negatively charged amino acid residues (CP-Nt net charge = 0). A ZYMV-AGII truncation mutant lacking the first 20 aa of its CP-Nt (AGII-CP Delta 20; CP-Nt net charge = +2) was found to be systemically non-infectious even though AGII mutants harbouring larger CP-Nt deletions were previously demonstrated to be fully infectious. Nevertheless, AGII-CP Delta 20 infectivity was restored by fusion to its CP-Nt two Asp residues or a negatively charged Myc peptide, both predicted to neutralize CP-Nt net positive charge. To evaluate further the significance of CP-Nt net charge for AGII infectivity, a series of CP-Nt net charge mutants was generated and analysed for systemic infectivity of squash plants. AGII-CP(KKK) harbouring a CP-Nt amino fusion of three Lys residues (CP-Nt net charge = +3) was not systemically infectious. Addition of up to four Asp residues to CP-Nt did not abolish virus infectivity, although certain mutants were genetically unstable and had delayed infectivity. Addition of five negatively charged residues abolished infectivity (AGII-CP(DDDDD); CP-Nt net charge = -5) even though a recombinant CP(DDDDD) could assemble into potyviral-like particle in bacteria. Neutralization of CP-Nt net charge by fusing Asp or Lys residues recovered infectivity of AGII-CP(KKK) and AGII-CP(DDDDD). GFP-tagging of these mutants has demonstrated that both viruses have defective cell-to-cell movement. Together, these findings suggest that maintenance of CP-Nt net charge and not primary sequence is essential for ZYMV infectivity.

Negative charge emission due to excimer laser bombardment of sodium trisilicate glass

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

Langford, S.C.; Jensen, L.C.; Dickinson, J.T.

We describe measurements of negative charge emission accompanying irradiation of sodium trisilicate glass (Na{sub 2}O{center dot}3SiO{sub 2}) with 248-nm excimer laser light at fluences on the order of 2 J/cm{sup 2} per pulse, i.e., at the threshold for ablative etching of the glass surface. The negative charge emission consists of a very prompt photoelectron burst coincident with the laser pulse, followed by a much slower plume of electrons and negative ions traveling with a high density cloud of positive ions, previously identified as primarily Na{sup +}. Using combinations of {bold E} and {bold B} fields in conjunction with time-of-flight methods,more » the negative ions were successfully separated from the plume and tentatively identified as O{sup {minus}}, Si{sup {minus}}, NaO{sup {minus}}, and perhaps NaSi{sup {minus}}. These negative species are probably formed by gas phase collisions in the near-surface region which result in electron attachment.« less

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.

Optical pumping of the electronic and nuclear spin of single charge-tunable quantum dots.

PubMed

Bracker, A S; Stinaff, E A; Gammon, D; Ware, M E; Tischler, J G; Shabaev, A; Efros, Al L; Park, D; Gershoni, D; Korenev, V L; Merkulov, I A

2005-02-04

We present a comprehensive examination of optical pumping of spins in individual GaAs quantum dots as we change the net charge from positive to neutral to negative with a charge-tunable heterostructure. Negative photoluminescence polarization memory is enhanced by optical pumping of ground state electron spins, which we prove with the first measurements of the Hanle effect on an individual quantum dot. We use the Overhauser effect in a high longitudinal magnetic field to demonstrate efficient optical pumping of nuclear spins for all three charge states of the quantum dot.

Optical Pumping of the Electronic and Nuclear Spin of Single Charge-Tunable Quantum Dots

NASA Astrophysics Data System (ADS)

Bracker, A. S.; Stinaff, E. A.; Gammon, D.; Ware, M. E.; Tischler, J. G.; Shabaev, A.; Efros, Al. L.; Park, D.; Gershoni, D.; Korenev, V. L.; Merkulov, I. A.

2005-02-01

We present a comprehensive examination of optical pumping of spins in individual GaAs quantum dots as we change the net charge from positive to neutral to negative with a charge-tunable heterostructure. Negative photoluminescence polarization memory is enhanced by optical pumping of ground state electron spins, which we prove with the first measurements of the Hanle effect on an individual quantum dot. We use the Overhauser effect in a high longitudinal magnetic field to demonstrate efficient optical pumping of nuclear spins for all three charge states of the quantum dot.

Electrochemical supercapacitors

DOEpatents

Rudge, Andrew J.; Ferraris, John P.; Gottesfeld, Shimshon

1996-01-01

A new class of electrochemical capacitors provides in its charged state a positive electrode including an active material of a p-doped material and a negative electrode including an active material of an n-doped conducting polymer, where the p-doped and n-doped materials are separated by an electrolyte. In a preferred embodiment, the positive and negative electrode active materials are selected from conducting polymers consisting of polythiophene, polymers having an aryl group attached in the 3-position, polymers having aryl and alkyl groups independently attached in the 3- and 4-positions, and polymers synthesized from bridged dimers having polythiophene as the backbone. A preferred electrolyte is a tetraalykyl ammonium salt, such as tetramethylammonium trifluoromethane sulphonate (TMATFMS), that provides small ions that are mobile through the active material, is soluble in acetonitrile, and can be used in a variety of capacitor configurations.

Combinatorial effects of charge characteristics and hydrophobicity of silk fibroin on the sorption and release of charged dyes.

PubMed

Wongpanit, Panya; Rujiravanit, Ratana

2012-01-01

The present study was designed to examine the influence of the charge characteristics of silk fibroin on the sorption and release of charged dyes by varying the pH values of the sorption and release media as well as types of charged dyes. Negatively charged dyes (phenol red and chromotrope 2R) and positively charged dyes (crystal violet and indoine blue) were used as the model compounds. Silk fibroin films were prepared by using a solution casting technique. The prepared films were then treated with an aqueous methanol solution or annealed with water to control their conformation. The sorption behavior of the model compounds made by the methanol-treated and water-annealed silk fibroin films was investigated. Compared to the water- annealed silk fibroin films, a higher hydrophobicity of the methanol-treated silk fibroin films caused a higher sorption of the hydrophobic dyes. The dye molecules had a fairly high affinity to the silk fibroin film, even though the dye and the matrix possessed the same charge. However, in the presence of two charged groups in a single dye molecule, the electrostatic repulsion become more dominant. Stronger interaction was observed when the charges of the film and the dye were opposite. The results of dye sorption and release experiments showed that the degree of synergism or competition between electrostatic and hydrophobic interactions directly depended on the charges and chemical structure of the dye molecules and the environmental pH conditions of the existing silk fibroin film.

SH3-like motif-containing C-terminal domain of staphylococcal teichoic acid transporter suggests possible function.

PubMed

Ko, Tzu-Ping; Tseng, Shih-Ting; Lai, Shu-Jung; Chen, Sheng-Chia; Guan, Hong-Hsiang; Shin Yang, Chia; Jung Chen, Chun; Chen, Yeh

2016-09-01

The negatively charged bacterial polysaccharides-wall teichoic acids (WTAs) are synthesized intracellularly and exported by a two-component transporter, TagGH, comprising a transmembrane subunit TagG and an ATPase subunit TagH. We determined the crystal structure of the C-terminal domain of TagH (TagH-C) to investigate its function. The structure shows an N-terminal SH3-like subdomain wrapped by a C-terminal subdomain with an anti-parallel β-sheet and an outer shell of α-helices. A stretch of positively charged surface across the subdomain interface is flanked by two negatively charged regions, suggesting a potential binding site for negatively charged polymers, such as WTAs or acidic peptide chains. Proteins 2016; 84:1328-1332. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Negative space charge effects in photon-enhanced thermionic emission solar converters

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

Segev, G.; Weisman, D.; Rosenwaks, Y.

2015-07-06

In thermionic energy converters, electrons in the gap between electrodes form a negative space charge and inhibit the emission of additional electrons, causing a significant reduction in conversion efficiency. However, in Photon Enhanced Thermionic Emission (PETE) solar energy converters, electrons that are reflected by the electric field in the gap return to the cathode with energy above the conduction band minimum. These electrons first occupy the conduction band from which they can be reemitted. This form of electron recycling makes PETE converters less susceptible to negative space charge loss. While the negative space charge effect was studied extensively in thermionicmore » converters, modeling its effect in PETE converters does not account for important issues such as this form of electron recycling, nor the cathode thermal energy balance. Here, we investigate the space charge effect in PETE solar converters accounting for electron recycling, with full coupling of the cathode and gap models, and addressing conservation of both electric and thermal energy. The analysis shows that the negative space charge loss is lower than previously reported, allowing somewhat larger gaps compared to previous predictions. For a converter with a specific gap, there is an optimal solar flux concentration. The optimal solar flux concentration, the cathode temperature, and the efficiency all increase with smaller gaps. For example, for a gap of 3 μm the maximum efficiency is 38% and the optimal flux concentration is 628, while for a gap of 5 μm the maximum efficiency is 31% and optimal flux concentration is 163.« less

Enhancing biocompatibility of D-oligopeptide hydrogels by negative charges.

PubMed

Hyland, Laura L; Twomey, Julianne D; Vogel, Savannah; Hsieh, Adam H; Yu, Y Bruce

2013-02-11

Oligopeptide hydrogels are emerging as useful matrices for cell culture with commercial products on the market, but L-oligopeptides are labile to proteases. An obvious solution is to create D-oligopeptide hydrogels, which lack enzymatic recognition. However, D-oligopeptide matrices do not support cell growth as well as L-oligopeptide matrices. In addition to chiral interactions, many cellular activities are strongly governed by charge-charge interactions. In this work, the effects of chirality and charge on human mesenchymal stem cell (hMSC) behavior were studied using hydrogels assembled from oppositely charged oligopeptides. It was found that negative charges significantly improved hMSC viability and proliferation in D-oligopeptide gels but had little effect on their interactions with L-oligopeptide gels. This result points to the possibility of using charge and other factors to engineer biomaterials whose chirality is distinct from that of natural biomaterials, but whose performance is close to that of natural biomaterials.

Influence of humic acid concentration on nTiO2 attachment to quartz sand and Fe-coated quartz sand

NASA Astrophysics Data System (ADS)

Cheng, T.; Wu, Y.

2016-12-01

The transport of nano-scale or micro-scale titanium dioxide particles (nTiO2) in subsurface environments are strongly influenced by nTiO2 attachment to sediment grains. The objective of this study is to investigate the role of humic acid (HA) in the attachment of nTiO2 to sand at low HA concentrations that are relevant to typical groundwater conditions, so that mechanisms that control nTiO2 immobilization and transport in groundwater can be elucidated. nTiO2 may carry either positive or negative charges in natural water, therefore, environmental factors such as pH, humic substances, and Fe oxyhydroxide coatings on sediment grains, which are known to control the transport of negatively-charged colloids, may influence nTiO2 in different manners. Attachment of nTiO2 to quartz sand and Fe oxyhydroxide coated quartz sand are experimentally measured under a range of HA concentrations at fixed pH. Experimental results show that at pH 5, negatively-charged HA strongly adsorbs to positively-charged nTiO2 and Fe oxyhydroxide, which, at low HA concentrations, partially neutralizes the positive charges on nTiO2 and Fe oxyhydroxide, and therefore decreases the repulsive electrostatic forces between the surfaces, resulting in relatively high nTiO2 attachment. At high HA concentrations, adsorbed HA reverses the surface charges of nTiO2 and Fe oxyhydroxide, and makes nTiO2 and Fe oxyhydroxide strongly negatively charged, resulting in low nTiO2 attachment. At pH 9, HA, nTiO2, and Fe oxyhydroxide are all negatively charged, and HA adsorption is low and does not have a strong impact on the attachment of nTiO2. This study demonstrates that the changes in surface charges of nTiO2 and Fe oxyhydroxide coating caused by HA adsorption could be a key factor that controls the attachment of nTiO2 to sediment grains.

Lipids and topological rules of membrane protein assembly: balance between long and short range lipid-protein interactions.

PubMed

Vitrac, Heidi; Bogdanov, Mikhail; Heacock, Phil; Dowhan, William

2011-04-29

The N-terminal six-transmembrane domain (TM) bundle of lactose permease of Escherichia coli is uniformly inverted when assembled in membranes lacking phosphatidylethanolamine (PE). Inversion is dependent on the net charge of cytoplasmically exposed protein domains containing positive and negative residues, net charge of the membrane surface, and low hydrophobicity of TM VII acting as a molecular hinge between the two halves of lactose permease (Bogdanov, M., Xie, J., Heacock, P., and Dowhan, W. (2008) J. Cell Biol. 182, 925-935). Net neutral lipids suppress the membrane translocation potential of negatively charged amino acids, thus increasing the cytoplasmic retention potential of positively charged amino acids. Herein, TM organization of sucrose permease (CscB) and phenylalanine permease (PheP) as a function of membrane lipid composition was investigated to extend these principles to other proteins. For CscB, topological dependence on PE only becomes evident after a significant increase in the net negative charge of the cytoplasmic surface of the N-terminal TM bundle. High negative charge is required to overcome the thermodynamic block to inversion due to the high hydrophobicity of TM VII. Increasing the positive charge of the cytoplasmic surface of the N-terminal TM hairpin of PheP, which is misoriented in PE-lacking cells, favors native orientation in the absence of PE. PheP and CscB also display co-existing dual topologies dependent on changes in the charge balance between protein domains and the membrane lipids. Therefore, the topology of both permeases is dependent on PE. However, CscB topology is governed by thermodynamic balance between opposing lipid-dependent electrostatic and hydrophobic interactions.

Charging Properties of Cassiterite (alpha-SnO2) surfaces in NaCl and RbCl Ionic Media.

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

Rosenqvist, Jorgen K; Machesky, Michael L.; Vlcek, Lukas

2009-01-01

The acid-base properties of cassiterite (alpha-SnO2) surfaces at 10-50 degrees 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 of 4.0-4.5 under 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 degrees C, respectively. This is contrary to the situation on the isostructural alpha-TiO2 (rutile), apparently because of 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, whereas adsorbed rubidium ions form comparable numbers of bidentate and tetradentate complexes. Also, the distribution of adsorbed Na+ between the different complexes shows a considerable dependence on the surface charge density (pH), whereas 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 of this study (2.7-10). The complexation of medium cations increases significantly with increasing negative surface charge, and at pH 10, roughly 40% of the terminal sites are predicted to form cation complexes, whereas anion complexation is minor throughout the studied pH range.« less

Interactions of low molecular weight aromatic acids and amino acids with goethite, kaolinite and bentonite with or without organic matter coating

NASA Astrophysics Data System (ADS)

Gao, Jiajia; Jansen, Boris; Cerli, Chiara; Kalbitz, Karsten

2015-04-01

Interaction of organic matter molecules with the soil's solid phase is a key factor influencing the stabilization of carbon in soils and thus forms a crucial aspect of the global carbon cycle. While subject of much research attention so far, we still have much to learn about such interactions at the molecular level; in particular in the light of competition between different classes of organic molecules and in the presence of previously adsorbed soil organic matter. We studied the interaction of a group of low molecular weight (LMW) aromatic acids (salicylic, syringic, vanillic and ferulic acid) and amino acids (lysine, glutamic, leucine and phenylalanine) on goethite, kaolinite and bentonite with and without previously adsorbed dissolved organic matter (DOM). For this we used batch experiments at pH = 6.0 where some of the organic compounds were positively charged (i.e. lysine) or negatively charged (i.e. glutamic and salicylic acid) while the minerals also displayed positively (i.e. goethite) or negatively charged surfaces (i.e. bentonite). We found much higher sorption of salicylic acid and lysine than other compounds. On the bare minerals we found a great variety of sorption strength, with salicylic acid strongly adsorbed, while syringic, vanillic and ferulic acid showed little or no adsorption. For the amino acids, protonated lysine showed a stronger affinity to negatively charged kaolinite and bentonite than other amino acids. While deprotonated glutamic acid showed the strongest adsorption on goethite. Leucine and phenylalanine showed hardly any adsorption on any of the minerals. When present concurrently, amino acids decreased the sorption of salicylic acid on the three types of mineral, while the presence of LMW aromatic acids increased the sorption of lysine on kaolinite and bentonite and the sorption of glutamic acid on goethite. The presence of previously adsorbed DOM reduced the sorption of salicylic acid and lysine. The results confirm that interactions of different classes of organic molecules with solid soil phases cannot be understood in isolation, but must be interpreted in the context of the presence of other classes of molecules. It seems that the presence of methoxy groups decreases the adsorption of aromatic acids to minerals. We did not find evidence for protein conditioning of any mineral surface, i.e. increased adsorption of aromatic acids after adsorption of amino acids.

Biotemplated Synthesis of PZT Nanowires

DTIC Science & Technology

2013-11-25

this same experimental protocol would be successful with other biotemplates. M13 bacteriophage was chosen as a second template because (1) it possesses...and (3) it can be customized to bind compounds of interest with tailorable specificities based on the phage display process.14 M13 is a virus that is...coefficients (d33 < 8 pm/V). 50 As negatively charged carboxyl groups can bind cations,51 M13 phages were genetically engineered to display glutamate

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.

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.

Charge Segregation and Low Hydrophobicity Are Key Features of Ribosomal Proteins from Different Organisms*

PubMed Central

Fedyukina, Daria V.; Jennaro, Theodore S.; Cavagnero, Silvia

2014-01-01

Ribosomes are large and highly charged macromolecular complexes consisting of RNA and proteins. Here, we address the electrostatic and nonpolar properties of ribosomal proteins that are important for ribosome assembly and interaction with other cellular components and may influence protein folding on the ribosome. We examined 50 S ribosomal subunits from 10 species and found a clear distinction between the net charge of ribosomal proteins from halophilic and non-halophilic organisms. We found that ∼67% ribosomal proteins from halophiles are negatively charged, whereas only up to ∼15% of ribosomal proteins from non-halophiles share this property. Conversely, hydrophobicity tends to be lower for ribosomal proteins from halophiles than for the corresponding proteins from non-halophiles. Importantly, the surface electrostatic potential of ribosomal proteins from all organisms, especially halophiles, has distinct positive and negative regions across all the examined species. Positively and negatively charged residues of ribosomal proteins tend to be clustered in buried and solvent-exposed regions, respectively. Hence, the majority of ribosomal proteins is characterized by a significant degree of intramolecular charge segregation, regardless of the organism of origin. This key property enables the ribosome to accommodate proteins within its complex scaffold regardless of their overall net charge. PMID:24398678

Molecular and phenotypic aspects of CHD7 mutation in CHARGE syndrome

PubMed Central

Zentner, Gabriel E.; Layman, Wanda S.; Martin, Donna M.; Scacheri, Peter C.

2010-01-01

CHARGE syndrome (Coloboma of the eye, Heart defects, Atresia of the choanae, Retardation of growth and/or development, Genital and/or urinary abnormalities, and Ear abnormalities (including deafness) is a genetic disorder characterized by a specific and a recognizable pattern of anomalies. De novo mutations in the gene encoding chromodomain helicase DNA binding protein 7 (CHD7) are the major cause of CHARGE syndrome. Here, we review the clinical features of 379 CHARGE patients who tested positive or negative for mutations in CHD7. We found that CHARGE individuals with CHD7 mutations more commonly have ocular colobomas, temporal bone anomalies (semicircular canal hypoplasia/dysplasia), and facial nerve paralysis compared with mutation negative individuals. We also highlight recent genetic and genomic studies that have provided functional insights into CHD7 and the pathogenesis of CHARGE syndrome. PMID:20186815

Effect of Fe{sub 3}O{sub 4} nanoparticles on space charge distribution in propylene carbonate under impulse voltage

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

Sima, Wenxia, E-mail: cqsmwx@cqu.edu.cn; Song, He; Yang, Qing

2015-12-15

Addition of nanoparticles of the ferromagnetic material Fe{sub 3}O{sub 4} can increase the positive impulse breakdown voltage of propylene carbonate by 11.65%. To further investigate the effect of ferromagnetic nanoparticles on the space charge distribution in the discharge process, the present work set up a Kerr electro-optic field mapping measurement system using an array photodetector to carry out time-continuous measurement of the electric field and space charge distribution in propylene carbonate before and after modification. Test results show that fast electrons can be captured by Fe{sub 3}O{sub 4} nanoparticles and converted into relatively slow, negatively charged particles, inhibiting the generationmore » and transportation of the space charge, especially the negative space charge.« less

Polyplex formation between four-arm poly(ethylene oxide)-b-poly(2-(diethylamino)ethyl methacrylate) and plasmid DNA in gene delivery.

PubMed

He, E; Yue, C Y; Simeon, F; Zhou, L H; Too, H P; Tam, K C

2009-12-01

Amphiphilic polyelectrolytes comprising cationic and uncharged hydrophilic segments condensed negatively charged DNA to form a core-shell structure stabilized by a layer of hydrophilic corona chains. At physiological pH, four-arm star-shaped poly(ethylene oxide)-b-poly(2-(diethylamino)ethyl methacrylate) (four-arm PEO-b-PDEAEMA) block copolymer possessed positively charged amine groups that interacted with negatively charged plasmid DNA to form polymer/DNA complexes. The mechanism and physicochemical properties of the complex formation were investigated at varying molar ratio of amine groups on polymer chains and phosphate group on plasmid DNA segments (N/P ratio). The capability of the star block copolymer to condense DNA was demonstrated through gel electrophoresis and ethidium bromide exclusion assay. In the absence of salt, the hydrodynamic radius of polyplexes was about 94 nm at low polymer/DNA ratio, and it decreased to about 34 nm at large N/P ratios, forming a compact spherical structure with a weighted average molecular weight of 4.39 +/- 0.22 x 10(6) g/mol. Approximately 15 polymeric chains were required to condense a plasmid DNA. The addition of monovalent salt to the polyplexes significantly altered the size of the complexes, which would have an impact on cell transfection. Because of the electrostatic interaction induced by the diffusion of small ions, the polyplex increased in size to about 53 nm with a less compact structure. In vitro cytotoxicty of polymer and polymer/pDNA complexes were evaluated, and the polyplexes exhibited low toxicity at low N/P ratios. At N/P ratio of 4.5, the four-arm PEO-b-PDEAEMA showed the highest level of transfection in Neuro-2A cells. These observations showed that the star-shaped multi-arm polymers offers interesting properties in self-association and condensation ability for plasmid DNA and can serve as a nonviral DNA delivery system. Copyright 2008 Wiley Periodicals, Inc.

Hazardous particle binder, coagulant and re-aerosolization inhibitor

DOEpatents

Krauter, Paula [Livermore, CA; Zalk, David [San Jose, CA; Hoffman, D Mark [Livermore, CA

2011-04-12

A copolymer and water/ethanol solvent solution capable of binding with airborne contaminants or potential airborne contaminants, such as biological weapon agents or toxic particulates, coagulating as the solvent evaporates, and adhering the contaminants to a surface so as to inhibit the re-suspension of such contaminants. The solution uses a water or ethanol/water mixture for the solvent, and a copolymer having one of several functional group sets so as to have physical and chemical characteristics of high adhesion, low viscosity, low surface tension, negative electrostatic charge, substantially neutral pH, and a low pKa. Use of the copolymer solution prevents re-aerosolization and transport of unwanted, reactive species thus increasing health and safety for personnel charged with decontamination of contaminated buildings and areas.

Hazardous particle binder, coagulant and re-aerosolization inhibitor

DOEpatents

Krauter, Paula; Zalk, David; Hoffman, D. Mark

2012-07-10

A copolymer and water/ethanol solvent solution capable of binding with airborne contaminants or potential airborne contaminants, such as biological weapon agents or toxic particulates, coagulating as the solvent evaporates, and adhering the contaminants to a surface so as to inhibit the re-suspension of such contaminants. The solution uses a water or ethanol/water mixture for the solvent, and a copolymer having one of several functional group sets so as to have physical and chemical characteristics of high adhesion, low viscosity, low surface tension, negative electrostatic charge, substantially neutral pH, and a low pKa. Use of the copolymer solution prevents re-aerosolization and transport of unwanted, reactive species thus increasing health and safety for personnel charged with decontamination of contaminated buildings and areas.

Contribution of Charges in Polyvinyl Alcohol Networks to Marine Antifouling.

PubMed

Yang, Wufang; Lin, Peng; Cheng, Daocang; Zhang, Longzhou; Wu, Yang; Liu, Yupeng; Pei, Xiaowei; Zhou, Feng

2017-05-31

Semi-interpenetrated polyvinyl alcohol polymer networks (SIPNs) were prepared by integrating various charged components into polyvinyl alcohol polymer. Contact angle measurement, attenuated total reflection Fourier transform infrared spectroscopy, field emission scanning electron microscopy, and tensile tests were used to characterize the physicochemical properties of the prepared SIPNs. To investigate the contribution of charges to marine antifouling, the adhesion behaviors of green algae Dunaliella tertiolecta and diatoms Navicula sp. in the laboratory and of the actual marine animals in field test were studied for biofouling assays. The results suggest that less algae accumulation densities are observed for neutral-, anionic-, and zwitterionic-component-integrated SIPNs. However, for the cationic SIPNs, despite the hydration shell induced by the ion-dipole interaction, the resistance to biofouling largely depends on the amount of cationic component because of the possible favorable electrostatic attraction between the cationic groups in SIPNs and the negatively charged algae. Considering that the preparation of novel nontoxic antifouling coating is a long-standing and cosmopolitan industrial challenge, the SIPNs may provide a useful reference for marine antifouling and some other relevant fields.

Investigation of exotic stable calcium carbides using theory and experiment

DOE PAGES

Li, Yan-Ling; Wang, Sheng-Nan; Oganov, Artem R.; ...

2015-05-11

It is well known that pressure causes profound changes in the properties of atoms and chemical bonding, leading to the formation of many unusual materials. Here we systematically explore all stable calcium carbides at pressures from ambient to 100 GPa using variable-composition evolutionary structure predictions. We find that Ca 5C 2, Ca 2C, Ca 3C 2, CaC, Ca 2C 3, and CaC 2 have stability fields on the phase diagram. Among these, Ca2C and Ca2C3 are successfully synthesized for the first time via high-pressure experiments with excellent structural correspondence to theoretical predictions. Of particular significance are the base-centered monoclinic phasemore » (space group C 2/m) of Ca 2C, a quasi-two-dimensional metal with layers of negatively charged calcium atoms, and the primitive monoclinic phase (space group P21/c) of CaC with zigzag C 4 groups. Interestingly, strong interstitial charge localization is found in the structure of R-3m-Ca 5C 2 with semimetallic behaviour.« less

Influence of surface groups of proteins on water studied by freezing/thawing hysteresis and infrared spectroscopy.

PubMed

Zelent, Bogumil; Bryan, Michael A; Sharp, Kim A; Vanderkooi, Jane M

2009-05-01

The influence of proteins and solutes on hysteresis of freezing and melting of water was measured by infrared (IR) spectroscopy. Of the solutes examined, poly-L-arginine and flounder antifreeze protein produced the largest freezing point depression of water, with little effect on the melting temperature. Poly-L-lysine, poly-L-glutamate, cytochrome c and bovine serum albumin had less effect on the freezing of water. Small compounds used to mimic non-polar (trimethylamine N-oxide, methanol), positively charged (guanidinium chloride, NH(4)Cl, urea) and negatively charged (Na acetate) groups on protein surfaces were also examined. These molecules and ions depress water's freezing point and the melting profiles became broad. Since infrared absorption measures both bulk solvent and solvent bound to the solutes, this result is consistent with solutes interacting with liquid water. The amide I absorption bands of antifreeze protein and poly-L-arginine do not detectably change with the phase transition of water. An interpretation is that the antifreeze protein and poly-L-arginine order liquid water such that the water around the group is ice-like.

The voltage-dependent anion channel as a biological transistor: theoretical considerations.

PubMed

Lemeshko, V V; Lemeshko, S V

2004-07-01

The voltage-dependent anion channel (VDAC) is a porin of the mitochondrial outer membrane with a bell-shaped permeability-voltage characteristic. This porin restricts the flow of negatively charged metabolites at certain non-zero voltages, and thus might regulate their flux across the mitochondrial outer membrane. Here, we have developed a mathematical model illustrating the possibility of interaction between two steady-state fluxes of negatively charged metabolites circulating across the VDAC in a membrane. The fluxes interact by contributing to generation of the membrane electrical potential with subsequent closure of the VDAC. The model predicts that the VDAC might function as a single-molecule biological transistor and amplifier, because according to the obtained calculations a small change in the flux of one pair of different negatively charged metabolites causes a significant modulation of a more powerful flux of another pair of negatively charged metabolites circulating across the same membrane with the VDAC. Such transistor-like behavior of the VDAC in the mitochondrial outer membrane might be an important principle of the cell energy metabolism regulation under some physiological conditions.

An in situ generated carbon as integrated conductive additive for hierarchical negative plate of lead-acid battery

NASA Astrophysics Data System (ADS)

Saravanan, M.; Ganesan, M.; Ambalavanan, S.

2014-04-01

In this work, we report an in situ generated carbon from sugar as additive in the Negative Active Mass (NAM) which enhances the charge-discharge characteristics of the lead-acid cells. In situ formed sugar derived carbon (SDC) with leady oxide (LO) provides a conductive network and excellent protection against NAM irreversible lead sulfation. The effect of SDC and carbon black (CB) added negative plates are characterized by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), galvanostatic charge-discharge, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), respectively. The results show that subtle changes in the addition of carbon to NAM led to subsequent changes on the performance during partial-state-of-charge (PSoC) operations in lead-acid cells. Furthermore, SDC added cells exhibit remarkable improvement in the rate capability, active material utilization, cycle performance and charge acceptance compared to that of the conventional CB added cells. The impact of SDC with LO at various synthesis conditions on the electrochemical performance of the negative plate is studied systematically.

Functionalized nanoparticle interactions with polymeric membranes.

PubMed

Ladner, D A; Steele, M; Weir, A; Hristovski, K; Westerhoff, P

2012-04-15

A series of experiments was performed to measure the retention of a class of functionalized nanoparticles (NPs) on porous (microfiltration and ultrafiltration) membranes. The findings impact engineered water and wastewater treatment using membrane technology, characterization and analytical schemes for NP detection, and the use of NPs in waste treatment scenarios. The NPs studied were composed of silver, titanium dioxide, and gold; had organic coatings to yield either positive or negative surface charge; and were between 2 and 10nm in diameter. NP solutions were applied to polymeric membranes composed of different materials and pore sizes (ranging from ≈ 2 nm [3 kDa molecular weight cutoff] to 0.2 μm). Greater than 99% rejection was observed of positively charged NPs by negatively charged membranes even though pore diameters were up to 20 times the NP diameter; thus, sorption caused rejection. Negatively charged NPs were less well rejected, but behavior was dependent not only on surface functionality but on NP core material (Ag, TiO(2), or Au). NP rejection depended more upon NP properties than membrane properties; all of the negatively charged polymeric membranes behaved similarly. The NP-membrane interaction behavior fell into four categories, which are defined and described here. Copyright © 2011 Elsevier B.V. All rights reserved.

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.

Lightning Activity Relative to the Microphysical and Kinematic Structure of Storms during a Thunder-Snow Episode on 29-30 November 2006

NASA Astrophysics Data System (ADS)

Emersic, C.; Macgorman, D.; Schuur, T.; Lund, N.; Payne, C.; Bruning, E.

2007-12-01

We have examined lightning activity relative to the microphysical and kinematic structure of a winter thunderstorm complex (a thunder-snow episode) observed east of Norman, Oklahoma during the evening of 29-30 November 2006. Polarimetric radar provided information about the type of particles present in various regions of the storms. The Lightning Mapping Array (LMA) recorded VHF signals produced by developing lightning channels. The times of arrival of these lightning signals across the array were then used to reconstruct the location and structure of lightning, and these reconstructions were overlaid with radar data to examine the relationship between lightning properties and storm particle types. Four storms in this winter complex have been examined. It was inferred from lightning structure that, in their mature stage, all cells we examined had a positive tripole electrical structure (an upper positive charge center, a midlevel negative charge center, and a lower positive charge center). The storms began with lightning activity in the lower dipole (lower positive and midlevel negative regions), but this evolved into lightning activity throughout the tripole structure within approximately 15-20 minutes. In the longer lived storms, the mature stage lasted for approximately 1.5-2 hours. During this stage, the lower positive charge region was situated less than 5 km above ground, the midlevel negative charge region was typically above 5 km, and the upper positive charge region was located at an altitude of less than 10 km in all the storm cells analyzed. The charge regions descended over approximately the last 30 minutes of lightning activity, the lower charge regions eventually reaching ground. This resulted in the loss of the lower positive charge center and the subsequent diminishment of the lower negative charge center. Lightning initiation usually coincided with the edges of regions of high reflectivity and was coincident with the presence of graupel and ice crystals in the lower dipole. Radar data suggest that ice crystals were the dominant charge carriers in the upper positive region.

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.

Graphite anode surface modification with controlled reduction of specific aryl diazonium salts for improved microbial fuel cells power output.

PubMed

Picot, Matthieu; Lapinsonnière, Laure; Rothballer, Michael; Barrière, Frédéric

2011-10-15

Graphite electrodes were modified with reduction of aryl diazonium salts and implemented as anodes in microbial fuel cells. First, reduction of 4-aminophenyl diazonium is considered using increased coulombic charge density from 16.5 to 200 mC/cm(2). This procedure introduced aryl amine functionalities at the surface which are neutral at neutral pH. These electrodes were implemented as anodes in "H" type microbial fuel cells inoculated with waste water, acetate as the substrate and using ferricyanide reduction at the cathode and a 1000 Ω external resistance. When the microbial anode had developed, the performances of the microbial fuel cells were measured under acetate saturation conditions and compared with those of control microbial fuel cells having an unmodified graphite anode. We found that the maximum power density of microbial fuel cell first increased as a function of the extent of modification, reaching an optimum after which it decreased for higher degree of surface modification, becoming even less performing than the control microbial fuel cell. Then, the effect of the introduction of charged groups at the surface was investigated at a low degree of surface modification. It was found that negatively charged groups at the surface (carboxylate) decreased microbial fuel cell power output while the introduction of positively charged groups doubled the power output. Scanning electron microscopy revealed that the microbial anode modified with positively charged groups was covered by a dense and homogeneous biofilm. Fluorescence in situ hybridization analyses showed that this biofilm consisted to a large extent of bacteria from the known electroactive Geobacter genus. In summary, the extent of modification of the anode was found to be critical for the microbial fuel cell performance. The nature of the chemical group introduced at the electrode surface was also found to significantly affect the performance of the microbial fuel cells. The method used for modification is easy to control and can be optimized and implemented for many carbon materials currently used in microbial fuel cells and other bioelectrochemical systems. Copyright © 2011 Elsevier B.V. All rights reserved.

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.

Maxwell's conjecture on three point charges with equal magnitudes

NASA Astrophysics Data System (ADS)

Tsai, Ya-Lun

2015-08-01

Maxwell's conjecture on three point charges states that the number of non-degenerate equilibrium points of the electrostatic field generated by them in R3 is at most four. We prove the conjecture in the cases when three point charges have equal magnitudes and show the number of isolated equilibrium points can only be zero, two, three, or four. Specifically, fixing positions of two positive charges in R3, we know exactly where to place the third positive charge to have two, three, or four equilibrium points. All equilibrium points are isolated and there are no other possibilities for the number of isolated equilibrium points. On the other hand, if both two of the fixed charges have negative charge values, there are always two equilibrium points except when the third positive charge lies in the line segment connecting the two negative charges. The exception cases are when the field contains only a curve of equilibrium points. In this paper, computations assisted by computer involve symbolic and exact integer computations. Therefore, all the results are proved rigorously.

Physical Origin of Transient Negative Capacitance in a Ferroelectric Capacitor

NASA Astrophysics Data System (ADS)

Chang, Sou-Chi; Avci, Uygar E.; Nikonov, Dmitri E.; Manipatruni, Sasikanth; Young, Ian A.

2018-01-01

Transient negative differential capacitance, the dynamic reversal of transient capacitance in an electrical circuit, is of highly technological and scientific interest since it probes the foundation of ferroelectricity. We study a resistor-ferroelectric capacitor (R -FEC) network through a series of coupled equations based on Kirchhoff's law, electrostatics, and Landau theory. We show that transient negative capacitance (NC) in a R -FEC circuit originates from the mismatch in switching rate between the free charge on the metal plate and the bound charge in a ferroelectric (FE) capacitor during the polarization switching. This transient free charge-polarization mismatch is driven by the negative curvature of the FE free-energy landscape, and it is also analytically shown that a free-energy profile with a negative curvature is the only physical system that can describe transient NC in a R -FEC circuit. Furthermore, transient NC induced by the free charge-polarization mismatch is justified by its dependence on both external resistance and the intrinsic FE viscosity coefficient. The depolarization effect on FE capacitors emphasizes the importance of negative curvature to transient NC and also implies that transient and steady-state NC cannot be observed in a FE capacitor simultaneously. Finally, using the transient NC measurements, a procedure to experimentally determine the viscosity coefficient is presented to provide more insight into the relation between transient NC and the FE free-energy profile.

Receptor-Mediated Melanoma Targeting with Radiolabeled α-Melanocyte-Stimulating Hormone: Relevance of the Net Charge of the Ligand.

PubMed

Bapst, Jean-Philippe; Eberle, Alex N

2017-01-01

A majority of melanotic and amelanotic melanomas overexpress melanocortin type 1 receptors (MC1Rs) for α-melanocyte-stimulating hormone. Radiolabeled linear or cyclic analogs of α-MSH have a great potential as diagnostic or therapeutic tools for the management of malignant melanoma. Compounds such as [ 111 In]DOTA-NAP-amide exhibit high affinity for the MC1R in vitro , good tumor uptake in vivo , but they may suffer from relatively high kidney uptake and retention in vivo . We have shown previously that the introduction of negative charges into radiolabeled DOTA-NAP-amide peptide analogs may enhance their excretion and reduce kidney retention. To address the question of where to place negative charges within the ligand, we have extended these studies by designing two novel peptides, Ac-Nle-Asp-His-d-Phe-Arg-Trp-Gly-Lys(DOTA)-d-Asp-d-Asp-OH (DOTA-NAP-d-Asp-d-Asp) with three negative charges at the C -terminal end (overall net charge of the molecule -2) and DOTA-Gly-Tyr(P)-Nle-Asp-His-d-Phe-Arg-Trp-NH 2 (DOTA-Phospho-MSH 2-9 ) with two negative charges in the N -terminal region (net charge -1). The former peptide showed markedly reduced receptor affinity and biological activity by >10-fold compared to DOTA-NAP-amide as reference compound, and the latter peptide displayed similar bioactivity and receptor affinity as the reference compound. The uptake by melanoma tumor tissue of [ 111 In]DOTA-Phospho-MSH 2-9 was 7.33 ± 0.47 %ID/g 4 h after injection, i.e., almost equally high as with [ 111 In]DOTA-NAP-amide. The kidney retention was 2.68 ± 0.18 %ID/g 4 h after injection and hence 44% lower than that of [ 111 In]DOTA-NAP-amide. Over an observation period from 4 to 48 h, the tumor-to-kidney ratio of [ 111 In]DOTA-Phospho-MSH 2-9 was 35% more favorable than that of the reference compound. In a comparison of DOTA-NAP-d-Asp-d-Asp, DOTA-Phospho-MSH 2-9 and DOTA-NAP-amide with five previously published analogs of DOTA-NAP-amide that altogether cover a range of peptides with an overall net charge between +2 and -2, we now demonstrate that a net charge of -1, with the extra negative charges preferably placed in the N -terminal region, has led to the lowest kidney uptake and retention. Charges of +2 or -2 markedly increased kidney uptake and retention. In conclusion, the novel DOTA-Phospho-MSH 2-9 may represent a new lead compound for negatively charged linear MC1R ligands that can be further developed into a clinically relevant melanoma targeting radiopeptide.

