Modification of lignocellulosic materials by laccase

Treesearch

William Kenealy; John Klungness; Mandla Tshabalala; Roland Gleisner; Eric Horn; Masood Akhtar; Hilda Zulaica-Villagomez; Gisela Buschle-Diller

2003-01-01

Altering the surface properties of pulp can enhance binding, increase paper strength, and decrease the cost of fiber. In this study, we modified lignocellulosic materials (bark and pulp) with laccase and selected substrates to change the nature of the pulp surface. Modified pulps were evaluated by the amount of methylene blue (a cationic dye) that would bind to the...

Surfactant-Modified Ultrafine Gold Nanoparticles with Magnetic Responsiveness for Reversible Convergence and Release of Biomacromolecules.

PubMed

Xu, Lu; Dong, Shuli; Hao, Jingcheng; Cui, Jiwei; Hoffmann, Heinz

2017-03-28

It is difficult to synthesize magnetic gold nanoparticles (AuNPs) with ultrafine sizes (<2 nm) based on a conventional method via coating AuNPs using magnetic particles, compounds, or ions. Here, magnetic cationic surfactants C 16 H 33 N + (CH 3 ) 3 [CeCl 3 Br] - (CTACe) and C 16 H 33 N + (CH 3 ) 3 [GdCl 3 Br] - (CTAGd) are prepared by a one-step coordination reaction, i.e., C 16 H 33 N + (CH 3 ) 3 Br - (CTABr) + CeCl 3 or GdCl 3 → CTACe or CTAGd. A simple strategy for fabricate ultrafine (<2 nm) magnetic gold nanoparticles (AuNPs) via surface modification with weak oxidizing paramagnetic cationic surfactants, CTACe or CTAGd, is developed. The resulting AuNPs can highly concentrate the charges of cationic surfactants on their surfaces, thereby presenting strong electrostatic interaction with negatively charged biomacromolecules, DNA, and proteins. As a consequence, they can converge DNA and proteins over 90% at a lower dosage than magnetic surfactants or existing magnetic AuNPs. The surface modification with these cationic surfactants endows AuNPs with strong magnetism, which allows them to magnetize and migrate the attached biomacromolecules with a much higher efficiency. The native conformation of DNA and proteins can be protected during the migration. Besides, the captured DNA and proteins could be released after adding sufficient inorganic salts such as at c NaBr = 50 mmol·L -1 . Our results could offer new guidance for a diverse range of systems including gene delivery, DNA transfection, and protein delivery and separation.

Charge separation in photoredox reactions. Technical progress report, May 1, 1981-May 1, 1984. [N,N,N',N'-tetramethylbenzidine

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

Kevan, L.

1984-05-01

The structural aspects controlling charge separation in molecular photoionization reactions in organized molecular assemblies involving micelles and vesicles are being studied by optical and electron magnetic resonance techniques including the time domain technique of electron spin echo modulation (ESEM). Photoionization of N,N,N',N'-tetramethylbenzidine (TMB) to give the cation radical has been carried out in both liquid and frozen micellar and vesicular solutions. Cation-water interactions have been detected by ESEM analysis and indicate that the cation is localized asymmetrically within these organized molecular assemblies. x-Doxylstearic acid spin probes have been used to determine that the neutral TMB molecule before photoionization is alsomore » localized asymmetrically within such organized molecular assemblies. Electron spin echo detection of laser photogenerated TMB cation in liquid micellar solutions gives a direct measurement of the phase memory magnetic relaxation time which gives additional structural information. The photoionization efficiency has been related to cation-water interactions measured by ESEM. The photoionization efficiency is also dependent on surface charge and is about twofold greater in cationic micelles and vesicles compared to anionic micelles and vesicles. TMB is in a less polar environment in vesicles compared to micelles consistent with ESEM results. The preferential adsorption of metal species at micellar surfaces has been detected by ESEM. Modifications in the micelle surface have been effected by added salts and varying counterions which have been related to cation-water interactions and to the TMB photoionization efficiency. Corresponding changes in the surface and internal micellar structure have been investigated by x-doxylstearic acid spin probes and specifically deuterated surfactants. The decay kinetics of TMB cations in micelles have been interpreted in terms of a time dependent rate constant.« less

PEGylation of cationic, shell-crosslinked-knedel-like nanoparticles modulates inflammation and enhances cellular uptake in the lung

PubMed Central

Ibricevic, Aida; Guntsen, Sean P.; Zhang, Ke; Shrestha, Ritu; Liu, Yongjian; Sun, Jing Yi; Welch, Michael J.; Wooley, Karen L.; Brody, Steven L.

2013-01-01

The airway provides a direct route for administration of nanoparticles bearing therapeutic or diagnostic payloads to the lung, however optimization of nanoplatforms for intracellular delivery remains challenging. Poly(ethylene glycol) (PEG) surface modification improves systemic performance but less is known about PEGylated nanoparticles administered to the airway. To test this, we generated a library of cationic, shell crosslinked knedel-like nanoparticles (cSCKs), including PEG (1.5 kDa PEG; 2, 5, 10 molecules/polymer arm) on the outer shell. Delivery of PEGylated cSCK to the mouse airway showed significantly less inflammation in a PEG dose-dependent manner. PEGylation also enhanced the entry of cSCKs in lung alveolar epithelial cells and improved surfactant penetration. The PEGylation effect could be explained by the altered mechanism of endocytosis. While non-PEGylated cSCKs used the clathrin-dependent route for endocytosis, entry of PEGylated cSCK was clathrin-independent. Thus, nanoparticle surface modification with PEG represents an advantageous design for lung delivery. PMID:23453959

Effect of cations in the background electrolyte on the adsorption kinetics of copper and cadmium and the isoelectric point of imogolite.

PubMed

Arancibia-Miranda, Nicolás; Silva-Yumi, Jorge; Escudey, Mauricio

2015-12-15

Modification of surface charge and changes in the isoelectric point (IEP) of synthetic imogolite were studied for various cations in the background electrolyte (K(+), NH4(+), Mg(2+), and Ca(2+)). From the electrophoretic mobility data, it was established that the K(+) (KCl) concentration does not affect the IEP of imogolite; therefore, KCl is a suitable background electrolyte. In terms of the magnitude of changes in the IEP and surface charge, the cations may be ranked in the following order: Mg(2+)≈Ca(2+)>NH4(+)>K(+). Four different kinetic models were used to evaluate the influence of Mg(2+), Ca(2+), NH4(+), and K(+) on the adsorption of Cd and Cu on synthetic imogolite. When adsorption occurs in the presence of cations with the exception of K(+), the kinetics of the process is well described by the pseudo-first order model. On the other hand, when adsorption is conducted in the presence of K(+), the adsorption kinetics is well described by the pseudo-second order, Elovich, and Weber-Morris models. From the surface charge measurements, the affinity between imogolite and the cations and their effect on the adsorption of trace elements, namely Cu and Cd, were established. Copyright © 2015 Elsevier B.V. All rights reserved.

Attachment of nanoparticulate drug-release systems on poly(ε-caprolactone) nanofibers via a graftpolymer as interlayer.

PubMed

de Cassan, Dominik; Sydow, Steffen; Schmidt, Nadeschda; Behrens, Peter; Roger, Yvonne; Hoffmann, Andrea; Hoheisel, Anna Lena; Glasmacher, Birgit; Hänsch, Robert; Menzel, Henning

2018-03-01

Electrospun poly(ε-caprolactone) (PCL) fiber mats are modified using a chitosan grafted with PCL (CS-g-PCL), to improve the biological performance and to enable further modifications. The graft copolymer is immobilized by the crystallization of the PCL grafts on the PCL fiber surface as binding mechanism. In this way, the surface of the fibers is covered with chitosan bearing cationic amino groups, which allow adsorption of oppositely charged nanoparticulate drug-delivery systems. The modification of the fiber mats and the attachment of the drug delivery systems are easy and scalable dip processes. The process is also versatile; it is possible to attach different polymeric and inorganic nanoparticulate drug-release systems of cationic or anionic nature. The modifications are verified using scanning electron microscopy (SEM) and confocal laser scanning microscopy (CLSM). As proof of principle, the release of ciprofloxacin from silica nanoparticles attached to the modified fiber mats is shown; however, the method is also suited for other biologically active substances including growth factors. The initial cellular attachment and proliferation as well as vitality of the cells is improved by the modification with CS-g-PCL and is further influenced by the type of the drug delivery system attached. Hence, this method can be used to transfer PCL fiber mats into bioactive implants for in-situ tissue engineering applications. Copyright © 2018 Elsevier B.V. All rights reserved.

Efficient Removal of Cationic and Anionic Radioactive Pollutants from Water Using Hydrotalcite-Based Getters.

PubMed

Bo, Arixin; Sarina, Sarina; Liu, Hongwei; Zheng, Zhanfeng; Xiao, Qi; Gu, Yuantong; Ayoko, Godwin A; Zhu, Huaiyong

2016-06-29

Hydrotalcite (HT)-based materials are usually applied to capture anionic pollutants in aqueous solutions. Generally considered anion exchangers, their ability to capture radioactive cations is rarely exploited. In the present work, we explored the ability of pristine and calcined HT getters to effectively capture radioactive cations (Sr(2+) and Ba(2+)) which can be securely stabilized at the getter surface. It is found that calcined HT outperforms its pristine counterpart in cation removal ability. Meanwhile, a novel anion removal mechanism targeting radioactive I(-) is demonstrated. This approach involves HT surface modification with silver species, namely, Ag2CO3 nanoparticles, which can attach firmly on HT surface by forming coherent interface. This HT-based anion getter can be further used to capture I(-) in aqueous solution. The observed I(-) uptake mechanism is distinctly different from the widely reported ion exchange mechanism of HT and much more efficient. As a result of the high local concentrations of precipitants on the getters, radioactive ions in water can be readily immobilized onto the getter surface by forming precipitates. The secured ionic pollutants can be subsequently removed from water by filtration or sedimentation for safe disposal. Overall, these stable, inexpensive getters are the materials of choice for removal of trace ionic pollutants from bulk radioactive liquids, especially during episodic environmental crisis.

Modifying Silicates for Better Dispersion in Nanocomposites

NASA Technical Reports Server (NTRS)

Campbell, Sandi

2005-01-01

An improved chemical modification has been developed to enhance the dispersion of layered silicate particles in the formulation of a polymer/silicate nanocomposite material. The modification involves, among other things, the co-exchange of an alkyl ammonium ion and a monoprotonated diamine with interlayer cations of the silicate. The net overall effects of the improved chemical modification are to improve processability of the nanocomposite and maximize the benefits of dispersing the silicate particles into the polymer. Some background discussion is necessary to give meaning to a description of this development. Polymer/silicate nanocomposites are also denoted polymer/clay composites because the silicate particles in them are typically derived from clay particles. Particles of clay comprise layers of silicate platelets separated by gaps called "galleries." The platelet thickness is 1 nm. The length varies from 30 nm to 1 m, depending on the silicate. In order to fully realize the benefits of polymer/silicate nanocomposites, it is necessary to ensure that the platelets become dispersed in the polymer matrices. Proper dispersion can impart physical and chemical properties that make nanocomposites attractive for a variety of applications. In order to achieve nanometer-level dispersion of a layered silicate into a polymer matrix, it is typically necessary to modify the interlayer silicate surfaces by attaching organic functional groups. This modification can be achieved easily by ion exchange between the interlayer metal cations found naturally in the silicate and protonated organic cations - typically protonated amines. Long-chain alkyl ammonium ions are commonly chosen as the ion-exchange materials because they effectively lower the surface energies of the silicates and ease the incorporation of organic monomers or polymers into the silicate galleries. This completes the background discussion. In the present improved modification of the interlayer silicate surfaces, the co-ion exchange strengthens the polymer/silicate interface and ensures irreversible separation of the silicate layers. One way in which it does this is to essentially tether one amine of each diamine molecule to a silicate surface, leaving the second amine free for reaction with monomers during the synthesis of a polymer. In addition, the incorporation of alkyl ammonium ions into the galleries at low concentration helps to keep low the melt viscosity of the oligomer formed during synthesis of the polymer and associated processing - a consideration that is particularly important in the case of a highly cross-linked, thermosetting polymer. Because of the chemical bonding between the surface-modifying amines and the monomers, even when the alkyl ammonium ions become degraded at high processing temperature, the silicate layers do not aggregate and, hence, nanometer-level dispersion is maintained.

Antimicrobial membrane surfaces via efficient polyethyleneimine immobilization and cationization

NASA Astrophysics Data System (ADS)

Qiu, Wen-Ze; Zhao, Zi-Shu; Du, Yong; Hu, Meng-Xin; Xu, Zhi-Kang

2017-12-01

Biofouling control is a major task in membrane separation processes for water treatment and biomedical applications. In this work, N-alkylated polyethylenimine (PEI) is facilely and efficiently introduced onto the membrane surfaces via the co-deposition of catechol (CCh) and PEI, followed by further grafting of PEIs (600 Da, 70 kDa and 750 kDa) and cationization with methyl iodide (CH3I). The physical and chemical properties of the constructed membrane surfaces are characterized with scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, zeta potential and water contact angle measurements. Antibacterial assay reveals that the optimized membrane surfaces possess around 95% antibacterial efficiency against Gram-positive Staphylococcus aureus (S. aureus) with weak adhesion of bacteria cells after 24 h of bacterial contact. Additionally, the membrane surfaces also exhibit much enhanced antifouling property during the filtration of opposite charged bovine serum albumin (BSA). These results demonstrate a useful strategy for the surface modification of separation membranes by a kind of antimicrobial and antifouling coating.

Highly Stable Nanocontainer of APTES-Anchored Layered Titanate Nanosheet for Reliable Protection/Recovery of Nucleic Acid

NASA Astrophysics Data System (ADS)

Kim, Tae Woo; Kim, In Young; Park, Dae-Hwan; Choy, Jin-Ho; Hwang, Seong-Ju

2016-02-01

A universal technology for the encapsulative protection of unstable anionic species by highly stable layered metal oxide has been developed via the surface modification of a metal oxide nanosheet. The surface anchoring of (3-aminopropyl)triethoxysilane (APTES) on exfoliated titanate nanosheet yields a novel cationic metal oxide nanosheet, which can be universally used for the hybridization with various biological and inorganic anions. The encapsulation of deoxyribonucleic acid (DNA) in the cationic APTES-anchored titanate lattice makes possible the reliable long-term protection of DNA against enzymatic, chemical, and UV-vis light corrosions. The encapsulated DNA can be easily released from the titanate lattice via sonication, underscoring the functionality of the cationic APTES-anchored titanate nanosheet as a stable nanocontainer for DNA. The APTES-anchored titanate nanosheet can be also used as an efficient CO2 adsorbent and a versatile host material for various inorganic anions like polyoxometalates, leading to the synthesis of novel intercalative nanohybrids with unexplored properties and useful functionalities.

Highly Stable Nanocontainer of APTES-Anchored Layered Titanate Nanosheet for Reliable Protection/Recovery of Nucleic Acid.

PubMed

Kim, Tae Woo; Kim, In Young; Park, Dae-Hwan; Choy, Jin-Ho; Hwang, Seong-Ju

2016-02-24

A universal technology for the encapsulative protection of unstable anionic species by highly stable layered metal oxide has been developed via the surface modification of a metal oxide nanosheet. The surface anchoring of (3-aminopropyl)triethoxysilane (APTES) on exfoliated titanate nanosheet yields a novel cationic metal oxide nanosheet, which can be universally used for the hybridization with various biological and inorganic anions. The encapsulation of deoxyribonucleic acid (DNA) in the cationic APTES-anchored titanate lattice makes possible the reliable long-term protection of DNA against enzymatic, chemical, and UV-vis light corrosions. The encapsulated DNA can be easily released from the titanate lattice via sonication, underscoring the functionality of the cationic APTES-anchored titanate nanosheet as a stable nanocontainer for DNA. The APTES-anchored titanate nanosheet can be also used as an efficient CO2 adsorbent and a versatile host material for various inorganic anions like polyoxometalates, leading to the synthesis of novel intercalative nanohybrids with unexplored properties and useful functionalities.

Chitosan-edible oil based materials as upgraded adsorbents for textile dyes.

PubMed

Dos Santos, Clayane Carvalho; Mouta, Rodolpho; Junior, Manoel Carvalho Castro; Santana, Sirlane Aparecida Abreu; Silva, Hildo Antonio Dos Santos; Bezerra, Cícero Wellington Brito

2018-01-15

Biopolymer chitosan is a low cost, abundant, environmentally friendly, very selective and efficient anionic dyes adsorbent, being a promising material for large-scale removal of dyes from wastewater. However, raw chitosan (CS) is an ineffective cationic dyes adsorbent and its performance is pH sensitive, thus, CS modifications that address these issues need to be developed. Here, we report the preparation and characterization of two new CS modifications using edible oils (soybean oil or babassu oil), and their adsorption performance for two dyes, one anionic (remazol red, RR) and one cationic (methylene blue, MB). Both modifications extended the pH range of RR adsorption. The babassu oil modification increased adsorption capacity of the cationic dye MB, whereas the soybean oil modification increased that of RR. Such improvements demonstrate the potential of these two new CS modifications as adsorbent candidates for controlling dyes pollution in effluents. Copyright © 2017 Elsevier Ltd. All rights reserved.

Tea stains-inspired initiator primer for surface grafting of antifouling and antimicrobial polymer brush coatings.

PubMed

Pranantyo, Dicky; Xu, Li Qun; Neoh, Koon-Gee; Kang, En-Tang; Ng, Ying Xian; Teo, Serena Lay-Ming

2015-03-09

Inspired by tea stains, plant polyphenolic tannic acid (TA) was beneficially employed as the primer anchor for functional polymer brushes. The brominated TA (TABr) initiator primer was synthesized by partial modification of TA with alkyl bromide functionalities. TABr with trihydroxyphenyl moieties can readily anchor on a wide range of substrates, including metal, metal oxide, polymer, glass, and silicon. Concomitantly, the alkyl bromide terminals serve as initiation sites for atom transfer radical polymerization (ATRP). Cationic [2-(methacryloyloxy)ethyl]trimethylammonium chloride (META) and zwitterionic 2-methacryloyloxyethyl phosphorylcholine (MPC) and N-(3-sulfopropyl)-N-(methacryloxyethyl)-N,N-dimethylammonium betaine (SBMA) were graft-polymerized from the TABr-anchored stainless steel (SS) surface. The cationic polymer brushes on the modified surfaces are bactericidal, while the zwitterionic coatings exhibit resistance against bacterial adhesion. In addition, microalgal attachment (microfouling) and barnacle cyprid settlement (macrofouling) on the functional polymer-grafted surfaces were significantly reduced, in comparison to the pristine SS surface. Thus, the bifunctional TABr initiator primer provides a unique surface anchor for the preparation of functional polymer brushes for inhibiting both microfouling and macrofouling.

Hydrophobically-associating cationic polymers as micro-bubble surface modifiers in dissolved air flotation for cyanobacteria cell separation.

PubMed

Yap, R K L; Whittaker, M; Diao, M; Stuetz, R M; Jefferson, B; Bulmus, V; Peirson, W L; Nguyen, A V; Henderson, R K

2014-09-15

Dissolved air flotation (DAF), an effective treatment method for clarifying algae/cyanobacteria-laden water, is highly dependent on coagulation-flocculation. Treatment of algae can be problematic due to unpredictable coagulant demand during blooms. To eliminate the need for coagulation-flocculation, the use of commercial polymers or surfactants to alter bubble charge in DAF has shown potential, termed the PosiDAF process. When using surfactants, poor removal was obtained but good bubble adherence was observed. Conversely, when using polymers, effective cell removal was obtained, attributed to polymer bridging, but polymers did not adhere well to the bubble surface, resulting in a cationic clarified effluent that was indicative of high polymer concentrations. In order to combine the attributes of both polymers (bridging ability) and surfactants (hydrophobicity), in this study, a commercially-available cationic polymer, poly(dimethylaminoethyl methacrylate) (polyDMAEMA), was functionalised with hydrophobic pendant groups of various carbon chain lengths to improve adherence of polymer to a bubble surface. Its performance in PosiDAF was contrasted against commercially-available poly(diallyl dimethyl ammonium chloride) (polyDADMAC). All synthesised polymers used for bubble surface modification were found to produce positively charged bubbles. When applying these cationic micro-bubbles in PosiDAF, in the absence of coagulation-flocculation, cell removals in excess of 90% were obtained, reaching a maximum of 99% cell removal and thus demonstrating process viability. Of the synthesised polymers, the polymer containing the largest hydrophobic functionality resulted in highly anionic treated effluent, suggesting stronger adherence of polymers to bubble surfaces and reduced residual polymer concentrations. Copyright © 2014 Elsevier Ltd. All rights reserved.

Aqueous cationic, anionic and non-ionic multi-walled carbon nanotubes, functionalised with minimal framework damage, for biomedical application

PubMed Central

Chen, Shu; Hu, Sheng; Smith, Elizabeth F.; Ruenraroengsak, Pakatip; Thorley, Andrew J.; Menzel, Robert; Goode, Angela E.; Ryan, Mary P.; Tetley, Teresa D.; Porter, Alexandra E.; Shaffer, Milo S. P.

2014-01-01

The use of a thermochemical grafting approach provides a versatile means to functionalise as-synthesised, bulk multi-walled carbon nanotubes (MWNTs) without altering their inherent structure. The associated retention of properties is desirable for a wide range of commercial applications, including for drug delivery and medical purposes; it is also pertinent to studies of intrinsic toxicology. A systematic series of water-compatible MWNTs, with diameter around 12 nm have been prepared, to provide structurally-equivalent samples predominantly stabilised by anionic, cationic, or non-ionic groups. The surface charge of MWNTs was controlled by varying the grafting reagents and subsequent post-functionalisation modifications. The degree of grafting was established by thermal analysis (TGA). High resolution transmission electron microscope (HRTEM) and Raman measurements confirmed that the structural framework of the MWNTs was unaffected by the thermochemical treatment, in contrast to a conventional acid-oxidised control which was severely damaged. The effectiveness of the surface modification was demonstrated by significantly improved solubility and stability in both water and cell culture medium, and further quantified by zeta-potential analysis. The grafted MWNTs exhibited relatively low bioreactivity on human immortal alveolar epithelial type 1-like cells (TT1) following 24h exposure as demonstrated by 3-(4,5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium (MTS) and lactate dehydrogenase release (LDH) assays. The exposure of TT1 cells to MWNTs suppressed the release of the inflammatory mediators, interleukin 6 (IL-6) and interleukin 8 (IL-8). TEM cell uptake studies indicated efficient cellular entry of MWNTs into TT1 cells, via a range of mechanisms. Cationic MWNTs showed a more substantial interaction with TT1 cell membranes than anionic MWNTs, demonstrating a surface charge effect on cell uptake. PMID:24631251

Pore channel surface modification for enhancing anti-fouling membrane distillation

NASA Astrophysics Data System (ADS)

Qiu, Haoran; Peng, Yuelian; Ge, Lei; Villacorta Hernandez, Byron; Zhu, Zhonghua

2018-06-01

Membrane surface modification by forming a functional layer is an effective way to improve the anti-fouling properties of membranes; however, the additional layer and the potential blockage of bulk pores may increase the mass transfer resistance and reduce the permeability. In this study, we applied a novel method of preparing anti-fouling membranes for membrane distillation by dispersing graphene oxide (GO) on the channel surface of polyvinylidene fluoride membranes. The surface morphology and properties were characterized by scanning electron microscopy, atomic force microscope, and Fourier transform infrared spectrometry. Compared to the membrane surface modification by nanoparticles (e.g. SiO2), GO was mainly located on the pore surface of the membrane bulk, rather than being formed as an individual layer onto the membrane surface. The performance was evaluated via a direct-contact membrane distillation process with anionic and cationic surfactants as the foulants, separately. Compared to the pristine PVDF membrane, the anti-fouling behavior and distillate flux of the GO-modified membranes were improved, especially when using the anionic surfactant as the foulant. The enhanced anti-fouling performance can be attributed to the oxygen containing functional groups in GO and the healing of the membrane pore defects. This method may provide an effective route to manipulate membrane pore surface properties for anti-fouling separation without increasing mass transfer resistance.

Theoretical study of the atrazine pesticide interaction with pyrophyllite and Ca(2+) -montmorillonite clay surfaces.

PubMed

Belzunces, Bastien; Hoyau, Sophie; Benoit, Magali; Tarrat, Nathalie; Bessac, Fabienne

2017-01-30

Atrazine, a pesticide belonging to the s-triazine family, is one of the most employed pesticides. Due to its negative impact on the environment, it has been forbidden within the European Union since 2004 but remains abundant in soils. For these reasons, its behavior in soils and water at the atomic scale is of great interest. In this article, we have investigated, using DFT, the adsorption of atrazine onto two different clay surfaces: a pyrophyllite clay and an Mg-substituted clay named montmorillonite, with Ca 2+ compensating cations on its surface. The calculations show that the atrazine molecule is physisorbed on the pyrophyllite surface, evidencing the necessity to use dispersion-corrected computational methods. The adsorption energies of atrazine on montmorillonite are two to three times larger than on pyrophyllite, depending on the adsorption pattern. The computed adsorption energy is of about -30 kcal mol -1 for the two most stable montmorillonite-atrazine studied isomers. For these complexes, the large adsorption energy is related to the strong interaction between the chlorine atom of the atrazine molecule and one of the Ca 2+ compensating cations of the clay surface. The structural modifications induced by the adsorption are localized: for the surface, close to substitutions and particularly below the Ca 2+ cations; in the molecule, around the chlorine atom when Ca 2+ interacts strongly with this basic site in a monodentate mode. This study shows the important role of the alkaline earth cations on the adsorption of atrazine on clays, suggesting that the atrazine pesticide retention will be significant in Ca 2+ -montmorillonite clays. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Surface modification of montmorillonite on surface Acid-base characteristics of clay and thermal stability of epoxy/clay nanocomposites.

PubMed

Park, Soo-Jin; Seo, Dong-Il; Lee, Jae-Rock

2002-07-01

In this work, the effect of surface treatments on smectitic clay was investigated in surface energetics and thermal behaviors of epoxy/clay nanocomposites. The pH values, X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FT-IR) were used to analyze the effect of cation exchange on clay surface and the exfoliation phenomenon of clay interlayer. The surface energetics of clay and thermal properties of epoxy/clay nanocomposites were investigated in contact angles and thermogravimetric analysis (TGA), respectively. From the experimental results, the surface modification of clay by dodecylammonium chloride led to the increases in both distance between silicate layers of about 8 A and surface acid values, as well as in the electron acceptor component (gamma(+)(s)) of surface free energy, resulting in improved interfacial adhesion between basic (or electron donor) epoxy resins and acidic (electron acceptor) clay interlayers. Also, the thermal stability of nanocomposites was highly superior to pure epoxy resin due to the presence of the well-dispersed clay nanolayer, which has a barrier property in a composite system.

Surface Patterning Using Diazonium Ink Filled Nanopipette.

PubMed

Zhou, Min; Yu, Yun; Blanchard, Pierre-Yves; Mirkin, Michael V

2015-11-03

Molecular grafting of diazonium is a widely employed surface modification technique. Local electrografting of this species is a promising approach to surface doping and related properties tailoring. The instability of diazonium cation complicates this process, so that this species was generated in situ in many reported studies. In this Article, we report the egress transfer of aryl diazonium cation across the liquid/liquid interface supported at the nanopipette tip that can be used for controlled delivery this species to the external aqueous phase for local substrate patterning. An aryl diazonium salt was prepared with weakly coordinating and lipophilic tetrakis(pentafluorophenyl)borate anion stable as a solid and soluble in low polarity media. The chemically stable solution of this salt in 1,2-dichloroethane can be used as "diazonium ink". The ink-filled nanopipette was employed as a tip in the scanning electrochemical microscope (SECM) for surface patterning with the spatial resolution controlled by the pipette orifice radius and a few nanometers film thickness. The submicrometer-size grafted spots produced on the HOPG surface were located and imaged with the atomic force microscope (AFM).

Suppression of protein adsorption on a charged phospholipid polymer interface.

PubMed

Xu, Yan; Takai, Madoka; Ishihara, Kazuhiko

2009-02-09

High capability of a charged interface to suppress adsorption of both anionic and cationic proteins was reported. The interface was covalently constructed on quartz by modifying with an anionic phospholipid copolymer, poly(2-methacryloyloxyethyl phosphorylcholine (MPC)-co-n-butyl methacrylate (BMA)-co-potassium 3-methacryloyloxypropyl sulfonate (PMPS)-co-3-methacryloxypropyl trimethoxysilane (MPTMSi)) (PMBSSi). The PMBSSi interfaces were very hydrophilic and homogeneous and could function effectively for a long time even under long-term fluidic working conditions. The PMBSSi density on the interface, which was controllable by adjusting the PMBSSi concentration of the modification solution, affected the surface properties, including the surface contact angle, the surface roughness, and the surface zeta-potential. When a PMBSSi modification was applied, the adsorption of various proteins (isoelectric point varying from 1.0 to 11.0) on quartz was reduced to at least 87% in amount, despite the various electrical natures these proteins have. The protein adsorption behavior on the PMBSSi interface depended more on the PMBSSi density than on the surface charge. The PMBSSi modification had a stable impact on the surface, not only at the physiologic ionic strength, but also over a range of the ionic strength, suggesting that electrostatic interactions do not dominate the behavior of protein adsorption to the PMBSSi surface.

Layer by Layer, Nano-particle "Only" Surface Modification of Filtration Membranes

NASA Astrophysics Data System (ADS)

Escobar-Ferrand, Luis

Layer by Layer (LbL) deposition using primarily inorganic silica nanoparticles is employed for the modification of polymeric micro and ultrafiltration (MF/UF) membranes to produce thin film composites (TFC) with potential nanofiltration (NF) and reverse osmosis (RO) capabilities.. A variety of porous substrate membranes with different membrane surface characteristics are employed, but exhibiting in common that wicking of water does not readily occur into the pore structure, including polycarbonate track etched (PCTE), polyethersulfone (PES) and sulfonated PES (SPEES) MF/UF membranes. Both spherical (cationic/anionic) and eccentric elongated (anionic) silica nanoparticles are deposited using conditions similar to those reported by Lee et al. Appropriate selection of the pH's for anionic and cationic particle deposition enables the construction of nanoparticle only layers 100--1200 nm in thickness atop the original membrane substrates. The surface layer thickness varies monotonically with the number of bilayers (anionic/cationic deposition cycles) as expected. The deposition process is optimized to eliminate drying induced cracking and to improve mechanical durability via thickness control and post-deposition hydro-thermal treatment. The hydrodynamic permeability of these TFC membranes is measured to evaluate their performance under typical NF operating conditions using dead-end permeation experiments and their performance compared quantitatively with realistic hydrodynamic models, with favorable results. For track etched polycarbonate MF substrates, surface modification causes a permeability reduction of approximately two orders of magnitude with respect to the bare substrates, to values comparable to those for typical commercial NF membranes. Good quantitative agreement with hydrodynamic models with no adjustable parameters was also established for this case, providing indirect confirmation that the LbL deposited surface layers are largely defect (crack) free. Imaging of our TFC membranes after permeation tests confirmed that no significant mechanical damage resulted, indicating integrity and robustness of the LbL deposited surface layers in typical applications. The selectivity of these novel TFC membranes was also tested using standard "rejection" tests normally used to characterize NF and RO membranes for their capabilities in typical applications, such as water softening or desalination. We report the dextran standards molecular weight "cut-off" (MWCO) using mixed dextrans from 1.5 to 500 KDa in dead-end stir cells, and the percentage of rejection of standard bivalent and monovalent salt solutions using steady cross flow permeation experiments. The results confirm rejection of at least 60% of even the smallest dextrans, an estimated dextran MWCO of 20 KDa, and rejection of 10% and 20% for monovalent (NaCl) and bivalent (MgSO4) salts, respectively, for all the TFC membranes studied, while the unmodified membranes showed no rejection capability at all. The work supports that nanoparticle based LbL surface modification of MF/UF membranes can produce filtration quality media for important water purification applications, such as nanofiltration (NF) softening processes, natural organic matter (NOM) elimination and possibly reverse osmosis (RO) desalination.

A Chemical-Adsorption Strategy to Enhance the Reaction Kinetics of Lithium-Rich Layered Cathodes via Double-Shell Surface Modification.

PubMed

Guo, Lichao; Li, Jiajun; Cao, Tingting; Wang, Huayu; Zhao, Naiqin; He, Fang; Shi, Chunsheng; He, Chunnian; Liu, Enzuo

2016-09-21

Sluggish surface reaction kinetics hinders the power density of Li-ion battery. Thus, various surface modification techniques have been applied to enhance the electronic/ionic transfer kinetics. However, it is challenging to obtain a continuous and uniform surface modification layer on the prime particles with structure integration at the interface. Instead of classic physical-adsorption/deposition techniques, we propose a novel chemical-adsorption strategy to synthesize double-shell modified lithium-rich layered cathodes with enhanced mass transfer kinetics. On the basis of experimental measurement and first-principles calculation, MoO2S2 ions are proved to joint the layered phase via chemical bonding. Specifically, the Mo-O or Mo-S bonds can flexibly rotate to bond with the cations in the layered phase, leading to the good compatibility between the thiomolybdate adsorption layer and layered cathode. Followed by annealing treatment, the lithium-excess-spinel inner shell forms under the thiomolybdate adsorption layer and functions as favorable pathways for lithium and electron. Meanwhile, the nanothick MoO3-x(SO4)x outer shell protects the transition metal from dissolution and restrains electrolyte decomposition. The double-shell modified sample delivers an enhanced discharge capacity almost twice as much as that of the unmodified one at 1 A g(-1) after 100 cycles, demonstrating the superiority of the surface modification based on chemical adsorption.

Mitigating oxygen loss to improve the cycling performance of high capacity cation-disordered cathode materials

DOE PAGES

Lee, Jinhyuk; Papp, Joseph K.; Clément, Raphaële J.; ...

2017-10-17

Recent progress in the understanding of percolation theory points to cation-disordered lithium-excess transition metal oxides as high-capacity lithium-ion cathode materials. Nevertheless, the oxygen redox processes required for these materials to deliver high capacity can trigger oxygen loss, which leads to the formation of resistive surface layers on the cathode particles. Here, we demonstrate here that, somewhat surprisingly, fluorine can be incorporated into the bulk of disordered lithium nickel titanium molybdenum oxides using a standard solid-state method to increase the nickel content, and that this compositional modification is very effective in reducing oxygen loss, improving energy density, average voltage, and ratemore » performance. We argue that the valence reduction on the anion site, offered by fluorine incorporation, opens up significant opportunities for the design of high-capacity cation-disordered cathode materials.« less

Mitigating oxygen loss to improve the cycling performance of high capacity cation-disordered cathode materials

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

Lee, Jinhyuk; Papp, Joseph K.; Clément, Raphaële J.

Recent progress in the understanding of percolation theory points to cation-disordered lithium-excess transition metal oxides as high-capacity lithium-ion cathode materials. Nevertheless, the oxygen redox processes required for these materials to deliver high capacity can trigger oxygen loss, which leads to the formation of resistive surface layers on the cathode particles. Here, we demonstrate here that, somewhat surprisingly, fluorine can be incorporated into the bulk of disordered lithium nickel titanium molybdenum oxides using a standard solid-state method to increase the nickel content, and that this compositional modification is very effective in reducing oxygen loss, improving energy density, average voltage, and ratemore » performance. We argue that the valence reduction on the anion site, offered by fluorine incorporation, opens up significant opportunities for the design of high-capacity cation-disordered cathode materials.« less

Organo/Zn-Al LDH Nanocomposites for Cationic Dye Removal from Aqueous Media

NASA Astrophysics Data System (ADS)

Starukh, G.; Rozovik, O.; Oranska, O.

2016-04-01

Cationic dye sorption by Zn-Al-layered double hydroxides (LDHs) modified with anionic surfactants was examined using methylene blue (MB) dye as a compound model in aqueous solutions. The modification of Zn-Al LDHs was performed by reconstruction method using dodecyl sulfate anion (DS) solutions. DS contained Zn-Al LDHs were characterized by XRD, FTIR, thermogravimetric, and SEM analysis. The reconstructed organo/Zn-Al LDHs comprise the crystalline phases (DS-intercalated LDHs, hydrotalcite), and the amorphous phase. The intercalation of DS ions into the interlayer galleries and DS adsorption on the surface of the LDHs occurred causing the MB adsorption on the external and its sorption in the internal surfaces of modified LDHs. The presence of DS greatly increased the affinity of organo/Zn-Al LDHs for MB due to hydrophobic interactions between the surfactants and the dye molecules. The optical properties of sorbed MB were studied.

Recent advances on biosorption by aerobic granular sludge.

PubMed

Wang, Li; Liu, Xiang; Lee, Duu-Jong; Tay, Joo-Hwa; Zhang, Yi; Wan, Chun-Li; Chen, Xiao-Feng

2018-06-04

Aerobic granular sludge is a form of microbial auto-aggregation, and a promising biotechnology for wastewater treatment. This review aims at providing the first comprehensive, systematic, and in-depth overview on the application of aerobic granules as biosorbents. The target pollutants encompass heavy metals (both cationic and oxyanionic), nuclides, dyes, and inorganic non-metal substances. Different granule types are discussed, i.e. intact and fragmented, compact and fluffy, original and modified, and the effects of granule surface modification are introduced. A detailed comparison is conducted on the characteristics of granular biomass, the conditions of the adsorption tests, and the resultant performance towards various sorbates. Analytical and mathematical tools typically employed are presented, and possible interactions between the pollutants and granules are theorized, leading to an analysis on the mechanisms of the adsorption processes. Original granules appear highly effective towards cationic metals, while surface modification by organic and inorganic agents can expand their applicability to other pollutants. Combined with their advantages of high mechanical strength, density, and settling speed, aerobic granules possess exceptional potential in real wastewater treatment as biosorbents. Possible future research, both fundamental and practical, is suggested to gain more insights into the mechanism of their function, and to advance their industrial application. Copyright © 2018 Elsevier B.V. All rights reserved.

PRE- AND POST-SYNAPTIC EFFECTS OF MANIPULATING SURFACE CHARGE WITH DIVALENT CATIONS AT THE PHOTORECEPTOR SYNAPSE

PubMed Central

CADETTI, L.; THORESON, W. B.; PICCOLINO, M.

2006-01-01

Persistence of horizontal cell (HC) light responses in extracellular solutions containing low Ca2+ plus divalent cations to block Ca2+ currents (ICa) has been attributed to Ca2+-independent neurotransmission. Using a retinal slice preparation to record both ICa and light responses, we demonstrate that persistence of HC responses in low [Ca2+]o can instead be explained by a paradoxical increase of Ca2+ influx into photoreceptor terminals arising from surface charge-mediated shifts in ICa activation. Consistent with this explanation, application of Zn2+ or Ni2+ caused a hyperpolarizing block of HC light responses that was relieved by lowering [Ca2+]o. The same concentrations of Zn2+ and Ni2+ reduced the amplitude of ICa at the rod dark potential and this reduction was relieved by a hyperpolarizing shift in voltage dependence induced by lowering [Ca2+]o. Block of ICa by Mg2+, which has weak surface charge effects, was not relieved by low [Ca2+]o. Recovery of HC responses in low [Ca2+]o was assisted by enhancement of rod light responses. To bypass light stimulation, OFF bipolar cells were stimulated by steps to −40 mV applied to presynaptic rods during simultaneous paired recordings. Consistent with surface charge theory, the post-synaptic current was inhibited by Zn2+ and this inhibition was relieved by lowering [Ca2+]o. Nominally divalent-free media produced inversion of HC light responses even though rod light responses remained hyperpolarizing; HC response inversion can be explained by surface charge-mediated shifts in ICa. In summary, HC light responses modifications induced by low divalent cation solutions can be explained by effects on photoreceptor light responses and membrane surface charge without necessitating Ca2+-independent neurotransmission. Furthermore, these results suggest that surface charge effects accompanying physiological changing divalent cation levels in the synaptic cleft may provide a means for modulating synaptic output from photoreceptors. PMID:15541900

A facile method to modify bentonite nanoclay with silane

NASA Astrophysics Data System (ADS)

Abeywardena, Sujani B. Y.; Perera, Srimala; Nalin de Silva, K. M.; Tissera, Nadeeka P.

2017-07-01

Immobilization of smectite clay onto a desirable surface has received much attention, since its nanospace can be utilized for many applications in material science. Here, we present an efficient method to functionalize surface of bentonite nanoclay (BNC) through the grafting of 3-aminotriethoxysilane (APTES). Infrared spectroscopy and elemental analysis confirmed the presence of organic chains and amine groups in modified nanoclay. XRD analysis confirmed grafting of APTES on the surface of bentonite nanoclay without intercalation. The accomplishment of the surface modification was quantitatively proved by TGA analysis. Modified BNC can covalently couple with different material surfaces, allowing its nanospace to be utilized for intercalation of cations, bio-molecules, and polymeric materials, to be used in advanced military aerospace, pharmaceuticals, and many other commercial applications.

Engineered/designer biochar for contaminant removal/immobilization from soil and water: Potential and implication of biochar modification.

PubMed

Rajapaksha, Anushka Upamali; Chen, Season S; Tsang, Daniel C W; Zhang, Ming; Vithanage, Meththika; Mandal, Sanchita; Gao, Bin; Bolan, Nanthi S; Ok, Yong Sik

2016-04-01

The use of biochar has been suggested as a means of remediating contaminated soil and water. The practical applications of conventional biochar for contaminant immobilization and removal however need further improvements. Hence, recent attention has focused on modification of biochar with novel structures and surface properties in order to improve its remediation efficacy and environmental benefits. Engineered/designer biochars are commonly used terms to indicate application-oriented, outcome-based biochar modification or synthesis. In recent years, biochar modifications involving various methods such as, acid treatment, base treatment, amination, surfactant modification, impregnation of mineral sorbents, steam activation and magnetic modification have been widely studied. This review summarizes and evaluates biochar modification methods, corresponding mechanisms, and their benefits for contaminant management in soil and water. Applicability and performance of modification methods depend on the type of contaminants (i.e., inorganic/organic, anionic/cationic, hydrophilic/hydrophobic, polar/non-polar), environmental conditions, remediation goals, and land use purpose. In general, modification to produce engineered/designer biochar is likely to enhance the sorption capacity of biochar and its potential applications for environmental remediation. Copyright © 2016 Elsevier Ltd. All rights reserved.

Aqueous cationic, anionic and non-ionic multi-walled carbon nanotubes, functionalised with minimal framework damage, for biomedical application.

PubMed

Chen, Shu; Hu, Sheng; Smith, Elizabeth F; Ruenraroengsak, Pakatip; Thorley, Andrew J; Menzel, Robert; Goode, Angela E; Ryan, Mary P; Tetley, Teresa D; Porter, Alexandra E; Shaffer, Milo S P

2014-06-01

The use of a thermochemical grafting approach provides a versatile means to functionalise as-synthesised, bulk multi-walled carbon nanotubes (MWNTs) without altering their inherent structure. The associated retention of properties is desirable for a wide range of commercial applications, including for drug delivery and medical purposes; it is also pertinent to studies of intrinsic toxicology. A systematic series of water-compatible MWNTs, with diameter around 12 nm have been prepared, to provide structurally-equivalent samples predominantly stabilised by anionic, cationic, or non-ionic groups. The surface charge of MWNTs was controlled by varying the grafting reagents and subsequent post-functionalisation modifications. The degree of grafting was established by thermal analysis (TGA). High resolution transmission electron microscope (HRTEM) and Raman measurements confirmed that the structural framework of the MWNTs was unaffected by the thermochemical treatment, in contrast to a conventional acid-oxidised control which was severely damaged. The effectiveness of the surface modification was demonstrated by significantly improved solubility and stability in both water and cell culture medium, and further quantified by zeta-potential analysis. The grafted MWNTs exhibited relatively low bioreactivity on transformed human alveolar epithelial type 1-like cells (TT1) following 24 h exposure as demonstrated by 3-(4,5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium (MTS) and lactate dehydrogenase release (LDH) assays. The exposure of TT1 cells to MWNTs suppressed the release of the inflammatory mediators, interleukin 6 (IL-6) and interleukin 8 (IL-8). TEM cell uptake studies indicated efficient cellular entry of MWNTs into TT1 cells, via a range of mechanisms. Cationic MWNTs showed a more substantial interaction with TT1 cell membranes than anionic MWNTs, demonstrating a surface charge effect on cell uptake. Copyright © 2014 Elsevier Ltd. All rights reserved.

Salt- and pH-induced desorption: Comparison between non-aggregated and aggregated mussel adhesive protein, Mefp-1, and a synthetic cationic polyelectrolyte.

PubMed

Krivosheeva, Olga; Dedinaite, Andra; Claesson, Per M

2013-10-15

Mussel adhesive proteins are of great interest in many applications due to their ability to bind strongly to many types of surfaces under water. Effective use such proteins, for instance the Mytilus edulis foot protein - Mefp-1, for surface modification requires achievement of a large adsorbed amount and formation of a layer that is resistant towards desorption under changing conditions. In this work we compare the adsorbed amount and layer properties obtained by using a sample containing small Mefp-1 aggregates with that obtained by using a non-aggregated sample. We find that the use of the sample containing small aggregates leads to higher adsorbed amount, larger layer thickness and similar water content compared to what can be achieved with a non-aggregated sample. The layer formed by the aggregated Mefp-1 was, after removal of the protein from bulk solution, exposed to aqueous solutions with high ionic strength (up to 1M NaCl) and to solutions with low pH in order to reduce the electrostatic surface affinity. It was found that the preadsorbed Mefp-1 layer under all conditions explored was significantly more resistant towards desorption than a layer built by a synthetic cationic polyelectrolyte with similar charge density. These results suggest that the non-electrostatic surface affinity for Mefp-1 is larger than for the cationic polyelectrolyte. Copyright © 2013 The Authors. Published by Elsevier Inc. All rights reserved.

Epitope mapping of imidazolium cations in ionic liquid-protein interactions unveils the balance between hydrophobicity and electrostatics towards protein destabilisation.

PubMed

Silva, Micael; Figueiredo, Angelo Miguel; Cabrita, Eurico J

2014-11-14

We investigated imidazolium-based ionic liquid (IL) interactions with human serum albumin (HSA) to discern the level of cation interactions towards protein stability. STD-NMR spectroscopy was used to observe the imidazolium IL protons involved in direct binding and to identify the interactions responsible for changes in Tm as accessed by differential scanning calorimetry (DSC). Cations influence protein stability less than anions but still significantly. It was found that longer alkyl side chains of imidazolium-based ILs (more hydrophobic) are associated with a higher destabilisation effect on HSA than short-alkyl groups (less hydrophobic). The reason for such destabilisation lies on the increased surface contact area of the cation with the protein, particularly on the hydrophobic contacts promoted by the terminus of the alkyl chain. The relevance of the hydrophobic contacts is clearly demonstrated by the introduction of a polar moiety in the alkyl chain: a methoxy or alcohol group. Such structural modification reduces the degree of hydrophobic contacts with HSA explaining the lesser extent of protein destabilisation when compared to longer alkyl side chain groups: above [C2mim](+). Competition STD-NMR experiments using [C2mim](+), [C4mim](+) and [C2OHmim](+) also validate the importance of the hydrophobic interactions. The combined effect of cation and anion interactions was explored using (35)Cl NMR. Such experiments show that the nature of the cation has no influence on the anion-protein contacts, still the nature of the anion modulates the cation-protein interaction. Herein we propose that more destabilising anions are likely to be a result of a partial contribution from the cation as a direct consequence of the different levels of interaction (cation-anion pair and cation-protein).

Synergistic effect of cationic and anionic surfactants for the modification of Ca-montmorillonite

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

Zhang, Zepeng, E-mail: zhangzp@cugb.edu.cn; Zhang, Jichu; Liao, Libing, E-mail: bliao@cugb.edu.cn

2013-05-15

Highlights: ► The basal spacing of MMT–CTAB–SDS reaches 5.30 nm. ► MMT–CTAB–SDS shows perfect dispersion property and excellent heat resistance. ► SDS helped to improve the heat resistance and decrease the surface energy of the MMT–CTAB–SDS particles. - Abstract: The synergistic effect of cationic surfactant (CTAB) and anionic surfactant (SDS) for the modification of Ca-montmorillonite (Ca-MMT) has been developed, and the novel cation–anion modified organomontmorillonite (MMT–CTAB–SDS) was prepared. X-ray diffraction (XRD) analysis indicates that the interlayer spacing of montmorillonite was well expanded by the intercalation of CTAB and SDS and the basal spacing increased from 1.54 nm (Ca-MMT) to 5.30more » nm (MMT–CTAB–SDS). Thermogravimetric analysis (TG) showed that the MMT–CTAB–SDS displayed excellent heat resistance. Scanning electron microscopy (SEM) analysis proved that the MMT–CTAB–SDS exhibited excellent dispersion property and the plates with few silicate layers can be observed. Contact angle tests indicated that the hydrophilicity of MMT–CTAB–SDS was lower than that of Ca-MMT and higher than that of MMT–CTAB. It was verified that SDS contributed to expanding the interlayer space, further improved the heat resistance of the MMT–CTAB and decreased the surface energy of the MMT–CTAB–SDS particles.« less

A study on air bubble wetting: Role of surface wettability, surface tension, and ionic surfactants

NASA Astrophysics Data System (ADS)

George, Jijo Easo; Chidangil, Santhosh; George, Sajan D.

2017-07-01

Fabrication of hydrophobic/hydrophilic surfaces by biomimicking nature has attracted significant attention recently due to their potential usage in technologies, ranging from self-cleaning to DNA condensation. Despite the potential applications, compared to surfaces of tailored wettability, less attention has been paid towards development and understanding of air bubble adhesion and its dynamics on surfaces with varying wettability. In this manuscript, following the commonly used approach of oxygen plasma treatment, polydimethylsiloxane surfaces with tunable wettability are prepared. The role of plasma treatment conditions on the surface hydrophilicity and the consequent effect on adhesion dynamics of an underwater air bubble is explored for the first time. The ATR-FTIR spectroscopic analysis reveals that the change in hydrophilicity arises from the chemical modification of the surface, manifested as Si-OH vibrations in the spectra. The thickness of the formed thin liquid film at the surface responsible for the experimentally observed air bubble repellency is estimated from the augmented Young-Laplace equation. The concentration dependent studies using cationic as well as anionic surfactant elucidate that the reduced surface tension of the aqueous solution results in a stable thicker film and causes non-adherence of air bubble to the aerophilic surface. Furthermore, the study carried out to understand the combined effect of plasma treatment and surfactants reveals that even below critical micelle concentration, a negatively charged surface results in air bubble repellency for the anionic surfactant, whereas only enhanced air bubble contact angle is observed for the cationic surfactant.

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.

Surface degradation of Li1-xNi0.80Co0.15Al0.05O2 cathodes: Correlating charge transfer impedance with surface phase transformations

NASA Astrophysics Data System (ADS)

Sallis, S.; Pereira, N.; Mukherjee, P.; Quackenbush, N. F.; Faenza, N.; Schlueter, C.; Lee, T.-L.; Yang, W. L.; Cosandey, F.; Amatucci, G. G.; Piper, L. F. J.

2016-06-01

The pronounced capacity fade in Ni-rich layered oxide lithium ion battery cathodes observed when cycling above 4.1 V (versus Li/Li+) is associated with a rise in impedance, which is thought to be due to either bulk structural fatigue or surface reactions with the electrolyte (or combination of both). Here, we examine the surface reactions at electrochemically stressed Li1-xNi0.8Co0.15Al0.05O2 binder-free powder electrodes with a combination of electrochemical impedance spectroscopy, spatially resolving electron microscopy, and spatially averaging X-ray spectroscopy techniques. We circumvent issues associated with cycling by holding our electrodes at high states of charge (4.1 V, 4.5 V, and 4.75 V) for extended periods and correlate charge-transfer impedance rises observed at high voltages with surface modifications retained in the discharged state (2.7 V). The surface modifications involve significant cation migration (and disorder) along with Ni and Co reduction, and can occur even in the absence of significant Li2CO3 and LiF. These data provide evidence that surface oxygen loss at the highest levels of Li+ extraction is driving the rise in impedance.

Adsorptive behaviour of mercury on algal biomass: competition with divalent cations and organic compounds.

PubMed

Carro, Leticia; Barriada, José L; Herrero, Roberto; Sastre de Vicente, Manuel E

2011-08-15

Biosorption processes constitute an effective technique for mercury elimination. Sorption properties of native and acid-treated Sargassum muticum have been studied. Effect of pH, initial mercury concentration and contact time studies provided fundamental information about the sorption process. This information was used as the reference values to analyse mercury sorption under competition conditions. Saline effect has shown little influence in sorption, when only electrostatic modifications took place upon salt addition. On the contrary, if mercury speciation dramatically changed owing to the addition of an electrolyte, such as in the case of chloride salt, very large modifications in mercury sorption were observed. Competition with other divalent cations or organic compounds has shown little or none effect on mercury, indicating that a different mechanism is taking place during the removal of these pollutants. Finally, continuous flow experiments have clearly shown that a reduction process is also taking place during mercury removal. This fact is not obvious to elucidate under batch sorption experiments. Scanning Electron Microscopy analysis of the surface of the materials show deposits of mercury(I) and metallic mercury which is indicative of the reduction process proposed. Copyright © 2011 Elsevier B.V. All rights reserved.

Cationic polymer brush-modified cellulose nanocrystals for high-affinity virus binding

NASA Astrophysics Data System (ADS)

Rosilo, Henna; McKee, Jason R.; Kontturi, Eero; Koho, Tiia; Hytönen, Vesa P.; Ikkala, Olli; Kostiainen, Mauri A.

2014-09-01

Surfaces capable of high-affinity binding of biomolecules are required in several biotechnological applications, such as purification, transfection, and sensing. Therein, the rod-shaped, colloidal cellulose nanocrystals (CNCs) are appealing due to their large surface area available for functionalization. In order to exploit electrostatic binding, their intrinsically anionic surfaces have to be cationized as biological supramolecules are predominantly anionic. Here we present a facile way to prepare cationic CNCs by surface-initiated atom-transfer radical polymerization of poly(N,N-dimethylaminoethyl methacrylate) and subsequent quaternization of the polymer pendant amino groups. The cationic polymer brush-modified CNCs maintained excellent dispersibility and colloidal stability in water and showed a ζ-potential of +38 mV. Dynamic light scattering and electron microscopy showed that the modified CNCs electrostatically bind cowpea chlorotic mottle virus and norovirus-like particles with high affinity. Addition of only a few weight percent of the modified CNCs in water dispersions sufficed to fully bind the virus capsids to form micrometer-sized assemblies. This enabled the concentration and extraction of the virus particles from solution by low-speed centrifugation. These results show the feasibility of the modified CNCs in virus binding and concentrating, and pave the way for their use as transduction enhancers for viral delivery applications.Surfaces capable of high-affinity binding of biomolecules are required in several biotechnological applications, such as purification, transfection, and sensing. Therein, the rod-shaped, colloidal cellulose nanocrystals (CNCs) are appealing due to their large surface area available for functionalization. In order to exploit electrostatic binding, their intrinsically anionic surfaces have to be cationized as biological supramolecules are predominantly anionic. Here we present a facile way to prepare cationic CNCs by surface-initiated atom-transfer radical polymerization of poly(N,N-dimethylaminoethyl methacrylate) and subsequent quaternization of the polymer pendant amino groups. The cationic polymer brush-modified CNCs maintained excellent dispersibility and colloidal stability in water and showed a ζ-potential of +38 mV. Dynamic light scattering and electron microscopy showed that the modified CNCs electrostatically bind cowpea chlorotic mottle virus and norovirus-like particles with high affinity. Addition of only a few weight percent of the modified CNCs in water dispersions sufficed to fully bind the virus capsids to form micrometer-sized assemblies. This enabled the concentration and extraction of the virus particles from solution by low-speed centrifugation. These results show the feasibility of the modified CNCs in virus binding and concentrating, and pave the way for their use as transduction enhancers for viral delivery applications. Electronic supplementary information (ESI) available: CNC surface chain fraction and degree of substitution after BriBBr modification, NMR spectra of the SI-ATRP reaction mixture at 0 and 120 min, conversion of the DMAEMA monomer during SI-ATRP, DLS size distribution profiles of CNCs and CNC-g-P(QDMAEMA), TEM images of NoV-VLPs and their complexes with CNC-g-P(QDMAEMA) at 0 mM NaCl. See DOI: 10.1039/c4nr03584d

Surface modification of silk fibroin fabric using layer-by-layer polyelectrolyte deposition and heparin immobilization for small-diameter vascular prostheses.

PubMed

Elahi, M Fazley; Guan, Guoping; Wang, Lu; Zhao, Xinzhe; Wang, Fujun; King, Martin W

2015-03-03

There is an urgent need to develop a biologically active implantable small-diameter vascular prosthesis with long-term patency. Silk-fibroin-based small-diameter vascular prosthesis is a promising candidate having higher patency rate; however, the surface modification is indeed required to improve its further hemocompatibility. In this study, silk fibroin fabric was modified by a two-stage process. First, the surface of silk fibroin fabric was coated using a layer-by-layer polyelectrolyte deposition technique by stepwise dipping the silk fibroin fabric into a solution of cationic poly(allylamine hydrochloride) (PAH) and anionic poly(acrylic acid) (PAA) solution. The dipping procedure was repeated to obtain the PAH/PAA multilayers deposited on the silk fibroin fabrics. Second, the polyelectrolyte-deposited silk fibroin fabrics were treated in EDC/NHS-activated low-molecular-weight heparin (LMWH) solution at 4 °C for 24 h, resulting in immobilization of LMWH on the silk fibroin fabrics surface. Scanning electron microscopy, atomic force microscopy, and energy-dispersive X-ray data revealed the accomplishment of LMWH immobilization on the polyelectrolyte-deposited silk fibroin fabric surface. The higher the number of PAH/PAA coating layers on the silk fibroin fabric, the more surface hydrophilicity could be obtained, resulting in a higher fetal bovine serum protein and platelets adhesion resistance properties when tested in vitro. In addition, compared with untreated sample, the surface-modified silk fibroin fabrics showed negligible loss of bursting strength and thus reveal the acceptability of polyelectrolytes deposition and heparin immobilization approach for silk-fibroin-based small-diameter vascular prostheses modification.

Surface Electrochemical Modification of a Nickel Substrate to Prepare a NiFe-based Electrode for Water Oxidation.

PubMed

Guo, Dingyi; Qi, Jing; Zhang, Wei; Cao, Rui

2017-01-20

The slow kinetics of water oxidation greatly jeopardizes the efficiency of water electrolysis for H 2 production. Developing highly active water oxidation electrodes with affordable fabrication costs is thus of great importance. Herein, a Ni II Fe III surface species on Ni metal substrate was generated by electrochemical modification of Ni in a ferrous solution by a fast, simple, and cost-effective procedure. In the prepared Ni II Fe III catalyst film, Fe III was incorporated uniformly through controlled oxidation of Fe II cations on the electrode surface. The catalytically active Ni II originated from the Ni foam substrate, which ensured the close contact between the catalyst and the support toward improved charge-transfer efficiency. The as-prepared electrode exhibited high activity and long-term stability for electrocatalytic water oxidation. The overpotentials required to reach water oxidation current densities of 50, 100, and 500 mA cm -2 are 276, 290, and 329 mV, respectively. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mechanism-based post-translational modification and inactivation in terpene synthases

DOE PAGES

Kersten, Roland D.; Diedrich, Jolene K.; Yates, III, John R.; ...

2015-09-17

Terpenes are ubiquitous natural chemicals with diverse biological functions spanning all three domains of life. In specialized metabolism, the active sites of terpene synthases (TPSs) evolve in shape and reactivity to direct the biosynthesis of a myriad of chemotypes for organismal fitness. As most terpene biosynthesis mechanistically involves highly reactive carbocationic intermediates, the protein surfaces catalyzing these cascade reactions possess reactive regions possibly prone to premature carbocation capture and potentially enzyme inactivation. Here, we show using proteomic and X-ray crystallographic analyses that cationic intermediates undergo capture by conserved active site residues leading to inhibitory self-alkylation. Furthermore, the level of cation-mediatedmore » inactivation increases with mutation of the active site, upon changes in the size and structure of isoprenoid diphosphate substrates, and alongside increases in reaction temperatures. TPSs that individually synthesize multiple products are less prone to self-alkylation then TPSs possessing relatively high product specificity. In total, the results presented suggest that mechanism-based alkylation represents an overlooked mechanistic pressure during the evolution of cation-derived terpene biosynthesis.« less

Strong Cation Exchange Chromatography in Analysis of Posttranslational Modifications: Innovations and Perspectives

PubMed Central

Edelmann, Mariola J.

2011-01-01

Strong cation exchange (SCX) chromatography has been utilized as an excellent separation technique that can be combined with reversed-phase (RP) chromatography, which is frequently used in peptide mass spectrometry. Although SCX is valuable as the second component of such two-dimensional separation methods, its application goes far beyond efficient fractionation of complex peptide mixtures. Here I describe how SCX facilitates mapping of the protein posttranslational modifications (PTMs), specifically phosphorylation and N-terminal acetylation. The SCX chromatography has been mainly used for enrichment of these two PTMs, but it might also be beneficial for high-throughput analysis of other modifications that alter the net charge of a peptide. PMID:22174558

Degradation of oxygen reduction reaction kinetics in porous La0.6Sr0.4Co0.2Fe0.8O3-δ cathodes due to aging-induced changes in surface chemistry

NASA Astrophysics Data System (ADS)

Baqué, Laura C.; Soldati, Analía L.; Teixeira-Neto, Erico; Troiani, Horacio E.; Schreiber, Anja; Serquis, Adriana C.

2017-01-01

The modification of surface composition after long-term operation is one of the most reported degradation mechanisms of (La,Sr)(Co,Fe)O3-δ (LSCFO) cathodes for Solid Oxide Fuel Cells (SOFCs). Nevertheless, its effect on the oxygen reduction reaction kinetics of porous LSCFO cathodes has not been yet reliably established. In this work, La- and Sr-enrichment at the LSCFO surface of porous cathodes has been induced after 50 h aging at 800 °C under air. Such cation redistribution can extend up to ∼400 nm depth under the LSCFO surface as detected by high resolution Scanning Transmission Electron Microscopy-Energy Dispersive Spectroscopy maps acquired inside the cathode pores. The observed surface chemical changes hamper the oxygen surface exchange reaction at the LSCFO/gas interface. Accordingly, a suitable Electrochemical Impedance Spectroscopy analysis revealed that the oxygen ion conductivity remains practically unaltered during the aging treatment while the oxygen surface exchange resistance increases up to 1.8 times. As a result, the cathode impedance response deteriorates within the 10-0.1 Hz frequency range during the aging treatment, resulting in a total cathode area specific resistance increase of 150%. The methodology adopted has demonstrated to be very valuable for studying the degradation of SOFC cathodes produced by the modification of surface composition.

Improvement of charge separation in TiO{sub 2} by its modification with different tungsten compounds

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

Tryba, B., E-mail: beata.tryba@zut.edu.pl; Tygielska, M.; Grzeskowiak, M.

2016-04-15

Highlights: • Ammonium m-tungstate doped to TiO{sub 2} highly improved charge separation in TiO{sub 2}. • Negative electrokinetic potential of TiO{sub 2} facilitates holes migration to its surface. • Fast migration of holes to TiO{sub 2} surfaces increased yield of OH radicals formation. • Adsorption of dyes on photocatalyst increased its decomposition under visible light. - Abstract: Three different tungsten precursors were used for TiO{sub 2} modification: H{sub 2}WO{sub 4}, WO{sub 2}, and ammonium m-tungstate. It was proved that modification of TiO{sub 2} with tungsten compounds enhanced its photocatalytic activity through the improvement of charge separation. This effect was obtainedmore » by coating of TiO{sub 2} particles with tungsten compound, which changed their surficial electrokinetical potential from positive onto negative. The most efficient tungsten compound, which caused enhanced separation of free carriers was ammonium m-tungstate (AMT). Two dyes with different ionic potential were used for the photocatalytic decomposition. It appeared that cationic dye—Methylene Blue was highly adsorbed on the negatively charged surface of TiO{sub 2} modified by AMT and decomposed, however this photocatalyst was quickly deactivated whereas anionic dye—acid red was better adsorbed on the less acidic surface of TiO{sub 2} and was rapidly decomposed with almost the same rate in the five following cycles.« less

Localization of cesium on montmorillonite surface investigated by frequency modulation atomic force microscopy

NASA Astrophysics Data System (ADS)

Araki, Yuki; Satoh, Hisao; Okumura, Masahiko; Onishi, Hiroshi

2017-11-01

Cation exchange of clay mineral is typically analyzed without microscopic study of the clay surfaces. In order to reveal the distribution of exchangeable cations at the clay surface, we performed in situ atomic-scale observations of the surface changes in Na-rich montmorillonite due to exchange with Cs cations using frequency modulation atomic force microscopy (FM-AFM). Lines of protrusion were observed on the surface in aqueous CsCl solution. The amount of Cs of the montmorillonite particles analyzed by energy dispersive X-ray spectrometry was consistent with the ratio of the number of linear protrusions to all protrusions in the FM-AFM images. The results showed that the protrusions represent adsorbed Cs cations. The images indicated that Cs cations at the surface were immobile, and their occupancy remained constant at 10% of the cation sites at the surface with different immersion times in the CsCl solution. This suggests that the mobility and the number of Cs cations at the surface are controlled by the permanent charge of montmorillonite; however, the Cs distribution at the surface is independent of the charge distribution of the inner silicate layer. Our atomic-scale observations demonstrate that surface cations are distributed in different ways in montmorillonite and mica.

A Post-synthetic Modification of II–VI Nanoparticles to Create Tb3+ and Eu3+ Luminophores

PubMed Central

Mukherjee, Prasun; Sloan, Robin F.; Shade, Chad M.; Waldeck, David H.; Petoud, Stéphane

2013-01-01

We describe a novel method for creating luminescent lanthanide-containing nanoparticles in which the lanthanide cations are sensitized by the semiconductor nanoparticle’s electronic excitation. In contrast to previous strategies, this new approach creates such materials by addition of external salt to a solution of fully formed nanoparticles. We demonstrate this post-synthetic modification for the lanthanide luminescence sensitization of two visible emitting lanthanides (Ln), Tb3+ and Eu3+ ions, through ZnS nanoparticles in which the cations were added post-synthetically as external Ln(NO3)3·xH2O salt to solutions of ZnS nanoparticles. The post-synthetically treated ZnS nanoparticle systems display Tb3+ and Eu3+ luminescence intensities that are comparable to those of doped Zn(Ln)S nanoparticles, which we reported previously (J. Phys. Chem. A, 2011, 115, 4031–4041). A comparison with the synthetically doped systems is used to contrast the spatial distribution of the lanthanide ions, bulk versus surface localized. The post-synthetic strategy described in this work is fundamentally different from the synthetic incorporation (doping) approach and offers a rapid and less synthetically demanding protocol for Tb3+:ZnS and Eu3+:ZnS luminophores, thereby facilitating their use in a broad range of applications. PMID:23997842

Correlation between physicochemical properties of modified clinoptilolite and its performance in the removal of ammonia-nitrogen.

PubMed

Dong, Yingbo; Lin, Hai; He, Yinhai

2017-03-01

The physicochemical properties of the 24 modified clinoptilolite samples and their ammonia-nitrogen removal rates were measured to investigate the correlation between them. The modified clinoptilolites obtained by acid modification, alkali modification, salt modification, and thermal modification were used to adsorb ammonia-nitrogen. The surface area, average pore width, macropore volume, mecropore volume, micropore volume, cation exchange capacity (CEC), zeta potential, silicon-aluminum ratios, and ammonia-nitrogen removal rate of the 24 modified clinoptilolite samples were measured. Subsequently, the linear regression analysis method was used to research the correlation between the physicochemical property of the different modified clinoptilolite samples and the ammonia-nitrogen removal rate. Results showed that the CEC was the major physicochemical property affecting the ammonia-nitrogen removal performance. According to the impacts from strong to weak, the order was CEC > silicon-aluminum ratios > mesopore volume > micropore volume > surface area. On the contrary, the macropore volume, average pore width, and zeta potential had a negligible effect on the ammonia-nitrogen removal rate. The relational model of physicochemical property and ammonia-nitrogen removal rate of the modified clinoptilolite was established, which was ammonia-nitrogen removal rate = 1.415[CEC] + 173.533 [macropore volume] + 0.683 [surface area] + 4.789[Si/Al] - 201.248. The correlation coefficient of this model was 0.982, which passed the validation of regression equation and regression coefficients. The results of the significance test showed a good fit to the correlation model.