Receptor-Mediated Melanoma Targeting with Radiolabeled α-Melanocyte-Stimulating Hormone: Relevance of the Net Charge of the Ligand

PubMed Central

Bapst, Jean-Philippe; Eberle, Alex N.

2017-01-01

A majority of melanotic and amelanotic melanomas overexpress melanocortin type 1 receptors (MC1Rs) for α-melanocyte-stimulating hormone. Radiolabeled linear or cyclic analogs of α-MSH have a great potential as diagnostic or therapeutic tools for the management of malignant melanoma. Compounds such as [111In]DOTA-NAP-amide exhibit high affinity for the MC1R in vitro, good tumor uptake in vivo, but they may suffer from relatively high kidney uptake and retention in vivo. We have shown previously that the introduction of negative charges into radiolabeled DOTA-NAP-amide peptide analogs may enhance their excretion and reduce kidney retention. To address the question of where to place negative charges within the ligand, we have extended these studies by designing two novel peptides, Ac-Nle-Asp-His-d-Phe-Arg-Trp-Gly-Lys(DOTA)-d-Asp-d-Asp-OH (DOTA-NAP-d-Asp-d-Asp) with three negative charges at the C-terminal end (overall net charge of the molecule −2) and DOTA-Gly-Tyr(P)-Nle-Asp-His-d-Phe-Arg-Trp-NH2 (DOTA-Phospho-MSH2-9) with two negative charges in the N-terminal region (net charge −1). The former peptide showed markedly reduced receptor affinity and biological activity by >10-fold compared to DOTA-NAP-amide as reference compound, and the latter peptide displayed similar bioactivity and receptor affinity as the reference compound. The uptake by melanoma tumor tissue of [111In]DOTA-Phospho-MSH2-9 was 7.33 ± 0.47 %ID/g 4 h after injection, i.e., almost equally high as with [111In]DOTA-NAP-amide. The kidney retention was 2.68 ± 0.18 %ID/g 4 h after injection and hence 44% lower than that of [111In]DOTA-NAP-amide. Over an observation period from 4 to 48 h, the tumor-to-kidney ratio of [111In]DOTA-Phospho-MSH2-9 was 35% more favorable than that of the reference compound. In a comparison of DOTA-NAP-d-Asp-d-Asp, DOTA-Phospho-MSH2-9 and DOTA-NAP-amide with five previously published analogs of DOTA-NAP-amide that altogether cover a range of peptides with an overall net charge between +2 and −2, we now demonstrate that a net charge of −1, with the extra negative charges preferably placed in the N-terminal region, has led to the lowest kidney uptake and retention. Charges of +2 or −2 markedly increased kidney uptake and retention. In conclusion, the novel DOTA-Phospho-MSH2-9 may represent a new lead compound for negatively charged linear MC1R ligands that can be further developed into a clinically relevant melanoma targeting radiopeptide. PMID:28491052

Observation of negative differential resistance in mesoscopic graphene oxide devices.

PubMed

Rathi, Servin; Lee, Inyeal; Kang, Moonshik; Lim, Dongsuk; Lee, Yoontae; Yamacli, Serhan; Joh, Han-Ik; Kim, Seongsu; Kim, Sang-Woo; Yun, Sun Jin; Choi, Sukwon; Kim, Gil-Ho

2018-05-08

The fractions of various functional groups in graphene oxide (GO) are directly related to its electrical and chemical properties and can be controlled by various reduction methods like thermal, chemical and optical. However, a method with sufficient controllability to regulate the reduction process has been missing. In this work, a hybrid method of thermal and joule heating processes is demonstrated where a progressive control of the ratio of various functional groups can be achieved in a localized area. With this precise control of carbon-oxygen ratio, negative differential resistance (NDR) is observed in the current-voltage characteristics of a two-terminal device in the ambient environment due to charge-activated electrochemical reactions at the GO surface. This experimental observation correlates with the optical and chemical characterizations. This NDR behavior offers new opportunities for the fabrication and application of such novel electronic devices in a wide range of devices applications including switches and oscillators.

Electron kinetics at the plasma interface

NASA Astrophysics Data System (ADS)

Bronold, Franz Xaver; Fehske, Holger; Pamperin, Mathias; Thiessen, Elena

2018-05-01

The most fundamental response of an ionized gas to a macroscopic object is the formation of the plasma sheath. It is an electron depleted space charge region, adjacent to the object, which screens the object's negative charge arising from the accumulation of electrons from the plasma. The plasma sheath is thus the positively charged part of an electric double layer whose negatively charged part is inside the wall. In the course of the Transregional Collaborative Research Center SFB/TRR24 we investigated, from a microscopic point of view, the elementary charge transfer processes responsible for the electric double layer at a floating plasma-wall interface and made first steps towards a description of the negative part of the layer inside the wall. Below we review our work in a colloquial manner, describe possible extensions, and identify key issues which need to be resolved to make further progress in the understanding of the electron kinetics across plasma-wall interfaces. Contribution to the Topical Issue "Fundamentals of Complex Plasmas", edited by Jürgen Meichsner, Michael Bonitz, Holger Fehske, Alexander Piel.

Characteristics of space charge formed in a laminated LDPE/EVA dielectric under DC stress

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

Tanaka, Toshikatsu; Kisanuki, Osamu; Sakata, Masataka

1996-12-31

A laser-induced pressure pulse (LIPP) method was used for measuring the space charge distribution of LDPE/EVA laminate dielectrics under dc stress. The constant voltage up to {+-}20 kV was applied to a side of the laminates of 0.5 mm thickness for 30 minutes. The other side is grounded. When the amount of space charge was measured by LIPP, both sides were virtually grounded. Space charge built up in or near the interface between LDPE and EVA was mainly investigated. Positive and negative voltage was applied to the side of LDPE in the laminates. It was clarified that the space chargemore » was larger in case of LDPE negatively biased than in case of LDPE positively biased. The density of the space charge ranged around 1 nC/mm{sup 3}. The formation of interfacial space charge is analyzed.« less

Charge Effects on the Efflorescence in Single Levitated Droplets.

PubMed

Hermann, Gunter; Zhang, Yan; Wassermann, Bernhard; Fischer, Henry; Quennet, Marcel; Rühl, Eckart

2017-09-14

The influence of electrical excess charges on the crystallization from supersaturated aqueous sodium chloride solutions is reported. This is accomplished by efflorescence studies on single levitated microdroplets using optical and electrodynamic levitation. Specifically, a strong increase in efflorescence humidity is observed as a function of the droplet's negative excess charge, ranging up to -2.1 pC, with a distinct threshold behavior, increasing the relative efflorescence humidity, at which spontaneous nucleation occurs, from 44% for the neutral microparticle to 60%. These findings are interpreted by using molecular dynamics simulations for determining plausible structural patterns located near the particle surface that could serve as suitable precursors for the formation of critical clusters overcoming the nucleation barrier. These results, facilitating heterogeneous nucleation in the case of negatively charged microparticles, are compared to recent work on charge-induced nucleation of neat supercooled water, where a distinctly different nucleation behavior as a function of droplet charge has been observed.

Transmission of low-energy negative ions through insulating nanocapillaries

NASA Astrophysics Data System (ADS)

Zhang, Qi; Liu, Zhonglin; Li, Pengfei; Jin, Bo; Song, Guangyin; Jin, Dingkun; Niu, Ben; Wei, Long; Ha, Shuai; Xie, Yiming; Ma, Yue; Wan, Chengliang; Cui, Ying; Zhou, Peng; Zhang, Hongqiang; Chen, Ximeng

2018-04-01

A simulation is performed to study the transmission of low-energy C l- ions through A l2O3 nanocapillaries. For the trajectory simulations, there are several processes involved: the image forces induced by the projectile; the electrostatic force from the deposited charges; the scattering from the inner surface and charge exchange. The simulation reproduces the main features of the experiments; i.e., the double peak structure in the transmitted angular distribution and the transmitted fractions of C l- , C l+ , and C l0 were found in the charge state distribution. The transmitted C l- ions are centered around the beam direction while the transmitted fractions of C l0 and C l+ are centered around the tilt angles. The role of the deposited charge is also studied by simulations. With the deposited charge, it is found that C l- is dominant in the transmission and the majority of the ions, centered around the tilt angle, are mainly from the single deflection by the negative charge patches on the inner surfaces of the capillaries, and only a few directly transmitted C l- ions are centered around the incident direction. There are also a few transmitted fractions of C l0 and C l+ from close surface scatterings. In the case that there are no negative charge patches, the simulation agrees with the experiment in detail: The majority of the directly transmitted C l- ions are centered around the incident direction while only a few scattered C l- ions are centered around the tilt angle from the single close collisions with the inner surfaces of the capillaries. There is a portion, comparable to the transmitted fraction of C l- , of the transmitted fractions of C l0 and C l+ , centered around the tilt angle, from the single scatterings with the inner surfaces of the capillaries. This confirms that at the present experimental conditions there are most probably no negative charge patches formed to guide the negative ions through insulating A l2O3 nanocapillaries.

Lysozyme adsorption in pH-responsive hydrogel thin-films: the non-trivial role of acid-base equilibrium.

PubMed

Narambuena, Claudio F; Longo, Gabriel S; Szleifer, Igal

2015-09-07

We develop and apply a molecular theory to study the adsorption of lysozyme on weak polyacid hydrogel films. The theory explicitly accounts for the conformation of the network, the structure of the proteins, the size and shape of all the molecular species, their interactions as well as the chemical equilibrium of each titratable unit of both the protein and the polymer network. The driving forces for adsorption are the electrostatic attractions between the negatively charged network and the positively charged protein. The adsorption is a non-monotonic function of the solution pH, with a maximum in the region between pH 8 and 9 depending on the salt concentration of the solution. The non-monotonic adsorption is the result of increasing negative charge of the network with pH, while the positive charge of the protein decreases. At low pH the network is roughly electroneutral, while at sufficiently high pH the protein is negatively charged. Upon adsorption, the acid-base equilibrium of the different amino acids of the protein shifts in a nontrivial fashion that depends critically on the particular kind of residue and solution composition. Thus, the proteins regulate their charge and enhance adsorption under a wide range of conditions. In particular, adsorption is predicted above the protein isoelectric point where both the solution lysozyme and the polymer network are negatively charged. This behavior occurs because the pH in the interior of the gel is significantly lower than that in the bulk solution and it is also regulated by the adsorption of the protein in order to optimize protein-gel interactions. Under high pH conditions we predict that the protein changes its charge from negative in the solution to positive within the gel. The change occurs within a few nanometers at the interface of the hydrogel film. Our predictions show the non-trivial interplay between acid-base equilibrium, physical interactions and molecular organization under nanoconfined conditions, which leads to non-trivial adsorption behavior that is qualitatively different from what would be predicted from the state of the proteins in the bulk solution.

A new biphasic osteoinductive calcium composite material with a negative Zeta potential for bone augmentation

PubMed Central

Smeets, Ralf; Kolk, Andreas; Gerressen, Marcus; Driemel, Oliver; Maciejewski, Oliver; Hermanns-Sachweh, Benita; Riediger, Dieter; Stein, Jamal M

2009-01-01

The aim of the present study was to analyze the osteogenic potential of a biphasic calcium composite material (BCC) with a negative surface charge for maxillary sinus floor augmentation. In a 61 year old patient, the BCC material was used in a bilateral sinus floor augmentation procedure. Six months postoperative, a bone sample was taken from the augmented regions before two titanium implants were inserted at each side. We analyzed bone neoformation by histology, bone density by computed tomography, and measured the activity of voltage-activated calcium currents of osteoblasts and surface charge effects. Control orthopantomograms were carried out five months after implant insertion. The BCC was biocompatible and replaced by new mineralized bone after being resorbed completely. The material demonstrated a negative surface charge (negative Zeta potential) which was found to be favorable for bone regeneration and osseointegration of dental implants. PMID:19523239

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.

Modeling carbonaceous particle formation in an argon graphite cathode dc discharge

NASA Astrophysics Data System (ADS)

Michau, A.; Lombardi, G.; Colina Delacqua, L.; Redolfi, M.; Arnas, C.; Bonnin, X.; Hassouni, K.

2010-12-01

We develop a model for the nucleation, growth and transport of carbonaceous dust particles in a non-reactive gas dc discharge where the carbon source is provided by cathode sputtering. We consider only the initial phase of the discharge when the dust charge density remains small with respect to the electron density. We find that an electric field reversal at the entrance of the negative glow region promotes trapping of negatively charged clusters and dust particles, confining them for long times in the plasma and favoring molecular growth. An essential ingredient for this process is electron attachment, which negatively charges the initially neutral clusters. We perform sensitivity studies on several number parameters: size of the largest molecular edifice, sticking coefficient, etc.

Increase of the pharmacological and pharmacokinetic efficacy of negatively charged polypeptide recombinant hirudin in rats via parenteral route by association with cationic liposomes.

PubMed

Meng, Meng; Liu, Yu; Wang, Yi-Bo; Wang, Jian-Cheng; Zhang, Hua; Wang, Xue-Qing; Zhang, Xuan; Lu, Wan-Liang; Zhang, Qiang

2008-06-04

Two biodegradable cationic lipids, stearylamine and DC-Chol, were chosen to investigate the effect of cationic lipids on the in vitro and in vivo characteristics of hydrophilic proteins or peptides of low isoelectric point. Thrombin inhibitor recombinant hirudin variant-2 (rHV2) was selected as the model drug. The cationic lipids were found to achieve higher entrapment efficiency of rHV2 in liposomes than zwitterionic lipids. The positively charged liposomes became less positive and relatively stable in serum after loading rHV2. The cationic liposomes induced sustained release of rHV2 in the presence of plasma, significantly prolonged the antithrombotic efficacy and plasma level of rHV2 after intravenous injection in rats in comparison with neutral lipid liposomes, especially for stearylamine group. Both clotting times correlated well with plasma rHV2 levels. No serious adverse events were observed and physical state of rats was satisfactory for all the formulations. Electrostatic interaction between negative charge of rHV2 and cationic liposomes was confirmed and it might affect all the characteristics of rHV2 loaded cationic vehicles. The findings suggest that cationic liposomes may be a potential sustained-release delivery system for parenteral administration of hydrophilic proteins or peptides with low isoelectric point to prolong efficacy and improve bioavailability.

Vibrational spectroscopic and molecular docking study of (2E)-N-(4-chloro-2-oxo-1,2-dihydroquinolin-3-yl)-3-phenylprop-2-enamide.

PubMed

Ulahannan, Rajeev T; Panicker, C Yohannan; Varghese, Hema Tresa; Musiol, Robert; Jampilek, Josef; Van Alsenoy, Christian; War, Javeed Ahmad; Al-Saadi, Abdulaziz A

2015-01-01

FT-IR and FT-Raman spectra of (2E)-N-(4-chloro-2-oxo-1,2-dihydroquinolin-3-yl)-3-phenylprop-2-enamide were recorded and analyzed experimentally and theoretically. The synthesis, (1)H NMR and PES scan results are also discussed. Nonlinear optical behavior of the examined molecule was investigated by the determination of first hyperpolarizability. The calculated HOMO and LUMO energies show the chemical activity of the molecule. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using NBO analysis. From the MEP it is evident that the negative charge covers the carbonyl group and the positive region is over the NH group. The calculated geometrical parameters (SDD) are in agreement with that of similar derivatives. Molecular docking simulations against targets from Mycobacterium tuberculosis are reported and the results suggest that the compound might exhibit inhibitory activity against PknB. Copyright © 2015 Elsevier B.V. All rights reserved.

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

Rodriguez, Mark A.; Sava Gallis, Dorina F.; Chavez, James S.

We report here the synthesis of a neutral viologen derivative, C 24H 16N 2O 4·2H 2O. The non-solvent portion of the structure (Z-Lig) is a zwitterion, consisting of two positively charged pyridinium cations and two negatively charged carboxylate anions. The carboxylate group is almost coplanar [dihedral angle = 2.04 (11)°] with the benzene ring, whereas the dihedral angle between pyridine and benzene rings is 46.28 (5)°. TheZ-Lig molecule is positioned on a center of inversion (Fig. 1). The presence of the twofold axis perpendicular to thec-glide plane in space groupC2/c generates a screw-axis parallel to thebaxis that is shifted from themore » origin by 1/4 in theaandcdirections. This screw-axis replicates the molecule (and solvent water molecules) through space. TheZ-Lig molecule links to adjacent moleculesviaO—H...O hydrogen bonds involving solvent water molecules as well as intermolecular C—H...O interactions. There are also π–π interactions between benzene rings on adjacent molecules.« less

Role of glutamate-199 in the aging of cholinesterase. (Reannouncement with new availability information)

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

Saxena, A.; Doctor, B.P.; Maxwell, D.M.

1993-11-30

Aging of organophosphate-conjugated acetylcholinesterase results from the loss of an alkoxy group with concomitant stabilization of the conjugate to spontaneous or nucleophile-induced deacylation. We have examined the kinetics of aging in a pinacolylmethylphosphonofluoridate (soman)-inhibited mutant enzyme in which the glutamate (E199) located at the amino-terminal to the active-site sense (S200) was converted to glutamine (Q). For wild type enzyme, the soman-acetylcholinesterase conjugate aged immediately, giving rise to a form of enzyme resistant to reactivation by oximes. In contrast, the E199Q mutant enzyme was largely resistant to aging and could be reactivated by oximes. Since the pH dependence for aging wasmore » not altered appreciably, the primary influence of the loss of charge appears to be on the intrinsic rate of aging. The negative charge on E199 likely imparts an inductive effect on the conjugated organophosphate to facilitate removal of the alkoxy group. Cholinesterases, Aging, Organophosphate.« less

Nanoparticle coagulation in fractionally charged and charge fluctuating dusty plasmas

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

Nunomura, Shota; Kondo, Michio; Shiratani, Masaharu

2008-08-15

The kinetics of nanoparticle coagulation has been studied in fractionally charged and charge fluctuating dusty plasmas. The coagulation occurs when the mutual collision frequency among nanoparticles exceeds their charging and decharging/neutralization frequency. Interestingly, the coagulation is suppressed while a fraction (several percent) of nanoparticles are negatively charged in a plasma, in which stochastic charging plays an important role. A model is developed to predict a phase diagram of the coagulation and its suppression.

A Brief 30-Year Review: Research Highlights from Lightning Mapping Systems 1970-2000

NASA Astrophysics Data System (ADS)

MacGorman, D. R.

2016-12-01

Modern lightning mapping began in the 1970s, the decade in which VHF mapping systems, acoustic mapping systems, and ground strike locating systems were introduced. Adding GPS synchronization of VHF systems in the late 1990s enabled real-time VHF mapping systems to be deployed more extensively. Data these systems provided by 2000 revolutionized our understanding of how storms produce lightning. Among key results: Electrostatics, not electrodynamics, governs where lightning is initiated and where it propagates, contrary to early expectations. Lightning is initiated in a region of large electric field magnitude, typically between a positive charge region and a negative charge region. The geometry of a storm's charge regions governs the spatial extent of each end of the flash. The flash initially propagates bidirectionally toward the two charge regions that initiated it, and once it reaches the charge regions and maximizes the ambient potential difference spanned by the flash structure, it extends through each charge region's ambient electric potential well until the total electric field magnitude at the ends of the flash drops below the threshold for continued propagation. The typical charge distribution producing a cloud-to-ground flash is a region of charge of the polarity being lowered to ground, above a lesser amount of charge of the opposite polarity; the lower region has too little charge to capture the downward propagating channel. Contrary to previous understanding, naturally occurring cloud-to-ground lightning often lowers positive charge to ground, instead of the usual negative charge, in several situations, including winter storms, stratiform precipitation regions, some severe storms, and storms on the High Plains of the United States. The reason cloud-to-ground activity in some storms is dominated by flashes that lower positive charge to ground is that the polarity of the main charge regions in those storms is inverted from the usual polarity, with the main mid-level charge being positive and the main upper-level charge being negative. This strongly implies that the dominant non-inductive electrification mechanism is inverted in those storms, probably because the liquid water content in the mixed phase region is larger than in most storms.

Investigation of Dusts Effect and Negative Ion in DC Plasmas by Electric Probes

NASA Astrophysics Data System (ADS)

Oh, Hye Taek; Kang, Inje; Bae, Min-Keun; Park, Insun; Lee, Seunghwa; Jeong, Seojin; Chung, Kyu-Sun

2017-10-01

Dust is typically negatively charged by electron attachment whose thermal velocities are fast compared to that of the heavier ions. The negatively charged particles can play a role of negative ions which affect the quasi-neutrality of background plasma. To investigate effect of metal dusts and negative ion on plasma and materials, metal dusts are injected into background Ar plasma which is generated by tungsten filament using dust dispenser on Cubical Plasma Device (CPD). The CPD has following conditions: size =24x24x24cm3, plasma source =DC filament plasma (ne 1x10x1010, Te 2eV), background gas =Ar, dusts =tungsten powder (diameter 1.89micron). The dust dispenser is developed to quantitate of metal dust by ultrasonic transducer. Electronegative plasmas are generated by adding O2 + Ar plasma to compare negative ion and dust effect. A few grams of micron-sized dusts are placed in the dust dispenser which is located at the upper side of the Cubical Plasma Device. The falling particles by dust dispenser are mainly charged up by the collection of the background plasma. The change in parameters due to negative ion production are characterized by measuring the floating and plasma potential, electron temperature and negative ion density using electric probes.

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.

A threshold effect for spacecraft charging

NASA Technical Reports Server (NTRS)

Olsen, R. C.

1983-01-01

The borderline case between no charging and large (kV) negative potentials for eclipse charging events on geosynchronous satellites is investigated, and the dependence of this transition on a threshold energy in the ambient plasma is examined. Data from the Applied Technology Satellite 6 and P78-2 (SCATHA) show that plasma sheet fluxes must extend above 10 keV for these satellites to charge in eclipse. The threshold effect is a result of the shape of the normal secondary yield curve, in particular the high energy crossover, where the secondary yield drops below 1. It is found that a large portion of the ambient electron flux must exceed this energy for a negative current to exist.

Negative Differential Conductance in Polyporphyrin Oligomers with Nonlinear Backbones.

PubMed

Kuang, Guowen; Chen, Shi Zhang; Yan, Linghao; Chen, Ke Qiu; Shang, Xuesong; Liu, Pei Nian; Lin, Nian

2018-01-17

We study negative differential conductance (NDC) effects in polyporphyrin oligomers with nonlinear backbones. Using a low-temperature scanning tunneling microscope, we selectively controlled the charge transport path in single oligomer wires. We observed robust NDC when charge passed through a T-shape junction, bistable NDC when charge passed through a 90° kink and no NDC when charge passed through a 120° kink. Aided by density functional theory with nonequilibrium Green's functions simulations, we attributed this backbone-dependent NDC to bias-modulated hybridization of the electrode states with the resonant transport molecular orbital. We argue this mechanism is generic in molecular systems, which opens a new route of designing molecular NDC devices.

Process and kinetics of bonelike apatite formation on sintered hydroxyapatite in a simulated body fluid.

PubMed

Kim, Hyun-Min; Himeno, Teruyuki; Kokubo, Tadashi; Nakamura, Takashi

2005-07-01

The surfaces of two hydroxyapatites (HA), which have been sintered at different temperatures of 800 and 1200 degrees C, was investigated as a function of soaking time in simulated body fluid (SBF) using transmission electron microscopy (TEM) attached with energy-dispersive spectrometry (EDX) and laser electrophoresis spectroscopy. The TEM-EDX indicated that after soaking in SBF, both the HAs form bonelike apatite by undergoing the same surface structural change, i.e., formations of a Ca-rich amorphous or nano-crystalline calcium phosphate (ACP) and a Ca-poor ACP, which eventually crystallized into bonelike apatite. Zeta potential characterized by the electrophoresis indicated that during exposure to SBF, the HA surfaces reveal negative surface charge, thereby interacting with the positive calcium ions in the fluid to form the Ca-rich ACP, which gains positive surface charge. The Ca-rich ACP on the HAs then interacts with the negative phosphate ions in the fluid to form the Ca-poor ACP, which stabilizes by being crystallized into bonelike apatite with a low solubility in the SBF. The exposure times for formations of these phases of the Ca-rich ACP, the Ca-poor ACP as well as the apatite were, however, all late on HA sintered at 1200 degrees C, compared with the HA sintered at 800 degrees C. This phenomenon was attributed to a lower initial negative surface charge of the HA sintered at 800 degrees C than of that one sintered at 1200 degrees C, owing to poverty in surface hydroxyl and phosphate groups which are responsible for the surface negativity of the HA. These indicate that sintered temperature of HA might influence not in terms of the process but in terms of the rate of formation of biologically active bonelike apatite on its surface, through which the HA integrates with living bone.

Stability of nTiO2 particles and their attachment to sand: Effects of humic acid at different pH.

PubMed

Wu, Yang; Cheng, Tao

2016-01-15

The fate and transport of nano-scale or micro-scale titanium dioxide particles (nTiO2) in subsurface environments are strongly influenced by the stability of nTiO2 and their attachment to sediment grains. nTiO2 may carry either positive or negative charges in natural water, therefore, environmental factors such as pH, humic substances, and Fe oxyhydroxide coatings on sediment grains, which are known to control the stability and transport of negatively-charged colloids, may influence nTiO2 in different manners. The objective of this study is to investigate the effects of pH and humic acid (HA) on the stability and attachment of nTiO2 to sand at HA concentrations that are relevant to typical groundwater conditions, so that mechanisms that control nTiO2 immobilization and transport in natural systems can be elucidated. Stability and attachment of nTiO2 to quartz sand and Fe oxyhydroxide coated quartz sand are experimentally measured under a range of HA concentrations at pH5 and 9. Results show that at pH5, negatively-charged HA strongly adsorbs to positively-charged nTiO2 and Fe oxyhydroxide, which, at low HA concentrations, partially neutralizes the positive charges on nTiO2 and Fe oxyhydroxide, and therefore decreases the repulsive electrostatic forces between the surfaces, resulting in nTiO2 aggregation and attachment. At high HA concentrations, adsorbed HA reverses the surface charges of nTiO2 and Fe oxyhydroxide, and makes nTiO2 and Fe oxyhydroxide strongly negatively charged, resulting in stable nTiO2 suspension and low nTiO2 attachment. At pH9, HA, nTiO2, and Fe oxyhydroxide are all negatively charged, and HA adsorption is low and does not have a strong impact on the stability and attachment of nTiO2. Overall, this study shows that changes in surface charges of nTiO2 and Fe oxyhydroxide coating caused by HA adsorption is a key factor that influences the stability and attachment of nTiO2. Copyright © 2015 Elsevier B.V. All rights reserved.

Charge-dependent flow and the search for the chiral magnetic wave in Pb-Pb collisions at s N N = 2.76 TeV

DOE PAGES

Adam, J.; Adamová, D.; Aggarwal, M. M.; ...

2016-04-08

We report on measurements of a charge-dependent flow using a novel three-particle correlator with ALICE in Pb-Pb collisions at the CERN Large Hadron Collider (LHC), and discuss the implications for observation of local parity violation and the chiral magnetic wave (CMW) in heavy-ion collisions. Charge-dependent flow is reported for different collision centralities as a function of the event charge asymmetry. While our results are in qualitative agreement with expectations based on the CMW, the nonzero signal observed in higher harmonics correlations indicates a possible significant background contribution. We also present results on a differential correlator, where the flow of positivemore » and negative charges is reported as a function of the mean charge of the particles and their pseudorapidity separation. We argue that this differential correlator is better suited to distinguish the differences in positive and negative charges expected due to the CMW and the background effects, such as local charge conservation coupled with strong radial and anisotropic flow.« less

Charge-dependent flow and the search for the chiral magnetic wave in Pb-Pb collisions at √{sN N}=2.76 TeV

NASA Astrophysics Data System (ADS)

Adam, J.; Adamová, D.; Aggarwal, M. M.; Aglieri Rinella, G.; Agnello, M.; Agrawal, N.; Ahammed, Z.; Ahn, S. U.; Aiola, S.; Akindinov, A.; Alam, S. N.; Aleksandrov, D.; Alessandro, B.; Alexandre, D.; Alfaro Molina, R.; Alici, A.; Alkin, A.; Almaraz, J. R. M.; Alme, J.; Alt, T.; Altinpinar, S.; Altsybeev, I.; Alves Garcia Prado, C.; Andrei, C.; Andronic, A.; Anguelov, V.; Anielski, J.; Antičić, T.; Antinori, F.; Antonioli, P.; Aphecetche, L.; Appelshäuser, H.; Arcelli, S.; Arnaldi, R.; Arnold, O. W.; Arsene, I. C.; Arslandok, M.; Audurier, B.; Augustinus, A.; Averbeck, R.; Azmi, M. D.; Badalà, A.; Baek, Y. W.; Bagnasco, S.; Bailhache, R.; Bala, R.; Balasubramanian, S.; Baldisseri, A.; Baral, R. C.; Barbano, A. M.; Barbera, R.; Barile, F.; Barnaföldi, G. G.; Barnby, L. S.; Barret, V.; Bartalini, P.; Barth, K.; Bartke, J.; Bartsch, E.; Basile, M.; Bastid, N.; Basu, S.; Bathen, B.; Batigne, G.; Batista Camejo, A.; Batyunya, B.; Batzing, P. C.; Bearden, I. G.; Beck, H.; Bedda, C.; Behera, N. K.; Belikov, I.; Bellini, F.; Bello Martinez, H.; Bellwied, R.; Belmont, R.; Belmont-Moreno, E.; Belyaev, V.; Benacek, P.; Bencedi, G.; Beole, S.; Berceanu, I.; Bercuci, A.; Berdnikov, Y.; Berenyi, D.; Bertens, R. A.; Berzano, D.; Betev, L.; Bhasin, A.; Bhat, I. R.; Bhati, A. K.; Bhattacharjee, B.; Bhom, J.; Bianchi, L.; Bianchi, N.; Bianchin, C.; Bielčík, J.; Bielčíková, J.; Bilandzic, A.; Biro, G.; Biswas, R.; Biswas, S.; Bjelogrlic, S.; Blair, J. T.; Blau, D.; Blume, C.; Bock, F.; Bogdanov, A.; Bøggild, H.; Boldizsár, L.; Bombara, M.; Book, J.; Borel, H.; Borissov, A.; Borri, M.; Bossú, F.; Botta, E.; Bourjau, C.; Braun-Munzinger, P.; Bregant, M.; Breitner, T.; Broker, T. A.; Browning, T. A.; Broz, M.; Brucken, E. J.; Bruna, E.; Bruno, G. E.; Budnikov, D.; Buesching, H.; Bufalino, S.; Buncic, P.; Busch, O.; Buthelezi, Z.; Butt, J. B.; Buxton, J. T.; Caffarri, D.; Cai, X.; Caines, H.; Calero Diaz, L.; Caliva, A.; Calvo Villar, E.; Camerini, P.; Carena, F.; Carena, W.; Carnesecchi, F.; Castillo Castellanos, J.; Castro, A. J.; Casula, E. A. R.; Ceballos Sanchez, C.; Cerello, P.; Cerkala, J.; Chang, B.; Chapeland, S.; Chartier, M.; Charvet, J. L.; Chattopadhyay, S.; Chattopadhyay, S.; Chauvin, A.; Chelnokov, V.; Cherney, M.; Cheshkov, C.; Cheynis, B.; Chibante Barroso, V.; Chinellato, D. D.; Cho, S.; Chochula, P.; Choi, K.; Chojnacki, M.; Choudhury, S.; Christakoglou, P.; Christensen, C. H.; Christiansen, P.; Chujo, T.; Chung, S. U.; Cicalo, C.; Cifarelli, L.; Cindolo, F.; Cleymans, J.; Colamaria, F.; Colella, D.; Collu, A.; Colocci, M.; Conesa Balbastre, G.; Conesa Del Valle, Z.; Connors, M. E.; Contreras, J. G.; Cormier, T. M.; Corrales Morales, Y.; Cortés Maldonado, I.; Cortese, P.; Cosentino, M. R.; Costa, F.; Crochet, P.; Cruz Albino, R.; Cuautle, E.; Cunqueiro, L.; Dahms, T.; Dainese, A.; Danu, A.; Das, D.; Das, I.; Das, S.; Dash, A.; Dash, S.; de, S.; de Caro, A.; de Cataldo, G.; de Conti, C.; de Cuveland, J.; de Falco, A.; de Gruttola, D.; De Marco, N.; de Pasquale, S.; Deisting, A.; Deloff, A.; Dénes, E.; Deplano, C.; Dhankher, P.; di Bari, D.; di Mauro, A.; di Nezza, P.; Diaz Corchero, M. A.; Dietel, T.; Dillenseger, P.; Divià, R.; Djuvsland, Ø.; Dobrin, A.; Domenicis Gimenez, D.; Dönigus, B.; Dordic, O.; Drozhzhova, T.; Dubey, A. K.; Dubla, A.; Ducroux, L.; Dupieux, P.; Ehlers, R. J.; Elia, D.; Endress, E.; Engel, H.; Epple, E.; Erazmus, B.; Erdemir, I.; Erhardt, F.; Espagnon, B.; Estienne, M.; Esumi, S.; Eum, J.; Evans, D.; Evdokimov, S.; Eyyubova, G.; Fabbietti, L.; Fabris, D.; Faivre, J.; Fantoni, A.; Fasel, M.; Feldkamp, L.; Feliciello, A.; Feofilov, G.; Ferencei, J.; Fernández Téllez, A.; Ferreiro, E. G.; Ferretti, A.; Festanti, A.; Feuillard, V. J. G.; Figiel, J.; Figueredo, M. A. S.; Filchagin, S.; Finogeev, D.; Fionda, F. M.; Fiore, E. M.; Fleck, M. G.; Floris, M.; Foertsch, S.; Foka, P.; Fokin, S.; Fragiacomo, E.; Francescon, A.; Frankenfeld, U.; Fronze, G. G.; Fuchs, U.; Furget, C.; Furs, A.; Fusco Girard, M.; Gaardhøje, J. J.; Gagliardi, M.; Gago, A. M.; Gallio, M.; Gangadharan, D. R.; Ganoti, P.; Gao, C.; Garabatos, C.; Garcia-Solis, E.; Gargiulo, C.; Gasik, P.; Gauger, E. F.; Germain, M.; Gheata, A.; Gheata, M.; Ghosh, P.; Ghosh, S. K.; Gianotti, P.; Giubellino, P.; Giubilato, P.; Gladysz-Dziadus, E.; Glässel, P.; Goméz Coral, D. M.; Gomez Ramirez, A.; Gonzalez, V.; González-Zamora, P.; Gorbunov, S.; Görlich, L.; Gotovac, S.; Grabski, V.; Grachov, O. A.; Graczykowski, L. K.; Graham, K. L.; Grelli, A.; Grigoras, A.; Grigoras, C.; Grigoriev, V.; Grigoryan, A.; Grigoryan, S.; Grinyov, B.; Grion, N.; Gronefeld, J. M.; Grosse-Oetringhaus, J. F.; Grossiord, J.-Y.; Grosso, R.; Guber, F.; Guernane, R.; Guerzoni, B.; Gulbrandsen, K.; Gunji, T.; Gupta, A.; Gupta, R.; Haake, R.; Haaland, Ø.; Hadjidakis, C.; Haiduc, M.; Hamagaki, H.; Hamar, G.; Hamon, J. C.; Harris, J. W.; Harton, A.; Hatzifotiadou, D.; Hayashi, S.; Heckel, S. T.; Helstrup, H.; Herghelegiu, A.; Herrera Corral, G.; Hess, B. A.; Hetland, K. F.; Hillemanns, H.; Hippolyte, B.; Horak, D.; Hosokawa, R.; Hristov, P.; Huang, M.; Humanic, T. J.; Hussain, N.; Hussain, T.; Hutter, D.; Hwang, D. S.; Ilkaev, R.; Inaba, M.; Incani, E.; Ippolitov, M.; Irfan, M.; Ivanov, M.; Ivanov, V.; Izucheev, V.; Jacazio, N.; Jacobs, P. M.; Jadhav, M. B.; Jadlovska, S.; Jadlovsky, J.; Jahnke, C.; Jakubowska, M. J.; Jang, H. J.; Janik, M. A.; Jayarathna, P. H. S. Y.; Jena, C.; Jena, S.; Jimenez Bustamante, R. T.; Jones, P. G.; Jung, H.; Jusko, A.; Kalinak, P.; Kalweit, A.; Kamin, J.; Kang, J. H.; Kaplin, V.; Kar, S.; Karasu Uysal, A.; Karavichev, O.; Karavicheva, T.; Karayan, L.; Karpechev, E.; Kebschull, U.; Keidel, R.; Keijdener, D. L. D.; Keil, M.; Mohisin Khan, M.; Khan, P.; Khan, S. A.; Khanzadeev, A.; Kharlov, Y.; Kileng, B.; Kim, D. W.; Kim, D. J.; Kim, D.; Kim, H.; Kim, J. S.; Kim, M.; Kim, M.; Kim, S.; Kim, T.; Kirsch, S.; Kisel, I.; Kiselev, S.; Kisiel, A.; Kiss, G.; Klay, J. L.; Klein, C.; Klein, J.; Klein-Bösing, C.; Klewin, S.; Kluge, A.; Knichel, M. L.; Knospe, A. G.; Kobdaj, C.; Kofarago, M.; Kollegger, T.; Kolojvari, A.; Kondratiev, V.; Kondratyeva, N.; Kondratyuk, E.; Konevskikh, A.; Kopcik, M.; Kour, M.; Kouzinopoulos, C.; Kovalenko, O.; Kovalenko, V.; Kowalski, M.; Koyithatta Meethaleveedu, G.; Králik, I.; Kravčáková, A.; Kretz, M.; Krivda, M.; Krizek, F.; Kryshen, E.; Krzewicki, M.; Kubera, A. M.; Kučera, V.; Kuhn, C.; Kuijer, P. G.; Kumar, A.; Kumar, J.; Kumar, L.; Kumar, S.; Kurashvili, P.; Kurepin, A.; Kurepin, A. B.; Kuryakin, A.; Kweon, M. J.; Kwon, Y.; La Pointe, S. L.; La Rocca, P.; Ladron de Guevara, P.; Lagana Fernandes, C.; Lakomov, I.; Langoy, R.; Lara, C.; Lardeux, A.; Lattuca, A.; Laudi, E.; Lea, R.; Leardini, L.; Lee, G. R.; Lee, S.; Lehas, F.; Lemmon, R. C.; Lenti, V.; Leogrande, E.; León Monzón, I.; León Vargas, H.; Leoncino, M.; Lévai, P.; Li, S.; Li, X.; Lien, J.; Lietava, R.; Lindal, S.; Lindenstruth, V.; Lippmann, C.; Lisa, M. A.; Ljunggren, H. M.; Lodato, D. F.; Loenne, P. I.; Loginov, V.; Loizides, C.; Lopez, X.; López Torres, E.; Lowe, A.; Luettig, P.; Lunardon, M.; Luparello, G.; Lutz, T. H.; Maevskaya, A.; Mager, M.; Mahajan, S.; Mahmood, S. M.; Maire, A.; Majka, R. D.; Malaev, M.; Maldonado Cervantes, I.; Malinina, L.; Mal'Kevich, D.; Malzacher, P.; Mamonov, A.; Manko, V.; Manso, F.; Manzari, V.; Marchisone, M.; Mareš, J.; Margagliotti, G. V.; Margotti, A.; Margutti, J.; Marín, A.; Markert, C.; Marquard, M.; Martin, N. A.; Martin Blanco, J.; Martinengo, P.; Martínez, M. I.; Martínez García, G.; Martinez Pedreira, M.; Mas, A.; Masciocchi, S.; Masera, M.; Masoni, A.; Massacrier, L.; Mastroserio, A.; Matyja, A.; Mayer, C.; Mazer, J.; Mazzoni, M. A.; McDonald, D.; Meddi, F.; Melikyan, Y.; Menchaca-Rocha, A.; Meninno, E.; Mercado Pérez, J.; Meres, M.; Miake, Y.; Mieskolainen, M. M.; Mikhaylov, K.; Milano, L.; Milosevic, J.; Minervini, L. M.; Mischke, A.; Mishra, A. N.; Miśkowiec, D.; Mitra, J.; Mitu, C. M.; Mohammadi, N.; Mohanty, B.; Molnar, L.; Montaño Zetina, L.; Montes, E.; Moreira de Godoy, D. A.; Moreno, L. A. P.; Moretto, S.; Morreale, A.; Morsch, A.; Muccifora, V.; Mudnic, E.; Mühlheim, D.; Muhuri, S.; Mukherjee, M.; Mulligan, J. D.; Munhoz, M. G.; Munzer, R. H.; Murakami, H.; Murray, S.; Musa, L.; Musinsky, J.; Naik, B.; Nair, R.; Nandi, B. K.; Nania, R.; Nappi, E.; Naru, M. U.; Natal da Luz, H.; Nattrass, C.; Navarro, S. R.; Nayak, K.; Nayak, R.; Nayak, T. K.; Nazarenko, S.; Nedosekin, A.; Nellen, L.; Ng, F.; Nicassio, M.; Niculescu, M.; Niedziela, J.; Nielsen, B. S.; Nikolaev, S.; Nikulin, S.; Nikulin, V.; Noferini, F.; Nomokonov, P.; Nooren, G.; Noris, J. C. C.; Norman, J.; Nyanin, A.; Nystrand, J.; Oeschler, H.; Oh, S.; Oh, S. K.; Ohlson, A.; Okatan, A.; Okubo, T.; Olah, L.; Oleniacz, J.; Oliveira da Silva, A. C.; Oliver, M. H.; Onderwaater, J.; Oppedisano, C.; Orava, R.; Ortiz Velasquez, A.; Oskarsson, A.; Otwinowski, J.; Oyama, K.; Ozdemir, M.; Pachmayer, Y.; Pagano, P.; Paić, G.; Pal, S. K.; Pan, J.; Pandey, A. K.; Papcun, P.; Papikyan, V.; Pappalardo, G. S.; Pareek, P.; Park, W. J.; Parmar, S.; Passfeld, A.; Paticchio, V.; Patra, R. N.; Paul, B.; Pei, H.; Peitzmann, T.; Pereira da Costa, H.; Peresunko, D.; Pérez Lara, C. E.; Perez Lezama, E.; Peskov, V.; Pestov, Y.; Petráček, V.; Petrov, V.; Petrovici, M.; Petta, C.; Piano, S.; Pikna, M.; Pillot, P.; Pimentel, L. O. D. L.; Pinazza, O.; Pinsky, L.; Piyarathna, D. B.; Płoskoń, M.; Planinic, M.; Pluta, J.; Pochybova, S.; Podesta-Lerma, P. L. M.; Poghosyan, M. G.; Polichtchouk, B.; Poljak, N.; Poonsawat, W.; Pop, A.; Porteboeuf-Houssais, S.; Porter, J.; Pospisil, J.; Prasad, S. K.; Preghenella, R.; Prino, F.; Pruneau, C. A.; Pshenichnov, I.; Puccio, M.; Puddu, G.; Pujahari, P.; Punin, V.; Putschke, J.; Qvigstad, H.; Rachevski, A.; Raha, S.; Rajput, S.; Rak, J.; Rakotozafindrabe, A.; Ramello, L.; Rami, F.; Raniwala, R.; Raniwala, S.; Räsänen, S. S.; Rascanu, B. T.; Rathee, D.; Read, K. F.; Redlich, K.; Reed, R. J.; Rehman, A.; Reichelt, P.; Reidt, F.; Ren, X.; Renfordt, R.; Reolon, A. R.; Reshetin, A.; Revol, J.-P.; Reygers, K.; Riabov, V.; Ricci, R. A.; Richert, T.; Richter, M.; Riedler, P.; Riegler, W.; Riggi, F.; Ristea, C.; Rocco, E.; Rodríguez Cahuantzi, M.; Rodriguez Manso, A.; Røed, K.; Rogochaya, E.; Rohr, D.; Röhrich, D.; Romita, R.; Ronchetti, F.; Ronflette, L.; Rosnet, P.; Rossi, A.; Roukoutakis, F.; Roy, A.; Roy, C.; Roy, P.; Rubio Montero, A. J.; Rui, R.; Russo, R.; Ryabinkin, E.; Ryabov, Y.; Rybicki, A.; Sadovsky, S.; Šafařík, K.; Sahlmuller, B.; Sahoo, P.; Sahoo, R.; Sahoo, S.; Sahu, P. K.; Saini, J.; Sakai, S.; Saleh, M. A.; Salzwedel, J.; Sambyal, S.; Samsonov, V.; Šándor, L.; Sandoval, A.; Sano, M.; Sarkar, D.; Sarma, P.; Scapparone, E.; Scarlassara, F.; Schiaua, C.; Schicker, R.; Schmidt, C.; Schmidt, H. R.; Schuchmann, S.; Schukraft, J.; Schulc, M.; Schuster, T.; Schutz, Y.; Schwarz, K.; Schweda, K.; Scioli, G.; Scomparin, E.; Scott, R.; Šefčík, M.; Seger, J. E.; Sekiguchi, Y.; Sekihata, D.; Selyuzhenkov, I.; Senosi, K.; Senyukov, S.; Serradilla, E.; Sevcenco, A.; Shabanov, A.; Shabetai, A.; Shadura, O.; Shahoyan, R.; Shangaraev, A.; Sharma, A.; Sharma, M.; Sharma, M.; Sharma, N.; Shigaki, K.; Shtejer, K.; Sibiriak, Y.; Siddhanta, S.; Sielewicz, K. M.; Siemiarczuk, T.; Silvermyr, D.; Silvestre, C.; Simatovic, G.; Simonetti, G.; Singaraju, R.; Singh, R.; Singha, S.; Singhal, V.; Sinha, B. C.; Sinha, T.; Sitar, B.; Sitta, M.; Skaali, T. B.; Slupecki, M.; Smirnov, N.; Snellings, R. J. M.; Snellman, T. W.; Søgaard, C.; Song, J.; Song, M.; Song, Z.; Soramel, F.; Sorensen, S.; de Souza, R. D.; Sozzi, F.; Spacek, M.; Spiriti, E.; Sputowska, I.; Spyropoulou-Stassinaki, M.; Stachel, J.; Stan, I.; Stankus, P.; Stefanek, G.; Stenlund, E.; Steyn, G.; Stiller, J. H.; Stocco, D.; Strmen, P.; Suaide, A. A. P.; Sugitate, T.; Suire, C.; Suleymanov, M.; Suljic, M.; Sultanov, R.; Šumbera, M.; Szabo, A.; Szanto de Toledo, A.; Szarka, I.; Szczepankiewicz, A.; Szymanski, M.; Tabassam, U.; Takahashi, J.; Tambave, G. J.; Tanaka, N.; Tangaro, M. A.; Tarhini, M.; Tariq, M.; Tarzila, M. G.; Tauro, A.; Tejeda Muñoz, G.; Telesca, A.; Terasaki, K.; Terrevoli, C.; Teyssier, B.; Thäder, J.; Thomas, D.; Tieulent, R.; Timmins, A. R.; Toia, A.; Trogolo, S.; Trombetta, G.; Trubnikov, V.; Trzaska, W. H.; Tsuji, T.; Tumkin, A.; Turrisi, R.; Tveter, T. S.; Ullaland, K.; Uras, A.; Usai, G. L.; Utrobicic, A.; Vajzer, M.; Vala, M.; Valencia Palomo, L.; Vallero, S.; van der Maarel, J.; van Hoorne, J. W.; van Leeuwen, M.; Vanat, T.; Vande Vyvre, P.; Varga, D.; Vargas, A.; Vargyas, M.; Varma, R.; Vasileiou, M.; Vasiliev, A.; Vauthier, A.; Vechernin, V.; Veen, A. M.; Veldhoen, M.; Velure, A.; Venaruzzo, M.; Vercellin, E.; Vergara Limón, S.; Vernet, R.; Verweij, M.; Vickovic, L.; Viesti, G.; Viinikainen, J.; Vilakazi, Z.; Villalobos Baillie, O.; Villatoro Tello, A.; Vinogradov, A.; Vinogradov, L.; Vinogradov, Y.; Virgili, T.; Vislavicius, V.; Viyogi, Y. P.; Vodopyanov, A.; Völkl, M. A.; Voloshin, K.; Voloshin, S. A.; Volpe, G.; von Haller, B.; Vorobyev, I.; Vranic, D.; Vrláková, J.; Vulpescu, B.; Wagner, B.; Wagner, J.; Wang, H.; Wang, M.; Watanabe, D.; Watanabe, Y.; Weber, M.; Weber, S. G.; Weiser, D. F.; Wessels, J. P.; Westerhoff, U.; Whitehead, A. M.; Wiechula, J.; Wikne, J.; Wilde, M.; Wilk, G.; Wilkinson, J.; Williams, M. C. S.; Windelband, B.; Winn, M.; Yaldo, C. G.; Yang, H.; Yang, P.; Yano, S.; Yasar, C.; Yin, Z.; Yokoyama, H.; Yoo, I.-K.; Yoon, J. H.; Yurchenko, V.; Yushmanov, I.; Zaborowska, A.; Zaccolo, V.; Zaman, A.; Zampolli, C.; Zanoli, H. J. C.; Zaporozhets, S.; Zardoshti, N.; Zarochentsev, A.; Závada, P.; Zaviyalov, N.; Zbroszczyk, H.; Zgura, I. S.; Zhalov, M.; Zhang, H.; Zhang, X.; Zhang, Y.; Zhang, C.; Zhang, Z.; Zhao, C.; Zhigareva, N.; Zhou, D.; Zhou, Y.; Zhou, Z.; Zhu, H.; Zhu, J.; Zichichi, A.; Zimmermann, A.; Zimmermann, M. B.; Zinovjev, G.; Zyzak, M.; Alice Collaboration