Rapid and extensive debromination of decabromodiphenyl ether by smectite clay-templated subnanoscale zero-valent iron.

PubMed

Yu, Kai; Gu, Cheng; Boyd, Stephen A; Liu, Cun; Sun, Cheng; Teppen, Brian J; Li, Hui

2012-08-21

Subnanoscale zerovalent iron (ZVI) synthesized using smectite clay as a template was utilized to investigate reduction of decabromodiphenyl ether (DBDE). The results revealed that DBDE was rapidly debrominated by the prepared smectite-templated ZVI with a reaction rate 10 times greater than that by conventionally prepared nanoscale ZVI. This enhanced reduction is plausibly attributed to the smaller-sized smectite-templated ZVI clusters (∼0.5 nm) vs that of the conventional nanoscale ZVI (∼40 nm). The degradation of DBDE occurred in a stepwise debromination manner. Pentabromodiphenyl ethers were the terminal products in an alkaline suspension (pH 9.6) of smectite-templated ZVI, whereas di-, tri-, and tetrabromodiphenyl ethers formed at the neutral pH. The presence of tetrahydrofuran (THF) as a cosolvent at large volume fractions (e.g., >70%) in water reduced the debromination rates due to enhanced aggregation of clay particles and/or diminished adsorption of DBDE to smectite surfaces. Modification of clay surfaces with tetramethylammonium (TMA) attenuated the colsovent effect on the aggregation of clay particles, resulting in enhanced debromination rates. Smectite clay provides an ideal template to form subnanoscale ZVI, which demonstrated superior debromination reactivity with DBDE compared with other known forms of ZVIs. The ability to modify the nature of smectite clay surface by cation exchange reaction utilizing organic cations can be harnessed to create surface properties compatible with various contaminated sites.

The use of Interferometric Microscopy to assess 3D modifications of deteriorated medieval glass.

NASA Astrophysics Data System (ADS)

Gentaz, L.; Lombardo, T.; Chabas, A.

2012-04-01

Due to low durability, Northern European medieval glass undergoes the action of the atmospheric environment leading in some cases to a state of dramatic deterioration. Modification features varies from a simple loss of transparency to a severe material loss. In order to understand the underlying mechanisms and preserve this heritage, fundamental research is necessary too. In this optic, field exposure of analogues and original stained glass was carried out to study the early stages of the glass weathering. Model glass and original stained glass (after removal of deterioration products) were exposed in real conditions in an urban site (Paris) for 48 months. A regular withdrawal of samples allowed a follow-up of short-term glass evolution. Morphological modifications of the exposed samples were investigated through conventional and non destructive microscopy, using respectively a Scanning Electron Microscope (SEM) and an Interferometric Microscope (IM). This latter allows a 3D quantification of the object with no sample preparation. For all glasses, both surface recession and build-up of deposit were observed as a consequence of a leaching process (interdiffusion of protons and glass cations). The build-up of a deposit comes from the reaction between the extracted glass cations and atmospheric gases. Instead, surface recession is due mainly to the formation of brittle layer of altered glass at the sub-surface, where a fracture network can appear, leading to the scaling of parts of this modified glass. Finally, dissolution of the glass takes place, inducing the formation of pits and craters. The arithmetic roughness (Ra) was used as an indicator of weathering increase, in order to evaluate the deterioration state. For instance, the Ra grew from few tens of nm for pristine glass to thousands of nm for scaled areas. This technique also allowed a precise quantification of dimensions (height, depth and width) of deposits and pits, and the estimation of their overall distribution. Finally, IM allows the quantification of the volume of lost matter due to scaling, by studying the surface coverage of the different depths. The preliminary studies show that IM is a very effective, non-destructive and non-intrusive technique for the quantification of glass weathering, to be used complementarily to other investigations. Further applications, especially to the description of the depositions, are currently under way.

T-style keratoprosthesis based on surface-modified poly (2-hydroxyethyl methacrylate) hydrogel for cornea repairs.

PubMed

Xiang, Jun; Sun, Jianguo; Hong, Jiaxu; Wang, Wentao; Wei, Anji; Le, Qihua; Xu, Jianjiang

2015-05-01

Corneal disease is a common cause of blindness, and keratoplasty is considered as an effective treatment method. However, there is a severe shortage of donor corneas worldwide. This paper presents a novel T-style design of a keratoprosthesis and its preparation methods, in which a mechanically and structurally effective artificial cornea is made based on a poly(2-hydroxyethyl methacrylate) hydrogel. The porous skirt was modified with hyaluronic acid and cationized gelatin, and the bottom of the optical column was coated with poly(ethylene glycol). The physical properties of the T-style Kpro were analyzed using ultraviolet and visible spectrophotometry and electron scanning microscopy. The surface chemical properties were characterized using Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The surface modification in the spongy skirt promoted cell adhesion and produced a firm bond between the corneal tissue and the implant device, while the surface modification in the optic column resisted cell adhesion and prevented retroprosthetic membrane formation. Through improved surgical techniques, the novel T-style keratoprosthesis provides enough mechanical stability to facilitate long-term biointegration with the host environment. In vivo implantation experiments showed that the T-style keratoprosthesis is a promising cornea alternative for patients with severe limbal stem cell deficiency and corneal opacity. Copyright © 2015 Elsevier B.V. All rights reserved.

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

A stable lithium-rich surface structure for lithium-rich layered cathode materials

PubMed Central

Kim, Sangryun; Cho, Woosuk; Zhang, Xiaobin; Oshima, Yoshifumi; Choi, Jang Wook

2016-01-01

Lithium ion batteries are encountering ever-growing demand for further increases in energy density. Li-rich layered oxides are considered a feasible solution to meet this demand because their specific capacities often surpass 200 mAh g−1 due to the additional lithium occupation in the transition metal layers. However, this lithium arrangement, in turn, triggers cation mixing with the transition metals, causing phase transitions during cycling and loss of reversible capacity. Here we report a Li-rich layered surface bearing a consistent framework with the host, in which nickel is regularly arranged between the transition metal layers. This surface structure mitigates unwanted phase transitions, improving the cycling stability. This surface modification enables a reversible capacity of 218.3 mAh g−1 at 1C (250 mA g−1) with improved cycle retention (94.1% after 100 cycles). The present surface design can be applied to various battery electrodes that suffer from structural degradations propagating from the surface. PMID:27886178

Cesium-Induced Ionic Conduction through a Single Nanofluidic Pore Modified with Calixcrown Moieties.

PubMed

Ali, Mubarak; Ahmed, Ishtiaq; Ramirez, Patricio; Nasir, Saima; Cervera, Javier; Mafe, Salvador; Niemeyer, Christof M; Ensinger, Wolfgang

2017-09-12

We demonstrate experimentally and theoretically a nanofluidic device for the selective recognition of the cesium ion by exploiting host-guest interactions inside confined geometry. For this purpose, a host molecule, i.e., the amine-terminated p-tert-butylcalix[4]arene-crown (t-BuC[4]C-NH 2 ), is successfully synthesized and functionalized on the surface of a single conical nanopore fabricated in a poly(ethylene terephthalate) (PET) membrane through carbodiimide coupling chemistry. On exposure to the cesium cation, the t-BuC[4]C-Cs + complex is formed through host-guest interaction, leading to the generation of positive fixed charges on the pore surface. The asymmetrical distribution of these groups along the conical nanopore leads to the electrical rectification observed in the current-voltage (I-V) curve. On the contrary, other alkali cations are not able to induce any significant change in the rectification characteristics of the nanopore. The success of the chemical modification is monitored from the changes in the electrical readout of the nanopore. Theoretical results based on the Nernst-Planck and Poisson equations further demonstrate the validity of the experimental approach to the cesium-induced ionic conduction of the nanopore.

Modification of wheat gluten for improvement of binding capacity with keratin in hair

NASA Astrophysics Data System (ADS)

Wang, Shukun; Meng, Danyang; Wang, Sisi; Zhang, Zhong; Yang, Ruijin; Zhao, Wei

2018-02-01

In this study, enzymatic hydrolysis and cationization with epoxypropyldodecyldimethylammonium chloride of wheat protein, an economic protein complex containing great amount of disulfide bonds, were conducted to improve properties such as solubility and disassociation behaviour for recovery of damaged hair when used in shampoo. The optimal conditions for enzymatic hydrolysis were pH 8.2, 55°C with Alcalase for 60 min. After the selected hydrolysis, the degree of hydrolysis, nitrogen solubility index, foaming capacity index, foam stability index, emulsifying activity index and emulsion stability index of hydrolysate with 58.71% of short-chain peptides (less than 1000 Da) were 8.81%, 39.07%, 225%, 56.67%, 9.62 m2 g-1 and 49.08, respectively. The cationization was followed to raise the isoelectric point of wheat protein hydrolysate from 7.0 to 10.0, which could facilitate the quaternized protein hydrolysate to adhere to the surface of hair at the range of pH 5-6 of hair care products to form more disulfide bonds. The results show that a shampoo with quaternized wheat proteins hydrolysate possesses excellent properties in recovering damaged hair, making the surface of hair smooth and compact.

Modification of wheat gluten for improvement of binding capacity with keratin in hair

PubMed Central

Meng, Danyang; Wang, Sisi; Zhang, Zhong; Yang, Ruijin; Zhao, Wei

2018-01-01

In this study, enzymatic hydrolysis and cationization with epoxypropyldodecyldimethylammonium chloride of wheat protein, an economic protein complex containing great amount of disulfide bonds, were conducted to improve properties such as solubility and disassociation behaviour for recovery of damaged hair when used in shampoo. The optimal conditions for enzymatic hydrolysis were pH 8.2, 55°C with Alcalase for 60 min. After the selected hydrolysis, the degree of hydrolysis, nitrogen solubility index, foaming capacity index, foam stability index, emulsifying activity index and emulsion stability index of hydrolysate with 58.71% of short-chain peptides (less than 1000 Da) were 8.81%, 39.07%, 225%, 56.67%, 9.62 m2 g−1 and 49.08, respectively. The cationization was followed to raise the isoelectric point of wheat protein hydrolysate from 7.0 to 10.0, which could facilitate the quaternized protein hydrolysate to adhere to the surface of hair at the range of pH 5–6 of hair care products to form more disulfide bonds. The results show that a shampoo with quaternized wheat proteins hydrolysate possesses excellent properties in recovering damaged hair, making the surface of hair smooth and compact. PMID:29515840

Efficient stabilization of Saccharomyces cerevisiae external invertase by immobilisation on modified beidellite nanoclays.

PubMed

Andjelković, Uroš; Milutinović-Nikolić, Aleksandra; Jović-Jovičić, Nataša; Banković, Predrag; Bajt, Teja; Mojović, Zorica; Vujčić, Zoran; Jovanović, Dušan

2015-02-01

The external invertase isoform 1 (EINV1) was immobilised on eight differently modified beidellite nanoclays. Modifications were composed of organo-modification with different amounts of surfactant - hexadecyl trimethylammonium cation (HDTMA), pillaring with Al/Fe containing polyhydroxy cations and acid modification of Na-enriched and pillared clays. The modified nanoclays were characterised by XRD, N2-physisorption, SEM and FT-IR spectroscopy. The amount of bound enzyme activity was significantly influenced by the modification of beidellite ranging from 50 to remarkable 2200U/g. Biochemical characterization was performed for five modified nanoclays showing the highest enzyme activity after invertase immobilisation. The investigation demonstrated that after immobilisation the structure and the catalytic properties of invertase were preserved, while Km values were slightly increased from 26 to 37mM. immobilisation significantly improved thermal and storage stability of EINV1. Results indicate that beidellite nanoclays obtained by low cost modifications can be applied as a suitable support for the immobilisation of invertase. The immobilizate can be efficiently engaged in sucrose hydrolysis in batch reactor. Copyright © 2014 Elsevier Ltd. All rights reserved.

Influence of pyrolysis temperature on lead immobilization by chemically modified coconut fiber-derived biochars in aqueous environments.

PubMed

Wu, Weidong; Li, Jianhong; Niazi, Nabeel Khan; Müller, Karin; Chu, Yingchao; Zhang, Lingling; Yuan, Guodong; Lu, Kouping; Song, Zhaoliang; Wang, Hailong

2016-11-01

Biochar has received widespread attention as an eco-friendly and efficient material for immobilization of toxic heavy metals in aqueous environments. In the present study, three types of coconut fiber-derived biochars were obtained by pyrolyzing at three temperatures, i.e., 300, 500, and 700 °C. In addition, nine types of biochars were prepared by chemical modification with ammonia, hydrogen peroxide, and nitric acid, respectively, which were used to investigate changes in physico-chemical properties by inter alia, Fourier transformation infrared spectrophotometry (FTIR), scanning electron microscope (SEM), and BET specific surface area analysis. Batch sorption experiments were carried out to determine the sorption capacity of the biochars for lead (Pb) in aqueous solutions. Results showed that the cation exchange capacity of biochar pyrolyzed at 300 °C and modified with nitric acid increased threefold compared to the control. Loosely corrugated carbon surface and uneven carbon surface of the biochar pyrolyzed at 300 °C were produced during ammonia and nitric acid modifications. Removal rate of Pb by the coconut biochar pyrolyzed at 300 °C and modified with ammonia was increased from 71.8 to 99.6 % compared to the untreated biochar in aqueous solutions containing 100 mg L -1 Pb. However, chemical modification did not enhance adsorption of Pb of the biochars pyrolyzed at higher temperatures (e.g., 500 or 700 °C), indicating that resistance of biochars to chemical treatment increased with pyrolysis temperature.

Ternary mixtures of ionic liquids for better salt solubility, conductivity and cation transference number improvement

PubMed Central

Karpierz, E.; Niedzicki, L.; Trzeciak, T.; Zawadzki, M.; Dranka, M.; Zachara, J.; Żukowska, G. Z.; Bitner-Michalska, A.; Wieczorek, W.

2016-01-01

We hereby present the new class of ionic liquid systems in which lithium salt is introduced into the solution as a lithium cation−glyme solvate. This modification leads to the reorganisation of solution structure, which entails release of free mobile lithium cation solvate and hence leads to the significant enhancement of ionic conductivity and lithium cation transference numbers. This new approach in composing electrolytes also enables even three-fold increase of salt concentration in ionic liquids. PMID:27767069

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

NASA Astrophysics Data System (ADS)

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

2011-05-01

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

Electronic modification of Cu-based chalcopyrite semiconductors induced by lattice deformation and composition alchemy

NASA Astrophysics Data System (ADS)

Jiang, F. D.; Feng, J. Y.

2008-02-01

Using first principles calculation, we systematically investigate the electronic modification of Cu-based chalcopyrite semiconductors induced by lattice deformation and composition alchemy. It is shown that the optical band gap Eg is remarkably sensitive to the anion displacement μ, resulting from the opposite shifts of conduction band minimum and valence band maximum. Meanwhile, the dependence of structural parameters of alloyed compounds on alloy composition x is demonstrated for both cation and anion alloying. The d orbitals of group-III cations are found to be of great importance in the calculation. Abnormal changes in the optical band gap Eg induced by anion alloying are addressed.

Electrografting of thionine diazonium cation onto the graphene edges and decorating with Au nano-dendrites or glucose oxidase: Characterization and electrocatalytic applications.

PubMed

Shervedani, Reza Karimi; Amini, Akbar; Sadeghi, Nima

2016-03-15

Thionine (Th) diazonium cation is covalently attached onto the glassy carbon (GC) electrode via graphene nanosheets (GNs) (GC-GNs-Th). The GC-GNs-Th electrode is subjected to further modifications to fabricate (i) glucose and (ii) nitrite sensors. Further modifications include: (i) direct immobilization of glucose oxidase (GOx) and (ii) electrodeposition of gold dendrite-like nanostructures (DGNs) on the GC-GNs-Th surface, constructing GC-GNs-Th-GOx and GC-GNs-Th-DGNs modified electrodes, respectively. The GC-GNs-Th-GOx biosensor exhibited a linear response range to glucose, from 0.5 to 6.0mM, with a limit of detection (LOD) of 9.6 μM and high sensitivity of 43.2 µAcm(-2)mM(-1). Also, the GC-GNs-Th-DGNs sensor showed a wide dynamic response range for NO2(-) ion with two linear parts, from 0.05 μM to 1.0 μM and 30.0 μM to 1.0mM, a sensitivity of 263.2 μAmM(-1) and a LOD of 0.01 μM. Applicability of the modified electrodes was successfully tested by determination of glucose in human blood serum and nitrite in water based on addition/recovery tests. Copyright © 2015 Elsevier B.V. All rights reserved.

Hybrid Nanomaterial Complexes for Advanced Phage-guided Gene Delivery

PubMed Central

Yata, Teerapong; Lee, Koon-Yang; Dharakul, Tararaj; Songsivilai, Sirirurg; Bismarck, Alexander; Mintz, Paul J; Hajitou, Amin

2014-01-01

Developing nanomaterials that are effective, safe, and selective for gene transfer applications is challenging. Bacteriophages (phage), viruses that infect bacteria only, have shown promise for targeted gene transfer applications. Unfortunately, limited progress has been achieved in improving their potential to overcome mammalian cellular barriers. We hypothesized that chemical modification of the bacteriophage capsid could be applied to improve targeted gene delivery by phage vectors into mammalian cells. Here, we introduce a novel hybrid system consisting of two classes of nanomaterial systems, cationic polymers and M13 bacteriophage virus particles genetically engineered to display a tumor-targeting ligand and carry a transgene cassette. We demonstrate that the phage complex with cationic polymers generates positively charged phage and large aggregates that show enhanced cell surface attachment, buffering capacity, and improved transgene expression while retaining cell type specificity. Moreover, phage/polymer complexes carrying a therapeutic gene achieve greater cancer cell killing than phage alone. This new class of hybrid nanomaterial platform can advance targeted gene delivery applications by bacteriophage. PMID:25118171

Modification of carbon nanotubes with fluorinated ionic liquid for improving processability of fluoro-ethylene-propylene

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

Ma, Hongyang; Chu, Benjamin; Hsiao, Benjamin S.

Fluorinated ionic liquid (F-IL), 1-(3-perfluorooctylpropyl)-3-methylimidazolium bis(perfluoroethylsufonyl)amine, had been successfully prepared and employed to modify multi-wall carbon nanotubes (MWCNTs) for improving the processability of fluoro-ethylene-propylene (FEP). The thermally decomposed temperature of F-IL was higher than 350 °C measured by thermal gravimetric analysis (TGA) which indicated that the fluorinated ionic liquid could be suitable for melting blend with FEP (blending at 290 °C) by a twin-screw extruder. Through “cation-π” interaction between the imidazolium cation of F-IL and the graphene surface of MWCNTs, MWCNTs can be modified with F-IL and used as nanofillers to improve the dispersity of MWCNTs in fluorocopolymer FEP verifiedmore » by SEM images of the FEP nanocomposite. The structural characterization and mechanical property of FEP nanocomposite during the deformation were investigated by tensile experiments and simultaneous time-resolved wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) techniques.« less

The effects of cations and anions on hydrogen chemisorption at Pt

NASA Technical Reports Server (NTRS)

Huang, J. C.; Ogrady, W. E.; Yeager, E.

1977-01-01

Experimental evidence based on linear sweep voltammetry is presented to substantiate the view that ionic adsorption substantially shifts electrode potentials in addition to the relative heights of the hydrogen adsorption peaks. HClO4 and HF are chosen as better reference electrolytes for anion studies. The voltammetry curves for 0.1M HF and 0.1M HClO4 as well as the effect of adding successively increasing amounts of H2SO4 to these electrolytes are discussed. The measurements are also extended to alkaline solutions. Mechanisms whereby the addition of various cations and anions to electrolytes such as HF and HClO4 can induce changes in the structure of the hydrogen adsorption region in the voltammetry curves are identified: (1) blocking of sites by anion adsorption and coupling of hydrogen adsorption and anion desorption, (2) modification in the hydrogen adsorption energies for sites adjacent to adsorbed anions, (3) changes in the potential distribution across the interface, and (4) surface restructuring.

Effect of pH on the adsorption of dodecylamine on montmorillonite: Insights from experiments and molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Peng, Chenliang; Min, Fanfei; Liu, Lingyun

2017-12-01

The hydrophobic aggregation in cationic surfactant suspension is an effective method to enhance the dewatering of clay-rich tailing. The solution pH can affect the adsorption behavior of cationic surfactant on clay mineral. The effect of pH on the adsorption of dodecylamine (DDA) on montmorillonite was investigated by the sedimentation test and the characterization of flocs images, contact angle, adsorption quantity, and fourier transform infrared (FTIR) spectroscopy, as well as molecular dynamics (MD) simulation. It was found that DDA ions were adsorbed on montmorillonite basal surfaces mainly by physical adsorption, including the electrostatic attraction and hydrogen bonding. A certain number of neutral DDA molecules can favor the adsorption of DDA. At pH around 8, the effect of hydrophobic modification was the best because DDA molecules and ions form compact and well-organized monolayer. The MD simulation results were in good agreement with that of contact angle, adsorption quantity and FTIR.

Elucidating the role of surface chemistry on cationic phosphorus dendrimer-siRNA complexation.

PubMed

Deriu, Marco A; Tsapis, Nicolas; Noiray, Magali; Grasso, Gianvito; El Brahmi, Nabil; Mignani, Serge; Majoral, Jean-Pierre; Fattal, Elias; Danani, Andrea

2018-06-14

In the field of dendrimers targeting small interfering RNA (siRNA) delivery, dendrimer structural properties, such as the flexibility/rigidity ratio, play a crucial role in the efficiency of complexation. However, advances in organic chemistry have enabled the development of dendrimers that differ only by a single atom on their surface terminals. This is the case for cationic phosphorus dendrimers functionalized with either pyrrolidinium (DP) or morpholinium (DM) terminal groups. This small change was shown to strongly affect the dendrimer-siRNA complexation, leading to more efficient anti-inflammatory effects in the case of DP. Reasons for this different behavior can hardly be inferred only by biological in vitro and in vivo experiments due to the high number of variables and complexity of the investigated biological system. However, an understanding of how small chemical surface changes may completely modify the overall dendrimer-siRNA complexation is a significant breakthrough towards the design of efficient dendrimers for nucleic acid delivery. Herein, we present experimental and computational approaches based on isothermal titration calorimetry and molecular dynamics simulations to elucidate the molecular reasons behind different efficiencies and activities of DP and DM. Results of the present research highlight how chemical surface modifications may drive the overall dendrimer-siRNA affinity by influencing enthalpic and entropic contributions of binding free energy. Moreover, this study elucidates molecular reasons related to complexation stoichiometry that may be crucial in determining the dendrimer complexation efficiency.

Cask weeping mitigation

DOEpatents

Krumhansl, James L.; Brady, Patrick V.; Teter, David M.; McConnell, Paul

2007-09-18

A method (and concomitant kit) for treating a surface to reduce subsequent .sup.137Cs nuclide desorption comprising contacting the surface with a first cation-containing solution, the cation being one or more of Cs.sup.+, Rb.sup.+, Ag.sup.+, Tl.sup.+, K.sup.+, and NH.sub.4.sup.+, and contacting the surface with a second cation-containing solution, the cation being one or more of Cs.sup.+, Rb.sup.+, Ag.sup.+, Tl.sup.+, K.sup.+, and NH.sub.4.sup.+, thereby reducing amounts of radioactive cesium embedded in clays found on the surface.

Sequence and Structure Dependent DNA-DNA Interactions

NASA Astrophysics Data System (ADS)

Kopchick, Benjamin; Qiu, Xiangyun

Molecular forces between dsDNA strands are largely dominated by electrostatics and have been extensively studied. Quantitative knowledge has been accumulated on how DNA-DNA interactions are modulated by varied biological constituents such as ions, cationic ligands, and proteins. Despite its central role in biology, the sequence of DNA has not received substantial attention and ``random'' DNA sequences are typically used in biophysical studies. However, ~50% of human genome is composed of non-random-sequence DNAs, particularly repetitive sequences. Furthermore, covalent modifications of DNA such as methylation play key roles in gene functions. Such DNAs with specific sequences or modifications often take on structures other than the canonical B-form. Here we present series of quantitative measurements of the DNA-DNA forces with the osmotic stress method on different DNA sequences, from short repeats to the most frequent sequences in genome, and to modifications such as bromination and methylation. We observe peculiar behaviors that appear to be strongly correlated with the incurred structural changes. We speculate the causalities in terms of the differences in hydration shell and DNA surface structures.

Assembly of RNA nanostructures on supported lipid bilayers

PubMed Central

Dabkowska, Aleksandra P.; Michanek, Agnes; Jaeger, Luc; Rabe, Michael; Chworos, Arkadiusz; Höök, Fredrik; Nylander, Tommy; Sparr, Emma

2014-01-01

The assembly of nucleic acid nanostructures with controlled size and shape has large impact in the fields of nanotechnology, nanomedicine and synthetic biology. The directed arrangement of nanostructures at interfaces is important for many applications. In spite of this, the use of laterally mobile lipid bilayers to control RNA three-dimensional nanostructure formation on surfaces remains largely unexplored. Here, we direct the self-assembly of RNA building blocks into three-dimensional structures of RNA on fluid lipid bilayers composed of cationic 1,2-dioleoyl-3-trimethylammonium-propane (DOTAP) or mixtures of zwitterionic 1,2-dioleoyl-sn-glycero-3-phosphatidylcholine (DOPC) and cationic sphingosine. We demonstrate the stepwise supramolecular assembly of discrete building blocks through specific and selective RNA-RNA interactions, based on results from quartz crystal microbalance with dissipation (QCM-D), ellipsometry, fluorescence recovery after photobleaching (FRAP) and total internal reflection fluorescence microscopy (TIRF) experiments. The assembly can be controlled to give a densely packed single layer of RNA polyhedrons at the fluid lipid bilayer surface. We show that assembly of the 3D structure can be modulated by sequence specific interactions, surface charge and changes in the salt composition and concentration. In addition, the tertiary structure of the RNA polyhedron can be controllably switched from an extended structure to one that is dense and compact. The versatile approach to building up three-dimensional structures of RNA does not require modification of the surface or the RNA molecules, and can be used as a bottom-up means of nanofabrication of functionalized bio-mimicking surfaces. PMID:25417592

Mechanisms of metal sorption by biochars: Biochar characteristics and modifications.

PubMed

Li, Hongbo; Dong, Xiaoling; da Silva, Evandro B; de Oliveira, Letuzia M; Chen, Yanshan; Ma, Lena Q

2017-07-01

Biochar produced by thermal decomposition of biomass under oxygen-limited conditions has received increasing attention as a cost-effective sorbent to treat metal-contaminated waters. However, there is a lack of information on the roles of different sorption mechanisms for different metals and recent development of biochar modification to enhance metal sorption capacity, which is critical for biochar field application. This review summarizes the characteristics of biochar (e.g., surface area, porosity, pH, surface charge, functional groups, and mineral components) and main mechanisms governing sorption of As, Cr, Cd, Pb, and Hg by biochar. Biochar properties vary considerably with feedstock material and pyrolysis temperature, with high temperature producing biochars with higher surface area, porosity, pH, and mineral contents, but less functional groups. Different mechanisms dominate sorption of As (complexation and electrostatic interactions), Cr (electrostatic interactions, reduction, and complexation), Cd and Pb (complexation, cation exchange, and precipitation), and Hg (complexation and reduction). Besides sorption mechanisms, recent advance in modifying biochar by loading with minerals, reductants, organic functional groups, and nanoparticles, and activation with alkali solution to enhance metal sorption capacity is discussed. Future research needs for field application of biochar include competitive sorption mechanisms of co-existing metals, biochar reuse, and cost reduction of biochar production. Published by Elsevier Ltd.

Photophysical and antibacterial properties of complex systems based on smectite, a cationic surfactant and methylene blue.

PubMed

Donauerová, Alena; Bujdák, Juraj; Smolinská, Miroslava; Bujdáková, Helena

2015-10-01

Solid or colloidal materials with embedded photosensitizers are promising agents from the medical or environmental perspective, where the direct use of photoactive solutions appears to be problematic. Colloids based on layered silicates of the saponite (Sap) and montmorillonite (Mon) type, including those modified with dodecylammonium cations (C12) and photosensitizer--methylene blue (MB) were studied. Two representatives of bacteria, namely Enterobacter cloacae and Escherichia coli, were selected for this work. A spectral study showed that MB solutions and also colloids with Sap including C12 exhibited the highest photoactivities. The antimicrobial properties of the smectite colloids were not directly linked to the photoactivity of the adsorbed MB cations. They were also influenced by other parameters, such as light vs. dark conditions, the spectrum, power and duration of the light used for the irradiation; growth phases, and the pre-treatment of microorganisms. Both the photoactivity and antimicrobial properties of the colloids were improved upon pre-modification with C12. Significantly higher antimicrobial properties were observed for the colloids based on Mon with MB in the form of molecular aggregates without significant photoactivities. The MB/Mon colloids, both modified and non-modified with C12 cations, exhibited higher antimicrobial effects than pure MB solution. Besides the direct effect of photosensitization, the surface properties of the silicate particles likely played a crucial role in the interactions with microorganisms. Copyright © 2015 Elsevier B.V. All rights reserved.

Surface modification of TiO{sub 2} nanoparticles with carotenoids. EPR study

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

Konovalova, T.A.; Kispert, L.D.; Konovalov, V.V.

1999-06-03

Among the semiconductors, titanium dioxide is the most suitable for many environmental applications. EPR measurements demonstrate efficient charge separation on carotenoid-modified titanium dioxide nanoparticles (7 nm). Strong complexation of carotenoids containing terminal carboxy groups ({minus}CO{sub 2}H) with the TiO{sub 2} surface leads to electron transfer from the adsorbed carotenoid molecule to the surface trapping site. For these systems, EPR signals of the carotenoid radical cations Car{sup {sm_bullet}+} and the electrons trapped on the TiO{sub 2} are observed before irradiation (77 K). Their UV-visible spectra show an absorption band with a maximum near 650 nm that is characteristic of the trappedmore » electrons. Surface modification of the TiO{sub 2} by other carotenoids results in the formation of a complex with an optical absorption band near 545 nm. These systems form charge-separated pairs [Car{sup {sm_bullet}+}{hor_ellipsis}TiO{sub 2}(e{sup {minus}}{sub tr}){sub surf}. TiO{sub 2}(e{sup {minus}}{sub tr}){sub latt}] only upon 365--600 nm illumination at 77 K. Complexation of the TiO{sub 2} colloids with carotenoids enhances spatial charge separation, shifts the absorption threshold into the visible region, and thus greatly improves the reducing ability of the semiconductor. Photoreduction of acceptor molecules such as 2,5-dichloro-1,4-benzoquinone, nitrobenzene, and oxygen is demonstrated.« less

DNA Is an Antimicrobial Component of Neutrophil Extracellular Traps

PubMed Central

Halverson, Tyler W.R.; Wilton, Mike; Poon, Karen K. H.; Petri, Björn; Lewenza, Shawn

2015-01-01

Neutrophil extracellular traps (NETs) comprise an ejected lattice of chromatin enmeshed with granular and nuclear proteins that are capable of capturing and killing microbial invaders. Although widely employed to combat infection, the antimicrobial mechanism of NETs remains enigmatic. Efforts to elucidate the bactericidal component of NETs have focused on the role of NET-bound proteins including histones, calprotectin and cathepsin G protease; however, exogenous and microbial derived deoxyribonuclease (DNase) remains the most potent inhibitor of NET function. DNA possesses a rapid bactericidal activity due to its ability to sequester surface bound cations, disrupt membrane integrity and lyse bacterial cells. Here we demonstrate that direct contact and the phosphodiester backbone are required for the cation chelating, antimicrobial property of DNA. By treating NETs with excess cations or phosphatase enzyme, the antimicrobial activity of NETs is neutralized, but NET structure, including the localization and function of NET-bound proteins, is maintained. Using intravital microscopy, we visualized NET-like structures in the skin of a mouse during infection with Pseudomonas aeruginosa. Relative to other bacteria, P. aeruginosa is a weak inducer of NETosis and is more resistant to NETs. During NET exposure, we demonstrate that P. aeruginosa responds by inducing the expression of surface modifications to defend against DNA-induced membrane destabilization and NET-mediated killing. Further, we show induction of this bacterial response to NETs is largely due to the bacterial detection of DNA. Therefore, we conclude that the DNA backbone contributes both to the antibacterial nature of NETs and as a signal perceived by microbes to elicit host-resistance strategies. PMID:25590621

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.

Self-Assembled Multivalent (SAMul) Polyanion Binding-Impact of Hydrophobic Modifications in the Micellar Core on DNA and Heparin Binding at the Peripheral Cationic Ligands.

PubMed

Albanyan, Buthaina; Laurini, Erik; Posocco, Paola; Pricl, Sabrina; Smith, David K

2017-05-05

This paper reports a small family of cationic surfactants designed to bind polyanions such as DNA and heparin. Each molecule has the same hydrophilic cationic ligand and a hydrophobic aliphatic group with eighteen carbon atoms with one, two, or three alkene groups within the hydrophobic chain (C18-1, C18-2 and C18-3). Dynamic light scattering indicates that more alkenes lead to geometric distortion, giving rise to larger self-assembled multivalent (SAMul) nanostructures. Mallard Blue and Ethidium Bromide dye displacement assays demonstrate that heparin and DNA have markedly different binding preferences, with heparin binding most effectively to C18-1, and DNA to C18-3, even though the molecular structural differences of these SAMul systems are buried in the hydrophobic core. Multiscale modelling suggests that adaptive heparin maximises enthalpically favourable interactions with C18-1, while shape-persistent DNA forms a similar number of interactions with each ligand display, but with slightly less entropic cost for binding to C18-3-fundamental thermodynamic differences in SAMul binding of heparin or DNA. This study therefore provides unique insight into electrostatic molecular recognition between highly charged nanoscale surfaces in biologically relevant systems. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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

2015-04-01

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

Surface Enrichment in Equimolar Mixtures of Non-Functionalized and Functionalized Imidazolium-Based Ionic Liquids.

PubMed

Heller, Bettina S J; Kolbeck, Claudia; Niedermaier, Inga; Dommer, Sabine; Schatz, Jürgen; Hunt, Patricia; Maier, Florian; Steinrück, Hans-Peter

2018-04-12

For equimolar mixtures of ionic liquids with imidazolium-based cations of very different electronic structure, we observe very pronounced surface enrichment effects by angle-resolved X-ray photoelectron spectroscopy (XPS). For a mixture with the same anion, that is, 1-methyl-3-octylimidazolium hexafluorophosphate+1,3-di(methoxy)imidazolium hexafluorophosphate ([C 8 C 1 Im][PF 6 ]+[(MeO) 2 Im][PF 6 ]), we find a strong enrichment of the octyl chain-containing [C 8 C 1 Im] + cation and a corresponding depletion of the [(MeO) 2 Im] + cation in the topmost layer. For a mixture with different cations and anions, that is, [C 8 C 1 Im][Tf 2 N]+[(MeO) 2 Im][PF 6 ], we find both surface enrichment of the [C 8 C 1 Im] + cation and the [Tf 2 N] - (bis[(trifluoromethyl)sulfonyl]imide) anion, while [(MeO) 2 Im] + and [PF 6 ] - are depleted from the surface. We propose that the observed behavior in these mixtures is due to a lowering of the surface tension by the enriched components. Interestingly, we observe pronounced differences in the chemical shifts of the imidazolium ring signals of the [(MeO) 2 Im] + cations as compared to the non-functionalized cations. Calculations of the electronic structure and the intramolecular partial charge distribution of the cations contribute to interpreting these shifts for the two different cations. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Diazonium-protein adducts for graphite electrode microarrays modification: direct and addressed electrochemical immobilization.

PubMed

Corgier, Benjamin P; Marquette, Christophe A; Blum, Loïc J

2005-12-28

Diazonium cation electrodeposition was investigated for the direct and electro-addressed immobilization of proteins. For the first time, this reaction was triggered directly onto diazonium-modified proteins. Screen-printed (SP) graphite electrode microarrays were studied as active support for this immobilization. A 10-microelectrode (eight working electrodes, 0.2 mm2 each; one reference; and one auxiliary) setup was used to study the addressing possibilities of the method. These electrode microarrays were shown to be able to covalently graft diazonium cations through electrochemical reduction. Cyclic voltammetry and X-ray photoelectron spectroscopy were used to characterize the electrochemical grafting onto our SP graphite surface and suggested that a diazonium monolayer was deposited. Rabbit and human immunoglobulins (IgGs) were then chemically coupled to an aniline derivative (4-carboxymethylaniline), followed by diazotation to form an aryl diazonium function available for the electrodeposition. These modified proteins were both successfully electro-addressed at the surface of the graphite electrodes without cross-talk or interference. The immuno-biochip obtained using this novel approach enabled the specific detection of anti-rabbit IgG antibodies with a detection limit of 50 fmol of protein. A promising strategy to immobilize markedly different biological entities was then presented, providing an excellent spatial specificity of the electro-addressing.

Phosphoethanolamine Transferase LptA in Haemophilus ducreyi Modifies Lipid A and Contributes to Human Defensin Resistance In Vitro.

PubMed

Trombley, Michael P; Post, Deborah M B; Rinker, Sherri D; Reinders, Lorri M; Fortney, Kate R; Zwickl, Beth W; Janowicz, Diane M; Baye, Fitsum M; Katz, Barry P; Spinola, Stanley M; Bauer, Margaret E

2015-01-01

Haemophilus ducreyi resists the cytotoxic effects of human antimicrobial peptides (APs), including α-defensins, β-defensins, and the cathelicidin LL-37. Resistance to LL-37, mediated by the sensitive to antimicrobial peptide (Sap) transporter, is required for H. ducreyi virulence in humans. Cationic APs are attracted to the negatively charged bacterial cell surface. In other gram-negative bacteria, modification of lipopolysaccharide or lipooligosaccharide (LOS) by the addition of positively charged moieties, such as phosphoethanolamine (PEA), confers AP resistance by means of electrostatic repulsion. H. ducreyi LOS has PEA modifications at two sites, and we identified three genes (lptA, ptdA, and ptdB) in H. ducreyi with homology to a family of bacterial PEA transferases. We generated non-polar, unmarked mutants with deletions in one, two, or all three putative PEA transferase genes. The triple mutant was significantly more susceptible to both α- and β-defensins; complementation of all three genes restored parental levels of AP resistance. Deletion of all three PEA transferase genes also resulted in a significant increase in the negativity of the mutant cell surface. Mass spectrometric analysis revealed that LptA was required for PEA modification of lipid A; PtdA and PtdB did not affect PEA modification of LOS. In human inoculation experiments, the triple mutant was as virulent as its parent strain. While this is the first identified mechanism of resistance to α-defensins in H. ducreyi, our in vivo data suggest that resistance to cathelicidin LL-37 may be more important than defensin resistance to H. ducreyi pathogenesis.

Methods and energy storage devices utilizing electrolytes having surface-smoothing additives

DOEpatents

Xu, Wu; Zhang, Jiguang; Graff, Gordon L; Chen, Xilin; Ding, Fei

2015-11-12

Electrodeposition and energy storage devices utilizing an electrolyte having a surface-smoothing additive can result in self-healing, instead of self-amplification, of initial protuberant tips that give rise to roughness and/or dendrite formation on the substrate and anode surface. For electrodeposition of a first metal (M1) on a substrate or anode from one or more cations of M1 in an electrolyte solution, the electrolyte solution is characterized by a surface-smoothing additive containing cations of a second metal (M2), wherein cations of M2 have an effective electrochemical reduction potential in the solution lower than that of the cations of M1.

Synthesis of Core-shell Lanthanide-doped Upconversion Nanocrystals for Cellular Applications.

PubMed

Ai, Xiangzhao; Lyu, Linna; Mu, Jing; Hu, Ming; Wang, Zhimin; Xing, Bengang

2017-11-10

Lanthanide-doped upconversion nanocrystals (UCNs) have attracted much attention in recent years based on their promising and controllable optical properties, which allow for the absorption of near-infrared (NIR) light and can subsequently convert it into multiplexed emissions that span over a broad range of regions from the UV to the visible to the NIR. This article presents detailed experimental procedures for high-temperature co-precipitation synthesis of core-shell UCNs that incorporate different lanthanide ions into nanocrystals for efficiently converting deep-tissue penetrable NIR excitation (808 nm) into a strong blue emission at 480 nm. By controlling the surface modification with biocompatible polymer (polyacrylic acid, PAA), the as-prepared UCNs acquires great solubility in buffer solutions. The hydrophilic nanocrystals are further functionalized with specific ligands (dibenzyl cyclooctyne, DBCO) for localization on the cell membrane. Upon NIR light (808 nm) irradiation, the upconverted blue emission can effectively activate the light-gated channel protein on the cell membrane and specifically regulate the cation (e.g., Ca 2+ ) influx in the cytoplasm. This protocol provides a feasible methodology for the synthesis of core-shell lanthanide-doped UCNs and subsequent biocompatible surface modification for further cellular applications.

Scalable imprinting of shape-specific polymeric nanocarriers using a release layer of switchable water solubility.

PubMed

Agarwal, Rachit; Singh, Vikramjit; Jurney, Patrick; Shi, Li; Sreenivasan, S V; Roy, Krishnendu

2012-03-27

There is increasing interest in fabricating shape-specific polymeric nano- and microparticles for efficient delivery of drugs and imaging agents. The size and shape of these particles could significantly influence their transport properties and play an important role in in vivo biodistribution, targeting, and cellular uptake. Nanoimprint lithography methods, such as jet-and-flash imprint lithography (J-FIL), provide versatile top-down processes to fabricate shape-specific, biocompatible nanoscale hydrogels that can deliver therapeutic and diagnostic molecules in response to disease-specific cues. However, the key challenges in top-down fabrication of such nanocarriers are scalable imprinting with biological and biocompatible materials, ease of particle-surface modification using both aqueous and organic chemistry as well as simple yet biocompatible harvesting. Here we report that a biopolymer-based sacrificial release layer in combination with improved nanocarrier-material formulation can address these challenges. The sacrificial layer improves scalability and ease of imprint-surface modification due to its switchable solubility through simple ion exchange between monovalent and divalent cations. This process enables large-scale bionanoimprinting and efficient, one-step harvesting of hydrogel nanoparticles in both water- and organic-based imprint solutions. © 2012 American Chemical Society

Proteomic Analysis of Serum Opsonins Impacting Biodistribution and Cellular Association of Porous Silicon Microparticles

PubMed Central

Serda, Rita E.; Blanco, Elvin; Mack, Aaron; Stafford, Susan J.; Amra, Sarah; Li, Qingpo; van de Ven, Anne L.; Tanaka, Takemi; Torchilin, Vladimir P.; Wiktorowicz, John E.; Ferrari, Mauro

2014-01-01

Mass transport of drug delivery vehicles is guided by particle properties, such as shape, composition and surface chemistry, as well as biomolecules and serum proteins that adsorb to the particle surface. In an attempt to identify serum proteins influencing cellular associations and biodistribution of intravascularly injected particles, we used two dimensional gel electrophoresis and mass spectrometry to identify proteins eluted from the surface of cationic and anionic silicon microparticles. Cationic microparticles displayed a 25-fold greater abundance of Ig light chain variable region, fibrinogen, and complement component 1 compared to their anionic counterparts. The anionic-surface favored equal accumulation of microparticles in the liver and spleen, while cationic-surfaces favored preferential accumulation in the spleen. Immunohistochemistry supported macrophage internalization of both anionic and cationic silicon microparticles in the liver, as well as evidence of association of cationic microparticles with hepatic endothelial cells. Furthermore, scanning electron micrographs supported cellular competition for cationic microparticles by endothelial cells and macrophages. Despite high macrophage content in the lungs and tumor, microparticle uptake by these cells was minimal, supporting differences in the repertoire of surface receptors expressed by tissue-specific macrophages. In summary, particle surface chemistry drives selective binding of serum components impacting cellular interactions and biodistribution. PMID:21303614

Liquid-Vapor Interfacial Properties of Aqueous Solutions of Guanidinium and Methyl Guanidinium Chloride: Influence of Molecular Orientation on Interface Fluctuations

PubMed Central

Ou, Shuching; Cui, Di; Patel, Sandeep

2014-01-01

The guanidinium cation (C(NH2)3+) is a highly stable cation in aqueous solution due to its efficient solvation by water molecules and resonance stabilization of the charge. Its salts increase the solubility of nonpolar molecules (”salting-in”) and decrease the ordering of water. It is one of the strongest denaturants used in biophysical studies of protein folding. We investigate the behavior of guanidinium and its derivative, methyl guanidinium (an amino acid analogue) at the air-water surface, using atomistic molecular dynamics (MD) simulations and calculation of potentials of mean force. Methyl guanidinium cation is less excluded from the air-water surface than guanidinium cation, but both cations show orientational dependence of surface affinity. Parallel orientations of the guanidinium ring (relative to the Gibbs dividing surface) show pronounced free energy minima in the interfacial region, while ring orientations perpendicular to the GDS exhibit no discernible surface stability. Calculations of surface fluctuations demonstrate that near the air-water surface, the parallel-oriented cations generate significantly greater interfacial fluctuations compared to other orientations, which induces more long-ranged perturbations and solvent density redistribution. Our results suggest a strong correlation with induced interfacial fluctuations and ion surface stability. These results have implications for interpreting molecular-level, mechanistic action of this osmolyte’s interaction with hydrophobic interfaces as they impact protein denaturation (solubilization). PMID:23937431

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

Laskin, Julia; Johnson, Grant E.; Prabhakaran, Venkateshkumar

Immobilization of complex molecules and clusters on supports plays an important role in a variety of disciplines including materials science, catalysis and biochemistry. In particular, deposition of clusters on surfaces has attracted considerable attention due to their non-scalable, highly size-dependent properties. The ability to precisely control the composition and morphology of clusters and small nanoparticles on surfaces is crucial for the development of next generation materials with rationally tailored properties. Soft- and reactive landing of ions onto solid or liquid surfaces introduces unprecedented selectivity into surface modification by completely eliminating the effect of solvent and sample contamination on the qualitymore » of the film. The ability to select the mass-to-charge ratio of the precursor ion, its kinetic energy and charge state along with precise control of the size, shape and position of the ion beam on the deposition target makes soft-landing an attractive approach for surface modification. High-purity uniform thin films on surfaces generated using mass-selected ion deposition facilitate understanding of critical interfacial phenomena relevant to catalysis, energy generation and storage, and materials science. Our efforts have been directed toward understanding charge retention by soft-landed metal and metal-oxide cluster ions, which may affect both their structure and reactivity. Specifically, we have examined the effect of the surface on charge retention by both positively and negatively charged cluster ions. We found that the electronic properties of the surface play an important role in charge retention by cluster cations. Meanwhile, the electron binding energy is a key factor determining charge retention by cluster anions. These findings provide the scientific foundation for the rational design of interfaces for advanced catalysts and energy storage devices. Further optimization of electrode-electrolyte interfaces for applications in energy storage and electrocatalysis may be achieved by understanding and controlling the properties of soft-landed cluster ions.« less

Electrocurtain coating process for coating solar mirrors

DOEpatents

Kabagambe, Benjamin; Boyd, Donald W.; Buchanan, Michael J.; Kelly, Patrick; Kutilek, Luke A.; McCamy, James W.; McPheron, Douglas A.; Orosz, Gary R.; Limbacher, Raymond D.

2013-10-15

An electrically conductive protective coating or film is provided over the surface of a reflective coating of a solar mirror by flowing or directing a cation containing liquid and an anion containing liquid onto the conductive surface. The cation and the anion containing liquids are spaced from, and preferably out of contact with one another on the surface of the reflective coating as an electric current is moved through the anion containing liquid, the conductive surface between the liquids and the cation containing liquid to coat the conductive surface with the electrically conductive coating.

Removal of oil droplets from water using carbonized rice husk: enhancement by surface modification using polyethylenimine.

PubMed

Lin, Kun-Yi Andrew; Yang, Hongta; Petit, Camille; Chen, Shen-Yi

2015-06-01

Carbonized rice husk (CRH) is a promising material to separate oil from water owing to its abundance, low-cost, and environmentally benign characteristics. However, CRH's performance is somewhat limited by its similar surface charge to that of oil, leading to repulsive interactions. To improve the separation efficiency of CRH, CRH was modified via impregnation with a cationic biocompatible polymer, polyethlyenimine (PEI) to form PEI-CRH. The modified sample exhibits a remarkably higher (10-50 times) oil/water (O/W) separation efficiency than that of the unmodified one. Small PEI-CRH particles (about 64 μm) are found to adsorb oil droplets faster and larger quantities than bigger particles (about 113 and 288 μm). PEI-CRH exhibits higher separation efficiency at high temperatures owing to the destabilization of the emulsion. It is also found that the oil adsorption mechanism involves a chemical interaction between PEI-CRH and oil droplets. The addition of NaCl considerably improves the separation efficiency, while the addition of a cationic surfactant has the opposite effect. In acidic emulsions, PEI-CRH adsorbs more oil than in neutral or basic conditions owing to favorable attractive forces between oil droplets and the surface of PEI-CRH. PEI-CRH can be easily regenerated by washing with ethanol. These promising features of PEI-CRH indicate that PEI-CRH could be an efficient and low-cost adsorbent for the O/W separation applications.

USE OF CATIONIC SURFACTANTS TO MODIFY SOIL SURFACES TO PROMOTE SORPTION AND RETARD MIGRATION OF HYDROPHOBIC ORGANIC COMPOUNDS

EPA Science Inventory

Cationic surfactants can be used to modify surfaces of soils and subsurface materials to promote adsorption of hydrophobic organic compounds (HOC). Batch and column experiments were performed to investigate this phenomenon with the cationic surfactant dodecylpyridinium (DP), a se...

New Perspective in the Formulation and Characterization of Didodecyldimethylammonium Bromide (DMAB) Stabilized Poly(Lactic-co-Glycolic Acid) (PLGA) Nanoparticles

PubMed Central

Gossmann, Rebecca; Langer, Klaus; Mulac, Dennis

2015-01-01

Over the last few decades the establishment of nanoparticles as suitable drug carriers with the transport of drugs across biological barriers such as the gastrointestinal barrier moved into the focus of many research groups. Besides drug transport such carrier systems are well suited for the protection of drugs against enzymatic and chemical degradation. The preparation of biocompatible and biodegradable nanoparticles based on poly(lactic-co-glycolic acid) (PLGA) is intensively described in literature, while especially nanoparticles with cationic properties show a promising increased cellular uptake. This is due to the electrostatic interaction between the cationic surface and the negatively charged lipid membrane of the cells. Even though several studies achieved the successful preparation of nanoparticles stabilized with the cationic surfactants such as didodecyldimethylammonium bromide (DMAB), in most cases insufficient attention was paid to a precise analytical characterization of the nanoparticle system. The aim of the present work was to overcome this deficit by presenting a new perspective in the formulation and characterization of DMAB-stabilized PLGA nanoparticles. Therefore these nanoparticles were carefully examined with regard to particle diameter, zeta potential, the effect of variation in stabilizer concentration, residual DMAB content, and electrolyte stability. Without any steric stabilization, the DMAB-modified nanoparticles were sensitive to typical electrolyte concentrations of biological environments due to compression of the electrical double layer in conjunction with a decrease in zeta potential. To handle this problem, the present study proposed two modifications to enable electrolyte stability. Both polyvinyl alcohol (PVA) and polyethylene glycol (PEG) modified DMAB-PLGA-nanoparticles were stable during electrolyte addition. Furthermore, in contrast to unmodified DMAB-PLGA-nanoparticles and free DMAB, such modifications led to a lower cytotoxic activity against Caco-2 cells. In conclusion this study offers a closer and critical point of view on preparation, in vitro and analytical evaluation of DMAB-stabilized PLGA nanoparticles for the physiological use. PMID:26147338

New Perspective in the Formulation and Characterization of Didodecyldimethylammonium Bromide (DMAB) Stabilized Poly(Lactic-co-Glycolic Acid) (PLGA) Nanoparticles.

PubMed

Gossmann, Rebecca; Langer, Klaus; Mulac, Dennis

2015-01-01

Over the last few decades the establishment of nanoparticles as suitable drug carriers with the transport of drugs across biological barriers such as the gastrointestinal barrier moved into the focus of many research groups. Besides drug transport such carrier systems are well suited for the protection of drugs against enzymatic and chemical degradation. The preparation of biocompatible and biodegradable nanoparticles based on poly(lactic-co-glycolic acid) (PLGA) is intensively described in literature, while especially nanoparticles with cationic properties show a promising increased cellular uptake. This is due to the electrostatic interaction between the cationic surface and the negatively charged lipid membrane of the cells. Even though several studies achieved the successful preparation of nanoparticles stabilized with the cationic surfactants such as didodecyldimethylammonium bromide (DMAB), in most cases insufficient attention was paid to a precise analytical characterization of the nanoparticle system. The aim of the present work was to overcome this deficit by presenting a new perspective in the formulation and characterization of DMAB-stabilized PLGA nanoparticles. Therefore these nanoparticles were carefully examined with regard to particle diameter, zeta potential, the effect of variation in stabilizer concentration, residual DMAB content, and electrolyte stability. Without any steric stabilization, the DMAB-modified nanoparticles were sensitive to typical electrolyte concentrations of biological environments due to compression of the electrical double layer in conjunction with a decrease in zeta potential. To handle this problem, the present study proposed two modifications to enable electrolyte stability. Both polyvinyl alcohol (PVA) and polyethylene glycol (PEG) modified DMAB-PLGA-nanoparticles were stable during electrolyte addition. Furthermore, in contrast to unmodified DMAB-PLGA-nanoparticles and free DMAB, such modifications led to a lower cytotoxic activity against Caco-2 cells. In conclusion this study offers a closer and critical point of view on preparation, in vitro and analytical evaluation of DMAB-stabilized PLGA nanoparticles for the physiological use.

The crystal structure of Haloferax volcanii proliferating cell nuclear antigen reveals unique surface charge characteristics due to halophilic adaptation

PubMed Central

Winter, Jody A; Christofi, Panayiotis; Morroll, Shaun; Bunting, Karen A

2009-01-01

Background The high intracellular salt concentration required to maintain a halophilic lifestyle poses challenges to haloarchaeal proteins that must stay soluble, stable and functional in this extreme environment. Proliferating cell nuclear antigen (PCNA) is a fundamental protein involved in maintaining genome integrity, with roles in both DNA replication and repair. To investigate the halophilic adaptation of such a key protein we have crystallised and solved the structure of Haloferax volcanii PCNA (HvPCNA) to a resolution of 2.0 Å. Results The overall architecture of HvPCNA is very similar to other known PCNAs, which are highly structurally conserved. Three commonly observed adaptations in halophilic proteins are higher surface acidity, bound ions and increased numbers of intermolecular ion pairs (in oligomeric proteins). HvPCNA possesses the former two adaptations but not the latter, despite functioning as a homotrimer. Strikingly, the positive surface charge considered key to PCNA's role as a sliding clamp is dramatically reduced in the halophilic protein. Instead, bound cations within the solvation shell of HvPCNA may permit sliding along negatively charged DNA by reducing electrostatic repulsion effects. Conclusion The extent to which individual proteins adapt to halophilic conditions varies, presumably due to their diverse characteristics and roles within the cell. The number of ion pairs observed in the HvPCNA monomer-monomer interface was unexpectedly low. This may reflect the fact that the trimer is intrinsically stable over a wide range of salt concentrations and therefore additional modifications for trimer maintenance in high salt conditions are not required. Halophilic proteins frequently bind anions and cations and in HvPCNA cation binding may compensate for the remarkable reduction in positive charge in the pore region, to facilitate functional interactions with DNA. In this way, HvPCNA may harness its environment as opposed to simply surviving in extreme halophilic conditions. PMID:19698123

Hydrophobic kenaf nanocrystalline cellulose for the binding of curcumin.

PubMed

Zainuddin, Norhidayu; Ahmad, Ishak; Kargarzadeh, Hanieh; Ramli, Suria

2017-05-01

Nanocrystalline cellulose (NCC) extracted from lignocellulosic materials has been actively investigated as a drug delivery excipients due to its large surface area, high aspect ratio, and biodegradability. In this study, the hydrophobically modified NCC was used as a drug delivery excipient of hydrophobic drug curcumin. The modification of NCC with a cationic surfactant, cetyl trimethylammonium bromide (CTAB) was used to modulate the loading of hydrophobic drugs that would not normally bind to NCC. The FTIR, Elemental analysis, XRD, TGA, and TEM were used to confirm the modification of NCC with CTAB. The effect of concentration of CTAB on the binding efficiency of hydrophobic drug curcumin was investigated. The amounts of curcumin bound onto the CTAB-NCC nanoparticles were analyzed by UV-vis Spectrophotometric. The result showed that the modified CTAB-NCC bound a significant amount of curcumin, in a range from 80% to 96% curcumin added. Nevertheless, at higher concentration of CTAB resulted in lower binding efficiency. Copyright © 2017 Elsevier Ltd. All rights reserved.

Static and dynamic wetting behaviour of ionic liquids.

PubMed

Delcheva, Iliana; Ralston, John; Beattie, David A; Krasowska, Marta

2015-08-01

Ionic liquids (ILs) are a unique family of molecular liquids ('molten salts') that consist of a combination of bulky organic cations coupled to inorganic or organic anions. The net result of steric hindrance and strong hydrogen bonding between components results in a material that is liquid at room temperature. One can alter the properties of ionic liquids through chemical modification of anion and cation, thus tailoring the IL for a given application. One such property that can be controlled or selected is the wettability of an IL on a particular solid substrate. However, the study of wetting of ionic liquids is complicated by the care required for accurate and reproducible measurement, due to both the susceptibility of the IL properties to water content, as well as to the sensitivity of wettability measurements to the state of the solid surface. This review deals with wetting studies of ILs to date, including both static and dynamic wetting, as well as issues concerning line tension and the formation of precursor and wetting films. Copyright © 2014 Elsevier B.V. All rights reserved.

Heparin/heparan sulfate analysis by covalently modified reverse polarity capillary zone electrophoresis-mass spectrometry.

PubMed

Sanderson, Patience; Stickney, Morgan; Leach, Franklin E; Xia, Qiangwei; Yu, Yanlei; Zhang, Fuming; Linhardt, Robert J; Amster, I Jonathan

2018-04-13

Reverse polarity capillary zone electrophoresis coupled to negative ion mode mass spectrometry (CZE-MS) is shown to be an effective and sensitive tool for the analysis of glycosaminoglycan mixtures. Covalent modification of the inner wall of the separation capillary with neutral or cationic reagents produces a stable and durable surface that provides reproducible separations. By combining CZE-MS with a cation-coated capillary and a sheath flow interface, a rapid and reliable method has been developed for the analysis of sulfated oligosaccharides from dp4 to dp12. Several different mixtures have been separated and detected by mass spectrometry. The mixtures were selected to test the capability of this approach to resolve subtle differences in structure, such as sulfation position and epimeric variation of the uronic acid. The system was applied to a complex mixture of heparin/heparan sulfate oligosaccharides varying in chain length from dp3 to dp12 and more than 80 molecular compositions were identified by accurate mass measurement. Copyright © 2018 Elsevier B.V. All rights reserved.

Comparison of analytical protein separation characteristics for three amine-based capillary-channeled polymer (C-CP) stationary phases.

PubMed

Jiang, Liuwei; Marcus, R Kenneth

2016-02-01

Capillary-channeled polymer (C-CP) fiber stationary phases are finding utility in the realms of protein analytics as well as downstream processing. We have recently described the modification of poly(ethylene terephthalate) (PET) C-CP fibers to affect amine-rich phases for the weak anion-exchange (WAX) separation of proteins. Polyethylenimine (PEI) is covalently coupled to the PET surface, with subsequent cross-linking imparted by treatment with 1,4-butanediol diglycidyl ether (BUDGE). These modifications yield vastly improved dynamic binding capacities over the unmodified fibers. We have also previously employed native (unmodified) nylon 6 C-CP fibers as weak anion/cation-exchange (mixed-mode) and hydrophobic interaction chromatography (HIC) phases for protein separations. Polyamide, nylon 6, consists of amide groups along the polymer backbone, with primary amines and carboxylic acid end groups. The analytical separation characteristics of these three amine-based C-CP fiber phases are compared here. Each of the C-CP fiber columns in this study was shown to be able to separate a bovine serum albumin/hemoglobin/lysozyme mixture at high mobile phase linear velocity (∼70 mm s(-1)) but with different elution characteristics. These differences reflect the types of protein-surface interactions that are occurring, based on the active group composition of the fiber surfaces. This study provides important fundamental understanding for the development of surface-modified C-CP fiber columns for protein separation.

Cation Exchange in the Presence of Oil in Porous Media

PubMed Central

2017-01-01

Cation exchange is an interfacial process during which cations on a clay surface are replaced by other cations. This study investigates the effect of oil type and composition on cation exchange on rock surfaces, relevant for a variety of oil-recovery processes. We perform experiments in which brine with a different composition than that of the in situ brine is injected into cores with and without remaining oil saturation. The cation-exchange capacity (CEC) of the rocks was calculated using PHREEQC software (coupled to a multipurpose transport simulator) with the ionic composition of the effluent histories as input parameters. We observe that in the presence of crude oil, ion exchange is a kinetically controlled process and its rate depends on residence time of the oil in the pore, the temperature, and kinetic rate of adsorption of the polar groups on the rock surface. The cation-exchange process occurs in two stages during two phase flow in porous media. Initially, the charged sites of the internal surface of the clays establish a new equilibrium by exchanging cations with the aqueous phase. At later stages, the components of the aqueous and oleic phases compete for the charged sites on the external surface or edges of the clays. When there is sufficient time for crude oil to interact with the rock (i.e., when the core is aged with crude oil), a fraction of the charged sites are neutralized by the charged components stemming from crude oil. Moreover, the positively charged calcite and dolomite surfaces (at the prevailing pH environment of our experiments) are covered with the negatively charged components of the crude oil and therefore less mineral dissolution takes place when oil is present in porous media. PMID:28580442

A study on the nature of interactions of mixed-mode ligands HEA and PPA HyperCel using phenylglyoxal modified lysozyme.

PubMed

Pezzini, J; Cabanne, C; Dupuy, J-W; Gantier, R; Santarelli, X

2014-06-01

Mixed mode chromatography, or multimodal chromatography, involves the exploitation of combinations of several interactions in a controlled manner, to facilitate the rapid capture of proteins. Mixed-mode ligands like HEA and PPA HyperCel™ facilitate different kinds of interactions (hydrophobic, ionic, etc.) under different conditions. In order to better characterize the nature of this multi-modal interaction, we sought to study a protein, lysozyme, which is normally not retained by these mixed mode resins under normal binding conditions. Lysozyme was modified specifically at Arginine residues by the action of phenylglyoxal, and was extensively studied in this work to better characterize the mixed-mode interactions of HEA HyperCel™ and PPA HyperCel™ chromatographic supports. We show here that the adsorption behaviour of lysozyme on HEA and PPA HyperCel™ mixed mode sorbents varies depending on the degree of charge modification at the surface of the protein. Experiments using conventional cation exchange and hydrophobic interaction chromatography confirm that both charge and hydrophobicity modification occurs at the surface of the protein after lysozyme reaction with phenylglyoxal. The results emanating from this work using HEA and PPA HyperCel sorbents strongly suggest that mixed mode chromatography can efficiently separate closely related proteins of only minor surface charge and/or hydrophobicity differences. Copyright © 2014 Elsevier B.V. All rights reserved.

[Adsorptive Stabilization of Soil Cr (VI) Using HDTMA Modified Montmorillonite].

PubMed

2016-03-15

A series of organo-montomorillonites were prepared using Na-montomorillonite and hexadecyl trimethyl ammonium bromide (HDTMA). The organo-montomorillonites were then investigated for the remediation of Cr(VI) contaminated soils. FT-IR, XRD, SEM and N2 -BET, CEC, Zeta potential measurement were conducted to understand the structural changes of montmorillonites as different amounts of HDTMAs were added as modifier. The characterization results indicated that the clay interlayer spacing distance increased from 1. 25 nm to 2. 13 nm, the clay surface roughness decreased, the clay surface area reduced from 38.91 m² · g⁻¹ to 0.42 m² · g⁻¹, the clay exchangeable cation amount reduced from 62 cmol · kg⁻¹ to 9.9 cmol · kg⁻¹ and the clay surface charge changed from -29.1 mV to 5.59 mV as the dosage of HDTMA in montmorillonite was increased. The TCLP (toxicity characteristic leaching procedure) was used to evaluate the leachate toxicity of Cr(VI). The effects of the initial soil Cr(VI) concentration, montmorillonites dosage, reaction time and HDTMA modification amount were investigated, respectively. The results revealed that modification of montmorillonites would manifest an attenuated physical adsorptive effect and an enhanced electrostatic adsorptive effect on Cr(VI), suggesting electrostatic effect was the major force that resulted in improved Cr(VI) adsorption onto HDTMA modified montmorillonites.

Cholesterol-based cationic lipids for gene delivery: contribution of molecular structure factors to physico-chemical and biological properties.

PubMed

Sheng, Ruilong; Luo, Ting; Li, Hui; Sun, Jingjing; Wang, Zhao; Cao, Amin

2014-04-01

In this work, we prepared a series of cholesterol-based cationic (Cho-cat) lipids bearing cholesterol hydrophobe, natural amino acid headgroups (lysine/histidine) and linkage (carbonate ester/ether) bonds. In which, the natural amino acid headgroups made dominant contribution to their physico-chemical and biological properties. Among the lipids, the l-lysine headgroup bearing lipids (Cho-es/et-Lys) showed higher pDNA binding affinity and were able to form larger sized and higher surface charged lipoplexes than that of l-histidine headgroup bearing lipids (Cho-es/et-His), they also demonstrated higher transfection efficacy and higher membrane disruption capacities than that of their l-histidine headgroup bearing counterparts. However, compared to the contributions of the headgroups, the (carbonate ester/ether) linkage bonds showed much less affects. Besides, it could be noted that, Cho-es/et-Lys lipids exhibited very high luciferase gene transfection efficiency that almost reached the transfection level of "gold standard" bPEI-25k, made them potential transfection reagents for practical application. Moreover, the results facilitated the understanding for the structure-activity relationship of the cholesterol-based cationic lipids, and also paved a simple and efficient way for achieving high transfection efficiency by modification of suitable headgroups on lipid gene carriers. Copyright © 2014 Elsevier B.V. All rights reserved.

Ab initio simulation of structure and surface energy of low-index surfaces of stoichiometric α-Fe2O3

NASA Astrophysics Data System (ADS)

Stirner, Thomas; Scholz, David; Sun, Jizhong

2018-05-01

The structure and surface energy of a series of low-index surfaces of stoichiometric α-Fe2O3 (hematite) are investigated using the periodic Hartree-Fock approach with an a posteriori correction of the correlation energy. The simulations show that, amongst the modeled facets, (01 1 bar2) and (0001) are the most stable surfaces of hematite, which is consistent with the fact that the latter are the dominant growth faces exposed on natural α-Fe2O3. The Fe-terminated (0001) surface is shown to exhibit a large relaxation of the surface atoms. It is argued that this arises mainly due to the fact that the surface cations are located opposite empty cation sites in the filled-filled-unfilled cation sequence along the c-axis. In contrast, the (01 1 bar2) plane cuts the crystal through a plane of empty cation sites, thus giving rise to relatively small relaxations and surface energies. The small relaxations and concomitant exposure of five-coordinate cation sites may be important for the catalytic activity of hematite. The simulations also show that the relative stability of the investigated surfaces changes after a full lattice relaxation with the (0001) and (11 2 bar6) facets relaxing disproportionately large. Wherever possible, the simulations are compared with previous simulation data and experimental results. A Wulff-Gibbs construction is also presented.

A More Flexible Approach to Valuing Flexibility

DTIC Science & Technology

2011-04-01

remaining life of the program? Almost certainly. Next is the cost assessment step. This is executed in the context of whatever design options we...methodology is essentially a modifi- cation of the current life cycle model and is premised on the notion that the need for capabili- ty changes in a program...valuing the inherent ability of a system or design to accommodate change. The proposed methodology is essentially a modifi-cation of the current life

Polyamide desalination membrane characterization and surface modification to enhance fouling resistance.

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

Sharma, Mukul M.; Freeman, Benny D.; Van Wagner, Elizabeth M.