2016-04-01

We report on measurements of a charge-dependent flow using a novel three-particle correlator with ALICE in Pb-Pb collisions at the CERN Large Hadron Collider (LHC), and discuss the implications for observation of local parity violation and the chiral magnetic wave (CMW) in heavy-ion collisions. Charge-dependent flow is reported for different collision centralities as a function of the event charge asymmetry. While our results are in qualitative agreement with expectations based on the CMW, the nonzero signal observed in higher harmonics correlations indicates a possible significant background contribution. We also present results on a differential correlator, where the flow of positive and negative charges is reported as a function of the mean charge of the particles and their pseudorapidity separation. We argue that this differential correlator is better suited to distinguish the differences in positive and negative charges expected due to the CMW and the background effects, such as local charge conservation coupled with strong radial and anisotropic flow.

Ionization Efficiency of Doubly Charged Ions Formed from Polyprotic Acids in Electrospray Negative Mode

NASA Astrophysics Data System (ADS)

Liigand, Piia; Kaupmees, Karl; Kruve, Anneli

2016-07-01

The ability of polyprotic acids to give doubly charged ions in negative mode electrospray was studied and related to physicochemical properties of the acids via linear discriminant analysis (LDA). It was discovered that the compound has to be strongly acidic (low p K a1 and p K a2) and to have high hydrophobicity (log P ow) to become multiply charged. Ability to give multiply charged ions in ESI/MS cannot be directly predicted from the solution phase acidities. Therefore, for the first time, a quantitative model to predict the charge state of the analyte in ESI/MS is proposed and validated for small anions. Also, a model to predict ionization efficiencies of these analytes was developed. Results indicate that acidity of the analyte, its octanol-water partition coefficient, and charge delocalization are important factors that influence ionization efficiencies as well as charge states of the analytes. The pH of the solvent was also found to be an important factor influencing the ionization efficiency of doubly charged ions.

Carbodiimide EDC induces cross-links that stabilize RNase A C-dimer against dissociation: EDC adducts can affect protein net charge, conformation, and activity.

PubMed

López-Alonso, Jorge P; Diez-García, Fernando; Font, Josep; Ribó, Marc; Vilanova, Maria; Scholtz, J Martin; González, Carlos; Vottariello, Francesca; Gotte, Giovanni; Libonati, Massimo; Laurents, Douglas V

2009-08-19

RNase A self-associates under certain conditions to form a series of domain-swapped oligomers. These oligomers show high catalytic activity against double-stranded RNA and striking antitumor actions that are lacking in the monomer. However, the dissociation of these metastable oligomers limits their therapeutic potential. Here, a widely used conjugating agent, 1-ethyl-3-(3-dimethylaminoisopropyl) carbodiimide (EDC), has been used to induce the formation of amide bonds between carboxylate and amine groups of different subunits of the RNase A C-dimer. A cross-linked C-dimer which does not dissociate was isolated and was found have augmented enzymatic activity toward double-stranded RNA relative to the unmodified C-dimer. Characterization using chromatography, electrophoresis, mass spectrometry, and NMR spectroscopy revealed that the EDC-treated C-dimer retains its structure and contains one to three novel amide bonds. Moreover, both the EDC-treated C-dimer and EDC-treated RNase A monomer were found to carry an increased number of positive charges (about 6 ± 2 charges per subunit). These additional positive charges are presumably due to adduct formation with EDC, which neutralizes a negatively charged carboxylate group and couples it to a positively charged tertiary amine. The increased net positive charge endowed by EDC adducts likely contributes to the heightened cleavage of double-stranded RNA of the EDC-treated monomer and EDC-treated C-dimer. Further evidence for EDC adduct formation is provided by the reaction of EDC with a dipeptide Ac-Asp-Ala-NH(2) monitored by NMR spectroscopy and mass spectrometry. To determine if EDC adduct formation with proteins is common and how this affects protein net charge, conformation, and activity, four well-characterized proteins, ribonuclease Sa, hen lysozyme, carbonic anhydrase, and hemoglobin, were incubated with EDC and the products were characterized. EDC formed adducts with all these proteins, as judged by mass spectrometry and electrophoresis. Moreover, all suffered conformational changes ranging from slight structural modifications in the case of lysozyme, to denaturation for hemoglobin as measured by NMR spectroscopy and enzyme assays. We conclude that EDC adduct formation with proteins can affect their net charge, conformation, and enzymatic activity.

Probing the origins of catalytic discrimination between phosphate and sulfate monoester hydrolysis: comparative analysis of alkaline phosphatase and protein tyrosine phosphatases.

PubMed

Andrews, Logan D; Zalatan, Jesse G; Herschlag, Daniel

2014-11-04

Catalytic promiscuity, the ability of enzymes to catalyze multiple reactions, provides an opportunity to gain a deeper understanding of the origins of catalysis and substrate specificity. Alkaline phosphatase (AP) catalyzes both phosphate and sulfate monoester hydrolysis reactions with a ∼10(10)-fold preference for phosphate monoester hydrolysis, despite the similarity between these reactions. The preponderance of formal positive charge in the AP active site, particularly from three divalent metal ions, was proposed to be responsible for this preference by providing stronger electrostatic interactions with the more negatively charged phosphoryl group versus the sulfuryl group. To test whether positively charged metal ions are required to achieve a high preference for the phosphate monoester hydrolysis reaction, the catalytic preference of three protein tyrosine phosphatases (PTPs), which do not contain metal ions, were measured. Their preferences ranged from 5 × 10(6) to 7 × 10(7), lower than that for AP but still substantial, indicating that metal ions and a high preponderance of formal positive charge within the active site are not required to achieve a strong catalytic preference for phosphate monoester over sulfate monoester hydrolysis. The observed ionic strength dependences of kcat/KM values for phosphate and sulfate monoester hydrolysis are steeper for the more highly charged phosphate ester with both AP and the PTP Stp1, following the dependence expected based on the charge difference of these two substrates. However, the dependences for AP were not greater than those of Stp1 and were rather shallow for both enzymes. These results suggest that overall electrostatics from formal positive charge within the active site is not the major driving force in distinguishing between these reactions and that substantial discrimination can be attained without metal ions. Thus, local properties of the active site, presumably including multiple positioned dipolar hydrogen bond donors within the active site, dominate in defining this reaction specificity.

pH-Dependence of Binding Constants and Desorption Rates of Phosphonate- and Hydroxamate-Anchored [Ru(bpy)3]2+ on TiO2 and WO3.

PubMed

Esarey, Samuel L; Bartlett, Bart M

2018-04-17

The binding constants and rate constants for desorption of the modified molecular dye [Ru(bpy) 3 ] 2+ anchored by either phosphonate or hydroxamate on the bipyridine ligand to anatase TiO 2 and WO 3 have been measured. In aqueous media at pH 1-10, repulsive electrostatic interactions between the negatively charged anchor and the negatively charged surface govern phosphonate desorption under neutral and basic conditions for TiO 2 anatase due to the high acidity of phosphonic acid (p K a,4 = 5.1). In contrast, the lower acidity of hydroxamate (p K a,1 = 6.5, p K a,2 = 9.1) leads to little change in adsorption/desorption properties as a function of pH from 1 to 7. The binding constant for hydroxamate is 10 3 in water, independent of pH in this range. These results are true for WO 3 as well, but are not reported at pH > 4 due to its Arrhenius acidity. Kinetics for desorption as a function of pH are reported, with a proposed mechanism for phosphonate desorption at high pH being the electrostatic repulsion of negative charges between the surface and the anionic anchor. Further, the hydroxamic acid anchor itself is likely the site of quasi-reversible redox activity in [Ru(bpy) 2 (2,2'-bpy-4,4'-(C(O)N(OH)) 2 )] 2+ , which does not lead to any measurable deterioration of the complex within 2 h of dark cyclic voltammogram scans in aqueous media. These results posit phosphonate as the preferred anchoring group under acidic conditions and hydroxamate for neutral/basic conditions.

Solubilization of Therapeutic Agents in Micellar Nanomedicines

PubMed Central

Vuković, Lela; Madriaga, Antonett; Kuzmis, Antonina; Banerjee, Amrita; Tang, Alan; Tao, Kevin; Shah, Neil; Král, Petr; Onyuksel, Hayat

2014-01-01

We use atomistic molecular dynamics simulations to reveal the binding mechanisms of therapeutic agents in PEG-ylated micellar nanocarriers (SSM). In our experiments, SSM in buffer solutions can solubilize either ≈ 11 small bexarotene molecules or ≈ 6 (2 in low ionic strength buffer) human vasoactive intestinal peptide (VIP) molecules. Free energy calculations reveal that molecules of the poorly water soluble drug bexarotene can reside at the micellar ionic interface of the PEG corona, with their polar ends pointing out. Alternatively, they can reside in the alkane core center, where several bexarotene molecules can self-stabilize by forming a cluster held together by a network of hydrogen bonds. We also show that highly charged molecules, such as VIP, can be stabilized at the SSM ionic interface by Coulombic coupling between their positively charged residues and the negatively charged phosphate head-groups of the lipids. The obtained results illustrate that atomistic simulations can reveal drug solubilization character in nanocarriers and be used in efficient optimization of novel nanomedicines. PMID:24283508

Aquabis[1-hydroxy-2-(imidazol-3-ium-1-yl)-1,1′-ethylidenediphophonato-κ2 O,O′]zinc(II) dihydrate

PubMed Central

Freire, Eleonora; Vega, Daniel R.

2009-01-01

In the title complex, [Zn(C5H9NO7P2)2(H2O)]·2H2O, the zinc atom is coordinated by two zoledronate anions [zoledronate = (2-(1-imidazole)-1-hydr­oxy-1,1′-ethyl­idenediphophonate)] and one water mol­ecule. The coordination number is 5. There is one half-mol­ecule in the asymmetric unit, the zinc atom being located on a twofold rotation axis passing through the metal centre and the coordinating water O atom. The anion exists as a zwitterion with an overall charge of −1; the protonated nitro­gen in the ring has a positive charge and the two phospho­nates groups each have a single negative charge. Inter­molecular O—H⋯O hydrogen bonds link the mol­ecules. An N—H⋯O inter­action is also present. PMID:21578165

Increasing Photovoltaic Performance of an Organic Cationic Chromophore by Anion Exchange

PubMed Central

Gesevičius, Donatas; Neels, Antonia; Jenatsch, Sandra; Hack, Erwin; Viani, Lucas; Athanasopoulos, Stavros; Heier, Jakob

2017-01-01

Abstract A symmetrical cyanine dye chromophore is modified with different counteranions to study the effect on crystal packing, polarizability, thermal stability, optical properties, light absorbing layer morphology, and organic photovoltaic (OPV) device parameters. Four sulfonate‐based anions and the bulky bistriflylimide anion are introduced to the 2‐[5‐(1,3‐dihydro‐1,3,3‐trimethyl‐2H‐indol‐2‐ylidene)‐1,3‐pentadien‐1‐yl]‐1,3,3‐trimethyl‐3H‐indolium chromophore using an Amberlyst A26 (OH− form) anion exchanger. Anionic charge distribution clearly correlates with device performance, whereby an average efficiency of 2% was reached in a standard bilayer organic solar. Evidence is given that the negative charge of the anion distributed over a large number of atoms is significantly more important than the size of the organic moieties of the sulfonate charge carrying group. This provides a clear strategy for future design of more efficient cyanine dyes for OPV applications. PMID:29610723

[Using of Spherocelle sorbents for construction of immobilized probiotics].

PubMed

Bondarenko, V M; Rybal'chenko, O V; Boldyrev, A G; Potokin, I L; Orlova, O G; Dobritsa, V P

2009-01-01

To assess sorption properties of Spherocelle beads consisting of particles of macroporous celiulose with various charges in relation to bacterial cells of manufacturing probiotic strains from different taxonomic groups. The following manufacturing strains: Bifidobacterium bifidum 1, Lactobacillus plantarum 8PA-3 and Escherichia coli M-17, as well as 3 variants of Spherocelles' matrix: neutral, with positive and negative charges, were used. Spherocelle globules DEAE with a positive charge of the matrix were successively used for designing of immobilized probiotic preparations. Efficacy of sorbent is determined by sorption of > or =1000 viable cells as well as bacterial metabolites interacting in conditions of sorbent-regulated pH on each globule with diameter 100-180 microm. It provides, on the one hand, prolonged viability of probiotic bacteria in culture fluid within 6 months and, on the other hand, optimal pharmacokinetics of preparation due to gradual desorption of metabolites from sorbent globules. Sorbent Spherocell DEAE is biocompatible with cells of manufacturing strains of lactobacilli, bifidobacteria and E. coli and recommended for designing of immobilized probiotics.

Whole body acid-base modeling revisited.

PubMed

Ring, Troels; Nielsen, Søren

2017-04-01

The textbook account of whole body acid-base balance in terms of endogenous acid production, renal net acid excretion, and gastrointestinal alkali absorption, which is the only comprehensive model around, has never been applied in clinical practice or been formally validated. To improve understanding of acid-base modeling, we managed to write up this conventional model as an expression solely on urine chemistry. Renal net acid excretion and endogenous acid production were already formulated in terms of urine chemistry, and we could from the literature also see gastrointestinal alkali absorption in terms of urine excretions. With a few assumptions it was possible to see that this expression of net acid balance was arithmetically identical to minus urine charge, whereby under the development of acidosis, urine was predicted to acquire a net negative charge. The literature already mentions unexplained negative urine charges so we scrutinized a series of seminal papers and confirmed empirically the theoretical prediction that observed urine charge did acquire negative charge as acidosis developed. Hence, we can conclude that the conventional model is problematic since it predicts what is physiologically impossible. Therefore, we need a new model for whole body acid-base balance, which does not have impossible implications. Furthermore, new experimental studies are needed to account for charge imbalance in urine under development of acidosis. Copyright © 2017 the American Physiological Society.

Modeling the total dust production of Enceladus from stochastic charge equilibrium and simulations

NASA Astrophysics Data System (ADS)

Meier, Patrick; Motschmann, Uwe; Schmidt, Jürgen; Spahn, Frank; Hill, Thomas W.; Dong, Yaxue; Jones, Geraint H.; Kriegel, Hendrik

2015-12-01

Negatively and positively charged nano-sized ice grains were detected in the Enceladus plume by the Cassini Plasma Spectrometer (CAPS). However, no data for uncharged grains, and thus for the total amount of dust, are available. In this paper we estimate this population of uncharged grains based on a model of stochastic charging in thermodynamic equilibrium and on the assumption of quasi-neutrality in the plasma-dust system. This estimation is improved upon by combining simulations of the dust component of the plume and simulations for the plasma environment into one self-consistent model. Calibration of this model with CAPS data provides a total dust production rate of about 12 kg s-1, including larger dust grains up to a few microns in size. We find that the fraction of charged grains dominates over that of the uncharged grains. Moreover, our model reproduces densities of both negatively and positively charged nanograins measured by Cassini CAPS. In Enceladus' plume ion densities up to ~104cm-3 are required by the self-consistent model, resulting in an electron depletion of about 50% in the plasma, because electrons are attached to the negatively charged nanograins. These ion densities correspond to effective ionization rates of about 10-7s-1, which are about two orders of magnitude higher than expected.

Electrolyte effects in a model of proton discharge on charged electrodes

NASA Astrophysics Data System (ADS)

Wiebe, Johannes; Kravchenko, Kateryna; Spohr, Eckhard

2015-01-01

We report results on the influence of NaCl electrolyte dissolved in water on proton discharge reactions from aqueous solution to charged platinum electrodes. We have extended a recently developed combined proton transfer/proton discharge model on the basis of empirical valence bond theory to include NaCl solutions with several different concentrations of cations and anions, both stoichiometric (1:1) compositions and non-stoichiometric ones with an excess of cations. The latter solutions partially screen the electrostatic potential from the surface charge of the negatively charged electrode. 500-1000 trajectories of a discharging proton were integrated by molecular dynamics simulations until discharge occurred, or for at most 1.5 ns. The results show a strong dependence on ionic strength, but only a weak dependence on the screening behavior, when comparing stoichiometric and non-stoichiometric solutions. Overall, the Na+ cations exert a more dominant effect on the discharge reaction, which we argue is likely due to the very rigid arrangements of the cations on the negatively polarized electrode surface. Thus, our model predicts, for the given and very high negative surface charge densities, the fastest discharge reaction for pure water, but obviously cannot take into account the fact that such high charge densities are even more out of reach experimentally than for higher electrolyte concentrations.

Role of electrostatic interactions in the toxicity of titanium dioxide nanoparticles toward Escherichia coli.

PubMed

Pagnout, Christophe; Jomini, Stéphane; Dadhwal, Mandeep; Caillet, Céline; Thomas, Fabien; Bauda, Pascale

2012-04-01

The increasing production and use of titanium dioxide nanoparticles (NP-TiO(2)) has led to concerns about their possible impact on the environment. Bacteria play crucial roles in ecosystem processes and may be subject to the toxicity of these nanoparticles. In this study, we showed that at low ionic strength, the cell viability of Escherichia coli was more severely affected at pH 5.5 than at pH 7.0 and pH 9.5. At pH 5.5, nanoparticles (positively charged) strongly interacted with the bacterial cells (negatively charged) and accumulated on their surfaces. This phenomenon was observed in a much lower degree at pH 7.0 (NP-TiO(2) neutrally charged and cells negatively charged) and pH 9.5 (both NP-TiO(2) and cells negatively charged). It was also shown that the addition of electrolytes (NaCl, CaCl(2), Na(2)SO(4)) resulted in a gradual reduction of the NP-TiO(2) toxicity at pH 5.5 and an increase in this toxicity at pH 9.5, which was closely related to the reduction of the NP-TiO(2) and bacterial cell electrostatic charges. Crown Copyright © 2011. Published by Elsevier B.V. All rights reserved.

Membrane Permeabilization Induced by Sphingosine: Effect of Negatively Charged Lipids

PubMed Central

Jiménez-Rojo, Noemi; Sot, Jesús; Viguera, Ana R.; Collado, M. Isabel; Torrecillas, Alejandro; Gómez-Fernández, J.C.; Goñi, Félix M.; Alonso, Alicia

2014-01-01

Sphingosine [(2S, 3R, 4E)-2-amino-4-octadecen-1, 3-diol] is the most common sphingoid long chain base in sphingolipids. It is the precursor of important cell signaling molecules, such as ceramides. In the last decade it has been shown to act itself as a potent metabolic signaling molecule, by activating a number of protein kinases. Moreover, sphingosine has been found to permeabilize phospholipid bilayers, giving rise to vesicle leakage. The present contribution intends to analyze the mechanism by which this bioactive lipid induces vesicle contents release, and the effect of negatively charged bilayers in the release process. Fluorescence lifetime measurements and confocal fluorescence microscopy have been applied to observe the mechanism of sphingosine efflux from large and giant unilamellar vesicles; a graded-release efflux has been detected. Additionally, stopped-flow measurements have shown that the rate of vesicle permeabilization increases with sphingosine concentration. Because at the physiological pH sphingosine has a net positive charge, its interaction with negatively charged phospholipids (e.g., bilayers containing phosphatidic acid together with sphingomyelins, phosphatidylethanolamine, and cholesterol) gives rise to a release of vesicular contents, faster than with electrically neutral bilayers. Furthermore, phosphorous 31-NMR and x-ray data show the capacity of sphingosine to facilitate the formation of nonbilayer (cubic phase) intermediates in negatively charged membranes. The data might explain the pathogenesis of Niemann-Pick type C1 disease. PMID:24940775

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.

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

Charge Induced Dynamics of Water in a Graphene–Mica Slit Pore

PubMed Central

2017-01-01

We use atomic force microscopy to in situ investigate the dynamic behavior of confined water at the interface between graphene and mica. The graphene is either uncharged, negatively charged, or positively charged. At high humidity, a third water layer will intercalate between graphene and mica. When graphene is negatively charged, the interface fills faster with a complete three layer water film, compared to uncharged graphene. As charged positively, the third water layer dewets the interface, either by evaporation into the ambient or by the formation of three-dimensional droplets under the graphene, on top of the bilayer. Our experimental findings reveal novel phenomena of water at the nanoscale, which are interesting from a fundamental point of view and demonstrate the direct control over the wetting properties of the graphene/water interface. PMID:28985466

Negative Charge Neutralization in the Loops and Turns of Outer Membrane Phospholipase A Impacts Folding Hysteresis at Neutral pH.

PubMed

McDonald, Sarah K; Fleming, Karen G

2016-11-08

Hysteresis in equilibrium protein folding titrations is an experimental barrier that must be overcome to extract meaningful thermodynamic quantities. Traditional approaches to solving this problem involve testing a spectrum of solution conditions to find ones that achieve path independence. Through this procedure, a specific pH of 3.8 was required to achieve path independence for the water-to-bilayer equilibrium folding of outer membrane protein OmpLA. We hypothesized that the neutralization of negatively charged side chains (Asp and Glu) at pH 3.8 could be the physical basis for path-independent folding at this pH. To test this idea, we engineered variants of OmpLA with Asp → Asn and Glu → Gln mutations to neutralize the negative charges within various regions of the protein and tested for reversible folding at neutral pH. Although not fully resolved, our results show that these mutations in the periplasmic turns and extracellular loops are responsible for 60% of the hysteresis in wild-type folding. Overall, our study suggests that negative charges impact the folding hysteresis in outer membrane proteins and their neutralization may aid in protein engineering applications.

a Moessbauer Effect and Fenske-Hall Molecular Orbital Study of the Electronic Properties of Organoiron Clusters.

NASA Astrophysics Data System (ADS)

Buhl, Margaret Linn

The electronic properties of trinuclear iron, tetranuclear iron butterfly, iron-cobalt, and iron-copper clusters have been studied experimentally at 78K by the Mossbauer effect and theoretically by Fenske-Hall molecular orbital calculations. The Mossbauer effect isomer shift is very sensitive to the differences in the iron s-electron densities in these clusters and, as expected, decreases as the sum of the iron 4s Mulliken population and the Clementi and Raimondi effective nuclear charge increases. The molecular orbital wave functions and the Mulliken atomic charges are used to calculate the electric field gradient at the metal nuclei and the iron Mossbauer effect quadrupole splittings. The valence contribution was found to be the major component of the electric field gradient in all the clusters studied. In general the calculated value of Delta E_ {Q} is larger than the observed value, as a result of neglect of the valence Sternheimer factor, R. The metal charge depends upon its electronegativity and upon the nature of its Lewis base ligands. The carbonyl ligand carbon charge becomes more positive as the metal electronegativity increases. The oxygen charge becomes more negative as the anionic cluster charge increases, and in so doing, yields the maximum anionic charge separation. The electronic properties of the terminal carbonyl ligands are similar to those of carbon monoxide, whereas the electronic properties of the bridging carbonyl ligands are similar to those of the carbonyl group found in aldehydes and ketones.

Comparative experimental study of gas evolution and gas consumption reactions in sealed Ni-Cd and Ni-MH cells

NASA Astrophysics Data System (ADS)

Cha, Chuansin; Yu, Jingxian; Zhang, Jixiao

The behavior of the sealed Ni-Cd and Ni-MH systems are compared experimentally with regard to their ability to consume gaseous products generated during the overcharge stage of these systems. It was found that the Ni-Cd system could only consume oxygen, while the Ni-MH system possesses the additional ability to adsorb hydrogen and to catalyze the recombination reaction of hydrogen and oxygen. The internal pressure within both sealed Ni-Cd cells and sealed Ni-MH cells can be kept well under control during the charge/overcharge processes if the rate of overcharge is not too high and if there is sufficient surplus of charging capacity at the negative electrodes. However, the internal pressure can rise to dangerously high levels if the rate of overcharge is too high or there is a deficiency of the charging capacity at the negative electrodes. The various factors that may affect the surplus of charging capacity of the negative electrodes are also discussed.

Stimuli responsive charge-switchable lipids: Capture and release of nucleic acids.

PubMed

Hersey, Joseph S; LaManna, Caroline M; Lusic, Hrvoje; Grinstaff, Mark W

2016-03-01

Stimuli responsive lipids, which enable control over the formation, transformation, and disruption of supramolecular assemblies, are of interest for biosensing, diagnostics, drug delivery, and basic transmembrane protein studies. In particular, spatiotemporal control over a supramolecular structure can be achieved using light activated compounds to induce significant supramolecular rearrangements. As such, a family of cationic lipids are described which undergo a permanent switch in charge upon exposure to 365 nm ultraviolet (UV) light to enable the capture of negatively charged nucleic acids within the self-assembled supramolecular structure of the lipids and subsequent release of these macromolecules upon exposure to UV light and disruption of the assemblies. The lipids are composed of either two different tripeptide head groups, Lysine-Glycine-Glycine (KGG) and Glycine-Glycine-Glycine (GGG) and three different hydrocarbon chain lengths (C6, C10, or C14) terminated by a UV light responsive 1-(2-nitrophenyl)ethanol (NPE) protected carboxylic acid. The photolysis of the NPE protected lipid is measured as a function of time, and the resulting changes in net molecular charge are observed using zeta potential analysis for each head group and chain length combination. A proof of concept study for the capture and release of both linear DNA (calf thymus) and siRNA is presented using an ethidium bromide quenching assay where a balance between binding affinity and supramolecular stability are found to be the key to optimal nucleic acid capture and release. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Implication of the solvent effect, metal ions and topology in the electronic structure and hydrogen bonding of human telomeric G-quadruplex DNA.

PubMed

Poudel, Lokendra; Steinmetz, Nicole F; French, Roger H; Parsegian, V Adrian; Podgornik, Rudolf; Ching, Wai-Yim

2016-08-03

We present a first-principles density functional study elucidating the effects of solvent, metal ions and topology on the electronic structure and hydrogen bonding of 12 well-designed three dimensional G-quadruplex (G4-DNA) models in different environments. Our study shows that the parallel strand structures are more stable in dry environments and aqueous solutions containing K(+) ions within the tetrad of guanine but conversely, that the anti-parallel structure is more stable in solutions containing the Na(+) ions within the tetrad of guanine. The presence of metal ions within the tetrad of the guanine channel always enhances the stability of the G4-DNA models. The parallel strand structures have larger HOMO-LUMO gaps than antiparallel structures, which are in the range of 0.98 eV to 3.11 eV. Partial charge calculations show that sugar and alkali ions are positively charged whereas nucleobases, PO4 groups and water molecules are all negatively charged. Partial charges on each functional group with different signs and magnitudes contribute differently to the electrostatic interactions involving G4-DNA and favor the parallel structure. A comparative study between specific pairs of different G4-DNA models shows that the Hoogsteen OH and NH hydrogen bonds in the guanine tetrad are significantly influenced by the presence of metal ions and water molecules, collectively affecting the structure and the stability of G4-DNA.

Phosphonium-based ionic liquids and their use in the capture of polluting gases

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

Dai, Sheng; Wang, Congmin; Luo, Huimin

2017-06-06

An ionic liquid composition having the following chemical structural formula: ##STR00001## wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are independently selected from hydrocarbon groups containing at least 1 and up to 20 carbon atoms, and X.sup.- is a cyclic anion that possesses a negatively-charged group reactive with a gaseous electrophilic species, particularly carbon dioxide or sulfur dioxide. Methods for capturing a gaseous electrophilic species, such as CO.sub.2 or SO.sub.2, by contacting the gaseous electrophilic species with an ionic liquid according to Formula (1) are also described.

Fluorination effect of activated carbons on performance of asymmetric capacitive deionization

NASA Astrophysics Data System (ADS)

Jo, Hanjoo; Kim, Kyung Hoon; Jung, Min-Jung; Park, Jae Hyun; Lee, Young-Seak

2017-07-01

Activated carbons (ACs) were fluorinated and fabricated into electrodes to investigate the effect of fluorination on asymmetric capacitive deionization (CDI). Fluorine functional groups were introduced on the AC surfaces via fluorination. The specific capacitance of the fluorinated AC (Fsbnd AC) electrode increased drastically from 261 to 337 F/g compared with the untreated AC (Rsbnd AC) electrode at a scan rate of 5 mV/s, despite a decrease in the specific surface area and total pore volume after fluorination. The desalination behavior of asymmetric CDI cells assembled with an Rsbnd AC electrode as the counter electrode and an Fsbnd AC electrode as the cathode (R || F-) or anode (R || F +) was studied. For R || F-, the salt adsorption capacity and charge efficiency increased from 10.6 mg/g and 0.58-12.4 mg/g and 0.75, respectively, compared with the CDI cell assembled with identical Rsbnd AC electrodes at 1 V. This CDI cell exhibited consistently better salt adsorption capacity and charge efficiency at different applied voltages because Fsbnd AC electrodes have a cation attractive effect originating from the partially negatively charged fluorine functional groups on the AC surface. Therefore, co-ion expulsion in the Fsbnd AC electrode as the cathode is effectively diminished, leading to enhanced CDI performance.

Video, LMA and ULF observations of a negative gigantic jet in North Texas

NASA Astrophysics Data System (ADS)

Bruning, E. C.; Cummer, S.; Palivec, K.; Lyons, W. A.; Chmielewski, V.; MacGorman, D. R.

2017-12-01

On 8 September 2016 at 0125:38 UTC video of a negative gigantic jet was captured from Hawley, TX. VHF Lightning Mapping Arrays in West Texas and Oklahoma also observed the parent flash (duration of about 1 s) and, for the first time, mapped dozens of points along ascending negative leaders, lasting about 50 ms, which extended well above cloud top to about 35 km MSL altitude. A few well-located VHF sources were also detected near 50 km. Together, the video and VHF observations provide additional confirmation of the altitude at which the leader-to-streamer transition takes place in gigantic jet discharges. ULF magnetic field data from the Duke iCMC network show a current excursion associated with the onset of the upward movement of negative charge and leaders in the VHF. As the gigantic jet reached its full height, current spiked to 80 kA, followed by several hundred milliseconds of continuing current of 10-20 kA. Total charge moment change was about 6000 C km. The storm complex produced predominantly negative large charge moment change events, which is characteristic of storms that produce negative gigantic jets.

[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.

Contribution of Charged Groups to the Enthalpic Stabilization of the Folded States of Globular Proteins

PubMed Central

Dadarlat, Voichita M.; Post, Carol Beth

2016-01-01

In this paper we use the results from all atom MD simulations of proteins and peptides to assess individual contribution of charged atomic groups to the enthalpic stability of the native state of globular proteins and investigate how the distribution of charged atomic groups in terms of solvent accessibility relates to protein enthalpic stability. The contributions of charged groups is calculated using a comparison of nonbonded interaction energy terms from equilibrium simulations of charged amino acid dipeptides in water (the “unfolded state”) and charged amino acids in globular proteins (the “folded state”). Contrary to expectation, the analysis shows that many buried, charged atomic groups contribute favorably to protein enthalpic stability. The strongest enthalpic contributions favoring the folded state come from the carboxylate (COO−) groups of either Glu or Asp. The contributions from Arg guanidinium groups are generally somewhat stabilizing, while NH3+ groups from Lys contribute little toward stabilizing the folded state. The average enthalpic gain due to the transfer of a methyl group in an apolar amino acid from solution to the protein interior is described for comparison. Notably, charged groups that are less exposed to solvent contribute more favorably to protein native-state enthalpic stability than charged groups that are solvent exposed. While solvent reorganization/release has favorable contributions to folding for all charged atomic groups, the variation in folded state stability among proteins comes mainly from the change in the nonbonded interaction energy of charged groups between the unfolded and folded states. A key outcome is that the calculated enthalpic stabilization is found to be inversely proportional to the excess charge density on the surface, in support of an hypothesis proposed previously. PMID:18303881

Biosafety evaluations of well-dispersed mesoporous silica nanoparticles: towards in vivo-relevant conditions

NASA Astrophysics Data System (ADS)

Liu, Tsang-Pai; Wu, Si-Han; Chen, Yi-Ping; Chou, Chih-Ming; Chen, Chien-Tsu

2015-04-01

This study aimed to investigate how mesoporous silica nanoparticles (MSNs), especially focussing on their surface functional groups, interacted with Raw 264.7 macrophages, as well as with zebrafish embryos. Upon introducing nanoparticles into a biological milieu, adsorption of proteins and biomolecules onto the nanoparticle surface usually progresses rapidly. Nanoparticles bound with proteins can result in physiological and pathological changes, but the mechanisms remain to be elucidated. In order to evaluate how protein corona affected MSNs and the subsequent cellular immune responses, we experimented in both serum and serum-deprived conditions. Our findings indicated that the level of p-p38 was significantly elevated by the positively charged MSNs, whereas negatively charged MSNs resulted in marked ROS production. Most significantly, our experiments demonstrated that the presence of protein efficiently mitigated the potential nano-hazard. On the other hand, strongly positively charged MSNs caused 94% of the zebrafish embryos to die. In that case, the toxicity caused by the quaternary ammonium ligands on the surface of those nanoparticles was exerted in a dose-dependent manner. In summary, these fundamental studies here provide valuable insights into the design of better biocompatible nanomaterials in the future.This study aimed to investigate how mesoporous silica nanoparticles (MSNs), especially focussing on their surface functional groups, interacted with Raw 264.7 macrophages, as well as with zebrafish embryos. Upon introducing nanoparticles into a biological milieu, adsorption of proteins and biomolecules onto the nanoparticle surface usually progresses rapidly. Nanoparticles bound with proteins can result in physiological and pathological changes, but the mechanisms remain to be elucidated. In order to evaluate how protein corona affected MSNs and the subsequent cellular immune responses, we experimented in both serum and serum-deprived conditions. Our findings indicated that the level of p-p38 was significantly elevated by the positively charged MSNs, whereas negatively charged MSNs resulted in marked ROS production. Most significantly, our experiments demonstrated that the presence of protein efficiently mitigated the potential nano-hazard. On the other hand, strongly positively charged MSNs caused 94% of the zebrafish embryos to die. In that case, the toxicity caused by the quaternary ammonium ligands on the surface of those nanoparticles was exerted in a dose-dependent manner. In summary, these fundamental studies here provide valuable insights into the design of better biocompatible nanomaterials in the future. Electronic supplementary information (ESI) available: TEM image, size distribution histogram of as-synthesized wn-R-MSN@PEG. TGA measurements. Cellular uptake efficiency. WST-1 analysis. Western blot assays. Confocal images and zebrafish mortality. See DOI: 10.1039/c4nr07421a

S1-S3 counter charges in the voltage sensor module of a mammalian sodium channel regulate fast inactivation.

PubMed

Groome, James R; Winston, Vern

2013-05-01

The movement of positively charged S4 segments through the electric field drives the voltage-dependent gating of ion channels. Studies of prokaryotic sodium channels provide a mechanistic view of activation facilitated by electrostatic interactions of negatively charged residues in S1 and S2 segments, with positive counterparts in the S4 segment. In mammalian sodium channels, S4 segments promote domain-specific functions that include activation and several forms of inactivation. We tested the idea that S1-S3 countercharges regulate eukaryotic sodium channel functions, including fast inactivation. Using structural data provided by bacterial channels, we constructed homology models of the S1-S4 voltage sensor module (VSM) for each domain of the mammalian skeletal muscle sodium channel hNaV1.4. These show that side chains of putative countercharges in hNaV1.4 are oriented toward the positive charge complement of S4. We used mutagenesis to define the roles of conserved residues in the extracellular negative charge cluster (ENC), hydrophobic charge region (HCR), and intracellular negative charge cluster (INC). Activation was inhibited with charge-reversing VSM mutations in domains I-III. Charge reversal of ENC residues in domains III (E1051R, D1069K) and IV (E1373K, N1389K) destabilized fast inactivation by decreasing its probability, slowing entry, and accelerating recovery. Several INC mutations increased inactivation from closed states and slowed recovery. Our results extend the functional characterization of VSM countercharges to fast inactivation, and support the premise that these residues play a critical role in domain-specific gating transitions for a mammalian sodium channel.

Colloidal Stability of Gold Nanoparticles Coated with Multithiol-Poly(ethylene glycol) Ligands: Importance of Structural Constraints of the Sulfur Anchoring Groups

DTIC Science & Technology

2013-08-13

21-45 Citric acid has been the most commonly used ligand when negatively charged surfaces or a rather loose ligand shell is required for further...biomolecules in biological serum (e.g., proteins, peptides, nucleic acids ); (5) resistance to heat treatments (e.g., >80 °C for DNA hybridization).6-8, 16...demonstrated by a variety of thiol-based ligands such as mercaptopropionic acid ,36 glutathione,37 thiol-terminated poly(ethylene glycol) (PEG-SH), 19

Molecular understanding of osmosis in semipermeable membranes.

PubMed

Raghunathan, A V; Aluru, N R

2006-07-14

We investigate single-file osmosis of water through a semipermeable membrane with an uncharged, a positively and a negatively charged nanopore. Molecular dynamics simulations indicate that the osmotic flux through a negatively charged pore (J_) is higher compared to the osmotic flux in a positively charged pore (J+) followed by the osmotic flux in the uncharged pore (J(0)), i.e., J_ > J+ > J(0). The molecular mechanisms governing osmosis, steady state osmosis, and the observed osmotic flux dependence on the nanopore charge are explained by computing all the molecular interactions involved and identifying the molecular interactions that play an important role during and after osmosis. This study helps in a fundamental understanding of osmosis and in the design of advanced nanoporous membranes for various applications of osmosis.

Controlling the electrophoretic mobility of single-walled carbon nanotubes: a comparison of theory and experiment.

PubMed

Usrey, Monica L; Nair, Nitish; Agnew, Daniel E; Pina, Cesar F; Strano, Michael S

2007-07-03

The electrophoretic mobilities of single-walled carbon nanotubes (SWNTs) in agarose gels subjected to negatively charged covalent functionalization and noncovalent anionic surfactant adsorption are compared using a simplified hydrodynamic model. Net charges are calculated on the basis of estimated friction coefficients for cylindrical rodlike particles. The effects of functionalization with negatively charged 4-hydroxybenzene diazonium and anionic sodium cholate are quantified and compared with model predictions. The adsorption of Na+ counterions into the nonionic surfactant layer adsorbed on SWNTs (Triton-X-405) is shown to induce a positive charge and reverse the mobility under select conditions. This effect has not been identified or quantified for nanoparticle systems and may be important in the processing of these systems.

The effects of vortex like distributed electron in magnetized multi-ion dusty plasmas

NASA Astrophysics Data System (ADS)

Haider, Md. Masum; Ferdous, Tahmina; Duha, Syed S.

2014-09-01

The nonlinear propagation of small but finite amplitude dust-ion-acoustic solitary waves in a magnetized, collisionless dusty plasma is investigated theoretically. It has been assumed that the electrons are trapped following the vortex-like distribution and that the negatively and positively charged ions are mobile with the presence of charge fluctuating stationary dusts, where ions mass provide the inertia and restoring forces are provided by the thermal pressure of hot electrons. A reductive perturbation method was employed to obtain a modified Korteweg-de Vries (mK-dV) equation for the first-order potential and a stationary solution is obtained. The effect of the presence of trapped electrons, negatively and positively charged ions and arbitrary charged dust grains are discussed.

The Role of Nanoparticle Surface Functionality in the Disruption of Model Cell Membranes

PubMed Central

Moghadam, Babak Y.; Hou, Wen-Che; Corredor, Charlie; Westerhoff, Paul; Posner, Jonathan D.

2012-01-01

Lipid bilayers are biomembranes common to cellular life and constitute a continuous barrier between cells and their environment. Understanding the interaction of engineered nanomaterials (ENMs) with lipid bilayers is an important step toward predicting subsequent biological effects. In this study, we assess the effect of varying the surface functionality and concentration of 10 nm-diameter gold (Au) and titanium dioxide (TiO2) ENMs on the disruption of negatively charged lipid bilayer vesicles (liposomes) using a dye leakage assay. Our findings show that Au ENMs having both positive and negative surface charge induce leakage that reaches a steady state after several hours. Positively charged particles with identical surface functionality and different core composition show similar leakage effects and result in faster and greater leakage than negatively charged particles, which suggests that surface functionality, not particle core composition, is a critical factor in determining the interaction between ENMs and lipid bilayers. The results suggest that particles permanently adsorb to bilayers and that only one positively charged particle is required to disrupt a liposome and trigger leakage of its entire contents in contrast to mellitin molecules, the most widely studied membrane lytic peptide, which requires hundred of molecules to generate leakage. PMID:22921268

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.

Negative measurement sensitivity values of planar capacitive imaging probes

NASA Astrophysics Data System (ADS)

Yin, Xiaokang; Chen, Guoming; Li, Wei; Hutchins, David

2014-02-01

The measurement sensitivity distribution of planar capacitive imaging (CI) probes describes how effectively each region in the sensing area is contributing to the measured charge signal on the sensing electrode. It can be used to determine the imaging ability of a CI probe. It is found in previous work that, there are regions in the sensing area where the change of the charge output and the change of targeting physical parameter are of opposite trends. This opposite correlation implies that the measurement sensitivity values in such regions are negative. In this work, the cause of negative sensitivity is discussed. Experiments are also designed and performed so as to verify the existence of negative sensitivity and study the factors that may affect the negative sensitivity distributions.

Cost-effectiveness of negative pressure wound therapy in patients with many comorbidities and severe wounds of various etiology.

PubMed

Driver, Vickie R; Eckert, Kristen A; Carter, Marissa J; French, Michael A

2016-11-01

This study analyzed a cross-section of patients with severe chronic wounds and multiple comorbidities at an outpatient wound clinic, with regard to the cost-effectiveness and cost-benefit of negative pressure wound therapy (intervention) vs. no negative pressure wound therapy (control) at 1 and 2 years. Medicare reimbursement charges for wound care were used to calculate costs. Amputation charges were assessed using diagnosis-related groups. Cost-benefit analysis was based on ulcer-free months and cost-effectiveness on quality-adjusted life-years. Undiscounted costs, benefits, quality-adjusted life-years, undiscounted and discounted incremental net health benefits, and incremental cost-effectiveness ratios were calculated for unmatched and matched cohorts. There were 150 subjects in the intervention group and 154 controls before matching and 103 subjects in each of the matched cohorts. Time to heal for the intervention cohort was significantly shorter compared to the controls (270 vs. 635 days, p = 1.0 × 10 -7 , matched cohorts). The intervention cohort had higher benefits and quality-adjusted life-year gains compared to the control cohort at years 1 and 2; by year 2, the gains were 68-73% higher. In the unmatched cohorts, the incremental net health benefit was $9,933 per ulcer-free month at year 2 for the intervention; the incremental cost-effectiveness ratio was -825,271 per quality-adjusted life-year gained (undiscounted costs and benefits). For the matched cohorts, the incremental net health benefits was only $1,371 per ulcer-free month for the intervention, but the incremental cost-effectiveness ratio was $366,683 per quality-adjusted life-year gained for year 2 (discounted costs and benefits). In a patient population with severe chronic wounds and serious comorbidities, negative pressure wound therapy resulted in faster healing wounds and was more cost-effective with greater cost-benefits than not using negative pressure wound therapy. Regarding overall cost-effectiveness, the intervention was still expensive, but that is the reality amidst limited treatment options for such serious cases of chronic wounds. © 2016 by the Wound Healing Society.

Assessment and Control of Spacecraft Charging Risks on the International Space Station

NASA Technical Reports Server (NTRS)

Koontz, Steve; Edeen, Marybeth; Spetch, William; Dalton, Penni; Keening, Thomas

2003-01-01

Electrical interactions between the F2 region ionospheric plasma and the 160V photovoltaic (PV) electrical power system on the International Space Station (ISS) can produce floating potentials (FP) on the ISS conducting structure of greater magnitude than are usually observed on spacecraft in low-Earth orbit. Flight through the geomagnetic field also causes magnetic induction charging of ISS conducting structure. Charging processes resulting from interaction of ISS with auroral electrons may also contribute to charging albeit rarely. The magnitude and frequency of occurrence of possibly hazardous charging events depends on the ISS assembly stage (six more 160V PV arrays will be added to ISS), ISS flight configuration, ISS position (latitude and longitude), and the natural variability in the ionospheric flight environment. At present, ISS is equipped with two plasma contactors designed to control ISS FP to within 40 volts of the ambient F2 plasma. The negative-polarity grounding scheme utilized in the ISS 160V power system leads, naturally, to negative values of ISS FP. A negative ISS structural FP leads to application of electrostatic fields across the dielectrics that separate conducting structure from the ambient F2 plasma, thereby enabling dielectric breakdown and arcing. Degradation of some thermal control coatings and noise in electrical systems can result. Continued review and evaluation of the putative charging hazards, as required by the ISS Program Office, revealed that ISS charging could produce a risk of electric shock to the ISS crew during extra vehicular activity. ISS charging risks are being evaluated in ongoing ISS charging measurements and analysis campaigns. The results of ISS charging measurements are combined with a recently developed detailed model of the ISS charging process and an extensive analysis of historical ionospheric variability data, to assess ISS charging risks using Probabilistic Risk Assessment (PRA) methods. The PRA analysis (estimated frequency of occurrence and severity of the charging hazards) are then used to select the hazard control strategy that provides the best overall safety and mission success environment for ISS and the ISS crew. This paper presents: 1) a summary of ISS spacecraft charging analysis, measurements, observations made to date, 2) plans for future ISS spacecraft charging measurement campaigns, and 3) a detailed discussion of the PRA strategy used to assess ISS spacecraft charging risks and select charging hazard control strategies

Assessment and Control of International Space Station Spacecraft Charging Risks

NASA Astrophysics Data System (ADS)

Koontz, S.; Edeen, M.; Spetch, W.; Dalton, P.; Keeping, T.; Minow, J.

2003-12-01

Electrical interactions between the F2 region ionospheric plasma and the 160V photovoltaic (PV) electrical power system on the International Space Station (ISS) can produce floating potentials (FP) on ISS conducting structure of greater magnitude than are usually observed on spacecraft in low-Earth orbit. Flight through the geomagnetic field also causes magnetic induction charging of ISS conducting structure. Charging processes resulting from interaction of ISS with auroral electrons may also contribute to charging, albeit rarely. The magnitude and frequency of occurrence of possibly hazardous charging events depends on the ISS assembly stage (six more 160V PV arrays will be added to ISS), ISS flight configuration, ISS position (latitude and longitude), and the natural variability in the ionospheric flight environment. At present, ISS is equipped with two plasma contactors designed to control ISS FP to within 40 volts of the ambient F2 plasma. The negative-polarity grounding scheme utilized in the ISS 160V power system leads, naturally, to negative values of ISS FP. A negative ISS structural FP leads to application of electrostatic fields across the dielectrics that separate conducting structure from the ambient F2 plasma, thereby enabling dielectric breakdown and arcing. Degradation of some thermal control coatings and noise in electrical systems can result. Continued review and evaluation of the putative charging hazards, as required by the ISS Program Office, revealed that ISS charging could produce a risk of electric shock to the ISS crew during extra vehicular activity. ISS charging risks are being evaluated in ongoing ISS charging measurements and analysis campaigns. The results of ISS charging measurements are combined with a recently developed detailed model of the ISS charging process and an extensive analysis of historical ionospheric variability data, to assess ISS charging risks using Probabilistic Risk Assessment (PRA) methods. The PRA analysis (estimated frequency of occurrence and severity of the charging hazards) are then used to select the hazard control strategy that provides the best overall safety and mission success environment for ISS and the ISS crew. This paper presents: 1) a summary of ISS spacecraft charging analysis, measurements, observations made to date, 2) plans for future ISS spacecraft charging measurement campaigns, and 3) a detailed discussion of the PRA strategy used to assess ISS spacecraft charging risks and select charging hazard control strategies.

Protein charge ladders reveal that the net charge of ALS-linked superoxide dismutase can be different in sign and magnitude from predicted values

PubMed Central

Shi, Yunhua; Abdolvahabi, Alireza; Shaw, Bryan F

2014-01-01

This article utilized “protein charge ladders”—chemical derivatives of proteins with similar structure, but systematically altered net charge—to quantify how missense mutations that cause amyotrophic lateral sclerosis (ALS) affect the net negative charge (Z) of superoxide dismutase-1 (SOD1) as a function of subcellular pH and Zn2+ stoichiometry. Capillary electrophoresis revealed that the net charge of ALS-variant SOD1 can be different in sign and in magnitude—by up to 7.4 units per dimer at lysosomal pH—than values predicted from standard pKa values of amino acids and formal oxidation states of metal ions. At pH 7.4, the G85R, D90A, and G93R substitutions diminished the net negative charge of dimeric SOD1 by up to +2.29 units more than predicted; E100K lowered net charge by less than predicted. The binding of a single Zn2+ to mutant SOD1 lowered its net charge by an additional +2.33 ± 0.01 to +3.18 ± 0.02 units, however, each protein regulated net charge when binding a second, third, or fourth Zn2+ (ΔZ < 0.44 ± 0.07 per additional Zn2+). Both metalated and apo-SOD1 regulated net charge across subcellular pH, without inverting from negative to positive at the theoretical pI. Differential scanning calorimetry, hydrogen-deuterium exchange, and inductively coupled plasma mass spectrometry confirmed that the structure, stability, and metal content of mutant proteins were not significantly affected by lysine acetylation. Measured values of net charge should be used when correlating the biophysical properties of a specific ALS-variant SOD1 protein with its observed aggregation propensity or clinical phenotype. PMID:25052939

Frequency-Dependent Capacitance of Hydrophobic Membranes Containing Fixed Negative Charges

PubMed Central

Ilani, Asher

1968-01-01

Filters containing fixed negative charges were saturated with hydrophobic solvent and interposed between aqueous solutions. The capacitance of such membranes was measured in the frequency range of 0.05-30 kc. The capacitance increased with decrease in frequency. The frequency dependence of the capacitance was sensitive to nature of the cation present and to salt concentration in the aqueous solution. It is suggested that variation of membrane resistivity in the space charge region of the membrane is responsible for this phenomenon. Possible effects of the potential and counterion concentration profiles at the membrane-water interface are discussed. PMID:5699796

Charging Properties of Cassiterite (alpha-SnO2) Surfaces in NaCl and RbCl Ionic Media.

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

Rosenqvist, Jorgen K; Machesky, Michael L.; Vlcek, Lukas

2009-01-01

The acid-base properties of cassiterite ({alpha}-SnO{sub 2}) 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 of 4.0-4.5 under 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 SnOH{sub 2} group is more acidic than the bridging Sn{sub 2}OH group, with protonation constants (log K{sub H}) of 3.60 and 5.13 at 25 C, respectively. This is contrary to the situation on the isostructural {alpha}-TiO{sub 2} (rutile), apparently because of the difference in electronegativity between Ti and Sn. MD simulations and speciation calculations indicated considerable differences in the speciation of Na{sup +} and Rb{sup +}, despite the similarities in overall charging. Adsorbed sodium ions are almost exclusively found in bidentate surface complexes, whereas adsorbed rubidium ions form comparable numbers of bidentate and tetradentate complexes. Also, the distribution of adsorbed Na{sup +} between the different complexes shows a considerable dependence on the surface charge density (pH), whereas the distribution of adsorbed Rb{sup +} 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{sup +}/Rb{sup +} was formulated. According to the SCM, the deprotonated terminal group (SnOH{sup -0.40}) and the protonated bridging group (Sn{sub 2}OH{sup +0.36}) dominate the surface speciation over the entire pH range of this study (2.7-10). The complexation of medium cations increases significantly with increasing negative surface charge, and at pH 10, roughly 40% of the terminal sites are predicted to form cation complexes, whereas anion complexation is minor throughout the studied pH range.« less

Versatile organic (fullerene)-inorganic (CdTe nanoparticle) nanoensembles.

PubMed

Guldi, Dirk M; Zilbermann, Israel; Anderson, Greg; Kotov, Nicholas A; Tagmatarchis, Nikos; Prato, Maurizio

2004-11-10

Novel organic (positively charged fullerene)-inorganic (negatively charged CdTe nanoparticle) nanoensembles were devised through electrostatic interactions and probed as versatile donor-acceptor hybrids. Photoirradiation of their homogeneous solutions, containing the electrostatically packed components, let to very long-lived (1.3 ms) charge separated states.

Capillary electrophoresis of covalently functionalized single-chirality carbon nanotubes.

PubMed

He, Pingli; Meany, Brendan; Wang, Chunyan; Piao, Yanmei; Kwon, Hyejin; Deng, Shunliu; Wang, YuHuang

2017-07-01

We demonstrate the separation of chirality-enriched single-walled carbon nanotubes (SWCNTs) by degree of surface functionalization using high-performance CE. Controlled amounts of negatively charged and positively charged functional groups were attached to the sidewall of chirality-enriched SWCNTs through covalent functionalization using 4-carboxybenzenediazonium tetrafluoroborate or 4-diazo-N,N-diethylaniline tetrafluoroborate, respectively. Surfactant- and pH-dependent studies confirmed that under conditions that minimized ionic screening effects, separation of these functionalized SWCNTs was strongly dependent on the surface charge density introduced through covalent surface chemistry. For both heterogeneous mixtures and single-chirality-enriched samples, covalently functionalized SWCNTs showed substantially increased peak width in electropherogram spectra compared to nonfunctionalized SWCNTs, which can be attributed to a distribution of surface charges along the functionalized nanotubes. Successful separation of functionalized single-chirality SWCNTs by functional density was confirmed with UV-Vis-NIR absorption and Raman scattering spectroscopies of fraction collected samples. These results suggest a high degree of structural heterogeneity in covalently functionalized SWCNTs, even for chirality-enriched samples, and show the feasibility of applying CE for high-performance separation of nanomaterials based on differences in surface functional density. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

Interactions and diffusion in fine-stranded β-lactoglobulin gels determined via FRAP and binding.

PubMed

Schuster, Erich; Hermansson, Anne-Marie; Ohgren, Camilla; Rudemo, Mats; Lorén, Niklas

2014-01-07

The effects of electrostatic interactions and obstruction by the microstructure on probe diffusion were determined in positively charged hydrogels. Probe diffusion in fine-stranded gels and solutions of β-lactoglobulin at pH 3.5 was determined using fluorescence recovery after photobleaching (FRAP) and binding, which is widely used in biophysics. The microstructures of the β-lactoglobulin gels were characterized using transmission electron microscopy. The effects of probe size and charge (negatively charged Na2-fluorescein (376Da) and weakly anionic 70kDa FITC-dextran), probe concentration (50 to 200 ppm), and β-lactoglobulin concentration (9% to 12% w/w) on the diffusion properties and the electrostatic interaction between the negatively charged probes and the positively charged gels or solutions were evaluated. The results show that the diffusion of negatively charged Na2-fluorescein is strongly influenced by electrostatic interactions in the positively charged β-lactoglobulin systems. A linear relationship between the pseudo-on binding rate constant and the β-lactoglobulin concentration for three different probe concentrations was found. This validates an important assumption of existing biophysical FRAP and binding models, namely that the pseudo-on binding rate constant equals the product of the molecular binding rate constant and the concentration of the free binding sites. Indicators were established to clarify whether FRAP data should be analyzed using a binding-diffusion model or an obstruction-diffusion model. Copyright © 2014 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Carbon Dioxide Removal by Salty Aerosols

NASA Astrophysics Data System (ADS)

Gokturk, H.

2016-12-01

Aerosols consisting of salt ions dissolved in water are observed in nature as sea spray particles generated by breaking waves. Such aerosols can be also generated artificially by spraying seawater to the atmosphere to create clouds, which was suggested as a method of solar radiation management (SRM). Salty aerosols can be utilized not only for SRM, but also for carbon dioxide removal from the atmosphere, if salt ions carrying charges -2 or more negative are added to the seawater. CO2 is a very stable molecule where carbon to oxygen double bond has a bond strength of 8.3 eV (190 kcal/mol). Therefore the approach chosen here to modify CO2 is to further oxidize it to CO3. Quantum mechanical calculations indicate that CO2 reacts readily with hydroxyl minus ion (OH-) or oxygen double minus ion (O-) to form HCO3- or CO3-, respectively. What is studied in this paper is the utilization of hydrated negative salt ions to create OH- and possibly even O-. The negative ions chosen are chlorine minus ion (Cl-), sulfate double minus ion (SO4-), phosphate triple minus ion (PO4--) and silicate quadruple minus ion (SiO4--). The former two ions exist in seawater, but the latter two ions do not, though they are available as part of water soluble salts such as potassium phosphate. Using quantum mechanical calculations, following reactions were investigated: R1: (Cl-) + H2O => HCl + (OH-), R2: (SO4-) + H2O => (HSO4-) + (OH-), R3: (PO4--) + H2O => (HPO4-) + (OH-), R4: (SiO4--) + H2O => (HSiO4--) + (OH-), R5: (HPO4-) + H2O => (H2PO4-) + (OH-), R6: (HSiO4--) + H2O => (H2SiO4-) + (OH-), R7: (H2SiO4-) + H2O => (H3SiO4-) + (OH-), R8: (SiO4--) + H2O => (H2SiO4-) + (O-). Results indicate that singly charged negative salt ions, such as Cl- in R1, cannot create OH-. Doubly charged negative salt ions, such as SO4- in R2, can create OH-, though the amount of SO4- in seawater is relatively small. Triply or quadruply charged negative ions are even more favorable than doubly charged ions in creating OH- (R3, R4, R6). Quadruply charged negative ions can also create O- (R8), however in practice O- is likely to react with other water molecules to create more OH-. In conclusion, seawater fortified with highly charged negative salt ions and sprayed into the atmosphere has the potential to create aerosols containing OH- which can react with the CO2 and modify it to a carbonate.

Probing the influence of cell surface polysaccharides on nanodendrimer binding to Gram-negative and Gram-positive bacteria using single-nanoparticle force spectroscopy.

PubMed

Beaussart, Audrey; Beloin, Christophe; Ghigo, Jean-Marc; Chapot-Chartier, Marie-Pierre; Kulakauskas, Saulius; Duval, Jérôme F L

2018-06-27

The safe use and design of nanoparticles (NPs) ask for a comprehensive interpretation of their potentially adverse effects on (micro)organisms. In this respect, the prior assessment of the interactions experienced by NPs in the vicinity of - and in contact with - complex biological surfaces is mandatory. It requires the development of suitable techniques for deciphering the processes that govern nano-bio interactions when a single organism is exposed to an extremely low dose of NPs. Here, we used atomic force spectroscopy (AFM)-based force measurements to investigate at the nanoscale the interactions between carboxylate-terminated polyamidoamine (PAMAM) nanodendrimers (radius ca. 4.5 nm) and two bacteria with very distinct surface properties, Escherichia coli and Lactococcus lactis. The zwitterionic nanodendrimers exhibit a negative peripheral surface charge and/or a positive intraparticulate core depending on the solution pH and salt concentration. Following an original strategy according to which a single dendrimer NP is grafted at the very apex of the AFM tip, the density and localization of NP binding sites are probed at the surface of E. coli and L. lactis mutants expressing different cell surface structures (presence/absence of the O-antigen of the lipopolysaccharides (LPS) or of a polysaccharide pellicle). In line with electrokinetic analysis, AFM force measurements evidence that adhesion of NPs onto pellicle-decorated L. lactis is governed by their underlying electrostatic interactions as controlled by the pH-dependent charge of the peripheral and internal NP components, and the negatively-charged cell surface. In contrast, the presence of the O-antigen on E. coli systematically suppresses the adhesion of nanodendrimers onto cells, may the apparent NP surface charge be determined by the peripheral carboxylate groups or by the internal amine functions. Altogether, this work highlights the differentiated roles played by surface polysaccharides in mediating NP attachment to Gram-positive and Gram-negative bacteria. It further demonstrates that the assessment of NP bioadhesion features requires a critical analysis of the electrostatic contributions stemming from the various structures composing the stratified cell envelope, and those originating from the bulk and surface NP components. The joint use of electrokinetics and AFM provides a valuable option for rapidly addressing the binding propensity of NPs to microorganisms, as urgently needed in NP risk assessments.

Membrane binding of an acyl-lactoferricin B antimicrobial peptide from solid-state NMR experiments and molecular dynamics simulations.

PubMed

Romo, Tod D; Bradney, Laura A; Greathouse, Denise V; Grossfield, Alan

2011-08-01

One approach to the growing health problem of antibiotic resistant bacteria is the development of antimicrobial peptides (AMPs) as alternative treatments. The mechanism by which these AMPs selectively attack the bacterial membrane is not well understood, but is believed to depend on differences in membrane lipid composition. N-acylation of the small amidated hexapeptide, RRWQWR-NH(2) (LfB6), derived from the 25 amino acid bovine lactoferricin (LfB25) can be an effective means to improve its antimicrobial properties. Here, we investigate the interactions of C6-LfB6, N-acylated with a 6 carbon fatty acid, with model lipid bilayers with two distinct compositions: 3:1 POPE:POPG (negatively charged) and POPC (zwitterionic). Results from solid-state (2)H and (31)P NMR experiments are compared with those from an ensemble of all-atom molecular dynamic simulations running in aggregate more than 8.6ms. (2)H NMR spectra reveal no change in the lipid acyl chain order when C6-LfB6 is bound to the negatively charged membrane and only a slight decrease in order when it is bound to the zwitterionic membrane. (31)P NMR spectra show no significant perturbation of the phosphate head groups of either lipid system in the presence of C6-LfB6. Molecular dynamic simulations show that for the negatively charged membrane, the peptide's arginines drive the initial association with the membrane, followed by attachment of the tryptophans at the membrane-water interface, and finally by the insertion of the C6 tails deep into the bilayer. In contrast, the C6 tail leads the association with the zwitterionic membrane, with the tryptophans and arginines associating with the membrane-water interface in roughly the same amount of time. We find similar patterns in the order parameters from our simulations. Moreover, we find in the simulations that the C6 tail can insert 1-2Å more deeply into the zwitterionic membrane and can exist in a wider range of angles than in the negatively charged membrane. We propose this is due to the larger area per lipid in the zwitterionic membrane, which provides more space for the C6 to insert and assume different orientations. Copyright © 2011 Elsevier B.V. All rights reserved.

Effect of Primary-Ion Current Density on Charge Compensation in SIMS Analysis of a Quartz Glass

NASA Astrophysics Data System (ADS)

Inoue, Kazuyuki; Isogai, Akio

1988-05-01

In secondary ion mass spectrometry (SIMS) analysis of a quartz glass by means of negative ion bombardment, the effect of the negative ion current density (Ji) has been investigated. The results show that under lower Ji (<20 μA/cm2), time is required to compensate for the surface charge and the time is inversely proportional to Ji.

Radiation transport codes for potential applications related to radiobiology and radiotherapy using protons, neutrons, and negatively charged pions

NASA Technical Reports Server (NTRS)

Armstrong, T. W.

1972-01-01

Several Monte Carlo radiation transport computer codes are used to predict quantities of interest in the fields of radiotherapy and radiobiology. The calculational methods are described and comparisions of calculated and experimental results are presented for dose distributions produced by protons, neutrons, and negatively charged pions. Comparisons of calculated and experimental cell survival probabilities are also presented.

Double layer of platinum electrodes: Non-monotonic surface charging phenomena and negative double layer capacitance

NASA Astrophysics Data System (ADS)

Huang, Jun; Zhou, Tao; Zhang, Jianbo; Eikerling, Michael

2018-01-01

In this study, a refined double layer model of platinum electrodes accounting for chemisorbed oxygen species, oriented interfacial water molecules, and ion size effects in solution is presented. It results in a non-monotonic surface charging relation and a peculiar capacitance vs. potential curve with a maximum and possibly negative values in the potential regime of oxide-formation.

Molecular insight into the electrostatic membrane surface potential by 14n/31p MAS NMR spectroscopy: nociceptin-lipid association.

PubMed

Lindström, Fredrick; Williamson, Philip T F; Gröbner, Gerhard

2005-05-11

Exploiting naturally abundant (14)N and (31)P nuclei by high-resolution MAS NMR (magic angle spinning nuclear magnetic resonance) provides a molecular view of the electrostatic potential present at the surface of biological model membranes, the electrostatic charge distribution across the membrane interface, and changes that occur upon peptide association. The spectral resolution in (31)P and (14)N MAS NMR spectra is sufficient to probe directly the negatively charged phosphate and positively charged choline segment of the electrostatic P(-)-O-CH(2)-CH(2)-N(+)(CH(3))(3) headgroup dipole of zwitterionic DMPC (dimyristoylphosphatidylcholine) in mixed-lipid systems. The isotropic shifts report on the size of the potential existing at the phosphate and ammonium group within the lipid headgroup while the chemical shielding anisotropy ((31)P) and anisotropic quadrupolar interaction ((14)N) characterize changes in headgroup orientation in response to surface potential. The (31)P/(14)N isotropic chemical shifts for DMPC show opposing systematic changes in response to changing membrane potential, reflecting the size of the electrostatic potential at opposing ends of the P(-)-N(+) dipole. The orientational response of the DMPC lipid headgroup to electrostatic surface variations is visible in the anisotropic features of (14)N and (31)P NMR spectra. These features are analyzed in terms of a modified "molecular voltmeter" model, with changes in dynamic averaging reflecting the tilt of the C(beta)-N(+)(CH)(3) choline and PO(4)(-) segment. These properties have been exploited to characterize the changes in surface potential upon the binding of nociceptin to negatively charged membranes, a process assumed to proceed its agonistic binding to its opoid G-protein coupled receptor.

Acid base activity of live bacteria: Implications for quantifying cell wall charge

NASA Astrophysics Data System (ADS)

Claessens, Jacqueline; van Lith, Yvonne; Laverman, Anniet M.; Van Cappellen, Philippe

2006-01-01

To distinguish the buffering capacity associated with functional groups in the cell wall from that resulting from metabolic processes, base or acid consumption by live and dead cells of the Gram-negative bacterium Shewanella putrefaciens was measured in a pH stat system. Live cells exhibited fast consumption of acid (pH 4) or base (pH 7, 8, 9, and 10) during the first few minutes of the experiments. At pH 5.5, no acid or base was required to maintain the initial pH constant. The initial amounts of acid or base consumed by the live cells at pH 4, 8, and 10 were of comparable magnitudes as those neutralized at the same pHs by intact cells killed by exposure to gamma radiation or ethanol. Cells disrupted in a French press required higher amounts of acid or base, due to additional buffering by intracellular constituents. At pH 4, acid neutralization by suspensions of live cells stopped after 50 min, because of loss of viability. In contrast, under neutral and alkaline conditions, base consumption continued for the entire duration of the experiments (5 h). This long-term base neutralization was, at least partly, due to active respiration by the cells, as indicated by the build-up of succinate in solution. Qualitatively, the acid-base activity of live cells of the Gram-positive bacterium Bacillus subtilis resembled that of S. putrefaciens. The pH-dependent charging of ionizable functional groups in the cell walls of the live bacteria was estimated from the initial amounts of acid or base consumed in the pH stat experiments. From pH 4 to 10, the cell wall charge increased from near-zero values to about -4 × 10 -16 mol cell -1 and -6.5 × 10 -16 mol cell -1 for S. putrefaciens and B. subtilis, respectively. The similar cell wall charging of the two bacterial strains is consistent with the inferred low contribution of lipopolysaccharides to the buffering capacity of the Gram-negative cell wall (of the order of 10%).

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.

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.

The impact of prescription charges on asthma patients is uneven and unpredictable: evidence from qualitative interviews.

PubMed

Schafheutle, Ellen I

2009-12-01

To explore whether, and how, prescription charges affect asthma patients' disease management behaviour. Thirty qualitative interviews. Interviewees were aged between 21 and 59, 21 were women, 24 were paying individual prescription charges, and six had prepayment certificates (PPCs). Most had a beta2-agonist 'reliever' and a steroid 'preventer' inhaler. Prescription charges posed affordability issues for some, and for two patients cost-related reduction in 'preventer' use affected asthma control negatively. Many described various ways of keeping medication cost down. Affordability issues, negative views on paying charges, and whether interviewees viewed their asthma medication as essential, were influential factors. Steroid inhalers were viewed more commonly as being less essential and affected by cost. The episodic nature of asthma meant that predicting benefit from PPCs was difficult. This study strengthens existing evidence that medication cost is a factor in asthma patients' management decisions, with a potential cost-related impact on asthma control.

Plasma bullet current measurements in a free-stream helium capillary jet

NASA Astrophysics Data System (ADS)

Oh, Jun-Seok; Walsh, James L.; Bradley, James W.

2012-06-01

A commercial current monitor has been used to measure the current associated with plasma bullets created in both the positive and negative half cycles of the sinusoidal driving voltage sustaining a plasma jet. The maximum values of the positive bullet current are typically ˜750 µA and persist for 10 µs, while the peaks in the negative current of several hundred μA are broad, persisting for about 40 µs. From the time delay of the current peaks with increasing distance from the jet nozzle, an average bullet propagation speed has been measured; the positive and negative bullets travel at 17.5 km s-1 and 3.9 km s-1 respectively. The net space charge associated with the bullet(s) has also been calculated; the positive and negative bullets contain a similar net charge of the order of 10-9 C measured at all monitor positions, with estimated charged particle densities nb of ˜1010-1011 cm-3 in the bullet.

Hydrogel, aerogel and film of cellulose nanofibrils functionalized with silver nanoparticles.