2010-08-01

The market for polyamide desalination membranes is expected to continue to grow during the coming decades. Purification of alternative water sources will also be necessary to meet growing water demands. Purification of produced water, a byproduct of oil and gas production, is of interest due to its dual potential to provide water for beneficial use as well as to reduce wastewater disposal costs. However, current polyamide membranes are prone to fouling, which decreases water flux and shortens membrane lifetime. This research explored surface modification using poly(ethylene glycol) diglycidyl ether (PEGDE) to improve the fouling resistance of commercial polyamide membranes. Characterizationmore » of commercial polyamide membrane performance was a necessary first step before undertaking surface modification studies. Membrane performance was found to be sensitive to crossflow testing conditions. Concentration polarization and feed pH strongly influenced NaCl rejection, and the use of continuous feed filtration led to higher water flux and lower NaCl rejection than was observed for similar tests performed using unfiltered feed. Two commercial polyamide membranes, including one reverse osmosis and one nanofiltration membrane, were modified by grafting PEGDE to their surfaces. Two different PEG molecular weights (200 and 1000) and treatment concentrations (1% (w/w) and 15% (w/w)) were studied. Water flux decreased and NaCl rejection increased with PEGDE graft density ({micro}g/cm{sup 2}), although the largest changes were observed for low PEGDE graft densities. Surface properties including hydrophilicity, roughness and charge were minimally affected by surface modification. The fouling resistance of modified and unmodified membranes was compared in crossflow filtration studies using model foulant solutions consisting of either a charged surfactant or an oil in water emulsion containing n-decane and a charged surfactant. Several PEGDE-modified membranes demonstrated improved fouling resistance compared to unmodified membranes of similar initial water flux, possibly due to steric hindrance imparted by the PEG chains. Fouling resistance was higher for membranes modified with higher molecular weight PEG. Fouling was more extensive for feeds containing the cationic surfactant, potentially due to electrostatic attraction with the negatively charged membranes. However, fouling was also observed in the presence of the anionic surfactant, indicating hydrodynamic forces are also responsible for fouling.« less

Cation effects on phosphatidic acid monolayers at various pH conditions.

PubMed

Zhang, Ting; Cathcart, Matthew G; Vidalis, Andrew S; Allen, Heather C

2016-10-01

The impact of pH and cations on phase behavior, stability, and surface morphology for dipalmitoylphosphatidic acid (DPPA) monolayers was investigated. At pH<10, DPPA monolayers on water are predominantly populated by neutral species and display the highest packing density. Cations are found to expand and stabilize the monolayer in the following order of increasing magnitude at pH 5.6: Na + >K + ∼Mg 2+ >Ca 2+ . Additionally, cation complexation is tied to the pH and protonation state of DPPA, which are the primary factors controlling the monolayer surface behavior. The binding affinity of cations to the headgroup and thus deprotonation capability of the cation, ranked in the order of Ca 2+ >Mg 2+ >Na + >K + , is found to be well explained by the law of matching water affinities. Nucleation of surface 3D lipid structures is observed from Ca 2+ , Mg 2+ , and Na + , but not from K + , consistent with the lowest binding affinity of K + . Unraveling cation and pH effects on DPPA monolayers is useful in further understanding the surface properties of complex systems such as organic-coated marine aerosols where organic films are directly influenced by the pH and ionic composition of the underlying aqueous phase. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Adsorption of guanidinium collectors on aluminosilicate minerals - a density functional study.

PubMed

Nulakani, Naga Venkateswara Rao; Baskar, Prathab; Patra, Abhay Shankar; Subramanian, Venkatesan

2015-10-07

In this density functional theory based investigation, we have modelled and studied the adsorption behaviour of guanidinium cations and substituted (phenyl, methoxy phenyl, nitro phenyl and di-nitro phenyl) guanidinium cationic collectors on the basal surfaces of kaolinite and goethite. The adsorption behaviour is assessed in three different media, such as gas, explicit water and pH medium, to understand the affinity of GC collectors to the SiO4 tetrahedral and AlO6 octahedral surfaces of kaolinite. The tetrahedral siloxane surface possesses a larger binding affinity to GC collectors than the octahedral sites due to the presence of surface exposed oxygen atoms that are active in the intermolecular interactions. Furthermore, the inductive electronic effects of substituted guanidinium cations also play a key role in the adsorption mechanism. Highly positive cations result in a stronger electrostatic interaction and preferential adsorption with the kaolinite surfaces than low positive cations. Computed interaction energies and electron densities at the bond critical points suggest that the adsorption of guanidinium cations on the surfaces of kaolinite and goethite is due to the formation of intra/inter hydrogen bonding networks. Also, the electrostatic interaction favours the high adsorption ability of GC collectors in the pH medium than gas phase and water medium. The structures and energies of GC collectors pave an intuitive view for future experimental studies on mineral flotation.

Triphenylphosphonium cation: a valuable functional group for antimicrobial photodynamic therapy.

PubMed

Bresolí-Obach, Roger; Gispert, Ignacio; García Peña, Diego; Boga, Sonia; Gulias, Óscar; Agut, Montserrat; Vázquez, M Eugenio; Nonell, Santi

2018-06-08

Light-mediated killing of pathogens by cationic photosensitisers is a promising antimicrobial approach that avoids the development of resistance inherent to the use of antimicrobials. In this study, we demonstrate that modification of different photosensitisers with the triphenylphosphonium cation yields derivatives with excellent photoantimicrobial activity against Gram-positive bacteria (i.e., S. aureus and E. faecalis). Thus, the triphenylphosphonium functional group should be considered for the development of photoantimicrobials for the selective killing of Gram-positive bacteria in the presence of Gram-negative species. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

Extracellular DNA-induced antimicrobial peptide resistance mechanisms in Pseudomonas aeruginosa

PubMed Central

Lewenza, Shawn

2013-01-01

Extracellular DNA (eDNA) is in the environment, bodily fluids, in the matrix of biofilms, and accumulates at infection sites. eDNA can function as a nutrient source, a universal biofilm matrix component, and an innate immune effector in eDNA traps. In biofilms, eDNA is required for attachment, aggregation, and stabilization of microcolonies. We have recently shown that eDNA can sequester divalent metal cations, which has interesting implications on antibiotic resistance. eDNA binds metal cations and thus activates the Mg2+-responsive PhoPQ and PmrAB two-component systems. In Pseudomonas aeruginosa and many other Gram-negative bacteria, the PhoPQ/PmrAB systems control various genes required for virulence and resisting killing by antimicrobial peptides (APs), including the pmr genes (PA3552–PA3559) that are responsible for the addition of aminoarabinose to lipid A. The PA4773–PA4775 genes are a second DNA-induced cluster and are required for the production of spermidine on the outer surface, which protects the outer membrane from AP treatment. Both modifications mask the negative surface charges and limit membrane damage by APs. DNA-enriched biofilms or planktonic cultures have increased antibiotic resistance phenotypes to APs and aminoglycosides. These dual antibiotic resistance and immune evasion strategies may be expressed in DNA-rich environments and contribute to long-term survival. PMID:23419933

Mass spectrometry based structural analysis and systems immunoproteomics strategies for deciphering the host response to endotoxin.

PubMed

Khan, Mohd M; Ernst, Orna; Sun, Jing; Fraser, Iain D C; Ernst, Robert K; Goodlett, David R; Nita-Lazar, Aleksandra

2018-06-24

One cause of sepsis is systemic maladaptive immune response of the host to bacteria and specifically, to Gram-negative bacterial outer membrane glycolipid lipopolysaccharide (LPS). On the host myeloid cell surface, proinflammatory LPS activates the innate immune system via Toll-like receptor-4 (TLR4)/myeloid differentiation factor-2 (MD2) complex. Intracellularly, LPS is also sensed by the noncanonical inflammasome through caspase-11 in mice and 4/5 in humans. The minimal functional determinant for innate immune activation is the membrane anchor of LPS called lipid A. Even subtle modifications to the lipid A scaffold can enable, diminish, or abolish immune activation. Bacteria are known to modify their LPS structure during environmental stress, and infection of hosts to alter cellular immune phenotypes. In this review, we describe how mass spectrometry (MS)-based structural analysis of endotoxin helped uncover major determinations of molecular pathogenesis. Through characterization of LPS modifications, we now better understand resistance to antibiotics and cationic antimicrobial peptides, as well as how the environment impacts overall endotoxin structure. In addition, MS-based systems immunoproteomics approaches can assist in elucidating the immune response against LPS. Many regulatory proteins have been characterized through proteomics and global/targeted analysis of protein modifications, enabling the discovery and characterization of novel endotoxin-mediated protein translational modifications (PTMs). Copyright © 2018. Published by Elsevier Ltd.

Polynuclear Speciation of Trivalent Cations near the Surface of an Electrolyte Solution

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

Bera, Mrinal K.; Antonio, Mark R.

Despite long-standing efforts, there is no agreed upon structural model for electrolyte solutions at air-liquid interfaces. We report the simultaneous detection of the near-surface and bulk coordination environments of a trivalent metal cation (europium) in an aqueous solution by use of X-ray absorption spectroscopy. Within the first few nanometers of the liquid surface, the cations exhibit oxygen coordination typical of inner-sphere hydration of an aquated Eu3+ cation. Beyond that, outer-sphere ion-ion correlations are observed that are otherwise not present in the bulk electrolyte. The combination of near-surface and bulk sensitivities to probe metal ion speciation in electrolyte solutions is achievedmore » by detecting electron-yield and X-ray fluorescence signals from an inverted pendant drop. The results provide new knowledge about the near-surface chemistry of aqueous solutions of relevance to aerosols and ion transport processes in chemical separations and biological systems.« less

Alkyl chain interaction at the surface of room temperature ionic liquids: systematic variation of alkyl chain length (R = C(1)-C(4), C(8)) in both cation and anion of [RMIM][R-OSO(3)] by sum frequency generation and surface tension.

PubMed

Santos, Cherry S; Baldelli, Steven

2009-01-29

The gas-liquid interface of halide-free 1,3-dialkylimidazolium alkyl sulfates [RMIM][R-OSO(3)] with R chain length from C(1)-C(4) and C(8) has been studied systematically using the surface-specific sum frequency generation (SFG) vibrational spectroscopy and surface tension measurements. From the SFG spectra, vibrational modes from the methyl group of both cation and anion are observed for all ionic liquid samples considered in the present study. These results suggest the presence of both ions at the gas-liquid interface, which is further supported by surface tension measurements. Surface tension data show a decreasing trend as the alkyl chain in the imidazolium cation is varied from methyl to butyl chain, with a specific anion. A similar trend is observed when the alkyl chain of the anion is modified and the cation is fixed.

Conserved Aromatic Residue Confers Cation Selectivity in Claudin-2 and Claudin-10b*

PubMed Central

Li, Jiahua; Zhuo, Min; Pei, Lei; Yu, Alan S. L.

2013-01-01

In tight junctions, both claudin-2 and claudin-10b form paracellular cation-selective pores by the interaction of the first ECL 1 with permeating ions. We hypothesized that a highly conserved aromatic residue near the pore selectivity filter of claudins contributes to cation selectivity by cation-π interaction with the permeating cation. To test this, we generated MDCK I Tet-off cells stably transfected with claudin-2 Tyr67 mutants. The Y67L mutant showed reduced cation selectivity compared with wild-type claudin-2 due to a decrease in Na+ permeability, without affecting the Cl− permeability. The Y67A mutant enlarged the pore size and further decreased the charge selectivity due to an increase in Cl− permeability. The Y67F mutant restored the Na+ permeability, Cl− permeability, and pore size back to wild-type. The accessibility of Y67C to methanethiosulfonate modification indicated that its side chain faces the lumen of the pore. In claudin-10b, the F66L mutant reduced cation selectivity, and the F66A mutant lost pore conductance. We conclude that the conserved aromatic residue near the cation pore domain of claudins contributes to cation selectivity by a dual role of cation-π interaction and a luminal steric effect. Our findings provide new insight into how ion selectivity is achieved in the paracellular pore. PMID:23760508

Dynamics of Pseudomonas aeruginosa association with anionic hydrogel surfaces in the presence of aqueous divalent-cation salts

PubMed Central

Tran, Victoria B.; Sung, Ye Suel; Fleiszig, Suzanne M.J.; Evans, David J.; Radke, C.J.

2013-01-01

Binding of bacteria to solid surfaces is complex with many aspects incompletely understood. We investigate Pseudomonas aeruginosa uptake kinetics onto hydrogel surfaces representative of soft-contact lenses made of nonionic poly(2-hydroxyethylmethacrylate) (p-HEMA), anionic poly(methacrylic acid) (p-MAA), and anionic poly(acrylic acid) (p-AA). Using a parallel-plate flow cell under phase-contrast microscopy, we document a kinetic “burst” at the anionic hydrogel surface: dilute aqueous P. aeruginosa first rapidly accumulates and then rapidly depletes. Upon continuing flow, divalent cations in the suspending solution sorb into the hydrogel network causing the previously surface-accumulated bacteria to desorb. The number of bacteria eventually bound to the surface is low compared to the nonionic p-HEMA hydrogel. We propose that the kinetic burst is due to reversible divalent-cation bridging between the anionic bacteria and the negatively charged hydrogel surface. The number of surface bridging sites diminishes as divalent cations impregnate into and collapse the gel. P. aeruginosa association with the surface then falls. Low eventual binding of P. aeruginosa to the anionic hydrogel is ascribed to increased surface hydrophilicity compared to the counterpart nonionic p-HEMA hydrogel. PMID:21723562

Hydrophobic matrix-free graphene-oxide composites with isotropic and nematic states

NASA Astrophysics Data System (ADS)

Wåhlander, Martin; Nilsson, Fritjof; Carlmark, Anna; Gedde, Ulf W.; Edmondson, Steve; Malmström, Eva

2016-08-01

We demonstrate a novel route to synthesise hydrophobic matrix-free composites of polymer-grafted graphene oxide (GO) showing isotropic or nematic alignment and shape-memory effects. For the first time, a cationic macroinitiator (MI) has been immobilised on anionic GO and subsequently grafted with hydrophobic polymer grafts. Dense grafts of PBA, PBMA and PMMA with a wide range of average graft lengths (MW: 1-440 kDa) were polymerised by surface-initiated controlled radical precipitation polymerisation from the statistical MI. The surface modification is designed similarly to bimodal graft systems, where the cationic MI generates nanoparticle repulsion, similar to dense short grafts, while the long grafts offer miscibility in non-polar environments and cohesion. The state-of-the-art dispersions of grafted GO were in the isotropic state. Transparent and translucent matrix-free GO-composites could be melt-processed directly using only grafted GO. After processing, birefringence due to nematic alignment of grafted GO was observed as a single giant Maltese cross, 3.4 cm across. Permeability models for composites containing aligned 2D-fillers were developed, which were compared with the experimental oxygen permeability data and found to be consistent with isotropic or nematic states. The storage modulus of the matrix-free GO-composites increased with GO content (50% increase at 0.67 wt%), while the significant increases in the thermal stability (up to 130 °C) and the glass transition temperature (up to 17 °C) were dependent on graft length. The tuneable matrix-free GO-composites with rapid thermo-responsive shape-memory effects are promising candidates for a vast range of applications, especially selective membranes and sensors.We demonstrate a novel route to synthesise hydrophobic matrix-free composites of polymer-grafted graphene oxide (GO) showing isotropic or nematic alignment and shape-memory effects. For the first time, a cationic macroinitiator (MI) has been immobilised on anionic GO and subsequently grafted with hydrophobic polymer grafts. Dense grafts of PBA, PBMA and PMMA with a wide range of average graft lengths (MW: 1-440 kDa) were polymerised by surface-initiated controlled radical precipitation polymerisation from the statistical MI. The surface modification is designed similarly to bimodal graft systems, where the cationic MI generates nanoparticle repulsion, similar to dense short grafts, while the long grafts offer miscibility in non-polar environments and cohesion. The state-of-the-art dispersions of grafted GO were in the isotropic state. Transparent and translucent matrix-free GO-composites could be melt-processed directly using only grafted GO. After processing, birefringence due to nematic alignment of grafted GO was observed as a single giant Maltese cross, 3.4 cm across. Permeability models for composites containing aligned 2D-fillers were developed, which were compared with the experimental oxygen permeability data and found to be consistent with isotropic or nematic states. The storage modulus of the matrix-free GO-composites increased with GO content (50% increase at 0.67 wt%), while the significant increases in the thermal stability (up to 130 °C) and the glass transition temperature (up to 17 °C) were dependent on graft length. The tuneable matrix-free GO-composites with rapid thermo-responsive shape-memory effects are promising candidates for a vast range of applications, especially selective membranes and sensors. Electronic supplementary information (ESI) available: Figures of LCST, polymerization kinetics, melt-processed films, DLS, TGA, precipitated fiber and powder, TEM (of isotropic GO), birefringence, OP-data, DMTA-data and DSC. See DOI: 10.1039/c6nr01502f

Aluminium substitution in iron(II-III)-layered double hydroxides: Formation and cationic order

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

Ruby, Christian; Abdelmoula, Mustapha; Aissa, Rabha

The formation and the modifications of the structural properties of an aluminium-substituted iron(II-III)-layered double hydroxide (LDH) of formula Fe{sub 4}{sup II}Fe{sub (2-6y)}{sup III}Al{sub 6y}{sup III} (OH){sub 12} SO{sub 4}, 8H{sub 2}O are followed by pH titration curves, Moessbauer spectroscopy and high-resolution X-ray powder diffraction using synchrotron radiation. Rietveld refinements allow to build a structural model for hydroxysulphate green rust, GR(SO{sub 4}{sup 2-}), i.e. y=0, in which a bilayer of sulphate anions points to the Fe{sup 3+} species. A cationic order is proposed to occur in both GR(SO{sub 4}{sup 2-}) and aluminium-substituted hydroxysulphate green rust when y<0.08. Variation of the cellmore » parameters and a sharp decrease in average crystal size and anisotropy are detected for an aluminium content as low as y=0.01. The formation of Al-GR(SO{sub 4}{sup 2-}) is preceded by the successive precipitation of Fe{sup III} and Al{sup III} (oxy)hydroxides. Adsorption of more soluble Al{sup III} species onto the initially formed ferric oxyhydroxide may be responsible for this slowdown of crystal growth. Therefore, the insertion of low aluminium amount (y{approx}0.01) could be an interesting way for increasing the surface reactivity of iron(II-III) LDH that maintains constant the quantity of the reactive Fe{sup II} species of the material. - Graphical abstract: (a) Crystallographical structure of sulphated green rust: SO{sub 4}{sup 2-} point to the Fe{sup 3+} cations (red) that form an ordered array with the Fe{sup 2+} cations (green). (b) Width and asymmetry of the synchrotron XRD peaks increase rapidly when some Al{sup 3+} species substitute the Fe{sup 3+} cations; z is molar ratio Al{sup 3+}/Fe{sup 3+}.« less

Exchangeable cations-mediated photodegradation of polycyclic aromatic hydrocarbons (PAHs) on smectite surface under visible light.

PubMed

Jia, Hanzhong; Li, Li; Chen, Hongxia; Zhao, Yue; Li, Xiyou; Wang, Chuanyi

2015-04-28

Clay minerals saturated with different exchangeable cations are expected to play various roles in photodegradation of polycyclic aromatic hydrocarbons (PAHs) via direct and/or indirect pathways on clay surfaces. In the present study, anthracene and phenanthrene were selected as molecule probes to investigate the roles of exchangeable cations on their photodegradation under visible light irradiation. For five types of cation-modified smectite clays, the photodegradation rate of anthracene and phenanthrene follows the order: Fe(3+)>Al(3+)>Cu(2+)>Ca(2+)>K(+)>Na(+), which is consistent with the binding energy of cation-π interactions between PAHs and exchangeable cations. The result suggests that PAHs photolysis rate depends on cation-π interactions on clay surfaces. Meanwhile, the deposition of anthracene at the Na(+)-smectite and K(+)-smectite surface favors solar light absorption, resulting in enhanced direct photodecomposition of PAHs. On the other hand, smectite clays saturated with Fe(3+), Al(3+), and Cu(2+) are highly photoreactive and can act as potential catalysts giving rise to oxidative radicals such as O2(-) , which initiate the transformation of PAHs. The present work provides valuable insights into understanding the transformation and fate of PAHs in the natural soil environment and sheds light on the development of technologies for contaminated land remediation. Copyright © 2015 Elsevier B.V. All rights reserved.

The influence of ionic strength and organic compounds on nanoparticle TiO2 (n-TiO2) aggregation.

PubMed

Lee, Jaewoong; Bartelt-Hunt, Shannon L; Li, Yusong; Gilrein, Erica Jeanne

2016-07-01

This study investigated the aggregation of n-TiO2 in the presence of humic acid (HA) and/or 17β-estradiol (E2) under high ionic strength conditions simulating levels detected in landfill leachate. Aggregation of n-TiO2 was strongly influenced by ionic strength as well as ionic valence in that divalent cations (Ca(2+)) were more effective than monovalent (Na(+)) at the surface modification. HA or E2 enhanced aggregation of n-TiO2 in 20 mM CaCl2, however little aggregation was observed in 100 mM NaCl. Similarly, we observed only the increased aggregation of n-TiO2 in the presence of HA/E2. These results showed the critical role of particles' surface charges on the aggregation behaviors of n-TiO2 that HA plays more significantly than E2. However, the slightly increased zeta potential and aggregation of n-TiO2 in the combination of HA and E2 at both 20 mM CaCl2 and 100 mM NaCl means that E2 has influenced on the surface modification of n-TiO2 by adsorption. Based on the aggregation of n-TiO2 under high ionic strength with HA and/or E2, we simulated the mobility of aggregated n-TiO2 in porous media. As a result, we observed that the mobility distance of aggregated n-TiO2 was dramatically influenced by the surface modification with both HA and/or E2 between particles and media. Furthermore, larger mobility distance was observed with larger aggregation of n-TiO2 particles that can be explained by clean bed filtration (CFT) theory. Copyright © 2016 Elsevier Ltd. All rights reserved.

Barcoded materials based on photoluminescent hybrid system of lanthanide ions-doped metal organic framework and silica via ion exchange.

PubMed

Shen, Xiang; Yan, Bing

2016-04-15

A multicolored photoluminescent hybrid system based on lanthanide ions-doped metal organic frameworks/silica composite host has potential in display and barcode applications. By controlling the stoichiometry of the lanthanides via cation exchange, proportional various lanthanide ions are successfully introduced into metal organic frameworks, whose emission intensity is correspondingly proportional to its amount. The resulting luminescent barcodes depend on the lanthanide ions ratios and compositions. Subsequently, the lanthanide ions located in the channels of metal organic frameworks are protected from any interaction with the environment after the modification of silica on the surface. The optical and thermal stability of the hybrid materials are improved for technological application. Copyright © 2016 Elsevier Inc. All rights reserved.

Role of organic cations on hybrid halide perovskite CH3NH3PbI3 surfaces

NASA Astrophysics Data System (ADS)

Teng, Qiang; Shi, Ting-Ting; Tian, Ren-Yu; Yang, Xiao-Bao; Zhao, Yu-Jun

2018-02-01

Organic-inorganic hybrid halide perovskite CH3NH3PbI3 (MAPbI3) has received rapid progress in power conversion efficiency as promising photovoltaic materials, yet the surface structures and the role of MA cations are not well understood. In this work, we investigated the structural stability and electronic properties of (001) surface of cubic, (001) and (110) surfaces of tetragonal and orthorhombic phases of MAPbI3 with considering the orientation of MA cations, by density functional theory calculations. We demonstrate that the orientation of MA cations has profound consequences on the structural stability and the electronic properties of the surfaces, in contrast to the bulk phases. Compared with the MA-I terminated surfaces, the Pb-I2 terminated ones generally have smaller band gaps and the advantage to enable the photo-excited holes to transfer to the hole-transport materials in both tetragonal and orthorhombic phases. Overall, we suggest that the films with Pb-I2 terminated surfaces would prevail in high performance solar energy absorbers.

Assembly of RNA nanostructures on supported lipid bilayers

NASA Astrophysics Data System (ADS)

Dabkowska, Aleksandra P.; Michanek, Agnes; Jaeger, Luc; Rabe, Michael; Chworos, Arkadiusz; Höök, Fredrik; Nylander, Tommy; Sparr, Emma

2014-12-01

The assembly of nucleic acid nanostructures with controlled size and shape has large impact in the fields of nanotechnology, nanomedicine and synthetic biology. The directed arrangement of nano-structures at interfaces is important for many applications. In spite of this, the use of laterally mobile lipid bilayers to control RNA three-dimensional nanostructure formation on surfaces remains largely unexplored. Here, we direct the self-assembly of RNA building blocks into three-dimensional structures of RNA on fluid lipid bilayers composed of cationic 1,2-dioleoyl-3-trimethylammonium-propane (DOTAP) or mixtures of zwitterionic 1,2-dioleoyl-sn-glycero-3-phosphatidylcholine (DOPC) and cationic sphingosine. We demonstrate the stepwise supramolecular assembly of discrete building blocks through specific and selective RNA-RNA interactions, based on results from quartz crystal microbalance with dissipation (QCM-D), ellipsometry, fluorescence recovery after photobleaching (FRAP) and total internal reflection fluorescence microscopy (TIRF) experiments. The assembly can be controlled to give a densely packed single layer of RNA polyhedrons at the fluid lipid bilayer surface. We show that assembly of the 3D structure can be modulated by sequence specific interactions, surface charge and changes in the salt composition and concentration. In addition, the tertiary structure of the RNA polyhedron can be controllably switched from an extended structure to one that is dense and compact. The versatile approach to building up three-dimensional structures of RNA does not require modification of the surface or the RNA molecules, and can be used as a bottom-up means of nanofabrication of functionalized bio-mimicking surfaces.The assembly of nucleic acid nanostructures with controlled size and shape has large impact in the fields of nanotechnology, nanomedicine and synthetic biology. The directed arrangement of nano-structures at interfaces is important for many applications. In spite of this, the use of laterally mobile lipid bilayers to control RNA three-dimensional nanostructure formation on surfaces remains largely unexplored. Here, we direct the self-assembly of RNA building blocks into three-dimensional structures of RNA on fluid lipid bilayers composed of cationic 1,2-dioleoyl-3-trimethylammonium-propane (DOTAP) or mixtures of zwitterionic 1,2-dioleoyl-sn-glycero-3-phosphatidylcholine (DOPC) and cationic sphingosine. We demonstrate the stepwise supramolecular assembly of discrete building blocks through specific and selective RNA-RNA interactions, based on results from quartz crystal microbalance with dissipation (QCM-D), ellipsometry, fluorescence recovery after photobleaching (FRAP) and total internal reflection fluorescence microscopy (TIRF) experiments. The assembly can be controlled to give a densely packed single layer of RNA polyhedrons at the fluid lipid bilayer surface. We show that assembly of the 3D structure can be modulated by sequence specific interactions, surface charge and changes in the salt composition and concentration. In addition, the tertiary structure of the RNA polyhedron can be controllably switched from an extended structure to one that is dense and compact. The versatile approach to building up three-dimensional structures of RNA does not require modification of the surface or the RNA molecules, and can be used as a bottom-up means of nanofabrication of functionalized bio-mimicking surfaces. Electronic supplementary information (ESI) available: Table with sequences of tRNA units used in this study; schematic structures of the RNA polyhedron and its building blocks; gel electrophoresis characterization of the RNA polyhedron and squares; AFM characterization of RNA tectosquare; schematic structures of RNA-9 and RNA-10 and their association with lipid bilayers; QCM-D frequency and dissipation data (as function of time) for adsorption of RNA polyhedrons, RNA squares and RNA9-10 TIRF images of RNA with Gelstar after photobleaching with analysis; Correlation plot in change of shear viscosity for TS3 and TO3-4 models for the stoichiometry of TS; QCM-D dissipation data for the sequential experiment in Fig. 5a; QCM-D and for the assembly of building blocks at the bilayer scaffold at varying bulk concentrations; QCM-D of adsorption of TS3. See DOI: 10.1039/c4nr05968a

Tuning the Magnetic Properties of Metal Oxide Nanocrystal Heterostructures by Cation Exchange

PubMed Central

2013-01-01

For three types of colloidal magnetic nanocrystals, we demonstrate that postsynthetic cation exchange enables tuning of the nanocrystal’s magnetic properties and achieving characteristics not obtainable by conventional synthetic routes. While the cation exchange procedure, performed in solution phase approach, was restricted so far to chalcogenide based semiconductor nanocrystals, here ferrite-based nanocrystals were subjected to a Fe2+ to Co2+ cation exchange procedure. This allows tracing of the compositional modifications by systematic and detailed magnetic characterization. In homogeneous magnetite nanocrystals and in gold/magnetite core shell nanocrystals the cation exchange increases the coercivity field, the remanence magnetization, as well as the superparamagnetic blocking temperature. For core/shell nanoheterostructures a selective doping of either the shell or predominantly of the core with Co2+ is demonstrated. By applying the cation exchange to FeO/CoFe2O4 core/shell nanocrystals the Neél temperature of the core material is increased and exchange-bias effects are enhanced so that vertical shifts of the hysteresis loops are obtained which are superior to those in any other system. PMID:23362940

2'-O-[2-[2-(N,N-Dimethylamino)ethoxy]ethyl] Modified Antisense Oligonucleotides: Symbiosis of Charge Interaction Factors and Stereoelectronic Effects

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

Prhavc, M.; Prakash, T.P.; Minasov, G.

Oligonucleotides with a novel, 2'-O-[2-[2-(N,N-dimethylamino)ethoxy]ethyl] (2'-O-DMAEOE) modification have been synthesized. This modification, a cationic analogue of the 2'-O-(2-methoxyethyl) (2'-O-MOE) modification, exhibits high binding affinity to target RNA (but not to DNA) and exceptional resistance to nuclease degradation. Analysis of the crystal structure of a self-complementary oligonucleotide containing a single 2'-O-DMAEOE modification explains the importance of charge factors and gauche effects on the observed antisense properties. 2'-O-DMAEOE modified oligonucleotides are ideal candidates for antisense drugs.

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

NASA Astrophysics Data System (ADS)

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

2014-05-01

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

Growth and Surface Modification of LaFeO3 Thin Films Induced By Reductive Annealing

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

Flynn, Brendan T.; Zhang, Hongliang; Shutthanandan, V.

2015-03-01

The electronic and ionic conductivity of perovskite oxides has enabled their use in diverse applications such as automotive exhaust catalysts, solid oxide fuel cell cathodes, and visible light photocatalysts. The redox chemistry at the surface of perovskite oxides is largely dependent on the oxidation state of the metal cations as well as the oxide surface stoichiometry. In this study, LaFeO3 (LFO) thin films grown on yttria-stabilized zirconia (YSZ) was characterized using both bulk and surface sensitive techniques. A combination of in situ reflection high energy electron diffraction (RHEED), x-ray diffraction (XRD), transmission electron microscopy (TEM) and Rutherford backscattering spectrometry (RBS)more » demonstrated that the film is highly oriented and stoichiometric. The film was annealed in an ultra-high vacuum chamber to simulate reducing conditions and studied by angle-resolved x-ray photoelectron spectroscopy (XPS). Iron was found to exist as Fe(0), Fe(II), and Fe(III) depending on the annealing conditions and the depth within the film. A decrease in the concentration of surface oxygen species was correlated with iron reduction. These results should help guide and enhance the design of perovskite materials for catalysts.« less

Post-Synthetic Modification of Porphyrin-Encapsulating Metal-Organic Materials by Cooperative Addition of Inorganic Salts to Enhance CO 2/CH 4 Selectivity

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

Zhang, Zhenjie; Gao, Wen-Yang; Wojtas, Lukasz

Keeping MOM: Reaction of biphenyl-3,4',5-tricarboxylate and Cd(NO 3) 2 in the presence of meso-tetra(N-methyl-4-pyridyl)porphine tetratosylate afforded porph@MOM-11, a microporous metal–organic material (MOM) that encapsulates cationic porphyrins and solvent in alternating open channels. Porph@MOM-11 has cation and anion binding sites that facilitate cooperative addition of inorganic salts (such as M +Cl -) in a stoichiometric fashion.

Comparison of cation adsorption by isostructural rutile and cassiterite.

PubMed

Machesky, Michael; Wesolowski, David; Rosenqvist, Jörgen; Předota, Milan; Vlcek, Lukas; Ridley, Moira; Kohli, Vaibhav; Zhang, Zhan; Fenter, Paul; Cummings, Peter; Lvov, Serguei; Fedkin, Mark; Rodriguez-Santiago, Victor; Kubicki, James; Bandura, Andrei

2011-04-19

Macroscopic net proton charging curves for powdered rutile and cassiterite specimens with the (110) crystal face predominant, as a function of pH in RbCl and NaCl solutions, trace SrCl(2) in NaCl, and trace ZnCl(2) in NaCl and Na Triflate solutions, are compared to corresponding molecular-level information obtained from static DFT optimizations and classical MD simulations, as well as synchrotron X-ray methods. The similarities and differences in the macroscopic charging behavior of rutile and cassiterite largely reflect the cation binding modes observed at the molecular level. Cation adsorption is primarily inner-sphere on both isostructural (110) surfaces, despite predictions that outer-sphere binding should predominate on low bulk dielectric constant oxides such as cassiterite (ε(bulk) ≈ 11). Inner-sphere adsorption is also significant for Rb(+) and Na(+) on neutral surfaces, whereas Cl(-) binding is predominately outer-sphere. As negative surface charge increases, relatively more Rb(+), Na(+), and especially Sr(2+) are bound in highly desolvated tetradentate fashion on the rutile (110) surface, largely accounting for enhanced negative charge development relative to cassiterite. Charging curves in the presence of Zn(2+) are very steep but similar for both oxides, reflective of Zn(2+) hydrolysis (and accompanying proton release) during the adsorption process, and the similar binding modes for ZnOH(+) on both surfaces. These results suggest that differences in cation adsorption between high and low bulk dielectric constant oxides are more subtly related to the relative degree of cation desolvation accompanying inner-sphere binding (i.e., more tetradentate binding on rutile), rather than distinct inner- and outer-sphere adsorption modes. Cation desolvation may be favored at the rutile (110) surface in part because inner-sphere water molecules are bound further from and less tightly than on the cassiterite (110) surface. Hence, their removal upon inner-sphere cation binding is relatively more favorable. © 2011 American Chemical Society

Modeling uranium(VI) adsorption onto montmorillonite under varying carbonate concentrations: A surface complexation model accounting for the spillover effect on surface potential

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

Tournassat, C.; Tinnacher, R. M.; Grangeon, S.

The prediction of U(VI) adsorption onto montmorillonite clay is confounded by the complexities of: (1) the montmorillonite structure in terms of adsorption sites on basal and edge surfaces, and the complex interactions between the electrical double layers at these surfaces, and (2) U(VI) solution speciation, which can include cationic, anionic and neutral species. Previous U(VI)-montmorillonite adsorption and modeling studies have typically expanded classical surface complexation modeling approaches, initially developed for simple oxides, to include both cation exchange and surface complexation reactions. However, previous models have not taken into account the unique characteristics of electrostatic surface potentials that occur at montmorillonitemore » edge sites, where the electrostatic surface potential of basal plane cation exchange sites influences the surface potential of neighboring edge sites (‘spillover’ effect).« less

Modeling uranium(VI) adsorption onto montmorillonite under varying carbonate concentrations: A surface complexation model accounting for the spillover effect on surface potential

DOE PAGES

Tournassat, C.; Tinnacher, R. M.; Grangeon, S.; ...

2017-10-06

The prediction of U(VI) adsorption onto montmorillonite clay is confounded by the complexities of: (1) the montmorillonite structure in terms of adsorption sites on basal and edge surfaces, and the complex interactions between the electrical double layers at these surfaces, and (2) U(VI) solution speciation, which can include cationic, anionic and neutral species. Previous U(VI)-montmorillonite adsorption and modeling studies have typically expanded classical surface complexation modeling approaches, initially developed for simple oxides, to include both cation exchange and surface complexation reactions. However, previous models have not taken into account the unique characteristics of electrostatic surface potentials that occur at montmorillonitemore » edge sites, where the electrostatic surface potential of basal plane cation exchange sites influences the surface potential of neighboring edge sites (‘spillover’ effect).« less

Electromers of the benzene dimer radical cation.

PubMed

Błoch-Mechkour, Anna; Bally, Thomas

2015-04-28

The well-studied benzene dimer radical cation, which is prototypical for this class of species, has been reinvestigated computationally. Thereby it turned out that both the σ-hemibonded and the half-shifted sandwich structures of the benzene dimer cation, which had been independently proposed, represent stationary points on the B2PLYP-D potential energy surfaces. However, these structures belong to distinct electronic states, both of which are associated with potential surfaces that are very flat with regard to rotation of the two benzene rings in an opposite sense relative to each other. The surfaces of these two "electromers" of the benzene dimer cation are separated by only 3-4 kcal mol(-1) and do not intersect along the rotation coordinate, which represents a rather unique electronic structure situation. When moving on either of the two surfaces the title complex is an extremely fluxional species, in spite of its being bound by over 20 kcal mol(-1).

Contact angles and wettability of ionic liquids on polar and non-polar surfaces.

PubMed

Pereira, Matheus M; Kurnia, Kiki A; Sousa, Filipa L; Silva, Nuno J O; Lopes-da-Silva, José A; Coutinho, João A P; Freire, Mara G

2015-12-21

Many applications involving ionic liquids (ILs) require the knowledge of their interfacial behaviour, such as wettability and adhesion. In this context, herein, two approaches were combined aiming at understanding the impact of the IL chemical structures on their wettability on both polar and non-polar surfaces, namely: (i) the experimental determination of the contact angles of a broad range of ILs (covering a wide number of anions of variable polarity, cations, and cation alkyl side chain lengths) on polar and non-polar solid substrates (glass, Al-plate, and poly-(tetrafluoroethylene) (PTFE)); and (ii) the correlation of the experimental contact angles with the cation-anion pair interaction energies generated by the Conductor-like Screening Model for Real Solvents (COSMO-RS). The combined results reveal that the hydrogen-bond basicity of ILs, and thus the IL anion, plays a major role through their wettability on both polar and non-polar surfaces. The increase of the IL hydrogen-bond accepting ability leads to an improved wettability of more polar surfaces (lower contact angles) while the opposite trend is observed on non-polar surfaces. The cation nature and alkyl side chain lengths have however a smaller impact on the wetting ability of ILs. Linear correlations were found between the experimental contact angles and the cation-anion hydrogen-bonding and cation ring energies, estimated using COSMO-RS, suggesting that these features primarily control the wetting ability of ILs. Furthermore, two-descriptor correlations are proposed here to predict the contact angles of a wide variety of ILs on glass, Al-plate, and PTFE surfaces. A new extended list is provided for the contact angles of ILs on three surfaces, which can be used as a priori information to choose appropriate ILs before a given application.

Modification of the erythrocyte membrane dielectric constant by alcohols.

PubMed

Orme, F W; Moronne, M M; Macey, R I

1988-08-01

Aliphatic alcohols are found to stimulate the transmembrane fluxes of a hydrophobic cation (tetraphenylarsonium, TPA) and anion (AN-12) 5-20 times in red blood cells. The results are analyzed using the Born-Parsegian equation (Parsegian, A., 1969, Nature (London) 221:844-846), together with the Clausius-Mossotti equation to calculate membrane dielectric energy barriers. Using established literature values of membrane thickness, native membrane dielectric constant, TPA ionic radius, and alcohol properties (partition coefficient, molar volume, dielectric constant), the TPA permeability data is predicted remarkably well by theory. If the radius of AN-12 is taken as 1.9 A, its permeability in the presence of butanol is also described by our analysis. Further, the theory quantitatively accounts for the data of Gutknecht and Tosteson (Gutknecht, J., Tosteson, D.C., 1970, J. Gen. Physiol. 55:359-374) covering alcohol-induced conductivity changes of 3 orders of magnitude in artificial bilayers. Other explanations including perturbations of membrane fluidity, surface charge, membrane thickness, and dipole potential are discussed. However, the large magnitude of the stimulation, the more pronounced effect on smaller ions, and the acceleration of both anions and cations suggest membrane dielectric constant change as the primary basis of alcohol effects.

Nanostructured multilayer thin films of multiwalled carbon nanotubes/gold nanoparticles/glutathione for the electrochemical detection of dopamine

NASA Astrophysics Data System (ADS)

Detsri, Ekarat; Rujipornsakul, Sirilak; Treetasayoot, Tanapong; Siriwattanamethanon, Pawarit

2016-10-01

In the present study, multiwalled carbon nanotubes (MWCNTs), gold nanoparticles (AuNPs), and glutathione (GSH) were used to fabricate multilayer nanoscale thin films. The composite thin films were fabricated by layer-by-layer technique as the films were constructed by the alternate deposition of cationic and anionic polyelectrolytes. The MWCNTs were modified via a noncovalent surface modification method using poly(diallydimethylammonium chloride) to form a cationic polyelectrolyte. An anionic polyelectrolyte was prepared by the chemical reduction of HAuCl4 using sodium citrate as both the stabilizing and reducing agent to form anionic AuNPs. GSH was used as an electrocatalyst toward the electro-oxidation of dopamine. The constructed composite electrode exhibits excellent electrocatalytic activity toward dopamine with a short response time and a wide linear range from 1 to 100 μmol/L. The limits of detection and quantitation of dopamine are (0.316 ± 0.081) μmol/L and (1.054 ± 0.081) μmol/L, respectively. The method is satisfactorily applied for the determination of dopamine in plasma and urine samples to obtain the recovery in the range from 97.90% to 105.00%.

Substantiating In Vivo Magnetic Brain Tumor Targeting of Cationic Iron Oxide Nanocarriers via Adsorptive Surface Masking

PubMed Central

Chertok, Beata; David, Allan E.; Moffat, Bradford A.; Yang, Victor C.

2009-01-01

Cationic magnetic nanoparticles are attractive as potential vehicles for tumor drug delivery due to their favorable interactions with both the tumor milieu and the therapeutic cargo. However, systemic delivery of these nanoparticles to the tumor site is compromised by their rapid plasma clearance. We developed a simple method for in vivo protection of cationic nanocarriers, using non-covalent surface masking with a conjugate of low molecular weight heparin and polyethylene glycol. Surface masking resulted in an 11-fold increase in plasma AUC and a 2-fold increase in the magnetic capture of systemically injected nanoparticles in orthotopic rodent brain tumors. Overall, the described methodology could expand the prospective applications for cationic magnetic nanoparticles in magnetically-mediated gene/drug delivery. PMID:19782394

High Temperature Thermosetting Polyimide Nanocomposites Prepared with Reduced Charge Organoclay

NASA Technical Reports Server (NTRS)

Campbell, Sandi; Liang, Margaret I.

2005-01-01

The naturally occurring sodium and calcium cations found in bentonite clay galleries were exchanged with lithium cations. Following the cation exchange, a series of reduced charge clays were prepared by heat treatment of the lithium bentonite at 130 C, 150 C, or 170 C. Inductively coupled plasma (ICP) analysis showed that heating the lithium clay at elevated temperatures reduced its cation exchange capacity. Ion exchange of heat-treated clays with either a protonated alkyl amine or a protonated aromatic diamine resulted in decreasing amounts of the organic modifier incorporated into the lithium clay. The level of silicate dispersion in a thermosetting polyimide matrix was dependent upon the temperature of Li-clay heat treatment as well as the organic modification. In general, clays treated at 150 C or 170 C, and exchanged with protonated octadcylamine or protonated 2,2'-dimethlybenzidine (DMBZ) showed a higher degree of dispersion than clays treated at 130 C, or exchanged with protonated dodecylamine. Dynamic mechanical analysis showed little change in the storage modulus or T(sub g) of the nanocomposites compared to the base resin. However, long term isothermal aging of the samples showed a significant decrease in the resin oxidative weight loss. Nanocomposite samples aged in air for 1000 hours at 288 C showed of to a decrease in weight loss compared to that of the base resin. This again was dependent on the temperature at which the Li-clay was heated and the choice of organic modification.

Evaluation of crumb rubber modification of Louisiana mixtures : [research project capsule].

DOT National Transportation Integrated Search

2015-11-01

The Louisiana Department of : Transportation and Development : (DOTD) has been allowing crumb rubber : modi cation (CRM) of asphalt mixtures : since 2008. Initially, the performance : of roadways constructed with CRM was : adequate. The in uenc...

Detection of anions by normal Raman spectroscopy and surface-enhanced Raman spectroscopy of cationic-coated substrates.

PubMed

Mosier-Boss, P A; Lieberman, S H

2003-09-01

The use of normal Raman spectroscopy and surface-enhanced Raman spectroscopy (SERS) of cationic-coated silver and gold substrates to detect polyatomic anions in aqueous environments is examined. For normal Raman spectroscopy, using near-infrared excitation, linear concentration responses were observed. Detection limits varied from 84 ppm for perchlorate to 2600 ppm for phosphate. In general, detection limits in the ppb to ppm concentration range for the polyatomic anions were achieved using cationic-coated SERS substrates. Adsorption of the polyatomic anions on the cationic-coated SERS substrates was described by a Frumkin isotherm. The SERS technique could not be used to detect dichromate, as this anion reacted with the coatings to form thiol esters. A competitive complexation method was used to evaluate the interaction of chloride ion with the cationic coatings. Hydrogen bonding and pi-pi interactions play significant roles in the selectivity of the cationic coatings.

Spontaneous modification of graphite anode by anthraquinone-2-sulfonic acid for microbial fuel cells.

PubMed

Tang, Xinhua; Li, Haoran; Du, Zhuwei; Ng, How Yong

2014-07-01

In this study, anthraquinone-2-sulfonic acid (AQS), an electron transfer mediator, was immobilized onto graphite felt surface via spontaneous reduction of the in situ generated AQS diazonium cations. Cyclic voltammetry (CV) and energy dispersive spectrometry (EDS) characterizations of AQS modified graphite demonstrated that AQS was covalently grafted onto the graphite surface. The modified graphite, with a surface AQS concentration of 5.37 ± 1.15 × 10(-9)mol/cm(2), exhibited good electrochemical activity and high stability. The midpoint potential of the modified graphite was about -0.248 V (vs. normal hydrogen electrode, NHE), indicating that electrons could be easily transferred from NADH in bacteria to the electrode. AQS modified anode in MFCs increased the maximum power density from 967 ± 33 mW/m(2) to 1872 ± 42 mW/m(2). These results demonstrated that covalently modified AQS functioned as an electron transfer mediator to facilitate extracellular electron transfer from bacteria to electrode and significantly enhanced the power production in MFCs. Copyright © 2014 Elsevier Ltd. All rights reserved.

The electrokinetic characterization of gold nanoparticles, functionalized with cationic functional groups, and its' interaction with DNA.

PubMed

Lazarus, Geraldine Genevive; Revaprasadu, Neerish; López-Viota, Julián; Singh, Moganavelli

2014-09-01

Gold nanoparticles have attracted strong biomedical interest for drug delivery due to their low toxic nature, surface plasmon resonance and capability of increasing the stability of the payload. However, gene transfection represents another important biological application. Considering that cellular barriers keep enclosed their secret to deliver genes using nanoparticles, an important step can be achieved by studying the functionalization of nanoparticles with DNA. In the present contribution the synthesis of nanoparticles consisting of a gold core coated with one or more layers of amino acid (l-lysine), and cationic polyelectrolytes (poly-ethyleneimine and poly-l-lysine) is reported. All nanoparticles were subjected to dynamic light scattering, electrophoretic mobility measurements, UV-vis optical spectrophotometry analysis and transmission electron microscopy imaging. In addition, the adsorption of DNA plasmid (pSGS) with linear and supercoiled configurations was studied for those gold nanoparticles under the most suitable surface modifications. Preliminary results showed that the gold nanoparticles functionalized with poly-ethyleneimine and poly-l-lysine, respectively, and bound to linear DNA configurations, present in absolute value a higher electrophoretic mobility irrespective of the pH of the media, compared to the supercoiled and nicked configuration. The findings from this study suggest that poly-ethyleneimine and poly-l-lysine functionalized gold nanoparticles are biocompatible and may be promising in the chemical design and future optimization of nanostructures for biomedical applications such as gene and drug delivery. Copyright © 2014 Elsevier B.V. All rights reserved.

Production and characterization of carbonized sorbent products optimized for anionic contaminants

NASA Astrophysics Data System (ADS)

Viglasova, Eva; Fristak, Vladimir; Galambos, Michal; Hood-Nowotny, Rebecca; Soja, Gerhard

2017-04-01

Processing conditions, production methods and feedstock characteristics have been shown to affect the final sorption properties of biochar-based sorbents that have been produced in pyrolysis reactors. The content of O-containing carboxyl, phenolic and hydroxyl functional groups on the biochar surfaces plays a crucial role in sorption chemistry of hazardous materials. The sorption process can be affected by the presence of non-carbonized fractions in biochar matter as well. All these characteristics indicate that biochar shows good potential as a new tool in removal and separation technologies of various pollutants from waste water or contaminated soils. The sorption potential of wood-based biochars for cationic forms of heavy metals has been studied intensively and has already led to successful pilot applications in the field. However, anionic compounds (e.g. phosphate, nitrate, sulphate, As-, Cr-compounds) do not sorb well to unmodified biochar and need specific surface modification of biochar. Based on this fact, we try to obtain data about the sorptive separation of anionic forms of various contaminants from model aqueous solutions by different types of biochar-derived sorbents, or mineral-enriched biochar-derived sorbents. An important part of this research is the assesment of the effects of varying process parameters during biomass carbonisation, the role of biomass feedstock and pre-and/or post-treatment of the biochars onto sorption processes. We specify the most appropriate application strategies with biochar for remediation purposes of waste water or contaminated waters with elevated toxic metal concentrations that might compromise the quality of surface waters. The main aim of research is the preparation of modified biochar sorbent, the characterization of its surface and the investigation about new possibilities of modified biochar sorbent applications for sorption of various contaminants, mainly their anionic forms (e.g. phosphates, nitrates, arsenates). Modification of bamboo-based biochar with clay minerals, the preparation of its composites, could increase the surface area of bamboo-based biochar from 3 to 5 times. Other ways of modification e.g. by using FeCl3 ṡ 6H2O caused a significant increase of sorption ability for anionic forms

Inversion of membrane surface charge by trivalent cations probed with a cation-selective channel

PubMed Central

Gurnev, Philip A.; Bezrukov, Sergey M.

2014-01-01

We demonstrate that the cation-selective channel formed by gramicidin A can be used as a reliable sensor for studying the multivalent ion accumulation at the surfaces of charged lipid membranes and the “charge inversion” phenomenon. In asymmetrically charged membranes with the individual leaflets formed from pure negative and positive lipids bathed by 0.1 M CsCl solutions the channel exhibits current rectification which is comparable to that of a typical n/p semiconductor diode. We show that even at these highly asymmetrical conditions the channel conductance can be satisfactorily described by the electrodiffusion equation in the constant field approximation but, due to predictable limitations, only when the applied voltages do not exceed 50 mV. Analysis of the changes in the voltage-dependent channel conductance upon addition of trivalent cations allows us to gauge their interactions with the membrane surface. The inversion of the sign of the effective surface charge takes place at the concentrations which correlate with the cation size. Specifically, these concentrations are close to 0.05 mM for lanthanum, 0.25 mM for hexaamminecobalt, and 4 mM for spermidine. PMID:23088396

Inversion of membrane surface charge by trivalent cations probed with a cation-selective channel.

PubMed

Gurnev, Philip A; Bezrukov, Sergey M

2012-11-13

We demonstrate that the cation-selective channel formed by gramicidin A can be used as a reliable sensor for studying the multivalent ion accumulation at the surfaces of charged lipid membranes and the "charge inversion" phenomenon. In asymmetrically charged membranes with the individual leaflets formed from pure negative and positive lipids bathed by 0.1 M CsCl solutions the channel exhibits current rectification, which is comparable to that of a typical n/p semiconductor diode. We show that even at these highly asymmetrical conditions the channel conductance can be satisfactorily described by the electrodiffusion equation in the constant field approximation but, due to predictable limitations, only when the applied voltages do not exceed 50 mV. Analysis of the changes in the voltage-dependent channel conductance upon addition of trivalent cations allows us to gauge their interactions with the membrane surface. The inversion of the sign of the effective surface charge takes place at the concentrations, which correlate with the cation size. Specifically, these concentrations are close to 0.05 mM for lanthanum, 0.25 mM for hexaamminecobalt, and 4 mM for spermidine.

The Effect of n vs. iso Isomerization on the Thermophysical Properties of Aromatic and Non-aromatic Ionic Liquids.

PubMed

Rodrigues, Ana S M C; Almeida, Hugo F D; Freire, Mara G; Lopes-da-Silva, José A; Coutinho, João A P; Santos, Luís M N B F

2016-09-15

This work explores the n vs. iso isomerization effects on the physicochemical properties of different families of ionic liquids (ILs) with variable aromaticity and ring size. This study comprises the experimental measurements, in a wide temperature range, of the ILs' thermal behavior, heat capacities, densities, refractive indices, surface tensions, and viscosities. The results here reported show that the presence of the iso -alkyl group leads to an increase of the temperature of the glass transition, T g . The iso- pyrrolidinium (5 atoms ring cation core) and iso -piperidinium (6 atoms ring cation core) ILs present a strong differentiation in the enthalpy and entropy of melting. Non-aromatic ILs have higher molar heat capacities due to the increase of the atomic contribution, whereas it was not found any significant differentiation between the n and iso -alkyl isomers. A small increase of the surface tension was observed for the non-aromatic ILs, which could be related to their higher cohesive energy of the bulk, while the lower surface entropy observed for the iso isomers indicates a structural resemblance between the IL bulk and surface. The significant differentiation between ILs with a 5 and 6 atoms ring cation in the n -alkyl series (where 5 atoms ring cations have higher surface entropy) is an indication of a more efficient arrangement of the non-polar region at the surface in ILs with smaller cation cores. The ILs constituted by non-aromatic piperidinium cation, and iso -alkyl isomers were found to be the most viscous among the studied ILs due to their higher energy barriers for shear stress.

Self-Assembled Carbon-Polyoxometalate Composites for Electrochemical Capacitors

NASA Astrophysics Data System (ADS)

Genovese, Matthew

The development of high performance yet cost effective energy storage devices is critical for enabling the growth of important emerging sectors from the internet of things to grid integration of renewable energy. Material costs are by far the largest contributor to the overall cost of energy storage devices and thus research into cost effective energy storage materials will play an important role in developing technology to meet real world storage demands. In this thesis, low cost high performance composite electrode materials for supercapacitors (SCs) have been developed through the surface modification of electrochemically double layer capacitive (EDLC) carbon substrates with pseudocapacitive Polyoxometalates (POMs). Significant fundamental contributions have been made to the understanding of all components of the composite electrode including the POM active layer, cation linker, and carbon substrate. The interaction of different POM chemistries in solution has been studied to elucidate the novel ways in which these molecules combine and the mechanism underlying this combination. A more thorough understanding regarding the cation linker's role in electrode fabrication has been developed through examining the linker properties which most strongly affect electrode performance. The development of porosity in biomass derived carbon materials has also been examined leading to important insights regarding the effect of substrate porosity on POM modification and electrochemical properties. These fundamental contributions enabled the design and performance optimization of POM-carbon composite SC electrodes. Understanding how POMs combine in solution, allowed for the development of mixed POM molecular coatings with tunable electrochemical properties. These molecular coatings were used to modify low cost biomass derived carbon substrates that had been structurally optimized to accommodate POM molecules. The resulting electrode composites utilizing low cost materials fabricated through simple scalable techniques demonstrated (i) high capacitance (361 F g-1), (ii) close to ideal pseudocapacitive behavior, (iii) stable cycling, and (iv) good rate performance.

Surface functionalization of Cu-Ni alloys via grafting of a bactericidal polymer for inhibiting biocorrosion by Desulfovibrio desulfuricans in anaerobic seawater.

PubMed

Yuan, S J; Liu, C K; Pehkonen, S O; Bai, R B; Neoh, K G; Ting, Y P; Kang, E T

2009-01-01

A novel surface modification technique was developed to provide a copper nickel alloy (M) surface with bactericidal and anticorrosion properties for inhibiting biocorrosion. 4-(chloromethyl)-phenyl tricholorosilane (CTS) was first coupled to the hydroxylated alloy surface to form a compact silane layer, as well as to confer the surface with chloromethyl functional groups. The latter allowed the coupling of 4-vinylpyridine (4VP) to generate the M-CTS-4VP surface with biocidal functionality. Subsequent surface graft polymerization of 4VP, in the presence of benzoyl peroxide (BPO) initiator, from the M-CTS-4VP surface produced the poly(4-vinylpyridine) (P(4VP)) grafted surface, or the M-CTS-P(4VP) surface. The pyridine nitrogen moieties on the M-CTS-P(4VP) surface were quaternized with hexylbromide to produce a high concentration of quaternary ammonium groups. Each surface functionalization step was ascertained by X-ray photoelectron spectroscopy (XPS) and static water contact angle measurements. The alloy with surface-quaternized pyridinium cation groups (N+) exhibited good bactericidal efficiency in a Desulfovibrio desulfuricans-inoculated seawater-based modified Barr's medium, as indicated by viable cell counts and fluorescence microscopy (FM) images of the surface. The anticorrosion capability of the organic layers was verified by the polarization curve and electrochemical impedance spectroscopy (EIS) measurements. In comparison, the pristine (surface hydroxylated) Cu-Ni alloy was found to be readily susceptible to biocorrosion under the same environment.

Synthesis, structural characterization and antibacterial activity of cotton fabric modified with a hydrogel containing barium hexaferrite nanoparticles

NASA Astrophysics Data System (ADS)

Staneva, Desislava; Koutzarova, Tatyana; Vertruyen, Benedicte; Vasileva-Tonkova, Evgenia; Grabchev, Ivo

2017-01-01

Barium hexaferrite nanoparticles were synthesized by co-precipitation of Ba2+ and Fe3+ cations with NaOH under of high-power ultrasound. The nanoparticles were dispersed in an aqueous solution of the hydrogel precursors. This solution was used to impregnate the cotton fabric dyed with a photoinitiator. The composite material BaFe12O19 nanoparticles-hydrogel-cotton fabric was prepared by surface initiate photopolymerization under visible light. The modification of the cotton fabric and uniform distribution of the nanoparticles in the structure of the hydrogel were analyzed by scanning electron microscopy (SEM), IR spectroscopy, X-ray diffraction analysis (XRD), fluorescence and colourimetric analyses. The antibacterial efficacy of the material was evaluated against Gram-negative Escherichia coli and Pseudomonas aeruginosa.

Chemical and Physical Characteristics of Soy Proteins for New Industrial Applications

NASA Astrophysics Data System (ADS)

Arboleda Fernandez, Julio Cesar

Despite of being environmentally friendly, biocompatible, rich in chemical functionality and abundant as residual materials, soy proteins (SPs) are used for low added value applications. In this work, SPs were studied and used as potentially useful biomacromolecules for different industrial applications with high added value. Initially the effect of acid hydrolysis of soy proteins as a potential route for subsequent surface modification was studied, finding that SP hydrolysates tend to form less aggregates and to adsorb at faster rates compared with unmodified SP; nevertheless, it was also found that the amount of protein adsorbed and water contact angle of the treated surface does not change significantly. Secondly, the gel forming properties of SPs were used to produce aerogels with densities in the order of 0.1 g/cm3. To improve their mechanical properties, the reinforcement of these materials with cellulose nanofibers was studied, obtaining composite aerogels with SP loadings as high as ca. 70% that display a compression modulus of 4.4 MPa, very close to the value obtained from the pure nanofibers aerogels. The composite materials gain moisture (up to 5%) in equilibrium with 50% RH air. Futhermore, their physical integrity is unchanged upon immersion in polar and non-polar solvents, exhibiting sorption rates dependent on the aerogel composition, morphology and swelling abilities. Finally, different soy protein based products and derivatives were used to enhance the dry strength properties of wood fibers in paper production. Experiments using soy flour, soy protein isolate, soy protein isolate hydrolysates, cationized soy flour, and soy flour combined with cationic starch and chitosan were done, obtaining satisfactory results when soy protein flour was utilized in combination with conventional treatments involving cationic polymers. The current results confirm the opportunity to valorize residual soy products that are underutilized today as alternatives to oil derived chemicals used in chemical processes.

Surfactant adsorption and aggregate structure of silica nanoparticles: a versatile stratagem for the regulation of particle size and surface modification

NASA Astrophysics Data System (ADS)

Chaudhary, Savita; Rohilla, Deepak; Mehta, S. K.

2014-03-01

The area of silica nanoparticles is incredibly polygonal. Silica particles have aroused exceptional deliberation in bio-analysis due to great progress in particular arenas, for instance, biocompatibility, unique properties of modifiable pore size and organization, huge facade areas and pore volumes, manageable morphology and amendable surfaces, elevated chemical and thermal stability. Currently, silica nanoparticles participate in crucial utilities in daily trade rationales such as power storage, chemical and genetic sensors, groceries dispensation and catalysis. Herein, the size-dependent interfacial relation of anionic silica nanoparticles with twelve altered categories of cationic surfactants has been carried out in terms of the physical chemical facets of colloid and interface science. The current analysis endeavours to investigate the virtual consequences of different surfactants through the development of the objective composite materials. The nanoparticle size controls, the surface-to-volume ratio and surface bend relating to its interaction with surfactant will also be addressed in this work. More importantly, the simulated stratagem developed in this work can be lengthened to formulate core-shell nanostructures with functional nanoparticles encapsulated in silica particles, making this approach valuable and extensively pertinent for employing sophisticated materials for catalysis and drug delivery.

Impacts of chemical modification on the toxicity of diverse nanocellulose materials to developing zebrafish

PubMed Central

Harper, Bryan J.; Clendaniel, Alicea; Sinche, Federico; Way, Daniel; Hughes, Michael; Schardt, Jenna; Simonsen, John; Stefaniak, Aleksandr B.

2016-01-01

Cellulose is an abundant and renewable resource currently being investigated for utility in nanomaterial form for various promising applications ranging from medical and pharmaceutical uses to mechanical reinforcement and biofuels. The utility of nanocellulose and wide implementation ensures increasing exposure to humans and the environment as nanocellulose-based technologies advance. Here, we investigate how differences in aspect ratio and changes to surface chemistry, as well as synthesis methods, influence the biocompatibility of nanocellulose materials using the embryonic zebrafish. Investigations into the toxicity of neutral, cationic and anionic surface functionalities revealed that surface chemistry had a minimal influence on the overall toxicity of nanocellulose materials. Higher aspect ratio cellulose nanofibers produced by mechanical homogenization were, in some cases, more toxic than other cellulose-based nanofibers or nanocrystals produced by chemical synthesis methods. Using fluorescently labeled nanocellulose we were able to show that nanocellulose uptake did occur in embryonic zebrafish during development. We conclude that the benign nature of nanocellulose materials makes them an ideal platform to systematically investigate the inherent surface features driving nanomaterial toxicity in order to create safer design principles for engineered nanoparticles. PMID:27468180

Modification of molybdenum surface by low-energy oxygen implantation at room temperature

NASA Astrophysics Data System (ADS)

Kavre Piltaver, Ivna; Jelovica Badovinac, Ivana; Peter, Robert; Saric, Iva; Petravic, Mladen

2017-12-01

We have studied the initial stages of oxide formation on molybdenum surfaces under 1 keV O2+ ion bombardment at room temperature (RT), using x-ray photoelectron spectroscopy around Mo 3d or O 1s core-levels and the valence band photoemission. The results are compared with the oxidation mechanism of thermally oxidized Mo at RT. The thermal oxidation reveals the formation of a very thin MoO2 layer that prevents any further adsorption of oxygen at higher oxygen doses. Oxygen implantation is more efficient in creating thicker oxide films with the simultaneous formation of several oxide compounds. The oxidation rates of MoO2 and Mo2O5 follow the parabolic growth rate consistent with the mass transport driven by diffusion of either neutral or singly and doubly charged oxygen interstitials. The oxidation of MoO3, which occurs at a later oxidation stage, follows the logarithmic rate driven by the diffusion of cations in an electric field.

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.

Dual functions of zirconium modification on improving the electrochemical performance of Ni-rich LiNi0.8Co0.1Mn0.1O2

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

Li, Xing; Zhang, Kangjia; Wang, Mingshan

2018-02-28

Trace amount of Zirconium (Zr) has been adopted to modify the crystal structure and surface of the Ni-rich LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode material. During cycling at 1.0C, the Zr-modified NCM811 shows an improved capacity retention of 92% after 100 cycles, higher than 75% for pristine NMC811. In addition, the Zr-modified NCM811 is capable of delivering a discharge capacity of 107 mAh g-1 at 10.0C rate, much higher than 28 mAh g-1 delivered by pristine material. These improved electrochemical performances are ascribed to the dual functions of Zr modification. On one hand, part of the Zr enters the crystal lattice, which ismore » beneficial for reducing the Li/Ni cation mixing and enhancing the crystal stability of the cathode. On the other hand, the rest of the Zr forms a 1~2 nm thick coating layer on the surface of the NCM811 cathode, which effectively prevents the direct contact between NCM and the electrolyte, thus suppressing the detrimental interfacial reactions. Therefore, the Zr-modified LiNi0.8Co0.1Mn0.1O2 exhibited significantly enhanced cycling stability and charging/discharging rate capability in comparison with the untreated counterpart.« less

Novel approach for modifying microporous filters for virus concentration from water.

PubMed Central

Preston, D R; Vasudevan, T V; Bitton, G; Farrah, S R; Morel, J L

1988-01-01

Electronegative microporous filters composed of epoxyfiberglass (Filterite) were treated with cationic polymers to enhance their virus-adsorbing properties. This novel and inexpensive approach to microporous filter modification entails soaking filters in an aqueous solution of a cationic polymer such as polyethyleneimine (PEI) for 2 h at room temperature and then allowing the filters to air dry overnight on absorbent paper towels. PEI-treated filters were evaluated for coliphage (MS2, T2, and phi X174) and enterovirus (poliovirus type 1 and coxsackievirus type B5) adsorption from buffer at pH 3.5 to 9.0 and for indigenous coliphages from unchlorinated secondary effluent at ambient pH. Adsorbed viruses were recovered with 3% beef extract (pH 9). Several other cationic polymers were used to modify epoxyfiberglass filters and were evaluated for their ability to concentrate viruses from water. Zeta potentials of disrupted filter material indicated that electronegative epoxyfiberglass filters were made more electropositive when treated with cationic polymers. In general, epoxyfiberglass filters treated with cationic polymers were found to adsorb a greater percentage of coliphages and enteroviruses than were untreated filters. PMID:2843091

Role of cationic size in the optical properties of the LiCl crystal surface: theoretical study.

PubMed

Abdel Halim, Wael Salah; Abdullah, Noha; Abdel-Aal, Safaa; Shalabi, A S

2012-06-01

The size of the cations (either Ca(2+), Sr(2+), Ga(+), or Au(+)) at the F(A1)-type color centers on the (100) surface of LiCl crystal plays an important role in the optical properties of this surface. In this work, double-well potentials at this surface were investigated using ab initio quantum mechanical methods. Quantum clusters were embedded in simulated Coulomb fields that closely approximate the Madelung fields of the host surface, and the ions that were the nearest neighbors to the F(A1) site were allowed to relax to equilibrium. The calculated Stokes-shifted optical transition bands, optical-optical conversion efficiency, and relaxed excited states of the defect-containing surface, as well as the orientational destruction of the color centers, recording sensitivity, exciton (energy) transfer, and the Glasner-Tompkins empirical relation were all found to be sensitive to the size of the dopant cation.

Surface-induced dissociation of methanol cations: A non-ergodic process

DOE PAGES

Shukla, Anil K.

2017-09-01

Here, dissociation of methanol molecular cations, CH 3OH +, to CH 2OH + on collision with a self-assembled monolayer surface of fluorinated alkyl thiol on gold 111 crystal has been studied at 12.5 eV collision energy. Two energetically and spatially distinct processes contribute to the dissociation process: one involving loss of very large amount of energy approaching the initial kinetic energy of the primary ions with scattering of fragment ions over a broad angular range between surface normal and surface parallel while the second process results from small amount of energy loss with fragment ions scattered over a narrow angularmore » range close to the surface parallel. There is a third process with relatively small contribution to total dissociation whose characteristics are very similar to the low energy loss process. Finally, these results demonstrate that surface-induced dissociation of methanol cations via hydrogen loss is non-ergodic.« less

Surface-induced dissociation of methanol cations: A non-ergodic process

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

Shukla, Anil K.