PubMed

Dong, Hong; Snyder, James F; Tran, Dat T; Leadore, Julia L

2013-06-20

In this work, we describe hydrogels, aerogels and films of nanofibrillated cellulose (NFC) functionalized with metal nanoparticles using silver as an example. The TEMPO process used to produce NFC generates negatively charged surface carboxylate groups that provide high binding capability to transition metal species such as Ag(+). The gelation of NFC triggered by transition monovalent metal ions was revealed for the first time. The interaction was utilized to bind Ag(+) on the NFC surface and simultaneously induce formation of NFC-Ag(+) hydrogels, where Ag(+) was slowly reduced to Ag nanoparticles by hydroxyl groups on NFC without additional reducing agent. The NFC-Ag(+) hydrogel was initiated by strong association of carboxylate groups on NFC with Ag(+) and sufficient NFC surface charge reduction. The stiff hydrogel has a storage modulus leveled off at a plateau value of ~6800Pa. Porous aerogels and flat thin films comprising a continuous matrix of NFC were decorated with Ag nanoparticles through freeze-drying or solution-casting of NFC-Ag(+) dispersions with low contents of Ag(+), respectively, followed by UV reduction. The presence of Ag species on NFC reduced coalescence of nanofibrils in the film formation as revealed from AFM phase images. Copyright © 2013 Elsevier Ltd. All rights reserved.

Effect of Fatty Acyl Group and Sterol Composition on Sensitivity of Lecithin Liposomes to Imidazole Antimycotics

PubMed Central

Yamaguchi, Hideyo; Iwata, Kazuo

1979-01-01

The specific affinity for membrane lipids and the membrane selectivity of three imidazole derivatives, clotrimazole, miconazole, and econazole, were studied using various types of liposomes with respect to the lecithin fatty acyl group composition and the liposome content and composition of sterol as membrane models. The sensitivity of liposomes to these drugs was primarily dependent upon the lecithin fatty acyl group composition. With sterol-free liposome systems, each imidazole induced maximum release of trapped glucose as a marker from the unsaturated dioleoyl lecithin liposomes, minimum release from the saturated dipalmitoyl lecithin liposomes, and intermediate release from egg lecithin liposomes. The sensitivity of the dipalmitoyl lecithin liposomes to any imidazole drug was not influenced by the incorporation of cholesterol or ergosterol. On the other hand, clotrimazole-induced permeability changes of liposomes prepared from unsaturated dioleoyl lecithin or egg lecithin were greatly enhanced by the incorporation of ergosterol, whereas they were suppressed by cholesterol incorporation. The sensitivity of liposomes prepared from these unsaturated lecithins to miconazole and econazole was also augmented by ergosterol incorporation, although it was scarcely altered by cholesterol incorporation. Negatively charged liposomes were more sensitive to the three imidazole drugs than positively charged liposomes. PMID:525988

Effect of fatty acyl group and sterol composition on sensitivity of lecithin liposomes to imidazole antimycotics.

PubMed

Yamaguchi, H; Iwata, K

1979-05-01

The specific affinity for membrane lipids and the membrane selectivity of three imidazole derivatives, clotrimazole, miconazole, and econazole, were studied using various types of liposomes with respect to the lecithin fatty acyl group composition and the liposome content and composition of sterol as membrane models. The sensitivity of liposomes to these drugs was primarily dependent upon the lecithin fatty acyl group composition. With sterol-free liposome systems, each imidazole induced maximum release of trapped glucose as a marker from the unsaturated dioleoyl lecithin liposomes, minimum release from the saturated dipalmitoyl lecithin liposomes, and intermediate release from egg lecithin liposomes. The sensitivity of the dipalmitoyl lecithin liposomes to any imidazole drug was not influenced by the incorporation of cholesterol or ergosterol. On the other hand, clotrimazole-induced permeability changes of liposomes prepared from unsaturated dioleoyl lecithin or egg lecithin were greatly enhanced by the incorporation of ergosterol, whereas they were suppressed by cholesterol incorporation. The sensitivity of liposomes prepared from these unsaturated lecithins to miconazole and econazole was also augmented by ergosterol incorporation, although it was scarcely altered by cholesterol incorporation. Negatively charged liposomes were more sensitive to the three imidazole drugs than positively charged liposomes.

Plantaricin A, a cationic peptide produced by Lactobacillus plantarum, permeabilizes eukaryotic cell membranes by a mechanism dependent on negative surface charge linked to glycosylated membrane proteins.

PubMed

Sand, Sverre L; Nissen-Meyer, Jon; Sand, Olav; Haug, Trude M

2013-02-01

Lactobacillus plantarum C11 releases plantaricin A (PlnA), a cationic peptide pheromone that has a membrane-permeabilizing, antimicrobial effect. We have previously shown that PlnA may also permeabilize eukaryotic cells, with a potency that differs between cell types. It is generally assumed that cationic antimicrobial peptides exert their effects through electrostatic attraction to negatively charged phospholipids in the membrane. The aim of the present study was to investigate if removal of the negative charge linked to glycosylated proteins at the cell surface reduces the permeabilizing potency of PlnA. The effects of PlnA were tested on clonal rat anterior pituitary cells (GH(4) cells) using patch clamp and microfluorometric techniques. In physiological extracellular solution, GH(4) cells are highly sensitive to PlnA, but the sensitivity was dramatically reduced in solutions that partly neutralize the negative surface charge of the cells, in agreement with the notion that electrostatic interactions are probably important for the PlnA effects. Trypsination of cells prior to PlnA exposure also rendered the cells less sensitive to the peptide, suggesting that negative charges linked to membrane proteins are involved in the permeabilizing action. Finally, pre-exposure of cells to a mixture of enzymes that split carbohydrate residues from the backbone of glycosylated proteins also impeded the PlnA-induced membrane permeabilization. We conclude that electrostatic attraction between PlnA and glycosylated membrane proteins is probably an essential first step before PlnA can interact with membrane phospholipids. Deviating glycosylation patterns may contribute to the variation in PlnA sensitivity of different cell types, including cancerous cells and their normal counterparts. Copyright © 2012 Elsevier B.V. All rights reserved.

Method of making maximally dispersed heterogeneous catalysts

DOEpatents

Jennison, Dwight R [Albuquerque, NM

2005-11-15

A method of making a catalyst with monolayer or sub-monolayer metal by controlling the wetting characteristics on the support surface and increasing the adhesion between the catalytic metal and an oxide layer. There are two methods that have been demonstrated by experiment and supported by theory. In the first method, which is useful for noble metals as well as others, a negatively-charged species is introduced to the surface of a support in sub-ML coverage. The layer-by-layer growth of metal deposited onto the oxide surface is promoted because the adhesion strength of the metal-oxide interface is increased. This method can also be used to achieve nanoislands of metal upon sub-ML deposition. 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. Thus the negatively-charged species serve as anchors for the metal. In the second method, a chemical reaction that occurs when most metals are deposited on a fully hydroxylated oxide surface is used to create cationic metal species that bind strongly both to the substrate and to metallic metal atoms. These are incorporated into the top layer of the substrate and bind strongly both to the substrate and to metallic metal atoms. In this case, these oxidized metal atoms serve as the anchors. Here, as in the previous method, nanoislands of catalytic metal can be achieved to increase catalytic activity, or monolayers or bilayers of reactive metal can also be made.

Peptide:lipid ratio and membrane surface charge determine the mechanism of action of the antimicrobial peptide BP100. Conformational and functional studies.

PubMed

Manzini, Mariana C; Perez, Katia R; Riske, Karin A; Bozelli, José C; Santos, Talita L; da Silva, Marcia A; Saraiva, Greice K V; Politi, Mario J; Valente, Ana P; Almeida, Fábio C L; Chaimovich, Hernan; Rodrigues, Magali A; Bemquerer, Marcelo P; Schreier, Shirley; Cuccovia, Iolanda M

2014-07-01

The cecropin-melittin hybrid antimicrobial peptide BP100 (H-KKLFKKILKYL-NH2) is selective for Gram-negative bacteria, negatively charged membranes, and weakly hemolytic. We studied BP100 conformational and functional properties upon interaction with large unilamellar vesicles, LUVs, and giant unilamellar vesicles, GUVs, containing variable proportions of phosphatidylcholine (PC) and negatively charged phosphatidylglycerol (PG). CD and NMR spectra showed that upon binding to PG-containing LUVs BP100 acquires α-helical conformation, the helix spanning residues 3-11. Theoretical analyses indicated that the helix is amphipathic and surface-seeking. CD and dynamic light scattering data evinced peptide and/or vesicle aggregation, modulated by peptide:lipid ratio and PG content. BP100 decreased the absolute value of the zeta potential (ζ) of LUVs with low PG contents; for higher PG, binding was analyzed as an ion-exchange process. At high salt, BP100-induced LUVS leakage requires higher peptide concentration, indicating that both electrostatic and hydrophobic interactions contribute to peptide binding. While a gradual release took place at low peptide:lipid ratios, instantaneous loss occurred at high ratios, suggesting vesicle disruption. Optical microscopy of GUVs confirmed BP100-promoted disruption of negatively charged membranes. The mechanism of action of BP100 is determined by both peptide:lipid ratio and negatively charged lipid content. While gradual release results from membrane perturbation by a small number of peptide molecules giving rise to changes in acyl chain packing, lipid clustering (leading to membrane defects), and/or membrane thinning, membrane disruption results from a sequence of events - large-scale peptide and lipid clustering, giving rise to peptide-lipid patches that eventually would leave the membrane in a carpet-like mechanism. Copyright © 2014 Elsevier B.V. All rights reserved.

A lower isoelectric point increases signal sequence-mediated secretion of recombinant proteins through a bacterial ABC transporter.

PubMed

Byun, Hyunjong; Park, Jiyeon; Kim, Sun Chang; Ahn, Jung Hoon

2017-12-01

Efficient protein production for industrial and academic purposes often involves engineering microorganisms to produce and secrete target proteins into the culture. Pseudomonas fluorescens has a TliDEF ATP-binding cassette transporter, a type I secretion system, which recognizes C-terminal LARD3 signal sequence of thermostable lipase TliA. Many proteins are secreted by TliDEF in vivo when recombined with LARD3, but there are still others that cannot be secreted by TliDEF even when LARD3 is attached. However, the factors that determine whether or not a recombinant protein can be secreted through TliDEF are still unknown. Here, we recombined LARD3 with several proteins and examined their secretion through TliDEF. We found that the proteins secreted via LARD3 are highly negatively charged with highly-acidic isoelectric points (pI) lower than 5.5. Attaching oligo-aspartate to lower the pI of negatively-charged recombinant proteins improved their secretion, and attaching oligo-arginine to negatively-charged proteins blocked their secretion by LARD3. In addition, negatively supercharged green fluorescent protein (GFP) showed improved secretion, whereas positively supercharged GFP did not secrete. These results disclosed that proteins' acidic pI and net negative charge are major factors that determine their secretion through TliDEF. Homology modeling for TliDEF revealed that TliD dimer forms evolutionarily-conserved positively-charged clusters in its pore and substrate entrance site, which also partially explains the pI dependence of the TliDEF-dependent secretions. In conclusion, lowering the isoelectric point improved LARD3-mediated protein secretion, both widening the range of protein targets for efficient production via secretion and signifying an important aspect of ABC transporter-mediated secretions. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

Concentration of poliovirus from tap water using positively charged microporous filters.

PubMed Central

Sobsey, M D; Jones, B L

1979-01-01

Microporous filters that are more electropositive than the negatively charged filters currently used for virus concentrations from water by filter adsorption-elution methods were evaluated for poliovirus recovery from tap water. Zeta Plus filters composed of diatomaceous earth-cellulose-"charge-modified" resin mixtures and having a net positive charge of up to pH 5 to 6 efficiently adsorbed poliovirus from tap water at ambient pH levels 7.0 to 7.5 without added multivalent cation salts. The adsorbed virus were eluted with glycine-NaOH, pH 9.5 to 11.5. Electropositive asbestos-cellulose filters efficiently adsorbed poliovirus from tap water without added multivalent cation salts between pH 3.5 and 9.0, and the absorbed viruses could be eluted with 3% beef extract, pH 9, but not with pH 9.5 to 11.5 glycine-NaOH. Under water quality conditions in which poliovirus recoveries from large volumes of water were less than 5% with conventional negatively charged filters and standard methods, recoveries with Zeta Plus filters averaged 64 and 22.5% for one- and two-stage concentration procedures, respectively. Electropositive filters appear to offer distinct advantages over conventional negatively charged filters for concentrating enteric viruses from water, and their behavior tends to confirm the importance of electrostatic forces in virus recovery from water by microporous filter adsorption-elution methods. PMID:36844

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.

Constrained Surface Complexation Modeling: Rutile in RbCl, NaCl, and NaCF 3SO 3 Media to 250 °C

DOE PAGES

Machesky, Michael L.; Předota, Milan; Ridley, Moira K.; ...

2015-06-01

In this paper, a comprehensive set of molecular-level results, primarily from classical molecular dynamics (CMD) simulations, are used to constrain CD-MUSIC surface complexation model (SCM) parameters describing rutile powder titrations conducted in RbCl, NaCl, and NaTr (Tr = triflate, CF 3SO 3 –) electrolyte media from 25 to 250 °C. Rb + primarily occupies the innermost tetradentate binding site on the rutile (110) surface at all temperatures (25, 150, 250 °C) and negative charge conditions (-0.1 and -0.2 C/m 2) probed via CMD simulations, reflecting the small hydration energy of this large, monovalent cation. Consequently, variable SCM parameters (Stern-layer capacitancemore » values and intrinsic Rb + binding constants) were adjusted relatively easily to satisfactorily match the CMD and titration data. The larger hydration energy of Na + results in a more complex inner-sphere distribution, which shifts from bidentate to tetradentate binding with increasing negative charge and temperature, and this distribution was not matched well for both negative charge conditions, which may reflect limitations in the CMD and/or SCM approaches. Finally, in particular, the CMD axial density profiles for Rb + and Na + reveal that peak binding distances shift toward the surface with increasing negative charge, suggesting that the CD-MUSIC framework may be improved by incorporating CD or Stern-layer capacitance values that vary with charge.« less

Constrained Surface Complexation Modeling: Rutile in RbCl, NaCl, and NaCF 3SO 3 Media to 250 °C

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

Machesky, Michael L.; Předota, Milan; Ridley, Moira K.

In this paper, a comprehensive set of molecular-level results, primarily from classical molecular dynamics (CMD) simulations, are used to constrain CD-MUSIC surface complexation model (SCM) parameters describing rutile powder titrations conducted in RbCl, NaCl, and NaTr (Tr = triflate, CF 3SO 3 –) electrolyte media from 25 to 250 °C. Rb + primarily occupies the innermost tetradentate binding site on the rutile (110) surface at all temperatures (25, 150, 250 °C) and negative charge conditions (-0.1 and -0.2 C/m 2) probed via CMD simulations, reflecting the small hydration energy of this large, monovalent cation. Consequently, variable SCM parameters (Stern-layer capacitancemore » values and intrinsic Rb + binding constants) were adjusted relatively easily to satisfactorily match the CMD and titration data. The larger hydration energy of Na + results in a more complex inner-sphere distribution, which shifts from bidentate to tetradentate binding with increasing negative charge and temperature, and this distribution was not matched well for both negative charge conditions, which may reflect limitations in the CMD and/or SCM approaches. Finally, in particular, the CMD axial density profiles for Rb + and Na + reveal that peak binding distances shift toward the surface with increasing negative charge, suggesting that the CD-MUSIC framework may be improved by incorporating CD or Stern-layer capacitance values that vary with charge.« less

Effective cytoplasmic release of siRNA from liposomal carriers by controlling the electrostatic interaction of siRNA with a charge-invertible peptide, in response to cytoplasmic pH

NASA Astrophysics Data System (ADS)

Itakura, Shoko; Hama, Susumu; Matsui, Ryo; Kogure, Kentaro

2016-05-01

Condensing siRNA with cationic polymers is a major strategy used in the development of siRNA carriers that can avoid degradation by nucleases and achieve effective delivery of siRNA into the cytoplasm. However, ineffective release of siRNA from such condensed forms into the cytoplasm is a limiting step for induction of RNAi effects, and can be attributed to tight condensation of siRNA with the cationic polymers, due to potent electrostatic interactions. Here, we report that siRNA condensed with a slightly acidic pH-sensitive peptide (SAPSP), whose total charge is inverted from positive to negative in response to cytoplasmic pH, is effectively released via electrostatic repulsion of siRNA with negatively charged SAPSP at cytoplasmic pH (7.4). The condensed complex of siRNA and positively-charged SAPSP at acidic pH (siRNA/SAPSP) was found to result in almost complete release of siRNA upon charge inversion of SAPSP at pH 7.4, with the resultant negatively-charged SAPSP having no undesirable interactions with endogenous mRNA. Moreover, liposomes encapsulating siRNA/SAPSP demonstrated knockdown efficiencies comparable to those of commercially available siRNA carriers. Taken together, SAPSP may be very useful as a siRNA condenser, as it facilitates effective cytoplasmic release of siRNA, and subsequent induction of specific RNAi effects.Condensing siRNA with cationic polymers is a major strategy used in the development of siRNA carriers that can avoid degradation by nucleases and achieve effective delivery of siRNA into the cytoplasm. However, ineffective release of siRNA from such condensed forms into the cytoplasm is a limiting step for induction of RNAi effects, and can be attributed to tight condensation of siRNA with the cationic polymers, due to potent electrostatic interactions. Here, we report that siRNA condensed with a slightly acidic pH-sensitive peptide (SAPSP), whose total charge is inverted from positive to negative in response to cytoplasmic pH, is effectively released via electrostatic repulsion of siRNA with negatively charged SAPSP at cytoplasmic pH (7.4). The condensed complex of siRNA and positively-charged SAPSP at acidic pH (siRNA/SAPSP) was found to result in almost complete release of siRNA upon charge inversion of SAPSP at pH 7.4, with the resultant negatively-charged SAPSP having no undesirable interactions with endogenous mRNA. Moreover, liposomes encapsulating siRNA/SAPSP demonstrated knockdown efficiencies comparable to those of commercially available siRNA carriers. Taken together, SAPSP may be very useful as a siRNA condenser, as it facilitates effective cytoplasmic release of siRNA, and subsequent induction of specific RNAi effects. Electronic supplementary information (ESI) available: De-condensation of siRNA cores by addition of heparin; time-lapse moving image of the siRNA release. See DOI: 10.1039/c5nr08365f

First results of the Colombia Lightning Mapping Array

NASA Astrophysics Data System (ADS)

López, Jesus; Montanyà, Joan; van der Velde, Oscar; Romero, David; Fabró, Ferran; Taborda, John; Aranguren, Daniel; Torres, Horacio

2016-04-01

In April 2015 the 3D Lightning Mapping Array (COLMA) network was installed on Santa Marta area (north of Colombia). The COLMA maps VHF radio emissions of lightning leaders in three dimensions by the time-of-arrival technique (Rison et al., 1999). This array has six sensors with base lines between 5 km to 20 km. The COLMA is the first VHF 3D network operating in the tropics and it has been installed in the frame of ASIM (Atmosphere-Space Interactions Monitor) ESA's mission in order to investigate the electrical characteristics of tropical thunderstorms favorable for the production of Terrestrial Gamma ray Flashes (TGF). In this paper we present COLMA data of several storms. We discuss lightning activity, lightning leader altitudes and thunderstorm charge structures compared to data form our ELMA (Ebro Lightning Mapping Array) at the north-east coast of Spain. The data confirm what we expected, lightning leaders can propagate at higher altitudes compared to mid latitude thunderstorms because the higher vertical development of tropical thunderstorms. A simple inspection of a ten minute period of the 16th of November of 2015 storm shows a tripolar electric charge structure. In that case, the midlevel negative charge region was located between 7 to 9 km. The structure presented a lower positive charge below the midlevel negative and centred at 6.5 km and an upper positive charge region extending from 9 km to slightly more than 15 km. This vertical extension of the upper positive charge where negative leaders evolve is significantly larger compared to the storms at the ELMA area in Spain. COLMA has shown frequent activity of negative leaders reaching altitudes of more than 15 km.

Urinary Alpha-1-Acid Glycoprotein Is a Sensitive Marker of Glomerular Protein Leakage at Altitude.

PubMed

Talks, Ben J; Bradwell, Susie B; Delamere, John; Rayner, Will; Clarke, Alex; Lewis, Chris T; Thomas, Owen D; Bradwell, Arthur R

2018-06-11

Talks, Ben J., Susie B. Bradwell, John Delamere, Will Rayner, Alex Clarke, Chris T. Lewis, Owen D. Thomas, and Arthur R. Bradwell. Urinary alpha-1-acid glycoprotein is a sensitive marker of glomerular protein leakage at altitude. High Alt Med Biol 00:000-000, 2018. Proteinuria is an established feature of ascent to altitude and may be caused by a loss of negative charges on glomerular capillary walls (GCWs). To test this hypothesis, we measured two similar sized but oppositely charged proteins in urine: negatively charged alpha-1-acid glycoprotein (α1-AGP, 41-43 kDa) and positively charged dimeric lambda free light chains (λ-FLCs, 50 kDa). Twenty-four-hour urinary leakage was compared with albumin, a 66 kDa negatively charged protein. We studied 23 individuals (ages 23-78 years, male = 17) at baseline (140 m) and daily during an expedition to 5035 m. The results showed a significant increase in median urinary leakage of α1-AGP (p < 0.0001; 6.85-fold) and albumin (p = 0.0006; 1.65-fold) with ascent to altitude, but no significant increase in leakage of λ-FLCs (p = 0.39; 1.14-fold). α1-AGP correlated with the daily ascent profile (p = 0.0026) and partial pressure of oxygen (p = 0.01), whereas albumin showed no correlation (p = 0.19). Urinary α1-AGP was a more sensitive marker of altitude proteinuria than urinary albumin and λ-FLCs, and supported the possibility of loss of GCW negative charges at altitude.

Electrostatic Charging and Particle Interactions in Microscopic Insulating Grains

NASA Astrophysics Data System (ADS)

Lee, Victor

In this thesis, we experimentally investigate the electrostatic charging as well as the particle interactions in microscopic insulating grains. First, by tracking individual grains accelerated in an electric field, we quantitatively demonstrate that tribocharging of same-material grains depends on particle size. Large grains tend to charge positively, and small ones tend to charge negatively. Theories based on the transfer of trapped electrons can explain this tendency but have not been validated. Here we show that the number of trapped electrons, measured independently by a thermoluminescence technique, is orders of magnitude too small to be responsible for the amount of charge transferred. This result reveals that trapped electrons are not responsible for same-material tribocharging of dielectric particles. Second, same-material tribocharging in grains can result in important long-range electrostatic interactions. However, how these electrostatic interactions contribute to particle clustering remains elusive, primarily due to the lack of direct, detailed observations. Using a high-speed camera that falls with a stream charged grains, we observe for the first time how charged grains can undergo attractive as well as repulsive Kepler-like orbits. Charged particles can be captured in their mutual electrostatic potential and form clusters via multiple bounces. Dielectric polarization effects are directly observed, which lead to additional attractive forces and stabilize "molecule-like" arrangements of charged particles. Third, we have developed a new method to study the charge transfer of microscopic particles based on acoustic levitation techniques. This method allows us to narrow the complex problem of many-particle charging down to precise charge measurements of a single sub-millimeter particle colliding with a target plate. By simply attaching nonpolar groups onto glass surfaces, we show that the contact charging of a particle is highly dependent on hydrophobicity. Charging between a hydrophilic and a hydrophobic surface is enhanced in a basic atmosphere and suppressed in an acidic one. Moreover, hydrophobicity is also found to play a key role in particle charging driven by an external electric field. These results strongly support the idea that aqueous-ion transfer is responsible for the particle contact charging phenomenon.

Describing long-range charge-separation processes with subsystem density-functional theory

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

Solovyeva, Alisa; Neugebauer, Johannes, E-mail: j.neugebauer@uni-muenster.de; Pavanello, Michele, E-mail: m.pavanello@rutgers.edu

2014-04-28

Long-range charge-transfer processes in extended systems are difficult to describe with quantum chemical methods. In particular, cost-effective (non-hybrid) approximations within time-dependent density functional theory (DFT) are not applicable unless special precautions are taken. Here, we show that the efficient subsystem DFT can be employed as a constrained DFT variant to describe the energetics of long-range charge-separation processes. A formal analysis of the energy components in subsystem DFT for such excitation energies is presented, which demonstrates that both the distance dependence and the long-range limit are correctly described. In addition, electronic couplings for these processes as needed for rate constants inmore » Marcus theory can be obtained from this method. It is shown that the electronic structure of charge-separated states constructed by a positively charged subsystem interacting with a negatively charged one is difficult to converge — charge leaking from the negative subsystem to the positive one can occur. This problem is related to the delocalization error in DFT and can be overcome with asymptotically correct exchange–correlation (XC) potentials or XC potentials including a sufficiently large amount of exact exchange. We also outline an approximate way to obtain charge-transfer couplings between locally excited and charge-separated states.« less

Trajectories of Moving Charges in Static Electric Fields.

ERIC Educational Resources Information Center

Kirkup, L.

1986-01-01

Describes the implementation of a trajectory-plotting program for a microcomputer; shows how it may be used to demonstrate the focusing effect of a simple electrostatic lens. The computer program is listed and diagrams are included that show comparisons of trajectories of negative charges in the vicinity of positive charges. (TW)

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

Gendron, Frederic; Fleischauer, Valerie R.; Duignan, Thomas J.

Here, we present a combined ab initio theoretical and experimental study of the magnetic circular dichroism (MCD) spectrum of the octahedral UCl 6- complex ion in the UV-Vis spectral region. The ground state is an orbitally non-degenerate doublet E 5/2u and the MCD is a $C$-term spectrum caused by spin–orbit coupling. Calculations of the electronic spectrum at various levels of theory indicate that differential dynamic electron correlation has a strong influence on the energies of the dipole-allowed transitions and the envelope of the MCD spectrum. The experimentally observed bands are assigned to dipole-allowed ligand-to-metal charge transfer into the 5f shell,more » and 5f to 6d transitions. Charge transfer excitations into the U 6d shell appear at much higher energies. The MCD-allowed transitions can be assigned via their signs of the $C$-terms: Under O h double group symmetry, E 5/2u → E 5/2g transitions have negative $C$-terms whereas E 5/2u → F 3/2g transitions have positive $C$-terms if the ground state g-factor is negative, as it is the case for UCl 6-.« less

A comparative study on the effect of Curcumin and Chlorin-p6 on the diffusion of two organic cations across a negatively charged lipid bilayer probed by second harmonic spectroscopy

NASA Astrophysics Data System (ADS)

Saini, R. K.; Varshney, G. K.; Dube, A.; Gupta, P. K.; Das, K.

2014-09-01

The influence of Curcumin and Chlorin-p6 (Cp6) on the real time diffusion kinetics of two organic cations, LDS (LDS-698) and Malachite Green (MG) across a negatively charged phospholipid bilayer is investigated by Second Harmonic (SH) spectroscopy. The diffusion time constant of LDS at neutral pH in liposomes containing either Curcumin or Cp6 is significantly reduced, the effect being more pronounced with Curcumin. At acidic pH, the quantum of reduction in the diffusion time constant of MG by both the drugs was observed to be similar. The relative changes in the average diffusion time constants of the cations with increasing drug concentration at pH 5.0 and 7.4 shows a substantial pH effect for Curcumin induced membrane permeability, while a modest pH effect was observed for Cp6 induced membrane permeability. Based on available evidence this can be attributed to the increased interaction between the drug and the polar head groups of the lipid at pH 7.4 where the drug resides closer to the lipid-water interface.

Integration Assessment of Visiting Vehicle Induced Electrical Charging of the International Space Station Structure

NASA Technical Reports Server (NTRS)

Kramer, Leonard; Kerslake, Thomas W.; Galofaro, Joel T.

2010-01-01

The International Space Station (ISS) undergoes electrical charging in low Earth orbit (LEO) due to positively biased, exposed conductors on solar arrays that collect electrical charges from the space plasma. Exposed solar array conductors predominately collect negatively charged electrons and thus drive the metal ISS structure electrical ground to a negative floating potential (FP) relative to plasma. This FP is variable in location and time as a result of local ionospheric conditions. ISS motion through Earth s magnetic field creates an addition inductive voltage up to 20 positive and negative volts across ISS structure depending on its attitude and location in orbit. ISS Visiting Vehicles (VVs), such as the planned Orion crew exploration vehicle, contribute to the ISS plasma charging processes. Upon physical contact with ISS, the current collection properties of VVs combine with ISS. This is an ISS integration concern as FP must be controlled to minimize arcing of ISS surfaces and ensure proper management of extra vehicular activity crewman shock hazards. This report is an assessment of ISS induced charging from docked Orion vehicles employing negatively grounded, 130 volt class, UltraFlex (ATK Space Systems) solar arrays. To assess plasma electron current collection characteristics, Orion solar cell test coupons were constructed and subjected to plasma chamber current collection measurements. During these tests, coupon solar cells were biased between 0 and 120 V while immersed in a simulated LEO plasma. Tests were performed using several different simulated LEO plasma densities and temperatures. These data and associated theoretical scaling of plasma properties, were combined in a numerical model which was integrated into the Boeing Plasma Interaction Model. It was found that the solar array design for Orion will not affect the ISS FP by more than about 2 V during worst case charging conditions. This assessment also motivated a trade study to determine acceptable plasma electron current levels that can be collected by a single or combined fleet of ISS-docked VVs.

Kinetics and thermodynamics of chlorpromazine interaction with lipid bilayers: effect of charge and cholesterol.

PubMed

Martins, Patrícia T; Velazquez-Campoy, Adrian; Vaz, Winchil L C; Cardoso, Renato M S; Valério, Joana; Moreno, Maria João

2012-03-07

Passive transport across cell membranes is the major route for the permeation of xenobiotics through tight endothelia such as the blood–brain barrier. The rate of passive permeation through lipid bilayers for a given drug is therefore a critical step in the prediction of its pharmacodynamics. We describe a detailed study on the kinetics and thermodynamics for the interaction of chlorpromazine (CPZ), an antipsychotic drug used in the treatment of schizophrenia, with neutral and negatively charged lipid bilayers. Isothermal titration calorimetry was used to study the partition and translocation of CPZ in lipid membranes composed of pure POPC, POPC:POPS (9:1), and POPC:Chol:POPS (6:3:1). The membrane charge due to the presence of POPS as well as the additional charge resulting from the introduction of CPZ in the membrane were taken into account, allowing the calculation of the intrinsic partition coefficients (K(P)) and the enthalpy change (ΔH) associated with the process. The enthalpy change upon partition to all lipid bilayers studied is negative, but a significant entropy contribution was also observed for partition to the neutral membrane. Because of the positive charge of CPZ, the presence of negatively charged lipids in the bilayer increases both the observed amount of CPZ that partitions to the membrane (KP(obs)) and the magnitude of ΔH. However, when the electrostatic effects are discounted, the intrinsic partition coefficient was smaller, indicating that the hydrophobic contribution was less significant for the negatively charged membrane. The presence of cholesterol strongly decreases the affinity of CPZ for the bilayer in terms of both the amount of CPZ that associates with the membrane and the interaction enthalpy. A quantitative characterization of the rate of CPZ translocation through membranes composed of pure POPC and POPC:POPS (9:1) was also performed using an innovative methodology developed in this work based on the kinetics of the heat evolved due to the interaction of CPZ with the membranes. © 2012 American Chemical Society

Production of negatively charged radioactive ion beams

DOE PAGES

Liu, Y.; Stracener, D. W.; Stora, T.

2017-02-15

Beams of short-lived radioactive nuclei are needed for frontier experimental research in nuclear structure, reactions, and astrophysics. Negatively charged radioactive ion beams have unique advantages and allow for the use of a tandem accelerator for post-acceleration, which can provide the highest beam quality and continuously variable energies. Negative ion beams can be obtained with high intensity and some unique beam purification techniques based on differences in electronegativity and chemical reactivity can be used to provide beams with high purity. This article describes the production of negative radioactive ion beams at the former holifield radioactive ion beam facility at Oak Ridgemore » National Laboratory and at the CERN ISOLDE facility with emphasis on the development of the negative ion sources employed at these two facilities.« less

Colorimetric detection of mercury(II) in a high-salinity solution using gold nanoparticles capped with 3-mercaptopropionate acid and adenosine monophosphate.

PubMed

Yu, Cheng-Ju; Tseng, Wei-Lung

2008-11-04

A new colorimetric sensor for sensing Hg2+ in a high-salinity solution has been developed using gold nanoparticles (AuNPs) decorated with 3-mercaptopropionate acid (MPA) and adenosine monophosphate (AMP). Because of the high negative charge density of AMP on each AuNP surface, MPA/AMP-capped AuNPs are well dispersed in a high-salt solution. In contrast, the aggregation of MPA-capped AuNPs was induced by sodium ions, which shield the negative charges of the carboxylic groups of MPA. Through the coordination between the carboxylic group of MPA and Hg2+, the selectivity of MPA/AMP-capped AuNPs for Hg2+ in a high-salt solution is remarkably high over that of the other metals without the addition of a masking agent or a change in the temperature. We have carefully investigated the effect of the AMP concentration on the stability and sensitivity of MPA/AMP-capped AuNPs. Under optimum conditions, the lowest detectable concentration of Hg2+ using this probe was 500 nM on the basis of the measurement of the ratio of absorption at 620 nm to that at 520 nm. The sensitivity to Hg2+ can be further improved by modifying the MPA/AMP-capped AuNPs with highly fluorescent rhodamine 6G (R6G). By monitoring the fluorescence enhancement, the lowest detectable concentration of Hg2+ using R6G/MPA/AMP-capped AuNPs was 50 nM.

A novel highly charged exopolysaccharide produced by two strains of Stenotrophomonas maltophilia recovered from patients with cystic fibrosis.

PubMed

Cescutti, Paola; Cuzzi, Bruno; Liut, Gianfranco; Segonds, Christine; Di Bonaventura, Giovanni; Rizzo, Roberto

2011-09-27

Stenotrophomonas maltophilia is a non-fermenting Gram-negative microorganism capable of causing chronic pulmonary infection in cystic fibrosis patients and its ability to form biofilms on polystyrene and glass surfaces, as well as on cystic fibrosis-derived bronchial epithelial IB3-I cells was recently demonstrated. The latter evidence might explain the power of S. maltophilia to produce persistent lung infections, despite intensive antibiotic treatment. In addition to being important components of the extracellular biofilm matrix, polysaccharides are involved in virulence, as they contribute to bacterial survival in a hostile environment. With the aim of contributing to the elucidation of S. maltophilia virulence factors, the exopolysaccharides produced by two mucoid clinical isolates of S. maltophilia obtained from two cystic fibrosis patients were completely characterised, mainly by means of ESI-MS and NMR spectroscopy. The results showed that, although the two isolates were recovered from two different patients living in different countries (Italy and France), the exopolysaccharides produced have an identical primary structure, with the following repeating unit: The exopolysaccharide is highly negatively charged for the presence of three uronic acids on four residues in the repeating unit. Moreover, an ether-linked d-lactate substituent is located on C-3 and one O-acetyl group on C-4 of the galacturonic acid side chain. Another O-acetyl group substitutes C-2 of the galacturonic acid in the backbone, making this primary structure unique. Copyright © 2011 Elsevier Ltd. All rights reserved.

Two-electron states of a group-V donor in silicon from atomistic full configuration interactions

NASA Astrophysics Data System (ADS)

Tankasala, Archana; Salfi, Joseph; Bocquel, Juanita; Voisin, Benoit; Usman, Muhammad; Klimeck, Gerhard; Simmons, Michelle Y.; Hollenberg, Lloyd C. L.; Rogge, Sven; Rahman, Rajib

2018-05-01

Two-electron states bound to donors in silicon are important for both two-qubit gates and spin readout. We present a full configuration interaction technique in the atomistic tight-binding basis to capture multielectron exchange and correlation effects taking into account the full band structure of silicon and the atomic-scale granularity of a nanoscale device. Excited s -like states of A1 symmetry are found to strongly influence the charging energy of a negative donor center. We apply the technique on subsurface dopants subjected to gate electric fields and show that bound triplet states appear in the spectrum as a result of decreased charging energy. The exchange energy, obtained for the two-electron states in various confinement regimes, may enable engineering electrical control of spins in donor-dot hybrid qubits.

Development of hyaluronic acid-Fe2O3 hybrid magnetic nanoparticles for targeted delivery of peptides.

PubMed

Kumar, Arun; Sahoo, Bishwabhusan; Montpetit, Alison; Behera, Sumita; Lockey, Richard F; Mohapatra, Shyam S

2007-06-01

Novel hybrid nanoparticles comprised of hyaluronic acid (HA) and iron oxide were synthesized and characterized for the first time with the average diameter of less than 160 nm. The iron oxide (Fe2O3) particles are hybridized between HA layers by electrostatic interactions between the positive surface charge of the Fe2O3 nanoparticles and the negative charge of the carboxylate groups of HA, forming a corral-like structure. The particles were also characterized by FTIR and NMR to verify the hybridization. The particles were tested for their ability to deliver peptides to the cells using HEK293 and A549 cells. Results show that these particles delivered peptides at about 100% level. These HA-iron oxide nanoparticles are expected to be useful in developing effective tissue and cell targeting systems.

Ion counting in supercapacitor electrodes using NMR spectroscopy.

PubMed

Griffin, John M; Forse, Alexander C; Wang, Hao; Trease, Nicole M; Taberna, Pierre-Louis; Simon, Patrice; Grey, Clare P

2014-01-01

(19)F NMR spectroscopy has been used to study the local environments of anions in supercapacitor electrodes and to quantify changes in the populations of adsorbed species during charging. In the absence of an applied potential, anionic species adsorbed within carbon micropores (in-pore) are distinguished from those in large mesopores and spaces between particles (ex-pore) by a characteristic nucleus-independent chemical shift (NICS). Adsorption experiments and two-dimensional exchange experiments confirm that anions are in dynamic equilibrium between the in- and ex-pore environments with an exchange rate in the order of tens of Hz. (19)F in situ NMR spectra recorded at different charge states reveal changes in the intensity and NICS of the in-pore resonances, which are interpreted in term of changes in the population and local environments of the adsorbed anions that arise due to the charge-storage process. A comparison of the results obtained for a range of electrolytes reveals that several factors influence the charging mechanism. For a tetraethylammonium tetrafluoroborate electrolyte, positive polarisation of the electrode is found to proceed by anion adsorption at a low concentration, whereas increased ion exchange plays a more important role for a high concentration electrolyte. In contrast, negative polarization of the electrode proceeds by cation adsorption for both concentrations. For a tetrabutylammonium tetrafluoroborate electrolyte, anion expulsion is observed in the negative charging regime; this is attributed to the reduced mobility and/or access of the larger cations inside the pores, which forces the expulsion of anions in order to build up ionic charge. Significant anion expulsion is also observed in the negative charging regime for alkali metal bis(trifluoromethane)sulfonimide electrolytes, suggesting that more subtle factors also affect the charging mechanism.

Quantitative measurements and modeling of cargo–motor interactions during fast transport in the living axon

PubMed Central

Seamster, Pamela E; Loewenberg, Michael; Pascal, Jennifer; Chauviere, Arnaud; Gonzales, Aaron; Cristini, Vittorio; Bearer, Elaine L

2013-01-01

The kinesins have long been known to drive microtubule-based transport of sub-cellular components, yet the mechanisms of their attachment to cargo remain a mystery. Several different cargo-receptors have been proposed based on their in vitro binding affinities to kinesin-1. Only two of these—phosphatidyl inositol, a negatively charged lipid, and the carboxyl terminus of the amyloid precursor protein (APP-C), a trans-membrane protein—have been reported to mediate motility in living systems. A major question is how these many different cargo, receptors and motors interact to produce the complex choreography of vesicular transport within living cells. Here we describe an experimental assay that identifies cargo–motor receptors by their ability to recruit active motors and drive transport of exogenous cargo towards the synapse in living axons. Cargo is engineered by derivatizing the surface of polystyrene fluorescent nanospheres (100 nm diameter) with charged residues or with synthetic peptides derived from candidate motor receptor proteins, all designed to display a terminal COOH group. After injection into the squid giant axon, particle movements are imaged by laser-scanning confocal time-lapse microscopy. In this report we compare the motility of negatively charged beads with APP-C beads in the presence of glycine-conjugated non-motile beads using new strategies to measure bead movements. The ensuing quantitative analysis of time-lapse digital sequences reveals detailed information about bead movements: instantaneous and maximum velocities, run lengths, pause frequencies and pause durations. These measurements provide parameters for a mathematical model that predicts the spatiotemporal evolution of distribution of the two different types of bead cargo in the axon. The results reveal that negatively charged beads differ from APP-C beads in velocity and dispersion, and predict that at long time points APP-C will achieve greater progress towards the presynaptic terminal. The significance of this data and accompanying model pertains to the role transport plays in neuronal function, connectivity, and survival, and has implications in the pathogenesis of neurological disorders, such as Alzheimer’s, Huntington and Parkinson’s diseases. PMID:23011729

Quantitative measurements and modeling of cargo-motor interactions during fast transport in the living axon

NASA Astrophysics Data System (ADS)

Seamster, Pamela E.; Loewenberg, Michael; Pascal, Jennifer; Chauviere, Arnaud; Gonzales, Aaron; Cristini, Vittorio; Bearer, Elaine L.

2012-10-01

The kinesins have long been known to drive microtubule-based transport of sub-cellular components, yet the mechanisms of their attachment to cargo remain a mystery. Several different cargo-receptors have been proposed based on their in vitro binding affinities to kinesin-1. Only two of these—phosphatidyl inositol, a negatively charged lipid, and the carboxyl terminus of the amyloid precursor protein (APP-C), a trans-membrane protein—have been reported to mediate motility in living systems. A major question is how these many different cargo, receptors and motors interact to produce the complex choreography of vesicular transport within living cells. Here we describe an experimental assay that identifies cargo-motor receptors by their ability to recruit active motors and drive transport of exogenous cargo towards the synapse in living axons. Cargo is engineered by derivatizing the surface of polystyrene fluorescent nanospheres (100 nm diameter) with charged residues or with synthetic peptides derived from candidate motor receptor proteins, all designed to display a terminal COOH group. After injection into the squid giant axon, particle movements are imaged by laser-scanning confocal time-lapse microscopy. In this report we compare the motility of negatively charged beads with APP-C beads in the presence of glycine-conjugated non-motile beads using new strategies to measure bead movements. The ensuing quantitative analysis of time-lapse digital sequences reveals detailed information about bead movements: instantaneous and maximum velocities, run lengths, pause frequencies and pause durations. These measurements provide parameters for a mathematical model that predicts the spatiotemporal evolution of distribution of the two different types of bead cargo in the axon. The results reveal that negatively charged beads differ from APP-C beads in velocity and dispersion, and predict that at long time points APP-C will achieve greater progress towards the presynaptic terminal. The significance of this data and accompanying model pertains to the role transport plays in neuronal function, connectivity, and survival, and has implications in the pathogenesis of neurological disorders, such as Alzheimer’s, Huntington and Parkinson's diseases.

Enhanced performance of Zn(II)-doped lead-acid batteries with electrochemical active carbon in negative mass

NASA Astrophysics Data System (ADS)

Xiang, Jiayuan; Hu, Chen; Chen, Liying; Zhang, Dong; Ding, Ping; Chen, Dong; Liu, Hao; Chen, Jian; Wu, Xianzhang; Lai, Xiaokang

2016-10-01

The effect and mechanism of Zn(II) on improving the performances of lead-acid cell with electrochemical active carbon (EAC) in negative mass is investigated. The hydrogen evolution of the cell is significantly reduced due to the deposition of Zn on carbon surface and the increased porosity of negative mass. Zn(II) additives can also improve the low-temperature and high-rate capacities of the cell with EAC in negative mass, which ascribes to the formation of Zn on lead and carbon surface that constructs a conductive bridge among the active mass. Under the co-contribution of EAC and Zn(II), the partial-state-of-charge cycle life is greatly prolonged. EAC optimizes the NAM structure and porosity to enhance the charge acceptance and retard the lead sulfate accumulation. Zn(II) additive reduces the hydrogen evolution during charge process and improves the electric conductivity of the negative electrode. The cell with 0.6 wt% EAC and 0.006 wt% ZnO in negative mass exhibits 90% reversible capacity of the initial capacity after 2100 cycles. In contrast, the cell with 0.6 wt% EAC exhibits 84% reversible capacity after 2100 cycles and the control cell with no EAC and Zn(II) exhibits less than 80% reversible capacity after 1350 cycles.

Measurements of Lunar Dust Charging Properties by Electron Impact

NASA Technical Reports Server (NTRS)

Abbas, Mian M.; Tankosic, Dragana; Craven, Paul D.; Schneider, Todd A.; Vaughn, Jason A.; LeClair, Andre; Spann, James F.; Norwood, Joseph K.

2009-01-01

Dust grains in the lunar environment are believed to be electrostatically charged predominantly by photoelectric emissions resulting from solar UV radiation on the dayside, and on the nightside by interaction with electrons in the solar wind plasma. In the high vacuum environment on the lunar surface with virtually no atmosphere, the positive and negative charge states of micron/submicron dust grains lead to some unusual physical and dynamical dust phenomena. Knowledge of the electrostatic charging properties of dust grains in the lunar environment is required for addressing their hazardous effect on the humans and mechanical systems. It is well recognized that the charging properties of individual small micron size dust grains are substantially different from the measurements on bulk materials. In this paper we present the results of measurements on charging of individual Apollo 11 and Apollo 17 dust grains by exposing them to mono-energetic electron beams in the 10-100 eV energy range. The charging/discharging rates of positively and negatively charged particles of approx. 0.1 to 5 micron radii are discussed in terms of the sticking efficiencies and secondary electron yields. The secondary electron emission process is found to be a complex and effective charging/discharging mechanism for incident electron energies as low as 10-25 eV, with a strong dependence on particle size. Implications of the laboratory measurements on the nature of dust grain charging in the lunar environment are discussed.

Advances in Charge-Compensation in Secondary Ion Mass Spectrometry (SIMS)

NASA Astrophysics Data System (ADS)

Hervig, R. L.; Chen, J.; Schauer, S.; Stanley, B. D.; Moore, G. M.; Roggensack, K.

2012-12-01

In secondary ion mass spectrometry (SIMS), a sample is bombarded by a charged particle beam (the primary ion) and sputtered positive or negative secondary ions are analyzed in a mass spectrometer. When the target is not conducting (like many geological materials), sample charging can result in variable deflection of secondary ions away from the mass spectrometer and a low, unstable, or absent signal. Applying a thin conducting coat (e.g., C, Au) to polished samples is required, and if the primary ion beam is negatively-charged, the build-up of negative charge can be alleviated by secondary electrons draining to the conducting coat at the edge of the crater (if a positive potential is applied to the sample for the collection of positive secondary ions) or accelerated away from the crater (if a negative potential is applied for negative ion study). Unless the sputtered crater in the conducting coat becomes too large, sample charging can be kept at a controllable level, and high-quality trace element analyses and isotope ratios have been obtained using this technique over the past 3+ decades. When a positive primary beam is used, the resulting build-up of positive charge in the sample requires an electron gun to deliver sufficient negative charge to the sputtered crater. While there are many examples of successful analyses using this approach, the purpose of this presentation is to describe a very simple technique for aligning the electron gun on Cameca nf and 1270/80 SIMS instruments. This method allows reproducible analyses of insulating phases with a Cs+ primary beam and detection of negative secondary ions. Normally, the filament voltage on the E-gun is the same as the sample voltage; thus electrons do not strike the sample except when a positive charge has built up (e.g., in the analysis crater!). In this method, we decrease the sample voltage by 3 or more kV, so that the impact energy of the electrons is sufficient to induce a cathodoluminescent (CL) image on an appropriate sample (e.g., GaN). The CL image is made circular and homogeneous by adjusting the deflectors and a lens in the electron steering assembly, and the sample voltage is subsequently returned to the same value as the filament. Very minor corrections of the electron tuning (mostly by an external magnet known as Bx or B1) will then produce a uniform secondary ion image on a test insulator (a gold-coated glass slide) under Cs bombardment. The uniform electron density is correlated with reproducible calibration for hydrogen and carbon concentrations over a multi-day session and from session to session over a period of months. Outside visitors to the lab can use this set-up and obtain high-quality analyses with little to no previous training. Obtaining a homogeneous distribution of electrons over a maximum diameter (100+ microns) also reduces problems associated with changes in the position of the electron beam induced by stray magnetic fields. As a result, analyses of hydrogen isotopes and/or multi-element analysis routines using elemental H species are simplified.

Effect of charged and excited states on the decomposition of 1,1-diamino-2,2-dinitroethylene molecules

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

Kimmel, Anna V.; Sushko, Peter V.; Shluger, Alexander L.

The authors have calculated the electronic structure of individual 1,1-diamino-2,2-dinitroethylene molecules (FOX-7) in the gas phase by means of density functional theory with the hybrid B3LYP functional and 6-31+G(d,p) basis set and considered their dissociation pathways. Positively and negatively charged states as well as the lowest excited states of the molecule were simulated. They found that charging and excitation can not only reduce the activation barriers for decomposition reactions but also change the dominating chemistry from endo- to exothermic type. In particular, they found that there are two competing primary initiation mechanisms of FOX-7 decomposition: C-NO{sub 2} bond fission andmore » C-NO{sub 2} to CONO isomerization. Electronic excitation or charging of FOX-7 disfavors CONO formation and, thus, terminates this channel of decomposition. However, if CONO is formed from the neutral FOX-7 molecule, charge trapping and/or excitation results in spontaneous splitting of an NO group accompanied by the energy release. Intramolecular hydrogen transfer is found to be a rare event in FOX-7 unless free electrons are available in the vicinity of the molecule, in which case HONO formation is a feasible exothermic reaction with a relatively low energy barrier. The effect of charged and excited states on other possible reactions is also studied. Implications of the obtained results to FOX-7 decomposition in condensed state are discussed.« less

High negative charge of a dust particle in a hot cathode discharge.

PubMed

Arnas, C; Mikikian, M; Doveil, F

1999-12-01

Dust particle levitation experiments in a plasma produced by a hot filament discharge, operating at low argon pressure, are presented. The basic characteristics of a dust grain trapped in a plate sheath edge in these experimental conditions are reported. Taking into account the sheath potential profiles measured with a differential emissive probe diagnostic, the forces applied to an isolated dust grain can be determined. Two different experimental methods yield approximately the same value for the dust charge. The observed high negative charge is mainly due to the contribution of the primary electrons emitted by the filaments as predicted by a simple model.

Optical pumping of electron and nuclear spin in a negatively-charged quantum dot

NASA Astrophysics Data System (ADS)

Bracker, Allan; Gershoni, David; Korenev, Vladimir

2005-03-01

We report optical pumping of electron and nuclear spins in an individual negatively-charged quantum dot. With a bias-controlled heterostructure, we inject one electron into the quantum dot. Intense laser excitation produces negative photoluminescence polarization, which is easily erased by the Hanle effect, demonstrating optical pumping of a long-lived resident electron. The electron spin lifetime is consistent with the influence of nuclear spin fluctuations. Measuring the Overhauser effect in high magnetic fields, we observe a high degree of nuclear spin polarization, which is closely correlated to electron spin pumping.

Diffusion of beta-lactam antibiotics through the porin channels of Escherichia coli K-12.

PubMed Central

Yoshimura, F; Nikaido, H

1985-01-01

Diffusion rates of various beta-lactam antibiotics through the OmpF and OmpC porin channels of Escherichia coli K-12 were measured by the use of reconstituted proteoliposomes. The results can be interpreted on the basis of the gross physicochemical properties of the antibiotics along the following lines. (i) As noted previously (Nikaido et al., J. Bacteriol., 153:232-240, 1983), there was a monotonous dependence of the penetration rate on the hydrophobicity of the molecule among the classical monoanionic beta-lactams, and a 10-fold increase in the octanol-water partition coefficient of the uncharged molecule decreased the penetration rate by a factor of 5 to 6. (ii) Compounds with exceptionally bulky side chains, such as mezlocillin, piperacillin, and cefoperazone, showed much slower penetration rates than expected from their hydrophobicity. (iii) The substituted oxime side chain on the alpha-carbon of the substituent group at position 7 of the cephem nucleus decreased the penetration rate almost by an order of magnitude; this appears to be largely due to the steric effect. (iv) The presence of a methoxy group at position 7 of the cephalosporins also reduced the penetration rate by 20%, probably also due to the steric hindrance. (v) Zwitterionic compounds penetrated very rapidly, and the correlation between the rate and hydrophobicity appeared to be much weaker than with the monoanionic compounds. Imipenem showed the highest permeability among the compounds tested, presumably due, at least in part, to its compact molecular structure. (vi) Compounds with two negative charges penetrated more slowly than did analogs with only one negatively charged group. Among them, only moxalactam, ceftriaxone, and azthreonam showed penetration rates corresponding to, or higher than, 10% of that of imipenem. PMID:2580479

Transport of steroid 3-sulfates and steroid 17-sulfates by the sodium-dependent organic anion transporter SOAT (SLC10A6).

PubMed

Grosser, Gary; Bennien, Josefine; Sánchez-Guijo, Alberto; Bakhaus, Katharina; Döring, Barbara; Hartmann, Michaela; Wudy, Stefan A; Geyer, Joachim

2018-05-01

The sodium-dependent organic anion transporter SOAT/Soat shows highly specific transport activity for sulfated steroids. SOAT substrates identified so far include dehydroepiandrosterone sulfate, 16α-hydroxydehydroepiandrosterone sulfate, estrone-3-sulfate, pregnenolone sulfate, 17β-estradiol-3-sulfate, and androstenediol sulfate. Apart from these compounds, many other sulfated steroids occur in mammals. Therefore, we aimed to expand the substrate spectrum of SOAT and analyzed the SOAT-mediated transport of eight different sulfated steroids by combining in vitro transport experiments in SOAT-transfected HEK293 cells with LC-MS/MS analytics of cell lysates. In addition, we aimed to better understand the structural requirements for SOAT substrates and so selected structural pairs varying only at specific positions: 3α/3β-sulfate, 17α/17β-sulfate, mono-sulfate/di-sulfate, and 17α-hydroxylation. We found significant and sodium-dependent SOAT-mediated transport of 17α-hydroxypregnenolone sulfate, 17β-estradiol-17-sulfate, androsterone sulfate, epiandrosterone sulfate, testosterone sulfate, epitestosterone sulfate, and 5α-dihydrotestosterone sulfate. However, 17β-estradiol-3,17-disulfate was not transported by SOAT. SOAT substrates from the group of sulfated steroids are characterized by a planar and lipophilic steroid backbone in trans-trans-trans conformation of the rings and a negatively charged mono-sulfate group at positions 3' or 17' with flexibility for α- or β- orientation. Furthermore, 5α-reduction, 16α-hydroxylation, and 17α-hydroxylation are acceptable for SOAT substrate recognition, whereas addition of a second negatively charged sulfate group seems to abolish substrate binding to SOAT, and so 17β-estradiol-3,17-disulfate is not transported by SOAT. Copyright © 2017 Elsevier Ltd. All rights reserved.

Measuring the isoelectric point of the edges of clay mineral particles: the case of montmorillonite.

PubMed

Pecini, Eliana M; Avena, Marcelo J

2013-12-03

The isoelectric point (IEP) of the edge surface of a montmorillonite sample was determined by using electrophoretic mobility measurements. This parameter, which is fundamental for the understanding of the charging behavior of clay mineral surfaces, was never measured so far because of the presence of permanent negative charges within the montmorillonite structure, charges that mask the electrokinetic behavior of the edges. The strategy was to block or neutralize the structural charges with two different cations, methylene blue (MB(+)) and tetraethylenepentaminecopper(II) ([Cu(tetren)](2+)), so that the charging behavior of the particles becomes that of the edge surfaces. Adsorption isotherms of MB(+) and [Cu(tetren)](2+) at different ionic strengths (NaCl) were performed to establish the uptakes that neutralize the cation exchange capacity (CEC, 0.96 meq g(-1)) of the sample. At high adsorptive concentrations, there was a superequivalent adsorption of MB(+) (adsorption exceeding the CEC) and an equivalent adsorption of [Cu(tetren)](2+) (adsorption reaching the CEC). In both cases, structural charges were neutralized at uptakes very close to the CEC. Zeta potential (ζ) vs pH data at different ionic strengths of montmorillonite with adsorbed MB(+) allowed to estimate an upper limit of the edge's IEP, 5.3 ± 0.2. The same kind of data obtained with adsorbed [Cu(tetren)](2+) provided a lower limit of the IEP, 4.0 ± 0.2. These values are in agreement with previously informed IEP and point of zero charge of pyrophyllite, which is structurally analogous to montmorillonite but carries no permanent charges. The importance of knowing the IEP of the edge surface of clay minerals is discussed. This value characterizes the intrinsic reactivity of edges, that is, the protonating capacity of edge groups in absence of any electric field generated by structural charges. It also allows us to correct relative edge charge vs pH curves obtained by potentiometric titrations and to obtain the true edge charge vs pH curves at different electrolyte concentrations.

Characteristics of M-component in rocket-triggered lightning and a discussion on its mechanism

NASA Astrophysics Data System (ADS)

Jiang, Rubin; Qie, Xiushu; Yang, Jing; Wang, Caixia; Zhao, Yang

2013-09-01

The current and electric field pulses associated with M-component following dart leader-return stroke sequences in negative rocket-triggered lightning flashes were analyzed in detail by using the data from Shandong Artificially Triggering Lightning Experiment, conducted from 2005 to 2010. For 63 M-components with current waveforms superimposed on the relatively steady continuing current, the geometric mean values of the peak current, duration, and charge transfer were 276 A, 1.21 ms, and 101 mC, respectively. The behaviors of the channel base current versus close electric field changes and the observation facts by different authors were carefully examined for investigation on mechanism of the M-component. A modified model based on Rakov's "two-wave" theory is proposed and confirms that the evolution of M-component through the lightning channel involves a downward wave transferring negative charge from the upper to the lower channel and an upward wave draining the charge transported by the downward wave. The upward wave serves to deplete the negative charge by the downward wave at its interface and makes the charge density of the channel beneath the interface layer to be roughly zero. Such modified concept is recognized to be reasonable by the simulated results showing a good agreement between the calculated and the measured E-field waveforms.

Interaction of gold and silver nanoparticles with human plasma: Analysis of protein corona reveals specific binding patterns.

PubMed

Lai, Wenjia; Wang, Qingsong; Li, Lumeng; Hu, Zhiyuan; Chen, Jiankui; Fang, Qiaojun

2017-04-01

Determining how nanomaterials interact with plasma will assist in understanding their effects on the biological system. This work presents a systematic study of the protein corona formed from human plasma on 20nm silver and gold nanoparticles with three different surface modifications, including positive and negative surface charges. The results show that all nanoparticles, even those with positive surface modifications, acquire negative charges after interacting with plasma. Approximately 300 proteins are identified on the coronas, while 99 are commonly found on each nanomaterial. The 20 most abundant proteins account for over 80% of the total proteins abundance. Remarkably, the surface charge and core of the nanoparticles, as well as the isoelectric point of the plasma proteins, are found to play significant roles in determining the nanoparticle coronas. Albumin and globulins are present at levels of less than 2% on these nanoparticle coronas. Fibrinogen, which presents in the plasma but not in the serum, preferably binds to negatively charged gold nanoparticles. These observations demonstrate the specific plasma protein binding pattern of silver and gold nanoparticles, as well as the importance of the surface charge and core in determining the protein corona compositions. The potential downstream biological impacts of the corona proteins were also investigated. Copyright © 2017 Elsevier B.V. All rights reserved.

Modeling the Electric Potential and Surface Charge Density Near Charged Thunderclouds

NASA Astrophysics Data System (ADS)

Neel, Matthew Stephen

2018-03-01

Thundercloud charge separation, or the process by which the bottom portion of a cloud gathers charge and the top portion of the cloud gathers the opposite charge, is still not thoroughly understood. Whatever the mechanism, though, a charge separation definitely exists and can lead to electrostatic discharge via cloud-to-cloud lightning and cloud-to-ground lightning. We wish to examine the latter form, in which upward leaders from Earth connect with downward leaders from the cloud to form a plasma channel and produce lightning. Much of the literature indicates that the lower part of a thundercloud becomes negatively charged while the upper part becomes positively charged via convective charging, although the opposite polarity can certainly exist along with various, complex intra-cloud currents. It is estimated that >90% of cloud-to-ground lightning is "negative lightning," or the flow of charges from the bottom of the cloud, while the remaining <10% of lightning strikes is "positive lightning," or the flow of charges from the top of the cloud. We wish to understand the electric potential surrounding charged thunderclouds as well as the resulting charge density on the surface of Earth below them. In this paper we construct a simple and adaptable model that captures the very basic features of the cloud/ground system and that exhibits conditions favorable for both forms of lightning. In this way, we provide a practical application of electrostatic dipole physics as well as the method of images that can serve as a starting point for further modeling and analysis by students.

4,4'-([4,4'-Bipyridine]-1,1'-diium-1,1'-diyl)dibenzoate dihydrate

DOE PAGES

Rodriguez, Mark A.; Sava Gallis, Dorina F.; Chavez, James S.; ...

2016-06-01

We report here the synthesis of a neutral viologen derivative, C 24H 16N 2O 4·2H 2O. The non-solvent portion of the structure (Z-Lig) is a zwitterion, consisting of two positively charged pyridinium cations and two negatively charged carboxylate anions. The carboxylate group is almost coplanar [dihedral angle = 2.04 (11)°] with the benzene ring, whereas the dihedral angle between pyridine and benzene rings is 46.28 (5)°. TheZ-Lig molecule is positioned on a center of inversion (Fig. 1). The presence of the twofold axis perpendicular to thec-glide plane in space groupC2/c generates a screw-axis parallel to thebaxis that is shifted from themore » origin by 1/4 in theaandcdirections. This screw-axis replicates the molecule (and solvent water molecules) through space. TheZ-Lig molecule links to adjacent moleculesviaO—H...O hydrogen bonds involving solvent water molecules as well as intermolecular C—H...O interactions. There are also π–π interactions between benzene rings on adjacent molecules.« less

Theoretical Study on Effects of Hydrogen-Bonding and Molecule-Cation Interactions on the Sensitivity of HMX.

PubMed

Li, Yunlu; Wu, Junpeng; Cao, Duanlin; Wang, Jianlong

2016-10-04

To assess the effects of weak interactions on the sensitivity of HMX, eleven complexes of HMX (where six of them are hydrogen-bonding complexes, and the other five are molecular-cation complexes) have been studied via quantum chemical treatment. The geometric and electronic structures were determined using DFT-B3LYP and MP2(full) methods with the 6-311++G(2df, 2p) and aug-cc-pVTZ basis sets. The changes of the bond dissociation energy (BDE) of the trigger bond (N-NO2 in HMX) and nitro group charge have been computed on the detail consideration to access the sensitivity changes of HMX. The results indicate that upon complex forming, the BDE increases and the charge of nitro group turns more negative in complexes, suggesting that the strength of the N-NO2 trigger bond is enhanced then the sensitivity of HMX is reduced. Atom-in-molecules analysis have also been carried to understand the nature of intermolecular interactions and the strength of trigger bonds.

Separation of negatively charged carbohydrates by capillary electrophoresis.

PubMed

Linhardt, R J; Pervin, A

1996-01-12

Capillary electrophoresis (CE) has recently emerged as a highly promising technique consuming an extremely small amount of sample and capable of the rapid, high-resolution separation, characterization, and quantitation of analytes. CE has been used for the separation of biopolymers, including acidic carbohydrates. Since CE is basically an analytical method for ions, acidic carbohydrates that give anions in weakly acid, neutral, or alkaline media are often the direct objects of this method. The scope of this review is limited to the use of CE for the analysis of carbohydrates containing carboxylate, sulfate, and phosphate groups as well as neutral carbohydrates that have been derivatized to incorporate strongly acidic functionality, such as sulfonate groups.

Electromagnetic Radiation in the Atmosphere Generated by Excess Negative Charge in a Nuclear-Electromagnetic Cascade

NASA Astrophysics Data System (ADS)

Malyshevsky, V. S.; Fomin, G. V.

2017-01-01

On the basis of the analytical model "PARMA" (PHITS-based Analytical Radiation Model in the Atmosphere), developed to model particle fluxes of secondary cosmic radiation in the Earth's atmosphere, we have calculated the characteristics of radio waves emitted by excess negative charge in an electromagnetic cascade. The results may be of use in an analysis of experimental data on radio emission of electron-photon showers in the atmosphere.

Spectroscopic and calorimetric investigations on the influence of calcium ions on the polyamine negatively charged phospholipid molecular interactions

NASA Astrophysics Data System (ADS)

Bertoluzza, Alessandro; Bonora, S.; Fini, G.; Morelli, M. A.

1993-06-01

Polyamines do not interact with neutral phospholipids (phosphatidylcholines) but they do interact in the presence of bivalent and trivalent cations. The effect of polyvalent cations is explained in terms of dehydration of the bilayer surface. Polyamines interact strongly with negatively charged phospholipids; the presence of bivalent and trivalent cations do not change sensitively the type of interaction between polyamines and phosphatidic acids.

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.

Gelation of soybean protein and polysaccharides delays digestion.

PubMed

Hu, Bing; Chen, Qing; Cai, Qimeng; Fan, Yun; Wilde, Peter J; Rong, Zhen; Zeng, Xiaoxiong

2017-04-15

Xanthan gum and carrageenan, representing the medium and highly negatively charged polysaccharides, were heated respectively together with soybean protein isolate (SPI) at different biopolymer ratios. Upon mixing with simulated stomach juice (SSJ), the xanthan-SPI and carrageenan-SPI at biopolymer ratios higher than 0.01 leads to self-assembled gelation immediately. Stronger gel is formed under higher biopolymer ratios. Highly negatively charged carrageenan forms a stronger gel than that composed with xanthan gum. SDS-PAGE results show the digestibility of SPI is delayed after incorporation with the polysaccharides, which is enhanced with the increase of the biopolymer mass ratios. And the polysaccharide with higher negative charge has stronger potential in delaying the digestion of SPI. Furthermore, the microstructure of the xanthan-SPI and carrageenan-SPI gel before and after simulated stomach digestion was characterized by scanning electron microscope (SEM), which also confirms that the gel delays the digestion of soybean protein. Copyright © 2016 Elsevier Ltd. All rights reserved.

The Lunar Dust Pendulum

NASA Technical Reports Server (NTRS)

Kuntz, Kip; Collier, Michael R.; Stubbs, Timothy J.; Farrell, William M.

2011-01-01

Shadowed regions on the lunar surface acquire a negative potential. In particular, shadowed craters can have a negative potential with respect to the surrounding lunar regolith in sunlight, especially near the terminator regions. Here we analyze the motion of a positively charged lnnar dust grain in the presence of a shadowed crater at a negative potential in vacuum. Previous models describing the transport of charged lunar dust close to the surface have typically been limited to one-dimensional motion in the vertical direction, e.g. electrostatic levitation; however. the electric fields in the vicinity of shadowed craters will also have significant components in the horizontal directions. We propose a model that includes both the horizontal and vertical motion of charged dust grains near shadowed craters. We show that the dust grains execute oscillatory trajectories and present an expression for the period of oscillation drawing an analogy to the motion of a pendulum.

The Lunar Dust Pendulum

NASA Technical Reports Server (NTRS)

Collier, Michael R.; Stubbs, Timothy J.; Farrell, William M.

2011-01-01

Shadowed regions on the lunar surface acquire a negative potential. In particular, shadowed craters can have a negative potential with respect to the surrounding lunar regolith in sunlight, especially near the terminator regions. Here we analyze the motion of a positively charged lunar dust grain in the presence of a shadowed crater at a negative potential in vacuum. Previous models describing the transport of charged lunar dust close to the surface have typically been limited to one-dimensional motion in the vertical direction, e.g. electrostatic levitation; however, the electric fields in the vicinity of shadowed craters will also have significant components in the horizontal directions. We propose a model that includes both the horizontal and vertical motion of charged dust grains near shadowed craters. We show that the dust grains execute oscillatory trajectories and present an expression for the period of oscillation drawing an analogy to the motion of a pendulum.

Behavior of collisional sheath in electronegative plasma with q-nonextensive electron distribution

NASA Astrophysics Data System (ADS)

Borgohain, Dima Rani; Saharia, K.

2018-03-01

Electronegative plasma sheath is addressed in a collisional unmagnetized plasma consisting of q-nonextensive electrons, Boltzmann distributed negative ions and cold fluid positive ions. Considering the positive ion-neutral collisions and ignoring the effects of ionization and collisions between negative species and positive ions (neutrals), a modified Bohm sheath criterion and hence floating potential are derived by using multifluid model. Using the modified Bohm sheath criterion, the sheath characteristics such as spatial profiles of density, potential and net space charge density have been numerically investigated. It is found that increasing values of q-nonextensivity, electronegativity and collisionality lead to a decrease of the sheath thickness and an increase of the sheath potential and the net space charge density. With increasing values of the electron temperature to negative ion temperature ratio, the sheath thickness increases and the sheath potential as well as the net space charge density in the sheath region decreases.

Biocompatibility, endocytosis, and intracellular trafficking of mesoporous silica and polystyrene nanoparticles in ovarian cancer cells: effects of size and surface charge groups

PubMed Central

Ekkapongpisit, Maneerat; Giovia, Antonino; Follo, Carlo; Caputo, Giuseppe; Isidoro, Ciro

2012-01-01

Background and methods Nanoparticles engineered to carry both a chemotherapeutic drug and a sensitive imaging probe are valid tools for early detection of cancer cells and to monitor the cytotoxic effects of anticancer treatment simultaneously. Here we report on the effect of size (10–30 nm versus 50 nm), type of material (mesoporous silica versus polystyrene), and surface charge functionalization (none, amine groups, or carboxyl groups) on biocompatibility, uptake, compartmentalization, and intracellular retention of fluorescently labeled nanoparticles in cultured human ovarian cancer cells. We also investigated the involvement of caveolae in the mechanism of uptake of nanoparticles. Results We found that mesoporous silica nanoparticles entered via caveolae-mediated endocytosis and reached the lysosomes; however, while the 50 nm nanoparticles permanently resided within these organelles, the 10 nm nanoparticles soon relocated in the cytoplasm. Naked 10 nm mesoporous silica nanoparticles showed the highest and 50 nm carboxyl-modified mesoporous silica nanoparticles the lowest uptake rates, respectively. Polystyrene nanoparticle uptake also occurred via a caveolae-independent pathway, and was negatively affected by serum. The 30 nm carboxyl-modified polystyrene nanoparticles did not localize in lysosomes and were not toxic, while the 50 nm amine-modified polystyrene nanoparticles accumulated within lysosomes and eventually caused cell death. Ovarian cancer cells expressing caveolin-1 were more likely to endocytose these nanoparticles. Conclusion These data highlight the importance of considering both the physicochemical characteristics (ie, material, size and surface charge on chemical groups) of nanoparticles and the biochemical composition of the cell membrane when choosing the most suitable nanotheranostics for targeting cancer cells. PMID:22904626

The accessibility of etheno-nucleotides to collisional quenchers and the nucleotide cleft in G- and F-actin.

PubMed Central

Root, D. D.; Reisler, E.

1992-01-01

Recent publication of the atomic structure of G-actin (Kabsch, W., Mannherz, H. G., Suck, D., Pai, E. F., & Holmes, K. C., 1990, Nature 347, 37-44) raises questions about how the conformation of actin changes upon its polymerization. In this work, the effects of various quenchers of etheno-nucleotides bound to G- and F-actin were examined in order to assess polymerization-related changes in the nucleotide phosphate site. The Mg(2+)-induced polymerization of actin quenched the fluorescence of the etheno-nucleotides by approximately 20% simultaneously with the increase in light scattering by actin. A conformational change at the nucleotide binding site was also indicated by greater accessibility of F-actin than G-actin to positively, negatively, and neutrally charged collisional quenchers. The difference in accessibility between G- and F-actin was greatest for I-, indicating that the environment of the etheno group is more positively charged in the polymerized form of actin. Based on calculations of the change in electric potential of the environment of the etheno group, specific polymerization-related movements of charged residues in the atomic structure of G-actin are suggested. The binding of S-1 to epsilon-ATP-G-actin increased the accessibility of the etheno group to I- even over that in Mg(2+)-polymerized actin. The quenching of the etheno group by nitromethane was, however, unaffected by the binding of S-1 to actin. Thus, the binding of S-1 induces conformational changes in the cleft region of actin that are different from those caused by Mg2+ polymerization of actin.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:1304380

A docking study of enhanced intracellular survival protein from Mycobacterium tuberculosis with human DUSP16/MKP-7.

PubMed

Yoon, Hye Jin; Kim, Kyoung Hoon; Yang, Jin Kuk; Suh, Se Won; Kim, Hyunsik; Jang, Soonmin

2013-11-01

The intracellular pathogen Mycobacterium tuberculosis (Mtb) causes tuberculosis, and one of its secreted effector proteins, called enhanced intracellular survival (Eis) protein, enhances its survival in macrophages. Mtb Eis activates JNK-specific dual-specificity protein phosphatase 16 (DUSP16)/mitogen-activated protein kinase phosphatase-7 (MKP-7) through the acetylation on Lys55, thus inactivating JNK by dephosphorylation. Based on the recently reported crystal structure of Mtb Eis, a docking model for the binding of Mtb Eis to DUSP16/MKP-7 was generated. In the docking model, the substrate helix containing Lys55 of DUSP16/MKP-7 fits nicely into the active-site cleft of Mtb Eis; the twisted β-sheet of Eis domain II embraces the substrate helix from one side. Most importantly, the side-chain of Lys55 is inserted toward acetyl-CoA and the resulting distance is 4.6 Å between the NZ atom of Lys55 and the carbonyl carbon of the acetyl group in acetyl-CoA. The binding of Mtb Eis and DUSP16/MKP-7 is maintained by strong electrostatic interactions. The active-site cleft of Mtb Eis has a negatively charged surface formed by Asp25, Glu138, Asp286, Glu395 and the terminal carboxylic group of Phe396. In contrast, DUSP16/MKP-7 contains five basic residues, Lys52, Lys55, Arg56, Arg57 and Lys62, which point toward the negatively charged surface of the active-site pocket of Mtb Eis. Thus, the current docking model suggests that the binding of DUSP16/MKP-7 to Mtb Eis should be established by charge complementarity in addition to a very favorable geometric arrangement. The suggested mode of binding requires the dissociation of the hexameric Mtb Eis into dimers or monomers. This study may be useful for future studies aiming to develop inhibitors of Mtb Eis as a new anti-tuberculosis drug candidate.

Cannabis Use Has Negligible Effects Following Severe Traumatic Injury.

PubMed

AbdelFattah, Kareem R; Edwards, Courtney R; Cripps, Michael W; Minshall, Christian T; Phelan, Herb A; Minei, Joseph P; Eastman, Alexander L

Nearly half of all states have legalized medical marijuana or recreational-use marijuana. As more states move toward legalization, the effects on injured patients must be evaluated. This study sought to determine effects of cannabis positivity at the time of severe injury on hospital outcomes compared with individuals negative for illicit substances and those who were users of other illicit substances. A Level I trauma center performed a retrospective chart review covering subjects over a 2-year period with toxicology performed and an Injury Severity Score (ISS) of more than 16. These individuals were divided into the negative and positive toxicology groups, further divided into the marijuana-only, other drugs-only, and mixed-use groups. Differences in presenting characteristics, hospital length of stay, intensive care unit (ICU) stays, ventilator days, and death were compared. A total of 8,441 subjects presented during the study period; 2,134 (25%) of these had toxicology performed; 843 (40%) had an ISS of more than 16, with 347 having negative tests (NEG); 70 (8.3%) substance users tested positive only for marijuana (MO), 323 (38.3%) for other drugs-only, excluding marijuana (OD), and 103 (12.2%) subjects showed positivity for mixed-use (MU). The ISS was similar for all groups. No differences were identified in Glasgow Coma Scale (GCS), ventilator days, blood administration, or ICU/hospital length of stay when comparing the MO group with the NEG group. Significant differences occurred between the OD group and the NEG/MO/MU groups for GCS, ICU length of stay, and hospital charges. Cannabis users suffering from severe injury demonstrated no detrimental outcomes in this study compared with nondrug users.

Negative hyperconjugation and red-, blue- or zero-shift in X-Z∙∙∙Y complexes.

PubMed

Joy, Jyothish; Jemmis, Eluvathingal D; Vidya, Kaipanchery

2015-01-01

A generalized explanation is provided for the existence of the red- and blue-shifting nature of X-Z bonds (Z=H, halogens, chalcogens, pnicogens, etc.) in X-Z∙∙∙Y complexes based on computational studies on a selected set of weakly bonded complexes and analysis of existing literature data. The additional electrons and orbitals available on Z in comparison to H make for dramatic differences between the H-bond and the rest of the Z-bonds. The nature of the X-group and its influence on the X-Z bond length in the parent X-Z molecule largely controls the change in the X-Z bond length on X-Z∙∙∙Y bond formation; the Y-group usually influences only the magnitude of the effects controlled by X. The major factors which control the X-Z bond length change are: (a) negative hyperconjugative donation of electron density from X-group to X-Z σ* antibonding molecular orbital (ABMO) in the parent X-Z, (b) induced negative hyperconjugation from the lone pair of electrons on Z to the antibonding orbitals of the X-group, and (c) charge transfer (CT) from the Y-group to the X-Z σ* orbital. The exchange repulsion from the Y-group that shifts partial electron density at the X-Z σ* ABMO back to X leads to blue-shifting and the CT from the Y-group to the σ* ABMO of X-Z leads to red-shifting. The balance between these two opposing forces decides red-, zero- or blue-shifting. A continuum of behaviour of X-Z bond length variation is inevitable in X-Z∙∙∙Y complexes.

Spatiotemporal electrochemical measurements across an electric double layer capacitor electrode with application to aqueous sodium hybrid batteries

NASA Astrophysics Data System (ADS)

Tully, Katherine C.; Whitacre, Jay F.; Litster, Shawn

2014-02-01

This paper presents in-situ spatiotemporal measurements of the electrolyte phase potential within an electric double layer capacitor (EDLC) negative electrode as envisaged for use in an aqueous hybrid battery for grid-scale energy storage. The ultra-thick electrodes used in these batteries to reduce non-functional material costs require sufficiently fast through-plane mass and charge transport to attain suitable charging and discharging rates. To better evaluate the through-plane transport, we have developed an electrode scaffold (ES) for making in situ electrolyte potential distribution measurements at discrete known distances across the thickness of an uninterrupted EDLC negative electrode. Using finite difference methods, we calculate local current, volumetric charging current and charge storage distributions from the spatiotemporal electrolyte potential measurements. These potential distributions provide insight into complex phenomena that cannot be directly observed using other existing methods. Herein, we use the distributions to identify areas of the electrode that are underutilized, assess the effects of various parameters on the cumulative charge storage distribution, and evaluate an effectiveness factor for charge storage in EDLC electrodes.