Here, dissociation of methanol molecular cations, CH 3OH +, to CH 2OH + on collision with a self-assembled monolayer surface of fluorinated alkyl thiol on gold 111 crystal has been studied at 12.5 eV collision energy. Two energetically and spatially distinct processes contribute to the dissociation process: one involving loss of very large amount of energy approaching the initial kinetic energy of the primary ions with scattering of fragment ions over a broad angular range between surface normal and surface parallel while the second process results from small amount of energy loss with fragment ions scattered over a narrow angularmore » range close to the surface parallel. There is a third process with relatively small contribution to total dissociation whose characteristics are very similar to the low energy loss process. Finally, these results demonstrate that surface-induced dissociation of methanol cations via hydrogen loss is non-ergodic.« less

Facile synthesis of surface-functionalized magnetic nanocomposites for effectively selective adsorption of cationic dyes

NASA Astrophysics Data System (ADS)

Hua, Yani; Xiao, Juan; Zhang, Qinqin; Cui, Chang; Wang, Chuan

2018-04-01

A new magnetic nano-adsorbent, polycatechol modified Fe3O4 magnetic nanoparticles (Fe3O4/PCC MNPs) were prepared by a facile chemical coprecipitation method using iron salts and catechol solution as precursors. Fe3O4/PCC MNPs owned negatively charged surface with oxygen-containing groups and showed a strong adsorption capacity and fast adsorption rates for the removal of cationic dyes in water. The adsorption capacity of methylene blue (MB), cationic turquoise blue GB (GB), malachite green (MG), crystal violet (CV) and cationic pink FG (FG) were 60.06 mg g- 1, 70.97 mg g- 1, 66.84 mg g- 1, 66.01 mg g- 1 and 50.27 mg g- 1, respectively. The adsorption mechanism was proposed by the analyses of the adsorption isotherms and adsorption kinetics of cationic dyes on Fe3O4/PCC MNPs. Moreover, the cationic dyes adsorbed on the MNPs as a function of contact time, pH value, temperature, coexisting cationic ions and ion strength were also investigated. These results suggested that the Fe3O4/PCC MNPs is promising to be used as a magnetic adsorbent for selective adsorption of cationic dyes in wastewater treatment.

Adsorption and transport of charged vs. neutral hydrophobic molecules at the membrane of murine erythroleukemia (MEL) cells.

PubMed

Zeng, Jia; Eckenrode, Heather M; Dai, Hai-Lung; Wilhelm, Michael J

2015-03-01

The adsorption and transport of hydrophobic molecules at the membrane surface of pre- and post-DMSO induced differentiated murine erythroleukemia (MEL) cells were examined by time- and wavelength-resolved second harmonic light scattering. Two medium (<600 Da) hydrophobic molecules, cationic malachite green (MG) and neutral bromocresol purple (BCP), were investigated. While it was observed that the MG cation adsorbs onto the surface of the MEL cell, neutral BCP does not. It is suggested that an electrostatic interaction between the opposite charges of the cation and the MEL cell surface is the primary driving force for adsorption. Comparisons of adsorption density and free energy, measured at different pH and cell morphology, indicate that the interaction is predominantly through sialic acid carboxyl groups. MG cation adsorption densities have been determined as (0.6±0.3)×10(6) μm(-2) on the surface of undifferentiated MEL cells, and (1.8±0.5)×10(7) μm(-2) on differentiated MEL cells, while the deduced adsorption free energies are effectively identical (ca. -10.9±0.1 and -10.8±0.1 kcal mol(-1), respectively). The measured MG densities indicate that the total number of surface carboxyl groups is largely conserved following differentiation, and therefore the density of carboxylic groups is much larger on the differentiated cell surface than the undifferentiated one. Finally, in contrast to synthetic liposomes and bacterial membranes, surface adsorbed MG cations are unable to traverse the MEL cell membrane. Copyright © 2015 Elsevier B.V. All rights reserved.

Polymer-Based Surfaces Designed to Reduce Biofilm Formation: From Antimicrobial Polymers to Strategies for Long-Term Applications.

PubMed

Riga, Esther K; Vöhringer, Maria; Widyaya, Vania Tanda; Lienkamp, Karen

2017-10-01

Contact-active antimicrobial polymer surfaces bear cationic charges and kill or deactivate bacteria by interaction with the negatively charged parts of their cell envelope (lipopolysaccharides, peptidoglycan, and membrane lipids). The exact mechanism of this interaction is still under debate. While cationic antimicrobial polymer surfaces can be very useful for short-term applications, they lose their activity once they are contaminated by a sufficiently thick layer of adhering biomolecules or bacterial cell debris. This layer shields incoming bacteria from the antimicrobially active cationic surface moieties. Besides discussing antimicrobial surfaces, this feature article focuses on recent strategies that were developed to overcome the contamination problem. This includes bifunctional materials with simultaneously presented antimicrobial and protein-repellent moieties; polymer surfaces that can be switched from an antimicrobial, cell-attractive to a cell-repellent state; polymer surfaces that can be regenerated by enzyme action; degradable antimicrobial polymers; and antimicrobial polymer surfaces with removable top layers. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of ionic strength, anions, cations, and natural organic matter on the adsorption of pharmaceuticals to silica.

PubMed

Bui, Tung Xuan; Choi, Heechul

2010-08-01

The adsorption of four wide-use pharmaceuticals (carbamazepine, diclofenac, ibuprofen, and ketoprofen) onto a porous silica was investigated under varied ionic strengths, different anions, divalent cations (Ca(2+) and Mg(2+)), trivalent cations (Al(3+) and Fe(3+)), and natural organic matter (NOM). The experiments demonstrated that at a given pH the adsorption was most affected by ionic strength, trivalent cations, and properties of pharmaceuticals. The increase of ionic strength resulted in an increase in the adsorption of ketoprofen, but a decrease in the adsorption of carbamazepine. Trivalent metal cations made intense increases in the adsorption of three acidic pharmaceuticals, which could be due to the formation of inner-sphere complex of the cations on the surface and/or complexation of the pharmaceuticals with both surface and aqueous metal species. It was found that the adsorption of carbamazepine was not affected by divalent and trivalent cations, whereas the adsorption of diclofenac was solely impacted by the presence of Al(3+). Moreover, divalent cations at low concentration could slightly enhance the adsorption of ibuprofen and ketoprofen, whereas NOM caused a reduction in the adsorption of the tested pharmaceuticals except for diclofenac. These results suggest that ionic strength, divalent cations, trivalent cations, and NOM are notable factors affecting the adsorption of pharmaceuticals and thus the ultimate fate of pharmaceuticals in the aqueous environment. Copyright 2010 Elsevier Ltd. All rights reserved.

Effects of exchanged cation and layer charge on the sorption of water and EGME vapors on montmorillonite clays

USGS Publications Warehouse

Chiou, Cary T.; Rutherford, David W.

1997-01-01

The effects of exchanged cation and layer charge on the sorption of water and ethylene glycol monoethyl ether (EGME) vapors on montmorillonite have been studied on SAz-1 and SWy-1 source clays, each exchanged respectively with Ca, Na, K, Cs and tetramethylammonium (TMA) cations. The corresponding lattice expansions were also determined, and the corresponding N2 adsorption data were provided for comparison. For clays exchanged with cations of low hydrating powers (such as K, Cs and TMA), water shows a notably lower uptake than does N2 at low relative pressures (P/P0). By contrast, EGME shows higher uptakes than N2 on all exchanged clays at all P/P0. The anomaly for water is attributed to its relatively low attraction for siloxane surfaces of montmorillonite because of its high cohesive energy density. In addition to solvating cations and expanding interlayers, water and EGME vapors condense into small clay pores and interlayer voids created by interlayer expansion. The initial (dry) interlayer separation varies more significantly with cation type than with layer charge; the water-saturated interlayer separation varies more with cation type than the EGME-saturated interlayer separation. Because of the differences in surface adsorption and interlayer expansion for water and EGME, no general correspondence is found between the isotherms of water and EGME on exchanged clays, nor is a simple relation observed between the overall uptake of either vapor and the cation solvating power. The excess interlayer capacities of water and of EGME that result from lattice expansion of the exchanged clays are estimated by correcting for amounts of vapor adsorption on planar clay surfaces and of vapor condensation into intrinsic clay pores. The resulting data follow more closely the relative solvating powers of the exchanged cations.

Physical properties of ionic liquids consisting of the 1-butyl-3-methylimidazolium cation with various anions and the bis(trifluoromethylsulfonyl)imide anion with various cations.

PubMed

Jin, Hui; O'Hare, Bernie; Dong, Jing; Arzhantsev, Sergei; Baker, Gary A; Wishart, James F; Benesi, Alan J; Maroncelli, Mark

2008-01-10

Physical properties of 4 room-temperature ionic liquids consisting of the 1-butyl-3-methylimidazolium cation with various perfluorinated anions and the bis(trifluoromethylsulfonyl)imide (Tf2N-) anion with 12 pyrrolidinium-, ammonium-, and hydroxyl-containing cations are reported. Electronic structure methods are used to calculate properties related to the size, shape, and dipole moment of individual ions. Experimental measurements of phase-transition temperatures, densities, refractive indices, surface tensions, solvatochromic polarities based on absorption of Nile Red, 19F chemical shifts of the Tf2N- anion, temperature-dependent viscosities, conductivities, and cation diffusion coefficients are reported. Correlations among the measured quantities as well as the use of surface tension and molar volume for estimating Hildebrand solubility parameters of ionic liquids are also discussed.

Modification of zeolite 4A for use as an adsorbent for glyphosate and as an antibacterial agent for water.

PubMed

Zavareh, Siamak; Farrokhzad, Zahra; Darvishi, Farshad

2018-07-15

The aim of this work was to design a low cost adsorbent for efficient and selective removal of glyphosate from water at neutral pH conditions. For this purpose, zeolite 4A, a locally abundant and cheap mineral material, was ion-exchanged with Cu 2+ to produce Cu-zeolite 4A. The FTIR results revealed that the modification has no important effect on chemical structure of zeolite 4A. After modification, highly crystalline zeolite 4A was converted to amorphous Cu-zeolite 4A according to XRD studies. The SEM images showed spherical-like particles with porous surfaces for Cu-zeolite 4A compared to cubic particles with smooth surfaces for zeolite 4A. Adsorption equilibrium data were well fitted with non-linear forms of Langmuir, Freundlich and Temkin isotherms. The maximum adsorption capacity for Cu-zeolite 4A was calculated to be 112.7 mg g -1 based on the Langmuir model. The adsorption of glyphosate by the modified adsorbent had fast kinetics fitted both pseudo-first-order and pseudo-second-order models. A mechanism based on chemical adsorption was proposed for the removal process. The modified adsorbent had a good selectivity to glyphosate over natural waters common cations and anions. It also showed desired regeneration ability as an important feature for practical uses. The potential use of the developed material as antibacterial agent for water disinfection filters was also investigated by MIC method. Relatively strong antibacterial activity was observed for Cu-zeolite 4A against Gram-positive and Gram-negative model bacteria while zeolite 4A had no antibacterial properties. No release of Cu 2+ to aqueous solutions was detected as unique feature of the developed material. Copyright © 2018 Elsevier Inc. All rights reserved.

Cationic Exchanger with Activated Clay. Part I. Characteristics of the Materials and Preparation of the Cationic Exchanger. Part II. Chemical Separation. Part III. Effect of Thermal Treatment and Gamma Irradiation on the Internal Surface and Capacity of Acidic Montmorillonite; SCAMBIO CATIONICO CON ARGILLE ATTIVATE. PARTE I. CARATTERISTICHE DEI MATERIALI E PREPARAZIONE DELLO SCAMBIATORE CATIONICO. PARTE II. SEPARAZIONI CHIMICHE. PARTE III. EFFETTO DEL TRATTAMENTO TERMICO E DELLA IRRADIAZIONE GAMMA SULLA SUPERFICIE INTERNA E SULLA CAPACITA DELLE MONTMORILLONITI ACIDE

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

Cerrai, E.; Ronchetti, C.; Triulzi, C.

1963-05-01

The preparation of an acidic cationic exchanger from a calcium bentonite is described. The behavior and properties of acidic montmorillonite and activated clay are given as well as the effect of thermal treatment and gamma irradiation on cationic exchange capacity and internal surface area. (auth)

All-inorganic Germanium nanocrystal films by cationic ligand exchange

DOE PAGES

Wheeler, Lance M.; Nichols, Asa W.; Chernomordik, Boris D.; ...

2016-01-21

In this study, we introduce a new paradigm for group IV nanocrystal surface chemistry based on room temperature surface activation that enables ionic ligand exchange. Germanium nanocrystals synthesized in a gas-phase plasma reactor are functionalized with labile, cationic alkylammonium ligands rather than with traditional covalently bound groups. We employ Fourier transform infrared and 1H nuclear magnetic resonance spectroscopies to demonstrate the alkylammonium ligands are freely exchanged on the germanium nanocrystal surface with a variety of cationic ligands, including short inorganic ligands such as ammonium and alkali metal cations. This ionic ligand exchange chemistry is used to demonstrate enhanced transport inmore » germanium nanocrystal films following ligand exchange as well as the first photovoltaic device based on an all-inorganic germanium nanocrystal absorber layer cast from solution. This new ligand chemistry should accelerate progress in utilizing germanium and other group IV nanocrystals for optoelectronic applications.« less

Pentachlorophenol radical cations generated on Fe(III)-montmorillonite initiate octachlorodibenzo-p-dioxin formation in clays: DFT and FTIR studies

PubMed Central

Gu, Cheng; Liu, Cun; Johnston, Cliff T.; Teppen, Brian J.; Li, Hui; Boyd, Stephen A.

2011-01-01

Octachlorodibenzodioxin (OCDD) forms spontaneously from pentachlorophenol (PCP) on the surfaces of Fe(III)-saturated smectite clay (1). Here, we used in situ FTIR methods and quantum mechanical calculations to determine the mechanism by which this reaction is initiated. As the clay was dehydrated, vibrational spectra showed new peaks that grew and then reversibly disappeared as the clay rehydrated. First principle DFT calculations of hydrated Fe-PCP clusters reproduced these transient FTIR peaks when inner-sphere complexation and concomitant electron transfer produced Fe(II) and PCP radical cations. Thus, our experimental (FTIR) and theoretical (quantum mechanical) results mutually support the hypothesis that OCDD formation on Fe-smectite surfaces is initiated by the reversible formation of metastable PCP radical cations via single electron transfer from PCP to Fe(III). The negatively charged clay surface apparently selects for this reaction mechanism by stabilizing PCP radical cations. PMID:21254769

Comparative Studies on Dyeability with Direct, Acid and Reactive Dyes after Chemical Modification of Jute with Mixed Amino Acids Obtained from Extract of Waste Soya Bean Seeds

NASA Astrophysics Data System (ADS)

Bhaumik, Nilendu Sekhar; Konar, Adwaita; Roy, Alok Nath; Samanta, Ashis Kumar

2017-12-01

Jute fabric was treated with mixed natural amino acids obtained from waste soya bean seed extract for chemical modification of jute for its cataionization and to enhance its dyeability with anionic dyes (like direct, reactive and acid dye) as well enabling soya modified jute for salt free dyeing with anionic reactive dyes maintaining its eco-friendliness. Colour interaction parameters including surface colour strength were assessed and compared for both bleached and soya-modified jute fabric for reactive dyeing and compared with direct and acid dye. Improvement in K/S value (surface colour strength) was observed for soya-modified jute even in absence of salt applied in dye bath for reactive dyes as well as for direct and acid dyes. In addition, reactive dye also shows good dyeability even in acid bath in salt free conditions. Colour fastness to wash was evaluated for bleached and soya-modified jute fabric after dyeing with direct, acid and reactive dyes are reported. Treatment of jute with soya-extracted mixed natural amino acids showed anchoring of some amino/aldemine groups on jute cellulosic polymer evidenced from Fourier Transform Infra-Red (FTIR) Spectroscopy. This amino or aldemine group incorporation in bleached jute causes its cationization and hence when dyed in acid bath for reactive dye (instead of conventional alkali bath) showed dye uptake for reactive dyes. Study of surface morphology by Scanning Electron Microscopy (SEM) of said soya-modified jute as compared to bleached jute was studied and reported.

Effect of Organic Cations on Hydrogen Oxidation Reaction of Carbon Supported Platinum

DOE PAGES

Chung, Hoon Taek; Choe, Yong-Kee; Martinez, Ulises; ...

2016-11-02

Effect of organic cations on hydrogen oxidation reaction (HOR) of carbon supported platinum (Pt/C) is investigated using three 0.1 M alkaline electrolytes, tetramethylammonium hydroxide (TMAOH), tetrabutylammonium hydroxide (TBAOH) and tetrabutylphosphonium hydroxide (TBPOH). Rotating disk electrode experiments indicate that the HOR of Pt/C is adversely impacted by time-dependent and potential-driven chemisorption of organic cations. In-situ infrared reflection adsorption spectroscopy experiments indicated that the specific chemisorption of organic cations drives the hydroxide co-adsorption on Pt surface. The co-adsorption of TMA + and hydroxide at 0.1 V vs. reversible hydrogen electrode is the strongest; consequently, complete removal of the co-adsorbed layer from Ptmore » surface is difficult even after exposure the Pt surface to 1.2 V. Conversely, the chemisorption of TBP+ is the weakest, yet notable decrease of HOR current density is still observed. The adsorption energies, ΔE, for TMA +, TBA +, and TBP + on Pt (111) surface from density functional theory are computed to be -2.79, -2.42 and -2.00 eV, respectively. The relatively low adsorption energy of TBP + is explained by the steric hindrance and electronic effect. This study emphasizes the importance of cationic group on HOR activity of alkaline anion exchange membrane fuel cells.« less

The adsorption of cationic and amphoteric copolymers on glass surfaces: zeta potential measurements, adsorption isotherm determination, and FT Raman characterization.

PubMed

Tartakovsky, Alla; Drutis, Dane M; Carnali, Joseph O

2003-07-15

The adsorption of cationic and amphoteric copolymers onto controlled pore glass (CPG) powders has been studied by measurement of the powder particle zeta (zeta) potential, by determination of the adsorption isotherm, and by FT Raman measurements of the polymer-coated powder. The cationic polymers consisted chiefly of homopolymers of dimethyldiallylammonium chloride (DMDAAC) or copolymers of DMDAAC and acrylamide. The amphoteric polymers studied included copolymers of DMDAAC and acrylic acid. The comonomer ratio was varied to explore the dependence of cationic charge density on the extent and effect of adsorption. Both types of polymers adsorb onto the anionic glass surface via an ion-exchange mechanism. Consequently, a correspondingly higher mass of a low-charge-density copolymer adsorbs than of a cationic homopolymer. The presence of the anionic portion in the amphoteric polymers does not significantly alter this picture. The zeta potential, however, reflects the overall nature of the polymer. Cationic polymers effectively neutralize the glass surface, while amphoteric polymers leave the zeta potential net negative. Adsorption isotherms, determined via the depletion technique using colloidal titration, were used to "calibrate" a FT Raman method. The latter was used to determined the amount of adsorbed polymer under solution conditions in which colloidal titration could not be performed.

Potential of coconut shell activated carbon (CSAC) in removing contaminants for water quality improvement: A critical review

NASA Astrophysics Data System (ADS)

Akhir, Muhammad Fitri Mohd; Saad, Noor Aida; Zakaria, Nor Azazi

2017-10-01

Commonly, water contaminations occur due to human-induced conditions such as industrial discharge and urban activities. The widely identified contaminants are heavy metal. The toxicity of those heavy metal elements is high and very poisonous to humans' health and environment even at lower dose or concentration of exposure. Chronic poisoning can cause fatal or defect to one's body or environment. Organic contaminants such as oil and microbial are also found due to decomposition of organic matter. The excellent quality adsorption of contaminants is highly related to surface area, pore size, pore volume, and amount plus type of functional group on surface of CSAC. The higher the surface area and pore volume, the higher adsorption that CSAC have towards contaminants. In comparison to meso-pore and macro-pore, micro-pore is better for trapping and adsorbing water contaminants. The purpose of this article is to critically review the potential of CSAC in increasing adsorption to remove contaminants for water quality improvement. A critical review is implemented using search engine like Science Direct. Alkali-modification is shown to have good adsorption in anion elements and organic matter due to improvement of hydrophobic organic compound (HOC) while acid-modification is good in cation elements adsorption. Strong alkali impregnated solution makes CSAC more hydrophobic and positively charge especially after increasing the impregnation dosage. Strong acid of adsorbate affects the quality of adsorption by reducing the surface area, pore volume and it also breaks the Van der Waals forces between adsorbent and adsorbate. However, the formation of oxygen helps the activated carbon surface to become more hydrophilic and negative charge is produced. It helps the effectiveness of metal adsorption. Therefore, by controlling dosage and types of functional groups on surface of CSAC and the pH of adsorbate, it can contribute to high adsorption of organic and inorganic contaminants in the water.

Anionized and cationized hemeundecapeptides as probes for cell surface charge and permeability studies: differentiated labeling of endothelial plasmalemmal vesicles

PubMed Central

1985-01-01

To obtain small membrane markers easily accessible to the charged groups of the cell surface, we prepared, from hemeundecapeptide (HUP), three derivatives that maintain the peroxidatic activity: the anionized hemeundecapeptide, Mr 1,963, estimated diameter 1.68 nm, pl 3.5, for the detection of basic groups; and both a cationized hemeundecapeptide containing predominantly tertiary amino groups, Mr 2,215, estimated diameter 1.75 nm, pl 9.0, and a cationized hemeundecapeptide containing only primary amino groups, Mr 2,271, estimated diameter 1.75 nm, pl 10.6, for labeling acidic residues. The markers were perfused in situ in mice to label the luminal surface of fenestrated endothelium of pancreatic capillaries. Specimens were processed through the cytochemical reaction for peroxidatic activity and examined by electron microscopy. The anionized HUP and HUP (pl 4.85) marked the plasmalemma proper, the coated pits, and the membrane and diaphragms of plasmalemmal vesicles and transendothelial channels. The cationized HUP containing predominantly tertiary amino groups (pl 9.0) decorated all cell surface components with the exception of plasmalemmal vesicles and channels; the latter were, however, labeled by the cationized HUP containing only primary groups (pl 10.6), which suggests that these structures contain on their luminal surface very weak acidic residues of high pKa values. The fact that the membrane of plasmalemmal vesicles can discriminate against permeant cationic macromolecules only up to a pl of approximately 9.0 indicates that in the electrostatic restriction there is a charge limit. In the case of fenestrated capillary endothelium, the upper charge limit seems to be a pl of approximately 9.0. In these vessels, the charge discrimination is effective for molecules as small as 2 nm. PMID:3968182

Anionized and cationized hemeundecapeptides as probes for cell surface charge and permeability studies: differentiated labeling of endothelial plasmalemmal vesicles.

PubMed

Ghinea, N; Simionescu, N

1985-02-01

To obtain small membrane markers easily accessible to the charged groups of the cell surface, we prepared, from hemeundecapeptide (HUP), three derivatives that maintain the peroxidatic activity: the anionized hemeundecapeptide, Mr 1,963, estimated diameter 1.68 nm, pl 3.5, for the detection of basic groups; and both a cationized hemeundecapeptide containing predominantly tertiary amino groups, Mr 2,215, estimated diameter 1.75 nm, pl 9.0, and a cationized hemeundecapeptide containing only primary amino groups, Mr 2,271, estimated diameter 1.75 nm, pl 10.6, for labeling acidic residues. The markers were perfused in situ in mice to label the luminal surface of fenestrated endothelium of pancreatic capillaries. Specimens were processed through the cytochemical reaction for peroxidatic activity and examined by electron microscopy. The anionized HUP and HUP (pl 4.85) marked the plasmalemma proper, the coated pits, and the membrane and diaphragms of plasmalemmal vesicles and transendothelial channels. The cationized HUP containing predominantly tertiary amino groups (pl 9.0) decorated all cell surface components with the exception of plasmalemmal vesicles and channels; the latter were, however, labeled by the cationized HUP containing only primary groups (pl 10.6), which suggests that these structures contain on their luminal surface very weak acidic residues of high pKa values. The fact that the membrane of plasmalemmal vesicles can discriminate against permeant cationic macromolecules only up to a pl of approximately 9.0 indicates that in the electrostatic restriction there is a charge limit. In the case of fenestrated capillary endothelium, the upper charge limit seems to be a pl of approximately 9.0. In these vessels, the charge discrimination is effective for molecules as small as 2 nm.

Enhanced Lifetime of Polymer Solar Cells by Surface Passivation of Metal Oxide Buffer Layers.

PubMed

Venkatesan, Swaminathan; Ngo, Evan; Khatiwada, Devendra; Zhang, Cheng; Qiao, Qiquan

2015-07-29

The role of electron selective interfaces on the performance and lifetime of polymer solar cells were compared and analyzed. Bilayer interfaces consisting of metal oxide films with cationic polymer modification namely poly ethylenimine ethoxylated (PEIE) were found to enhance device lifetime compared to bare metal oxide films when used as an electron selective cathode interface. Devices utilizing surface-modified metal oxide layers showed enhanced lifetimes, retaining up to 85% of their original efficiency when stored in ambient atmosphere for 180 days without any encapsulation. The work function and surface potential of zinc oxide (ZnO) and ZnO/PEIE interlayers were evaluated using Kelvin probe and Kelvin probe force microscopy (KPFM) respectively. Kelvin probe measurements showed a smaller reduction in work function of ZnO/PEIE films compared to bare ZnO films when aged in atmospheric conditions. KPFM measurements showed that the surface potential of the ZnO surface drastically reduces when stored in ambient air for 7 days because of surface oxidation. Surface oxidation of the interface led to a substantial decrease in the performance in aged devices. The enhancement in the lifetime of devices with a bilayer interface was correlated to the suppressed surface oxidation of the metal oxide layers. The PEIE passivated surface retained a lower Fermi level when aged, which led to lower trap-assisted recombination at the polymer-cathode interface. Further photocharge extraction by linearly increasing voltage (Photo-CELIV) measurements were performed on fresh and aged samples to evaluate the field required to extract maximum charges. Fresh devices with a bare ZnO cathode interlayer required a lower field than devices with ZnO/PEIE cathode interface. However, aged devices with ZnO required a much higher field to extract charges while aged devices with ZnO/PEIE showed a minor increase compared to the fresh devices. Results indicate that surface modification can act as a suitable passivation layer to suppress oxidation in metal oxide thin films for enhanced lifetime in inverted organic solar cells.

Research on plasma and saliva levels of some bivalent cations in patients with chronic periodontitis (salivary cations in chronic periodontitis).

PubMed

Manea, A; Nechifor, M

2014-01-01

The purpose of this study was to determine whether chronic periodontitis can stand behind modifications in the salivary and blood concentration of some bivalent cations (Calcium, Magnesium, Zinc and Copper). For this purpose, we formed a group of 30 adult patients with clinically onset chronic periodontitis, and another one of 30 healthy patients as control. Both groups were free from acute oral pathology and general illnesses. The groups were divided again according to the habit of smoking. Total saliva samples were obtained as "first time in the morning", then weighed and processed. Cations were read on Atomic Absorption Spectrophotometer and by Ion Chromatography (Magnesium). The same patients were required to undergo laboratory blood tests for Calcium, Magnesium and Zinc. Data obtained was normalised, then statistically interpreted using two-tailed heteroscedastic t-Student tests. Our data confirmed the existence of a connection between salivary calcium, magnesium, zinc and copper, and of blood magnesium, and chronic periodontitis. Salivary calcium and magnesium are affected by smoking.

Cation distribution of Ni-Zn-Mn ferrite nanoparticles

NASA Astrophysics Data System (ADS)

Parvatheeswara Rao, B.; Dhanalakshmi, B.; Ramesh, S.; Subba Rao, P. S. V.

2018-06-01

Mn substituted Ni-Zn ferrite nanoparticles, Ni0.4Zn0.6-xMnxFe2O4 (x = 0.00-0.25 in steps of 0.05), using metal nitrates were prepared by sol-gel autocombustion in citric acid matrix. The samples were examined by X-ray diffraction and vibrating sample magnetometer techniques. Rietveld structural refinements using the XRD data were performed on the samples to consolidate various structural parameters like phase (spinel), crystallite size (24.86-37.43 nm), lattice constant (8.3764-8.4089 Å) etc and also to determine cation distributions based on profile matching and integrated intensity ratios. Saturation magnetization values (37.18-68.40 emu/g) were extracted from the measured M-H loops of these nanoparticles to estimate their magnetic moments. Experimental and calculated magnetic moments and lattice constants were used to confirm the derived cation distributions from Rietveld analysis. The results of these ferrite nanoparticles are discussed in terms of the compositional modifications, particle sizes and the corresponding cation distributions as a result of Mn substitutions.

Improved chemical and electrochemical stability of perovskite oxides with less reducible cations at the surface

DOE PAGES

Tsvetkov, Nikolai; Lu, Qiyang; Sun, Lixin; ...

2016-06-13

Segregation and phase separation of aliovalent dopants on perovskite oxide (ABO 3 ) surfaces are detrimental to the performance of energy conversion systems such as solid oxide fuel/electrolysis cells and catalysts for thermochemical H 2 O and CO 2 splitting. One key reason behind the instability of perovskite oxide surfaces is the electrostatic attraction of the negatively charged A-site dopants (for example, Sr La ') by the positively charged oxygen vacancies (Vmore » $$••\\atop{o}$$) enriched at the surface. Here we show that reducing the surface V $$••\\atop{o}$$ concentration improves the oxygen surface exchange kinetics and stability significantly, albeit contrary to the well-established understanding that surface oxygen vacancies facilitate reactions with O 2 molecules. We take La 0.8 Sr 0.2 CoO 3 (LSC) as a model perovskite oxide, and modify its surface with additive cations that are more and less reducible than Co on the B-site of LSC. By using ambient-pressure X-ray absorption and photoelectron spectroscopy, we proved that the dominant role of the less reducible cations is to suppress the enrichment and phase separation of Sr while reducing the concentration of V $$••\\atop{o}$$ and making the LSC more oxidized at its surface. Consequently, we found that these less reducible cations significantly improve stability, with up to 30 times faster oxygen exchange kinetics after 54 h in air at 530 °C achieved by Hf addition onto LSC. Finally, the results revealed a 'volcano' relation between the oxygen exchange kinetics and the oxygen vacancy formation enthalpy of the binary oxides of the additive cations. This volcano relation highlights the existence of an optimum surface oxygen vacancy concentration that balances the gain in oxygen exchange kinetics and the chemical stability loss.« less

Improved chemical and electrochemical stability of perovskite oxides with less reducible cations at the surface

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

Tsvetkov, Nikolai; Lu, Qiyang; Sun, Lixin

Segregation and phase separation of aliovalent dopants on perovskite oxide (ABO 3 ) surfaces are detrimental to the performance of energy conversion systems such as solid oxide fuel/electrolysis cells and catalysts for thermochemical H 2 O and CO 2 splitting. One key reason behind the instability of perovskite oxide surfaces is the electrostatic attraction of the negatively charged A-site dopants (for example, Sr La ') by the positively charged oxygen vacancies (Vmore » $$••\\atop{o}$$) enriched at the surface. Here we show that reducing the surface V $$••\\atop{o}$$ concentration improves the oxygen surface exchange kinetics and stability significantly, albeit contrary to the well-established understanding that surface oxygen vacancies facilitate reactions with O 2 molecules. We take La 0.8 Sr 0.2 CoO 3 (LSC) as a model perovskite oxide, and modify its surface with additive cations that are more and less reducible than Co on the B-site of LSC. By using ambient-pressure X-ray absorption and photoelectron spectroscopy, we proved that the dominant role of the less reducible cations is to suppress the enrichment and phase separation of Sr while reducing the concentration of V $$••\\atop{o}$$ and making the LSC more oxidized at its surface. Consequently, we found that these less reducible cations significantly improve stability, with up to 30 times faster oxygen exchange kinetics after 54 h in air at 530 °C achieved by Hf addition onto LSC. Finally, the results revealed a 'volcano' relation between the oxygen exchange kinetics and the oxygen vacancy formation enthalpy of the binary oxides of the additive cations. This volcano relation highlights the existence of an optimum surface oxygen vacancy concentration that balances the gain in oxygen exchange kinetics and the chemical stability loss.« less

Metal adsorption onto bacterial surfaces: development of a predictive approach

NASA Astrophysics Data System (ADS)

Fein, Jeremy B.; Martin, Aaron M.; Wightman, Peter G.

2001-12-01

Aqueous metal cation adsorption onto bacterial surfaces can be successfully modeled by means of a surface complexation approach. However, relatively few stability constants for metal-bacterial surface complexes have been measured. In order to determine the bacterial adsorption behavior of cations that have not been studied in the laboratory, predictive techniques are required that enable estimation of the stability constants of bacterial surface complexes. In this study, we use a linear free-energy approach to compare previously measured stability constants for Bacillus subtilis metal-carboxyl surface complexes with aqueous metal-organic acid anion stability constants. The organic acids that we consider are acetic, oxalic, citric, and tiron. We add to this limited data set by conducting metal adsorption experiments onto Bacillus subtilis, determining bacterial surface stability constants for Co, Nd, Ni, Sr, and Zn. The adsorption behavior of each of the metals studied here was described well by considering metal-carboxyl bacterial surface complexation only, except for the Zn adsorption behavior, which required carboxyl and phosphoryl complexation to obtain a suitable fit to the data. The best correlation between bacterial carboxyl surface complexes and aqueous organic acid anion stability constants was obtained by means of metal-acetate aqueous complexes, with a linear correlation coefficient of 0.97. This correlation applies only to unhydrolyzed aqueous cations and only to carboxyl binding of those cations, and it does not predict the binding behavior under conditions where metal binding to other bacterial surface site types occurs. However, the relationship derived in this study permits estimation of the carboxyl site adsorption behavior of a wide range of aqueous metal cations for which there is an absence of experimental data. This technique, coupled with the observation of similar adsorption behaviors across bacterial species (Yee and Fein, 2001), enables estimation of the effects of bacterial adsorption on metal mobilities for a large number of environmental and geologic applications.

The C4H7+ cation. A theoretical investigation

NASA Technical Reports Server (NTRS)

Koch, W.; Liu, B.; DeFrees, D. J.

1988-01-01

The potential energy surface of the C4H7+ cation has been investigated with ab initio quantum chemical theory. Extended basis set calculations, including electronic correlation, show that cyclobutyl and cyclopropylcarbinyl cation are equally stable isomers. The saddle point connecting these isomers lies 0.6 kcal/mol above the minima. The global C4H7+ minimum corresponds to the 1-methylallyl cation, which is 9.0 kcal/mol more stable than the cyclobutyl and the cyclopropylcarbinyl cation and 9.5 kcal/mol below the 2-methylallyl cation. These results are in excellent agreement with experimental data.

Binding of Daptomycin to Anionic Lipid Vesicles Is Reduced in the Presence of Lysyl-Phosphatidylglycerol

PubMed Central

Khatib, Tala O.; Stevenson, Heather; Yeaman, Michael R.; Bayer, Arnold S.

2016-01-01

The cytoplasmic membrane of Staphylococcus aureus contains ∼20 mol% of the net cationic lipid lysyl-phosphatidylglycerol (LPG). Elevated fractions of LPG are associated with increased resistance to cationic antibiotics, including the lipopeptide daptomycin (DAP). Although the surface charge of the bacterial cytoplasmic membrane is altered by LPG, surface binding of DAP was found to be only moderately affected in anionic vesicles containing 20 mol% LPG. These results suggest that charge repulsion cannot fully explain LPG-mediated resistance to cationic peptides. PMID:27216066

Dynamic secondary ion mass spectroscopy of Au nanoparticles on Si wafer using Bi3+ as primary ion coupled with surface etching by Ar cluster ion beam: The effect of etching conditions on surface structure

NASA Astrophysics Data System (ADS)

Park, Eun Ji; Choi, Chang Min; Kim, Il Hee; Kim, Jung-Hwan; Lee, Gaehang; Jin, Jong Sung; Ganteför, Gerd; Kim, Young Dok; Choi, Myoung Choul

2018-01-01

Wet-chemically synthesized Au nanoparticles were deposited on Si wafer surfaces, and the secondary ions mass spectra (SIMS) from these samples were collected using Bi3+ with an energy of 30 keV as the primary ions. In the SIMS, Au cluster cations with a well-known, even-odd alteration pattern in the signal intensity were observed. We also performed depth profile SIMS analyses, i.e., etching the surface using an Ar gas cluster ion beam (GCIB), and a subsequent Bi3+ SIMS analysis was repetitively performed. Here, two different etching conditions (Ar1600 clusters of 10 keV energy or Ar1000 of 2.5 keV denoted as "harsh" or "soft" etching conditions, respectively) were used. Etching under harsh conditions induced emission of the Au-Si binary cluster cations in the SIMS spectra of the Bi3+ primary ions. The formation of binary cluster cations can be induced by either fragmentation of Au nanoparticles or alloying of Au and Si, increasing Au-Si coordination on the sample surface during harsh GCIB etching. Alternatively, use of the soft GCIB etching conditions resulted in exclusive emission of pure Au cluster cations with nearly no Au-Si cluster cation formation. Depth profile analyses of the Bi3+ SIMS combined with soft GCIB etching can be useful for studying the chemical environments of atoms at the surface without altering the original interface structure during etching.

Potential effect of cationic liposomes on interactions with oral bacterial cells and biofilms.

PubMed

Sugano, Marika; Morisaki, Hirobumi; Negishi, Yoichi; Endo-Takahashi, Yoko; Kuwata, Hirotaka; Miyazaki, Takashi; Yamamoto, Matsuo

2016-01-01

Although oral infectious diseases have been attributed to bacteria, drug treatments remain ineffective because bacteria and their products exist as biofilms. Cationic liposomes have been suggested to electrostatically interact with the negative charge on the bacterial surface, thereby improving the effects of conventional drug therapies. However, the electrostatic interaction between oral bacteria and cationic liposomes has not yet been examined in detail. The aim of the present study was to examine the behavior of cationic liposomes and Streptococcus mutans in planktonic cells and biofilms. Liposomes with or without cationic lipid were prepared using a reverse-phase evaporation method. The zeta potentials of conventional liposomes (without cationic lipid) and cationic liposomes were -13 and 8 mV, respectively, and both had a mean particle size of approximately 180 nm. We first assessed the interaction between liposomes and planktonic bacterial cells with a flow cytometer. We then used a surface plasmon resonance method to examine the binding of liposomes to biofilms. We confirmed the binding behavior of liposomes with biofilms using confocal laser scanning microscopy. The interactions between cationic liposomes and S. mutans cells and biofilms were stronger than those of conventional liposomes. Microscopic observations revealed that many cationic liposomes interacted with the bacterial mass and penetrated the deep layers of biofilms. In this study, we demonstrated that cationic liposomes had higher affinity not only to oral bacterial cells, but also biofilms than conventional liposomes. This electrostatic interaction may be useful as a potential drug delivery system to biofilms.

Zwitterionic poly(carboxybetaine)-based cationic liposomes for effective delivery of small interfering RNA therapeutics without accelerated blood clearance phenomenon.

PubMed

Li, Yan; Liu, Ruiyuan; Shi, Yuanjie; Zhang, Zhenzhong; Zhang, Xin

2015-01-01

For efficient delivery of small interfering RNA (siRNA) to the target diseased site in vivo, it is important to design suitable vehicles to control the blood circulation of siRNA. It has been shown that surface modification of cationic liposome/siRNA complexes (lipoplexes) with polyethylene glycol (PEG) could enhance the circulation time of lipoplexes. However, the first injection of PEGylated lipoplexes in vivo induces accelerated blood clearance and enhances hepatic accumulation of the following injected PEGylated lipoplexes, which is known as the accelerated blood clearance (ABC) phenomenon. Herein, we developed zwitterionic poly(carboxybetaine) (PCB) modified lipoplexes for the delivery of siRNA therapeutics, which could avoid protein adsorption and enhance the stability of lipoplexes as that for PEG. Quite different from the PEGylation, the PCBylated lipoplexes could avoid ABC phenomenon, which extended the blood circulation time and enhanced the tumor accumulation of lipoplexes in vivo. After accumulation in tumor site, the PCBylation could promote the cellular uptake and endosomal/lysosomal escape of lipoplexes due to its unique chemical structure and pH-sensitive ability. With excellent tumor accumulation, cellular uptake and endosomal/lysosomal escape abilities, the PCBylated lipoplexes significantly inhibited tumor growth and induced tumor cell apoptosis.

Predicting Organic Cation Sorption Coefficients: Accounting for Competition from Sorbed Inorganic Cations Using a Simple Probe Molecule.

PubMed

Jolin, William C; Goyetche, Reaha; Carter, Katherine; Medina, John; Vasudevan, Dharni; MacKay, Allison A

2017-06-06

With the increasing number of emerging contaminants that are cationic at environmentally relevant pH values, there is a need for robust predictive models of organic cation sorption coefficients (K d ). Current predictive models fail to account for the differences in the identity, abundance, and affinity of surface-associated inorganic exchange ions naturally present at negatively charged receptor sites on environmental solids. To better understand how organic cation sorption is influenced by surface-associated inorganic exchange ions, sorption coefficients of 10 organic cations (including eight pharmaceuticals and two simple probe organic amines) were determined for six homoionic forms of the aluminosilicate mineral, montmorillonite. Organic cation sorption coefficients exhibited consistent trends for all compounds across the various homoionic clays with sorption coefficients (K d ) decreasing as follows: K d Na + > K d NH 4 + ≥ K d K + > K d Ca 2+ ≥ K d Mg 2+ > K d Al 3+ . This trend for competition between organic cations and exchangeable inorganic cations is consistent with the inorganic cation selectivity sequence, determined for exchange between inorganic ions. Such consistent trends in competition between organic and inorganic cations suggested that a simple probe cation, such as phenyltrimethylammonium or benzylamine, could capture soil-to-soil variations in native inorganic cation identity and abundance for the prediction of organic cation sorption to soils and soil minerals. Indeed, sorption of two pharmaceutical compounds to 30 soils was better described by phenyltrimethylammonium sorption than by measures of benzylamine sorption, effective cation exchange capacity alone, or a model from the literature (Droge, S., and Goss, K. Environ. Sci. Technol. 2013, 47, 14224). A hybrid approach integrating structural scaling factors derived from this literature model of organic cation sorption, along with phenyltrimethylammonium K d values, allowed for estimation of K d values for more structurally complex organic cations to homoionic montmorillonites and to heteroionic soils (mean absolute error of 0.27 log unit). Accordingly, we concluded that the use of phenyltrimethylammonium as a probe compound was a promising means to account for the identity, affinity, and abundance of natural exchange ions in the prediction of organic cation sorption coefficients for environmental solids.

Surface modification of calcium-copper hydroxyapatites using polyaspartic acid

NASA Astrophysics Data System (ADS)

Othmani, Masseoud; Aissa, Abdallah; Bachoua, Hassen; Debbabi, Mongi

2013-01-01

Mixed calcium-copper hydroxyapatite (Ca-CuHAp), with general formula Ca(10-x)Cux(PO4)6(OH)2, where 0 ≤ x ≤ 0.75 was prepared in aqueous medium in the presence of different concentrations of poly-L-aspartic acid (PASP). XRD, IR, TG-DTA, TEM-EDX, AFM and chemical analyses were used to characterize the structure, morphology and composition of the products. All techniques show the formation of new hybrid compounds Ca-CuHAp-PASP. The presence of the grafting moiety on the apatitic material is more significant with increasing of copper amount and/or organic concentration in the starting solution. These increases lead to the affectation of apatite crystallinity. The IR spectroscopy shows the conservation of (Psbnd OH) band of (HPO4)2- groups, suggesting that PASP acid was interacted only with metallic cations of hydroxyapatite.

Using ion exchange chromatography to purify a recombinantly expressed protein.

PubMed

Duong-Ly, Krisna C; Gabelli, Sandra B

2014-01-01

Ion exchange chromatography (IEX) separates molecules by their surface charge, a property that can vary vastly between different proteins. There are two types of IEX, cation exhange and anion exchange chromatography. The protocol that follows was designed by the authors for anion exchange chromatography of a recombinantly expressed protein having a pI of 4.9 and containing two cysteine residues and one tryptophan residue, using an FPLC system. Prior to anion exchange, the protein had been salted out using ammonium sulfate precipitation and partially purified via hydrophobic interaction chromatography (see Salting out of proteins using ammonium sulfate precipitation and Use and Application of Hydrophobic Interaction Chromatography for Protein Purification). Slight modifications to this protocol may be made to accommodate both the protein of interest and the availability of equipment. © 2014 Elsevier Inc. All rights reserved.

Effect of cellulose nanocrystals on crystallization kinetics of polycaprolactone

NASA Astrophysics Data System (ADS)

Migler, Kalman; Roy, Debjani; Kotula, Anthony; Natarajan, Bharath; Gilman, Jeffrey; Fox, Douglas

The development of biocompatible polymer composites that enhance mechanical properties while maintaining thermoplastic processability is a longstanding goal in sustainable materials. Here we compatibilize a crystallizable polymer and a nano-fiber via surface modification and study the properties and crystallization kinetics of the resulting composite. First we demonstrate that polycaprolactone (PCL) and cellulose nanocrystals (CNCs) can be well-compatibilized by replacing the Na+ of sulfated cellulose nanocrystals (Na-CNCs) with tertiary butyl ammonium cations and then melt mixing via twin-screw extrusion. Transmission electron microscope and high temperature melt rheology show that the modified CNCs were dispersed in the polymer matrix. We find the crystallization kinetics are substantially affected by the CNC as indicated by the simultaneous measures of modulus and conformational states; higher loadings of CNCs accelerated the kinetics. We further correlate the crystallization kinetics, mechanical properties and stability.

The relationship between surface tension and the industrial performance of water-soluble polymers prepared from acid hydrolysis lignin, a saccharification by-product from woody materials.

PubMed

Matsushita, Yasuyuki; Imai, Masanori; Iwatsuki, Ayuko; Fukushima, Kazuhiko

2008-05-01

In this study, water-soluble anionic and cationic polymers were prepared from sulfuric acid lignin (SAL), an acid hydrolysis lignin, and the relationship between the surface tension of these polymers and industrial performance was examined. The SAL was phenolized (P-SAL) to enhance its solubility and reactivity. Sulfonation and the Mannich reaction with aminocarboxylic acids produced water-soluble anionic polymers and high-dispersibility gypsum paste. The dispersing efficiency increased as the surface tension decreased, suggesting that the fluidity of the gypsum paste increased with the polymer adsorption on the gypsum particle surface. Water-soluble cationic polymers were prepared using the Mannich reaction with dimethylamine. The cationic polymers showed high sizing efficiency under neutral papermaking conditions; the sizing efficiency increased with the surface tension. This suggests that the polymer with high hydrophilicity spread in the water and readily adhered to the pulp surface and the rosin, showing good retention.

Controlling the Photophysical Properties of Semiconductor Quantum Dot Arrays by Strategically Altering Their Surface Chemistry

NASA Astrophysics Data System (ADS)

Marshall, Ashley R.

Semiconductor quantum dots (QDs) are interesting materials that, after less than 40 years of research, are used in commercial products. QDs are now found in displays, such as Samsung televisions and the Kindle Fire, and have applications in lighting, bio-imaging, quantum computing, and photovoltaics. They offer a large range of desirable properties: a controllable band gap, solution processability, controlled energy levels, and are currently the best materials for multiple exciton generation. The tunable optoelectronic properties of QDs can be controlled using size, shape, composition, and surface treatments--as shown here. Due to the quasi-spherical shape of QDs the surface to volume ratio is high, i.e. many of the constituent atoms are found on the QD surface. This makes QDs highly sensitive to surface chemistry modifications. This thesis encompasses the effects of surface treatments for QDs of two semiconducting materials: lead chalcogenides and CsPbI3. Our group developed a new synthetic technique for lead chalcogenide QDs via the cation exchange of cadmium chalcogenides. An in-depth chemical analysis is paired with optical and electrical studies and we find that metal halide residue contributes to the oxidative stability and decreased trap state density in cation-exchanged PbS QDs. We exploit these properties to make air-stable QD photovoltaic devices from both PbS and PbSe QD materials. Beyond the effects of residual atoms left from the synthetic technique, I investigated how to controllably add atoms onto the surface of QDs. I found that by introducing metal halides as a post-treatment in an electronically coupled array I am able to control the performance parameters in QD photovoltaic devices. These treatments fully infiltrate the assembled film, even under short exposure times and allow me to add controlled quantities of surface atoms to study their effects on film properties and photovoltaic device performance. Finally, I sought to apply the knowledge of the lead chalcogenide QD surfaces to produce QD photovoltaics from a new material: CsPbI3. I fabricated the first perovskite QD photovoltaic devices and using similar treatment methods as the lead chalcogenide QD arrays, I am able to influence the photophysical properties of CsPbI3 QD arrays.

Water-wettable polypropylene fibers by facile surface treatment based on soy proteins.

PubMed

Salas, Carlos; Genzer, Jan; Lucia, Lucian A; Hubbe, Martin A; Rojas, Orlando J

2013-07-24

Modification of the wetting behavior of hydrophobic surfaces is essential in a variety of materials, including textiles and membranes that require control of fluid interactions, adhesion, transport processes, sensing, etc. This investigation examines the enhancement of wettability of an important class of textile materials, viz., polypropylene (PP) fibers, by surface adsorption of different proteins from soybeans, including soy flour, isolate,glycinin, and β-conglycinin. Detailed investigations of soy adsorption from aqueous solution (pH 7.4, 25 °C) on polypropylene thin films is carried out using quartz crystal microbalance (QCM) and surface plasmon resonance (SPR). A significant amount of protein adsorbs onto the PP surfaces primarily due to hydrophobic interactions. We establish that adsorption of a cationic surfactant, dioctadecyldimethylammonium bromide (DODA) onto PP surfaces prior to the protein deposition dramatically enhances its adsorption. The adsorption of proteins from native (PBS buffer, pH 7.4, 25 °C) and denatured conditions (PBS buffer, pH 7.4, 95 °C) onto DODA-treated PP leads to a high coverage of the proteins on the PP surface as confirmed by a significant improvement in water wettability. A shift in the contact angle from 128° to completely wettable surfaces (≈0°) is observed and confirmed by imaging experiments conducted with fluorescence tags. Furthermore, the results from wicking tests indicate that hydrophobic PP nonwovens absorb a significant amount of water after protein treatment, i.e., the PP-modified surfaces become completely hydrophilic.

[Time-evolution study on the cation exchange in the process of reinforcing slip soil by laser-induced breakdown spectroscopy].

PubMed

Liu, Lu-Wen; Zeng, Wei-Li; Zhu, Xiang-Fei; Wu, Jin-Quan; Lin, Zhao-Xiang

2014-03-01

In the present paper, the time evolution study on slip soils treated by different proportions of ionic soil stabilizer (ISS) water solution was conducted by the LIBS system and the relationship between the cation exchange and such engineering properties of reinforcing soil as plasticity index, cohesive force and coefficient of compressibility were analyzed. The results showed that the cation exchange velocity of the proportion of 1:200 ISS reinforcing soil is the fastest among the three proportions (1:100, 1:200 and 1:300) and the modification effect of engineering performance index is quite obvious. These studies provide an experimental basis for the ISS applied to curing project, and monitoring geotechnical engineering performance by LIBS technology also provides a new way of thinking for the curing project monitoring.

Chemical modification of Nafion membranes by protic ionic liquids: the key role of ionomer-cation interactions.

PubMed

Lu, Fei; Gao, Xinpei; Xie, Shuting; Sun, Nan; Zheng, Liqiang

2014-10-21

Chemically modified Nafion composite membranes were successfully fabricated using five kinds of protic ionic liquids (PILs) with different cations, 1-butylammonium methanesulfonate (BA-MS), tributylammonium methanesulfonate (TBA-MS), 2,4,6-trimethylphenylammonium methanesulfonate (TMA-MS), butane-1,4-diammonium methanesulfonate (BDA-MS), and N-(2-aminoethyl)ethane-1,2-diammonium methanesulfonate (DETA-MS). The PIL incorporated Nafion composite membranes were characterized by impedance spectroscopy, small-angle X-ray scattering (SAXS), dynamic-mechanical analysis (DMA) and thermogravimetric analysis (TGA). In general, the Nafion/PIL composite membranes exhibit a significant increase in the ionic conductivities than Nafion under anhydrous conditions. The interactions between the Nafion ionomer and different geometric cations of PILs were also discussed by the comparison of nanostructures, dynamic-mechanical properties and thermal stabilities of the Nafion/PIL composite membranes.

ENVIRONMENTAL RESEARCH BRIEF: USE OF CATIONIC SURFACTANTS TO MODIFY AQUIFER MATERIALS TO REDUCE THE MOBILITY OF HYDROPHOBIC ORGANIC COMPOUNDS

EPA Science Inventory

Cationic surfactants can be used to modify surfaces of soils and subsurface materials to promote sorption of hydrophobic organic compounds (HOC) and retard their migration. For example, cationic surfactants could be injected into an aquifer downgradient from a source of HOC conta...

Influence of cationic lipid concentration on properties of lipid-polymer hybrid nanospheres for gene delivery.

PubMed

Bose, Rajendran J C; Arai, Yoshie; Ahn, Jong Chan; Park, Hansoo; Lee, Soo-Hong

2015-01-01

Nanoparticles have been widely used for nonviral gene delivery. Recently, cationic hybrid nanoparticles consisting of two different materials were suggested as a promising delivery vehicle. In this study, nanospheres with a poly(D,L-lactic-co-glycolic acid) (PLGA) core and cationic lipid shell were prepared, and the effect of cationic lipid concentrations on the properties of lipid polymer hybrid nanocarriers investigated. Lipid-polymer hybrid nanospheres (LPHNSs) were fabricated by the emulsion-solvent evaporation method using different concentrations of cationic lipids and characterized for size, surface charge, stability, plasmid DNA-binding capacity, cytotoxicity, and transfection efficiency. All LPHNSs had narrow size distribution with positive surface charges (ζ-potential 52-60 mV), and showed excellent plasmid DNA-binding capacity. In vitro cytotoxicity measurements with HEK293T, HeLa, HaCaT, and HepG2 cells also showed that LPHNSs exhibited less cytotoxicity than conventional transfection agents, such as Lipofectamine and polyethyleneimine-PLGA. As cationic lipid concentrations increased, the particle size of LPHNSs decreased while their ζ-potential increased. In addition, the in vitro transfection efficiency of LPHNSs increased as lipid concentration increased.

Development of large-surface Nafion-metal composite actuator and its electrochemical characterization

NASA Astrophysics Data System (ADS)

Noh, Taegeun; Tak, Yong Suk; Nam, Jaedo; Jeon, Jaewook; Kim, Hunmo; Choi, Hyoukryeol; Bae, Sang Sik

2001-07-01

Behaviors of nafion-based actuators are significantly affected by interfacial area between electrode and polymer electrolyte. Replication method was utilized to manufacture a large surface-area composite actuator. Etched aluminum foil was used as a template for replication using liquid nafion solution. Measurement of double layer charging and scanning electron microscopy indicated that interfacial area was greatly increased by replication method. Higher surface area induced a better bending performance of ionic polymer metal composite (IPMC). In parallel, the effect of cations on IPMC was interpreted with constant current experiment, linear sweep voltammetry and electrochemical impedance spectroscopy. For univalent cations, ion size is the most influencing parameter on ionic mobility inside membrane. However, ion-ion interaction affects an ionic mobility for divalent cations.

Biosensors Fabricated through Electrostatic Assembly of Enzymes/Polyelectrolyte Hybrid Layers on Carbon Nanotubes

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

Lin, Yuehe; Liu, Guodong; Wang, Jun

2006-06-01

Carbon nanotubes (CNTs) have emerged as new class of nanomaterials that is receiving considerable interest because of their unique structure, mechanical, and electronic properties. One promising application of CNTs is to fabricate highly sensitive chemo/biosensors.1-4 For construction of these CNT-based sensors, the CNTs first have to be modified with some molecules specific to the interests. Generally, covalent binding, affinity, and electrostatic interaction have been utilized for the modification of CNTs. Among them, the electrostatic method is attractive due to its simplicity and high efficiency. In present work, we have developed highly sensitively amperometric biosensors for glucose, choline, organophosphate pesticide (OPP)more » and nerve agents (NAs) based on electrostatically assembling enzymes on the surface of CNTs. All these biosensors were fabricated by immobilization of enzymes on the negatively charged CNTs surface through alternately assembling a cationic poly(diallydimethylammonium chloride) (PDDA) layer and an enzyme layer. Using this layer-by-layer (LBL) technique, a bioactive nanocomposite film was fabricated on the electrode surface. Owing to the electrocatalytic effect of CNTs, an amplified electrochemical signal was achieved, which leads to low detections limits for glucose, choline, and OPP and NAs.« less

MODIFICATION OF METAL PARTITIONING BY SUPPLEMENTING ACID VOLATILE SULFIDE IN FRESHWATER SEDIMENTS

EPA Science Inventory

Acid volatile sulfide is a component of sediments which complexes some cationic metals and thereby influences the toxicity of these metals to benthic organisms. EPA has proposed AVS as a key normalization phase for the development of sediment quality criteria for metals. Experime...

Surface Modification of Intraocular Lenses

PubMed Central

Huang, Qi; Cheng, George Pak-Man; Chiu, Kin; Wang, Gui-Qin

2016-01-01

Objective: This paper aimed to review the current literature on the surface modification of intraocular lenses (IOLs). Data Sources: All articles about surface modification of IOLs published up to 2015 were identified through a literature search on both PubMed and ScienceDirect. Study Selection: The articles on the surface modification of IOLs were included, but those on design modification and surface coating were excluded. Results: Technology of surface modification included plasma, ion beam, layer-by-layer self-assembly, ultraviolet radiation, and ozone. The main molecules introduced into IOLs surface were poly (ethylene glycol), polyhedral oligomeric silsesquioxane, 2-methacryloyloxyethyl phosphorylcholine, TiO2, heparin, F-heparin, titanium, titanium nitride, vinyl pyrrolidone, and inhibitors of cytokines. The surface modification either resulted in a more hydrophobic lens, a more hydrophilic lens, or a lens with a hydrophilic anterior and hydrophobic posterior surface. Advances in research regarding surface modification of IOLs had led to a better biocompatibility in both in vitro and animal experiments. Conclusion: The surface modification is an efficient, convenient, economic and promising method to improve the biocompatibility of IOLs. PMID:26830993

Preconditioning with cations increases the attachment of Anoxybacillus flavithermus and Geobacillus species to stainless steel.

PubMed

Somerton, Ben; Flint, Steve; Palmer, Jon; Brooks, John; Lindsay, Denise

2013-07-01

Preconditioning of Anoxybacillus flavithermus E16 and Geobacillus sp. strain F75 with cations prior to attachment often significantly increased (P ≤ 0.05) the number of viable cells that attached to stainless steel (by up to 1.5 log CFU/cm(2)) compared with unconditioned bacteria. It is proposed that the transition of A. flavithermus and Geobacillus spp. from milk formulations to stainless steel product contact surfaces in milk powder manufacturing plants is mediated predominantly by bacterial physiological factors (e.g., surface-exposed adhesins) rather than the concentrations of cations in milk formulations surrounding bacteria.

A hydrophobic filter confers the cation selectivity of Zygosaccharomyces rouxii plasma-membrane Na+/H+ antiporter.

PubMed

Kinclova-Zimmermannova, Olga; Falson, Pierre; Cmunt, Denis; Sychrova, Hana

2015-04-24

Na(+)/H(+) antiporters may recognize all alkali-metal cations as substrates but may transport them selectively. Plasma-membrane Zygosaccharomyces rouxii Sod2-22 antiporter exports Na(+) and Li(+), but not K(+). The molecular basis of this selectivity is unknown. We combined protein structure modeling, site-directed mutagenesis, phenotype analysis and cation efflux measurements to localize and characterize the cation selectivity region. A three-dimensional model of the ZrSod2-22 transmembrane domain was generated based on the X-ray structure of the Escherichia coli NhaA antiporter and primary sequence alignments with homologous yeast antiporters. The model suggested a close proximity of Thr141, Ala179 and Val375 from transmembrane segments 4, 5 and 11, respectively, forming a hydrophobic hole in the putative cation pathway's core. A series of mutagenesis experiments verified the model and showed that structural modifications of the hole resulted in altered cation selectivity and transport activity. The triple ZrSod2-22 mutant T141S-A179T-V375I gained K(+) transport capacity. The point mutation A179T restricted the antiporter substrate specificity to Li(+) and reduced its transport activity, while serine at this position preserved the native cation selectivity. The negative effect of the A179T mutation can be eliminated by introducing a second mutation, T141S or T141A, in the preceding transmembrane domain. Our experimental results confirm that the three residues found through modeling play a central role in the determination of cation selectivity and transport activity in Z. rouxii Na(+)/H(+) antiporter and that the cation selectivity can be modulated by repositioning a single local methyl group. Copyright © 2015 Elsevier Ltd. All rights reserved.

Divalent cations in tears, and their influence on tear film stability in humans and rabbits.

PubMed

Wei, Xiaojia Eric; Markoulli, Maria; Millar, Thomas J; Willcox, Mark D P; Zhao, Zhenjun

2012-06-05

Reduced tear film stability is reported to contribute to dry eye. Rabbits are known to have a more stable tear film than humans. Thus, we sought to examine the tears of rabbits and humans for metal cations, and to test how they influence tear film stability. Tears were collected from 10 healthy humans and 6 rabbits. Tear osmolality was measured by vapor pressure osmometer, and metals analyzed using inductively coupled plasma (ICP) mass spectrometry or ICP atomic emission spectroscopy. The influence of divalent cations on tears was analyzed by measuring surface tension using the Langmuir trough in vitro, using different concentrations of cations in the subphase, and grading the tear break-up in rabbits in vivo after instillation of chelating agents. Rabbit tears had a higher osmolality compared to humans. Major metals did not differ between species; however, rabbits had higher levels of Mg(2+) (1.13 vs. 0.39 mM) and Ca(2+) (0.75 vs. 0.36 mM). In rabbit tears in vitro, diminishing divalent cations resulted in a decrease in the maximum surface pressure from 37 to 30 mN/m. In vivo, an increase in the amount of tear film that was broken-up was found. In contrast, when changing divalent cation concentrations in human tears, the maximum surface pressure remained at 26 mN/m. The normal osmolality of rabbit tears is significantly higher than that in humans. While divalent cations had little influence on human tears, they appear to have an important role in maintaining tear film stability in rabbits.

Understanding ionic conductivity trends in polyborane solid electrolytes from ab initio molecular dynamics

NASA Astrophysics Data System (ADS)

Varley, Joel; Kweon, Kyoung; Mehta, Prateek; Shea, Patrick; Heo, Tae Wook; Stavila, Vitalie; Udovic, Terrence; Wood, Brandon

Polyborane salts based on B12H122- , B10H102- , and their carboborane counterparts CB11H12- and CB9H10- demonstrate extraordinary Li and Na superionic conductivity that make them attractive as electrolytes in all-solid-state batteries. Their rich chemical and structural diversity creates a versatile design space that could be used to optimize materials with even higher conductivity at lower temperatures; however, many mechanistic details remain enigmatic, including reasons why certain modifications lead to improved performance. Here, we use extensive ab initio molecular dynamics simulations to broadly explore the dependence of ionic conductivity on cation/anion pair combinations for Li and Na polyborane salts. Further simulations based on Li2B12H12 as a model system are used to probe the additional influence of local perturbations, including modifications to chemistry, stoichiometry, and composition. Carbon doping, anion alloying, and cation off-stoichiometry are found to be favorable because they introduce intrinsic disorder, which facilitates local deviations from the expected cation population. Anion reorientations are also discovered to be critical for conduction, with benefits associated with lattice expansion traceable to the facilitation of anion rotation at larger volumes. This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

Water and Carbon Dioxide Adsorption at Olivine Surfaces

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

Kerisit, Sebastien N.; Bylaska, Eric J.; Felmy, Andrew R.

2013-11-14

Plane-wave density functional theory (DFT) calculations were performed to simulate water and carbon dioxide adsorption at the (010) surface of five olivine minerals, namely, forsterite (Mg2SiO4), calcio-olivine (Ca2SiO4), tephroite (Mn2SiO4), fayalite (Fe2SiO4), and Co-olivine (Co2SiO4). Adsorption energies per water molecule obtained from energy minimizations varied from -78 kJ mol-1 for fayalite to -128 kJ mol-1 for calcio-olivine at sub-monolayer coverage and became less exothermic as coverage increased. In contrast, carbon dioxide adsorption energies at sub-monolayer coverage ranged from -20 kJ mol-1 for fayalite to -59 kJ mol-1 for calcio-olivine. Therefore, the DFT calculations show a strong driving force for carbonmore » dioxide displacement by water at the surface of all olivine minerals in a competitive adsorption scenario. Additionally, adsorption energies for both water and carbon dioxide were found to be more exothermic for the alkaline-earth (AE) olivines than for the transition-metal (TM) olivines and to not correlate with the solvation enthalpies of the corresponding divalent cations. However, a correlation was obtained with the charge of the surface divalent cation indicating that the more ionic character of the AE cations in the olivine structure relative to the TM cations leads to greater interactions with adsorbed water and carbon dioxide molecules at the surface and thus more exothermic adsorption energies for the AE olivines. For calcio-olivine, which exhibits the highest divalent cation charge of the five olivines, ab initio molecular dynamics simulations showed that this effect leads both water and carbon dioxide to react with the surface and form hydroxyl groups and a carbonate-like species, respectively.« less

Interfacial Electron Transfer at Sensitized Nanocrystalline TiO2 Electrolyte Interfaces: Influence of Surface Electric Fields and Lewis-Acidic Cations

NASA Astrophysics Data System (ADS)

Barr, Timothy J.

Interfacial electron transfer reactions facilitate charge separation and recombination in dye-sensitized solar cells (DSSCs). Understanding what controls these electron transfer reactions is necessary to develop efficient DSSCs. Gerischer proposed a theory for interfacial electron transfer where the rate constant was related to the energetic overlap between the donor and acceptor states. The present work focuses on understanding how the composition of the CH3CN electrolyte influenced this overlap. It was found that the identity of the electrolyte cation tuned the energetic position of TiO2 electron acceptor states, similar to how pH influences the flatband potential of bulk semiconductors in aqueous electrolytes. For example, the onset for absorption changes, that were attributed to electrons in the TiO2 thin film, were 0.5 V more positive in Mg2+ containing electrolyte than TBA+, where TBA+ is tetrabutylammonium. Similar studies performed on mesoporous, nanocrystalline SnO2 thin films reported a similar cation dependence, but also found evidence for electrons that did not absorb in the visible region that were termed ‘phantom electrons.’. Electron injection is known to generate surface electric fields on the order of 2 MV/cm. The rearrangement of cations in response to surface electric fields, termed screening, was investigated. It was found that magnitude of the electric field and the screening dynamics were dependent on the identity of the electrolyte cation. The rate of charge recombination to the anionic iodide/triiodide redox mediator correlated with the screening ability of the cation, and was initially thought to control charge recombination. However, it was difficult to determine whether electron diffusion or driving force were also cation dependent. Therefore, a in-lab built apparatus, termed STRiVE, was constructed that could disentangle the influence electron diffusion, driving force, and electric fields had on charge recombination. It was found that electron diffusion was independent of the electrolyte cation. Furthermore, charge recombination displayed the same cation-sensitivity using both anionic and cationic redox mediators, indicating electric fields did not cause the cation-dependence of charge recombination. Instead, it was found that the electrolyte cation tuned the energetic position of the TiO2 acceptor states and modulated the driving force for charge recombination.

Sorption of the organic cation metoprolol on silica gel from its aqueous solution considering the competition of inorganic cations.

PubMed

Kutzner, Susann; Schaffer, Mario; Börnick, Hilmar; Licha, Tobias; Worch, Eckhard

2014-05-01

Systematic batch experiments with the organic monovalent cation metoprolol as sorbate and the synthetic material silica gel as sorbent were conducted with the aim of characterizing the sorption of organic cations onto charged surfaces. Sorption isotherms for metoprolol (>99% protonated in the tested pH of around 6) in competition with mono- and divalent inorganic cations (Na(+), NH4(+), Ca(2+), and Mg(2+)) were determined in order to assess their influence on cation exchange processes and to identify the role of further sorptive interactions. The obtained sorption isotherms could be described well by an exponential function (Freundlich isotherm model) with consistent exponents (about 0.8). In general, a decreasing sorption of metoprolol with increasing concentrations in inorganic cations was observed. Competing ions of the same valence showed similar effects. A significant sorption affinity of metoprolol with ion type dependent Freundlich coefficients KF,0.77 between 234.42 and 426.58 (L/kg)(0.77) could still be observed even at very high concentrations of competing inorganic cations. Additional column experiments confirm this behavior, which suggests the existence of further relevant interactions beside cation exchange. In subsequent batch experiments, the influence of mixtures with more than one competing ion and the effect of a reduced negative surface charge at a pH below the point of zero charge (pHPZC ≈ 2.5) were also investigated. Finally, the study demonstrates that cation exchange is the most relevant but not the sole mechanism for the sorption of metoprolol on silica gel. Copyright © 2014 Elsevier Ltd. All rights reserved.