Insight into the split and asymmetry of charge distribution in biased M-structure superlattice

NASA Astrophysics Data System (ADS)

Liu, Lu; Bi, Han; Zhao, Yunhao; Zhao, Xuebing; Han, Xi; Wang, Guowei; Xu, Yingqiang; Li, Yuesheng; Che, Renchao

2017-07-01

The charge distribution in real space of an insertion variant based on an InAs/GaSb superlattice for an infrared detector is illustrated by in situ electron microscopy. The localization split of positive charge can be directly observed in the InAs/GaSb/AlSb/GaSb superlattice (M-structure) rather than in the InAs/GaSb superlattice. With the applied bias increasing from 0 to 4.5 V, the double peaks of positive charge density become asymmetrical gradually, with the peak integral ratio ranging from 1.13 to 2.54. Simultaneously, the negative charges move along the direction of the negative electric field. Without inserting the AlSb layer, the charge inversion occurs in both the hole wells and the electron wells of the InAs/GaSb superlattice under high bias. Such a discrepancy between the M-structure superlattice and the traditional superlattice suggests an effective reduction of tunneling probability of the M-structure design. Our result is of great help to understand the carrier immigration mechanism of the superlattice-based infrared detector.

Modelling CEC variations versus structural iron reduction levels in dioctahedral smectites. Existing approaches, new data and model refinements.

PubMed

Hadi, Jebril; Tournassat, Christophe; Ignatiadis, Ioannis; Greneche, Jean Marc; Charlet, Laurent

2013-10-01

A model was developed to describe how the 2:1 layer excess negative charge induced by the reduction of Fe(III) to Fe(II) by sodium dithionite buffered with citrate-bicarbonate is balanced and applied to nontronites. This model is based on new experimental data and extends structural interpretation introduced by a former model [36-38]. The 2:1 layer negative charge increase due to Fe(III) to Fe(II) reduction is balanced by an excess adsorption of cations in the clay interlayers and a specific sorption of H(+) from solution. Prevalence of one compensating mechanism over the other is related to the growing lattice distortion induced by structural Fe(III) reduction. At low reduction levels, cation adsorption dominates and some of the incorporated protons react with structural OH groups, leading to a dehydroxylation of the structure. Starting from a moderate reduction level, other structural changes occur, leading to a reorganisation of the octahedral and tetrahedral lattice: migration or release of cations, intense dehydroxylation and bonding of protons to undersaturated oxygen atoms. Experimental data highlight some particular properties of ferruginous smectites regarding chemical reduction. Contrary to previous assumptions, the negative layer charge of nontronites does not only increase towards a plateau value upon reduction. A peak is observed in the reduction domain. After this peak, the negative layer charge decreases upon extended reduction (>30%). The decrease is so dramatic that the layer charge of highly reduced nontronites can fall below that of its fully oxidised counterpart. Furthermore, the presence of a large amount of tetrahedral Fe seems to promote intense clay structural changes and Fe reducibility. Our newly acquired data clearly show that models currently available in the literature cannot be applied to the whole reduction range of clay structural Fe. Moreover, changes in the model normalising procedure clearly demonstrate that the investigated low tetrahedral bearing nontronites (SWa-1, GAN and NAu-1) all exhibit the same behaviour at low reduction levels. Consequently, we restricted our model to the case of moderate reduction (<30%) in low tetrahedral Fe-bearing nontronites. Our adapted model provides the relative amounts of Na(+) (p) and H(+) (ni) cations incorporated in the structure as a function of the amount of Fe reduction. Two equations enable the investigated systems to be described: p=m/(1+Kr·ω·mrel) and ni=Kr·ω·m·mrel/(1+Kr·ω·mrel); where m is the Fe(II) content, mrel, the reduction level (m/mtot), ω, the cation exchange capacity (CEC, and Kr, an empirical constant specific to the system. Copyright © 2013 Elsevier Inc. All rights reserved.

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.

Effect of negative air ions on the potential for bacterial contamination of plastic medical equipment.

PubMed

Shepherd, Simon J; Beggs, Clive B; Smith, Caroline F; Kerr, Kevin G; Noakes, Catherine J; Sleigh, P Andrew

2010-04-12

In recent years there has been renewed interest in the use of air ionizers to control the spread of infection in hospitals and a number of researchers have investigated the biocidal action of ions in both air and nitrogen. By comparison, the physical action of air ions on bacterial dissemination and deposition has largely been ignored. However, there is clinical evidence that air ions might play an important role in preventing the transmission of Acinetobacter infection. Although the reasons for this are unclear, it is hypothesized that a physical effect may be responsible: the production of air ions may negatively charge items of plastic medical equipment so that they repel, rather than attract, airborne bacteria. By negatively charging both particles in the air and items of plastic equipment, the ionizers minimize electrostatic deposition on these items. In so doing they may help to interrupt the transmission of Acinetobacter infection in certain healthcare settings such as intensive care units. A study was undertaken in a mechanically ventilated room under ambient conditions to accurately measure changes in surface potential exhibited by items of plastic medical equipment in the presence of negative air ions. Plastic items were suspended on nylon threads, either in free space or in contact with a table surface, and exposed to negative ions produced by an air ionizer. The charge build-up on the specimens was measured using an electric field mill while the ion concentration in the room air was recorded using a portable ion counter. The results of the study demonstrated that common items of equipment such as ventilator tubes rapidly developed a large negative charge (i.e. generally >-100V) in the presence of a negative air ionizer. While most items of equipment tested behaved in a similar manner to this, one item, a box from a urological collection and monitoring system (the only item made from styrene acrylonitrile), did however develop a positive charge in the presence of the ionizer. The findings of the study suggest that the action of negative air ionizers significantly alters the electrostatic landscape of the clinical environment, and that this has the potential to cause any Acinetobacter-bearing particles in the air to be strongly repelled from some plastic surfaces and attracted to others. In so doing, this may prevent critical items of equipment from becoming contaminated with the bacterium.

Contributions of molecular size, charge distribution, and specific amino acids to the iron-binding capacity of sea cucumber (Stichopus japonicus) ovum hydrolysates.

PubMed

Sun, Na; Cui, Pengbo; Jin, Ziqi; Wu, Haitao; Wang, Yixing; Lin, Songyi

2017-09-01

This study investigated the contributions of molecular size, charge distribution and specific amino acids to the iron-binding capacity of sea cucumber (Stichopus japonicus) ovum hydrolysates (SCOHs), and further explored their iron-binding sites. It was demonstrated that enzyme type and degree of hydrolysis (DH) significantly influenced the iron-binding capacity of the SCOHs. The SCOHs produced by alcalase at a DH of 25.9% possessed the highest iron-binding capacity at 92.1%. As the hydrolysis time increased, the molecular size of the SCOHs decreased, the negative charges increased, and the hydrophilic amino acids were exposed to the surface, facilitating iron binding. Furthermore, the Fourier transform infrared spectra, combined with amino acid composition analysis, revealed that iron bound to the SCOHs primarily through interactions with carboxyl oxygen of Asp, guanidine nitrogen of Arg or nitrogen atoms in imidazole group of His. The formed SCOHs-iron complexes exhibited a fold and crystal structure with spherical particles. Copyright © 2017 Elsevier Ltd. All rights reserved.

Immobilization of E. coli with autodisplayed Z-domains to a surface-modified microplate for immunoassay.

PubMed

Yoo, Gu; Park, Min; Lee, Eun-Hang; Jose, Joachim; Pyun, Jae-Chul

2011-11-30

Escherichia coli with autodisplayed Z-domains was reported to improve the sensitivity of immunoassays by the orientation control of antibodies. In this work, a sensitive microplate-based immunoassay is presented by immobilizing E. coli cells to a surface-modified microplate. The microplate was prepared by coating parylene-H film with formyl groups, and then covalently coupling poly-L-lysine to the parylene-H film. The E. coli cells were bound to the microplate by charge interactions between the negatively charged E. coli outer membrane and the positively charged microplate surface. In this work, the preparation of the microplate coated with poly-L-lysine is presented. The immobilization efficiency of E. coli to the modified surface was estimated to be far higher than non-specific interaction by fluorescence microscope and the optical transmittance of the modified microplate was measured to be feasible for immunoassay. The microplate-based immunoassay is demonstrated to be feasible for medical diagnosis of inflammatory diseases by using C-reactive protein as a target analyte for the medical diagnosis of inflammatory diseases. Copyright © 2011 Elsevier B.V. All rights reserved.

Diaqua­bis[1-hydroxy-2-(imidazol-3-ium-1-yl)-1,1′-ethyl­idenediphophonato-κ2 O,O′]zinc(II)

PubMed Central

Freire, Eleonora; Vega, Daniel R.

2009-01-01

In the title complex, [Zn(C5H9NO7P2)2(H2O)2], the zinc atom is coordinated by two bidentate zoledronate [zoledronate = (2-(1-imidazole)-1-hydr­oxy-1,1′-ethyl­idenediphophonate)] ligands and two water mol­ecules. The coordination number is 6. There is one half-mol­ecule in the asymmetric unit with the zinc atom located on a crystallographic inversion centre. The anion exists as a zwitterion with an overall charge of −1; the protonated nitro­gen in the ring has a positive charge and the two phospho­nates groups each have a single negative charge. There are two intra­molecular O—H⋯O hydrogen bonds. The mol­ecules are linked into a chain by inter­molecular O—H⋯O hydrogen bonds. Adjacent chains are further linked by O—H⋯O hydrogen bonds involving the aqua ligands. An N—H⋯O inter­action is also observed. PMID:21578164

Multistage Mechanism of Lithium Intercalation into Graphite Anodes in the Presence of the Solid Electrolyte Interface.

PubMed

Dinkelacker, Franz; Marzak, Philipp; Yun, Jeongsik; Liang, Yunchang; Bandarenka, Aliaksandr S

2018-04-25

A so-called solid electrolyte interface (SEI) in a lithium-ion battery largely determines the performance of the whole system. However, it is one of the least understood objects in these types of batteries. SEIs are formed during the initial charge-discharge cycles, prevent the organic electrolytes from further decomposition, and at the same time govern lithium intercalation into the graphite anodes. In this work, we use electrochemical impedance spectroscopy and atomic force microscopy to investigate the properties of a SEI film and an electrified "graphite/SEI/electrolyte interface". We reveal a multistage mechanism of lithium intercalation and de-intercalation in the case of graphite anodes covered by SEI. On the basis of this mechanism, we propose a relatively simple model, which perfectly explains the impedance response of the "graphite/SEI/electrolyte" interface at different temperatures and states of charge. From the whole data obtained in this work, it is suggested that not only Li + but also negatively charged species, such as anions from the electrolyte or functional groups of the SEI, likely interact with the surface of the graphite anode.

New serine-derived gemini surfactants as gene delivery systems.

PubMed

Cardoso, Ana M; Morais, Catarina M; Cruz, A Rita; Silva, Sandra G; do Vale, M Luísa; Marques, Eduardo F; de Lima, Maria C Pedroso; Jurado, Amália S

2015-01-01

Gemini surfactants have been extensively used for in vitro gene delivery. Amino acid-derived gemini surfactants combine the special aggregation properties characteristic of the gemini surfactants with high biocompatibility and biodegradability. In this work, novel serine-derived gemini surfactants, differing in alkyl chain lengths and in the linker group bridging the spacer to the headgroups (amine, amide and ester), were evaluated for their ability to mediate gene delivery either per se or in combination with helper lipids. Gemini surfactant-based DNA complexes were characterized in terms of hydrodynamic diameter, surface charge, stability in aqueous buffer and ability to protect DNA. Efficient formulations, able to transfect up to 50% of the cells without causing toxicity, were found at very low surfactant/DNA charge ratios (1/1-2/1). The most efficient complexes presented sizes suitable for intravenous administration and negative surface charge, a feature known to preclude potentially adverse interactions with serum components. This work brings forward a new family of gemini surfactants with great potential as gene delivery systems. Copyright © 2014 Elsevier B.V. All rights reserved.

Negative differential conductance in InAs wire based double quantum dot induced by a charged AFM tip

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

Zhukov, A. A., E-mail: azhukov@issp.ac.ru; Volk, Ch.; Winden, A.

We investigate the conductance of an InAs nanowire in the nonlinear regime in the case of low electron density where the wire is split into quantum dots connected in series. The negative differential conductance in the wire is initiated by means of a charged atomic force microscope tip adjusting the transparency of the tunneling barrier between two adjoining quantum dots. We confirm that the negative differential conductance arises due to the resonant tunneling between these two adjoining quantum dots. The influence of the transparency of the blocking barriers and the relative position of energy states in the adjoining dots onmore » a decrease of the negative differential conductance is investigated in detail.« less

Electron-molecule chemistry and charging processes on organic ices and Titan's icy aerosol surrogates

NASA Astrophysics Data System (ADS)

Pirim, C.; Gann, R. D.; McLain, J. L.; Orlando, T. M.

2015-09-01

Electron-induced polymerization processes and charging events that can occur within Titan's atmosphere or on its surface were simulated using electron irradiation and dissociative electron attachment (DEA) studies of nitrogen-containing organic condensates. The DEA studies probe the desorption of H- from hydrogen cyanide (HCN), acetonitrile (CH3CN), and aminoacetonitrile (NH2CH2CN) ices, as well as from synthesized tholin materials condensed or deposited onto a graphite substrate maintained at low temperature (90-130 K). The peak cross sections for H- desorption during low-energy (3-15 eV) electron irradiation were measured and range from 3 × 10-21 to 2 × 10-18 cm2. Chemical and structural transformations of HCN ice upon 2 keV electron irradiation were investigated using X-ray photoelectron and Fourier-transform infrared spectroscopy techniques. The electron-beam processed materials displayed optical properties very similar to tholins produced by conventional discharge methods. Electron and negative ion trapping lead to 1011 charges cm-2 on a flat surface which, assuming a radius of 0.05 μm for Titan aerosols, is ∼628 charges/radius (in μm). The facile charge trapping indicates that electron interactions with nitriles and complex tholin-like molecules could affect the conductivity of Titan's atmosphere due to the formation of large negative ion complexes. These negatively charged complexes can also precipitate onto Titan's surface and possibly contribute to surface reactions and the formation of dunes.

The Influence of Fluorocarbon and Hydrocarbon Acyl Groups at the Surface of Bovine Carbonic Anhydrase II on the Kinetics of Denaturation by Sodium Dodecyl Sulfate

PubMed Central

Lee, Andrew; Mirica, Katherine A.; Whitesides, George M.

2011-01-01

This paper examines the influence of acylation of the Lys-ε-NH3+ groups of bovine carbonic anhydrase (BCA, E.C. 4.2.1.1) to Lys-ε-NHCOR (R = -CH3, -CH2CH3, and -CH(CH3)2, -CF3) on the rate of denaturation of this protein in buffer containing sodium dodecyl sulfate (SDS). Analysis of the rates suggested separate effects due to electrostatic charge and hydrophobic interactions. Rates of denaturation (kAc,n) of each series of acylated derivatives depended on the number of acylations (n). Plots of log kAc,n vs. n followed U-shaped curves. Within each series of derivatives, rates of denaturation decreased as n increased to ~7; this decrease was compatible with increasingly unfavorable electrostatic interactions between SDS and protein. In this range of n, rates of denaturation also depended on the choice of the acyl group as n increased to ~7, in a manner compatible with favorable hydrophobic interactions between SDS and the -NHCOR groups. As n increased in the range 7 < n < 14 however, rates of denaturation stayed approximately constant; analysis suggested these rates were compatible with an increasingly important contribution to denaturation that depended both on the net negative charge of the protein and on the hydrophobicity of the R group. The mechanism of denaturation thus seems to change with the extent of acylation of the protein. For derivatives with the same net electrostatic charge, rates of denaturation increased with the acyl group (by a factor of ~3 for n ~ 14) in the order CH3CONH- < CH3CH2CONH- < (CH3)2CHCONH- < CF3CONH-. These results suggested that the hydrophobicity of CF3CONH- is slightly greater (by a factor of < 2) than that of RHCONH- similar in surface area. PMID:21182314

Influence of fluorocarbon and hydrocarbon acyl groups at the surface of bovine carbonic anhydrase II on the kinetics of denaturation by sodium dodecyl sulfate.

PubMed

Lee, Andrew; Mirica, Katherine A; Whitesides, George M

2011-02-10

This paper examines the influence of acylation of the Lys-ε-NH(3)(+) groups of bovine carbonic anhydrase (BCA, EC 4.2.1.1) to Lys-ε-NHCOR (R = -CH(3), -CH(2)CH(3), and -CH(CH(3))(2), -CF(3)) on the rate of denaturation of this protein in buffer containing sodium dodecyl sulfate (SDS). Analysis of the rates suggested separate effects due to electrostatic charge and hydrophobic interactions. Rates of denaturation (k(Ac,n)) of each series of acylated derivatives depended on the number of acylations (n). Plots of log k(Ac,n) vs n followed U-shaped curves. Within each series of derivatives, rates of denaturation decreased as n increased to ∼7; this decrease was compatible with increasingly unfavorable electrostatic interactions between SDS and protein. In this range of n, rates of denaturation also depended on the choice of the acyl group as n increased to ∼7, in a manner compatible with favorable hydrophobic interactions between SDS and the -NHCOR groups. As n increased in the range 7 < n < 14, however, rates of denaturation stayed approximately constant; analysis suggested that these rates were compatible with an increasingly important contribution to denaturation that depended both on the net negative charge of the protein and on the hydrophobicity of the R group. The mechanism of denaturation thus seems to change with the extent of acylation of the protein. For derivatives with the same net electrostatic charge, rates of denaturation increased with the acyl group (by a factor of ∼3 for n ∼ 14) in the order CH(3)CONH- < CH(3)CH(2)CONH- < (CH(3))(2)CHCONH- < CF(3)CONH-. These results suggested that the hydrophobicity of CF(3)CONH- is slightly greater (by a factor of <2) than that of RHCONH- with similar surface area.

Vibrational spectroscopic (FT-IR and FT-Raman) studies, HOMO-LUMO, NBO analysis and MEP of 6-methyl-1-({[(2E)-2-methyl-3-phenyl-prop-2-en-1-yl]oxy}methyl)-1,2,3,4-tetra-hydroquinazoline-2,4-dione, a potential chemotherapeutic agent, using density functional methods.

PubMed

Sebastian, Sr S H Roseline; Al-Tamimi, Abdul-Malek S; El-Brollosy, Nasser R; El-Emam, Ali A; Yohannan Panicker, C; Van Alsenoy, Christian

2015-01-05

6-Methyl-1-({[(2E)-2-methyl-3-phenyl-prop-2-en-1-yl]oxy}methyl)-1,2,3,4-tetra-hydro quinazoline-2,4-dione was prepared via treatment of silylated 6-methylquinazoline-2,4-dione with bis-[(E)-2-methyl-3-phenylallyloxy]methane. FT-IR and FT-Raman spectra were recorded and analyzed. The vibrational wavenumbers were computed using DFT methods and are assigned with the help of potential energy distribution method. The first hyperpolarizability, infrared intensities and Raman activities also reported. The geometrical parameters of the title compound obtained from XRD studies are in agreement with the calculated (B3LYP) values. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using NBO analysis. The HOMO and LUMO analysis are used to determine the charge transfer within the molecule. MEP was performed by the B3LYP method and from the MEP it is evident that the negative charge covers the CO group and the positive region is over the phenyl ring and NH group. Copyright © 2014 Elsevier B.V. All rights reserved.

Theoretical Studies of Interactions between O-Phosphorylated and Standard Amino-Acid Side-Chain Models in Water

PubMed Central

Wiśniewska, Marta; Sobolewski, Emil; Ołdziej, Stanisław; Liwo, Adam; Scheraga, Harold A.; Makowski, Mariusz

2015-01-01

Phosphorylation is a common post-translational modification of the amino-acid side chains (serine, tyrosine, and threonine) that contain hydroxyl groups. The transfer of the negatively charged phosphate group from an ATP molecule to such amino-acid side chains leads to changes in the local conformations of proteins and the pattern of interactions with other amino-acid side-chains. A convenient characteristic of the side chain–side chain interactions in the context of an aqueous environment is the potential of mean force (PMF) in water. A series of umbrella-sampling molecular dynamic (MD) simulations with the AMBER force field were carried out for pairs of O-phosphorylated serine (pSer), threonine (pThr), and tyrosine, (pTyr) with natural amino acids in a TIP3P water model as a solvent at 298 K. The weighted-histogram analysis method was used to calculate the four-dimensional potentials of mean force. The results demonstrate that the positions and depths of the contact minima and the positions and heights of the desolvation maxima, including their dependence on the relative orientation depend on the character of the interacting pairs. More distinct minima are observed for oppositely charged pairs such as, e.g., O-phosphorylated side-chains and positively charged ones, such as the side-chains of lysine and arginine. PMID:26100791

Dielectric boundary force and its crucial role in gramicidin

NASA Astrophysics Data System (ADS)

Nadler, Boaz; Hollerbach, Uwe; Eisenberg, R. S.

2003-08-01

In an electrostatic problem with nonuniform geometry, a charge Q in one region induces surface charges [called dielectric boundary charges (DBC)] at boundaries between different dielectrics. These induced surface charges, in return, exert a force [called dielectric boundary force (DBF)] on the charge Q that induced them. The DBF is often overlooked. It is not present in standard continuum theories of (point) ions in or near membranes and proteins, such as Gouy-Chapman, Debye-Huckel, Poisson-Boltzmann or Poisson-Nernst- Planck. The DBF is important when a charge Q is near dielectric interfaces, for example, when ions permeate through protein channels embedded in biological membranes. In this paper, we define the DBF and calculate it explicitly for a planar dielectric wall and for a tunnel geometry resembling the ionic channel gramicidin. In general, we formulate the DBF in a form useful for continuum theories, namely, as a solution of a partial differential equation with boundary conditions. The DBF plays a crucial role in the permeation of ions through the gramicidin channel. A positive ion in the channel produces a DBF of opposite sign to that of the fixed charge force (FCF) produced by the permanent charge of the gramicidin polypeptide, and so the net force on the positive ion is reduced. A negative ion creates a DBF of the same sign as the FCF and so the net (repulsive) force on the negative ion is increased. Thus, a positive ion can permeate the channel, while a negative ion is excluded from it. In gramicidin, it is this balance between the FCF and DBF that allows only singly charged positive ions to move into and through the channel. The DBF is not directly responsible, however, for selectivity between the alkali metal ions (e.g., Li+, Na+, K+): we prove that the DBF on a mobile spherical ion is independent of the ion’s radius.

The Origins of Positive and Negative in Electricity

ERIC Educational Resources Information Center

Jensen, William B.

2005-01-01

Benjamin Franklin first introduced the terms positive and negative into electrical theory in the year 1747. The positive and negative terms originally had nothing to do with inherent electrical charge, but rather indicated which object had an excess of electrical fluid indicating positive, and which had a deficiency, indicating negative.

Flash propagation and inferred charge structure relative to radar-observed ice alignment signatures in a small Florida mesoscale convective system

NASA Astrophysics Data System (ADS)

Biggerstaff, Michael I.; Zounes, Zackery; Addison Alford, A.; Carrie, Gordon D.; Pilkey, John T.; Uman, Martin A.; Jordan, Douglas M.

2017-08-01

A series of vertical cross sections taken through a small mesoscale convective system observed over Florida by the dual-polarimetric SMART radar were combined with VHF radiation source locations from a lightning mapping array (LMA) to examine the lightning channel propagation paths relative to the radar-observed ice alignment signatures associated with regions of negative specific differential phase (KDP). Additionally, charge layers inferred from analysis of LMA sources were related to the ice alignment signature. It was found that intracloud flashes initiated near the upper zero-KDP boundary surrounding the negative KDP region. The zero-KDP boundary also delineated the propagation path of the lightning channel with the negative leaders following the upper boundary and positive leaders following the lower boundary. Very few LMA sources were found in the negative KDP region. We conclude that rapid dual-polarimetric radar observations can diagnose strong electric fields and may help identify surrounding regions of charge.

Thermal equilibrium concentrations and effects of negatively charged Ga vacancies in n-type GaAs

NASA Astrophysics Data System (ADS)

Tan, T. Y.; You, H.-M.; Gösele, U. M.

1993-03-01

We have calculated the thermal equilibrium concentrations of the various negatively charged Ga vacancy species in GaAs. The triply-negatively-charged Ga vacancy, V {Ga/3-}, has been emphasized, since it dominates Ga self-diffusion and Ga-Al interdiffusion under intrinsic and n-doping conditions, as well as the diffusion of Si donor atoms occupying Ga sites. Under strong n-doping conditions, the thermal equilibrium V {Ga/3-}concentration, C_{V_{_{Ga} }^{3 - } }^{eq} (n), has been found to exhibit a temperature independence or a negative temperature dependence, i.e., the C_{V_{_{Ga} }^{3 - } }^{eq} (n) value is either unchanged or increases as the temperature is lowered. This is quite contrary to the normal point defect behavior for which the point defect thermal equilibrium concentration decreases as the temperature is lowered. This C_{V_{_{Ga} }^{3 - } }^{eq} (n) property provides explanations to a number of outstanding experimental results, either requiring the interpretation that V {Ga/3-}has attained its thermal equilibrium concentration at the onset of each experiment, or requiring mechanisms involving point defect non-equilibrium phenomena.

Rationally Designed Sensing Selectivity and Sensitivity of an Aerolysin Nanopore via Site-Directed Mutagenesis.

PubMed

Wang, Ya-Qian; Cao, Chan; Ying, Yi-Lun; Li, Shuang; Wang, Ming-Bo; Huang, Jin; Long, Yi-Tao

2018-04-27

Selectivity and sensitivity are two key parameters utilized to describe the performance of a sensor. In order to investigate selectivity and sensitivity of the aerolysin nanosensor, we manipulated its surface charge at different locations via single site-directed mutagenesis. To study the selectivity, we replaced the positively charged R220 at the entrance of the pore with negatively charged glutamic acid, resulting in barely no current blockages for sensing negatively charged oligonucleotides. For the sensitivity, we substituted the positively charged lumen-exposed amino acid K238 located at trans-ward third of the β-barrel stem with glutamic acid. This leads to a surprisingly longer duration time at +140 mV, which is about 20 times slower in translocation speed for Poly(dA) 4 compared to that of wild-type aerolysin, indicating the stronger pore-analyte interactions and enhanced sensitivity. Therefore, it is both feasible and understandable to rationally design confined biological nanosensors for single molecule detection with high selectivity and sensitivity.

Tridodecylamine, an efficient charge control agent in non-polar media for electrophoretic inks application

NASA Astrophysics Data System (ADS)

Noel, Amélie; Mirbel, Déborah; Cloutet, Eric; Fleury, Guillaume; Schatz, Christophe; Navarro, Christophe; Hadziioannou, Georges; CyrilBrochon

2018-01-01

In order to obtain efficient electrophoretic inks, Tridodecylamine (Dod3N), has been studied as charge control agent (CCA) in a non-polar paraffin solvent (Isopar G) for various inorganic pigments (TiO2 and Fe2O3). All hydrophobic mineral oxides, i.e. treated with octyltrimethoxysilane (C8) or dodecyltrimethoxysilane (C12), were found to be negatively charged in presence of Dod3N. The electrophoretic mobilities of inorganic pigments seemed to be strongly dependent of their isoelectric point (IEP) and also of the concentration of dod3N with an optimum range between 10 and 20 mM depending on the pigments. Finally, an electrophoretic ink constituted of hydrophobic mineral oxides in presence of Dod3N was tested in a device. Its efficiency as charge control agent to negatively charge hydrophobic particles was confirmed through good optical properties and fast response time (220 ms at 200 kV m-1).

Studies on surface morphology and electrical conductivity of PEDOT:PSS thin films in presence of gold nanoparticles

NASA Astrophysics Data System (ADS)

Bhowal, Ashim Chandra; Kundu, Sarathi

2018-04-01

PEDOT:PSS is a water soluble conducting polymer consists of positively charged PEDOT and negatively charged PSS. However, this polymer suffers low conductivity problem which restrict its use. In this paper, electrical conductivity of PEDOT:PSS thin films is improved by using charged gold nanoparticles. The nanoparticles used are synthesized using lysozyme protein. The nanoparticles coated with lysozyme protein possess positive zeta potential. In the presence of gold nanoparticles due to electrostatic interaction between positively charged nanoparticles and negatively charged PSS chains, modification takes place in the surface morphology and electrical behaviors of PEDOT:PSS thin films. The changes in the polymer matrix conformations in the presence of nanoparticles are studied by Fourier transformed Infra-red (FTIR) spectroscopy, whereas the surface morphology of prepared thin films before and after interaction with nanoparticles is investigated through atomic force microscopy (AFM). Four probe method is used to measure the variation of electrical conductivity from I-V characteristics curves.

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.

Characteristics of EMI generated by negative metal-positive dielectric voltage stresses due to spacecraft charging

NASA Technical Reports Server (NTRS)

Chaky, R. C.; Inouye, G. T.

1985-01-01

Charging of spacecraft surfaces by the environmental plasma can result in differential potentials between metallic structure and adjacent dielectric surfaces in which the relative polarity of the voltage stress is either negative dielectric/positive metal or negative metal/positive dielectric. Negative metal/positive dielectric is a stress condition that may arise if relatively large areas of spacecraft surface metals are shadowed from solar UV and/or if the UV intensity is reduced as in the situation in which the spacecraft is entering into or leaving eclipse. The results of experimental studies of negative metal/positive dielectric systems are given. Information is given on: enhanced electron emission I-V curves; e(3) corona noise vs e(3) steady-state current; the localized nature of e(3) and negative metal arc discharge currents; negative metal arc discharges at stress thresholds below 1 kilovolt; negative metal arc discharge characteristics; dependence of blowoff arc discharge current on spacecraft capacitance to space (linear dimension); and damage to second surface mirrors due to negative metal arcs.

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.

Isolated effects of external bath osmolality, solute concentration, and electrical charge on solute transport across articular cartilage.

PubMed

Pouran, Behdad; Arbabi, Vahid; Zadpoor, Amir A; Weinans, Harrie

2016-12-01

The metabolic function of cartilage primarily depends on transport of solutes through diffusion mechanism. In the current study, we use contrast enhanced micro-computed tomography to determine equilibrium concentration of solutes through different cartilage zones and solute flux in the cartilage, using osteochondral plugs from equine femoral condyles. Diffusion experiments were performed with two solutes of different charge and approximately equal molecular weight, namely iodixanol (neutral) and ioxaglate (charge=-1) in order to isolate the effects of solute's charge on diffusion. Furthermore, solute concentrations as well as bath osmolality were changed to isolate the effects of steric hindrance on diffusion. Bath concentration and bath osmolality only had minor effects on the diffusion of the neutral solute through cartilage at the surface, middle and deep zones, indicating that the diffusion of the neutral solute was mainly Fickian. The negatively charged solute diffused considerably slower through cartilage than the neutral solute, indicating a large non-Fickian contribution in the diffusion of charged molecules. The numerical models determined maximum solute flux in the superficial zone up to a factor of 2.5 lower for the negatively charged solutes (charge=-1) as compared to the neutral solutes confirming the importance of charge-matrix interaction in diffusion of molecules across cartilage. Copyright © 2016 IPEM. Published by Elsevier Ltd. All rights reserved.

Measurements of Charging of Apollo 17 Lunar Dust Grains by Electron Impact

NASA Technical Reports Server (NTRS)

Abbas, Mian M.; Tankosic, Dragana; Spann, James F.; Dube, Michael J.

2008-01-01

It is well known since the Apollo missions that the lunar surface is covered with a thick layer of micron size dust grains with unusually high adhesive characteristics. The dust grains observed to be levitated and transported on the lunar surface are believed to have a hazardous impact on the robotic and human missions to the Moon. The observed dust phenomena are attributed to the lunar dust being charged positively during the day by UV photoelectric emissions, and negatively during the night by the solar wind electrons. The current dust charging and the levitation models, however, do not fully explain the observed phenomena, with the uncertainty of dust charging processes and the equilibrium potentials of the individual dust grains. It is well recognized that the charging properties of individual dust grains are substantially different from those determined from measurements made on bulk materials that are currently available. An experimental facility has been developed in the Dusty Plasma Laboratory at MSFC for investigating the charging and optical properties of individual micron/sub-micron size positively or negatively charged dust grains by levitating them in an electrodynamic balance in simulated space environments. In this paper, we present the laboratory measurements on charging of Apollo 17 individual lunar dust grains by a low energy electron beam. The charging rates and the equilibrium potentials produced by direct electron impact and by secondary electron emission process are discussed.

Delivery of the high-mobility group box 1 box A peptide using heparin in the acute lung injury animal models.

PubMed

Song, Ji Hyun; Kim, Ji Yeon; Piao, Chunxian; Lee, Seonyeong; Kim, Bora; Song, Su Jeong; Choi, Joon Sig; Lee, Minhyung

2016-07-28

In this study, the efficacy of the high-mobility group box-1 box A (HMGB1A)/heparin complex was evaluated for the treatment of acute lung injury (ALI). HMGB1A is an antagonist against wild-type high-mobility group box-1 (wtHMGB1), a pro-inflammatory cytokine that is involved in ALIs. HMGB1A has positive charges and can be captured in the mucus layer after intratracheal administration. To enhance the delivery and therapeutic efficiency of HMGB1A, the HMGB1A/heparin complex was produced using electrostatic interactions, with the expectation that the nano-sized complex with a negative surface charge could efficiently penetrate the mucus layer. Additionally, heparin itself had an anti-inflammatory effect. Complex formation with HMGB1A and heparin was confirmed by atomic force microscopy. The particle size and surface charge of the HMGB1A/heparin complex at a 1:1 weight ratio were 113nm and -25mV, respectively. Intratracheal administration of the complex was performed into an ALI animal model. The results showed that the HMGB1A/heparin complex reduced pro-inflammatory cytokines, including tumor necrosis factor-α (TNF-α), interleukin-6 (IL-6), and IL-1β, more effectively than HMGB1A or heparin alone. Hematoxylin and eosin staining confirmed the decreased inflammatory reaction in the lungs after delivery of the HMGB1A/heparin complex. In conclusion, the HMGB1A/heparin complex might be useful to treat ALI. Copyright © 2016 Elsevier B.V. All rights reserved.

A unified engineering model of the first stroke in downward negative lightning

NASA Astrophysics Data System (ADS)

Nag, Amitabh; Rakov, Vladimir A.

2016-03-01

Each stroke in a negative cloud-to-ground lightning flash is composed of downward leader and upward return stroke processes, which are usually modeled individually. The first stroke leader is stepped and starts with preliminary breakdown (PB) which is often viewed as a separate process. We present the first unified engineering model for computing the electric field produced by a sequence of PB, stepped leader, and return stroke processes, serving to transport negative charge to ground. We assume that a negatively charged channel extends downward in a stepped fashion during both the PB and leader stages. Each step involves a current wave that propagates upward along the newly formed channel section. Once the leader attaches to ground, an upward propagating return stroke neutralizes the charge deposited along the channel. Model-predicted electric fields are in reasonably good agreement with simultaneous measurements at both near (hundreds of meters, electrostatic field component is dominant) and far (tens of kilometers, radiation field component is dominant) distances from the lightning channel. Relations between the features of computed electric field waveforms and model input parameters are examined. It appears that peak currents associated with PB pulses are similar to return stroke peak currents, and the observed variation of electric radiation field peaks produced by leader steps at different heights above ground is influenced by the ground corona space charge.

A combined rocket-borne and ground-based study of the sodium layer and charged dust in the upper mesosphere

NASA Astrophysics Data System (ADS)

Plane, John M. C.; Saunders, Russell W.; Hedin, Jonas; Stegman, Jacek; Khaplanov, Misha; Gumbel, Jörg; Lynch, Kristina A.; Bracikowski, Phillip J.; Gelinas, Lynette J.; Friedrich, Martin; Blindheim, Sandra; Gausa, Michael; Williams, Bifford P.

2014-10-01

The Hotel Payload 2 rocket was launched on January 31st 2008 at 20.14 LT from the Andøya Rocket Range in northern Norway (69.31° N, 16.01° E). Measurements in the 75-105 km region of atomic O, negatively-charged dust, positive ions and electrons with a suite of instruments on the payload were complemented by lidar measurements of atomic Na and temperature from the nearby ALOMAR observatory. The payload passed within 2.58 km of the lidar at an altitude of 90 km. A series of coupled models is used to explore the observations, leading to two significant conclusions. First, the atomic Na layer and the vertical profiles of negatively-charged dust (assumed to be meteoric smoke particles), electrons and positive ions, can be modelled using a self-consistent meteoric input flux. Second, electronic structure calculations and Rice-Ramsperger-Kassel-Markus theory are used to show that even small Fe-Mg-silicates are able to attach electrons rapidly and form stable negatively-charged particles, compared with electron attachment to O2 and O3. This explains the substantial electron depletion between 80 and 90 km, where the presence of atomic O at concentrations in excess of 1010 cm-3 prevents the formation of stable negative ions.

Korteweg-deVries-Burgers (KdVB) equation in a five component cometary plasma with kappa described electrons and ions

NASA Astrophysics Data System (ADS)

Michael, Manesh; Willington, Neethu T.; Jayakumar, Neethu; Sebastian, Sijo; Sreekala, G.; Venugopal, Chandu

2016-12-01

We investigate the existence of ion-acoustic shock waves in a five component cometary plasma consisting of positively and negatively charged oxygen ions, kappa described hydrogen ions, hot solar electrons, and slightly colder cometary electrons. The KdVB equation has been derived for the system, and its solution plotted for different kappa values, oxygen ion densities, as well as the temperature ratios for the ions. It is found that the amplitude of the shock wave decreases with increasing kappa values. The strength of the shock profile decreases with increasing temperatures of the positively charged oxygen ions and densities of negatively charged oxygen ions.

Lactoferricin B causes depolarization of the cytoplasmic membrane of Escherichia coli ATCC 25922 and fusion of negatively charged liposomes.

PubMed

Ulvatne, H; Haukland, H H; Olsvik, O; Vorland, L H

2001-03-09

Antimicrobial peptides have been extensively studied in order to elucidate their mode of action. Most of these peptides have been shown to exert a bactericidal effect on the cytoplasmic membrane of bacteria. Lactoferricin is an antimicrobial peptide with a net positive charge and an amphipatic structure. In this study we examine the effect of bovine lactoferricin (lactoferricin B; Lfcin B) on bacterial membranes. We show that Lfcin B neither lyses bacteria, nor causes a major leakage from liposomes. Lfcin B depolarizes the membrane of susceptible bacteria, and induces fusion of negatively charged liposomes. Hence, Lfcin B may have additional targets responsible for the antibacterial effect.

The transfer behavior of different ions across anion and cation exchange membranes under vanadium flow battery medium

NASA Astrophysics Data System (ADS)

Sun, Jiawei; Li, Xianfeng; Xi, Xiaoli; Lai, Qinzhi; Liu, Tao; Zhang, Huamin

2014-12-01

The transfer behavior of different ions (V2+, V3+, VO2+, VO2+, H+, SO42-) across ion exchange membranes is investigated under vanadium flow battery (VFB) operating condition. VX-20 anion exchange membrane (AEM) and Nafion 115 cation exchange membrane (CEM) are selected to investigate the influence of fixed charged groups on the transfer behavior of different ions. The interaction between different ions and water is discussed in detail aiming to ascertain the variation of different ions in the charge-discharge process. Under the VFB medium, the transfer behavior and function of different ions are very different for the AEM and CEM. V2+ ions at the negative side accumulate when VFB is assembled with Nafion 115, while the VO2+ ions at the positive side accumulate for VX-20. The SO42- ions will transfer across Nafion 115 to balance the charges and the protons can balance the charges of VX-20. Finally the capacity fade mechanism of different membranes is investigated, showing that the capacity decay of VFB assembled with Nafion 115 mainly results from the cross mix of vanadium ions across the membrane, however, for VX-20, the side reactions can be the major reason. This paper provides important information about electrolyte for the application of VFB.

Linking lipid architecture to bilayer structure and mechanics using self-consistent field modelling.