Cationic nanocarriers induce cell necrosis through impairment of Na+/K+-ATPase and cause subsequent inflammatory response

PubMed Central

Wei, Xiawei; Shao, Bin; He, Zhiyao; Ye, Tinghong; Luo, Min; Sang, Yaxiong; Liang, Xiao; Wang, Wei; Luo, Shuntao; Yang, Shengyong; Zhang, Shuang; Gong, Changyang; Gou, Maling; Deng, Hongxing; Zhao, Yinglan; Yang, Hanshuo; Deng, Senyi; Zhao, Chengjian; Yang, Li; Qian, Zhiyong; Li, Jiong; Sun, Xun; Han, Jiahuai; Jiang, Chengyu; Wu, Min; Zhang, Zhirong

2015-01-01

Nanocarriers with positive surface charges are known for their toxicity which has limited their clinical applications. The mechanism underlying their toxicity, such as the induction of inflammatory response, remains largely unknown. In the present study we found that injection of cationic nanocarriers, including cationic liposomes, PEI, and chitosan, led to the rapid appearance of necrotic cells. Cell necrosis induced by cationic nanocarriers is dependent on their positive surface charges, but does not require RIP1 and Mlkl. Instead, intracellular Na+ overload was found to accompany the cell death. Depletion of Na+ in culture medium or pretreatment of cells with the Na+/K+-ATPase cation-binding site inhibitor ouabain, protected cells from cell necrosis. Moreover, treatment with cationic nanocarriers inhibited Na+/K+-ATPase activity both in vitro and in vivo. The computational simulation showed that cationic carriers could interact with cation-binding site of Na+/K+-ATPase. Mice pretreated with a small dose of ouabain showed improved survival after injection of a lethal dose of cationic nanocarriers. Further analyses suggest that cell necrosis induced by cationic nanocarriers and the resulting leakage of mitochondrial DNA could trigger severe inflammation in vivo, which is mediated by a pathway involving TLR9 and MyD88 signaling. Taken together, our results reveal a novel mechanism whereby cationic nanocarriers induce acute cell necrosis through the interaction with Na+/K+-ATPase, with the subsequent exposure of mitochondrial damage-associated molecular patterns as a key event that mediates the inflammatory responses. Our study has important implications for evaluating the biocompatibility of nanocarriers and designing better and safer ones for drug delivery. PMID:25613571

Role of bond adaptability in the passivation of colloidal quantum dot solids.

PubMed

Thon, Susanna M; Ip, Alexander H; Voznyy, Oleksandr; Levina, Larissa; Kemp, Kyle W; Carey, Graham H; Masala, Silvia; Sargent, Edward H

2013-09-24

Colloidal quantum dot (CQD) solids are attractive materials for photovoltaic devices due to their low-cost solution-phase processing, high absorption cross sections, and their band gap tunability via the quantum size effect. Recent advances in CQD solar cell performance have relied on new surface passivation strategies. Specifically, cadmium cation passivation of surface chalcogen sites in PbS CQDs has been shown to contribute to lowered trap state densities and improved photovoltaic performance. Here we deploy a generalized solution-phase passivation strategy as a means to improving CQD surface management. We connect the effects of the choice of metal cation on solution-phase surface passivation, film-phase trap density of states, minority carrier mobility, and photovoltaic power conversion efficiency. We show that trap passivation and midgap density of states determine photovoltaic device performance and are strongly influenced by the choice of metal cation. Supported by density functional theory simulations, we propose a model for the role of cations, a picture wherein metals offering the shallowest electron affinities and the greatest adaptability in surface bonding configurations eliminate both deep and shallow traps effectively even in submonolayer amounts. This work illustrates the importance of materials choice in designing a flexible passivation strategy for optimum CQD device performance.

Unified molecular picture of the surfaces of aqueous acid, base, and salt solutions.

PubMed

Mucha, Martin; Frigato, Tomaso; Levering, Lori M; Allen, Heather C; Tobias, Douglas J; Dang, Liem X; Jungwirth, Pavel

2005-04-28

The molecular structure of the interfacial regions of aqueous electrolytes is poorly understood, despite its crucial importance in many biological, technological, and atmospheric processes. A long-term controversy pertains between the standard picture of an ion-free surface layer and the strongly ion specific behavior indicating in many cases significant propensities of simple inorganic ions for the interface. Here, we present a unified and consistent view of the structure of the air/solution interface of aqueous electrolytes containing monovalent inorganic ions. Molecular dynamics calculations show that in salt solutions and bases the positively charged ions, such as alkali cations, are repelled from the interface, whereas the anions, such as halides or hydroxide, exhibit a varying surface propensity, correlated primarily with the ion polarizability and size. The behavior of acids is different due to a significant propensity of hydronium cations for the air/solution interface. Therefore, both cations and anions exhibit enhanced concentrations at the surface and, consequently, these acids (unlike bases and salts) reduce the surface tension of water. The results of the simulations are supported by surface selective nonlinear vibrational spectroscopy, which reveals among other things that the hydronium cations are present at the air/solution interface. The ion specific propensities for the air/solution interface have important implications for a whole range of heterogeneous physical and chemical processes, including atmospheric chemistry of aerosols, corrosion processes, and bubble coalescence.

Enhanced photocatalytic activity of TiO2 by surface fluorination in degradation of organic cationic compound.

PubMed

Yang, Shi-ying; Chen, You-yuan; Zheng, Jian-guo; Cui, Ying-jie

2007-01-01

Experiments were carried out to investigate the influence of TiO2 surface fluorination on the photodegradation of a representative organic cationic compound, Methylene Blue (MB). The electropositive MB shows poor adsorption on TiO2 surface; its degradation performs a HO-radical-mediated mechanism. In the F-modified system, the kinetic reaction rate enlarged more than 2.5 fold that was attributed mainly to the accumulating adsorption of MB and the increased photogenerated hole available on the F-modified TiO2 surface.

Cationized milled pine bark as an adsorbent for orthophosphate anions

Treesearch

Mandla A. Tshabalala; K.G. Karthikeyan; D. Wang

2004-01-01

More efficient adsorption media are needed for removing dissolved phosphorus in surface water runoff. We studied the use of cationized pine bark as a sorbent for dissolved phosphorus in water. Cationized pine bark was prepared by treating extracted milled pine bark with polyallylamine hydrochloride (PAA HCl) and epichlorohydrin (ECH) in aqueous medium. Attachment of...

Spectroscopic study of carbaryl sorption on smectite from aqueous suspension.

PubMed

de Oliveira, Maurilio Fernandes; Johnston, Cliff T; Premachandra, G S; Teppen, Brian J; Li, Hui; Laird, David A; Zhu, Dongqiang; Boyd, Stephen A

2005-12-01

Sorption of carbaryl (1-naphthyl-N-methyl-carbamate) from aqueous suspension to smectite was studied using Fourier transform infrared (FTIR), high-performance liquid chromatography (HPLC) (for batch sorption), and quantum chemical methods. The amount of carbaryl sorbed was strongly dependent on the surface-charge density of the smectite with more sorption occurring on the two "low" surface-charge density smectites (SHCa-1 and SWy-2) compared to that of the high surface-charge SAz-1 smectite. In addition, the amount of carbaryl sorbed was strongly dependent on the nature of the exchangeable cation and followed the order of Ba approximately Cs approximately Ca > Mg approximately K > Na approximately Li for SWy-2. A similartrend was found for hectorite (SHCa-1) of Cs > Ba > Ca > K approximately Mg > Na approximately Li. Using the shift of the carbonyl stretching band as an indicator of the strength of interaction between carbaryl and the exchangeable cation, the observed order was Mg > Ca > Ba approximately K > Na > Cs. The position of the carbonyl stretching band shifted to lower wavenumbers with increasing ionic potential of the exchangeable cation. Density functional theory predicted a cation-induced lengthening of the C=O bond, resulting from the carbonyl group interacting directly with the exchangeable cation in support of the spectroscopic observations. Further evidence was provided by a concomitant shift in the opposite direction by several vibrational bands in the 1355-1375 cm(-1) region assigned to stretching bands of the carbamate N-Ccarbonyl and Oether-Ccarbonyl bonds. These data indicate that carbaryl sorption is due, in part, to site-specific interactions between the carbamate functional group and exchangeable cations, as evidenced by the FTIR data. However, these data suggest that hydrophobic interactions also contribute to the overall amount of carbaryl sorbed. For example, the FTIR data indicated thatthe weakest interaction occurred when Cs+ was the exchangeable cation. In contrast, the highest amount of carbaryl sorption was observed on Cs-exchanged smectite. Of all the cations studied, Cs has the lowest enthalpy of hydration. It is suggested that this low hydration energy provides the carbaryl with greater access to the hydrophobic regions of the siloxane surface.

Cation Effects on the Electron-Acceptor Side of Photosystem II.

PubMed

Khan, Sahr; Sun, Jennifer S; Brudvig, Gary W

2015-06-18

The normal pathway of electron transfer on the electron-acceptor side of photosystem II (PSII) involves electron transfer from quinone A, QA, to quinone B, QB. It is possible to redirect electrons from QA(-) to water-soluble Co(III) complexes, which opens a new avenue for harvesting electrons from water oxidation by immobilization of PSII on electrode surfaces. Herein, the kinetics of electron transfer from QA(-) to [Co(III)(terpy)2](3+) (terpy = 2,2';6',2″-terpyridine) are investigated with a spectrophotometric assay revealing that the reaction follows Michaelis-Menten saturation kinetics, is inhibited by cations, and is not affected by variation of the QA reduction potential. A negatively charged site on the stromal surface of the PSII protein complex, composed of glutamic acid residues near QA, is hypothesized to bind cations, especially divalent cations. The cations are proposed to tune the redox properties of QA through electrostatic interactions. These observations may thus explain the molecular basis of the effect of divalent cations like Ca(2+), Sr(2+), Mg(2+), and Zn(2+) on the redox properties of the quinones in PSII, which has previously been attributed to long-range conformational changes propagated from divalent cations binding to the Ca(II)-binding site in the oxygen-evolving complex on the lumenal side of the PSII complex.

Mixed Ionic Liquid Improves Electrolyte Dynamics in Supercapacitors

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

Osti, Naresh C.; Gallegos, Alejandro; Dyatkin, Boris

Well-tailored mixtures of distinct ionic liquids can act as optimal electrolytes that extend the operating electrochemical window and improve charge storage density in supercapacitors. Here, we explore two room-temperature ionic liquids, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EmimTFSI) and 1-ethyl-3-methylimidazolium tetrafluoroborate (EmimBF 4). We study their electric double-layer behavior in the neat state and as binary mixtures on the external surfaces of onion-like carbon electrodes using quasielastic neutron scattering (QENS) and classical density functional theory techniques. Computational results reveal that a mixture with 4:1 EmimTFSI/EmimBF 4 volume ratio displaces the larger [TFSI –] anions with smaller [BF 4 –] ions, leading to an excessmore » adsorption of [Emim +] cations near the electrode surface. These findings are corroborated by the manifestation of nonuniform ion diffusivity change, complementing the description of structural modifications with changing composition, from QENS measurements. In conclusion, molecular-level understanding of ion packing near electrodes provides insight for design of ionic liquid formulations that enhance the performance of electrochemical energy storage devices.« less

Mixed Ionic Liquid Improves Electrolyte Dynamics in Supercapacitors

DOE PAGES

Osti, Naresh C.; Gallegos, Alejandro; Dyatkin, Boris; ...

2018-04-19

Well-tailored mixtures of distinct ionic liquids can act as optimal electrolytes that extend the operating electrochemical window and improve charge storage density in supercapacitors. Here, we explore two room-temperature ionic liquids, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EmimTFSI) and 1-ethyl-3-methylimidazolium tetrafluoroborate (EmimBF 4). We study their electric double-layer behavior in the neat state and as binary mixtures on the external surfaces of onion-like carbon electrodes using quasielastic neutron scattering (QENS) and classical density functional theory techniques. Computational results reveal that a mixture with 4:1 EmimTFSI/EmimBF 4 volume ratio displaces the larger [TFSI –] anions with smaller [BF 4 –] ions, leading to an excessmore » adsorption of [Emim +] cations near the electrode surface. These findings are corroborated by the manifestation of nonuniform ion diffusivity change, complementing the description of structural modifications with changing composition, from QENS measurements. In conclusion, molecular-level understanding of ion packing near electrodes provides insight for design of ionic liquid formulations that enhance the performance of electrochemical energy storage devices.« less

Enhanced surface functionality and microbial fuel cell performance of chitosan membranes through phosphorylation.

PubMed

Holder, Shima L; Lee, Ching-Hwa; Popuri, Srinivasa R; Zhuang, Meng-Xin

2016-09-20

The effects of plasticization and cross-linking on the performance of chitosan as promising proton exchange membranes (PEMs) for bioelectricity generation in microbial fuel cells (MFCs) were investigated. The physico-chemical properties of chitosan (CS), sorbitol-chitosan (S-CS), phosphorylated-chitosan (CS-P) and phosphorylated-sorbitol-chitosan (S-CS-P) membranes were investigated by FESEM-EDS, FTIR-ATR, XRD, TGA, tensile strength and sorption studies. The performance of the fabricated PEMs was assessed by power density and cation exchange capacity (CEC). Maximum power densities achieved were 130.03, 20.76, 94.59 and 7.42mW/m(2) for CS-P, S-CS-P, S-CS and CS membranes respectively. Phosphorylation of the CS membranes increased CEC and tensile strength, attributed to an increase in bonded amide and phosphate ionic surface groups. Further, 49.07% COD removal from municipal wastewater was achieved with CS-P membranes. Thus, through chemical modifications, the physico-chemical and mechanical properties of natural abundant biopolymer chitosan can be enhanced for its use as an environmentally sustainable PEM in MFC technology. Copyright © 2016 Elsevier Ltd. All rights reserved.

Polyimide-Clay Composite Materials for Space Application

NASA Technical Reports Server (NTRS)

Orwoll, Robert A.; Connell, John W. (Technical Monitor)

2005-01-01

The introduction of nanometer-sized clay particles into a polyimide matrix has been shown to enhance the physical properties of specific polymer systems. The clay comprises large stacked platelets of the oxides of aluminum and silicon. These sheets have long dimensions on the order of tenths of a micrometer and thicknesses of several nanometers. Homogeneous dispersion of the clay platelets in the polymer matrix is necessary to achieve those enhancements in polymer properties. Natural montmorillonite with the empirical formula Na0.33Mg0.33Al1.67(OH)2(Si4O10) contains exchangeable inorganic cations. The clay lamellae stack together with the positive sodium ions situated between the surfaces of the individual sheets to balance negatively charged oxygen atoms that are on the surfaces of the sheets. These surface charges contribute to strong electrostatic forces which hold the sheets together tightly. Exfoliation can be accomplished only with unusual measures. In preparing clay nanocomposites, we have taken two steps to try to reduce these interlamellar forces in order to promote the separation (exfoliation) of the sheets and the dispersion of the individual clay particles throughout the organic polymer matrix. In the first step, some of the surface Na(+) ions are replaced with Li(+) ions. Unlike sodium cations, the lithium cations migrate into the interior of the lamellae when the system is heated. Their departure from the surface reduces the surface charge and therefore the attractive forces between the sheets. The loss of alkali metal cations from the surface can be measured as the cation exchange capacity (CEC) of the clay. For example, we found that the CEC of montmorillonite clay was reduced by almost two thirds by treating it with lithium ions and heating to 250 C for 24 hr. Lesser heating has a smaller effect on the CEC. X-ray diffraction measurements show that the d-spacing decreased from ca. 1.34 to 0.97 nm, apparently a consequence of a collapse of the clay layers. We observed that the d-spacing can be varied by altering the heat treatment. In the second part of our effort to reduce the interlamellar forces, the remaining inorganic surface cations were replaced by the trimethylphenylammonium ion (TMPA), the biphenyltrimethylammonium ion (BTMA), or the tetraphenylphosphonium ion (TPP).

Cation induced electrochromism in 2,4-dinitrophenylhydrazine (DNPH): Tuning optical properties of aromatic rings

NASA Astrophysics Data System (ADS)

Sanader, Željka; Brunet, Claire; Broyer, Michel; Antoine, Rodolphe; Dugourd, Philippe; Mitrić, Roland; Bonačić-Koutecký, Vlasta

2013-05-01

We have theoretically investigated the influence of protons and noble metal cations on optical properties of 2,4-dinitrophenylhydrazine (DNPH). We show that optical properties of aromatic rings can be tuned by cation-induced electrochromism in DNPH due to binding to specific NO2 groups. Our findings on cation-induced electrochromism in DNPH may open new routes in two different application areas, due to the fact that DNPH can easily bind to biological molecules and surface materials through carbonyl groups.

Precisely Controlling Nanochannels of Graphene Oxide Membranes through Lignin-Based Cation Decoration for Dehydration of Biofuels.

PubMed

Guan, Kecheng; Liu, Quan; Ji, Yufan; Zhang, Mengchen; Wu, Yulin; Zhao, Jing; Liu, Gongping; Jin, Wanqin

2018-05-07

Lignin-based cations introduced into graphene oxide (GO) have been found to bring about stabilization of the nanostructure and the active sites and to give rise to various interactions for subsequent modification with polyelectrolyte and nanospacers, with a view to precisely controlling the nanochannels of the GO-based membranes. The resulting membranes exhibited excellent performance in biofuel dehydration with water flux of 4000-6000 g m -2  h -1 , which exceeds that of the state-of-the-art polymeric and GO-based membranes. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Experimental investigation and DFT calculation of different amine/ammonium salts adsorption on kaolinite

NASA Astrophysics Data System (ADS)

Chen, Jun; Min, Fan-fei; Liu, Lingyun; Liu, Chunfu; Lu, Fangqin

2017-10-01

The adsorption of four different amine/ammonium salts of DDA (Dodecyl amine), MDA (N-methyldodecyl amine), DMDA (N,N-dimethyldodecyl amine) and DTAC (Dodecyl trimethyl ammonium chloride) on kaolinite particles was investigated in the study through the measurement of contact angles, zeta potentials, aggregation observation, adsorption and sedimentation. The results show that different amine/ammonium salts can adsorb on the kaolinite surface to enhance the hydrophobicity and reduce the electronegativity of kaolinite particle surface, and thus induce a strong hydrophobic aggregation of kaolinite particles which promotes the settlement of kaolinite. To explore the adsorption mechanism of these four amine/ammonium salts on kaolinite surfaces, the adsorptions of DDA+, MDA+, DMDA+ and DTAC+ on kaolinite (001) surface and (00 1 bar) surface are calculated with DFT (Density functional theory). The DFT calculation results indicate that different amine/ammonium cations can strongly adsorbed on kaolinite (001) surface and (00 1 bar) surface by forming Nsbnd H⋯O strong hydrogen bonds or Csbnd H⋯O weak hydrogen bonds, and there are strongly electrostatic attractions between different amine/ammonium cations and kaolinite surfaces. The main adsorption mechanism of amine/ammonium cations on kaolinite is hydrogen-bond interaction and electrostatic attraction.

Thermal treatment effects imposed on solid DNA cationic lipid complex with hexadecyltrimethylammonium chloride, observed by variable angle spectroscopic ellipsometry

NASA Astrophysics Data System (ADS)

Nizioł, Jacek

2014-12-01

DNA cationic lipid complexes are materials of properties required for applications in organic electronics and optoelectronics. Often, their thermal stability demonstrated by thermogravimetry is cited in the literature as important issue. However, little is known about processes occurring in heated solid DNA cationic lipid complexes. In frame of this work, thin films of Deoxyribonucleic acid-hexadecyltrimethylammonium chloride (DNA-CTMA) were deposited on silicon wafers. Samples were thermally annealed, and simultaneously, their optical functions were measured by spectroscopic ellipsometry. At lower temperatures, thermal expansion coefficient of solid DNA-CTMA was negative, but at higher temperatures positive. Thermally induced modification of absorption spectrum in UV-vis was observed. It occurred at a range of temperatures higher than this of DNA denaturation in solution. The observed phenomenon was irreversible, at least in time scale of the experiment (one day).

Photochemical properties and sensor applications of modified yellow fluorescent protein (YFP) covalently attached to the surfaces of etched optical fibers (EOFs).

PubMed

Veselov, Alexey A; Abraham, Bobin George; Lemmetyinen, Helge; Karp, Matti T; Tkachenko, Nikolai V

2012-01-01

Fluorescent proteins have the inherent ability to act as sensing components which function both in vitro and inside living cells. We describe here a novel study on a covalent site-specific bonding of fluorescent proteins to form self-assembled monolayers (SAMs) on the surface of etched optical fibers (EOFs). Deposition of fluorescent proteins on EOFs gives the opportunity to increase the interaction of guided light with deposited molecules relative to plane glass surfaces. The EOF modification is carried out by surface activation using 3-aminopropylthrimethoxysilane (APTMS) and bifunctional crosslinker sulfosuccinimidyl 4-[N-maleimidomethyl]cyclohexane-1-carboxylate (sulfo-SMCC) which exposes sulfhydryl-reactive maleimide groups followed by covalent site-specific coupling of modified yellow fluorescent protein (YFP). Steady-state and fluorescence lifetime measurements confirm the formation of SAM. The sensor applications of YPF SAMs on EOF are demonstrated by the gradual increase of emission intensity upon addition of Ca(2+) ions in the concentration range from a few tens of micromolars up to a few tens of millimolars. The studies on the effect of pH, divalent cations, denaturing agents, and proteases reveal the stability of YFP on EOFs at normal physiological conditions. However, treatments with 0.5% SDS at pH 8.5 and protease trypsin are found to denaturate or cleave the YFP from fiber surfaces.

Double layer effects in electrocatalysis: The oxygen reduction reaction and ethanol oxidation reaction on Au(111), Pt(111) and Ir(111) in alkaline media containing Na and Li cations

DOE PAGES

Lopes, Pietro P.; Strmcnik, Dusan; Jirkovsky, Jakub S.; ...

2015-09-28

Oxygen reduction and ethanol oxidation reactions were studied on Au(111), Pt(111) and Ir(111) in alkaline solutions containing sodium and/or lithium cations. By keeping the same (111) surface orientation and exploring oxophilicity trends and non-covalent interactions between OH ad and alkali metal cations (AMC n+), we were able to gain deep insights into the multiple roles that OH ad plays in these important electrocatalytic reactions. Cyclic voltammetry experiments revealed that OH ad formation initiates at distinct electrode potentials, governed by the oxophilicity of the specific metal surface, with further OH ad adlayer stabilization by non-covalent alkali-cation interactions and affecting the formationmore » of a “true oxide” layer at higher electrode potentials. Although OH ad is a simple spectator for the ORR, it promotes the ethanol oxidation reaction (EOR) at lower potentials and act as spectator at high OHad coverages. By changing the alkali metal cation at the interface (Li +) on more oxophilic surfaces, it was possible to promote the EOR even more, relative to Na +, without changing the product distribution for the reaction. This cation effect suggests that OH ad—Li +(H 2O) x clusters can stabilize the ethoxide adlayer, thus improving the EOR activity. Finally, our results indicate the importance of the entire electrochemical interface in determining the electrocatalytic activity during reaction.« less

Triboelectric energy harvesting with surface-charge-fixed polymer based on ionic liquid

PubMed Central

Sano, Chikako; Mitsuya, Hiroyuki; Ono, Shimpei; Miwa, Kazumoto; Toshiyoshi, Hiroshi; Fujita, Hiroyuki

2018-01-01

Abstract A novel triboelectric energy harvester has been developed using an ionic liquid polymer with cations fixed at the surface. In this report, the fabrication of the device and the characterization of its energy harvesting performance are detailed. An electrical double layer was induced in the ionic liquid polymer precursor to attract the cations to the surface where they are immobilized using a UV-based crosslinking reaction. The finalized polymer is capable of generating an electrical current when contacted by a metal electrode. Using this property, energy harvesting experiments were conducted by cyclically contacting a gold-surface electrode with the charge fixed surface of the polymer. Control experiments verified the effect of immobilizing the cations at the surface. By synthesizing a polymer with the optimal composition ratio of ionic liquid to macromonomer, an output of 77 nW/cm2 was obtained with a load resistance of 1 MΩ at 1 Hz. This tuneable power supply with a μA level current output may contribute to Internet of Things networks requiring numerous sensor nodes at remote places in the environment. PMID:29707070

Rectification of nanopores at surfaces

PubMed Central

Sa, Niya

2011-01-01

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

Impacts of Cation Type and Clay on Transport of Surface-modified Nanoparticles through Saturated Sand Columns

NASA Astrophysics Data System (ADS)

Torkzaban, S.; Wan, J.; Tokunaga, T. K.

2010-12-01

Transport of three different nanoparticles (NPs) was studied in columns packed with different sands (unwashed Accusand, washed Accusand, and ultrapure quartz) at different ionic strengths (IS) and cation types. The NPs were functionalized (polyacrylic acid) quantum dots (QDs), carboxylic-modified latex, and bare silica. Scanning electron microscopy (SEM) and energy-dispersive X-ray (EDX) analysis showed there were regions on the unwashed Accusand grains covered with clay particles. The SEM images of washed Accusand showed that the sand surfaces contained significantly less clay coatings. The breakthrough curves (BTCs) of QDs and latex NPs from unwashed Accusand columns showed minute deposition at 50 and 100 mM Na+. However, significant NP deposition occurred in unwashed Accusand columns at 0.5, 1, and 2 mM Ca2+. The amount of deposition increased as the Ca2+ concentration was increased. These results suggest that, in contrast to monovalent Na+, divalent Ca2+ enhanced deposition of the NPs. The BTCs of QDs and latex NPs in washed Accusand exhibited a similar trend as those of unwashed Accusand, however, much less deposition occurred at any given IS. The BTCs from the ultrapure quartz sand column showed negligible QD deposition at 2 mM Ca2+. Following completion of column experiments, a few Accusand sand grains were analyzed with SEM and the images showed that most of QDs were deposited on the clay surfaces. In contrast with our results from surface-modified NPs, the column experiments using bare silica NPs at 5 mM Ca2+ in unwashed Accusand showed negligible deposition. The enhanced deposition of surface-modified NPs may be attributed to cation bridging in which Ca2+ cations serve as a bridge between the NP, which contain carboxyl group on its surface, and negatively charged clay surfaces at 7. Because Ca2+ is commonly a major cation in groundwater, our results suggest that transport of carboxylic ligand-modified NPs may be very limited in subsurface environments.

Preconditioning with Cations Increases the Attachment of Anoxybacillus flavithermus and Geobacillus Species to Stainless Steel

PubMed Central

Flint, Steve; Palmer, Jon; Brooks, John; Lindsay, Denise

2013-01-01

Preconditioning of Anoxybacillus flavithermus E16 and Geobacillus sp. strain F75 with cations prior to attachment often significantly increased (P ≤ 0.05) the number of viable cells that attached to stainless steel (by up to 1.5 log CFU/cm2) compared with unconditioned bacteria. It is proposed that the transition of A. flavithermus and Geobacillus spp. from milk formulations to stainless steel product contact surfaces in milk powder manufacturing plants is mediated predominantly by bacterial physiological factors (e.g., surface-exposed adhesins) rather than the concentrations of cations in milk formulations surrounding bacteria. PMID:23645192

Structure and dynamics of microbe-exuded polymers and their interactions with calcite surfaces.

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

Cygan, Randall Timothy; Mitchell, Ralph; Perry, Thomas D.

2005-12-01

Cation binding by polysaccharides is observed in many environments and is important for predictive environmental modeling, and numerous industrial and food technology applications. The complexities of these organo-cation interactions are well suited to predictive molecular modeling studies for investigating the roles of conformation and configuration of polysaccharides on cation binding. In this study, alginic acid was chosen as a model polymer and representative disaccharide and polysaccharide subunits were modeled. The ability of disaccharide subunits to bind calcium and to associate with the surface of calcite was investigated. The findings were extended to modeling polymer interactions with calcium ions.

Development of a stable cation modified graphene oxide membrane for water treatment

NASA Astrophysics Data System (ADS)

Yu, Wenzheng; (Yet Yu, Tong; Graham, Nigel

2017-12-01

Membranes prepared from layers of graphene oxide (GO) offer substantial advantages over conventional materials for water treatment (e.g. greater flux), but the stability of GO membranes in water has not been achieved until now. In this study the behavior of GO membranes prepared with different quantities and species of cations has been investigated to establish the feasibility of their application in water treatment. A range of cation-modified GO membranes were prepared and exposed to aqueous solutions containing specific chemical constituents. In pure water, unmodified and Na-modified GO membranes were highly unstable, while GO membranes modified with multivalent cations were stable provided there were sufficient quantities of cations present; their relative capability to achieve GO stability was as follows: Al3+  >  Ca2+  >  Mg2+  >  Na+. It is believed that the mechanism of cross-linking, and membrane stability, is via metal-carboxylate chelates and cation-graphite surface interactions (cation-π interaction), and that the latter appears to increase with increasing cation valency. The instability of cation (Ca or Al)-modified GO membranes by NaCl solutions during permeation occurred as Na+ exchanged with the incorporated multivalent cations, but a high content of Al3+ in the GO membrane impeded Al3+/Na+ exchange and thus retained membrane stability. In solutions containing biopolymers representative of surface waters or seawater (protein and polysaccharide solutions), Ca-GO membranes (even with high Ca2+ content) were not stable, while Al-GO membranes were stable if the Al3+ content was sufficiently high; Al-formed membranes also had a greater flux than Ca-GO membranes.

Influence of cationic lipid concentration on properties of lipid–polymer hybrid nanospheres for gene delivery

PubMed Central

Bose, Rajendran JC; Arai, Yoshie; Ahn, Jong Chan; Park, Hansoo; Lee, Soo-Hong

2015-01-01

Nanoparticles have been widely used for nonviral gene delivery. Recently, cationic hybrid nanoparticles consisting of two different materials were suggested as a promising delivery vehicle. In this study, nanospheres with a poly(d,l-lactic-co-glycolic acid) (PLGA) core and cationic lipid shell were prepared, and the effect of cationic lipid concentrations on the properties of lipid polymer hybrid nanocarriers investigated. Lipid–polymer hybrid nanospheres (LPHNSs) were fabricated by the emulsion-solvent evaporation method using different concentrations of cationic lipids and characterized for size, surface charge, stability, plasmid DNA-binding capacity, cytotoxicity, and transfection efficiency. All LPHNSs had narrow size distribution with positive surface charges (ζ-potential 52–60 mV), and showed excellent plasmid DNA-binding capacity. In vitro cytotoxicity measurements with HEK293T, HeLa, HaCaT, and HepG2 cells also showed that LPHNSs exhibited less cytotoxicity than conventional transfection agents, such as Lipofectamine and polyethyleneimine–PLGA. As cationic lipid concentrations increased, the particle size of LPHNSs decreased while their ζ-potential increased. In addition, the in vitro transfection efficiency of LPHNSs increased as lipid concentration increased. PMID:26379434

An electrochemiluminescence sensor based on a Ru(bpy)3(2+)-silica-chitosan/nanogold composite film.

PubMed

Cai, Zhi-min; Wu, Yan-fang; Huang, Yun-he; Li, Qiu-ping; Chen, Xiao-mei; Chen, Xi

2012-05-30

Chitosan, a cationic polysaccharide containing amino and hydroxyl groups, was used to fabricate an electrochemiluminescence (ECL) sensor. In the sensor construction, a glassy carbon electrode (GCE) was first coated by a chitosan film which embedded gold nanoparticles, and then the film was modified by introducing carboxyl groups on the surface, which were used to immobilize tris(2,2'-bipyridyl)ruthenium(II) doped amino-functional silica nanoparticles (NH(2)-RuSiNPs) through amido links. The successful modification was confirmed by scanning electronic microscopy and cyclic voltammetry. A binding model between the chitosan/nanogold composite film and NH(2)-RuSiNPs was also proposed, in which the amido link was the dominant bonding, accompanied with hydrogen bond interaction. ECL studies revealed that the sensor had very good response to different concentrations of 2-(dibutylamino) ethanol. This sensor was also applied in methamphetamine determination. Copyright © 2012 Elsevier B.V. All rights reserved.

Ion adsorption-induced wetting transition in oil-water-mineral systems.

PubMed

Mugele, Frieder; Bera, Bijoyendra; Cavalli, Andrea; Siretanu, Igor; Maestro, Armando; Duits, Michel; Cohen-Stuart, Martien; van den Ende, Dirk; Stocker, Isabella; Collins, Ian

2015-05-27

The relative wettability of oil and water on solid surfaces is generally governed by a complex competition of molecular interaction forces acting in such three-phase systems. Herein, we experimentally demonstrate how the adsorption of in nature abundant divalent Ca(2+) cations to solid-liquid interfaces induces a macroscopic wetting transition from finite contact angles (≈ 10°) with to near-zero contact angles without divalent cations. We developed a quantitative model based on DLVO theory to demonstrate that this transition, which is observed on model clay surfaces, mica, but not on silica surfaces nor for monovalent K(+) and Na(+) cations is driven by charge reversal of the solid-liquid interface. Small amounts of a polar hydrocarbon, stearic acid, added to the ambient decane synergistically enhance the effect and lead to water contact angles up to 70° in the presence of Ca(2+). Our results imply that it is the removal of divalent cations that makes reservoir rocks more hydrophilic, suggesting a generalizable strategy to control wettability and an explanation for the success of so-called low salinity water flooding, a recent enhanced oil recovery technology.

Structure-transfection activity relationships in a series of novel cationic lipids with heterocyclic head-groups.

PubMed

Ivanova, Ekaterina A; Maslov, Mikhail A; Kabilova, Tatyana O; Puchkov, Pavel A; Alekseeva, Anna S; Boldyrev, Ivan A; Vlassov, Valentin V; Serebrennikova, Galina A; Morozova, Nina G; Zenkova, Marina A

2013-11-07

Cationic liposomes are promising candidates for the delivery of various therapeutic nucleic acids. Here, we report a convenient synthesis of carbamate-type cationic lipids with various hydrophobic domains (tetradecanol, dialkylglycerol, cholesterol) and positively charged head-groups (pyridinium, N-methylimidazolium, N-methylmorpholinium) and data on the structure-transfection activity relationships. It was found that single-chain lipids possess high surface activity, which correlates with high cytotoxicity due to their ability to disrupt the cellular membrane by combined hydrophobic and electrostatic interactions. Liposomes containing these lipids also display high cytotoxicity with respect to all cell lines. Irrespective of chemical structures, all cationic lipids form liposomes with similar sizes and surface potentials. The characteristics of complexes composed of cationic liposomes and nucleic acids depend mostly on the type of nucleic acid and P/N ratios. In the case of oligodeoxyribonucleotide delivery, the transfection activity depends on the type of cationic head-group regardless of the type of hydrophobic domain: all types of cationic liposomes mediate efficient oligonucleotide transfer into 80-90% of the eukaryotic cells, and liposomes based on lipids with N-methylmorpholinium cationic head-group display the highest transfection activity. In the case of plasmid DNA and siRNA, the type of hydrophobic domain determines the transfection activity: liposomes composed of cholesterol-based lipids were the most efficient in DNA transfer, while liposomes containing glycerol-based lipids exhibited reasonable activity in siRNA delivery under serum-free conditions.

On the concept of critical surface excess of micellization.

PubMed

Talens-Alesson, Federico I

2010-11-16

The critical surface excess of micellization (CSEM) should be regarded as the critical condition for micellization of ionic surfactants instead of the critical micelle concentration (CMC). There is a correspondence between the surface excesses Γ of anionic, cationic, and zwitterionic surfactants at their CMCs, which would be the CSEM values, and the critical association distance for ionic pair association calculated using Bjerrum's correlation. Further support to this concept is given by an accurate method for the prediction of the relative binding of alkali cations onto dodecylsulfate (NaDS) micelles. This method uses a relative binding strength parameter calculated from the values of surface excess Γ at the CMC of the alkali dodecylsulfates. This links both the binding of a given cation onto micelles and the onset for micellization of its surfactant salt. The CSEM concept implies that micelles form at the air-water interface unless another surface with greater affinity for micelles exists. The process would start when surfactant monomers are close enough to each other for ionic pairing with counterions and the subsequent assembly of these pairs becomes unavoidable. This would explain why the surface excess Γ values of different surfactants are more similar than their CMCs: the latter are just the bulk phase concentrations in equilibrium with chemicals with different hydrophobicity. An intriguing implication is that CSEM values may be used to calculate the actual critical distances of ionic pair formation for different cations, replacing Bjerrum's estimates, which only discriminate by the magnitude of the charge.

Simulation of a cellulose fiber in ionic liquid suggests a synergistic approach to dissolution

DOE PAGES

Mostofian, Barmak; Smith, Jeremy C.; Cheng, Xiaolin

2013-08-11

Ionic liquids dissolve cellulose in a more efficient and environmentally acceptable way than conventional methods in aqueous solution. An understanding of how ionic liquids act on cellulose is essential for improving pretreatment conditions and thus detailed knowledge of the interactions between the cations, anions and cellulose is necessary. Here in this study, to explore ionic liquid effects, we perform all-atom molecular dynamics simulations of a cellulose microfibril in 1-butyl-3-methylimidazolium chloride and analyze site–site interactions and cation orientations at the solute–solvent interface. The results indicate that Cl - anions predominantly interact with cellulose surface hydroxyl groups but with differences between chainsmore » of neighboring cellulose layers, referred to as center and origin chains; Cl- binds to C3-hydroxyls on the origin chains but to C2- and C6-hydroxyls on the center chains, thus resulting in a distinct pattern along glucan chains of the hydrophilic fiber surfaces. In particular, Cl - binding disrupts intrachain O3H–O5 hydrogen bonds on the origin chains but not those on the center chains. In contrast, Bmim + cations stack preferentially on the hydrophobic cellulose surface, governed by non-polar interactions with cellulose. Complementary to the polar interactions between Cl - and cellulose, the stacking interaction between solvent cation rings and cellulose pyranose rings can compensate the interaction between stacked cellulose layers, thus stabilizing detached cellulose chains. Moreover, a frequently occurring intercalation of Bmim + on the hydrophilic surface is observed, which by separating cellulose layers can also potentially facilitate the initiation of fiber disintegration. The results provide a molecular description why ionic liquids are ideal cellulose solvents, the concerted action of anions and cations on the hydrophobic and hydrophilic surfaces being key to the efficient dissolution of the amphiphilic carbohydrate.« less

Improved Photoactivity of Pyroxene Silicates by Cation Substitutions.

PubMed

Legesse, Merid; Park, Heesoo; El Mellouhi, Fedwa; Rashkeev, Sergey N; Kais, Sabre; Alharbi, Fahhad H

2018-04-17

We investigated the possibility of band structure engineering of pyroxene silicates with chemical formula A +1 B +3 Si 2 O 6 by proper cation substitution. Typically, band gaps of naturally formed pyroxene silicates such as NaAlSi 2 O 6 are quite high (≈5 eV). Therefore, it is important to find a way to reduce band gaps for these materials below 3 eV to make them usable for optoelectronic applications operating at visible light range of the spectrum. Using first-principles calculations, we found that appropriate substitutions of both A + and B 3+ cations can reduce the band gaps of these materials to as low as 1.31 eV. We also discuss how the band gap in this class of materials is affected by cation radii, electronegativity of constituent elements, spin-orbit coupling, and structural modifications. In particular, the replacement of Al 3+ in NaAlSi 2 O 6 by another trivalent cation Tl 3+ results in the largest band-gap reduction and emergence of intermediate bands. We also found that all considered materials are still thermodynamically stable. This work provides a design approach for new environmentally benign and abundant materials for use in photovoltaics and optoelectronic devices. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface modification effects on defect-related photoluminescence in colloidal CdS quantum dots.

PubMed

Lee, TaeGi; Shimura, Kunio; Kim, DaeGwi

2018-05-03

We investigated the effects of surface modification on the defect-related photoluminescence (PL) band in colloidal CdS quantum dots (QDs). A size-selective photoetching process and a surface modification technique with a Cd(OH)2 layer enabled the preparation of size-controlled CdS QDs with high PL efficiency. The Stokes shift of the defect-related PL band before and after the surface modification was ∼1.0 eV and ∼0.63 eV, respectively. This difference in the Stokes shifts suggests that the origin of the defect-related PL band was changed by the surface modification. Analysis by X-ray photoelectron spectroscopy revealed that the surface of the CdS QDs before and after the surface modification was S rich and Cd rich, respectively. These results suggest that Cd-vacancy acceptors and S-vacancy donors affect PL processes in CdS QDs before and after the surface modification, respectively.

Manipulating interactions between functional colloidal particles and polyethylene surfaces using interfacial engineering.

PubMed

Ziani, Khalid; Barish, Jeffrey A; McClements, David Julian; Goddard, Julie M

2011-08-01

The purpose of this study was to examine the interaction between lipid droplets and polyethylene surfaces, representative of those commonly used in food packaging. Lipid droplets with various surface charges were prepared by homogenizing corn oil and water in the presence of surfactants with different electrical characteristics: non-ionic (Tween 80, T80), cationic (lauric arginate, LAE), and/or anionic (sodium dodecyl sulfate, SDS). The ionic properties of polyethylene surfaces were modified by UV-treatment. Stable emulsions containing small droplets (d<200 nm) with nearly neutral (T80), cationic (T80: LAE), and anionic (T80: SDS) charges were prepared by adding different levels of the ionic surfactants to Tween 80 stabilized emulsions. Scanning electronic microscopy (SEM), confocal fluorescence microscopy, and ATR-FTIR showed that the number of droplets attached to the polyethylene surfaces depended on the droplet charge and the polyethylene surface characteristics. The greatest degree of droplet adsorption was observed for the cationic droplets to the UV-ozone treated polyethylene surfaces, which was attributed to electrostatic attraction. These results are important for understanding the behavior of encapsulated lipophilic components in food containers. Copyright © 2011 Elsevier Inc. All rights reserved.

Hydrophobic matrix-free graphene-oxide composites with isotropic and nematic states.

PubMed

Wåhlander, Martin; Nilsson, Fritjof; Carlmark, Anna; Gedde, Ulf W; Edmondson, Steve; Malmström, Eva

2016-08-21

We demonstrate a novel route to synthesise hydrophobic matrix-free composites of polymer-grafted graphene oxide (GO) showing isotropic or nematic alignment and shape-memory effects. For the first time, a cationic macroinitiator (MI) has been immobilised on anionic GO and subsequently grafted with hydrophobic polymer grafts. Dense grafts of PBA, PBMA and PMMA with a wide range of average graft lengths (MW: 1-440 kDa) were polymerised by surface-initiated controlled radical precipitation polymerisation from the statistical MI. The surface modification is designed similarly to bimodal graft systems, where the cationic MI generates nanoparticle repulsion, similar to dense short grafts, while the long grafts offer miscibility in non-polar environments and cohesion. The state-of-the-art dispersions of grafted GO were in the isotropic state. Transparent and translucent matrix-free GO-composites could be melt-processed directly using only grafted GO. After processing, birefringence due to nematic alignment of grafted GO was observed as a single giant Maltese cross, 3.4 cm across. Permeability models for composites containing aligned 2D-fillers were developed, which were compared with the experimental oxygen permeability data and found to be consistent with isotropic or nematic states. The storage modulus of the matrix-free GO-composites increased with GO content (50% increase at 0.67 wt%), while the significant increases in the thermal stability (up to 130 °C) and the glass transition temperature (up to 17 °C) were dependent on graft length. The tuneable matrix-free GO-composites with rapid thermo-responsive shape-memory effects are promising candidates for a vast range of applications, especially selective membranes and sensors.

From atactic to isotactic CO/p-methylstyrene copolymer by proper modification of Pd(II) catalysts bearing achiral alpha-diimines.

PubMed

Binotti, Barbara; Carfagna, Carla; Zuccaccia, Cristiano; Macchioni, Alceo

2005-01-07

Cationic Pd(II) complexes modified with achiral C(2v)-symmetric alpha-diimine ligands allow preparation of atactic or isotactic stereoblock CO/p-methylstyrene copolymers; both catalyst activity and polyketone microstructure depend on the choice of alpha-diimine substituents and counterion.

Synthesizing and Playing with Magnetic Nanoparticles: A Comprehensive Approach to Amazing Magnetic Materials

ERIC Educational Resources Information Center

Dalverny, Anne-Laure; Leyral, Géraldine; Rouessac, Florence; Bernaud, Laurent; Filhol, Jean-Sébastien

2018-01-01

Magnetic iron oxide nanoparticles were synthesized and stabilized using ammonium cations or poly(vinyl alcohol) to produce amazing materials such as safer aqueous ferrofluids, ferrogels, ferromagnetic inks, plastics, and nanopowders illustrating how versatile materials can be produced just by simple modifications. The synthesis is fast, reliable,…

Characterization of Surface Modification of Polyethersulfone Membrane

USDA-ARS?s Scientific Manuscript database

Surface modification of polyethersulfone (PES) membrane surface using UV/ozone-treated grafting and interfacial polymerization on membrane surface was investigated in order to improve the resistance of membrane surface to protein adsorption. These methods of surface modification were compared in te...

Investigating the sorption behavior of cadmium from aqueous solution by potassium permanganate-modified biochar: quantify mechanism and evaluate the modification method.

PubMed

Fan, Zixi; Zhang, Qian; Li, Meng; Niu, Dongyuan; Sang, Wenjiao; Verpoort, Francis

2018-03-01

In this work, a KMnO 4 -modified-biochar-based composite material with manganese oxide produced at 600 °C was fabricated to investigate the sorption mechanism of Cd(II) and to comprehensively evaluate the effect of the modification on biochar properties. Cd(II) adsorption mechanisms were mainly controlled by interaction with minerals, complexation with oxygen-containing functional groups, and cation-π interaction. The sorption capacity was significantly reduced after a deash treatment of biochar, almost shrunk by 3 and 3.5 times for pristine biochar (PBC) and modified biochar (MBC). For deashed PBC, oxygen-containing functional groups were the main contributor toward Cd(II) adsorption while interaction with minerals was significantly compromised and became negligible. The sorption capacity was also apparently decreased after the deash treatment of MBC; however, for deashed MBC, interaction with minerals still was the main contributor to the sorption ability, which could be attributed to the mechanism of interaction of Cd(II) with loaded MnO x on biochar. Cation-π interaction in MBC was notably enhanced compared to PBC due to the oxidation of KMnO 4 on biomass. Also, sorption performance by oxygen-containing functional groups was also enhanced. Hence, the modification by KMnO 4 has a significant effect on the Cd(II) sorption performance of biochar.

Another Strategy, Detouring Potential Decay by Fast Completion of Cation Mixing

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

Liu, Shuai; Feng, Xin; Wang, Xuelong

The Li-rich layer-structured oxides are regarded one of the most promising candidates of cathode materials for high energy-density Li-ion batteries. However, the uninterrupted migration of the transition metal (TM) ions during cycling and the resultant continuous fading of their discharge potentials bring challenges to the battery design and impede their commercial applications. Various efforts have been taken to suppress the migration of the TM ions such as surface modification and elemental substitution, but no success has been achieved to date. Another strategy hereby is proposed to address these issues, in which the TM migration is promoted and the layered materialmore » is transformed to a rocksalt in the first few charge/discharge cycles by specially designing a novel Li-rich layer-structured Li 1.2Mo 0.6Fe 0.2O 2 on the basis of density functional theory calculations. With such, the continuous falling of the discharge potential is detoured due to enhanced completion of the cation mixing. In-depth studies such as aberration-corrected scanning transmission electron microscopy confirm the drastic structural change at the atomic scale, and in situ X-ray absorption spectroscopy and Mössbauer spectroscopy clarify its charge compensation mechanism. In conclusion, this new strategy provides revelation for the development of the Li-rich layered oxides with mitigated potential decay and a longer lifespan.« less

Another Strategy, Detouring Potential Decay by Fast Completion of Cation Mixing

DOE PAGES

Liu, Shuai; Feng, Xin; Wang, Xuelong; ...

2018-02-12

The Li-rich layer-structured oxides are regarded one of the most promising candidates of cathode materials for high energy-density Li-ion batteries. However, the uninterrupted migration of the transition metal (TM) ions during cycling and the resultant continuous fading of their discharge potentials bring challenges to the battery design and impede their commercial applications. Various efforts have been taken to suppress the migration of the TM ions such as surface modification and elemental substitution, but no success has been achieved to date. Another strategy hereby is proposed to address these issues, in which the TM migration is promoted and the layered materialmore » is transformed to a rocksalt in the first few charge/discharge cycles by specially designing a novel Li-rich layer-structured Li 1.2Mo 0.6Fe 0.2O 2 on the basis of density functional theory calculations. With such, the continuous falling of the discharge potential is detoured due to enhanced completion of the cation mixing. In-depth studies such as aberration-corrected scanning transmission electron microscopy confirm the drastic structural change at the atomic scale, and in situ X-ray absorption spectroscopy and Mössbauer spectroscopy clarify its charge compensation mechanism. In conclusion, this new strategy provides revelation for the development of the Li-rich layered oxides with mitigated potential decay and a longer lifespan.« less

Surface hopping investigation of the relaxation dynamics in radical cations

DOE PAGES

Assmann, Mariana; Weinacht, Thomas; Matsika, Spiridoula

2016-01-19

Ionization processes can lead to the formation of radical cations with population in several ionic states. In this study, we examine the dynamics of three radical cations starting from an excited ionic state using trajectory surface hopping dynamics in combination with multiconfigurational electronic structure methods. The efficiency of relaxation to the ground state is examined in an effort to understand better whether fragmentation of cations is likely to occur directly on excited states or after relaxation to the ground state. The results on cyclohexadiene, hexatriene, and uracil indicate that relaxation to the ground ionic state is very fast in thesemore » systems, while fragmentation before relaxation is rare. Ultrafast relaxation is facilitated by the close proximity of electronic states and the presence of two- and three-state conical intersections. Furthermore, examining the properties of the systems in the Franck-Condon region can give some insight into the subsequent dynamics.« less

Nonadiabatic nuclear dynamics of the ammonia cation studied by surface hopping classical trajectory calculations

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

Belyaev, Andrey K., E-mail: belyaev@herzen.spb.ru; Domcke, Wolfgang, E-mail: wolfgang.domcke@ch.tum.de; Lasser, Caroline, E-mail: classer@ma.tum.de

The Landau–Zener (LZ) type classical-trajectory surface-hopping algorithm is applied to the nonadiabatic nuclear dynamics of the ammonia cation after photoionization of the ground-state neutral molecule to the excited states of the cation. The algorithm employs a recently proposed formula for nonadiabatic LZ transition probabilities derived from the adiabatic potential energy surfaces. The evolution of the populations of the ground state and the two lowest excited adiabatic states is calculated up to 200 fs. The results agree well with quantum simulations available for the first 100 fs based on the same potential energy surfaces. Three different time scales are detected formore » the nuclear dynamics: Ultrafast Jahn–Teller dynamics between the excited states on a 5 fs time scale; fast transitions between the excited state and the ground state within a time scale of 20 fs; and relatively slow partial conversion of a first-excited-state population to the ground state within a time scale of 100 fs. Beyond 100 fs, the adiabatic electronic populations are nearly constant due to a dynamic equilibrium between the three states. The ultrafast nonradiative decay of the excited-state populations provides a qualitative explanation of the experimental evidence that the ammonia cation is nonfluorescent.« less

Endosomal escape and siRNA delivery with cationic shell crosslinked knedel-like nanoparticles with tunable buffering capacities

PubMed Central

Shrestha, Ritu; Elsabahy, Mahmoud; Florez-Malaver, Stephanie; Samarajeewa, Sandani; Wooley, Karen L.

2012-01-01

Cationic shell crosslinked knedel-like nanoparticles (cSCKs) have emerged as a highly efficient transfection agent for nucleic acids delivery. In this study, a new class of cSCKs with tunable buffering capacities has been developed by altering the amounts of histamines and primary amines incorporated into their crosslinked shell regions. The effect of histamine content of these nanoparticles with a hydrodynamic diameter of ca. 20 nm, on the siRNA-binding affinity, cytotoxicity, immunogenicity, and transfection efficiency was investigated. The modification of cSCKs with histamine was found to reduce the siRNA-binding affinity and cellular binding. On the other hand, it significantly reduced the toxicity and immunogenicity of the nanoparticles with subsequent increase in the transfection efficiency. In addition, escape from endosomes was facilitated by having two species of low and high pKas (i.e. histamine and primary amine groups, respectively), as demonstrated by the potentiometric titration experiments and the effect of bafilomycin A1, an inhibitor of the endosomal acidification, on the transfection efficiency of cSCKs. Histamine modification of 15 mol% was a threshold, above which cSCKs with higher histamine content completely lost the ability to bind siRNA and to transfect cells. This study highlights the potential of histamine incorporation to augment the gene silencing activity of cationic nanoparticles, reduce their toxicity, and increase their biocompatibility, which is of particular importance in the design of nucleic acids delivery vectors. PMID:22901966

Mechanistic aspects of the photodynamic inactivation of Candida albicans induced by cationic porphyrin derivatives.

PubMed

Quiroga, Ezequiel D; Cormick, M Paula; Pons, Patricia; Alvarez, M Gabriela; Durantini, Edgardo N

2012-12-01

Photodynamic inactivation of Candida albicans produced by 5-(4-trifluorophenyl)-10,15,20-tris(4-N,N,N-trimethylammoniumphenyl)porphyrin (TFAP(3+)), 5,10,15,20-tetrakis(4-N,N,N-trimethylammoniumphenyl)porphyrin (TMAP(4+)) and 5,10,15,20-tetrakis(4-N-methylpyridyl)porphyrin (TMPyP(4+)) was investigated to obtain insight about the mechanism of cellular damage. In solution, absorption spectroscopic studies showed that these cationic porphyrins interact strongly with calf thymus DNA. The electrophoretic analysis indicated that photocleavage of DNA induced by TFAP(3+) took place after long irradiation periods (>5 h). In contrast, TMAP(4+) produced a marked reduction in DNA band after 1 h irradiation. In C. albicans, these cationic porphyrins produced a ∼3.5 log decrease in survival when the cell suspensions (10(7) cells/mL) were incubated with 5 μM photosensitizer and irradiated for 30 min with visible light (fluence 162 J/cm(2)). After this treatment, modifications of genomic DNA isolated from C. albicans cells were not found by electrophoresis. Furthermore, transmission electron microscopy showed structural changes with appearance of low density areas into the cells and irregularities in cell barriers. However, the photodamage to the cell envelope was insufficient to cause the release of intracellular biopolymers. Therefore, modifications in the cytoplasmic biomolecules and alteration in the cell barriers could be mainly involved in C. albicans photoinactivation. Copyright © 2012 Elsevier Masson SAS. All rights reserved.

Surface segregation in binary mixtures of imidazolium-based ionic liquids

NASA Astrophysics Data System (ADS)

Souda, Ryutaro

2010-09-01

Surface composition of binary mixtures of room-temperature ionic liquids has been investigated using time-of-flight secondary ion mass spectrometry at room temperature over a wide composition range. The imidazolium cations with longer aliphatic groups tend to segregate to the surface, and a bis(trifluoromethanesulfonyl)imide anion (Tf 2N -) is enriched at the surface relative to hexafluorophosphate (PF 6-). The surface of an equimolar mixture of Li[Tf 2N] and 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF 6]) has a nominal composition of [bmim][Tf 2N] because of surface segregation and ligand exchange. The surface segregation of cations and anions is likely to result from alignment of specific ligand-exchanged molecules at the topmost surface layer to exclude more hydrophobic part of the molecules.

Characterization and cell behavior of titanium surfaces with PLL/DNA modification via a layer-by-layer technique.

PubMed

Gao, Wenli; Feng, Bo; Lu, Xiong; Wang, Jianxin; Qu, Shuxin; Weng, Jie

2012-08-01

This study describes the fabrication of two types of multilayered films onto titanium by layer-by-layer (LBL) self-assembly, using poly-L-lysine (PLL) as the cationic polyelectrolyte and deoxyribonucleic acid (DNA) as the anionic polyelectrolyte. The assembling process of each component was studied using atomic force microscopy (AFM) and quartz crystal balance (QCM). Zeta potential of the LBL-coated microparticles was measured by dynamic light scattering. Titanium substrates with or without multilayered films were used in osteoblast cell culture experiments to study cell proliferation, viability, differentiation, and morphology. Results of AFM and QCM indicated the progressive build-up of the multilayered coatings. The surface morphology of three types of multilayered films showed elevations in the nanoscale range. The data of zeta potential showed that the surface terminated with PLL displayed positive charge while the surface terminated with DNA displayed negative charge. The proliferation of osteoblasts on modified titanium films was found to be greater than that on control (p < 0.05) after 3 and 7 days culture, respectively. Alamar blue measurement showed that the PLL/DNA-modified films have higher cell viability (p < 0.05) than the control. Still, the alkaline phosphatase activity assay revealed a better differentiated phenotype on three types of multilayered surfaces compared to noncoated controls. Collectively our results suggest that PLL/DNA were successfully used to surface engineer titanium via LBL technique, and enhanced its cell biocompatibility. Copyright © 2012 Wiley Periodicals, Inc.

Microscopic theory of cation exchange in CdSe nanocrystals.

PubMed

Ott, Florian D; Spiegel, Leo L; Norris, David J; Erwin, Steven C

2014-10-10

Although poorly understood, cation-exchange reactions are increasingly used to dope or transform colloidal semiconductor nanocrystals (quantum dots). We use density-functional theory and kinetic Monte Carlo simulations to develop a microscopic theory that explains structural, optical, and electronic changes observed experimentally in Ag-cation-exchanged CdSe nanocrystals. We find that Coulomb interactions, both between ionized impurities and with the polarized nanocrystal surface, play a key role in cation exchange. Our theory also resolves several experimental puzzles related to photoluminescence and electrical behavior in CdSe nanocrystals doped with Ag.

Sensitivity enhancement for nitrophenols using cationic surfactant-modified activated carbon for solid-phase extraction surface-assisted laser desorption/ionization mass spectrometry.

PubMed

Chen, Y C; Tsai, M F

2000-01-01

Previous work has demonstrated that a combination of solid-phase extraction with surface-assisted laser desorption/ionization (SPE-SALDI) mass spectrometry can be applied to the determination of trace nitrophenols in water. An improved method to lower the detection limit of this hyphenated technique is described in this present study. Activated carbon powder is used as both the SPE adsorbent and the SALDI solid in the analysis by SPE-SALDI. The surface of the activated carbon is modified by passing an aqueous solution of a cationic surfactant through the SPE cartridge. The results demonstrate that the sensitivity for nitrophenols in the analysis by SPE-SALDI can be improved by using cationic surfactants to modify the surface of the activated carbon. The detection limit for nitrophenols is about 25 ppt based on a signal-to-noise ratio of 3 by sampling from 100 mL of solution. Copyright 2000 John Wiley & Sons, Ltd.

Biological and surface-active properties of double-chain cationic amino acid-based surfactants.

PubMed

Greber, Katarzyna E; Dawgul, Małgorzata; Kamysz, Wojciech; Sawicki, Wiesław; Łukasiak, Jerzy

2014-08-01

Cationic amino acid-based surfactants were synthesized via solid phase peptide synthesis and terminal acylation of their α and ε positions with saturated fatty acids. Five new lipopeptides, N-α-acyl-N-ε-acyl lysine analogues, were obtained. Minimum inhibitory concentration and minimum bactericidal (fungicidal) concentration were determined on reference strains of bacteria and fungi to evaluate the antimicrobial activity of the lipopeptides. Toxicity to eukaryotic cells was examined via determination of the haemolytic activities. The surface-active properties of these compounds were evaluated by measuring the surface tension and formation of micelles as a function of concentration in aqueous solution. The cationic surfactants demonstrated diverse antibacterial activities dependent on the length of the fatty acid chain. Gram-negative bacteria and fungi showed a higher resistance than Gram-positive bacterial strains. It was found that the haemolytic activities were also chain length-dependent values. The surface-active properties showed a linear correlation between the alkyl chain length and the critical micelle concentration.

Experimental and Computational Evidence of Highly Active Fe Impurity Sites on the Surface of Oxidized Au for the Electrocatalytic Oxidation of Water in Basic Media

DOE PAGES

Klaus, Shannon; Trotochaud, Lena; Cheng, Mu-Jeng; ...

2015-10-22

Addition of Fe to Ni- and Co-based (oxy)hydroxides has been shown to enhance the activity of these materials for electrochemical oxygen evolution. Here we show that Fe cations bound to the surface of oxidized Au exhibit enhanced oxygen evolution reaction (OER) activity. We find that the OER activity increases with increasing surface concentration of Fe. Density functional theory analysis of the OER energetics reveals that oxygen evolution over Fe cations bound to a hydroxyl-terminated oxidized Au (Fe-Au 2O 3) occurs at an overpotential ~0.3V lower than over hydroxylated Au 2O 3 (0.82V). This finding agrees well with experimental observations andmore » is a consequence of the more optimal binding energetics of OER reaction intermediates at Fe cations bound to the surface of Au 2O 3. These findings suggest that the enhanced OER activity reported recently upon low-potential cycling of Au may be due to surface Fe impurities rather than to "superactive" Au(III) surfaquo species.« less

Post-synthetic modifications of cadmium-based knots and links.

PubMed

Prakasam, Thirumurugan; Bilbeisi, Rana A; Lusi, Matteo; Olsen, John-Carl; Platas-Iglesias, Carlos; Trabolsi, Ali

2016-05-31

Three topologically non-trivial cadmium(ii)-based complexes-Cd-[2]C, Cd-TK and Cd-SL-were simultaneously self-assembled in a dynamic library, individually isolated and fully characterized using solid-state, gas-phase and solution-phase techniques. Post-synthetic modifications, including reduction and transmetalation, were subsequently achieved. Imine bond reduction followed by demetallation led to the isolation of the corresponding organic molecules [2]C, TK and SL. Transmetalation of Cd-TK and Cd-SL with the zinc(ii) cation resulted in isolation of the corresponding zinc(ii)-containing complexes Zn-TK and Zn-SL.

Modified clay sorbents

DOEpatents

Fogler, H. Scott; Srinivasan, Keeran R.

1990-01-01

A novel modified clay sorbent and method of treating industrial effluents to remove trace pollutants, such as dioxins, biphenyls, and polyaromatics such as benzo(a)pyrene and pentachlorophenol. The novel clay sorbent has a composite structure in which the interlayer space of an expandable clay, such as smectite, is filled with polyvalent or multivalent inorganic cations which forces weaker surfactant cations to locate on the surface of the clay in such an orientation that the resulting composite is hydrophilic in nature. A specific example is cetylpyridinium-hydroxy aluminum-montmorillonite. In certain embodiments, a non-expanding clay, such as kaolinite, is used and surfactant cations are necessarily located on an external surface of the clay. A specific example is cetylpyridinium-kaolinite.

Improved efficiency of budesonide nebulization using surface-active agents.

PubMed

Bouwman, A M; Heijstra, M P; Schaefer, N C; Duiverman, E J; Lesouëf, P N; Devadason, S G

2006-01-01

Our aim was to improve the efficiency of nebulised budesonide using surface-active agents. Cationic, anionic, and nonionic detergents were added to commercial budesonide suspension, and the particle size distribution during nebulization was measured using both cascade impaction and laser diffraction. Our results showed that the emitted dose was increased after addition of cationic (p < 0.001) and nonionic detergents (p < 0.01) compared with the commercial formulation alone. The respirable fraction was increased for all detergent formulations (p < 0.001) compared with the commercial formulation. We concluded that cationic and nonionic detergent increased the total output of budesonide from the Sidestream. All detergent formulations increased the respirable fraction of nebulized budesonide.

A nonviral DNA delivery system based on surface modified silica-nanoparticles can efficiently transfect cells in vitro.

PubMed

Kneuer, C; Sameti, M; Bakowsky, U; Schiestel, T; Schirra, H; Schmidt, H; Lehr, C M

2000-01-01

Diverse polycationic polymers have been used as nonviral transfection agents. Here we report the ability of colloidal silica particles with covalently attached cationic surface modifications to transfect plasmid DNA in vitro and make an attempt to describe the structure of the resulting transfection complexes. In analogy to the terms lipoplex and polyplex, we propose to describe the nanoparticle-DNA complexes by the term "nanoplex". Three batches, Si10E, Si100E, and Si26H, sized between 10 and 100 nm and with zeta potentials ranging from +7 to +31 mV at pH 7.4 were evaluated. The galactosidase expression plasmid DNA pCMVbeta was immobilized on the particle surface and efficiently transfected Cos-1 cells. The transfection activity was accompanied by very low cytotoxicity, with LD(50) values in the milligrams per milliliter range. The most active batch, Si26H, was produced by modification of commercially available silica particles with N-(6-aminohexyl)-3-aminopropyltrimethoxysilane, yielding spherical nanoparticles with a mean diameter of 26 nm and a zeta potential of +31 mV at pH 7.4. Complexes of Si26H and pCMVbeta plasmid DNA formed at w/w ratios of 10 were most effective in promoting transfection of Cos-1 cells in the absence of serum. At this ratio, >90% of the DNA was associated with the particles, yielding nanoplexes with a net negative surface charge. When the transfection medium was supplemented with 10% serum, maximum gene expression was observed at a w/w ratio of 30, at which the resulting particle-DNA complexes possessed a positive surface charge. Transfection was strongly increased in the presence of 100 microM chloroquine in the incubation medium and reached approximately 30% of the efficiency of a 60 kDa polyethylenimine. In contrast to polyethylenimine, no toxicity was observed at the concentrations required. Atomic force microscopy of Si26H-DNA complexes revealed a spaghetti-meatball-like structure. The surface of complexes prepared at a w/w ratio of 30 was dominated by particles half-spheres. Complex sizes correlated well with those determined previously by dynamic light scattering.

Catalytic Activity and Stability of Oxides: The Role of Near-Surface Atomic Structures and Compositions.

PubMed

Feng, Zhenxing; Hong, Wesley T; Fong, Dillon D; Lee, Yueh-Lin; Yacoby, Yizhak; Morgan, Dane; Shao-Horn, Yang

2016-05-17

Electrocatalysts play an important role in catalyzing the kinetics for oxygen reduction and oxygen evolution reactions for many air-based energy storage and conversion devices, such as metal-air batteries and fuel cells. Although noble metals have been extensively used as electrocatalysts, their limited natural abundance and high costs have motivated the search for more cost-effective catalysts. Oxides are suitable candidates since they are relatively inexpensive and have shown reasonably high activity for various electrochemical reactions. However, a lack of fundamental understanding of the reaction mechanisms has been a major hurdle toward improving electrocatalytic activity. Detailed studies of the oxide surface atomic structure and chemistry (e.g., cation migration) can provide much needed insights for the design of highly efficient and stable oxide electrocatalysts. In this Account, we focus on recent advances in characterizing strontium (Sr) cation segregation and enrichment near the surface of Sr-substituted perovskite oxides under different operating conditions (e.g., high temperature, applied potential), as well as their influence on the surface oxygen exchange kinetics at elevated temperatures. We contrast Sr segregation, which is associated with Sr redistribution in the crystal lattice near the surface, with Sr enrichment, which involves Sr redistribution via the formation of secondary phases. The newly developed coherent Bragg rod analysis (COBRA) and energy-modulated differential COBRA are uniquely powerful ways of providing information about surface and interfacial cation segregation at the atomic scale for these thin film electrocatalysts. In situ ambient pressure X-ray photoelectron spectroscopy (APXPS) studies under electrochemical operating conditions give additional insights into cation migration. Direct COBRA and APXPS evidence for surface Sr segregation was found for La1-xSrxCoO3-δ and (La1-ySry)2CoO4±δ/La1-xSrxCoO3-δ oxide thin films, and the physical origin of segregation is discussed in comparison with (La1-ySry)2CoO4±δ/La1-xSrxCo0.2Fe0.8O3-δ. Sr enrichment in many electrocatalysts, such as La1-xSrxMO3-δ (M = Cr, Co, Mn, or Co and Fe) and Sm1-xSrxCoO3, has been probed using alternative techniques, including low energy ion scattering, secondary ion mass spectrometry, and X-ray fluorescence-based methods for depth-dependent, element-specific analysis. We highlight a strong connection between cation segregation and electrocatalytic properties, because cation segregation enhances oxygen transport and surface oxygen exchange kinetics. On the other hand, the formation of cation-enriched secondary phases can lead to the blocking of active sites, inhibiting oxygen exchange. With help from density functional theory, the links between cation migration, catalyst stability, and catalytic activity are provided, and the oxygen p-band center relative to the Fermi level can be identified as an activity descriptor. Based on these findings, we discuss strategies to increase a catalyst's activity while maintaining stability to design efficient, cost-effective electrocatalysts.

Facile Modification of Reverse Osmosis Membranes by Surfactant-Assisted Acrylate Grafting for Enhanced Selectivity.