PubMed

Pera, H; Kleijn, J M; Leermakers, F A M

2014-02-14

To understand how lipid architecture determines the lipid bilayer structure and its mechanics, we implement a molecularly detailed model that uses the self-consistent field theory. This numerical model accurately predicts parameters such as Helfrichs mean and Gaussian bending modulus kc and k̄ and the preferred monolayer curvature J(0)(m), and also delivers structural membrane properties like the core thickness, and head group position and orientation. We studied how these mechanical parameters vary with system variations, such as lipid tail length, membrane composition, and those parameters that control the lipid tail and head group solvent quality. For the membrane composition, negatively charged phosphatidylglycerol (PG) or zwitterionic, phosphatidylcholine (PC), and -ethanolamine (PE) lipids were used. In line with experimental findings, we find that the values of kc and the area compression modulus kA are always positive. They respond similarly to parameters that affect the core thickness, but differently to parameters that affect the head group properties. We found that the trends for k̄ and J(0)(m) can be rationalised by the concept of Israelachivili's surfactant packing parameter, and that both k̄ and J(0)(m) change sign with relevant parameter changes. Although typically k̄ < 0, membranes can form stable cubic phases when the Gaussian bending modulus becomes positive, which occurs with membranes composed of PC lipids with long tails. Similarly, negative monolayer curvatures appear when a small head group such as PE is combined with long lipid tails, which hints towards the stability of inverse hexagonal phases at the cost of the bilayer topology. To prevent the destabilisation of bilayers, PG lipids can be mixed into these PC or PE lipid membranes. Progressive loading of bilayers with PG lipids lead to highly charged membranes, resulting in J(0)(m) > 0, especially at low ionic strengths. We anticipate that these changes lead to unstable membranes as these become vulnerable to pore formation or disintegration into lipid disks.

An Instrumental Method to Identify Electric Charge Types with a Simple Device

ERIC Educational Resources Information Center

Isik, Hakan

2015-01-01

In this study, an easy and enjoyable activity to determine the type of electric charge is presented, using a readymade electronic test screw. A four-way usage of the tester is explained with an electroscope. In the activity, ebonite and glass rods are negatively and positively charged by rubbing with paper sheets, respectively.

ELECTROSTATIC FORCES IN WIND-POLLINATION: PART 1: MEASUREMENT OF THE ELECTROSTATIC CHARGE ON POLLEN

EPA Science Inventory

Under fair weather conditions, a weak electric field exists between negative charge induced on the surface of plants and positive charge in the air. This field is magnified around points (e.g. stigmas) and can reach values up to 3x10⁶ V m^-1. If wind-disperse...

Effect of hydration on interstitial distribution of charged albumin in rat dermis in vitro

PubMed Central

Wiig, Helge; Tenstad, Olav; Bert, Joel L

2005-01-01

At physiological pH, negatively charged glycosaminoglycans in the extracellular matrix may influence distribution volume of macromolecular probes, a phenomenon of importance for hydration of the interstitium and therefore for body fluid balance. We hypothesized that such charge effect was dependent on hydration. Human serum albumin (HSA) (the pH value for the isoelectric point (pI) = 4.9) was made neutral by cationization (cHSA) (pI = 7.6). Rat dermis was studied in vitro in a specially designed equilibration cell allowing control of hydration. Using a buffer containing labelled native HSA and cHSA, the distribution volumes were calculated relative to that of 51Cr-EDTA, an extracellular tracer. During changes in hydration (H), defined as (wet weight – dry weight) (dry weight)−1), the slope of the equation describing the relationship between extracellular fluid volume (Vx) (in g H2O (g dry weight)−1) and H (Vx = 0.925 H + 0.105) differed significantly from that for available volumes of cHSA (Va,cHSA = 0.624 H – 0.538) and HSA (Va,HSA = 0.518 H – 0.518). A gradual reduction in H led to a reduction in difference between available volumes for the two albumin species. Screening the fixed charges by 1 m NaCl resulted in similar available and excluded volumes of native HSA and neutral cHSA. We conclude that during gradual dehydration, there is a reduced effect of fixed negative charges on interstitial exclusion of charged macromolecules. This effect may be explained by a reduced hydration domain surrounding tissue and probe macromolecules in conditions of increased electrostatic interactions. Furthermore, screening of negative charges suggested that hyaluronan associated with collagen may influence intrafibrillar volume of collagen and thereby available and excluded volume fraction. PMID:16210353

Graphene wrapping as a protective clamping layer anchored to carbon nanofibers encapsulating Si nanoparticles for a Li-ion battery anode

NASA Astrophysics Data System (ADS)

Shin, Jungwoo; Park, Kyusung; Ryu, Won-Hee; Jung, Ji-Won; Kim, Il-Doo

2014-10-01

Carbon nanofibers encapsulating Si nanoparticles (CNFs/SiNPs) were prepared via an electrospinning method and chemically functionalized with 3-aminopropyltriethoxysilane (APS) to be grafted onto graphene oxide (GO). As a result, the thin and flexible GO, which exhibits a negative charge in aqueous solution, fully wrapped around the APS-functionalized CNFs with a positive surface charge via electrostatic self-assembly. After the formation of chemical bonds between the epoxy groups on GO and the amine groups in APS via an epoxy ring opening reaction, the GO was chemically reduced to a reduced graphene oxide (rGO). Electrochemical and morphological characterizations showed that capacity loss by structural degradation and electrolyte decomposition on Si surface were significantly suppressed in the rGO-wrapped CNFs/SiNPs (CNFs/SiNPs@rGO). Superior capacities were consequently maintained for up to 200 cycles at a high current density (1048 mA h g-1 at 890 mA g-1) compared to CNFs/SiNPs without the rGO wrapping (304 mA h g-1 at 890 mA g-1). Moreover, the resistance of the SEI layer and charge transfer resistance were also considerably reduced by 24% and 88%, respectively. The described graphene wrapping offers a versatile way to enhance the mechanical integrity and electrochemical stability of Si composite anode materials.Carbon nanofibers encapsulating Si nanoparticles (CNFs/SiNPs) were prepared via an electrospinning method and chemically functionalized with 3-aminopropyltriethoxysilane (APS) to be grafted onto graphene oxide (GO). As a result, the thin and flexible GO, which exhibits a negative charge in aqueous solution, fully wrapped around the APS-functionalized CNFs with a positive surface charge via electrostatic self-assembly. After the formation of chemical bonds between the epoxy groups on GO and the amine groups in APS via an epoxy ring opening reaction, the GO was chemically reduced to a reduced graphene oxide (rGO). Electrochemical and morphological characterizations showed that capacity loss by structural degradation and electrolyte decomposition on Si surface were significantly suppressed in the rGO-wrapped CNFs/SiNPs (CNFs/SiNPs@rGO). Superior capacities were consequently maintained for up to 200 cycles at a high current density (1048 mA h g-1 at 890 mA g-1) compared to CNFs/SiNPs without the rGO wrapping (304 mA h g-1 at 890 mA g-1). Moreover, the resistance of the SEI layer and charge transfer resistance were also considerably reduced by 24% and 88%, respectively. The described graphene wrapping offers a versatile way to enhance the mechanical integrity and electrochemical stability of Si composite anode materials. Electronic supplementary information (ESI) available: SEM images and XRD pattern of CNFs/SiNPs; photographs of CNFs/SiNPs@rGO solutions; SEM images of CNFs/SiNPs@rGO at different graphene concentrations; SEM images of CNFs@SiNPs@rGO without APS functionalization; Electrochemical cell performance of CNFs@SiNPs@rGO with different wrapping concentrations; and electrochemical impendence spectroscopy data for CNFs@SiNPs and CNFs@SiNPs@rGO after the first discharge. See DOI: 10.1039/c4nr03173c

Positive and negative ion outflow at Rhea as observed by Cassini

NASA Astrophysics Data System (ADS)

Desai, Ravindra; Jones, Geraint; Regoli, Leonardo; Cowee, Misa; Coates, Andrew; Kataria, Dhiren

2017-04-01

Rhea is Saturn's largest icy moon and hosts an ethereal oxygen and carbon-dioxide atmosphere as was detected when Cassini observed positive and negative pickup ions outflowing from the moon and an extended neutral exosphere. These pickup ions can form current systems which, with the resulting jxB force, act to slow-down the incident magneto-plasma and cause field-line draping. As well as impacting the plasma interaction, the composition and density of picked up ions provide key diagnostics of the moon's sputter-induced atmosphere and surface. During the first Cassini-Rhea encounter (R1), the Cassini Plasma Spectrometer (CAPS) observed positively and negatively charged pickup ions before and after passing through the moon's plasma wake respectively, in agreement with their anticipated cycloidal trajectories. On the subsequent more distant wake encounter (R1.5) however, only positively charged pickup ions were observed, indicating high loss rates of the negative ions in Saturn's magnetosphere. Here, using an updated model of Cassini's Electron Spectrometer response function, we are able to estimate the outward flux of negatively charged pickup ions, the first time such a plasma population has been constrained. Using test-particle simulations we trace both the positive and negative particles back to Rhea's exobase to better understand their production and loss processes and the implications for Rhea's sputter-induced exosphere. We also look to examine whether the calculated ion densities could generate ion cyclotron wave activity.

Sorption of perfluoroalkyl substances to two types of minerals.

PubMed

Hellsing, Maja S; Josefsson, Sarah; Hughes, Arwel V; Ahrens, Lutz

2016-09-01

The sorption of perfluoroalkyl substances (PFASs) was investigated for two model soil mineral surfaces, alumina (Al2O3) and silica (SiO2), on molecular level using neutron scattering. The PFASs were selected (i.e. perfluorohexanoic acid (PFHxA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), and perfluorooctane sulfonic acid (PFOS)) to examine the role of hydrophobic chain length and hydrophilic functional group on their sorption behaviour. All four PFASs were found to sorb to alumina surface (positively charged) forming a hydrated layer consisting of 50% PFASs. The PFAS solubility limit, which decrease with chain length, was found to strongly influence the sorption behaviour. The sorbed PFAS layer could easily be removed by gentle rinsing with water, indicating release upon rainfall in the environment. No sorption was observed for PFOA and PFOS at silica surface (negatively charged), showing electrostatic interaction being the driving force in the sorption process. Copyright © 2016 Elsevier Ltd. All rights reserved.

Increasing the Detection Limit of the Parkinson Disorder through a Specific Surface Chemistry Applied onto Inner Surface of the Titration Well.

PubMed

Mille, Caroline; Debarnot, Dominique; Zorzi, Willy; El Moualij, Benaïssa; Coudreuse, Arnaud; Legeay, Gilbert; Quadrio, Isabelle; Perret-Liaudet, Armand; Poncin-Epaillard, Fabienne

2012-04-18

The main objective of this paper was to illustrate the enhancement of the sensitivity of ELISA titration for neurodegenerative proteins by reducing nonspecific adsorptions that could lead to false positives. This goal was obtained thanks to the association of plasma and wet chemistries applied to the inner surface of the titration well. The polypropylene surface was plasma-activated and then, dip-coated with different amphiphilic molecules. These molecules have more or less long hydrocarbon chains and may be charged. The modified surfaces were characterized in terms of hydrophilic-phobic character, surface chemical groups and topography. Finally, the coated wells were tested during the ELISA titration of the specific antibody capture of the α-synuclein protein. The highest sensitivity is obtained with polar (Θ = 35°), negatively charged and smooth inner surface.

Increasing the Detection Limit of the Parkinson Disorder through a Specific Surface Chemistry Applied onto Inner Surface of the Titration Well

PubMed Central

Mille, Caroline; Debarnot, Dominique; Zorzi, Willy; Moualij, Benaïssa El; Coudreuse, Arnaud; Legeay, Gilbert; Quadrio, Isabelle; Perret-Liaudet, Armand; Poncin-Epaillard, Fabienne

2012-01-01

The main objective of this paper was to illustrate the enhancement of the sensitivity of ELISA titration for neurodegenerative proteins by reducing nonspecific adsorptions that could lead to false positives. This goal was obtained thanks to the association of plasma and wet chemistries applied to the inner surface of the titration well. The polypropylene surface was plasma-activated and then, dip-coated with different amphiphilic molecules. These molecules have more or less long hydrocarbon chains and may be charged. The modified surfaces were characterized in terms of hydrophilic—phobic character, surface chemical groups and topography. Finally, the coated wells were tested during the ELISA titration of the specific antibody capture of the α-synuclein protein. The highest sensitivity is obtained with polar (Θ = 35°), negatively charged and smooth inner surface. PMID:24955533

A novel alcohol dehydrogenase biosensor based on solid-state electrogenerated chemiluminescence by assembling dehydrogenase to Ru(bpy)(3)2+-Au nanoparticles aggregates.

PubMed

Zhang, Lihua; Xu, Zhiai; Sun, Xuping; Dong, Shaojun

2007-01-15

Based on electrogenerated chemiluminescence (ECL), a novel method for fabrication of alcohol dehydrogenase (ADH) biosensor by self-assembling ADH to Ru(bpy)(3)(2+)-AuNPs aggregates (Ru-AuNPs) on indium tin oxide (ITO) electrode surface has been developed. Positively charged Ru(bpy)(3)(2+) could be immobilized stably on the electrode surface with negatively charged AuNPs in the form of aggregate via electrostatic interaction. On the other hand, AuNPs are favourable candidates for the immobilization of enzymes because amine groups and cysteine residues in the enzymes are known to bind strongly with AuNPs. Moreover, AuNPs can act as tiny conduction centers to facilitate the transfer of electrons. Such biosensor combined enzymatic selectivity with the sensitivity of ECL detection for quantification of enzyme substrate, and it displayed wide linear range, high sensitivity and good stability.

Taub-Nut Crystal

NASA Astrophysics Data System (ADS)

Imazato, Harunobu; Mizoguchi, Shun'ya; Yata, Masaya

We consider the Gibbons-Hawking metric for a three-dimensional periodic array of multi-Taub-NUT centers, containing not only centers with a positive NUT charge but also ones with a negative NUT charge. The latter are regarded as representing the asymptotic form of the Atiyah-Hitchin metric. The periodic arrays of Taub-NUT centers have close parallels with ionic crystals, where the Gibbons-Hawking potential plays the role of the Coulomb static potential of the ions, and are similarly classified according to their space groups. After a periodic identification and a Z2 projection, the array is transformed by T-duality to a system of NS5-branes with the SU(2) structure, and a further standard embedding yields, though singular, a half-BPS heterotic 5-brane background with warped compact transverse dimensions. A discussion is given on the possibility of probing the singular geometry by two-dimensional gauge theories.

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

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

Surface modification for interaction study with bacteria and preosteoblast cells

NASA Astrophysics Data System (ADS)

Song, Qing

Surface modification plays a pivotal role in bioengineering. Polymer coatings can provide biocompatibility and biofunctionalities to biomaterials through surface modification. In this dissertation, initiated chemical vapor deposition (iCVD) was utilized to coat two-dimensional (2D) and three-dimensional (3D) substrates with differently charged polyelectrolytes in order to generate antimicrobial and osteocompatible biomaterials. ICVD is a modified CVD technique that enables surface modification in an all-dry condition without substrate damage and solvent contamination. The free-radical polymerization allows the vinyl polymers to conformally coat on various micro- and nano-structured substrates and maintains the delicate structure of the functional groups. The vapor deposition of polycations provided antimicrobial activity to planar and porous substrates through destroying the negatively charged bacterial membrane and brought about high contact-killing efficiency (99.99%) against Gram-positive Bacillus subtilis and Gram-negative Escherichia coli. Additionally, the polyampholytes synthesized by iCVD exhibited excellent antifouling performance against the adhesion of Gram-positive Listeria innocua and Gram-negative E. coli in phosphate buffered saline (PBS). Their antifouling activities were attributed to the electrostatic interaction and hydration layers that served as physical and energetic barriers to prevent bacterial adhesion. The contact-killing and antifouling polymers synthesized by iCVD can be applied to surface modification of food processing equipment and medical devices with the aim of reducing foodborne diseases and medical infections. Moreover, the charged polyelectrolyte modified 2D polystyrene surfaces displayed good osteocompatibility and enhanced osteogenesis of preosteoblast cells than the un-modified polystyrene surface. In order to promote osteoinduction of hydroxyapatite (HA) scaffolds, bioinspired polymer-controlled mineralization was conducted on the polyelectrolyte modified HA scaffolds. The mineralized scaffolds stimulated osteogenesis of preosteoblast cells compared with the control HA scaffolds. Therefore, the surface modification through vapor deposition of polyelectrolytes and polymer-controlled mineralization can improve osteoinduction of bone materials. In summary, the iCVD-mediated surface modification is a simple and promising approach to biofunctionalizing various structured substrates and generating antimicrobial and biocompatible biomaterials.

The potential of immobilized artificial membrane chromatography to predict human oral absorption.

PubMed

Tsopelas, Fotios; Vallianatou, Theodosia; Tsantili-Kakoulidou, Anna

2016-01-01

The potential of immobilized artificial membrane (IAM) chromatography to estimate human oral absorption (%HOA) was investigated. For this purpose, retention indices on IAM stationary phases reported previously by our group or measured by other authors under similar conditions were used to model %HOA data, compiled from literature sources. Considering the pH gradient in gastrointestinal tract, the highest logkw(IAM) values were considered, obtained either at pH7.4 or 5.5, defined as logkw(IAM)(best). Non linear models were established upon introduction of additional parameters and after exclusion of drugs which are substrates either to efflux or uptake transporters. The best model included Abraham's hydrogen-bond acidity parameter, molecular weight as well as the positively and negatively charged molecular fractions. For reasons of comparison between IAM chromatography and traditional lipophilicity, corresponding models were derived by replacing IAM retention factors with octanol-water distribution coefficients (logD). An overexpression of electrostatic interactions with phosphate anions was observed in the case of IAM retention as expressed by the negative contribution of the positively charged fraction F(+). The same parameter is statistically significant also in the logD model, but with a positive sign, indicating the attraction of basic drugs in the negatively charged inner membrane. To validate the obtained models a blind test set of 22 structurally diverse drugs was used, whose logkw(IAM)(best) values were determined and analyzed in the present study under similar conditions. IAM retention factors were further compared with MDCK cell lines permeability data taken from literature for a set of validation drugs. The overexpression of electrostatic interactions with phosphate anions on IAM surface was also evident in respect to MDCK permeability. In contrast to the clear classification between drugs with high and poor (or intermediate) absorption provided by MDCK permeability, %HOA plotted versus both IAM and logD data result in a saturation curve with a smoother ascending line. Copyright © 2015 Elsevier B.V. All rights reserved.

Protein Corona Composition of Superparamagnetic Iron Oxide Nanoparticles with Various Physico-Chemical Properties and Coatings

NASA Astrophysics Data System (ADS)

Sakulkhu, Usawadee; Mahmoudi, Morteza; Maurizi, Lionel; Salaklang, Jatuporn; Hofmann, Heinrich

2014-05-01

Because of their biocompatibility and unique magnetic properties, superparamagnetic iron oxide nanoparticles NPs (SPIONs) are recognized as some of the most prominent agents for theranostic applications. Thus, understanding the interaction of SPIONs with biological systems is important for their safe design and efficient applications. In this study, SPIONs were coated with 2 different polymers: polyvinyl alcohol polymer (PVA) and dextran. The obtained NPs with different surface charges (positive, neutral, and negative) were used as a model study of the effect of surface charges and surface polymer materials on protein adsorption using a magnetic separator. We found that the PVA-coated SPIONs with negative and neutral surface charge adsorbed more serum proteins than the dextran-coated SPIONs, which resulted in higher blood circulation time for PVA-coated NPs than the dextran-coated ones. Highly abundant proteins such as serum albumin, serotransferrin, prothrombin, alpha-fetoprotein, and kininogen-1 were commonly found on both PVA- and dextran-coated SPIONs. By increasing the ionic strength, soft- and hard-corona proteins were observed on 3 types of PVA-SPIONs. However, the tightly bound proteins were observed only on negatively charged PVA-coated SPIONs after the strong protein elution.

Power loss for high-voltage solar-cell arrays

NASA Technical Reports Server (NTRS)

Parker, L. W.

1979-01-01

Electric field particle collection and power loss are calculated in program written in FORTRAN IV for use on UNIVAC 1100/40 computer. Program incorporates positive and negative and negative charge flows and balance between positive and negative flows is performed by iteration.

Cassini CAPS-ELS observations of carbon-based anions and aerosol growth in Titan's ionosphere

NASA Astrophysics Data System (ADS)

Desai, Ravindra; Coates, Andrew; Wellbrock, Anne; Kataria, Dhiren; Jones, Geraint; Lewis, Gethyn; Waite, J.

2016-06-01

Cassini observations of Titans ionosphere revealed an atmosphere rich in positively charged ions with masses up to > 350 amu and negatively charged ions and aerosols with mass over charge ratios as high as 13,800 amu/q. The detection of negatively charged molecules by the Cassini CAPS Electron Spectrometer (CAPS-ELS) was particularly surprising and showed how the synthesis of large aerosol-size particles takes place at altitudes much greater than previously thought. Here, we present further analysis into this CAPS-ELS dataset, through an enhanced understanding of the instrument's response function. In previous studies the intrinsic E/E energy resolution of the instrument did not allow specific species to be identified and the detections were classified into broad mass ranges. In this study we use an updated fitting procedure to show how the ELS mass spectrum can be resolved into specific peaks at multiples of carbon-based anions up to > 100 amu/q. The negatively charged ions and aerosols in Titans ionosphere increase in mass with decreasing altitude, the lightest species being observed close to Titan's exobase of ˜1,450km and heaviest species observed at altitudes < 950km. We identify key stages in this apparent growth process and report on key intermediaries which appear to trigger the rapid growth of the larger aerosol-size particles.

An experiment to detect and locate lightning associated with eruptions of Redoubt Volcano

USGS Publications Warehouse

Hoblitt, R.P.

1994-01-01

A commercially-available lightning-detection system was temporarily deployed near Cook Inlet, Alaska in an attempt to remotely monitor volcanogenic lightning associated with eruptions of Redoubt Volcano. The system became operational on February 14, 1990; lightning was detected in 11 and located in 9 of the 13 subsequent eruptions. The lightning was generated by ash clouds rising from pyroclastic density currents produced by collapse of a lava dome emplaced near Redoubt's summit. Lightning discharge (flash) location was controlled by topography, which channeled the density currents, and by wind direction. In individual eruptions, early flashes tended to have a negative polarity (negative charge is lowered to ground) while late flashes tended to have a positive polarity (positive charge is lowered to ground), perhaps because the charge-separation process caused coarse, rapid-settling particles to be negatively charged and fine, slow-settling particles to be positively charged. Results indicate that lightning detection and location is a useful adjunct to seismic volcano monitoring, particularly when poor weather or darkness prevents visual observation. The simultaneity of seismicity and lightning near a volcano provides the virtual certainty that an ash cloud is present. This information is crucial for aircraft safety and to warn threatened communities of impending tephra falls. The Alaska Volcano Observatory has now deployed a permanent lightning-detection network around Cook Inlet. ?? 1994.

The influence of negative ions in helium-oxygen barrier discharges: III. Simulation of laser photodetachment and comparison with experiment

NASA Astrophysics Data System (ADS)

Nemschokmichal, Sebastian; Tschiersch, Robert; Meichsner, Jürgen

2017-11-01

The laser photodetachment experiment in a diffuse helium-oxygen barrier discharge is evaluated by a 1D fluid simulation. As in the experiment, the simulated discharge operates in helium with 400 {ppm} oxygen admixture at 500 {mbar} inside a discharge gap of 3 {mm}. The laser photodetachment is included by the interaction of negative ions with a temporally and spatially dependent photon flux. The simulation with the usually applied set of reactions and rate coefficients provides a much lower negative ion density than needed to explain the impact on the discharge characteristics in the experiment. Further processes for an enhanced negative ion formation and their capabilities of reproducing the experimental results are discussed. These further processes are additional attachment processes in the volume and the negative ion formation at the negatively charged dielectric. Both approaches are able to reproduce the measured laser photodetachment effect partially, but the best agreement with the experimental results is achieved with the formation of negative ions at the negatively charged dielectric.

D-region positive and negative ion concentration and mobilities during the February 1979 eclipse

NASA Astrophysics Data System (ADS)

Conley, T. D.; Narcisi, R. S.; Hegblom, E. R.

1983-07-01

Positive and negative ion concentrations and mobilities have been obtained from an analysis of Gerdien condenser measurements on rocket flights, A10.802-1 and A10.802-2, during and after eclipse totality. The aerodynamic instrument calibration and the data analysis techniques are discussed. The measured concentrations on both flights were about 10,000/cu cm in the altitudes range, 45-80 km. These high concentrations at very low altitudes suggest that a relativistic electron precipitation event was occurring during the measurements. The ion concentration measurements along with electron density measurements made by other groups during the eclipse were used to calculate the negative ion/ electron ratio, and the lumped parameter detachment rate. These results are compared with prior measurements during eclipse and solar proton events and code results. The analysis shows that the present negative ion model is incomplete. The reduced mobilities were also determined. The mobility distributions show that the heavy ions of both the positive and negative species dominate from 45 to 70 km. The data reveal more massive ions at higher altitudes than at low altitudes (1000 vs 300 a.m.u.) as well as possible evidence for multiply charged ions below about 60 km.

Transport model of controlled molecular rectifier showing unusual negative differential resistance effect.

PubMed

Granhen, Ewerton Ramos; Reis, Marcos Allan Leite; Souza, Fabrício M; Del Nero, Jordan

2010-12-01

We investigate theoretically the charge accumulated Q in a three-terminal molecular device in the presence of an external electric field. Our approach is based on ab initio Hartree-Fock and density functional theory methodology contained in Gaussian package. Our main finding is a negative differential resistance (NDR) in the charge Q as a function of an external electric field. To explain this NDR effect we apply a phenomenological capacitive model based on a quite general system composed of many localized levels (that can be LUMOs of a molecule) coupled to source and drain. The capacitance accounts for charging effects that can result in Coulomb blockade (CB) in the transport. We show that this CB effect gives rise to a NDR for a suitable set of phenomenological parameters, like tunneling rates and charging energies. The NDR profile obtained in both ab initio and phenomenological methodologies are in close agreement.

Is the ;Earth-ionosphere capacitor; a valid component in the atmospheric global electric circuit?

NASA Astrophysics Data System (ADS)

Haldoupis, Christos; Rycroft, Michael; Williams, Earle; Price, Colin

2017-11-01

This paper examines whether the Earth-ionosphere capacitor (EIC) model is correct, by comparing observed atmospheric electrical properties with those expected for a spherical capacitor, as defined in electrostatics. The comparisons suggest that the EIC concept cannot be reconciled with, and hence cannot account for, the observations, particularly the rapid reduction of the atmospheric electric field with height that is measured. This means that the spherical EIC concept is incorrect by being too simplistic; it is thus misleading. The reason for this flawed concept is simple: the model disregards the non-uniform conductivity of the atmosphere which requires the presence of a net positive charge in the lower atmosphere that equals in magnitude the Earth's negative charge. This positive charge shields the action of the Earth's negative charge from polarizing the ionosphere positively. Thus, the lower D region ionosphere remains electrically neutral, which makes the EIC concept inappropriate.

Arginine "Magic": Guanidinium Like-Charge Ion Pairing from Aqueous Salts to Cell Penetrating Peptides.

PubMed

Vazdar, Mario; Heyda, Jan; Mason, Philip E; Tesei, Giulio; Allolio, Christoph; Lund, Mikael; Jungwirth, Pavel

2018-06-19

It is a textbook knowledge that charges of the same polarity repel each other. For two monovalent ions in the gas phase at a close contact this repulsive interaction amounts to hundreds of kilojoules per mole. In aqueous solutions, however, this Coulomb repulsion is strongly attenuated by a factor equal to the dielectric constant of the medium. The residual repulsion, which now amounts only to units of kilojoules per mole, may be in principle offset by attractive interactions. Probably the smallest cationic pair, where a combination of dispersion and cavitation forces overwhelms the Coulomb repulsion, consists of two guanidinium ions in water. Indeed, by a combination of molecular dynamics with electronic structure calculations and electrophoretic, as well as spectroscopic, experiments, we have demonstrated that aqueous guanidinium cations form (weakly) thermodynamically stable like-charge ion pairs. The importance of pairing of guanidinium cations in aqueous solutions goes beyond a mere physical curiosity, since it has significant biochemical implications. Guanidinium chloride is known to be an efficient and flexible protein denaturant. This is due to the ability of the orientationally amphiphilic guanidinium cations to disrupt various secondary structural motifs of proteins by pairing promiscuously with both hydrophobic and hydrophilic groups, including guanidinium-containing side chains of arginines. The fact that the cationic guanidinium moiety forms the dominant part of the arginine side chain implies that the like-charge ion pairing may also play a role for interactions between peptides and proteins. Indeed, arginine-arginine pairing has been frequently found in structural protein databases. In particular, when strengthened by a presence of negatively charged glutamate, aspartate, or C-terminal carboxylic groups, this binding motif helps to stabilize peptide or protein dimers and is also found in or near active sites of several enzymes. The like-charge pairing of the guanidinium side-chain groups may also hold the key to the understanding of the arginine "magic", that is, the extraordinary ability of arginine-rich polypeptides to passively penetrate across cellular membranes. Unlike polylysines, which are also highly cationic but lack the ease in crossing membranes, polyarginines do not exhibit mutual repulsion. Instead, they accumulate at the membrane, weaken it, and might eventually cross in a concerted, "train-like" manner. This behavior of arginine-rich cell penetrating peptides can be exploited when devising smart strategies how to deliver in a targeted way molecular cargos into the cell.

[Cardiovascular medicine in the German diagnosis-related group--(G-DRG) system 2005].

PubMed

Fürstenberg, T; Bunzemeier, H; Roeder, N; Reinecke, H

2005-05-01

The German diagnosis-related Group (G-DRG) System has recently been published in its third version. From 2005 on, this system will be the definite measure for the budgets of nearly all german hospitals. The preliminary phase with no budget reduction or redistribution being made and in which an inappropriate classification system had no negative impact on reimbursement has, thus, come to an end. At present, many hospitals are struggling in an economic competition about the independence or maintenance of the hospital or several sub-departments. The changes in the classification system with regard to a marked increase in the number of G DRGs, a modified grouping-logic, more properly determined reductions and extra charges for low and high outlier as well as the introduction of further additional charges contribute thereby to a better covering of services and treatments of cardiovascular patients. However, while many of the known problems have been eliminated, there are still weaknesses in the G-DRG System even concerning cardiovascular medicine. The G-DRG System has to be adapted continuously with consultation of the clinical expertise of the respective medical societies. The most important new aspects and changes in the G-DRG System 2005 and the accompanied execution regulations are explained with special view on cardiology.

Hydrazino-methoxy-1,3,5-triazine Derivatives' Excellent Corrosion Organic Inhibitors of Steel in Acidic Chloride Solution.

PubMed

El-Faham, Ayman; Osman, Sameh M; Al-Lohedan, Hamad A; El-Mahdy, Gamal A

2016-06-01

The corrosion inhibition performance of 2-hydrazino-4,6-dimethoxy-1,3,5-tirazine (DMeHT), 2,4-dihydrazino-6-methoxy-1,3,5-triaizine (DHMeT), and 2,4,6-tridydrazino-1,3,5-triaizne (TH₃) on steel corrosion in acidic media was examined using electrochemical techniques. The results showed 2,4-Ddihydrazino-6-methoxy-1,3,5-triaizine (DHMeT) gave the best corrosion protection performance among the other hydrazino derivatives even at a low concentration of 25 ppm (95%). The number of hydrazino groups play an important role in the corrosion inhibition, where the two hydrazine groups increased the electrostatic interactions between the protonated tested compounds, the negatively charged steel surface resulted from the adsorption of the chloride anions, and the presence of the methoxy group made the compound more reliable for formation of film protection on the surface of steel through the lone pair of oxygen atoms. Electrochemical Impedance Spectroscopy (EIS) measurements suggested that the corrosion process of steel in presence of the hydrazino-s-triazine derivatives (TH₃, DMeHT and DHMeT) were being controlled by the charge transfer reaction. Polarization curves indicated that the examined TH₃, DMeHT and DHMeT behaved as mixed type inhibitors.

An improved fast multipole method for electrostatic potential calculations in a class of coarse-grained molecular simulations

NASA Astrophysics Data System (ADS)

Poursina, Mohammad; Anderson, Kurt S.

2014-08-01

This paper presents a novel algorithm to approximate the long-range electrostatic potential field in the Cartesian coordinates applicable to 3D coarse-grained simulations of biopolymers. In such models, coarse-grained clusters are formed via treating groups of atoms as rigid and/or flexible bodies connected together via kinematic joints. Therefore, multibody dynamic techniques are used to form and solve the equations of motion of such coarse-grained systems. In this article, the approximations for the potential fields due to the interaction between a highly negatively/positively charged pseudo-atom and charged particles, as well as the interaction between clusters of charged particles, are presented. These approximations are expressed in terms of physical and geometrical properties of the bodies such as the entire charge, the location of the center of charge, and the pseudo-inertia tensor about the center of charge of the clusters. Further, a novel substructuring scheme is introduced to implement the presented far-field potential evaluations in a binary tree framework as opposed to the existing quadtree and octree strategies of implementing fast multipole method. Using the presented Lagrangian grids, the electrostatic potential is recursively calculated via sweeping two passes: assembly and disassembly. In the assembly pass, adjacent charged bodies are combined together to form new clusters. Then, the potential field of each cluster due to its interaction with faraway resulting clusters is recursively calculated in the disassembly pass. The method is highly compatible with multibody dynamic schemes to model coarse-grained biopolymers. Since the proposed method takes advantage of constant physical and geometrical properties of rigid clusters, improvement in the overall computational cost is observed comparing to the tradition application of fast multipole method.

Central Charges and the Sign of Entanglement in 4D Conformal Field Theories.

PubMed

Perlmutter, Eric; Rangamani, Mukund; Rota, Massimiliano

2015-10-23

We explore properties of the universal terms in the entanglement entropy and logarithmic negativity in 4D conformal field theories, aiming to clarify the ways in which they behave like the analogous entanglement measures in quantum mechanics. We show that, unlike entanglement entropy in finite-dimensional systems, the sign of the universal part of entanglement entropy is indeterminate. In particular, if and only if the central charges obey a>c, the entanglement across certain classes of entangling surfaces can become arbitrarily negative, depending on the geometry and topology of the surface. The negative contribution is proportional to the product of a-c and the genus of the surface. Similarly, we show that in a>c theories, the logarithmic negativity does not always exceed the entanglement entropy.

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.

Characterization of N-Succinylation of L-Lysylphosphatidylglycerol in Bacillus subtilis Using Tandem Mass Spectrometry

NASA Astrophysics Data System (ADS)

Atila, Metin; Katselis, George; Chumala, Paulos; Luo, Yu

2016-10-01

Phospholipids generally dominate in bacterial lipids. The negatively charged nature of phospholipids renders bacteria susceptible to cationic antibiotic peptides. In comparison with Gram-negative bacteria, Gram-positive bacteria in general have much less zwitterionic phosphatidylethanolamine. However, they are known for producing aminoacylated phosphatidylglycerol (PG), especially positively charged l-lysyl-PG, which is catalyzed by lysyl-PG synthase MprF, which appears to have a broad range of specificity for l-aminoacyl transfer RNAs. In addition, many Gram-positive bacteria also have a dlt-gene-coded d-alanylation pathway for lipoteichoic acids and wall teichoic acids covalently attached to a glycolipid or peptidoglycan. d-Alanylation also masks the dominant negative charge of the phosphate-rich polymers of teichoic acids. Using mass spectrometry, we have recently observed that precursor scans in negative mode for deprotonated amino acid fragments were most sensitive for ester-linked amino acids. Such a scan for precursors generating an m/ z 145 lysyl anion revealed lysyl-PG as well as an additional species 100 m/ z units greater than lysyl-PG. This unexpected species corresponded precisely to the expected mass of N-succinylated lysyl-PG. Tandem mass spectrometry revealed a precise match to the fragmentation pattern of this putative new species. PG, lysyl-PG, and N-succinyl-lysyl-PG may form a complete loop of charge reversal from -1 to +1 and then back to -1. Analogous charge reversal by N-succinylation of lysine residues in the bacterial as well as eukaryotic proteomes has been recently discovered as a major posttranslational modification. Such modification in bacterial lipids is possibly catalyzed by an enzyme homologous to the enzymes that modify lysine residues in proteins.

Donnan membrane speciation of Al, Fe, trace metals and REEs in coastal lowland acid sulfate soil-impacted drainage waters.

PubMed

Jones, Adele M; Xue, Youjia; Kinsela, Andrew S; Wilcken, Klaus M; Collins, Richard N

2016-03-15

Donnan dialysis has been applied to forty filtered drainage waters collected from five coastal lowland acid sulfate soil (CLASS) catchments across north-eastern NSW, Australia. Despite having average pH values<3.9, 78 and 58% of Al and total Fe, respectively, were present as neutral or negatively-charged species. Complementary isotope dilution experiments with (55)Fe and (26)Al demonstrated that only soluble (i.e. no colloidal) species were present. Trivalent rare earth elements (REEs) were also mainly present (>70%) as negatively-charged complexes. In contrast, the speciation of the divalent trace metals Co, Mn, Ni and Zn was dominated by positively-charged complexes and was strongly correlated with the alkaline earth metals Ca and Mg. Thermodynamic equilibrium speciation calculations indicated that natural organic matter (NOM) complexes dominated Fe(III) speciation in agreement with that obtained by Donnan dialysis. In the case of Fe(II), however, the free cation was predicted to dominate under thermodynamic equilibrium, whilst our results indicated that Fe(II) was mainly present as neutral or negatively-charged complexes (most likely with sulfate). For all other divalent metals thermodynamic equilibrium speciation calculations agreed well with the Donnan dialysis results. The proportion of Al and REEs predicted to be negatively-charged was also grossly underestimated, relative to the experimental results, highlighting possible inaccuracies in the stability constants developed for these trivalent Me(SO4)2(-) and/or Me-NOM complexes and difficulties in modeling complex environmental samples. These results will help improve metal mobility and toxicity models developed for CLASS-affected environments, and also demonstrate that Australian CLASS environments can discharge REEs at concentrations an order of magnitude greater than previously reported. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

Formation mechanism of human serum albumin monolayers on positively charged polymer microparticles.

PubMed

Nattich-Rak, Małgorzata; Sadowska, Marta; Adamczyk, Zbigniew; Cieśla, Michał; Kąkol, Małgorzata

2017-11-01

Human serum albumin (HSA) adsorption on positively and negatively charged polystyrene microparticles was studied at various pHs and NaCl concentrations. Thorough electrophoretic mobility measurements were carried out that enabled to monitor in situ the progress of protein adsorption. The maximum coverage of irreversibly adsorbed HSA on microparticles was determined by different concentration depletion methods, one of them involving AFM imaging of residual molecules. An anomalous adsorption of HSA on the positive microparticles was observed at pH 3.5 where the maximum coverage attained 1.0mgm -2 for NaCl concentrations of 0.05M despite that the molecules were on average positively charged. For comparison, the maximum coverage of HSA on negatively charged microparticles was equal to 1.3mgm -2 at this pH and NaCl concentration. At pH 7.4 the maximum coverage on positive microparticles was equal to 2.1mgm -2 for 0.05M NaCl concentration. On the other hand, for negative microparticles, negligible adsorption of HSA was observed at pH 7.4 and 9.7. These experimental data were adequately interpreted in terms of the random sequential adsorption approach exploiting the bead model of the HSA molecule. Different orientations of adsorbed molecules, inert alia, the edge-on orientation prevailing for positively charged microparticles at pH 7.4, were confirmed. This was explained in terms of a heterogeneous charge distribution over the HSA molecule prevailing for a wide range of pHs. Copyright © 2017 Elsevier B.V. All rights reserved.