PubMed

Baransi-Karkaby, Katie; Bass, Maria; Levchenko, Stanislav; Eitan, Shahar; Freger, Viatcheslav

2017-02-21

The top polyamide layer of composite reverse osmosis (RO) membranes has a fascinatingly complex structure, yet nanoscale nonuniformities inherently present in polyamide layer may reduce selectivity, e.g., for boron rejection. This study examines improving selectivity by in situ "caulking" such nonuniformities using concentration polarization-enhanced graft-polymerization with a surfactant added to the reactive solution. The surfactant appears to enhance both polarization (via monomer solubilization in surfactant micelles) and adherence of graft-polymer to the membrane surface, which facilitates grafting and reduces monomer consumption. The effect of surfactant was particularly notable for a hydrophobic monomer glycidyl methacrylate combined with a nonionic surfactant Triton X-100. With Triton added at an optimal level, close to critical micellization concentration (CMC), monomer gets solubilized and highly concentrated within micelles, which results in a significantly increased degree of grafting and uniformity of the coating compared to a procedure with no surfactant added. Notably, no improvement was obtained for an anionic surfactant SDS or the cationic surfactant DTAB, in which cases the high CMC of surfactant precludes high monomer concentration within micelles. The modification procedure was also up-scalable to membranes elements and resulted in elements with permeability comparable to commercial brackish water RO elements with superior boric acid rejection.

Sediment deposition and sources into a Mississippi River floodplain lake; Catahoula Lake, Louisiana

USGS Publications Warehouse

Latuso, Karen D.; Keim, Richard F.; King, Sammy L.; Weindorf, David C.; DeLaune, Ronald D.

2017-01-01

Floodplain lakes are important wetlands on many lowland floodplains of the world but depressional floodplain lakes are rare in the Mississippi River Alluvial Valley. One of the largest is Catahoula Lake, which has existed with seasonally fluctuating water levels for several thousand years but is now in an increasingly hydrologically altered floodplain. Woody vegetation has been encroaching into the lake bed and the rate of this expansion has increased since major human hydrologic modifications, such as channelization, levee construction, and dredging for improvement of navigation, but it remains unknown what role those modifications may have played in altering lake sedimentation processes. Profiles of thirteen 137Cs sediment cores indicate sedimentation has been about 0.26 cm y− 1 over the past 60 years and has been near this rate since land use changes began about 200 years ago (210Pb, and 14C in Tedford, 2009). Carbon sequestration was low (10.4 g m− 2 y− 1), likely because annual drying promotes mineralization and export. Elemental composition (high Zr and Ti and low Ca and K) and low pH of recent (<~60 y) or surface sediments suggest Gulf Coastal Plain origin, but below the recent sediment deposits, 51% of sediment profiles showed influence of Mississippi River alluvium, rich in base cations such as K+, Ca2 +, and Mg2 +. The recent shift to dominance of Coastal Plain sediments on the lake-bed surface suggests hydrologic modification has disconnected the lake from sediment-bearing flows from the Mississippi River. Compared to its condition prior to hydrologic alterations that intensified in the 1930s, Catahoula Lake is about 15 cm shallower and surficial sediments are more acidic. Although these results are not sufficient to attribute ecological changes directly to sedimentological changes, it is likely the altered sedimentary and hydrologic environment is contributing to the increased dominance of woody vegetation.

Monitoring solute interactions with poly(ethylene oxide)-modified colloidal silica nanoparticles via fluorescence anisotropy decay.

PubMed

Tleugabulova, Dina; Duft, Andy M; Brook, Michael A; Brennan, John D

2004-01-06

The fluorescence-based nanosize metrology approach, proposed recently by Geddes and Birch (Geddes, C. D.; Birch, D. J. S. J. Non-Cryst. Solids 2000, 270, 191), was used to characterize the extent of binding of a fluorescent cationic solute, rhodamine 6G (R6G), to the surface of silica particles after modification of the surface with the hydrophilic polymer poly(ethylene oxide) (PEO) of various molecular weights. The measurement of the rotational dynamics of R6G in PEO solutions showed the absence of strong interactions between R6G and PEO chains in water and the ability of the dye to sense the presence of polymer clusters in 30 wt % solutions. Time-resolved anisotropy decays of polymer-modified Ludox provided direct evidence for distribution of the dye between bound and free states, with the bound dye showing two decay components: a nanosecond decay component that is consistent with local motions of bound probes and a residual anisotropy component due to slow rotation of large silica particles. The data showed that the dye was strongly adsorbed to unmodified silica nanoparticles, to the extent that less than 1% of the dye was present in the surrounding aqueous solution. Addition of PEO blocked the adsorption of the dye to a significant degree, with up to 50% of the probe being present in the aqueous solution for Ludox samples containing 30 wt % of low molecular weight PEO. The addition of such agents also decreased the value and increased the fractional contribution of the nanosecond rotational correlation time, suggesting that polymer adsorption altered the degree of local motion of the bound probe. Atomic force microscopy imaging studies provided no evidence for a change in the particle size upon surface modification but did suggest interparticle aggregation after polymer adsorption. Thus, this redistribution of the probe is interpreted as being due to coverage of particles with the polymer, resulting in lower adsorption of R6G to the silica. The data clearly show the power of time-resolved fluorescence anisotropy decay measurements for probing the modification of silica surfaces and suggest that this method should prove useful in characterization of new chromatographic stationary phases and nanocomposite materials.

Inositol trisphosphate modification of ion transport in rough endoplasmic reticulum.

PubMed

Muallem, S; Schoeffield, M; Pandol, S; Sachs, G

1985-07-01

The ion transport properties of the rough endoplasmic reticulum (RER) from liver have been defined by using measurements of active and potential gradient-driven transport. The Ca2+ pump is shown to be electrogenic, and both ATP and potential difference is able to drive vanadate-inhibitable Ca2+ uptake into the RER. ATP-dependent Ca2+ transport into the RER depends on the presence of tetraethylammonium-sensitive cation conductance and a furosemide-inhibited cation/chloride cotransport pathway. Inositol trisphosphate does not affect either of the monovalent ion translocation systems but activates a Ca2+ conductance in the RER, allowing efflux of RER Ca2+ stores into the cytosol in exchange for K+ uptake.

Inositol trisphosphate modification of ion transport in rough endoplasmic reticulum.

PubMed Central

Muallem, S; Schoeffield, M; Pandol, S; Sachs, G

1985-01-01

The ion transport properties of the rough endoplasmic reticulum (RER) from liver have been defined by using measurements of active and potential gradient-driven transport. The Ca2+ pump is shown to be electrogenic, and both ATP and potential difference is able to drive vanadate-inhibitable Ca2+ uptake into the RER. ATP-dependent Ca2+ transport into the RER depends on the presence of tetraethylammonium-sensitive cation conductance and a furosemide-inhibited cation/chloride cotransport pathway. Inositol trisphosphate does not affect either of the monovalent ion translocation systems but activates a Ca2+ conductance in the RER, allowing efflux of RER Ca2+ stores into the cytosol in exchange for K+ uptake. PMID:3874400

Adsorption Study of a Water Molecule on Vacancy-Defected Nonpolar CdS Surfaces

PubMed Central

2017-01-01

A detailed understanding of the water–semiconductor interface is of major importance for elucidating the molecular interactions at the photocatalyst’s surface. Here, we studied the effect of vacancy defects on the adsorption of a water molecule on the (101̅0) and (112̅0) CdS surfaces, using spin-polarized density functional theory. We observed that the local spin polarization did not persist for most of the cationic vacancies on the surfaces, unlike in bulk, owing to surface reconstructions caused by displaced S atoms. This result suggests that cationic vacancies on these surfaces may not be the leading cause of the experimentally observed magnetism in CdS nanostructures. The surface vacancies are predominantly nonmagnetic except for one case, where a magnetic cationic vacancy is relatively stable due to constraints posed by the (101̅0) surface geometry. At this particular magnetic defect site, we found a very strong interaction with the H2O molecule leading to a case of chemisorption, where the local spin polarization vanishes concurrently. At the same defect site, adsorption of an O2 molecule was also simulated, and the results were found to be consistent with experimental electron paramagnetic resonance findings for powdered CdS. The anion vacancies on these surfaces were always found to be nonmagnetic and did not affect the water adsorption at these surfaces. PMID:28539988

Role of interlayer hydration in lincomycin sorption by smectite clays.

PubMed

Wang, Cuiping; Ding, Yunjie; Teppen, Brian J; Boyd, Stephen A; Song, Cunyi; Li, Hui

2009-08-15

Lincomycin, an antibiotic widely administered as a veterinary medicine, is frequently detected in water. Little is known about the soil-water distribution of lincomycin despite the fact that this is a major determinant of its environmental fate and potential for exposure. Cation exchange was found to be the primary mechanism responsible for lincomycin sorption by soil clay minerals. This was evidenced by pH-dependent sorption, and competition with inorganic cations for sorptive sites. As solution pH increased, lincomycin sorption decreased. The extent of reduction was consistent with the decrease in cationic lincomycin species in solution. The presence of Ca2+ in solution diminished lincomycin sorption. Clay interlayer hydration status strongly influenced lincomycin adsorption. Smectites with the charge deficit from isomorphic substitution in tetrahedral layers (i.e., saponite) manifest a less hydrated interlayer environment resulting in greater sorption than that by octahedrally substituted clays (i.e., montmorillonite). Strongly hydrated exchangeable cations resulted in a more hydrated clay interlayer environment reducing sorption in the order of Ca- < K- < Cs-smectite. X-ray diffraction revealed that lincomycin was intercalated in smectite clay interlayers. Sorption capacity was limited by clay surface area rather than by cation exchange capacity. Smectite interlayer hydration was shown to be a major, yet previously unrecognized, factor influencing the cation exchange process of lincomycin on aluminosilicate mineral surfaces.

Cationic liposomes as vaccine adjuvants.

PubMed

Christensen, Dennis; Korsholm, Karen S; Rosenkrands, Ida; Lindenstrøm, Thomas; Andersen, Peter; Agger, Else Marie

2007-10-01

Cationic liposomes are lipid-bilayer vesicles with a positive surface charge that have re-emerged as a promising new adjuvant technology. Although there is some evidence that cationic liposomes themselves can improve the immune response against coadministered vaccine antigens, their main functions are to protect the antigens from clearance in the body and deliver the antigens to professional antigen-presenting cells. In addition, cationic liposomes can be used to introduce immunomodulators to enhance and modulate the immune response in a desirable direction and, thereby, represent an efficient tool when designing tailor-made adjuvants for specific disease targets. In this article we review the recent progress on cationic liposomes as vehicles, enhancing the effect of immunomodulators and the presentation of vaccine antigens.

A shell-resolved analysis of preferential solvation of coffee ingredients in aqueous mixtures of the ionic liquid 1-ethyl-3-methylimidazolium acetate

NASA Astrophysics Data System (ADS)

Zeindlhofer, Veronika; Berger, Magdalena; Steinhauser, Othmar; Schröder, Christian

2018-05-01

Ionic liquids increase the solubility of various coffee ingredients in aqueous solution but little is known about the underlying mechanism. Kirkwood-Buff integrals as well as the potential of mean force indicate that the imidazolium cations are accumulated at the surface of the solutes, removing water molecules from the solute surface. Although hydrogen bonding of the anions to hydroxy groups of the solutes can be detected, their concentration at the surface is less enhanced compared to the cations. The decomposition into solvation shells by Voronoi tessellation reveals that structural features are only observed in the first solvation shell. Nevertheless, the depletion of water and the excess concentration of the ions and, in particular, of the cations are visible in the next solvation shells as well. Therefore, classical arguments of hydrotropic theory fail to explain this behavior.

Cation specific binding with protein surface charges

PubMed Central

Hess, Berk; van der Vegt, Nico F. A.

2009-01-01

Biological organization depends on a sensitive balance of noncovalent interactions, in particular also those involving interactions between ions. Ion-pairing is qualitatively described by the law of “matching water affinities.” This law predicts that cations and anions (with equal valence) form stable contact ion pairs if their sizes match. We show that this simple physical model fails to describe the interaction of cations with (molecular) anions of weak carboxylic acids, which are present on the surfaces of many intra- and extracellular proteins. We performed molecular simulations with quantitatively accurate models and observed that the order K+ < Na+ < Li+ of increasing binding affinity with carboxylate ions is caused by a stronger preference for forming weak solvent-shared ion pairs. The relative insignificance of contact pair interactions with protein surfaces indicates that thermodynamic stability and interactions between proteins in alkali salt solutions is governed by interactions mediated through hydration water molecules. PMID:19666545

Antimicrobial Peptides in 2014

PubMed Central

Wang, Guangshun; Mishra, Biswajit; Lau, Kyle; Lushnikova, Tamara; Golla, Radha; Wang, Xiuqing

2015-01-01

This article highlights new members, novel mechanisms of action, new functions, and interesting applications of antimicrobial peptides reported in 2014. As of December 2014, over 100 new peptides were registered into the Antimicrobial Peptide Database, increasing the total number of entries to 2493. Unique antimicrobial peptides have been identified from marine bacteria, fungi, and plants. Environmental conditions clearly influence peptide activity or function. Human α-defensin HD-6 is only antimicrobial under reduced conditions. The pH-dependent oligomerization of human cathelicidin LL-37 is linked to double-stranded RNA delivery to endosomes, where the acidic pH triggers the dissociation of the peptide aggregate to release its cargo. Proline-rich peptides, previously known to bind to heat shock proteins, are shown to inhibit protein synthesis. A model antimicrobial peptide is demonstrated to have multiple hits on bacteria, including surface protein delocalization. While cell surface modification to decrease cationic peptide binding is a recognized resistance mechanism for pathogenic bacteria, it is also used as a survival strategy for commensal bacteria. The year 2014 also witnessed continued efforts in exploiting potential applications of antimicrobial peptides. We highlight 3D structure-based design of peptide antimicrobials and vaccines, surface coating, delivery systems, and microbial detection devices involving antimicrobial peptides. The 2014 results also support that combination therapy is preferred over monotherapy in treating biofilms. PMID:25806720

Interaction of pesticides with natural and synthetic solids. Evaluation in dynamic and equilibrium conditions.

PubMed

Otalvaro, Julián Ortiz; Brigante, Maximiliano

2018-03-01

Interactions between pesticides (paraquat, glyphosate, 2,4-D, atrazine, and metsulfuron methyl) and soil organic and inorganic components have been studied in batch experiments by performing adsorption, dissolution, and chemical and photochemical degradation under different conditions. The obtained results confirm that the affinity of a pesticide to the solid surface depends on the nature of both and shows that each reactant strongly affects the mobility of the other one, e.g., anionic pesticides promote the dissolution of the solid humic acid but if this last is retained into the inorganic matrix enhances the adsorption of a cationic pesticide. Adsorption also seems to protect the bonded specie to be chemical degraded, such as shown in two pesticide/clay systems at constant pH. The use of mesoporous silicas could result in a good alternative for pesticide remediation. In fact, the solid shows high adsorption capacity towards paraquat and its modification with TiO 2 nanoparticles increases not only the pesticide adsorption but also seems to catalyze its degradation under UV light to less-toxic metabolites. UV-VIS spectroscopy was relevant and novel in such sense. Electrostatic interactions, hydrogen and coordinative bonds formations, surface complexations and hydrophobic associations play a key role in the fate of mentioned pesticides on soil and ground/surface water environments.

ADSORPTION OF ORGANIC CATIONS TO NATURAL MATERIALS

EPA Science Inventory

The factors that control the extent of adsorption of amphiphilic organic cations on environmental and pristine surfaces have been studied. The sorbents were kaolinite, montmorillonite, two aquifer materials, and a soil; solutions contained various concentrations of NaCl and CaCl,...

Effect of PEG and water-soluble chitosan coating on moxifloxacin-loaded PLGA long-circulating nanoparticles.

PubMed

Mustafa, Sanaul; Devi, V Kusum; Pai, Roopa S

2017-02-01

Moxifloxacin (MOX) is a Mycobacterium tuberculosis DNA gyrase inhibitor. Due to its intense hydrophilicity, MOX is cleared from the body within 24 h and required for repetitive doses which may then result in hepatotoxicity and acquisition of MOX resistant-TB, related with its use. To overcome the aforementioned limitations, the current study aimed to develop PLGA nanoparticles (PLGA NPs), to act as an efficient carrier for controlled delivery of MOX. To achieve a substantial extension in blood circulation, a combined design, affixation of polyethylene glycol (PEG) to MOX-PLGA NPs and adsorption of water-soluble chitosan (WSC) (cationic deacetylated chitin) to particle surface, was rose for surface modification of NPs. Surface modified NPs (MOX-PEG-WSC NPs) were prepared to provide controlled delivery and circulate in the bloodstream for an extended period of time, thus minimizing dosing frequency. In vivo pharmacokinetic and in vivo biodistribution following oral administration were investigated. NP surface charge was closed to neutral +4.76 mV and significantly affected by the WSC coating. MOX-PEG-WSC NPs presented striking prolongation in blood circulation, reduced protein binding, and long-drawn-out the blood circulation half-life with resultant reduced liver sequestration vis-à-vis MOX-PLGA NPs. The studies, therefore, indicate the successful formulation development of MOX-PEG-WSC NPs that showed sustained release behavior from nanoparticles which indicates low frequency of dosing.

Modification of 1,2,4,5-tetrazine with cationic rhenium(I) polypyridine units to afford phosphorogenic bioorthogonal probes with enhanced reaction kinetics.

PubMed

Choi, Alex Wing-Tat; Tso, Karson Ka-Shun; Yim, Vicki Man-Wai; Liu, Hua-Wei; Lo, Kenneth Kam-Wing

2015-02-25

New phosphorogenic bioorthogonal probes derived from mononuclear and binuclear rhenium(I) polypyridine complexes containing a 1,2,4,5-tetrazine moiety were designed; these complexes displayed substantial dienophile-induced emission enhancement, and accelerated reaction kinetics and could target a protein conjugate in living cells.

Effect of interlayer cations of montmorillonite on the biodegradation and adsorption of crude oil polycyclic aromatic compounds.

PubMed

Ugochukwu, Uzochukwu C; Manning, David A C; Fialips, Claire I

2014-09-01

Cation exchange capacity, surface acidity and specific surface area are surface properties of clay minerals that make them act as catalysts or supports in most biogeochemical processes hence making them play important roles in environmental control. However, the role of homoionic clay minerals during the biodegradation of polycyclic aromatic compounds is not well reported. In this study, the effect of interlayer cations of montmorillonites in the removal of some crude oil polycyclic aromatic compounds during biodegradation was investigated in aqueous clay/oil microcosm experiments with a hydrocarbon degrading microorganism community. The homoionic montmorillonites were prepared via cation exchange reactions by treating the unmodified montmorillonite with the relevant metallic chloride. The study indicated that potassium-montmorillonite and zinc-montmorillonite did not enhance the biodegradation of the polycyclic aromatic hydrocarbons whereas calcium-montmorillonite, and ferric-montmorillonite enhanced their biodegradation significantly. Adsorption of polycyclic aromatic hydrocarbons was significant during biodegradation with potassium- and zinc-montmorillonite where there was about 45% removal of the polycyclic aromatic compounds by adsorption in the experimental microcosm containing 5:1 ratio (w/w) of clay to oil. Copyright © 2014 Elsevier Ltd. All rights reserved.

Organic molecules as sorbing tracers for the assessment of surface areas in consolidated aquifer systems

NASA Astrophysics Data System (ADS)

Schaffer, Mario; Warner, Wiebke; Kutzner, Susann; Börnick, Hilmar; Worch, Eckhard; Licha, Tobias

2017-03-01

Based on the assumption that the specific surface area to volume ratio Asurf/V of consolidated rock materials is proportional to the surface area available for sorption, several inorganic cations were recently proposed as sorbing (cation exchanging) tracers for estimating these ratios in aquifers (e.g., for deriving the efficient heat exchange area of geothermal reservoirs). The main disadvantages of inorganic ions, however, are the limited number of suitable ions, their potential geogenic background, and their challenging online detection at trace concentrations. In this work, the spectrum of chemical substances used as sorbing tracers expands by considering fluorescent organic compounds that are cationic. They have the advantage of being highly water soluble and easy to measure online at very low concentrations. Results from systematic lab column experiments with seven selected organic cations under various conditions (different salinities and temperatures) are presented, emphasizing the potential of organic molecules as alternative sorbing tracers especially in consolidated aquifer systems. This work is a first stepping stone in identifying suitable molecular structures that can be selected or even individually adapted to the requirements of the tracer tests and prevailing aquifer conditions.

Antiproliferative effects of mitochondria-targeted cationic antioxidants and analogs: Role of mitochondrial bioenergetics and energy-sensing mechanism

PubMed Central

Cheng, Gang; Zielonka, Jacek; McAllister, Donna; Hardy, Micael; Ouari, Olivier; Joseph, Joy; Dwinell, Michael B.; Kalyanaraman, Balaraman

2015-01-01

One of the proposed mechanisms for tumor proliferation involves redox signaling mediated by reactive oxygen species such as superoxide and hydrogen peroxide generated at moderate levels. Thus, the antiproliferative and anti-tumor effects of certain antioxidants were attributed to their ability to mitigate intracellular reactive oxygen species (ROS). Recent reports support a role for mitochondrial ROS in stimulating tumor cell proliferation. In this study, we compared the antiproliferative effects and the effects on mitochondrial bioenergetic functions of a mitochondria-targeted cationic carboxyproxyl nitroxide (Mito-CP), exhibiting superoxide dismutase (SOD)-like activity and a synthetic cationic acetamide analog (Mito-CP-Ac) lacking the nitroxide moiety responsible for the SOD activity. Results indicate that both Mito-CP and Mito-CP-Ac potently inhibited tumor cell proliferation. Both compounds altered mitochondrial and glycolytic functions, and intracellular citrate levels. Both Mito-CP and Mito-CP-Ac synergized with 2-deoxy-glucose (2-DG) to deplete intracellular ATP, inhibit cell proliferation and induce apoptosis in pancreatic cancer cells. We conclude that mitochondria-targeted cationic agents inhibit tumor proliferation via modification of mitochondrial bioenergetics pathways rather than by dismutating and detoxifying mitochondrial superoxide. PMID:26004344

Surface Modification of Biomaterials: A Quest for Blood Compatibility

PubMed Central

de Mel, Achala; Cousins, Brian G.; Seifalian, Alexander M.

2012-01-01

Cardiovascular implants must resist thrombosis and intimal hyperplasia to maintain patency. These implants when in contact with blood face a challenge to oppose the natural coagulation process that becomes activated. Surface protein adsorption and their relevant 3D confirmation greatly determine the degree of blood compatibility. A great deal of research efforts are attributed towards realising such a surface, which comprise of a range of methods on surface modification. Surface modification methods can be broadly categorized as physicochemical modifications and biological modifications. These modifications aim to modulate platelet responses directly through modulation of thrombogenic proteins or by inducing antithrombogenic biomolecules that can be biofunctionalised onto surfaces or through inducing an active endothelium. Nanotechnology is recognising a great role in such surface modification of cardiovascular implants through biofunctionalisation of polymers and peptides in nanocomposites and through nanofabrication of polymers which will pave the way for finding a closer blood match through haemostasis when developing cardiovascular implants with a greater degree of patency. PMID:22693509

Novel "anchor modification" of polymeric biomaterial surfaces by the utilization of cyclodextrin inclusion complex supramolecules.

PubMed

Zhao, Xiaobin; Courtney, James M

2009-07-01

In this article, a novel approach for the surface modification of polymeric biomaterials by the utilization of supramolecules was studied. The supramolecules selected were cyclodextrin inclusion complexes (CICs). The biomaterial selected for surface modification was plasticized poly (vinyl chloride) (PVC-P). Results indicate that when the CICs were blended into PVC-P, they tend to migrate and "anchor" on the surface to achieve a remarkable protein-resistant surface, with improved blood compatibility. In comparison with a physical mixture of cyclodextrins and a "guest" molecule, such as poly(ethylene oxide) (PEO)-poly(propylene oxide) (PPO)-PEO and PPO-PEO-PPO for PVC-P modification, CICs modified PVC-P are more consistent in processing and achieve reproducible surface characteristics. Based on this study, a novel "anchor modification" was proposed regarding CICs modified surface. This "anchor modification" is likely to reduce plasticizer extraction from PVC-P and also can be utilized for the modification of polymers other than PVC-P.

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.

Variation in whole DNA methylation in red maple (Acer rubrum) populations from a mining region: association with metal contamination and cation exchange capacity (CEC) in podzolic soils.

PubMed

Kalubi, K N; Mehes-Smith, M; Spiers, G; Omri, A

2017-04-01

Although a number of publications have provided convincing evidence that abiotic stresses such as drought and high salinity are involved in DNA methylation reports on the effects of metal contamination, pH, and cation exchange on DNA modifications are limited. The main objective of the present study is to determine the relationship between metal contamination and Cation exchange capacity (CEC) on whole DNA modifications. Metal analysis confirms that nickel and copper are the main contaminants in sampled sites within the Greater Sudbury Region (Ontario, Canada) and liming has increased soil pH significantly even after 30 years following dolomitic limestone applications. The estimated CEC values varied significantly among sites, ranging between 1.8 and 10.5 cmol(+) kg -1 , with a strong relationship being observed between CEC and pH (r = 0.96**). Cation exchange capacity, significantly lower in highly metal contaminated sites compared to both reference and less contaminated sites, was higher in the higher organic matter limed compared to unlimed sites. There was a significant variation in the level of cytosine methylation among the metal-contaminated sites. Significant and strong negative correlations between [5mdC]/[dG] and bioavailable nickel (r = -0.71**) or copper (r = -0.72**) contents were observed. The analysis of genomic DNA for adenine methylation in this study showed a very low level of [6N-mdA]/dT] in Acer rubrum plants analyzed ranging from 0 to 0.08%. Significant and very strong positive correlation was observed between [6N-mdA]/dT] and soil bioavailable nickel (r = 0.78**) and copper (r = 0.88**) content. This suggests that the increased bioavailable metal levels associated with contamination by nickel and copper particulates are associated with cytosine and adenine methylation.

The effect of polymer surface modification on polymer-protein interaction via interfacial polymerization and hydrophilic polymer grafting

USDA-ARS?s Scientific Manuscript database

Protein membrane separation is prone to fouling on the membrane surface resulting from protein adsorption onto the surface. Surface modification of synthetic membranes is one way to reduce fouling. We investigated surface modification of polyethersulfone (PES) as a way of improving hydrophilicity ...

Adsorption of the Three-phase Emulsion on Various Solid Surfaces.

PubMed

Enomoto, Yasutaka; Imai, Yoko; Tajima, Kazuo

2017-07-01

The present study investigates the adsorption of the three-phase emulsion on various solid/water interfaces. Vesicles can be used as emulsifiers in the three-phase emulsions and act as an independent phase unlike the surfactant used in conventional emulsions; therefore, it is expected that the three-phase emulsion formed by the adhesion of vesicles to the oil/water interface will adsorb on various solid/water interfaces. The cationic three-phase emulsion was prepared to encourage emulsion adsorption on negatively charged solid substrates in water. The emulsifier polyoxyethylene-(10) hydrogenated castor oil was rendered cationic by mixing with the surfactant cetyltrimethylammonium bromide and then used to prepare the cationic three-phase emulsion of hexadecane-in-water. Three solid substrates (silicon, glass, and copper) were dipped in the cationic emulsion and the emulsion was found to adsorb on the solid substrates while maintaining its structure. The amount of hexadecane adsorbed on the various surfaces was investigated by gas chromatography and found to increase with increasing hexadecane concentration in the emulsion and eventually plateaued just like molecular adsorption. The maximum surface coverage of the emulsion on the substrates was approximately 80%. However, even the equivalent nonionic three-phase emulsion was found to adsorb on the three solid surfaces. This was attributed to a novel mechanism of irreversible adhesion via the van der Waals attractive force.

Variations in the Degree of d-Alanylation of Teichoic Acids in Lactococcus lactis Alter Resistance to Cationic Antimicrobials but Have No Effect on Bacterial Surface Hydrophobicity and Charge▿

PubMed Central

Giaouris, Efstathios; Briandet, Romain; Meyrand, Mickael; Courtin, Pascal; Chapot-Chartier, Marie-Pierre

2008-01-01

An increase of the degree of d-alanylation of teichoic acids in Lactococcus lactis resulted in a significant increase of bacterial resistance toward the cationic antimicrobials nisin and lysozyme, whereas the absence of d-alanylation led to a decreased resistance toward the same compounds. In contrast, the same variations of the d-alanylation degree did not modify bacterial cell surface charge and hydrophobicity. Bacterial adhesion to polystyrene and glass surfaces was not modified either. PMID:18539809

Methods and electrolytes for electrodeposition of smooth films

DOEpatents

Zhang, Jiguang; Xu, Wu; Graff, Gordon L; Chen, Xilin; Ding, Fei; Shao, Yuyan

2015-03-17

Electrodeposition involving an electrolyte having a surface-smoothing additive can result in self-healing, instead of self-amplification, of initial protuberant tips that give rise to roughness and/or dendrite formation on the substrate and/or film surface. For electrodeposition of a first conductive material (C1) on a substrate from one or more reactants in an electrolyte solution, the electrolyte solution is characterized by a surface-smoothing additive containing cations of a second conductive material (C2), wherein cations of C2 have an effective electrochemical reduction potential in the solution lower than that of the reactants.

Growth and surface modification of LaFeO3 thin films induced by reductive annealing

NASA Astrophysics Data System (ADS)

Flynn, Brendan T.; Zhang, Kelvin H. L.; Shutthanandan, Vaithiyalingam; Varga, Tamas; Colby, Robert J.; Oleksak, Richard P.; Manandhar, Sandeep; Engelhard, Mark H.; Chambers, Scott A.; Henderson, Michael A.; Herman, Gregory S.; Thevuthasan, Suntharampillai

2015-03-01

The mixed electronic and ionic conductivity of perovskite oxides has enabled their use in diverse applications such as automotive exhaust catalysts, solid oxide fuel cell cathodes, and visible light photocatalysts. The redox chemistry at the surface of perovskite oxides is largely dependent on the oxidation state of the metal cations as well as the oxide surface stoichiometry. In this study, LaFeO3 (LFO) thin films grown on yttria-stabilized zirconia (YSZ) was characterized using both bulk and surface sensitive techniques. A combination of in situ reflection high-energy electron diffraction (RHEED), X-ray diffraction (XRD), and Rutherford backscattering spectrometry (RBS) demonstrated that the film is primarily textured in the [1 0 0] direction and is stoichiometric. High-resolution transmission electron microscopy measurements show regions that are dominated by [1 0 0] oriented LFO grains that are oriented with respect to the substrates lattice. However, selected regions of the film show multiple domains of grains that are not [1 0 0] oriented. The film was annealed in an ultra-high vacuum chamber to simulate reducing conditions and studied by angle-resolved X-ray photoelectron spectroscopy (XPS). Iron was found to exist as Fe(0), Fe(II), and Fe(III) depending on the annealing conditions and the depth within the film. A decrease in the concentration of surface oxygen species was correlated with iron reduction. These results should help guide and enhance the design of LFO materials for catalytic applications.

Understanding self-photorechargeability of WO(3) for H(2) generation without light illumination.

PubMed

Ng, Charlene; Iwase, Akihide; Ng, Yun Hau; Amal, Rose

2013-02-01

This work presents insight into the self-photorechargeability of WO(3), whereby the intercalation of positive alkali cations is accompanied by the simultaneous storage of photo-excited electrons. The cyclic voltammetry studies verify the photo-assisted intercalation and de-intercalation of Na(+) and K(+) from the flower structured WO(3). A storage capacity of up to 0.722 C cm(-2) can be achieved in a saturated (0.68 M) K(2)SO(4) electrolyte solution. However, the best photo recharge-discharge stability of the electrode are observed at a lower (0.1 M) cation concentration. At high electrolyte concentrations, the intercalated cations are firmly trapped, as indicated by the structural modifications observed in Raman analysis, resulting in much less photocharging and discharging abilities in subsequent cycles. The study also shows that the stored electrons can be successfully used to generate H(2) with 100 % faradaic efficiency in the absence of light. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of added sodium chloride on the molecular environment and photoionization of N,N,N',N'-tetramethylbenzidine in micellar solutions as studied by electron spin echo and electron spin resonance spectroscopy

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

Maldonado, R.; Kevan, L.; Szajdzinska-Pietek, E.

1984-11-01

The electron spin echo modulation (ESEM) and electron spin resonance (ESR) spectra of the cation radical of N,N,N',N'-tetramethylbenzidine (TMB) in frozen sodium dodecyl sulfate (SDS)= and dodecyltrimethylammonium chloride (DTAC) micelles were studied as a function of sodium chloride concentration. TMB/sup +center-dot/ was produced by photoionization at 350 nm of the parent compound in the micelles at 77 K. From the ESEM analysis it is found that the cation--water interactions increase with salt addition in both anionic and cationic micelles to a maximum near 0.2 M NaCl and then decrease somewhat. The increase is interpreted in terms of an increase inmore » the water density at the micellar surface due to an increased surface concentration of hydrated counterions. The decrease may be due to TMB moving further from the polar micellar surface with added salt. From ESR spectra the photoionization yields of TMB at 77 K were determined. For DTAC micelles the yields are found to decrease with salt addition as expected from electrostatic considerations. For SDS micelles the photoionization yields increase for salt concentrations up to about 0.15 M and decrease for greater salt concentrations up to 0.5 M. The initial increase in cation yield correlates with electrostatic expectations. The decrease may be due to TMB moving further from the polar micellar surface with added salt. The possible effect of differing TMB protonation equilibria between anionic and cationic micelles on the photoionization yields was found to be unimportant by adjusting the bulk solution pH. An important conclusion is that salt addition can be used to optimize charge separation for photoionized solutes in anionic micelles.« less

Polyethyleneimine Coating Enhances the Cellular Uptake of Mesoporous Silica Nanoparticles and Allows Safe Delivery of siRNA and DNA Constructs

PubMed Central

Xia, Tian; Kovochich, Michael; Liong, Monty; Meng, Huan; Kabehie, Sanaz; Zink, Jeffrey I.; Nel, Andre E.

2014-01-01

Surface-functionalized mesoporous silica nanoparticles (MSNP) can be used as an efficient and safe carrier for bioactive molecules. In order to make the MSNP a more efficient delivery system, we modified the surface of the particles by a functional group that enhances cellular uptake and allows nucleic acid delivery in addition to traditional drug delivery. Non-covalent attachment of polyethyleneimine (PEI) polymers to the surface not only increases MSNP cellular uptake, but also generates a cationic surface to which DNA and siRNA constructs could be attached. While efficient for intracellular delivery of these nucleic acids, the 25 KD PEI polymer unfortunately changes the safety profile of the MSNP that is otherwise very safe. By experimenting with several different polymer molecular weights, it was possible to retain high cellular uptake and transfection efficiency while reducing or even eliminating cationic MSNP cytotoxicity. The particles coated with the 10 KD PEI polymer was particularly efficient for transducing HEPA-1 cells with a siRNA construct that was capable of knocking down GFP expression. Similarly, transfection of a GFP plasmid induced effective expression of the fluorescent protein in > 70% cells in the population. These outcomes were quantitatively assessed by confocal microscopy and flow cytometry. We also demonstrated that the enhanced cellular uptake of the non-toxic cationic MSNP enhance the delivery of the hydrophobic anticancer drug, paclitaxel, to pancreatic cancer cells. In summary, we demonstrate that by a careful selection of PEI size, it is possible to construct cationic MSNP that are capable of nucleotide and enhanced drug delivery with minimal or no cytotoxicity. This novel use of a cationic MSNP extends its therapeutic use potential. PMID:19739605

Construction of porous cationic frameworks by crosslinking polyhedral oligomeric silsesquioxane units with N-heterocyclic linkers

NASA Astrophysics Data System (ADS)

Chen, Guojian; Zhou, Yu; Wang, Xiaochen; Li, Jing; Xue, Shuang; Liu, Yangqing; Wang, Qian; Wang, Jun

2015-06-01

In fields of materials science and chemistry, ionic-type porous materials attract increasing attention due to significant ion-exchanging capacity for accessing diversified applications. Facing the fact that porous cationic materials with robust and stable frameworks are very rare, novel tactics that can create new type members are highly desired. Here we report the first family of polyhedral oligomeric silsesquioxane (POSS) based porous cationic frameworks (PCIF-n) with enriched poly(ionic liquid)-like cationic structures, tunable mesoporosities, high surface areas (up to 1,025 m2 g-1) and large pore volumes (up to 0.90 cm3 g-1). Our strategy is designing the new rigid POSS unit of octakis(chloromethyl)silsesquioxane and reacting it with the rigid N-heterocyclic cross-linkers (typically 4,4‧-bipyridine) for preparing the desired porous cationic frameworks. The PCIF-n materials possess large surface area, hydrophobic and special anion-exchanging property, and thus are used as the supports for loading guest species PMo10V2O405- the resultant hybrid behaves as an efficient heterogeneous catalyst for aerobic oxidation of benzene and H2O2-mediated oxidation of cyclohexane.

Construction of porous cationic frameworks by crosslinking polyhedral oligomeric silsesquioxane units with N-heterocyclic linkers

PubMed Central

Chen, Guojian; Zhou, Yu; Wang, Xiaochen; Li, Jing; Xue, Shuang; Liu, Yangqing; Wang, Qian; Wang, Jun

2015-01-01

In fields of materials science and chemistry, ionic-type porous materials attract increasing attention due to significant ion-exchanging capacity for accessing diversified applications. Facing the fact that porous cationic materials with robust and stable frameworks are very rare, novel tactics that can create new type members are highly desired. Here we report the first family of polyhedral oligomeric silsesquioxane (POSS) based porous cationic frameworks (PCIF-n) with enriched poly(ionic liquid)-like cationic structures, tunable mesoporosities, high surface areas (up to 1,025 m2 g−1) and large pore volumes (up to 0.90 cm3 g−1). Our strategy is designing the new rigid POSS unit of octakis(chloromethyl)silsesquioxane and reacting it with the rigid N-heterocyclic cross-linkers (typically 4,4′-bipyridine) for preparing the desired porous cationic frameworks. The PCIF-n materials possess large surface area, hydrophobic and special anion-exchanging property, and thus are used as the supports for loading guest species PMo10V2O405−; the resultant hybrid behaves as an efficient heterogeneous catalyst for aerobic oxidation of benzene and H2O2-mediated oxidation of cyclohexane. PMID:26062725

Construction of porous cationic frameworks by crosslinking polyhedral oligomeric silsesquioxane units with N-heterocyclic linkers.

PubMed

Chen, Guojian; Zhou, Yu; Wang, Xiaochen; Li, Jing; Xue, Shuang; Liu, Yangqing; Wang, Qian; Wang, Jun

2015-06-11

In fields of materials science and chemistry, ionic-type porous materials attract increasing attention due to significant ion-exchanging capacity for accessing diversified applications. Facing the fact that porous cationic materials with robust and stable frameworks are very rare, novel tactics that can create new type members are highly desired. Here we report the first family of polyhedral oligomeric silsesquioxane (POSS) based porous cationic frameworks (PCIF-n) with enriched poly(ionic liquid)-like cationic structures, tunable mesoporosities, high surface areas (up to 1,025 m(2) g(-1)) and large pore volumes (up to 0.90 cm(3) g(-1)). Our strategy is designing the new rigid POSS unit of octakis(chloromethyl)silsesquioxane and reacting it with the rigid N-heterocyclic cross-linkers (typically 4,4'-bipyridine) for preparing the desired porous cationic frameworks. The PCIF-n materials possess large surface area, hydrophobic and special anion-exchanging property, and thus are used as the supports for loading guest species PMo10V2O40(5-); the resultant hybrid behaves as an efficient heterogeneous catalyst for aerobic oxidation of benzene and H2O2-mediated oxidation of cyclohexane.

Adsorption of Cationic Peptides to Solid Surfaces of Glass and Plastic

PubMed Central

Kristensen, Kasper; Henriksen, Jonas R.; Andresen, Thomas L.

2015-01-01

Cationic membrane-active peptides have been studied for years in the hope of developing them into novel types of therapeutics. In this article, we investigate an effect that might have significant experimental implications for investigators who wish to study these peptides, namely, that the peptides adsorb to solid surfaces of glass and plastic. Specifically, we use analytical HPLC to systematically quantify the adsorption of the three cationic membrane-active peptides mastoparan X, melittin, and magainin 2 to the walls of commonly used glass and plastic sample containers. Our results show that, at typical experimental peptide concentrations, 90% or more of the peptides might be lost from solution due to rapid adsorption to the walls of the sample containers. Thus, our results emphasize that investigators should always keep these adsorption effects in mind when designing and interpreting experiments on cationic membrane-active peptides. We conclude the article by discussing different strategies for reducing the experimental impact of these adsorption effects. PMID:25932639

The effects of size and surface modification of amorphous silica particles on biodistribution and liver metabolism in mice

NASA Astrophysics Data System (ADS)

Lu, Xiaoyan; Ji, Cai; Jin, Tingting; Fan, Xiaohui

2015-05-01

Engineered nanoparticles, with unconventional properties, are promising platforms for biomedical applications. Since they may interact with a wide variety of biomolecules, it is critical to understand the impact of the physicochemical properties of engineered nanoparticles on biological systems. In this study, the effects of particle size and surface modification alone or in combination of amorphous silica particles (SPs) on biological responses were determined using a suite of general toxicological assessments and metabonomics analysis in mice model. Our results suggested that amino or carboxyl surface modification mitigated the liver toxicity of plain-surface SPs. 30 nm SPs with amino surface modification were found to be the most toxic SPs among all the surface-modified SP treatments at the same dosage. When treatment dose was increased, submicro-sized SPs with amino or carboxyl surface modification also induced liver toxicity. Biodistribution studies suggested that 70 nm SPs were mainly accumulated in liver and spleen regardless of surface modifications. Interestingly, these two organs exhibited different uptake trends. Furthermore, metabonomics studies indicated that surface modification plays a more dominant role to affect the liver metabolism than particle size.

Visualization of DNA and Protein-DNA Complexes with Atomic Force Microscopy

PubMed Central

Lyubchenko, Yuri L.; Gall, Alexander A.; Shlyakhtenko, Luda S.

2014-01-01

This article describes sample preparation techniques for AFM imaging of DNA and protein–DNA complexes. The approach is based on chemical functionalization of the mica surface with aminopropyl silatrane (APS) to yield an APS-mica surface. This surface binds nucleic acids and nucleoprotein complexes in a wide range of ionic strengths, in the absence of divalent cations, and in a broad range of pH. The chapter describes the methodologies for the preparation of APS-mica surfaces and the preparation of samples for AFM imaging. The protocol for synthesis and purifi cation of APS is also provided. The AFM applications are illustrated with examples of images of DNA and protein–DNA complexes. PMID:24357372

Mixed titanium, silicon, and aluminum oxide nanostructures as novel adsorbent for removal of rhodamine 6G and methylene blue as cationic dyes from aqueous solution.

PubMed

Pal, Umapada; Sandoval, Alberto; Madrid, Sergio Isaac Uribe; Corro, Grisel; Sharma, Vivek; Mohanty, Paritosh

2016-11-01

Mixed oxide nanoparticles containing Ti, Si, and Al of 8-15 nm size range were synthesized using a combined sol-gel - hydrothermal method. Effects of composition on the structure, morphology, and optical properties of the nanoparticles were studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), microRaman spectroscopy, and diffuse reflectance spectroscopy (DRS). Dye removal abilities of the nanoparticles from aqueous solutions were tested for different cationic dyes. While all the mixed oxide nanoparticles revealed high and fast adsorption of cationic dyes, the particles containing Ti and Si turned out to be the best. The adsorption kinetics and equilibrium adsorption behavior of the adsorbate - adsorbent systems could be well described by pseudo-second-order kinetics and Langmuir isotherm model, respectively. Estimated thermodynamic parameters revealed the adsorption process is spontaneous, driven mainly by the electrostatic force between the cationic dye molecules and negative charge at nanoparticle surface. Highest dye adsorption capacity (162.96 mg MB/g) of the mixed oxide nanostructures containing Ti and Si is associated to their high specific surface area, and the presence of surface Si-O(δ-) groups, in addition to the hydroxyl groups of amorphous titania. Mixed oxide nanoparticles containing 75% Ti and 25% Si seen to be the most efficient adsorbents for removing cationic dye molecules from wastewater. Copyright © 2016 Elsevier Ltd. All rights reserved.

Loading capacity and interaction of DNA binding on catanionic vesicles with different cationic surfactants.

PubMed

Xu, Lu; Chen, Jingfei; Feng, Lei; Dong, Shuli; Hao, Jingcheng

2014-12-07

Cationic and anionic (catanionic) vesicles were constructed from the mixtures of sodium laurate (SL) and alkyltrimethylammonium bromide (CnTAB, n = 12, 14, and 16) and were used to control the loading capacity of DNA. The binding saturation point (BSP) of DNA to catanionic vesicles increases with the chain length of cationic surfactants, which is at 1.0, 1.3 and 1.5 for CnTAB with n = 12, 14, and 16, respectively. Our measurements showed that the loading capacity and affinity of DNA can be controlled by catanionic vesicles. It increases with the chain length of cationic surfactants. Because of a large reduction in surface charge density, catanionic vesicles are prone to undergo re-aggregation or fusion with the addition of DNA. DNA molecules can still maintain original coil state during the interaction with catanionic CnTAL vesicles. (1)H NMR data reveals that the obvious dissociation of anionic ions, L(-), from catanionic C14TAL vesicles is due to the interaction with DNA; however, this phenomenon cannot be observed in C12TAB-SL vesicles. Agarose gel electrophoresis (AGE) results demonstrate that the electrostatic interaction between the two oppositely charged cationic and anionic surfactants is stronger than that between DNA and cationic surfactant, CnTAB (n = 12, 14, and 16). Not only is the dissociation of L(-) simply determined by the charge competition, but it also depends largely on the variations in the surface charge density as well as the cationic and anionic surfactant competing ability in geometry configuration of catanionic vesicles. The complicated interaction between DNA and catanionic vesicles induces the deformation of cationic vesicles. Our results should provide clear guidance for choosing more proper vectors for DNA delivery and gene therapy in cell experiments.

Enhancing the Ion Transport in LiMn1.5Ni0.5O4 by Altering the Particle Wulff Shape via Anisotropic Surface Segregation.

PubMed

Huang, Jiajia; Liu, Haodong; Zhou, Naixie; An, Ke; Meng, Ying Shirley; Luo, Jian

2017-10-25

Spontaneous and anisotropic surface segregation of W cations in LiMn 1.5 Ni 0.5 O 4 particles can alter the Wulff shape and improve surface stability, thereby significantly improving the electrochemical performance. An Auger electron nanoprobe was employed to identify the anisotropic surface segregation, whereby W cations prefer to segregate to {110} surface facets to decrease its relative surface energy according to Gibbs adsorption theory and subsequently increase its surface area according to Wulff theory. Consequently, the rate performance is improved (e.g., by ∼5-fold at a high rate of 25C) because the {110} facets have more open channels for fast lithium ion diffusion. Furthermore, X-ray photoelectron spectroscopy (XPS) depth profiling suggested that the surface segregation and partial reduction of W cation inhibit the formation of Mn 3+ on surfaces to improve cycling stability via enhancing the cathode electrolyte interphase (CEI) stability at high charging voltages. This is the first report of using anisotropic surface segregation to thermodynamically control the particle morphology as well as enhancing CEI stability as a facile, and potentially general, method to significantly improve the electrochemical performance of battery electrodes. Combining neutron diffraction, an Auger electron nanoprobe, XPS, and other characterizations, we depict the underlying mechanisms of improved ionic transport and CEI stability in high-voltage LiMn 1.5 Ni 0.5 O 4 spinel materials.

Hexadimethrine-montmorillonite nanocomposite: Characterization and application as a pesticide adsorbent

NASA Astrophysics Data System (ADS)

Gámiz, B.; Hermosín, M. C.; Cornejo, J.; Celis, R.

2015-03-01

The goal of this work was to prepare and characterize a novel functional material by the modification of SAz-1 montmorillonite with the cationic polymer hexadimethrine (SA-HEXAD), and to explore the potential use of this nanocomposite as a pesticide adsorbent. Comparative preparation and characterization with the well-known hexadecyltrimethylammonium-modified SAz-1 montmorillonite (SA-HDTMA) was also assessed. The characterization was performed by elemental analysis, X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), physisorption of N2, scanning electron microscopy (SEM) and Z potential measurements. The characterization and adsorption experiments showed that the extent of pesticide adsorption was markedly subjected to the structure and features of the surface of each organo-clay and also to the nature of the considered pesticide. SA-HEXAD displayed a high affinity for anionic pesticides which, presumably, were adsorbed by electrostatic attraction on positively-charged ammonium groups of the polymer not directly interacting with the clay. In contrast, SA-HDTMA displayed great adsorption of both uncharged and anionic pesticides with predominance of hydrophobic interactions. This work provided information about the surface properties of a new organic-inorganic nanohybrid material, SA-HEXAD, and its potential as an adsorbent for the removal of anionic organic pollutants from aqueous solutions.

An uptake of cationized ferritin by alveolar type I cells in airway-instilled goat lung: distribution of anionic sites on the epithelial surface.

PubMed

Atwal, O S; Viel, L; Minhas, K J

1990-07-01

The present study has investigated ultrastructural localization of anionic sites on the luminal surface of the alveolar epithelium of goat lung by direct airway instillation of cationized ferritin (CF) in the cranial lobe of the right lung through a bronchoscope. The cationic probe decorated preferentially the luminal plasmalemmal vesicles and plasmalemma proper of alveolar type I cell. This indicated the presence of highly charged anionic microdomains at these binding sites. The ligand was internalized in the free plasmalemmal vesicles of alveolar type I cell within 2 min. Heavy decoration of vesicles at 5 min of perfusion indicated that the amount of CF internalization increased with its concentration in the alveoli. It is suggested that exposure of alveolar surface to several gases of ruminal-origin induces changes in the surface charge of luminal plasmalemma of alveolar type I cells. The significance of these anionic plasmalemmal sites is discussed in relation to the adjustment of osmotic pressure gradient across the alveolar-capillary membrane of the ruminant lung.

Reactions of methyl groups on a non-reducible metal oxide: The reaction of iodomethane on stoichiometric α-Cr 2O 3(0001)

DOE PAGES

Dong, Yujung; Brooks, John D.; Chen, Tsung-Liang; ...

2015-06-10

The reaction of iodomethane on the nearly stoichiometric α-Cr 2O 3(0001) surface produces gas phase ethylene, methane, and surface iodine adatoms. The reaction is first initiated by the dissociation of iodomethane into surface methyl fragments, -CH 3, and iodine adatoms. Methyl fragments bound at surface Cr cation sites undergo a rate-limiting dehydrogenation reaction to methylene, =CH 2. The methylene intermediates formed from methyl dehydrogenation can then undergo coupling reactions to produce ethylene via two principle reaction pathways: (1) direct coupling of methylene and (2) methylene insertion into the methyl surface bond to form surface ethyl groups which undergo β-H eliminationmore » to produce ethylene. The liberated hydrogen also combines with methyl groups to form methane. Iodine adatoms from the dissociation of iodomethane deactivate the surface by simple site blocking of the surface Cr 3+ cations.« less

Sorption of organic cations onto silica surfaces over a wide concentration range of competing electrolytes.

PubMed

Kutzner, Susann; Schaffer, Mario; Licha, Tobias; Worch, Eckhard; Börnick, Hilmar

2016-12-15

The fundamental understanding of organic cation-solid phase interactions is essential for improved predictions of the transport and ultimate environmental fates of widely used substances (e.g., pharmaceutical compounds) in the aquatic environment. We report sorption experiments of two cationic model compounds using two silica gels and a natural aquifer sediment. The sorbents were extensively characterized and the results of surface titrations under various background electrolyte concentrations were discussed. The salt dependency of sorption was systematically studied in batch experiments over a wide concentration range (five orders of magnitude) of inorganic ions in order to examine the influence of increasing competition on the sorption of organic cations. The organic cation uptake followed the Freundlich isotherm model and the sorption capacity decreases with an increase in the electrolyte concentration due to the underlying cation exchange processes. However, the sorption recovers considerably at high ionic strength (I>1M). To our knowledge, this effect has not been observed before and appears to be independent from the sorbent characteristics and sorbate structure. Furthermore, the recovery of sorption was attributed to specific, non-ionic interactions and a connection between the sorption coefficient and activity coefficient of the medium is presumed. Eventually, the reasons for the differing sorption affinities of both sorbates are discussed. Copyright © 2016 Elsevier Inc. All rights reserved.

FRET study of G-quadruplex forming fluorescent oligonucleotide probes at the lipid monolayer interface.

PubMed

Swiatkowska, Angelika; Kosman, Joanna; Juskowiak, Bernard

2016-01-05

Spectral properties and G-quadruplex folding ability of fluorescent oligonucleotide probes at the cationic dioctadecyldimethylammonium bromide (DODAB) monolayer interface are reported. Two oligonucleotides, a 19-mer bearing thrombin binding aptamer sequence and a 21-mer with human telomeric sequence, were end-labeled with fluorescent groups (FAM and TAMRA) to give FRET probes F19T and F21T, respectively. The probes exhibited abilities to fold into a quadruplex structure and to bind metal cations (Na(+) and K(+)). Fluorescence spectra of G-quadruplex FRET probes at the monolayer interface are reported for the first time. Investigations included film balance measurements (π-A isotherms) and fluorescence spectra recording using a fiber optic accessory interfaced with a spectrofluorimeter. The effect of the presence of DODAB monolayer, metal cations and the surface pressure of monolayer on spectral behavior of FRET probes were examined. Adsorption of probe at the cationic monolayer interface resulted in the FRET signal enhancement even in the absence of metal cations. Variation in the monolayer surface pressure exerted rather modest effect on the spectral properties of probes. The fluorescence energy transfer efficiency of monolayer adsorbed probes increased significantly in the presence of sodium or potassium ion in subphase, which indicated that the probes retained their cation binding properties when adsorbed at the monolayer interface. Copyright © 2015 Elsevier B.V. All rights reserved.

Contact angles and wettability of ionic liquids on polar and non-polar surfaces†

PubMed Central

Sousa, Filipa L.; Silva, Nuno J. O.; Lopes-da-Silva, José A.; Coutinho, João A. P.; Freire, Mara G.

2016-01-01

Many applications involving ionic liquids (ILs) require the knowledge of their interfacial behaviour, such as wettability and adhesion. In this context, herein, two approaches were combined aiming at understanding the impact of the IL chemical structures on their wettability on both polar and non-polar surfaces, namely: (i) the experimental determination of the contact angles of a broad range of ILs (covering a wide number of anions of variable polarity, cations, and cation alkyl side chain lengths) on polar and non-polar solid substrates (glass, Al-plate, and poly-(tetrafluoroethylene) (PTFE)); and (ii) the correlation of the experimental contact angles with the cation–anion pair interaction energies generated by the Conductor-like Screening Model for Real Solvents (COSMO-RS). The combined results reveal that the hydrogen-bond basicity of ILs, and thus the IL anion, plays a major role through their wettability on both polar and non-polar surfaces. The increase of the IL hydrogen-bond accepting ability leads to an improved wettability of more polar surfaces (lower contact angles) while the opposite trend is observed on non-polar surfaces. The cation nature and alkyl side chain lengths have however a smaller impact on the wetting ability of ILs. Linear correlations were found between the experimental contact angles and the cation–anion hydrogen-bonding and cation ring energies, estimated using COSMO-RS, suggesting that these features primarily control the wetting ability of ILs. Furthermore, two-descriptor correlations are proposed here to predict the contact angles of a wide variety of ILs on glass, Al-plate, and PTFE surfaces. A new extended list is provided for the contact angles of ILs on three surfaces, which can be used as a priori information to choose appropriate ILs before a given application. PMID:26554705

Nanoscale oxidation and complex oxide growth on single crystal iron surfaces and external electric field effects.

PubMed

Jeon, Byoungseon; Van Overmeere, Quentin; van Duin, Adri C T; Ramanathan, Shriram

2013-02-14

Oxidation of iron surfaces and oxide growth mechanisms have been studied using reactive molecular dynamics. Oxide growth kinetics on Fe(100), (110), and (111) surface orientations has been investigated at various temperatures and/or an external electric field. The oxide growth kinetics decreases in the order of (110), (111), and (100) surfaces at 300 K over 1 ns timescale while higher temperature increases the oxidation rate. The oxidation rate shows a transition after an initial high rate, implying that the oxide formation mechanism evolves, with iron cation re-ordering. In early stages of surface oxide growth, oxygen transport through iron interstitial sites is dominant, yielding non-stoichiometric wüstite characteristics. The dominant oxygen inward transport decreases as the oxide thickens, evolving into more stoichiometric oxide phases such as wüstite or hematite. This also suggests that cation outward transport increases correspondingly. In addition to oxidation kinetics simulations, formed oxide layers have been relaxed in the range of 600-1500 K to investigate diffusion characteristics, fitting these results into an Arrhenius relation. The activation energy of oxygen diffusion in oxide layers formed on Fe(100), (110), and (111) surfaces was estimated to be 0.32, 0.26, and 0.28 eV, respectively. Comparison between our modeling results and literature data is then discussed. An external electric field (10 MV cm(-1)) facilitates initial oxidation kinetics by promoting oxygen transport through iron lattice interstitial sites, but reaches self-limiting thickness, showing that similar oxide formation stages are maintained when cation transport increases. The effect of the external electric field on iron oxide structure, composition, and oxide activation energy is found to be minimal, whereas cation outward migration is slightly promoted.

Nanoengineered field induced charge separation membranes manufacture thereof

DOEpatents

O'Brien, Kevin C.; Haslam, Jeffery J.; Bourcier, William L.; Floyd, III, William Clary

2016-08-02

A device according to one embodiment includes a porous membrane having a surface charge and pore configuration characterized by a double layer overlap effect being present in pores of the membrane, where the porous membrane includes functional groups that preferentially interact with either cations or anions. A device according to another embodiment includes a porous membrane having a surface charge in pores thereof sufficient to impart anion or cation selectivity in the pores. Additional devices, systems and methods are also presented.

Polymer Coatings Reduce Electro-osmosis

NASA Technical Reports Server (NTRS)

Herren, Blair J.; Snyder, Robert; Shafer, Steven G.; Harris, J. Milton; Van Alstine, James M.

1989-01-01

Poly(ethylene glycol) film controls electrostatic potential. Electro-osmosis in quartz or glass chambers reduced or reversed by coating inside surface of chambers with monomacromolecular layers of poly(ethylene glycol). Stable over long times. Electrostatic potential across surface of untreated glass or plastic chamber used in electro-phoresis is negative and attracts cations in aqueous electrolyte. Cations solvated, entrains flow of electrolyte migrating toward cathode. Electro-osmotic flow interferes with desired electrophoresis of particles suspended in electrolyte. Polymer coats nontoxic, transparent, and neutral, advantageous for use in electrophoresis.

Interaction between the Pore and a Fast Gate of the Cardiac Sodium Channel

PubMed Central

Townsend, Claire; Horn, Richard

1999-01-01

Permeant ions affect a fast gating process observed in human cardiac sodium channels (Townsend, C., H.A. Hartmann, and R. Horn. 1997. J. Gen. Physiol. 110:11–21). Removal of extracellular permeant ions causes a reduction of open probability at positive membrane potentials. These results suggest an intimate relationship between the ion-conducting pore and the gates of the channel. We tested this hypothesis by three sets of manipulations designed to affect the binding of cations within the pore: application of intracellular pore blockers, mutagenesis of residues known to contribute to permeation, and chemical modification of a native cysteine residue (C373) near the extracellular mouth of the pore. The coupling between extracellular permeant ions and this fast gating process is abolished both by pore blockers and by a mutation that severely affects selectivity. A more superficial pore mutation or chemical modification of C373 reduces single channel conductance while preserving both selectivity of the pore and the modulatory effects of extracellular cations. Our results demonstrate a modulatory gating role for a region deep within the pore and suggest that the structure of the permeation pathway is largely preserved when a channel is closed. PMID:9925827

Polarizing the Nazarov cyclization: the impact of dienone substitution pattern on reactivity and selectivity.

PubMed

He, Wei; Herrick, Ildiko R; Atesin, Tulay A; Caruana, Patrick A; Kellenberger, Colleen A; Frontier, Alison J

2008-01-23

The impact of dienone substitution on the Nazarov cyclization has been examined in detail. Substrates bearing different substituents at each of four positions on the dienone backbone were systematically probed in order to identify trends leading to higher reactivity and better selectivity. Desymmetrization of the pentadienyl cation and oxyallyl cation intermediates through placement of polarizing groups at both the C-2 and C-4 positions was found to be particularly effective. These modifications allowed cyclizations to occur in the presence of catalytic amounts of mild Lewis acids. It was also found that stereoconvergent cyclization of mixtures of E and Z isomers of alkylidene beta-ketoesters occurred via an efficient isomerization process that occurred under the reaction conditions.

Quat co-formulations optimized for use with cotton nonwoven disposable wipes

USDA-ARS?s Scientific Manuscript database

Quaternary ammonium compounds, commonly referred to as quats, are cationic surfactants widely used as the active biocidal ingredient for disposable disinfecting wipes. The cationic nature of quats results in a strong ionic interaction and adsorption onto wipes materials that have an anionic surface...

In situ remediation process using divalent metal cations

DOEpatents

Brady, Patrick V.; Khandaker, Nadim R.; Krumhansl, James L.; Teter, David M.

2004-12-14

An in situ process for treating ambient solid materials (e.g., soils, aquifer solids, sludges) by adding one or more divalent metal cations to the ambient solid material. The added divalent metal cations, such as Cu.sup.2+ or Zn.sup.2+, combine with metal oxide/hydroxides (e.g., ferric oxide/hydroxide or aluminum oxide/hydroxide) already present in the ambient solid material to form an effective sorbent material having a large number of positively-charged surface complexes that binds and immobilizes anionic contaminant species (e.g., arsenic or chromate). Divalent metal cations can be added, for example, by injecting an aqueous solution of CuSO.sub.4 into an aquifer contaminated with arsenic or chromate. Also, sludges can be stabilized against leaching of anionic contaminants through the addition of divalent metal cations. Also, an inexpensive sorbent material can be easily formed by mixing divalent metal cations with soil that has been removed from the ground.

Surface characterization of imidazolium-based ionic liquids with cyano-functionalized anions at the gas-liquid interface using sum frequency generation spectroscopy.

PubMed

Peñalber, Chariz Y; Grenoble, Zlata; Baker, Gary A; Baldelli, Steven

2012-04-21

Advancement in the field of ionic liquid technology requires a comprehensive understanding of their surface properties, as a wide range of chemical reactions occur mainly at interfaces. As essential media currently used in several technological applications, their accurate molecular level description at the gas-liquid interface is of utmost importance. Due to the high degree of chemical information provided in the vibrational spectrum, vibrational spectroscopy gives the most detailed model for molecular structure. The inherently surface-sensitive technique, sum frequency generation (SFG) spectroscopy, in combination with bulk-sensitive vibrational spectroscopic techniques such as FTIR and Raman, has been used in this report to characterize the surface of cyano-containing ionic liquids, such as [BMIM][SCN], [BMIM][DCA], [BMIM][TCM] and [EMIM][TCB] at the gas-liquid interface. By structural variation of the anion while keeping the cation constant, emphasis on the molecular arrangement of the anion at the gas-liquid interface is reported, and its subsequent role (if any) in determining the surface molecular orientation of the cation. Vibrational modes seen in the C-H stretching region revealed the presence of the cation at the gas-liquid interface. The cation orientation is independent of the type of cyano-containing anion, however, a similar arrangement at the surface as reported in previous studies was found, with the imidazolium ring lying flat at the surface, and the alkyl chains pointing towards the gas phase. SFG results show that all three anions of varying symmetry, namely, [DCA](-) (C(2v)), [TCM](-)(D(3h)) and [TCB](-) (T(d)) in ionic liquids [BMIM]DCA], [BMIM][TCM] and [EMIM][TCB] are significantly tilted from the surface plane, while the linear [SCN](-) in [BMIM][SCN] exhibited poor ordering, as seen in the absence of its C-N stretching mode in the SFG vibrational spectra. This journal is © the Owner Societies 2012

Chemical modification of chitosan for efficient gene therapy.

PubMed

Jiang, Hu-Lin; Cui, Peng-Fei; Xie, Rong-Lin; Cho, Chong-Su

2014-01-01

Gene therapy involves the introduction of foreign genetic material into cells in order to exert a therapeutic effect. Successful gene therapy relies on effective vector system. Viral vectors are highly efficient in transfecting cells, but the undesirable complications limit their therapeutic applications. As a natural biopolymer, chitosan has been considered to be a good gene carrier candidate due to its ideal character which combines biocompatibility, low toxicity with high cationic density together. However, the low cell specificity and low transfection efficiency of chitosan as a gene carrier need to be overcome before undertaking clinical trials. This chapter is principally on those endeavors such as chemical modifications using cell-specific ligands and stimuli-response groups as well as penetrating modifications that have been done to increase the performances of chitosan in gene therapy. © 2014 Elsevier Inc. All rights reserved.

DNA immobilization and detection on cellulose paper using a surface grown cationic polymer via ATRP.

PubMed

Aied, Ahmed; Zheng, Yu; Pandit, Abhay; Wang, Wenxin

2012-02-01

Cationic polymers with various structures have been widely investigated in the areas of medical diagnostics and molecular biology because of their unique binding properties and capability to interact with biological molecules in complex biological environments. In this work, we report the grafting of a linear cationic polymer from an atom transfer radical polymerization (ATRP) initiator bound to cellulose paper surface. We show successful binding of ATRP initiator onto cellulose paper and grafting of polymer chains from the immobilized initiator with ATRP. The cellulose paper grafted polymer was used in combination with PicoGreen (PG) to demonstrate detection of nucleic acids in the nanogram range in homogeneous solution and in a biological sample (serum). The results showed specific identification of hybridized DNA after addition of PG in both solutions.

Determination of Surface Potential and Electrical Double-Layer Structure at the Aqueous Electrolyte-Nanoparticle Interface

NASA Astrophysics Data System (ADS)

Brown, Matthew A.; Abbas, Zareen; Kleibert, Armin; Green, Richard G.; Goel, Alok; May, Sylvio; Squires, Todd M.

2016-01-01

The structure of the electrical double layer has been debated for well over a century, since it mediates colloidal interactions, regulates surface structure, controls reactivity, sets capacitance, and represents the central element of electrochemical supercapacitors. The surface potential of such surfaces generally exceeds the electrokinetic potential, often substantially. Traditionally, a Stern layer of nonspecifically adsorbed ions has been invoked to rationalize the difference between these two potentials; however, the inability to directly measure the surface potential of dispersed systems has rendered quantitative measurements of the Stern layer potential, and other quantities associated with the outer Helmholtz plane, impossible. Here, we use x-ray photoelectron spectroscopy from a liquid microjet to measure the absolute surface potentials of silica nanoparticles dispersed in aqueous electrolytes. We quantitatively determine the impact of specific cations (Li+ , Na+ , K+ , and Cs+ ) in chloride electrolytes on the surface potential, the location of the shear plane, and the capacitance of the Stern layer. We find that the magnitude of the surface potential increases linearly with the hydrated-cation radius. Interpreting our data using the simplest assumptions and most straightforward understanding of Gouy-Chapman-Stern theory reveals a Stern layer whose thickness corresponds to a single layer of water molecules hydrating the silica surface, plus the radius of the hydrated cation. These results subject electrical double-layer theories to direct and falsifiable tests to reveal a physically intuitive and quantitatively verified picture of the Stern layer that is consistent across multiple electrolytes and solution conditions.

Enhancement strategies for Cu(II), Cr(III) and Cr(VI) remediation by a variety of seaweed species.

PubMed

Murphy, V; Hughes, H; McLoughlin, P

2009-07-15

Various chemical treatments have been applied to six brown, red and green seaweed species with a view to enhancing their metal removal for Cu(II), Cr(III) and Cr(VI). Treatment with acetone resulted in the greatest enhancement for both cationic and anionic species with relatively low mass losses (15-35%), indicating its low risk to biomass operational stability. Cation binding was increased by 69%, while the total Cr removal was augmented by 15%. Cr(VI) binding was shown to be an adsorption-coupled reduction, whereby Cr(VI) was bound to the biomass surface at pH 2 and subsequently reduced to Cr(III). Acetone treatment also resulted in biomasses that were capable of converting up to 83% of Cr(VI) in solution to Cr(III). Blocking of carboxyl and amino functionalities had significant negative effects both on total Cr removal as well as percentage conversion of Cr(VI) to Cr(III). Results therefore indicated the significant role played by these moieties in metal binding to these seaweeds. Potentiometric titrations displayed agreement between the degree of esterification and the decrease in Cu(II) removal for Ulva spp. and Polysiphonia lanosa. FTIR analysis identified changes in biomass functionality and availability after chemical modification, the results of which were in agreement with metal removal studies. In conclusion, these biosorbents represent suitable candidates to replace conventional removal technologies for metal bearing wastewaters, in particular for the detoxification of hazardous Cr(VI) waste streams.

Ceramic Spheres From Cation Exchange Beads

NASA Technical Reports Server (NTRS)

Dynys, F. W.

2003-01-01

Porous ZrO2 and hollow TiO2 spheres were synthesized from a strong acid cation exchange resin. Spherical cation exchange beads, polystyrene based polymer, were used as a morphological-directing template. Aqueous ion exchange reaction was used to chemically bind (ZrO)(2+) ions to the polystyrene structure. The pyrolysis of the polystyrene at 600 C produces porous ZrO2 spheres with a surface area of 24 sq m/g with a mean sphere size of 42 microns. Hollow TiO2 spheres were synthesized by using the beads as a micro-reactor. A direct surface reaction - between titanium isopropoxide and the resin beads forms a hydrous TiO2 shell around the polystyrene core. The pyrolysis of the polystyrene core at 600 C produces hollow anatase spheres with a surface area of 42 sq m/g with a mean sphere size of 38 microns. The formation of ceramic spheres was studied by XRD, SEM and B.E.T. nitrogen adsorption measurements.

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.

Spectroscopy and computational studies on the interaction of octyl, dodecyl, and hexadecyl derivatives of anionic and cationic surfactants with adenosine deaminase.

PubMed

Ajloo, Davood; Mahmoodabadi, Najmeh; Ghadamgahi, Maryam; Saboury, Ali Akbar

2016-07-01

Effects of sodium (octyl, dodecyl, hexadecyl) sulfate and their cationic analogous on the structure of adenosine deaminase (ADA) were investigated by fluorescence and circular dichroism spectroscopy as well as molecular dynamics simulation and docking calculation. Root-mean-square derivations, radius of gyration, solvent accessible surface area, and radial distribution function were obtained. The results showed that anionic and cationic surfactants reduce protein stability. Cationic surfactants have more effect on the ADA structure in comparison with anionic surfactants. More concentration and longer surfactants are parallel to higher denaturation. Furthermore, aggregation in the presence of anionic surfactants is more than cationic surfactants. Docking data showed that longer surfactants have more interaction energy and smaller ones bound to the active site.

In situ AFM investigation of electrochemically induced surface-initiated atom-transfer radical polymerization.

PubMed

Li, Bin; Yu, Bo; Zhou, Feng

2013-02-12

Electrochemically induced surface-initiated atom-transfer radical polymerization is traced by in situ AFM technology for the first time, which allows visualization of the polymer growth process. It affords a fundamental insight into the surface morphology and growth mechanism simultaneously. Using this technique, the polymerization kinetics of two model monomers were studied, namely the anionic 3-sulfopropyl methacrylate potassium salt (SPMA) and the cationic 2-(metharyloyloxy)ethyltrimethylammonium chloride (METAC). The growth of METAC is significantly improved by screening the ammonium cations by the addition of ionic liquid electrolyte in aqueous solution. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Organic light emitting diode with surface modification layer

DOEpatents

Basil, John D.; Bhandari, Abhinav; Buhay, Harry; Arbab, Mehran; Marietti, Gary J.

2017-09-12

An organic light emitting diode (10) includes a substrate (12) having a first surface (14) and a second surface (16), a first electrode (32), and a second electrode (38). An emissive layer (36) is located between the first electrode (32) and the second electrode (38). The organic light emitting diode (10) further includes a surface modification layer (18). The surface modification layer (18) includes a non-planar surface (30, 52).

Sub-nanometer surface chemistry and orbital hybridization in lanthanum-doped ceria nano-catalysts revealed by 3D electron microscopy.

PubMed

Collins, Sean M; Fernandez-Garcia, Susana; Calvino, José J; Midgley, Paul A

2017-07-14

Surface chemical composition, electronic structure, and bonding characteristics determine catalytic activity but are not resolved for individual catalyst particles by conventional spectroscopy. In particular, the nano-scale three-dimensional distribution of aliovalent lanthanide dopants in ceria catalysts and their effect on the surface electronic structure remains unclear. Here, we reveal the surface segregation of dopant cations and oxygen vacancies and observe bonding changes in lanthanum-doped ceria catalyst particle aggregates with sub-nanometer precision using a new model-based spectroscopic tomography approach. These findings refine our understanding of the spatially varying electronic structure and bonding in ceria-based nanoparticle aggregates with aliovalent cation concentrations and identify new strategies for advancing high efficiency doped ceria nano-catalysts.

Antimicrobial activity and interactions of cationic peptides derived from Galleria mellonella cecropin D-like peptide with model membranes.

PubMed

Oñate-Garzón, José; Manrique-Moreno, Marcela; Trier, Steven; Leidy, Chad; Torres, Rodrigo; Patiño, Edwin

2017-03-01

Antimicrobial peptides are effector molecules of the innate immune system against invading pathogens. The cationic charge in their structures has a strong correlation with antimicrobial activity, being responsible for the initial electrostatic interaction between peptides and the anionic microbial surface. This paper contains evidence that charge modification in the neutral peptide Gm cecropin D-like (WT) improved the antimicrobial activity of the modified peptides. Two cationic peptides derived from WT sequence named as ΔM1 and ΔM2, with net charge of +5 and +9, respectively, showed at least an eightfold increase in their antimicrobial activity in comparison to WT. The mechanism of action of these peptides was investigated using small unilamellar vesicles (SUVs) as model membranes. To study permeabilization effects of the peptides on cell membranes, entrapped calcein liposomes were used and the results showed that all peptides induced calcein release from 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoglycerol (POPG) SUVs, whereas in 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC), POPC/POPG and 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine (POPE)/POPG SUVs, only ΔM1 and ΔM2 induced a notable permeabilization. In addition, interactions of these peptides with phospholipids at the level of the glycerol backbone and hydrophobic domain were studied through observed changes in generalized polarization and fluorescence anisotropy using probes such as Laurdan and DPH, respectively. The results suggest that peptides slightly ordered the bilayer structure at the level of glycerol backbone and on the hydrophobic core in 1,2-dimyristoyl-sn-glycero-3-phosphoglycerol (DMPG) SUVs, whereas in 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC)/DMPG SUVs, only ΔM1 and ΔM2 peptides increased the order of bilayers. Thus, peptides would be inducing clustering of phospholipids creating phospholipid domains with a higher phase transition temperature.

Synthesis of iron composites on nano-pore substrates: identification and its application to removal of cyanide.

PubMed

Do, Si-Hyun; Jo, Young-Hoon; Park, Ho-Dong; Kong, Sung-Ho

2012-11-01

Two types of nano-pore substrates, waste-reclaimed (WR) and soil mineral (SM) with the relatively low density, were modified by the reaction with irons (i.e. Fe(II):Fe(III)=1:2) and the applicability of the modified substrates (i.e. Fe-WR and Fe-SM) on cyanide removal was investigated. Modification (i.e. Fe immobilization on substrate) decreased the BET surface area and PZC of the original substrates while it increased the pore diameter and the cation exchange capacity (CEC) of them. XRD analysis identified that maghemite (γ-Fe(2)O(3)) and iron silicate composite ((Mg, Fe)SiO(3)) existed on Fe-WR, while clinoferrosilite (FeSiO(3)) was identified on Fe-SM. Cyanide adsorption showed that WR adsorbed cyanide more favorably than SM. The adsorption ability of both original substrates was enhanced by the modification, which increased the negative charges of the surfaces. Without the pH adjustment, cyanide was removed as much as 97% by the only application of Fe-WR, but the undesirable transfer to hydrogen cyanide was possible because the pH was dropped to around 7.5. With a constant pH of 12, only 54% of cyanide was adsorbed on Fe-WR. On the other hand, the pH was kept as 12 without adjustment in Fe-WR/H(2)O(2) system and cyanide was effectively removed by not only adsorption but also the catalytic oxidation. The observed first-order rate constant (k(obs)) for cyanide removal were 0.49 (± 0.081) h(-1). Moreover, the more cyanate production with the modified substrates indicated the iron composites, especially maghemite, on substrates had the catalytic property to increase the reactivity of H(2)O(2). Copyright © 2012 Elsevier Ltd. All rights reserved.

Role of adsorbed surfactant in the reaction of aryl diazonium salts with single-walled carbon nanotubes.

PubMed

Hilmer, Andrew J; McNicholas, Thomas P; Lin, Shangchao; Zhang, Jingqing; Wang, Qing Hua; Mendenhall, Jonathan D; Song, Changsik; Heller, Daniel A; Barone, Paul W; Blankschtein, Daniel; Strano, Michael S

2012-01-17

Because covalent chemistry can diminish the optical and electronic properties of single-walled carbon nanotubes (SWCNTs), there is significant interest in developing methods of controllably functionalizing the nanotube sidewall. To date, most attempts at obtaining such control have focused on reaction stoichiometry or strength of oxidative treatment. Here, we examine the role of surfactants in the chemical modification of single-walled carbon nanotubes with aryl diazonium salts. The adsorbed surfactant layer is shown to affect the diazonium derivatization of carbon nanotubes in several ways, including electrostatic attraction or repulsion, steric exclusion, and direct chemical modification of the diazonium reactant. Electrostatic effects are most pronounced in the cases of anionic sodium dodecyl sulfate and cationic cetyltrimethylammonium bromide, where differences in surfactant charge can significantly affect the ability of the diazonium ion to access the SWCNT surface. For bile salt surfactants, with the exception of sodium cholate, we find that the surfactant wraps tightly enough such that exclusion effects are dominant. Here, sodium taurocholate exhibits almost no reactivity under the explored reaction conditions, while for sodium deoxycholate and sodium taurodeoxycholate, we show that the greatest extent of reaction is observed among a small population of nanotube species, with diameters between 0.88 and 0.92 nm. The anomalous reaction of nanotubes in this diameter range seems to imply that the surfactant is less effective at coating these species, resulting in a reduced surface coverage on the nanotube. Contrary to the other bile salts studied, sodium cholate enables high selectivity toward metallic species and small band gap semiconductors, which is attributed to surfactant-diazonium coupling to form highly reactive diazoesters. Further, it is found that the rigidity of anionic surfactants can significantly influence the ability of the surfactant layer to stabilize the diazonium ion near the nanotube surface. Such Coulombic and surfactant packing effects offer promise toward employing surfactants to controllably functionalize carbon nanotubes. © 2011 American Chemical Society

Biodistribution of charged F(ab')2 photoimmunoconjugates in a xenograft model of ovarian cancer.

PubMed

Duska, L R; Hamblin, M R; Bamberg, M P; Hasan, T

1997-01-01

The effect of charge modification of photoimmunoconjugates (PICs) on their biodistribution in a xenograft model of ovarian cancer was investigated. Chlorin(e6)c(e6) was attached site specifically to the F(ab')2 fragment of the murine monoclonal antibody OC125, directed against human ovarian cancer cells, via poly-1-lysine linkers carrying cationic or anionic charges. Preservation of immunoreactivity was checked by enzyme-linked immunosorbent assay (ELISA). PICs were radiolabelled with 125I and compared with non-specific rabbit IgG PICs after intraperitoneal (i.p.) injection into nude mice. Samples were taken from normal organs and tumour at 3 h and 24 h. Tumour to normal 125I ratios showed that the cationic OC125F(ab')2 PIC had the highest tumour selectivity. Ratios for c(e6) were uniformly higher than for 125I, indicating that c(e6) became separated from 125I. OC125F(ab')2 gave highest tissue values of 125I, followed by cationic OC125F(ab')2 PIC; other species were much lower. The amounts of c(e6) delivered per gram of tumour were much higher for cationic OC125F(ab')2 PIC than for other species. The results indicate that cationic charge stimulates the endocytosis and lysosomal degradation of the OC125F(ab')2-pl-c(e6) that has bound to the i.p. tumour. Positively charged PICs may have applications in the i.p. photoimmunotherapy of minimal residual ovarian cancer.

Modification of silicon nitride surfaces with GOPES and APTES for antibody immobilization: computational and experimental studies

NASA Astrophysics Data System (ADS)

Dien To, Thien; Nguyen, Anh Tuan; Nhat Thanh Phan, Khoa; Thu Thi Truong, An; Doan, Tin Chanh Duc; Mau Dang, Chien

2015-12-01

Chemical modification of silicon nitride (SiN) surfaces by silanization has been widely studied especially with 3-(aminopropyl)triethoxysilane (APTES) and 3-(glycidyloxypropyl) dimethylethoxysilane (GOPES). However few reports performed the experimental and computational studies together. In this study, surface modification of SiN surfaces with GOPES and APTES covalently bound with glutaraldehyde (GTA) was investigated for antibody immobilization. The monoclonal anti-cytokeratin-FITC (MACF) antibody was immobilized on the modified SiN surfaces. The modified surfaces were characterized by water contact angle measurements, atomic force microscopy and fluorescence microscopy. The FITC-fluorescent label indicated the existence of MACF antibody on the SiN surfaces and the efficiency of the silanization reaction. Absorption of APTES and GOPES on the oxidized SiN surfaces was computationally modeled and calculated by Materials Studio software. The computational and experimental results showed that modification of the SiN surfaces with APTES and GTA was more effective than the modification with GOPES.

Brucella melitensis MucR, an orthologue of Sinorhizobium meliloti MucR, is involved in resistance to oxidative, detergent, and saline stresses and cell envelope modifications.

PubMed

Mirabella, A; Terwagne, M; Zygmunt, M S; Cloeckaert, A; De Bolle, X; Letesson, J J

2013-02-01

Brucella spp. and Sinorhizobium meliloti are alphaproteobacteria that share not only an intracellular lifestyle in their respective hosts, but also a crucial requirement for cell envelope components and their timely regulation for a successful infectious cycle. Here, we report the characterization of Brucella melitensis mucR, which encodes a zinc finger transcriptional regulator that has previously been shown to be involved in cellular and mouse infections at early time points. MucR modulates the surface properties of the bacteria and their resistance to environmental stresses (i.e., oxidative stress, cationic peptide, and detergents). We show that B. melitensis mucR is a functional orthologue of S. meliloti mucR, because it was able to restore the production of succinoglycan in an S. meliloti mucR mutant, as detected by calcofluor staining. Similar to S. meliloti MucR, B. melitensis MucR also represses its own transcription and flagellar gene expression via the flagellar master regulator ftcR. More surprisingly, we demonstrate that MucR regulates a lipid A core modification in B. melitensis. These changes could account for the attenuated virulence of a mucR mutant. These data reinforce the idea that there is a common conserved circuitry between plant symbionts and animal pathogens that regulates the relationship they have with their hosts.

Measurements of myocardial flow vs. extraction of rubidium under varying physiological conditions

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

Budinger, T.F.; Yano, Y.; Moyer, B.R.

1984-01-01

The relationship between myocardial rubidium extraction (E) and flow (F) are well described by the single capillary model E = (1-exp(-PS/F)) with a permeability surface product PS = 0.87 cc/min/gm. Some effects of alkalosis and acidosis have been reported. Here the authors investigate the effects of dipyridamole, norepinephrine-atropine, exsanguination, pacing, ouabain and calcium on extraction using Rb-82 PET and Rb-86 acute studies with microspheres in dogs. Thoracotomies were performed for left atrial microsphere infusion. Anesthesia was by N/sub 2/O and methoxyflurane. The degree of exsanguination, drug levels administered and pacing rates were sufficient to produce flow modifications. Extraction was calculatedmore » by dividing FE from Rb observations by F from microsphere data. These results of extraction vs. flow do not show a significant dependence on the method used for flow modification. There was less than a 20% change in FE after an infusion of 0.04 mg/kg ouabain over 5 minutes in 3 replicate studies each on 4 dogs. An important finding not previously explained in flow vs. extraction studies is the occurrence of extraction values greater than 1.0 which is possible only if the distribution opportunities of small cations are greater than that of microspheres. This is equivalent to the well known hematocrit effect in small channels.« less

TOPICAL REVIEW: Surface modification and characterization for dispersion stability of inorganic nanometer-scaled particles in liquid media

NASA Astrophysics Data System (ADS)

Kamiya, Hidehiro; Iijima, Motoyuki

2010-08-01

Inorganic nanoparticles are indispensable for science and technology as materials, pigments and cosmetics products. Improving the dispersion stability of nanoparticles in various liquids is essential for those applications. In this review, we discuss why it is difficult to control the stability of nanoparticles in liquids. We also overview the role of surface interaction between nanoparticles in their dispersion and characterization, e.g. by colloid probe atomic force microscopy (CP-AFM). Two types of surface modification concepts, post-synthesis and in situ modification, were investigated in many previous studies. Here, we focus on post-synthesis modification using adsorption of various kinds of polymer dispersants and surfactants on the particle surface, as well as surface chemical reactions of silane coupling agents. We discuss CP-AFM as a technique to analyze the surface interaction between nanoparticles and the effect of surface modification on the nanoparticle dispersion in liquids.

Quantitative characterization of non-classic polarization of cations on clay aggregate stability.

PubMed

Hu, Feinan; Li, Hang; Liu, Xinmin; Li, Song; Ding, Wuquan; Xu, Chenyang; Li, Yue; Zhu, Longhui

2015-01-01

Soil particle interactions are strongly influenced by the concentration, valence and ion species and the pH of the bulk solution, which will also affect aggregate stability and particle transport. In this study, we investigated clay aggregate stability in the presence of different alkali ions (Li+, Na+, K+, and Cs+) at concentrations from10-5 to 10-1 mol L-1. Strong specific ion effects on clay aggregate stability were observed, and showed the order Cs+>K+>Na+>Li+. We found that it was not the effects of ion size, hydration, and dispersion forces in the cation-surface interactions but strong non-classic polarization of adsorbed cations that resulted in these specific effects. In this study, the non-classic dipole moments of each cation species resulting from the non-classic polarization were estimated. By comparing non-classic dipole moments with classic values, the observed dipole moments of adsorbed cations were up to 104 times larger than the classic values for the same cation. The observed non-classic dipole moments sharply increased with decreasing electrolyte concentration. We conclude that strong non-classic polarization could significantly suppress the thickness of the diffuse layer, thereby weakening the electric field near the clay surface and resulting in improved clay aggregate stability. Even though we only demonstrated specific ion effects on aggregate stability with several alkali ions, our results indicate that these effects could be universally important in soil aggregate stability.

Surface modification to prevent oxide scale spallation

DOEpatents

Stephens, Elizabeth V; Sun, Xin; Liu, Wenning; Stevenson, Jeffry W; Surdoval, Wayne; Khaleel, Mohammad A

2013-07-16

A surface modification to prevent oxide scale spallation is disclosed. The surface modification includes a ferritic stainless steel substrate having a modified surface. A cross-section of the modified surface exhibits a periodic morphology. The periodic morphology does not exceed a critical buckling length, which is equivalent to the length of a wave attribute observed in the cross section periodic morphology. The modified surface can be created using at least one of the following processes: shot peening, surface blasting and surface grinding. A coating can be applied to the modified surface.

How do silanes affect the lubricating properties of cationic double chain surfactant on silica surfaces?

PubMed

Beauvais, Muriel; Serreau, Laurence; Heitz, Caroline; Barthel, Etienne

2009-03-01

The effect of an aminosilane on the lubricant properties of a C(18) double-chained cationic surfactant has been investigated in the context of glass fiber forming process. The surfactant adsorption was studied on silica by Fourier transform infrared (FT-IR) spectroscopy in the attenuated total reflexion (ATR) mode as a function of the aminosilane concentration in an organic water based formulation (sizing) used to coat the glass fibers during the process. A reciprocating ball-on-plate tribometer was used to compare friction properties of silica in contact with the aminosilane-surfactant mixture and in presence of each component of the sizing. Surface forces were measured between silica and an atomic force microscope (AFM) silicon nitride tip in the sizing and in the pure cationic surfactant solution. The aminosilane on its own has no lubricant property and reduces or even suppresses the cationic surfactant adsorption on silica. However, the silica-silica contact is lubricated even if the infrared spectroscopy does not detect any surfactant adsorption. The repeated contacts and shear due to the friction experiment itself induce accumulation, organization and compactness of surfactant bilayers.

Mixed cation FA x PEA 1- x PbI 3 with enhanced phase and ambient stability toward high-performance perovskite solar cells

DOE PAGES

Li, Nan; Zhu, Zonglong; Chueh, Chu -Chen; ...

2016-09-26

In this study, different from the commonly explored strategy of incorporating a smaller cation, MA + and Cs + into FAPbI 3 lattice to improve efficiency and stability, it is revealed that the introduction of phenylethylammonium iodide (PEAI) into FAPbI 3 perovksite to form mixed cation FA xPEA 1–xPbI 3 can effectively enhance both phase and ambient stability of FAPbI 3 as well as the resulting performance of the derived devices. From our experimental and theoretical calculation results, it is proposed that the larger PEA cation is capable of assembling on both the lattice surface and grain boundaries to formmore » quais-3D perovskite structures. The surrounding of PEA + ions at the crystal grain boundaries not only can serve as molecular locks to tighten FAPbI 3 domains but also passivate the surface defects to improve both phase and moisture stablity. Consequently, a high-performance (PCE:17.7%) and ambient stable FAPbI 3 solar cell could be developed« less

Adsorption of dissymmetric cationic gemini surfactants at silica/water interface

NASA Astrophysics Data System (ADS)

Sun, Yuhai; Feng, Yujun; Dong, Hongwei; Chen, Zhi

2007-05-01

Adsorption of a series of cationic gemini surfactants 12-2- m ( m = 8, 12, 16) on the surface of silica was investigated. The critical micelle concentrations, cmcs, of cationic gemini surfactants in the initial solutions and in the supernatants were measured by conductometry and tensiometer. The changes in cmc values indicate that the ion exchanges take place between polar groups of gemini surfactants adsorbed and ions bound on the surface of silica. The adsorption isotherms of cationic gemini surfactants were obtained by a solution depletion method. Based on the driving force, the adsorption includes two steps, one of which is ion exchange, and the other is hydrophobic interaction. In each step, the tendency of surfactant molecules in the solution to form aggregates or to be adsorbed on the silica varies with their structures. The maximum adsorption amount of gemini surfactants on the silica, τmax, decreases as increasing in the length of one alkyl chain, m, from 8, 12 to 16. So the results show that the adsorption behaviors of gemini surfactants are closely related to the dissymmetry of gemini molecules.

Mesoporous nanocrystalline film architecture for capacitive storage devices

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

Dunn, Bruce S.; Tolbert, Sarah H.; Wang, John

A mesoporous, nanocrystalline, metal oxide construct particularly suited for capacitive energy storage that has an architecture with short diffusion path lengths and large surface areas and a method for production are provided. Energy density is substantially increased without compromising the capacitive charge storage kinetics and electrode demonstrates long term cycling stability. Charge storage devices with electrodes using the construct can use three different charge storage mechanisms immersed in an electrolyte: (1) cations can be stored in a thin double layer at the electrode/electrolyte interface (non-faradaic mechanism); (2) cations can interact with the bulk of an electroactive material which then undergoesmore » a redox reaction or phase change, as in conventional batteries (faradaic mechanism); or (3) cations can electrochemically adsorb onto the surface of a material through charge transfer processes (faradaic mechanism).« less

Core/shell-type nanorods of Tb3+-doped LaPO4, modified with amine groups, revealing reduced cytotoxicity

NASA Astrophysics Data System (ADS)

Runowski, Marcin; Dąbrowska, Krystyna; Grzyb, Tomasz; Miernikiewicz, Paulina; Lis, Stefan

2013-11-01

A simple co-precipitation reaction between Ln3+ cations (Ln = lanthanide) and phosphate ions in the presence of polyethylene glycol (PEG), including post-treatment under hydrothermal conditions, leads to the formation of Tb3+-doped LaPO4 crystalline nanorods. The nanoparticles obtained can be successfully coated with amorphous and porous silica, forming core/shell-type nanorods. Both products reveal intensive green luminescence under UV lamp irradiation. The surface of the core/shell-type product can also be modified with -NH2 groups via silylation procedure, using 3-aminopropyltriethoxysilane as a modifier. Powder X-ray diffraction, transmission electron microscopy, and scanning electron microscopy confirm the desired structure and needle-like shape of the products synthesized. Fourier transform infrared spectroscopy and specific surface area measurements by Brunauer-Emmett-Teller method reveal a successful surface modification with amine groups of the core/shell-type nanoparticles prepared. The nanomaterials synthesized exhibit green luminescence characteristic of Tb3+ ions, as solid powders and aqueous colloids, examined by spectrofluorometry. The in vitro cytotoxicity studies reveal different degree toxicity of the products. LaPO4:Tb3+@SiO2@NH2 exhibits the smallest toxicity against B16F0 mouse melanoma cancer cells and human skin microvascular endothelial cell lines, in contrast to the most toxic LaPO4:Tb3+@SiO2.

Core/shell-type nanorods of Tb3+-doped LaPO4, modified with amine groups, revealing reduced cytotoxicity.

PubMed

Runowski, Marcin; Dąbrowska, Krystyna; Grzyb, Tomasz; Miernikiewicz, Paulina; Lis, Stefan

2013-01-01

A simple co-precipitation reaction between Ln 3+ cations (Ln = lanthanide) and phosphate ions in the presence of polyethylene glycol (PEG), including post-treatment under hydrothermal conditions, leads to the formation of Tb 3+ -doped LaPO 4 crystalline nanorods. The nanoparticles obtained can be successfully coated with amorphous and porous silica, forming core/shell-type nanorods. Both products reveal intensive green luminescence under UV lamp irradiation. The surface of the core/shell-type product can also be modified with -NH 2 groups via silylation procedure, using 3-aminopropyltriethoxysilane as a modifier. Powder X-ray diffraction, transmission electron microscopy, and scanning electron microscopy confirm the desired structure and needle-like shape of the products synthesized. Fourier transform infrared spectroscopy and specific surface area measurements by Brunauer-Emmett-Teller method reveal a successful surface modification with amine groups of the core/shell-type nanoparticles prepared. The nanomaterials synthesized exhibit green luminescence characteristic of Tb 3+ ions, as solid powders and aqueous colloids, examined by spectrofluorometry. The in vitro cytotoxicity studies reveal different degree toxicity of the products. LaPO 4 :Tb 3+ @SiO 2 @NH 2 exhibits the smallest toxicity against B16F0 mouse melanoma cancer cells and human skin microvascular endothelial cell lines, in contrast to the most toxic LaPO 4 :Tb 3+ @SiO 2 .

The electrooxidation mechanism of formic acid on platinum and on lead ad-atoms modified platinum studied with the kinetic isotope effect

NASA Astrophysics Data System (ADS)

Bełtowska-Brzezinska, M.; Łuczak, T.; Stelmach, J.; Holze, R.

2014-04-01

Kinetics and mechanism of formic acid (FA) oxidation on platinum and upd-lead ad-atoms modified platinum electrodes have been studied using unlabelled and deuterated compounds. Poisoning of the electrode surface by CO-like species was prevented by suppression of dissociative chemisorption of FA due to a fast competitive underpotential deposition of lead ad-atoms on the Pt surface from an acidic solution containing Pb2+ cations. Modification of the Pt electrode with upd lead induced a catalytic effect in the direct electrooxidation of physisorbed FA to CO2. With increasing degree of H/D substitution, the rate of this reaction decreased in the order: HCOOH > DCOOH ≥ HCOOD > DCOOD. HCOOH was oxidized 8.5-times faster on a Pt/Pb electrode than DCOOD. This primary kinetic isotope effect proves that the C-H- and O-H-bonds are simultaneously cleaved in the rate determining step. A secondary kinetic isotope effect was found in the dissociative chemisorption of FA in the hydrogen adsorption-desorption range on a bare Pt electrode after H/D exchange in the C-H bond, wherein the influence of deuterium substitution in the O-H group was negligibly small. Thus the C-H bond cleavage is accompanied by the C-OH and not the O-H bond split in the FA decomposition, producing CO-like species on the Pt surface sites.

Ionic force field optimization based on single-ion and ion-pair solvation properties: Going beyond standard mixing rules

NASA Astrophysics Data System (ADS)

Fyta, Maria; Netz, Roland R.

2012-03-01

Using molecular dynamics (MD) simulations in conjunction with the SPC/E water model, we optimize ionic force-field parameters for seven different halide and alkali ions, considering a total of eight ion-pairs. Our strategy is based on simultaneous optimizing single-ion and ion-pair properties, i.e., we first fix ion-water parameters based on single-ion solvation free energies, and in a second step determine the cation-anion interaction parameters (traditionally given by mixing or combination rules) based on the Kirkwood-Buff theory without modification of the ion-water interaction parameters. In doing so, we have introduced scaling factors for the cation-anion Lennard-Jones (LJ) interaction that quantify deviations from the standard mixing rules. For the rather size-symmetric salt solutions involving bromide and chloride ions, the standard mixing rules work fine. On the other hand, for the iodide and fluoride solutions, corresponding to the largest and smallest anion considered in this work, a rescaling of the mixing rules was necessary. For iodide, the experimental activities suggest more tightly bound ion pairing than given by the standard mixing rules, which is achieved in simulations by reducing the scaling factor of the cation-anion LJ energy. For fluoride, the situation is different and the simulations show too large attraction between fluoride and cations when compared with experimental data. For NaF, the situation can be rectified by increasing the cation-anion LJ energy. For KF, it proves necessary to increase the effective cation-anion Lennard-Jones diameter. The optimization strategy outlined in this work can be easily adapted to different kinds of ions.

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

USGS Publications Warehouse

Kerns, Raymond L.; Mankin, Charles J.

1968-01-01

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

Atrial natriuretic peptide degradation by CPA47 cells: evidence for a divalent cation-independent cell-surface proteolytic activity.

PubMed

Frost, S J; Chen, Y M; Whitson, P A

1992-11-23

Atrial natriuretic peptide (ANP) is rapidly cleared and degraded in vivo. Nonguanylate-cyclase receptors (C-ANPR) and a metalloproteinase, neutral endopeptidase (EC 3.4.24.11) (NEP 24.11), are thought to be responsible for its metabolism. We investigated the mechanisms of ANP degradation by an endothelial-derived cell line, CPA47. CPA47 cells degraded 88% of 125I-ANP after 1 h at 37 degrees C as determined by HPLC. Medium preconditioned by these cells degraded 41% of the 125I-ANP, and this activity was inhibited by a divalent cation chelator, EDTA. Furthermore, a cell-surface proteolytic activity degraded 125I-ANP in the presence of EDTA when receptor-mediated endocytosis was inhibited either by low temperature (4 degrees C) or by hyperosmolarity at 37 degrees C. The metalloproteinase, NEP 24.11, is unlikely to be the cell-surface peptidase because 125I-ANP is degraded by CPA47 cells at 4 degrees C in the presence of 5 mM EDTA. These data indicate that CPA47 cells can degrade ANP by a novel divalent cation-independent cell-surface proteolytic activity.

Effective charge measurements reveal selective and preferential accumulation of anions, but not cations, at the protein surface in dilute salt solutions

PubMed Central

Gokarn, Yatin R; Fesinmeyer, R Matthew; Saluja, Atul; Razinkov, Vladimir; Chase, Susan F; Laue, Thomas M; Brems, David N

2011-01-01

Specific-ion effects are ubiquitous in nature; however, their underlying mechanisms remain elusive. Although Hofmeister-ion effects on proteins are observed at higher (>0.3M) salt concentrations, in dilute (<0.1M) salt solutions nonspecific electrostatic screening is considered to be dominant. Here, using effective charge (Q*) measurements of hen-egg white lysozyme (HEWL) as a direct and differential measure of ion-association, we experimentally show that anions selectively and preferentially accumulate at the protein surface even at low (<100 mM) salt concentrations. At a given ion normality (50 mN), the HEWL Q* was dependent on anion, but not cation (Li+, Na+, K+, Rb+, Cs+, GdnH+, and Ca2+), identity. The Q* decreased in the order F− > Cl− > Br− > NO3− ∼ I− > SCN− > ClO4− ≫ SO42−, demonstrating progressively greater binding of the monovalent anions to HEWL and also show that the SO42− anion, despite being strongly hydrated, interacts directly with the HEWL surface. Under our experimental conditions, we observe a remarkable asymmetry between anions and cations in their interactions with the HEWL surface. PMID:21432935

Atrial natriuretic peptide degradation by CPA47 cells - Evidence for a divalent cation-independent cell-surface proteolytic activity

NASA Technical Reports Server (NTRS)

Frost, S. J.; Chen, Y. M.; Whitson, P. A.

1992-01-01

Atrial natriuretic peptide (ANP) is rapidly cleared and degraded in vivo. Nonguanylate-cyclase receptors (C-ANPR) and a metalloproteinase, neutral endopeptidase (EC 3.4.24.11) (NEP 24.11), are thought to be responsible for its metabolism. We investigated the mechanisms of ANP degradation by an endothelial-derived cell line, CPA47. CPA47 cells degraded 88 percent of 125I-ANP after 1 h at 37 degrees C as determined by HPLC. Medium preconditioned by these cells degraded 41 percent of the 125I-ANP, and this activity was inhibited by a divalent cation chelator, EDTA. Furthermore, a cell-surface proteolytic activity degraded 125I-ANP in the presence of EDTA when receptor-mediated endocytosis was inhibited either by low temperature (4 degrees C) or by hyperosmolarity at 37 degrees C. The metalloproteinase, NEP 24.11, is unlikely to be the cell-surface peptidase because 125I-ANP is degraded by CPA47 cells at 4 degrees C in the presence of 5 mM EDTA. These data indicate that CPA47 cells can degrade ANP by a novel divalent cation-independent cell-surface proteolytic activity.

Mechanistic insights into allosteric regulation of the A 2A adenosine G protein-coupled receptor by physiological cations

DOE PAGES

Ye, Libin; Neale, Chris Andrew; Sljoka, Adnan; ...

2018-04-10

Cations play key roles in regulating G-protein-coupled receptors (GPCRs), although their mechanisms are poorly understood. Here, 19F NMR is used to delineate the effects of cations on functional states of the adenosine A 2A GPCR. While Na + reinforces an inactive ensemble and a partial-agonist stabilized state, Ca 2+ and Mg 2+ shift the equilibrium toward active states. Positive allosteric effects of divalent cations are more pronounced with agonist and a G-protein-derived peptide. In cell membranes, divalent cations enhance both the affinity and fraction of the high affinity agonist-bound state. Molecular dynamics simulations suggest high concentrations of divalent cations bridgemore » specific extracellular acidic residues, bringing TM5 and TM6 together at the extracellular surface and allosterically driving open the G-protein-binding cleft as shown by rigidity-transmission allostery theory. Lastly, an understanding of cation allostery should enable the design of allosteric agents and enhance our understanding of GPCR regulation in the cellular milieu.« less

Mechanistic insights into allosteric regulation of the A 2A adenosine G protein-coupled receptor by physiological cations

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

Ye, Libin; Neale, Chris Andrew; Sljoka, Adnan

Cations play key roles in regulating G-protein-coupled receptors (GPCRs), although their mechanisms are poorly understood. Here, 19F NMR is used to delineate the effects of cations on functional states of the adenosine A 2A GPCR. While Na + reinforces an inactive ensemble and a partial-agonist stabilized state, Ca 2+ and Mg 2+ shift the equilibrium toward active states. Positive allosteric effects of divalent cations are more pronounced with agonist and a G-protein-derived peptide. In cell membranes, divalent cations enhance both the affinity and fraction of the high affinity agonist-bound state. Molecular dynamics simulations suggest high concentrations of divalent cations bridgemore » specific extracellular acidic residues, bringing TM5 and TM6 together at the extracellular surface and allosterically driving open the G-protein-binding cleft as shown by rigidity-transmission allostery theory. Lastly, an understanding of cation allostery should enable the design of allosteric agents and enhance our understanding of GPCR regulation in the cellular milieu.« less

Crystal Structure of Garnet-Related Li-Ion Conductor Li7–3xGaxLa3Zr2O12: Fast Li-Ion Conduction Caused by a Different Cubic Modification?

PubMed Central

2016-01-01

Li-oxide garnets such as Li7La3Zr2O12 (LLZO) are among the most promising candidates for solid-state electrolytes to be used in next-generation Li-ion batteries. The garnet-structured cubic modification of LLZO, showing space group Ia-3d, has to be stabilized with supervalent cations. LLZO stabilized with Ga3+ shows superior properties compared to LLZO stabilized with similar cations; however, the reason for this behavior is still unknown. In this study, a comprehensive structural characterization of Ga-stabilized LLZO is performed by means of single-crystal X-ray diffraction. Coarse-grained samples with crystal sizes of several hundred micrometers are obtained by solid-state reaction. Single-crystal X-ray diffraction results show that Li7–3xGaxLa3Zr2O12 with x > 0.07 crystallizes in the acentric cubic space group I-43d. This is the first definite record of this cubic modification for LLZO materials and might explain the superior electrochemical performance of Ga-stabilized LLZO compared to its Al-stabilized counterpart. The phase transition seems to be caused by the site preference of Ga3+. 7Li NMR spectroscopy indicates an additional Li-ion diffusion process for LLZO with space group I-43d compared to space group Ia-3d. Despite all efforts undertaken to reveal structure–property relationships for this class of materials, this study highlights the potential for new discoveries. PMID:27019548

Synthesis and microwave modification of CuO nanoparticles: crystallinity and morphological variations, catalysis, and gas sensing.

PubMed

Yang, Chao; Xiao, Feng; Wang, Jide; Su, Xintai

2014-12-01

CuO nanoparticles with different morphologies were synthesized by chemical precipitation and subsequently modified by microwave hydrothermal processing. The nanoparticles were precipitated by the introduction of a strong base to an aqueous solution of copper cations in the presence/absence of the polyethylene glycol and urea additives. The modification of the nanoparticles was subsequently carried out by a microwave hydrothermal treatment of suspensions of the precipitates, precipitated with and without the additives. X-ray powder diffraction analysis indicated that the crystallinity and crystallite size of the CuO nanoparticles increased after the microwave hydrothermal modification. Microscopy observations revealed the morphology changes induced by microwave hydrothermal processing. The thermal decomposition of ammonium perchlorate and the detection of volatile gases were performed to evaluate the catalytic and gas sensing properties of the synthesized CuO nanoparticles. Copyright © 2014 Elsevier Inc. All rights reserved.

Protein modification via alkyne hydrosilylation using a substoichiometric amount of ruthenium(ii) catalyst† †Dedicated to Professor Stuart L. Schreiber on the occasion of his 60th birthday. ‡ ‡Electronic supplementary information (ESI) available. See DOI: 10.1039/c6sc05313k Click here for additional data file.

PubMed Central

Kwan, Terence T.-L.; Boutureira, Omar; Frye, Elizabeth C.; Walsh, Stephen J.; Gupta, Moni K.; Wallace, Stephen; Wu, Yuteng; Zhang, Fengzhi; Sore, Hannah F.; Galloway, Warren R. J. D.; Chin, Jason W.; Welch, Martin; Bernardes, Gonçalo J. L.

2017-01-01

Transition metal catalysis has emerged as a powerful strategy to expand synthetic flexibility of protein modification. Herein, we report a cationic Ru(ii) system that enables the first example of alkyne hydrosilylation between dimethylarylsilanes and O-propargyl-functionalized proteins using a substoichiometric amount or low-loading of Ru(ii) catalyst to achieve the first C–Si bond formation on full-length substrates. The reaction proceeds under physiological conditions at a rate comparable to other widely used bioorthogonal reactions. Moreover, the resultant gem-disubstituted vinylsilane linkage can be further elaborated through thiol–ene coupling or fluoride-induced protodesilylation, demonstrating its utility in further rounds of targeted modifications. PMID:28966779

Reconditioning perovskite films in vapor environments through repeated cation doping

NASA Astrophysics Data System (ADS)

Boonthum, Chirapa; Pinsuwan, Kusuma; Ponchai, Jitprabhat; Srikhirin, Toemsak; Kanjanaboos, Pongsakorn

2018-06-01

Perovskites have attracted considerable attention for application as high-efficiency photovoltaic devices owing to their low-cost and low-temperature fabrication. A good surface and high crystallinity are necessary for high-performance devices. We examine the negative effects of chemical ambiences on the perovskite crystal formation and morphology. The repeated cation doping (RCD) technique was developed to remedy these issues by gradually dropping methylammonium ions on top of about-to-form perovskite surfaces to cause recrystallization. RCD promotes pinhole-free, compact, and polygonal-like surfaces under various vapor conditions. Furthermore, it enhances the electronic properties and crystallization. The benefits of RCD extend beyond perovskites under vapor ambiences, as it can improve regular and wasted perovskites.

Quantitative analysis of adsorptive interactions of ionic and neutral pharmaceuticals and other chemicals with the surface of Escherichia coli cells in aquatic environment.

PubMed

Cho, Chul-Woong; Park, Jeong-Soo; Zhao, Yufeng; Yun, Yeoung-Sang

2017-08-01

Since Escherichia coli is ubiquitous in nature and has been applied to biological, chemical, and environmental processes, molecular-level understanding of adsorptive interactions between chemicals and the bacterial surface is of great importance. To characterise the adsorption properties of the surface of E. coli cells in aquatic environment, the binding affinities (log K d ) of calibration compounds were experimentally measured, and then based on the values and numerically well-defined molecular interaction forces, i.e. linear free energy relationship (LFER) descriptors, a predictive model was developed. The examined substances are composed of cations, anions, and neutral compounds, and the used LFER descriptors are excess molar refraction (E), dipolarity/polarisability (S), H-bonding acidity (A) and basicity (B), McGowan volume (V), and coulombic interactions of cations (J + ) and anions (J - ). In experimental results, adsorption of anions on the bacterial surface was not observed, while cations exhibited high affinities. In case of neutral compounds, their low quantities were adsorbed, however whose affinities were mostly lower than those of cations. In a LFER study, it was shown that cationic interaction term has the best correlation in R 2 of 0.691 and sequential additions of S, A, and V help to increase the prediction accuracy. The LFER model (log K d  = - 0.72-0.79 S + 0.81 A + 0.41 V + 0.85 J + ) could predict the log K d in R 2 of 0.871 and SE of 0.402 log unit, and then to check robustness and predictability of the model, we internally validated it by a leave-one-out cross validation (Q 2 LOO ) study. As a result, the Q 2 LOO value was estimated to be 0.826, which was larger than standard of model acceptability (>0.5). Copyright © 2017 Elsevier Ltd. All rights reserved.

X-Ray diffraction and resonance shear measurement of nano-confined ionic liquids.

PubMed

Tomita, Kazuhito; Mizukami, Masashi; Nakano, Shinya; Ohta, Noboru; Yagi, Naoto; Kurihara, Kazue

2018-05-23

X-ray diffraction measurement at the SPring-8 synchrotron was employed to investigate the structures of two types of imidazolium-based ionic liquids (ILs), 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C4mim][NTF2]) and 1-butyl-3-methylimidazolium tetrafluoroborate ([C4mim][BF4]), confined between silica surfaces by varying the surface separation distances of ca. 500 nm (bulk liquid), ca. 10 nm, and ca. 2 nm (hard wall thickness). The obtained diffraction profiles and intensities were discussed by considering the structures and properties of the nano-confined ILs between the silica surfaces investigated by resonance shear measurement (RSM) and molecular dynamics simulation (MD) in our previous reports. [C4mim][NTf2] showed two diffraction peaks at q = 8.8 nm-1 (spacing d = 0.71 nm) and at q = 14.0 nm-1 (spacing d = 0.45 nm) at the greatest distance (D = ca. 500 nm), which were assigned to the interval between the same ions (anion-anion or cation-cation) within the polar network of [C4mim][NTf2] and the interval between the neighboring anion-cation, respectively. The positions of these two peaks remained the same at D = ca. 10 nm and at the hard wall (D = ca. 2 nm) and their intensity factor increased, indicating that both the cation and anion existed in the same layer. This result was consistent with the checkerboard structure of [C4mim][NTf2] on the silica surface computer simulated in our previous studies. On the other hand, [C4mim][BF4] showed a peak at q = 15.4 nm-1 (spacing d = 0.41 nm) corresponding to the anion-cation interval at the greatest distance (D = ca. 500 nm). This peak became broader and weaker at D = ca. 12 nm and at D = ca. 2 nm.

Removal of contaminants from landfill leachates by filtration through glauconitic greensands

USGS Publications Warehouse

Spoljaric, N.; Crawford, W.A.

1979-01-01

Passing landfill leachate through glauconitic greensand filters reduces the heavy metal cation content, lessens the unpleasant odor, and diminishes the murkiness of the leachate. The capability of the greensand to trap metal cations is increased by prolonging the contact time between the leachate and the greensand. Flushing the charged greensand filter with water does not cause significant release of cations back into solution, suggesting that polluted greensand might be disposed of at landfill sites without endangering the quality of either ground or surface water. ?? 1979 Springer Verlag New York Inc.

Role of ion hydration for the differential capacitance of an electric double layer.

PubMed

Caetano, Daniel L Z; Bossa, Guilherme V; de Oliveira, Vinicius M; Brown, Matthew A; de Carvalho, Sidney J; May, Sylvio

2016-10-12

The influence of soft, hydration-mediated ion-ion and ion-surface interactions on the differential capacitance of an electric double layer is investigated using Monte Carlo simulations and compared to various mean-field models. We focus on a planar electrode surface at physiological concentration of monovalent ions in a uniform dielectric background. Hydration-mediated interactions are modeled on the basis of Yukawa potentials that add to the Coulomb and excluded volume interactions between ions. We present a mean-field model that includes hydration-mediated anion-anion, anion-cation, and cation-cation interactions of arbitrary strengths. In addition, finite ion sizes are accounted for through excluded volume interactions, described either on the basis of the Carnahan-Starling equation of state or using a lattice gas model. Both our Monte Carlo simulations and mean-field approaches predict a characteristic double-peak (the so-called camel shape) of the differential capacitance; its decrease reflects the packing of the counterions near the electrode surface. The presence of hydration-mediated ion-surface repulsion causes a thin charge-depleted region close to the surface, which is reminiscent of a Stern layer. We analyze the interplay between excluded volume and hydration-mediated interactions on the differential capacitance and demonstrate that for small surface charge density our mean-field model based on the Carnahan-Starling equation is able to capture the Monte Carlo simulation results. In contrast, for large surface charge density the mean-field approach based on the lattice gas model is preferable.

Simultaneous Sterilization With Surface Modification Of Plastic Bottle By Plasma-Based Ion Implantation

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

Sakudo, N.; Ikenaga, N.; Ikeda, F.

2011-01-07

Dry sterilization of polymeric material is developed. The technique utilizes the plasma-based ion implantation which is same as for surface modification of polymers. Experimental data for sterilization are obtained by using spores of Bacillus subtilis as samples. On the other hand we previously showed that the surface modification enhanced the gas barrier characteristics of plastic bottles. Comparing the implantation conditions for the sterilization experiment with those for the surface modification, we find that both sterilization and surface modification are simultaneously performed in a certain range of implantation conditions. This implies that the present bottling system for plastic vessels will bemore » simplified and streamlined by excluding the toxic peroxide water that has been used in the traditional sterilization processes.« less

Laser surface modification of Yttria Stabilized Zirconia (YSZ) thermal barrier coating on AISI H13 tool steel substrate

NASA Astrophysics Data System (ADS)

Reza, M. S.; Aqida, S. N.; Ismail, I.

2018-03-01

This paper presents laser surface modification of plasma sprayed yttria stabilized zirconia (YSZ) coating to seal porosity defect. Laser surface modification on plasma sprayed YSZ was conducted using 300W JK300HPS Nd: YAG laser at different operating parameters. Parameters varied were laser power and pulse frequency with constant residence time. The coating thickness was measured using IM7000 inverted optical microscope and surface roughness was analysed using two-dimensional Mitutoyo Surface Roughness Tester. Surface roughness of laser surface modification of YSZ H-13 tool steel decreased significantly with increasing laser power and decreasing pulse frequency. The re-melted YSZ coating showed higher hardness properties compared to as-sprayed coating surface. These findings were significant to enhance thermal barrier coating surface integrity for dies in semi-solid processing.

Nano-Al{sub 2}O{sub 3} multilayer film deposition on cotton fabrics by layer-by-layer deposition method

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

Ugur, Sule S., E-mail: sule@mmf.sdu.edu.tr; Sariisik, Merih; Aktas, A. Hakan

Highlights: {yields} Cationic charges were created on the cotton fibre surfaces with 2,3-epoxypropyltrimethylammonium chloride. {yields} Al{sub 2}O{sub 3} nanoparticles were deposited on the cotton fabrics by layer-by-layer deposition. {yields} The fabrics deposited with the Al{sub 2}O{sub 3} nanoparticles exhibit better UV-protection and significant flame retardancy properties. {yields} The mechanical properties were improved after surface film deposition. -- Abstract: Al{sub 2}O{sub 3} nanoparticles were used for fabrication of multilayer nanocomposite film deposition on cationic cotton fabrics by electrostatic self-assembly to improve the mechanical, UV-protection and flame retardancy properties of cotton fabrics. Cotton fabric surface was modified with a chemical reaction tomore » build-up cationic charge known as cationization. Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy, X-ray Photoelectron Spectroscopy and Scanning Electron Microscopy were used to verify the presence of deposited nanolayers. Air permeability, whiteness value, tensile strength, UV-transmittance and Limited Oxygen Index properties of cotton fabrics were analyzed before and after the treatment of Al{sub 2}O{sub 3} nanoparticles by electrostatic self-assemblies. It was proved that the flame retardancy, tensile strength and UV-transmittance of cotton fabrics can be improved by Al{sub 2}O{sub 3} nanoparticle additive through electrostatic self-assembly process.« less

Enhancement of perchlorate removal from groundwater by cationic granular activated carbon: Effect of preparation protocol and surface properties.

PubMed

Hou, Pin; Yan, Zhe; Cannon, Fred S; Yue, Ye; Byrne, Timothy; Nieto-Delgado, Cesar

2018-06-01

In order to obtain a high adsorption capacity for perchlorate, the epoxide-forming quaternary ammonium (EQA) compounds were chemically bonded onto granular activated carbon (GAC) surface by cationic reaction. The optimum preparation condition of the cationic GAC was achieved while applying softwood-based Gran C as the parent GAC, dosing EQA first at a pH of 12, preparation time of 48 h, preparation temperature of 50 °C, and mole ratio of EQA/oxygen groups of 2.5. The most favorable cationic GAC that had the QUAB360 pre-anchored exhibited the highest perchlorate adsorption capacity of 24.7 mg/g, and presented the longest bed volumes (3000 BV) to 2 ppb breakthrough during rapid small scale column tests (RSSCTs), which was 150 times higher than that for the pristine Gran C. This was attributed to its higher nitrogen amount (1.53 At%) and higher positive surface charge (0.036 mmol/g) at pH 7.5. Also, there was no leaching of the quaternary ammonium detected in the effluent of the RSSCTs, indicating there was no secondary pollution occurring during the perchlorate removal process. Overall, this study provides an effective and environmental-friendly technology for improving GAC perchlorate adsorption capacity for groundwater treatment. Copyright © 2018 Elsevier Ltd. All rights reserved.

Influence of alkyl chain length and anion species on ionic liquid structure at the graphite interface as a function of applied potential

NASA Astrophysics Data System (ADS)

Li, Hua; Wood, Ross J.; Endres, Frank; Atkin, Rob

2014-07-01

Atomic force microscopy (AFM) force measurements elucidate the effect of cation alkyl chain length and the anion species on ionic liquid (IL) interfacial structure at highly ordered pyrolytic graphite (HOPG) surfaces as a function of potential. Three ILs are examined: 1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([HMIM] FAP), 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([EMIM] FAP), and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM] TFSA). The step-wise force-distance profiles indicate the ILs adopt a multilayered morphology near the surface. When the surface is biased positively or negatively versus Pt quasireference electrode, both the number of steps, and the force required to rupture each step increase, indicating stronger interfacial structure. At all potentials, push-through forces for [HMIM] FAP are the highest, because the long alkyl chain results in strong cohesive interactions between cations, leading to well-formed layers that resist the AFM tip. The most layers are observed for [EMIM] FAP, because the C2 chains are relatively rigid and the dimensions of the cation and anion are similar, facilitating neat packing. [EMIM] TFSA has the smallest push-through forces and fewest layers, and thus the weakest interfacial structure. Surface-tip attractive forces are measured for all ILs. At the same potential, the attractions are the strongest for [EMIM] TFSA and the weakest for [HMIM] FAP because the interfacial layers are better formed for the longer alkyl chain cation. This means interfacial forces are stronger, which masks the weak attractive forces.

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

Chen, Zonghai; Amine, Khalil; Belharouak, Ilias

An active material for an electrochemical device wherein a surface of the active material is modified by a surface modification agent, wherein the surface modification agent is an organometallic compound.

Surface modification of porous titanium with rice husk as space holder

NASA Astrophysics Data System (ADS)

Wang, Xinsheng; Hou, Junjian; Liu, Yanpei

2018-06-01

Porous titanium was characterized after its surface modification by acid and alkali solution immersion. The results show that the acid surface treatment caused the emergence of flocculent sodium titanate and induced apatite formation. The surface modification of porous titanium promotes biological activation, and the application of porous titanium is also improved as an implant material because of the existence of C and Si.

The adsorption of alkyl-dimethyl-benzyl-ammonium chloride onto cotton nonwoven hydroentangled substrates at the solid-liquid interface is minimized by additive chemistries

USDA-ARS?s Scientific Manuscript database

Quaternary ammonium compounds, commonly referred to as quats, are cationic surfactants widely used as the active biocide ingredient for disposable disinfecting wipes. The cationic nature of quats results in a strong ionic interaction and adsorption onto wipes materials that have an anionic surface ...

Engineering of dendrimer surfaces to enhance transepithelial transport and reduce cytotoxicity.

PubMed

Jevprasesphant, Rachaneekorn; Penny, Jeffrey; Attwood, David; McKeown, Neil B; D'Emanuele, Antony

2003-10-01

To evaluate the cytotoxicity, permeation, and transport mechanisms of PAMAM dendrimers and surface-modified cationic PAMAM dendrimers using monolayers of the human colon adenocarcinoma cell line, Caco-2. Cytotoxicity was determined using the MTT assay. The effect of dendrimers on monolayer integrity was determined from measurements of transepithelial electrical resistance (TEER) and [14C]mannitol apparent permeability coefficient (Papp). The Papp of dendrimers through monolayers was measured in both the apical (A)-to-basolateral (B) and B --> A directions at 4 degrees C and 37 degrees C and also in the presence and absence of ethylenediamine tetraacetic acid (EDTA) and colchicine. The cytotoxicity and permeation of dendrimers increased with both concentration and generation. The cytotoxicity of cationic dendrimers (G2, G3, G4) was greater than that of anionic dendrimers (G2.5, G3.5) but was reduced by conjugation with lauroyl chloride: the least cytotoxic conjugates were those with six attached lauroyl chains. At 37 degrees C the Papp of cationic dendrimers was higher than that of anionic dendrimers and, in general, increased with the number of attached lipid chains. Cationic dendrimers decreased TEER and significantly increased the Papp of mannitol. Modified dendrimers also reduced TEER and caused a more marked increase in the Papp of mannitol. The Papp values of dendrimers and modified dendrimers were higher in the presence of EDTA, lower in the presence of colchicine, and lower at 4 degrees C than at 37 degrees C. The properties of dendrimers may be significantly modified by surface engineering. Conjugation of cationic PAMAM dendrimers with lauroyl chloride decreased their cytotoxicity and increased their permeation through Caco-2 cell monolayers. Both PAMAM dendrimers and lauroyl-PAMAM dendrimer conjugates can cross epithelial monolayers by paracellular and transcellular pathways.

Quantitative assessment of surface functionality effects on microglial uptake and retention of PAMAM dendrimers

NASA Astrophysics Data System (ADS)

Liaw, Kevin; Gök, Ozgul; DeRidder, Louis B.; Kannan, Sujatha; Kannan, Rangaramanujam M.

2018-04-01

Dendrimers are a promising class of polymeric nanoparticles for delivery of therapeutics and diagnostics. Polyamidoamine (PAMAM) dendrimers have shown significant efficacy in many animal models, with performance dependent on surface functionalities. Understanding the effects of end groups on biological interactions is critical for rational design of dendrimer-mediated therapies. In this study, we quantify the cellular trafficking kinetics (endocytosis and exocytosis) of generation 4 neutral (D4-OH), cationic (D4-NH2), anionic (D3.5-COOH), and generation 6 neutral (D6-OH) PAMAM dendrimers to investigate the nanoscale effects of surface functionality and size on cellular interactions. Resting and LPS-activated microglia were studied due to their central roles in dendrimer therapies for central nervous system disorders. D4-OH exhibits greater cellular uptake and lower retention than the larger D6-OH. D4-OH and D3.5-COOH exhibit similar trafficking kinetics, while D4-NH2 exhibits significant membrane interactions, resulting in faster cell association but lower internalization. Cationic charge may also enhance vesicular escape for greater cellular retention and preferential partitioning to nuclei. LPS activation further improves uptake of dendrimers, with smaller and cationic dendrimers experiencing the greatest increases in uptake compared to resting microglia. These studies have implications for the dependence of trafficking pathway on dendrimer properties and inform the design of dendrimer constructs tailored to specific therapeutic needs. Cationic dendrimers are ideal for delivering genetic materials to nuclei, but toxicity may be a limiting factor. Smaller, neutral dendrimers are best suited for delivering high levels of therapeutics in acute neuroinflammation, while larger or cationic dendrimers provide robust retention for sustained release of therapeutics in longer-term diseases.

Effect of La3+ substitution with Gd3+ on the resistive switching properties of La0.7Sr0.3MnO3 thin films

NASA Astrophysics Data System (ADS)

Lee, Hong-Sub; Park, Chang-Sun; Park, Hyung-Ho

2014-05-01

This study demonstrated that the resistive switching voltage of perovskite manganite material could be controlled by A-site cation substitution in "A" MnO3 perovskite manganite structure. A partial substitution of La3+ in La0.7Sr0.3MnO3 with smaller cation Gd3+ induced A-site vacancy of the largest Sr2+ cation with surface segregation of SrOy due to ionic size mismatch, and the induced vacancies reduced migration energy barrier. The operating voltage decreased from 3.5 V to 2.5 V due to a favorable condition for electrochemical migration and redox of oxygen ions. Moreover, surface-segregated SrOy was enhanced with Gd-substitution and the SrOy reduced Schottky-like barrier height and resistive switching ratio from the potential drop and screening effect. The relationship between A-site vacancy generation resulting in surface segregation of SrOy and resistive switching behavior was also investigated by energy resolved x-ray photoelectron spectroscopy, O 1s near edge x-ray absorption spectroscopy, and current voltage measurement.

Comparison of tetrachloromethane sorption to an alkylammonium-clay and an alkyldiammonium-clay

USGS Publications Warehouse

Smith, J.A.; Jaffe, P.R.

1991-01-01

The interlamellar space of Wyoming bentonite (clay) was modified by exchanging either decyltrimethyl-ammonium (DTMA) or decyltrimethyldiammonium (DTMDA) cations for inorganic ions, and tetrachloromethane sorption to the resulting two organoclays from water was studied at 10, 20, and 35??C. Only one end of the 10-carbon alkyl chain of the DTMA cation is attached to the silica surface of the clay mineral, and tetrachloromethane sorption of DTMA-clay is characterized by isotherm linearity, noncompetitive sorption, weak solute uptake, and a relatively low heat of sorption. Both ends of the 10-carbon chain of the DTMDA cation are attached to the silica surface of the clay mineral, and tetrachloromethane sorption to DTMDA-clay is characterized by nonlinear isotherms, competitive sorption, strong solute uptake, and a relatively high, exothermic heat of sorption that varies as a function of the mass of tetrachloromethane sorbed. Therefore, the attachment of both ends of the alkyl chain to the interlamellar mineral surface appears to change the sorption mechanism from a partition-dominated process to an adsorption-dominated process. ?? 1991 American Chemical Society.

Genetic Engineering of Single-Domain Magnetic Bacteria.

DTIC Science & Technology

1992-09-25

siderophore produc- cient but modification-proficient for all the three modifi- tion have been demonstrated in Serratia marcescens cation systems of S...characterization of 3-dehydroquinase cally novel iron(llll) transport system in Serratia marcescens . J from Eschenchia co/i. Biochem J 239: 699-704...should provide valuable infor- lion of rec.c4 mutants. rec.4-independen’t instabilit\\ of alciinatc mnation about the history of the evolution of this

Polyethyleneimine modified poly(Hyaluronic acid) particles with controllable antimicrobial and anticancer effects.

PubMed

Sahiner, Nurettin; Sagbas, Selin; Sahiner, Mehtap; Ayyala, Ramesh S

2017-03-01

Poly(hyaluronic acid) (p(HA)) particles with sizes from few hundred nm to few tens of micrometer were synthesized by using epoxy groups containing crosslinker glycerol diglycidyl ether (GDE) with high yield, 94±5%. P(HA) particles were oxidized by treatment with sodium periodate and then reacted with cationic polyethyleneimine (PEI) at 1:0.5, 1:1, and 1:2 wt ratio of p(HA):PEI to obtain p(HA)-PEI particles. From zeta potential measurements, isoelectronic points of bare p(HA) particles increased to pH 8.7 from 2.7 after modification with cationic PEI. New properties, such as antibacterial property, were attained for p(HA)-PEI after modification. The highest minimum bactericidal concentration (MBC) values were 0.5, 1, and 0.5mg/mL against Escherichia coli, Staphylococcus aureus, and Bacillus subtilis species for 1:0.5 ratio of p(HA)-PEI at 72h incubation time. Moreover, the p(HA)-PEI particles were found to be biocompatible with L929 fibroblast cells, and interestingly, p(HA)-PEI particles were found to inhibit MDA-MB-231 breast and H1299 cancer cell growth depending on amount of PEI in p(HA)-PEI particles. Copyright © 2016 Elsevier Ltd. All rights reserved.

Surface modification of medical implant materials with hydrophilic polymers for enhanced biocompatibility and delivery of therapeutic agents

NASA Astrophysics Data System (ADS)

Urbaniak, Daniel J.

2004-11-01

In the research reported here, the surface modification of medical grade poly(dimethyl siloxane), polyetherurethane, and stainless steel through gamma-radiation grafting of hydrophilic polymers was investigated. Emphasis was placed on developing improved and simplified surface modification methods that produce more stable and more bioacceptible hydrophilic graft surfaces. As a result of this research, new surface modification techniques were developed that yield significantly improved surface stability unachievable using previous surface modification techniques. The surface modification of poly(dimethyl siloxane) with hydrophilic polymers was carried out using gamma radiation initiated graft polymerization. The addition of alkali metal hydroxides afforded a unique way to enhance the grafting of N-vinyl-2 pyrrolidone, dimethylacryamide, 2-methacryloyloxyethyl phosphoryl choline, N,N-dimethyl-N-(methacryloyloxyethyl)-N-(3-sulfopropyl)-ammonium-betaine, N,N-dimethyl-N-(methacrylamidopropyl)-N-(3-sulfopropyl)-ammonium-betaine, and copolymers thereof to silicones. Ethanolamine was found to further enhance the grafting of some hydrophilic polymers to silicone. The resulting hydrophilic surface grafts were resistant to hydrophobic surface rearrangement. This process overcomes previous problems inherent in silicone surface modification. The technique was also found to moderately enhance the grafting of hydrophilic monomers to polyetherurethane and to 316-L stainless steel. The surface modification of 316-L stainless steel was further enhanced by treating the substrates with a chromium III methacrylate bonding agent prior to irradiation. The coatings were evaluated for their potential use as depots for delivering therapeutic agents. The release of ofloxacin from surface-modified poly(dimethyl siloxane) and dexamethasone from surface-modified 316-L stainless steel was evaluated by in-vitro experiments. Therapeutic levels of drugs were released from surface-modified specimens via a burst effect. Improved surface characterization methods were another aspect of this research. New nanomechanical testing techniques were developed and used to evaluate the viscoelastic surface mechanical properties of low modulus surface-modified specimens. Dynamic nanoindentation characterization techniques were designed to measure the storage modulus and loss modulus of compliant viscoelastic substrate surfaces. The results of these experiments were compared with modulus data obtained by conventional dynamic mechanical spectroscopy. Nanoscratch testing methods were also developed that qualitatively compared the abrasion resistance of surface-modified substrates. (Abstract shortened by UMI.)

Adsorption of Aqueous Crude Oil Components on the Basal Surfaces of Clay Minerals: Molecular Simulations Including Salinity and Temperature Effects

DOE PAGES

Greathouse, J. A.; Cygan, R. T.; Fredrich, J. T.; ...

2017-09-28

Molecular simulations of the adsorption of representative organic molecules onto the basal surfaces of various clay minerals were used to assess the mechanisms of enhanced oil recovery associated with salinity changes and water flooding. Simulations at the density functional theory (DFT) and classical levels provide insights into the molecular structure, binding energy, and interfacial behavior of saturate, aromatic, and resin molecules near clay mineral surfaces. Periodic DFT calculations reveal binding geometries and ion pairing mechanisms at mineral surfaces while also providing a basis for validating the classical force field approach. Through classical molecular dynamics simulations, the influence of aqueous cationsmore » at the interface and the role of water solvation are examined to better evaluate the dynamical nature of cation-organic complexes and their co-adsorption onto the clay surfaces. The extent of adsorption is controlled by the hydrophilic nature and layer charge of the clay mineral. All organic species studied showed preferential adsorption on hydrophobic mineral surfaces. However, the anionic form of the resin (decahydro-2-naphthoic acid)—expected to be prevalent at near-neutral pH conditions in petroleum reservoirs—readily adsorbs to the hydrophilic kaolinite surface through a combination of cation pairing and hydrogen bonding with surface hydroxyl groups. Analysis of cation-organic pairing in both the adsorbed and desorbed states reveals a strong preference for organic anions to coordinate with divalent calcium ions rather than monovalent sodium ions, lending support to current theories regarding low-salinity water flooding.« less

Adsorption of Aqueous Crude Oil Components on the Basal Surfaces of Clay Minerals: Molecular Simulations Including Salinity and Temperature Effects

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

Greathouse, J. A.; Cygan, R. T.; Fredrich, J. T.

Molecular simulations of the adsorption of representative organic molecules onto the basal surfaces of various clay minerals were used to assess the mechanisms of enhanced oil recovery associated with salinity changes and water flooding. Simulations at the density functional theory (DFT) and classical levels provide insights into the molecular structure, binding energy, and interfacial behavior of saturate, aromatic, and resin molecules near clay mineral surfaces. Periodic DFT calculations reveal binding geometries and ion pairing mechanisms at mineral surfaces while also providing a basis for validating the classical force field approach. Through classical molecular dynamics simulations, the influence of aqueous cationsmore » at the interface and the role of water solvation are examined to better evaluate the dynamical nature of cation-organic complexes and their co-adsorption onto the clay surfaces. The extent of adsorption is controlled by the hydrophilic nature and layer charge of the clay mineral. All organic species studied showed preferential adsorption on hydrophobic mineral surfaces. However, the anionic form of the resin (decahydro-2-naphthoic acid)—expected to be prevalent at near-neutral pH conditions in petroleum reservoirs—readily adsorbs to the hydrophilic kaolinite surface through a combination of cation pairing and hydrogen bonding with surface hydroxyl groups. Analysis of cation-organic pairing in both the adsorbed and desorbed states reveals a strong preference for organic anions to coordinate with divalent calcium ions rather than monovalent sodium ions, lending support to current theories regarding low-salinity water flooding.« less

The effect of surface charge on the thermal stability and ice recrystallization inhibition activity of antifreeze protein III (AFP III).

PubMed

Deller, R C; Carter, B M; Zampetakis, I; Scarpa, F; Perriman, A W

2018-01-01

The aim of this study was to examine the effect of chemical cationization on the structure and function of antifreeze protein III (AFP III) over an extreme temperature range (-40°C to +90°C) using far-UV synchrotron radiation circular dichroism (SRCD) and ice recrystallization inhibition (IRI) assays. Chemical cationization was able to produce a modified AFP III with a net cationic charge at physiological pH that had enhanced resistance to denaturation at elevated temperatures, with no immediate negative impact on protein structure at subzero temperatures. Furthermore, cationized AFP III retained an IRI activity similar to that of native AFP III. Consequently, chemical cationization may provide a pathway to the development of more robust antifreeze proteins as supplementary cryoprotectants in the cryopreservation of clinically relevant cells. Copyright © 2017. Published by Elsevier Inc.

Polymeric membranes: surface modification for minimizing (bio)colloidal fouling.

PubMed

Kochkodan, Victor; Johnson, Daniel J; Hilal, Nidal

2014-04-01

This paper presents an overview on recent developments in surface modification of polymer membranes for reduction of their fouling with biocolloids and organic colloids in pressure driven membrane processes. First, colloidal interactions such as London-van der Waals, electrical, hydration, hydrophobic, steric forces and membrane surface properties such as hydrophilicity, charge and surface roughness, which affect membrane fouling, have been discussed and the main goals of the membrane surface modification for fouling reduction have been outlined. Thereafter the recent studies on reduction of (bio)colloidal of polymer membranes using ultraviolet/redox initiated surface grafting, physical coating/adsorption of a protective layer on the membrane surface, chemical reactions or surface modification of polymer membranes with nanoparticles as well as using of advanced atomic force microscopy to characterize (bio)colloidal fouling have been critically summarized. Copyright © 2013 Elsevier B.V. All rights reserved.

Advances in the surface modification techniques of bone-related implants for last 10 years

PubMed Central

Qiu, Zhi-Ye; Chen, Cen; Wang, Xiu-Mei; Lee, In-Seop

2014-01-01

At the time of implanting bone-related implants into human body, a variety of biological responses to the material surface occur with respect to surface chemistry and physical state. The commonly used biomaterials (e.g. titanium and its alloy, Co–Cr alloy, stainless steel, polyetheretherketone, ultra-high molecular weight polyethylene and various calcium phosphates) have many drawbacks such as lack of biocompatibility and improper mechanical properties. As surface modification is very promising technology to overcome such problems, a variety of surface modification techniques have been being investigated. This review paper covers recent advances in surface modification techniques of bone-related materials including physicochemical coating, radiation grafting, plasma surface engineering, ion beam processing and surface patterning techniques. The contents are organized with different types of techniques to applicable materials, and typical examples are also described. PMID:26816626

Crystal structures of complexes of the cys-syn-cys isomer of dicyclohexano-18-crown-6 with oxonium hexafluorotantalate and oxonium hexafluoroniobate

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

Fonari, M. S.; Alekseeva, O. A.; Furmanova, N. G.

2007-03-15

The crystal structures of [(cys-syn-cys-dicyclohexano-18-crown-6 . H{sub 3}O)][TaF{sub 6}] and [(cys-syn-cys-dicyclohexano-18-crown-6 . H{sub 3}O)][NbF{sub 6}] complex compounds are determined using X-ray diffraction analysis. The tantalum complex has two polymorphic modifications, namely, the monoclinic (I) and triclinic (II) modifications. The unit cell parameters of these compounds are as follows: a = 8.507(4) A, b = 11.947(5) A, c = 27.392(12) A, {beta} = 93.11(1) deg., Z = 4, and space group P2{sub 1}/n for modification I; and a = 10.828(1) A, b = 11.204(1) A, c = 12.378(1) A, {alpha} = 72.12(1) deg., {beta} = 79.40(1) deg., {gamma} = 73.70(1) deg.,more » Z = 2, and space group P-1 for modification II. The triclinic niobium complex [(cys-syn-cys-dicyclohexano-18-crown-6 . H{sub 3}O)][NbF{sub 6}] (III) with the unit cell parameters a = 10.796(3) A, b = 11.183(3) A, c = 12.352(3) A, {alpha} = 72.364(5) deg., {beta} = 79.577(5) deg., {gamma} = 73.773(4) deg., Z = 2, and space group P-1 is isostructural with tantalum complex II. The structures of all three complexes are ionic in character. The oxonium cation in complexes I-III is encapsulated by the crown ether and thus forms one ordinary and two bifurcated hydrogen bonds with the oxygen atoms of the crown ether. This macrocyclic cation is bound to the anions through the C-H...F contacts (H...F, 2.48-2.58 A). The conformation of the macrocycle in complex I differs substantially from that in complex II (III)« less

EFFECT OF INORGANIC CATIONS ON BACTERICIDAL ACTIVITY OF ANIONIC SURFACTANTS

PubMed Central

Voss, J. G.

1963-01-01

Voss, J. G. (Procter & Gamble Co., Cincinnati, Ohio). Effect of inorganic cations on bactericidal activity of anionic surfactants. J. Bacteriol. 86:207–211. 1963.—The bactericidal effectiveness of two alkyl benzene sulfonates and of three other types of anionic surfactants against Staphylococcus aureus is increased in the presence of low concentrations of divalent cations, especially alkaline earths and metals of group IIB of the periodic table. The cations may act by decreasing the negative charge at the cell surface and increasing adsorption of the surfactant anions, leading to damage to the cytoplasmic membrane and death of the cell. Increased adsorption of surfactant is also found with Escherichia coli, but does not lead to death of the cell. PMID:14058942

Preparation and Characterization of Polyimide Nanocomposites

NASA Technical Reports Server (NTRS)

Orwoll, Robert A.

2002-01-01

Many properties of polymeric materials can be enhanced by dispersing small quantities of clay nanocomposites throughout the polymer. Among the enhancements are increases in modulus and resistance to erosion by atomic oxygen and reductions in thermal expansivity, gas permeability, and flammability. To achieve the full extent of enhancement with these polymer-clay nanocomposites, the clay nanoparticles, which have thicknesses of only one-to-several nanometers and lengths and widths of hundreds of nanometers to micrometers, must be exfoliated one from another and then individually dispersed throughout the polymer. This dispersion is achieved only after alkali metal cations (usually Na(+)) that reside on the surfaces of the nanoparticles have been replaced by organocations (typically a quaternary amine cation). This renders the surface of the nanoparticle a more hospitable interface for the organic polymer matrix. Following the cation exchange, the organic clay is either mixed directly into the polymer or is dispersed in monomer which is later polymerized around the nanoparticle.

Synthesis and characterization of cationic lipid coated magnetic nanoparticles using multiple emulsions as microreactors

NASA Astrophysics Data System (ADS)

Akbaba, Hasan; Karagöz, Uğur; Selamet, Yusuf; Kantarcı, A. Gülten

2017-03-01

The aim of this study was to develop a novel iron oxide nanoparticle synthesis method with in-situ surface coating. For this purpose multiple emulsions were used as microreactors for the first time and magnetic iron oxide particles synthesized in the core of cationic solid lipid nanoparticles. DLS, SEM, TEM, VSM, Raman Spectrometer, XRD, and XPS techniques were performed for characterization of the magnetic nanoparticles. Obtained magnetic nanoparticles are superparamagnetic and no additional process was needed for surface adjustments. They are positively charged as a result of cationic lipid coating and has appropriate particle size (<30 nm) for drug or nucleic acid delivery. Structure analysis showed that magnetic core material is in the form of magnetite. Saturation magnetization value was measured as 15-17 emu g-1 for lipid coated magnetic nanoparticles obtained by multiple emulsion method which is reasonably sufficient for magnetic targeting.

Antimicrobial agent-free hybrid cationic starch/sodium alginate polyelectrolyte films for food packaging materials.

PubMed

Şen, Ferhat; Uzunsoy, İrem; Baştürk, Emre; Kahraman, Memet Vezir

2017-08-15

This study aimed to develop polyelectrolyte structured antimicrobial food packaging materials that do not contain any antimicrobial agents. Cationic starch was synthesized and characterized by FT-IR spectroscopy and 1 H NMR spectroscopy. Its nitrogen content was determined by Kjeldahl method. Polyelectrolyte structured antimicrobial food packaging materials were prepared using starch, cationic starch and sodium alginate. Antimicrobial activity of materials was defined by inhibition zone method (disc diffusion method). Thermal stability of samples was evaluated by TGA and DSC. Hydrophobicity of samples was determined by contact angle measurements. Surface morphology of samples was investigated by SEM. Moreover, gel contents of samples were determined. The obtained results prove that produced food packaging materials have good thermal, antimicrobial and surface properties, and they can be used as food packaging material in many industries. Copyright © 2017 Elsevier Ltd. All rights reserved.

The Influence of Electrolytes on the Mixed Micellization of Equimolar (Monomeric and Dimeric) Surfactants

NASA Astrophysics Data System (ADS)

Alam, Md. Sayem; Siddiq, A. Mohammed; Mandal, Asit Baran

2018-01-01

The influence of halide ions of (sodium salt) electrolytes on the mixed micellization of a cationic gemini (dimeric) surfactant, hexanediyl-1,6-bis(dimethylcetylammonium) bromide (16-6-16) and a cationic conventional (monomeric) surfactant, cetyltrimethylammonium bromide (CTAB) have been investigated. The critical micelle concentration (CMC) of the mixed (16-6-16+CTAB) surfactants was measured by the surface tension measurements. The surface properties: viz., the surfactant concentration required to reduce the surface tension by 20 mN/m ( C 20), the surface pressure at the CMC (ΠCMC), the maximum surface excess concentration at the air/water interface (Γmax), the minimum area per surfactant molecule at the air/water interface ( A min), etc. of the mixed micellar surfactant systems were evaluated. In the absence and presence of electrolytes, the thermodynamic parameters of the mixed micellar surfactant systems were also evaluated.

Solid Solutions of Rare Earth Cations in Mesoporous Anatase Beads and Their Performances in Dye-Sensitized Solar Cells

PubMed Central

Cavallo, Carmen; Salleo, Alberto; Gozzi, Daniele; Di Pascasio, Francesco; Quaranta, Simone; Panetta, Riccardo; Latini, Alessandro

2015-01-01

Solid solutions of the rare earth (RE) cations Pr3+, Nd3+, Sm3+, Gd3+, Er3+ and Yb3+ in anatase TiO2 have been synthesized as mesoporous beads in the concentration range 0.1–0.3% of metal atoms. The solid solutions were have been characterized by XRD, SEM, diffuse reflectance UV-Vis spectroscopy, BET and BJH surface analysis. All the solid solutions possess high specific surface areas, up to more than 100 m2/g. The amount of adsorbed dye in each photoanode has been determined spectrophotometrically. All the samples were tested as photoanodes in dye-sensitized solar cells (DSSCs) using N719 as dye and a nonvolatile, benzonitrile based electrolyte. All the cells were have been tested by conversion efficiency (J–V), quantum efficiency (IPCE), electrochemical impedance spectroscopy (EIS) and dark current measurements. While lighter RE cations (Pr3+, Nd3+) limit the performance of DSSCs compared to pure anatase mesoporous beads, cations from Sm3+ onwards enhance the performance of the devices. A maximum conversion efficiency of 8.7% for Er3+ at a concentration of 0.2% has been achieved. This is a remarkable efficiency value for a DSSC employing N719 dye without co-adsorbents and a nonvolatile electrolyte. For each RE cation the maximum performances are obtained for a concentration of 0.2% metal atoms. PMID:26577287

Impact of managed moorland burning on peat nutrient and base cation status

NASA Astrophysics Data System (ADS)

Palmer, Sheila; Gilpin, Martin; Wearing, Catherine; Johnston, Kerrylyn; Holden, Joseph; Brown, Lee

2013-04-01

Controlled 'patch' burning of moorland vegetation has been used for decades in the UK to stimulate growth of heather (Calluna vulgaris) for game bird habitat and livestock grazing. Typically small patches (300-900 m2) are burned in rotations of 8-25 years. However, our understanding of the short-to-medium term environmental impacts of the practice on these sensitive upland areas has so far been limited by a lack of scientific data. In particular the effect of burning on concentrations of base cations and acid-base status of these highly organic soils has implications both for ecosystem nutrient status and for buffering of acidic waters. As part of the EMBER project peat chemistry data were collected in ten upland blanket peat catchments in the UK. Five catchments were subject to a history of prescribed rotational patch burning. The other five catchments acted as controls which were not subject to burning, nor confounded by other detrimental activities such as drainage or forestry. Soil solution chemistry was also monitored at two intensively studied sites (one regularly burned and one control). Fifty-centimetre soil cores, sectioned into 5-cm intervals, were collected from triplicate patches of four burn ages at each burned site, and from twelve locations at similar hillslope positions at each control site. At the two intensively monitored sites, soil solution chemistry was monitored at four depths in each patch. Across all sites, burned plots had significantly smaller cation exchange capacities, lower concentrations of exchangeable base cations and increased concentrations of exchangeable H+ and Al3+ in near-surface soil. C/N ratios were also lower in burned compared to unburned surface soils. There was no consistent trend between burn age and peat chemistry across all burned sites, possibly reflecting local controls on post-burn recovery rates or external influences on burn management decisions. At the intensively monitored site, plots burned less than two years prior to sampling had significantly smaller exchange capacities and lower concentrations of soil base cations in surface soils relative to plots burned 15-25 years previously. In contrast, surface soil solutions in recently burned plots were enriched in base cations relative to older plots and relative to the control site, possibly due to enhanced leaching at bare soil surfaces. The results offer evidence for an impact of burning on peat nutrient and acid-base status, but suggest that soils recover given time with no further burning.

Biodistribution of charged F(ab')2 photoimmunoconjugates in a xenograft model of ovarian cancer.

PubMed Central

Duska, L. R.; Hamblin, M. R.; Bamberg, M. P.; Hasan, T.

1997-01-01

The effect of charge modification of photoimmunoconjugates (PICs) on their biodistribution in a xenograft model of ovarian cancer was investigated. Chlorin(e6)c(e6) was attached site specifically to the F(ab')2 fragment of the murine monoclonal antibody OC125, directed against human ovarian cancer cells, via poly-1-lysine linkers carrying cationic or anionic charges. Preservation of immunoreactivity was checked by enzyme-linked immunosorbent assay (ELISA). PICs were radiolabelled with 125I and compared with non-specific rabbit IgG PICs after intraperitoneal (i.p.) injection into nude mice. Samples were taken from normal organs and tumour at 3 h and 24 h. Tumour to normal 125I ratios showed that the cationic OC125F(ab')2 PIC had the highest tumour selectivity. Ratios for c(e6) were uniformly higher than for 125I, indicating that c(e6) became separated from 125I. OC125F(ab')2 gave highest tissue values of 125I, followed by cationic OC125F(ab')2 PIC; other species were much lower. The amounts of c(e6) delivered per gram of tumour were much higher for cationic OC125F(ab')2 PIC than for other species. The results indicate that cationic charge stimulates the endocytosis and lysosomal degradation of the OC125F(ab')2-pl-c(e6) that has bound to the i.p. tumour. Positively charged PICs may have applications in the i.p. photoimmunotherapy of minimal residual ovarian cancer. PMID:9062404

Cationic antimicrobial peptides inactivate Shiga toxin-encoding bacteriophages

NASA Astrophysics Data System (ADS)

Del Cogliano, Manuel E.; Hollmann, Axel; Martinez, Melina; Semorile, Liliana; Ghiringhelli, Pablo D.; Maffía, Paulo C.; Bentancor, Leticia V.

2017-12-01

Shiga toxin (Stx) is the principal virulence factor during Shiga toxin-producing Escherichia coli (STEC) infections. We have previously reported the inactivation of bacteriophage encoding Stx after treatment with chitosan, a linear polysaccharide polymer with cationic properties. Cationic antimicrobial peptides (cAMPs) are short linear aminoacidic sequences, with a positive net charge, which display bactericidal or bacteriostatic activity against a wide range of bacterial species. They are promising novel antibiotics since they have shown bactericidal effects against multiresistant bacteria. To evaluate whether cationic properties are responsible for bacteriophage inactivation, we tested seven cationic peptides with proven antimicrobial activity as anti-bacteriophage agents, and one random sequence cationic peptide with no antimicrobial activity as a control. We observed bacteriophage inactivation after incubation with five cAMPs, but no inactivating activity was observed with the random sequence cationic peptide or with the non alpha helical cAMP Omiganan. Finally, to confirm peptide-bacteriophage interaction, zeta potential was analyzed by following changes on bacteriophage surface charges after peptide incubation. According to our results we could propose that: 1) direct interaction of peptides with phage is a necessary step for bacteriophage inactivation, 2) cationic properties are necessary but not sufficient for bacteriophage inactivation, and 3) inactivation by cationic peptides could be sequence (or structure) specific. Overall our data suggest that these peptides could be considered a new family of molecules potentially useful to decrease bacteriophage replication and Stx expression.

A computational study of anion-modulated cation-π interactions.

PubMed

Carrazana-García, Jorge A; Rodríguez-Otero, Jesús; Cabaleiro-Lago, Enrique M

2012-05-24

The interaction of anions with cation-π complexes formed by the guanidinium cation and benzene was thoroughly studied by means of computational methods. Potential energy surface scans were performed in order to evaluate the effect of the anion coming closer to the cation-π pair. Several structures of guanidinium-benzene complexes and anion approaching directions were examined. Supermolecule calculations were performed on ternary complexes formed by guanidinium, benzene, and one anion and the interaction energy was decomposed into its different two- and three-body contributions. The interaction energies were further dissected into their electrostatic, exchange, repulsion, polarization and dispersion contributions by means of local molecular orbital energy decomposition analysis. The results confirm that, besides the electrostatic cation-anion attraction, the effect of the anion over the cation-π interaction is mainly due to polarization and can be rationalized following the changes in the anion-π and the nonadditive (three-body) terms of the interaction. When the cation and the anion are on the same side of the π system, the three-body interaction is anticooperative, but when the anion and the cation are on opposite sides of the π system, the three-body interaction is cooperative. As far as we know, this is the first study where this kind of analysis is carried out with a structured cation as guanidinium with a significant biological interest.

3-Dimensional atomic scale structure of the ionic liquid-graphite interface elucidated by AM-AFM and quantum chemical simulations

NASA Astrophysics Data System (ADS)

Page, Alister J.; Elbourne, Aaron; Stefanovic, Ryan; Addicoat, Matthew A.; Warr, Gregory G.; Voïtchovsky, Kislon; Atkin, Rob

2014-06-01

In situ amplitude modulated atomic force microscopy (AM-AFM) and quantum chemical simulations are used to resolve the structure of the highly ordered pyrolytic graphite (HOPG)-bulk propylammonium nitrate (PAN) interface with resolution comparable with that achieved for frozen ionic liquid (IL) monolayers using STM. This is the first time that (a) molecular resolution images of bulk IL-solid interfaces have been achieved, (b) the lateral structure of the IL graphite interface has been imaged for any IL, (c) AM-AFM has elucidated molecular level structure immersed in a viscous liquid and (d) it has been demonstrated that the IL structure at solid surfaces is a consequence of both thermodynamic and kinetic effects. The lateral structure of the PAN-graphite interface is highly ordered and consists of remarkably well-defined domains of a rhomboidal superstructure composed of propylammonium cations preferentially aligned along two of the three directions in the underlying graphite lattice. The nanostructure is primarily determined by the cation. Van der Waals interactions between the propylammonium chains and the surface mean that the cation is enriched in the surface layer, and is much less mobile than the anion. The presence of a heterogeneous lateral structure at an ionic liquid-solid interface has wide ranging ramifications for ionic liquid applications, including lubrication, capacitive charge storage and electrodeposition.In situ amplitude modulated atomic force microscopy (AM-AFM) and quantum chemical simulations are used to resolve the structure of the highly ordered pyrolytic graphite (HOPG)-bulk propylammonium nitrate (PAN) interface with resolution comparable with that achieved for frozen ionic liquid (IL) monolayers using STM. This is the first time that (a) molecular resolution images of bulk IL-solid interfaces have been achieved, (b) the lateral structure of the IL graphite interface has been imaged for any IL, (c) AM-AFM has elucidated molecular level structure immersed in a viscous liquid and (d) it has been demonstrated that the IL structure at solid surfaces is a consequence of both thermodynamic and kinetic effects. The lateral structure of the PAN-graphite interface is highly ordered and consists of remarkably well-defined domains of a rhomboidal superstructure composed of propylammonium cations preferentially aligned along two of the three directions in the underlying graphite lattice. The nanostructure is primarily determined by the cation. Van der Waals interactions between the propylammonium chains and the surface mean that the cation is enriched in the surface layer, and is much less mobile than the anion. The presence of a heterogeneous lateral structure at an ionic liquid-solid interface has wide ranging ramifications for ionic liquid applications, including lubrication, capacitive charge storage and electrodeposition. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr01219d

Microscale surface modifications for heat transfer enhancement.

PubMed

Bostanci, Huseyin; Singh, Virendra; Kizito, John P; Rini, Daniel P; Seal, Sudipta; Chow, Louis C

2013-10-09

In this experimental study, two surface modification techniques were investigated for their effect on heat transfer enhancement. One of the methods employed the particle (grit) blasting to create microscale indentations, while the other used plasma spray coating to create microscale protrusions on Al 6061 (aluminum alloy 6061) samples. The test surfaces were characterized using scanning electron microscopy (SEM) and confocal scanning laser microscopy. Because of the surface modifications, the actual surface area was increased up to 2.8× compared to the projected base area, and the arithmetic mean roughness value (Ra) was determined to vary from 0.3 μm for the reference smooth surface to 19.5 μm for the modified surfaces. Selected samples with modified surfaces along with the reference smooth surface were then evaluated for their heat transfer performance in spray cooling tests. The cooling system had vapor-atomizing nozzles and used anhydrous ammonia as the coolant in order to achieve heat fluxes up to 500 W/cm(2) representing a thermal management setting for high power systems. Experimental results showed that the microscale surface modifications enhanced heat transfer coefficients up to 76% at 500 W/cm(2) compared to the smooth surface and demonstrated the benefits of these practical surface modification techniques to enhance two-phase heat transfer process.

Plasma assisted surface coating/modification processes - An emerging technology

NASA Technical Reports Server (NTRS)

Spalvins, T.

1987-01-01

A broad understanding of the numerous ion or plasma assisted surface coating/modification processes is sought. An awareness of the principles of these processes is needed before discussing in detail the ion nitriding technology. On the basis of surface modifications arising from ion or plasma energizing and interactions, it can be broadly classified as deposition of distinct overlay coatings (sputtering-dc, radio frequency, magnetron, reactive; ion plating-diode, triode) and surface property modification without forming a discrete coating (ion implantation, ion beam mixing, laser beam irradiation, ion nitriding, ion carburizing, plasma oxidation. These techniques offer a great flexibility and are capable in tailoring desirable chemical and structural surface properties independent of the bulk properties.

Plasma assisted surface coating/modification processes: An emerging technology

NASA Technical Reports Server (NTRS)

Spalvins, T.

1986-01-01

A broad understanding of the numerous ion or plasma assisted surface coating/modification processes is sought. An awareness of the principles of these processes is needed before discussing in detail the ion nitriding technology. On the basis of surface modifications arising from ion or plasma energizing and interactions, it can be broadly classified as deposition of distinct overlay coatings (sputtering-dc, radio frequency, magnetron, reactive; ion plating-diode, triode) and surface property modification without forming a discrete coating (ion implantation, ion beam mixing, laser beam irradiation, ion nitriding, ion carburizing, plasma oxidation). These techniques offer a great flexibility and are capable in tailoring desirable chemical and structural surface properties independent of the bulk properties.

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

PubMed

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

2016-05-18

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

Investigation of oxygen reduction and methanol oxidation reaction activity of PtAu nano-alloy on surface modified porous hybrid nanocarbon supports

NASA Astrophysics Data System (ADS)

Parambath Vinayan, Bhaghavathi; Nagar, Rupali; Ramaprabhu, Sundara

2016-09-01

We investigate the electrocatalytic activity of PtAu alloy nanoparticles supported on various chemically modified carbon morphologies towards oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR). The surface-modification of graphene nanosheets (f-G), multi-walled carbon nanotubes (f-MWNTs) and (graphene nanosheets-carbon nanotubes) hybrid support (f-G-MWNTs) were carried out by soft functionalization method using a cationic polyelectrolyte poly-(diallyldimethyl ammonium chloride). The Pt and PtAu alloy nanoparticles were dispersed over chemically modified carbon supports by sodium-borohydride assisted modified polyol reduction method. The electrochemical performance of all electrocatalysts were studied by half- and full-cell proton exchange membrane fuel cell (PEMFC) measurements and PtAu/f-G-MWNTs catalyst comparatively yielded the best catalytic performance. PEMFC full cell measurements of PtAu/f-G-MWNTs cathode electrocatalyst yield a maximum power density of 319 mW cm-2 at 60 °C without any back pressure,which is 2.1 times higher than that of cathode electrocatalyst Pt on graphene support. The high ORR and MOR activity of PtAu/f-G-MWNTs electrocatalyst is due to the alloying effect and inherent beneficial properties of porous hybrid nanocarbon support.

Geographical trends in 137Cs fallout from the Chernobyl accident and leaching from natural surface soil in Norway.

PubMed

Gjelsvik, Runhild; Steinnes, Eiliv

2013-12-01

In order to follow the turnover of (137)Cs in natural soils and estimate future trends in exposure of livestock, samples of natural surface soils were collected at 0-3 cm depth at 464 sites in 1995 and 463 sites in 2005 covering the country. In both cases the geographical pattern observed was similar to the original distribution from 1986, but the decline of (137)Cs activity in the surface soil was not the same everywhere. In 1995 the (137)Cs reduction since 1986 was found to be considerably greater in coastal areas than farther inland. The main reason for this appears to be the much greater deposition of marine cations such as Mg(2+) and Na(+) in the coastal areas, replacing Cs ions fixed on soil particle surfaces. This cation exchange appeared to be particularly strong near the southern coast where deposition of NH4(+) from transboundary air pollution is evident in addition to the marine cations. During 1995-2005 the (137)Cs decline in the surface soil was more uniform over the country than in the preceding 10-year period but still significantly higher in coastal areas than inland. Differences in precipitation chemistry may have influenced the uptake of (137)Cs in terrestrial food chains. Copyright © 2013 Elsevier Ltd. All rights reserved.

Selective removal of uranium ions from contaminated waters using modified-X nanozeolite.

PubMed

Shakur, H R; Rezaee Ebrahim Saraee, Kh; Abdi, M R; Azimi, G

2016-12-01

In order to efficiently remove of uranium anionic species (which are the most dominant species of uranium in natural water at neutral pH) from contaminated waters, nano-NaX zeolite was synthesized and then modified using various divalent cations (Mg 2+ , Ca 2+ , Mn 2+ ) and ZnO nanoparticles (from 1.7 to 10.3wt%). Different characterization techniques of XRF, XRD, FE-SEM, TEM, FT-IR, and AAS were used to characterize the final synthesized absorbents. Sorption experiments by batch technique were done to study the effect of solid-liquid ratio, initial uranium concentration, contact time and temperature under neutral condition of pH and presence of all anions and cations which are available in the waters. Results showed that although nano-NaX zeolite due to its negative framework charge had a low sorption capacity for adsorption of uranium anionic species, but modification of parent nano-NaX zeolite with ZnO nanoparticles and various cations effectively improved its uranium adsorption capacity. Also, results showed that under optimum condition of pH=7.56, contact time of 60min at 27°C with solid-liquid ratio of 20g/L a maximum uranium removal efficiency of 99.7% can be obtained in the presence of all anions and cations which are available in the drinking waters by NaX/ZnO nanocomposite. Copyright © 2016 Elsevier Ltd. All rights reserved.

Influence of the organic complex concentration on adsorption of herbicide in organic modified montmorillonite

NASA Astrophysics Data System (ADS)

Kaludjerovic, Lazar; Tomic, Zorica; Djurovic, Rada; Milosevic, Maja

2016-04-01

Pesticides are recognized as an important source of potential pollution to soil and water due to their mobility and degradation in soils. Results presented in this paper show impact of the organic complex concentration on the adsorption of herbicides (acetochlor) at the surface of the organic modified montmorillonite. In this work, natural montmorillonite from Bogovina, located near Boljevac municipality, was used for organic modification. Cation-exchange capacity of this montmorillonite was determined by extraction with ammonium acetate (86 mmol/100g of clay). Montmorillonite have been modified first with NaCl and than with two organic complexes, hexadecyltrimethylammonium bromide (HDTMA) and phenyltrimethylammonium chloride (PTMA). For both organic complexes, three saturation concentrations were selected for monitoring of the herbicide adsorption (43 mmol/100g of clay (0.5 CEC), 86 mmol/100g of clay (1 CEC) and 129 mmol/100g of clay (1.5 CEC)). Changes in the properties of the inorganic and organic bentonite have been examined using the X-ray powder diffraction (XRPD) and batch equilibrium method. Increase in basal spacing (d) of montmorillonites saturated with 1.5 CEC of organic cation indicate that sorption of PTMA and HDTMA can exceed the saturation of 1 CEC. Both organic montmorillonites have shown higher uptake of the herbicide, compared to the inorganic montmorillonite. Comparing the values Freundlich coefficients in batch equilibrium method, (presented in the form of log Kf and 1/n), it can be seen that the sorption decreases in the series: 0.5CEC> 1CEC> 1.5CEC> NaM, for both organic montmorillonites.

Synthesis of nanoporous TiO2 materials using a doubly surfactant system and applying them as useful adsorbents

NASA Astrophysics Data System (ADS)

Anbia, Mansoor; Khosravi, Faezeh

Hydrothermal and non-hydrothermal nanoporous TiO2 materials were synthesized via a doubly surfactant route by using cationic cetyltrimethylammonium bromide and anionic sodium dodecyl sulfate surfactants as the molecular template/structure directing agent. Hydrothermal treatment was performed for comparison. The bulk chemical and phase compositions, crystalline structures, particle morphologies, thermal stabilities and surface texturing were determined by means of X-ray powder analysis, SEM and N2 sorptiometry. The nanoporous TiO2 materials were found to have a spherical morphology with a diameter range of 50-200 nm and a high surface area (390 m2 g-1). Hydrothermal and non-hydrothermal nanoporous TiO2 materials were applied for adsorption of heavy metal cations and the toxic organic compound, copper phthalocyanine, from water for evaluation of their adsorption properties. Both nanoporous TiO2 materials were found to have similar adsorption capacities toward heavy metal cations and CuPc. Both hydrothermal and non-hydrothermal TiO2 nanoporous materials were found to have very good potential for application as a new adsorbent especially for adsorbing heavy metal cations from wastewaters.

Method for preparing a sodium/sulfur cell

DOEpatents

Weiner, Steven A.

1978-01-01

A method for preparing a sodium/sulfur cell comprising (A) inserting a solid sodium slug, adapted to be connected to an external circuit, into the anodic reaction zone of a cell subassembly maintained within an inert atmosphere, said cell subassembly comprising a cell container and a tubular cation-permeable barrier disposed within said container such that a first reaction zone is located within cation-permeable barrier and a second reaction zone is located between the outer surface of said cation-permeable barrier and the inner surface of said container, one of said reaction zones being said anodic reaction zone and the other of said reaction zone being a cathodic reaction zone containing a precast composite cathodic reactant comprising a sulfur impregnated porous conductive material connected to said cation permeable barrier and adapted to be connected to said external circuit; and (B) providing closure means for said subassembly and sealing the same to said subassembly at a temperature less than about 100.degree. C. The method of the invention overcomes deficiencies of the prior art methods by allowing preparation of a sodium/sulfur cell without the use of molten reactants and the fill spouts which are required when the cell is filled with molten reactants.

Phosphate barrier on pore-filled cation-exchange membrane for blocking complexing ions in presence of non-complexing ions

NASA Astrophysics Data System (ADS)

Chavan, Vivek; Agarwal, Chhavi; Shinde, Rakesh N.

2018-06-01

In present work, an approach has been used to form a phosphate groups bearing surface barrier on a cation-exchange membrane (CEM). Using optimized conditions, the phosphate bearing monomer bis[2-(methacryloyloxy)ethyl] phosphate has been grafted on the surface of the host poly(ethersulfone) membranes using UV light induced polymerization. The detailed characterizations have shown that less than a micron layer of phosphate barrier is formed without disturbing the original microporous structure of the host membrane. The pores of thus formed membrane have been blocked by cationic-gel formed by in situ UV-initiator induced polymerization of 2-acrylamido-2-methyl-1-propane sulphonic acid along with crosslinker ethylene glycol dimethacrylate in the pores of the membrane. UV-initiator is required for pore-filling as UV light would not penetrate the interior matrix of the membrane. The phosphate functionalized barrier membrane has been examined for permselectivity using a mixture of representative complexing Am3+ ions and non-complexing Cs+ ions. This experiment has demonstrated that complex forming Am3+ ions are blocked by phosphate barrier layer while non-complexing Cs+ ions are allowed to pass through the channels formed by the crosslinked cationic gel.

Chemical and thermal stability of N-heterocyclic ionic liquids in catalytic C-H activation reactions.

PubMed

Chen, Guanyi; Kang, Shujuan; Ma, Qisheng; Chen, Weiqun; Tang, Yongchun

2014-11-01

(1)H-NMR spectrum analyses are applied to study the chemical and thermal stability of selected N-heterocyclic ionic liquids within the reaction system that can highly efficiently activate a C-H bond of methane and convert it into the C-O bond in methanol. Our results indicate that under such reaction conditions involving using a powerful Pt-based catalyst and strong acidic solvent, the aromatic ring of an imidazolium cation becomes unstable generating an ammonium ion (NH(4)(+)). Our results also suggest that the instability of the imidazolium ring is more chemically (participation in reactions) than thermally based. Modifications of the aromatic ring structure such as pyrazolium and triazolium cations can increase the chemical/thermal stability of ionic liquids under these reaction conditions. Copyright © 2014 John Wiley & Sons, Ltd.

Quantitative mapping of intracellular cations in the human amniotic membrane

NASA Astrophysics Data System (ADS)

Moretto, Ph.; Llabador, Y.; Simonoff, M.; Razafindrabe, L.; Bara, M.; Guiet-Bara, A.

1993-05-01

The effect of magnesium and taurine on the permeability of cell membranes to monovalent cations has been investigated using the Bordeaux nuclear microprobe. PIXE and RBS techniques have been used to provide quantitative measurements and ion distributions in the isolated amniotic membrane. This physiological model for cellular exchanges allowed us to reveal the distribution of most elements involved in cellular pathways and the modifications under different experimental conditions of incubation in physiological fluids. The PIXE microanalysis provided an original viewpoint on these mechanisms. Following this first study, the amnion compact lamina was found to play a role which was not, up to now, taken into account in the interpretation of electrophysiological experimentations. The release of some ionic species, such as K +, from the epithelial cells, during immersion in isotonic fluids, could have been hitherto underestimated.

Organically Modified Nanoclay-Reinforced Rigid Polyurethane Films

NASA Astrophysics Data System (ADS)

Park, Yong Tae; Qian, Yuqiang; Lindsay, Chris; Stein, Andreas; Macosko, Christopher

2012-02-01

The nanodispersion of vermiculite in polyurethanes was investigated to produce organoclay-reinforced rigid gas barrier films. Reducing gas transport can improve the insulation performance of closed cell polyurethane foam. In a previous study, the dispersion of vermiculite in polyurethanes without organic modification was not sufficient due to the non-uniform dispersion morphology. When vermiculite was modified by cation exchange with long-chain quaternary ammonium cations, the dispersion in methylene diphenyl diisocyanate (MDI) was significantly improved. Dispersion was improved by combining high intensity dispersive mixing with efficient distributive mixing. Polymerization conditions were also optimized in order to provide a high state of nanodispersion in the polyurethane nanocomposite. The dispersions were characterized using rheological, microscopic and scattering/diffraction techniques. The final nanocomposites showed enhancement of mechanical properties and reduction in permeability to carbon dioxide at low clay concentration (around 2 wt percent).

Synthesis of Monodispersed Ag-Doped Bioactive Glass Nanoparticles via Surface Modification

PubMed Central

Kozon, Dominika; Zheng, Kai; Boccardi, Elena; Liu, Yufang; Liverani, Liliana; Boccaccini, Aldo R.

2016-01-01

Monodispersed spherical Ag-doped bioactive glass nanoparticles (Ag-BGNs) were synthesized by a modified Stöber method combined with surface modification. The surface modification was carried out at 25, 60, and 80 °C, respectively, to investigate the influence of processing temperature on particle properties. Energy-dispersive X-ray spectroscopy (EDS) results indicated that higher temperatures facilitate the incorporation of Ag. Hydroxyapatite (HA) formation on Ag-BGNs was detected upon immersion of the particles in simulated body fluid for 7 days, which indicated that Ag-BGNs maintained high bioactivity after surface modification. The conducted antibacterial assay confirmed that Ag-BGNs had an antibacterial effect on E. coli. The above results thereby suggest that surface modification is an effective way to incorporate Ag into BGNs and that the modified BGNs can remain monodispersed as well as exhibit bioactivity and antibacterial capability for biomedical applications. PMID:28773349

Covalent Surface Modifications of Carbon Nanotubes.

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

Pavia Sanders, Adriana; O'Bryan, Greg

A report meant to document the chemistries investigated by the author for covalent surface modification of CNTs. Oxidation, cycloaddition, and radical reactions were explored to determine their success at covalently altering the CNT surface. Characterization through infrared spectroscopy, Raman spectroscopy, and thermo gravimetric analysis was performed in order to determine the success of the chemistries employed. This report is not exhaustive and was performed for CNT surface modification exploration as it pertains to the "Next Gen" project.

Calorimetric Determination of Thermodynamic Stability of MAX and MXene Phases

DOE PAGES

Sharma, Geetu; Naguib, Michael; Feng, Dawei; ...

2016-11-19

MXenes are layered two dimensional materials with exciting properties useful to a wide range of energy applications. They are derived from ceramics (MAX phases) by leaching and their properties reflect their resulting complex compositions which include intercalating cations and anions and water. Their thermodynamic stability is likely linked to these functional groups but has not yet been addressed by quantitative experimental measurements. We report enthalpies of formation from the elements at 25 °C measured using high temperature oxide melt solution calorimetry for a layered Ti-Al-C MAX phase, and the corresponding Ti-C based MXene. The thermodynamic stability of the Ti 3Cmore » 2T x MXene (Tx stands for anionic surface moieties, and intercalated cations) was assessed by calculating the enthalpy of reaction of the MAX phase (ideal composition Ti 3AlC 2) to form MXene, The very exothermic enthalpy of reaction confirms the stability of MXene in an aqueous environment. The surface terminations (O, OH and F) and cations (Li) chemisorbed on the surface and intercalated in the interlayers play a major role in the thermodynamic stabilization of MXene. These findings help to understand and potentially improve properties and performance by characterizing the energetics of species binding to MXene surfaces during synthesis and in energy storage, water desalination and other applications.« less

Mixed oxide solid solutions

DOEpatents

Magno, Scott; Wang, Ruiping; Derouane, Eric

2003-01-01

The present invention is a mixed oxide solid solution containing a tetravalent and a pentavalent cation that can be used as a support for a metal combustion catalyst. The invention is furthermore a combustion catalyst containing the mixed oxide solid solution and a method of making the mixed oxide solid solution. The tetravalent cation is zirconium(+4), hafnium(+4) or thorium(+4). In one embodiment, the pentavalent cation is tantalum(+5), niobium(+5) or bismuth(+5). Mixed oxide solid solutions of the present invention exhibit enhanced thermal stability, maintaining relatively high surface areas at high temperatures in the presence of water vapor.

Laser modification of macroscopic properties of metal surface layer

NASA Astrophysics Data System (ADS)

Kostrubiec, Franciszek

1995-03-01

Surface laser treatment of metals comprises a number of diversified technological operations out of which the following can be considered the most common: oxidation and rendering surfaces amorphous, surface hardening of steel, modification of selected physical properties of metal surface layers. In the paper basic results of laser treatment of a group of metals used as base materials for electric contacts have been presented. The aim of the study was to test the usability of laser treatment from the viewpoint of requirements imposed on materials for electric contacts. The results presented in the paper refer to two different surface treatment technologies: (1) modification of infusible metal surface layer: tungsten and molybdenum through laser fusing of their surface layer and its crystallization, and (2) modification of surface layer properties of other metals through laser doping of their surface layer with foreign elements. In the paper a number of results of experimental investigations obtained by the team under the author's supervision are presented.

DEVELOPMENT OF A MODEL TO INVESTIGATE RED BLOOD CELL SURFACE CHARACTERISTICS AFTER CRYOPRESERVATION.

PubMed

Gordiyenko, O I; Anikieieva, M O; Rozanova, S L; Kovalenko, S Ye; Kovalenkol, I F; Gordiyenko, E O

2015-01-01

Maintaining cell surface properties after freezing and thawing, characterized in particular by the surface potential and associated with it cell ability to intercellular adhesion, could be used as a characteristic of successful cryopreservation. This study was conducted to research applying different erythrocytes freezing modes and analyses the regimes cryopreservation effect on the cell surface charge and adhesion to microorganisms. Human erythrocytes frozen by three modes. In order to determine adhesion index was used dried bacterial cells of S. thermophilus. The surface charge of erythrocytes was evaluated using Alcian blue cationic dye. The results showed the significant decrease in the lactobacillus adhesion to erythrocytes frozen glycerol and 1,2-propanediol. After erythrocytes were freezen with glycerol and 1,2-propanediol, the cationic dye binding to erythrocytes significantly reduced. AB binding to erythrocytes frozen with PEG-1500 does not differ from control data. Erythrocytes frozen with PEG-1500 mantained surface properties after thawing better, compared to erythrocytes cryopreserved by other methods.

Influence of Nanosegregation on the Surface Tension of Fluorinated Ionic Liquids

PubMed Central

Luís, Andreia; Shimizu, Karina; Araújo, João M. M.; Carvalho, Pedro J.; Lopes-da-Silva, José A.; Canongia Lopes, José N.; Rebelo, Luís Paulo N.; Coutinho, João A. P.; Freire, Mara G.; Pereiro, Ana B.

2017-01-01

We have investigated, both theoretically and experimentally, the balance between the presence of alkyl and perfluoroalkyl side chains on the surface organization and surface tension of fluorinated ionic liquids (FILs). A series of ILs composed of 1-alkyl-3-methylimidazolium cations ([CnC1im] with n = 2, 4, 6, 8, 10 or 12) combined with the perfluorobutanesulfonate anion was used. The surface tensions of the investigated liquid salts are considerably lower than those reported for non-fluorinated ionic liquids. The most surprising and striking feature was the identification, for the first time, of a minimum at n = 8 in the surface tension versus the length of the IL cation alkyl side chain. Supported by molecular dynamic simulations it was found that this trend is a result of the competition between the two nonpolar domains (perfluorinated and aliphatic) on pointing towards the gas-liquid interface, a phenomenon which occurs in ionic liquids with perfluorinated anions. Furthermore, these ionic liquids present the lowest surface entropy reported to date. PMID:27218210

Nanoprobing of the effect of Cu2+ cations on misfolding, interaction and aggregation of amyloid β peptide

PubMed Central

Lv, Zhengjian; Condron, Margaret M.; Teplow, David B.; Lyubchenko, Yuri L.

2012-01-01

Misfolding and aggregation of the amyloid β-protein (Aβ) are hallmarks of Alzheimer’s disease. Both processes are dependent on the environmental conditions, including the presence of divalent cations, such as Cu2+. Cu2+ cations regulate early stages of Aβ aggregation, but the molecular mechanism of Cu2+ regulation is unknown. In this study we applied single molecule AFM force spectroscopy to elucidate the role of Cu2+ cations on interpeptide interactions. By immobilizing one of two interacting Aβ42 molecules on a mica surface and tethering the counterpart molecule onto the tip, we were able to probe the interpeptide interactions in the presence and absence of Cu2+ cations at pH 7.4, 6.8, 6.0, 5.0, and 4.0. The results show that the presence of Cu2+ cations change the pattern of Aβ interactions for pH values between pH 7.4 and pH 5.0. Under these conditions, Cu2+ cations induce Aβ42 peptide structural changes resulting in N–termini interactions within the dimers. Cu2+ cations also stabilize the dimers. No effects of Cu2+ cations on Aβ–Aβ interactions were observed at pH 4.0, suggesting that peptide protonation changes the peptide-cation interaction. The effect of Cu2+ cations on later stages of Aβ aggregation was studied by AFM topographic images. The results demonstrate that substoichiometric Cu2+ cations accelerate the formation of fibrils at pH 7.4 and 5.0, whereas no effect of Cu2+ cations was observed at pH 4.0. Taken together, the combined AFM force spectroscopy and imaging analyses demonstrate that Cu2+ cations promote both the initial and the elongation stages of Aβ aggregation, but protein protonation diminishes the effect of Cu2+. PMID:23143330

Polydopamine-mediated surface modification of scaffold materials for human neural stem cell engineering.

PubMed

Yang, Kisuk; Lee, Jung Seung; Kim, Jin; Lee, Yu Bin; Shin, Heungsoo; Um, Soong Ho; Kim, Jeong Beom; Park, Kook In; Lee, Haeshin; Cho, Seung-Woo

2012-10-01

Surface modification of tissue engineering scaffolds and substrates is required for improving the efficacy of stem cell therapy by generating physicochemical stimulation promoting proliferation and differentiation of stem cells. However, typical surface modification methods including chemical conjugation or physical absorption have several limitations such as multistep, complicated procedures, surface denaturation, batch-to-batch inconsistencies, and low surface conjugation efficiency. In this study, we report a mussel-inspired, biomimetic approach to surface modification for efficient and reliable manipulation of human neural stem cell (NSC) differentiation and proliferation. Our study demonstrates that polydopamine coating facilitates highly efficient, simple immobilization of neurotrophic growth factors and adhesion peptides onto polymer substrates. The growth factor or peptide-immobilized substrates greatly enhance differentiation and proliferation of human NSCs (human fetal brain-derived NSCs and human induced pluripotent stem cell-derived NSCs) at a level comparable or greater than currently available animal-derived coating materials (Matrigel) with safety issues. Therefore, polydopamine-mediated surface modification can provide a versatile platform technology for developing chemically defined, safe, functional substrates and scaffolds for therapeutic applications of human NSCs. Copyright © 2012 Elsevier Ltd. All rights reserved.

Surface nucleation and independent growth of Ce(OH)4 within confinement space on modified carbon black surface to prepare nano-CeO2 without agglomeration

NASA Astrophysics Data System (ADS)

Zhang, Xinyue; Xia, Chunhui; Li, Kaitao; Lin, Yanjun

2018-06-01

Highly dispersed negative carboxyl groups can be formed on carbon black (CB) surface modified with strong nitric acid. Therefore positive cations can be uniformly absorbed by carboxyl groups and precipitated within a confinement space on modified CB surface to prepare highly dispersed nanomaterials. In this paper, the formation and dispersion status of surface negative carboxyl groups, adsorption status of Ce3+, surface confinement nucleation, crystallization and calcination process were studied by EDS, SEM, and laser particle size analysis. The results show that the carboxyl groups formed on modified CB surface are highly dispersed, and Ce3+ cations can be uniformly anchored by carboxyl groups. Therefore, highly dispersed Ce3+ can react with OH- within a confinement surface region to form positive nano-Ce(OH)4 nuclei which also can be adsorbed by electrostatic attraction. After independent growth of Ce(OH)4 without agglomeration, highly dispersed CeO2 nanoparticles without agglomeration can be prepared together with the help of effectively isolates by CO2 released in the combustion of CB.

Surface nucleation and independent growth of Ce(OH)4 within confinement space on modified carbon black surface to prepare nano-CeO2 without agglomeration

NASA Astrophysics Data System (ADS)

Zhang, Xinyue; Xia, Chunhui; Li, Kaitao; Lin, Yanjun

2018-04-01

Highly dispersed negative carboxyl groups can be formed on carbon black (CB) surface modified with strong nitric acid. Therefore positive cations can be uniformly absorbed by carboxyl groups and precipitated within a confinement space on modified CB surface to prepare highly dispersed nanomaterials. In this paper, the formation and dispersion status of surface negative carboxyl groups, adsorption status of Ce3+, surface confinement nucleation, crystallization and calcination process were studied by EDS, SEM, and laser particle size analysis. The results show that the carboxyl groups formed on modified CB surface are highly dispersed, and Ce3+ cations can be uniformly anchored by carboxyl groups. Therefore, highly dispersed Ce3+ can react with OH- within a confinement surface region to form positive nano-Ce(OH)4 nuclei which also can be adsorbed by electrostatic attraction. After independent growth of Ce(OH)4 without agglomeration, highly dispersed CeO2 nanoparticles without agglomeration can be prepared together with the help of effectively isolates by CO2 released in the combustion of CB.

Fabrication and surface-modification of implantable microprobes for neuroscience studies

NASA Astrophysics Data System (ADS)

Cao, H.; Nguyen, C. M.; Chiao, J. C.

2012-06-01

In this work implantable micro-probes for central nervous system (CNS) studies were developed on silicon and polyimide substrates. The probes which contained micro-electrode arrays with different surface modifications were designed for implantation in the CNS. The electrode surfaces were modified with nano-scale structures that could greatly increase the active surface area in order to enhance the electrochemical current outputs while maintaining micro-scale dimensions of the electrodes and probes. The electrodes were made of gold or platinum, and designed with different sizes. The silicon probes were modified by silicon nanowires fabricated with the vapor-liquid-solid mechanism at high temperatures. With polyimide substrates, the nanostructure modification was carried out by applying concentrated gold or silver colloid solutions onto the micro-electrodes at room temperature. The surfaces of electrodes before and after modification were observed by scanning electron microscopy. The silicon nanowire-modified surface was characterized by cyclic voltammetry. Experiments were carried out to investigate the improvement in sensing performance. The modified electrodes were tested with H2O2, electrochemical L-glutamate and dopamine. Comparisons between electrodes with and without nanostructure modification were conducted showing that the modifications have enhanced the signal outputs of the electrochemical neurotransmitter sensors.

Root Surface Bio-modification with Erbium Lasers- A Myth or a Reality??

PubMed Central

Lavu, Vamsi; Sundaram, Subramoniam; Sabarish, Ram; Rao, Suresh Ranga

2015-01-01

The objective of this literature review was to critically review the evidence available in the literature regarding the expediency of erbium family of lasers for root bio modification as a part of periodontal therapy. The literature search was performed on the Pubmed using MeSH words such as "lasers/therapeutic use, scaling, dental calculus, tooth root/anatomy and histology, ultrasonic therapy". The studies were screened and were grouped as follows: those evaluating a) efficacy for calculus removal with the Erbium family of laser b) root surface changes following Er YAG and Er Cr YSGG application c) comparative studies of the Er YAG, Er Cr YSGG lasers versus conventional methods of root surface modification d) Bio compatibility of root surface following Erbium laser treatment e) Studies on the combined efficacy of laser root modification with conventional methods towards root surface bio-modification f) Studies on effectiveness of root surface bio-modification prior to root coverage procedures. In conclusion, the erbium family has a proven anti-bacterial action, predictable calculus removal, minimal root substance removal, and appears to favor cell attachment. The Erbium family of lasers appears to be a useful adjunct for the management of periodontal disease. PMID:25713635

Synthesis and Characterization of Modified BiOCl and Their Application in Adsorption of Low-Concentration Dyes from Aqueous Solution

NASA Astrophysics Data System (ADS)

Zhao, Qihang; Xing, Yongxing; Liu, Zhiliang; Ouyang, Jing; Du, Chunfang

2018-03-01

The synthesis and characterization of BiOCl and Fe3+-grafted BiOCl (Fe/BiOCl) is reported that are developed as efficient adsorbents for the removal of cationic dyes rhodamine B (RhB) and methylene blue (MB) as well as anionic dyes methyl orange (MO) and acid orange (AO) from aqueous solutions with low concentration of 0.01 0.04 mmol/L. Characterizations by various techniques indicate that Fe3+ grafting induced more open porous structure and higher specific surface area. Both BiOCl and Fe/BiOCl with negatively charged surfaces showed excellent adsorption efficiency toward cationic dyes, which could sharply reach 99.6 and nearly 100% within 3 min on BiOCl and 97.0 and 98.0% within 10 min on Fe/BiOCl for removing RhB and MB, respectively. However, Fe/BiOCl showed higher adsorption capacity than BiOCl toward ionic dyes. The influence of initial dye concentration, temperature, and pH value on the adsorption capacity is comprehensively studied. The adsorption process of RhB conforms to Langmuir adsorption isotherm and pseudo-second-order kinetic feature. The excellent adsorption capacities of as-prepared adsorbents toward cationic dyes are rationalized on the basis of electrostatic attraction as well as open porous structure and high specific surface area. In comparison with Fe/BiOCl, BiOCl displays higher selective efficiency toward cationic dyes in mixed dye solutions.

Tuning light emission of PbS nanocrystals from infrared to visible range by cation exchange

PubMed Central

Binetti, Enrico; Striccoli, Marinella; Sibillano, Teresa; Giannini, Cinzia; Brescia, Rosaria; Falqui, Andrea; Comparelli, Roberto; Corricelli, Michela; Tommasi, Raffaele; Agostiano, Angela; Curri, M Lucia

2015-01-01

Colloidal semiconductor nanocrystals, with intense and sharp-line emission between red and near-infrared spectral regions, are of great interest for optoelectronic and bio-imaging applications. The growth of an inorganic passivation layer on nanocrystal surfaces is a common strategy to improve their chemical and optical stability and their photoluminescence quantum yield. In particular, cation exchange is a suitable approach for shell growth at the expense of the nanocrystal core size. Here, the cation exchange process is used to promote the formation of a CdS passivation layer on the surface of very small PbS nanocrystals (2.3 nm in diameter), blue shifting their optical spectra and yielding luminescent and stable nanostructures emitting in the range of 700–850 nm. Structural, morphological and compositional investigation confirms the nanocrystal size contraction after the cation-exchange process, while the PbS rock-salt crystalline phase is retained. Absorption and photoluminescence spectroscopy demonstrate the growth of a passivation layer with a decrease of the PbS core size, as inferred by the blue-shift of the excitonic peaks. The surface passivation strongly increases the photoluminescence intensity and the excited state lifetime. In addition, the nanocrystals reveal increased stability against oxidation over time. Thanks to their absorption and emission spectral range and the slow recombination dynamics, such highly luminescent nano-objects can find interesting applications in sensitized photovoltaic cells and light-emitting devices. PMID:27877842

Modification of clay barriers with a cationic surfactant to improve the retention of pesticides in soils.

PubMed

Rodríguez-Cruz, M S; Sánchez-Martín, M J; Andrades, M S; Sánchez-Camazano, M

2007-01-10

In this work, the efficiency of reactive clay barriers in the immobilisation of organic pesticides in a sandy soil was studied. Reactive barriers were prepared by modification of montmorillonite, kaolinite and palygorskite clay minerals, and of a clayey soil with the cationic surfactant octadecyltrimethylammonium bromide (ODTMA). Percolation curves of the pesticides linuron, atrazine and metalaxyl of different hydrophobic character, were obtained in columns packed with a natural sandy soil with these barriers intercalated under saturated flow conditions. The cumulative curves in the unmodified soil indicated a leaching of pesticides greater than 85% of the total amount of compound added. After barrier intercalation, the breakthrough curves (BTC) indicated a dramatic decrease in the amounts of linuron leached in all columns and a significant modification of the leaching kinetics of atrazine and metalaxyl. Retardation factors, R, of the pesticides in the columns were significantly correlated with the organic matter content (OM) derived from the ODTMA of the organo clay/soil barriers (r2>or=0.78). Significant correlations were also found between these R factors and the pore volume values corresponding to the maximum peaks of the BTCs (r2=0.83; p<0.01) or the total volumes leached (r2=0.44; p<0.05) for the pesticides atrazine and metalaxyl. The results obtained point to the interest in the use of reactive clay barriers for almost complete immobilisation of hydrophobic pesticides or for decreasing the leaching of moderately hydrophobic pesticides coming from point-like sources of pollution. These barriers would avoid the generation of elevated concentrations of these compounds in the soils due to their rapid washing.

The development of a wide field UV imager for planetary space missions

NASA Astrophysics Data System (ADS)

Molyneux, Philippa Mary

2012-03-01

This thesis describes experimental work carried out on bilayer manganites with the general composition R{2-2x}A{1+2x}Mn2O7, where R is a trivalent rare earth cation and A is a divalent alkaline-earth cation. Experiments have been carried out primarily using Scanning Tunnelling Microscopy (STM) and Spectroscopy (STS); bulk electrical transport, MPMS and LEED measurements have also been made. The primary results are obtained from single crystal samples of PrSr2Mn2O7. This compound provides a surface suitable for STM study when cleaved at low temperature in ultra-high vacuum: atomic resolution can be readily achieved. The expected square lattice is observed, together with a larger scale surface modulation which is not presently explained. In some areas of the PrSr2Mn2O7 surface a population of adatoms and surface vacancies is observed. STS data indicate that adatoms carry a negative charge compared to the rest of the surface, and vacancies a positive charge: the adatoms and vacancies are interpreted as oxygen adatoms and oxygen vacancies. A detailed study is made of the oxygen adatoms and vacancies: this is believed to be the firrst such study made on a manganite surface. Oxygen adatoms on the PrSr2Mn2O7 surface are found to be mobile: hopping and adatom-vacancy recombination are observed. Additional results are reported on the layered manganite compound La{2-2x}Sr{1+2x}Mn2O7 at a range of cation doping x. For the LaSr2Mn2O7 compound (x = 0.5) spectroscopic variation has been identified in a variable-temperature STS survey. This indicates the coexistence of two surface electronic phases, possibly the charge ordered and antiferromagnetic phases.

Non-Surface Activity of Cationic Amphiphilic Diblock Copolymers

NASA Astrophysics Data System (ADS)

Ranjan Nayak, Rati; Yamada, Tasuku; Matsuoka, Hideki

2011-09-01

Cationic amphiphilic diblock copolymers containing quaternized poly (2-vinylpyridine) chain as a hydrophilic segment (PIp-b-PNMe2VP) were synthesized by living anionic polymerization. By IR measurement, we confirmed the quaternization of the polymer (PIp-b-PNMe2VP), and determined the degree of quaternization by conductometric titration. The surface tension experiment showed that the polymers are non-surface active in nature. The foam formation of the polymer solutions was also investigated with or without added salt. Almost no foam formation behavior was observed without added salt, while a little foam was observed in the presence of 1M NaCl. The critical micelle concentration (cmc) of the diblock copolymers with 3 different chain lengths was measured by the static light scattering method. The cmc values obtained in this study were much lower than the values obtained for anionic non-surface active diblock polymers studied previously. The hydrodynamic radii of the polymer micelle increased slightly in the presence of 1 M NaCl. The transmission electron microscopic images revealed spherical micelles in pure water. In the presence of salt, the cmc values increased as was the case for anionic polymers, which is unlike conventional surfactant systems but consistent with non-surface active anionic block copolymers. The microviscosity of the micelle core was evaluated using Coumarin-153 as a fluorescent anisotropy probe using steady-sate fluorescence depolarization. Non-surface activity has been proved to be universal for ionic amphiphilic block copolymers both for anionic and cationic. Hence, the origin of non-surface activity is not the charged state of water surface itself, but should be an image charge repulsion at the air/water interface.

Non-surface activity and micellization behavior of cationic amphiphilic block copolymer synthesized by reversible addition-fragmentation chain transfer process.

PubMed

Ghosh, Arjun; Yusa, Shin-ichi; Matsuoka, Hideki; Saruwatari, Yoshiyuki

2011-08-02

Cationic amphiphilic diblock copolymers of poly(n-butylacrylate)-b-poly(3-(methacryloylamino)propyl)trimethylammonium chloride) (PBA-b-PMAPTAC) with various hydrophobic and hydrophilic chain lengths were synthesized by a reversible addition-fragmentation chain transfer (RAFT) process. Their molecular characteristics such as surface activity/nonactivity were investigated by surface tension measurements and foam formation observation. Their micelle formation behavior and micelle structure were investigated by fluorescence probe technique, static and dynamic light scattering (SLS and DLS), etc., as a function of hydrophilic and hydrophobic chain lengths. The block copolymers were found to be non-surface active because the surface tension of the aqueous solutions did not change with increasing polymer concentration. Critical micelle concentration (cmc) of the polymers could be determined by fluorescence and SLS measurements, which means that these polymers form micelles in bulk solution, although they were non-surface active. Above the cmc, the large blue shift of the emission maximum of N-phenyl-1-naphthylamine (NPN) probe and the low micropolarity value of the pyrene probe in polymer solution indicate the core of the micelle is nonpolar in nature. Also, the high value of the relative intensity of the NPN probe and the fluorescence anisotropy of the 1,6-diphenyl-1,3,5-hexatriene (DPH) probe indicated that the core of the micelle is highly viscous in nature. DLS was used to measure the average hydrodynamic radii and size distribution of the copolymer micelles. The copolymer with the longest PBA block had the poorest water solubility and consequently formed micelles with larger size while having a lower cmc. The "non-surface activity" was confirmed for cationic amphiphilic diblock copolymers in addition to anionic ones studied previously, indicating the universality of non-surface activity nature.

Kanamycin Sulphate Loaded PLGA-Vitamin-E-TPGS Long Circulating Nanoparticles Using Combined Coating of PEG and Water-Soluble Chitosan

PubMed Central

Mustafa, Sanaul

2017-01-01

Kanamycin sulphate (KS) is a Mycobacterium tuberculosis protein synthesis inhibitor. Due to its intense hydrophilicity, KS is cleared from the body within 8 h. KS has a very short plasma half-life (2.5 h). KS is used in high concentrations to reach the therapeutic levels in plasma, which results in serious nephrotoxicity/ototoxicity. To overcome aforementioned limitations, the current study aimed to develop KS loaded PLGA-Vitamin-E-TPGS nanoparticles (KS-PLGA-TPGS NPs), to act as an efficient carrier for controlled delivery of KS. To achieve a substantial extension in blood circulation, a combined design, affixation of polyethylene glycol (PEG) to KS-PLGA-TPGS NPs and adsorption of water-soluble chitosan (WSC) (cationic deacetylated chitin) to particle surface, was raised for surface modification of NPs. Surface modified NPs (KS-PEG-WSC NPs) were prepared to provide controlled delivery and circulate in the bloodstream for an extended period of time, thus minimizing dosing frequency. In vivo pharmacokinetics and in vivo biodistribution following intramuscular administration were investigated. NPs surface charge was close to neutral +3.61 mV and significantly affected by the WSC coating. KS-PEG-WSC NPs presented striking prolongation in blood circulation, reduced protein binding, and long drew-out the blood circulation half-life with resultant reduced kidney sequestration vis-à-vis KS-PLGA-TPGS NPs. The studies, therefore, indicate the successful formulation development of KS-PEG-WSC NPs with reduced frequency of dosing of KS indicating low incidence of nephrotoxicity/ototoxicity. PMID:28352475

Photoluminescence of CuInS2 nanocrystals: effect of surface modification

NASA Astrophysics Data System (ADS)

Kim, Young-Kuk; Cho, Young-Sang; Chung, Kookchae; Choi, Chul-Jin

2011-09-01

We have synthesized highly luminescent Cu-In-S(CIS) nanocrystals (NCs) by heating the mixture of metal carboxylates and alkylthiol under inert atmosphere. We modified the surface of CIS NCs with zinc carboxylate and subsequent injection of alkylthiol. As a result of the surface modification, highly luminescent CIS@ZnS core/shell nanocrystals were synthesized. The luminescence quantum yield (QY) of best CIS@ZnS NCs was above 50%, which is 10 times higher than the initial QY of CIS NCs before surface modification (QY=3%). Detailed study on the luminescence mechanism implies that etching of the surface of NCs by dissociated carboxylate group (CH3COO-) and formation of epitaxial shell by Zn with sulfur from alkylthiol efficiently removed the surface defects which are known to be major non-radiative recombination sites in semiconductor nanocrystals. In this study, we developed a novel surface modification route for monodispersed highly luminescent Cu-In-S NCs with less toxic and highly stable precursors. Investigation with the timeand the temperature-dependent photoluminescence showed that the trap related emission was minimized by surface modification and the donor-acceptor pair recombination was enhanced by controlling copper stoichiometry.xb

Sorption of chlorophenols on microporous minerals: mechanism and influence of metal cations, solution pH, and humic acid.

PubMed

Yang, Hui; Hu, Yuanan; Cheng, Hefa

2016-10-01

Sorption of 2-chlorophenol (2-CP), 2,4-dichlorophenol (2,4-DCP), and 2,4,6-trichlorophenol (2,4,6-TCP) on a range of dealuminated zeolites were investigated to understand the mechanism of their sorption on microporous minerals, while the influence of common metal cations, solution pH, and humic acid was also studied. Sorption of chlorophenols was found to increase with the hydrophobicity of the sorbates and that of the microporous minerals, indicating the important role of hydrophobic interactions, while sorption was also stronger in the micropores of narrower sizes because of greater enhancement of the dispersion interactions. The presence of metal cations could enhance chlorophenol sorption due to the additional electrostatic attraction between metal cations exchanged into the mineral micropores and the chlorophenolates, and this effect was apparent on the mineral sorbent with a high density of surface cations (2.62 sites/nm(2)) in its micropores. Under circum-neutral or acidic conditions, neutral chlorophenol molecules adsorbed into the hydrophobic micropores through displacing the "loosely bound" water molecules, while their sorption was negligible under moderately alkaline conditions due to electrostatic repulsion between the negatively charged zeolite framework and anionic chlorophenolates. The influence of humic acid on sorption of chlorophenols on dealuminated Y zeolites suggests that its molecules did not block the micropores but created a secondary sorption sites by forming a "coating layer" on the external surface of the zeolites. These mechanistic insights could help better understand the interactions of ionizable chlorophenols and metal cations in mineral micropores and guide the selection and design of reusable microporous mineral sorbents for sorptive removal of chlorophenols from aqueous stream.

Cation-Inhibited Transport of Graphene Oxide Nanomaterials in Saturated Porous Media: The Hofmeister Effects.

PubMed

Xia, Tianjiao; Qi, Yu; Liu, Jing; Qi, Zhichong; Chen, Wei; Wiesner, Mark R

2017-01-17

Transport of negatively charged nanoparticles in porous media is largely affected by cations. To date, little is known about how cations of the same valence may affect nanoparticle transport differently. We observed that the effects of cations on the transport of graphene oxide (GO) and sulfide-reduced GO (RGO) in saturated quartz sand obeyed the Hofmeister series; that is, transport-inhibition effects of alkali metal ions followed the order of Na + < K + < Cs + , and those of alkaline earth metal ions followed the order of Mg 2+ < Ca 2+ < Ba 2+ . With batch adsorption experiments and microscopic data, we verified that cations having large ionic radii (and thus being weakly hydrated) interacted with quartz sand and GO and RGO more strongly than did cations of small ionic radii. In particular, the monovalent Cs + and divalent Ca 2+ and Ba 2+ , which can form inner-sphere complexes, resulted in very significant deposition of GO and RGO via cation bridging between quartz sand and GO and RGO, and possibly via enhanced straining, due to the enhanced aggregation of GO and RGO from cation bridging. The existence of the Hofmeister effects was further corroborated with the interesting observation that cation bridging was more significant for RGO, which contained greater amounts of carboxyl and phenolic groups (i.e., metal-complexing moieties) than did GO. The findings further demonstrate that transport of nanoparticles is controlled by the complex interplay between nanoparticle surface functionalities and solution chemistry constituents.

Nanoscale surface modification of Li-rich layered oxides for high-capacity cathodes in Li-ion batteries

NASA Astrophysics Data System (ADS)

Lan, Xiwei; Xin, Yue; Wang, Libin; Hu, Xianluo

2018-03-01

Li-rich layered oxides (LLOs) have been developed as a high-capacity cathode material for Li-ion batteries, but the structural complexity and unique initial charging behavior lead to several problems including large initial capacity loss, capacity and voltage fading, poor cyclability, and inferior rate capability. Since the surface conditions are critical to electrochemical performance and the drawbacks, nanoscale surface modification for improving LLO's properties is a general strategy. This review mainly summarizes the surface modification of LLOs and classifies them into three types of surface pre-treatment, surface gradient doping, and surface coating. Surface pre-treatment usually introduces removal of Li2O for lower irreversible capacity while surface doping is aimed to stabilize the structure during electrochemical cycling. Surface coating layers with different properties, protective layers to suppress the interface side reaction, coating layers related to structural transformation, and electronic/ionic conductive layers for better rate capability, can avoid the shortcomings of LLOs. In addition to surface modification for performance enhancement, other strategies can also be investigated to achieve high-performance LLO-based cathode materials.

DNA molecules on periodically microstructured lipid membranes: Localization and coil stretching

NASA Astrophysics Data System (ADS)

Hochrein, Marion B.; Leierseder, Judith A.; Golubović, Leonardo; Rädler, Joachim O.

2007-02-01

We explore large scale conformations of DNA molecules adsorbed on curved surfaces. For that purpose, we investigate the behavior of DNA adsorbed on periodically shaped cationic lipid membranes. These unique membrane morphologies are supported on grooved, one-dimensionally periodic microstructured surfaces. Strikingly, we find that these periodically structured membranes are capable to stretch DNA coils. We elucidate this phenomenon in terms of surface curvature dependent potential energy attained by the adsorbed DNA molecules. Due to it, DNA molecules undergo a localization transition causing them to stretch by binding to highly curved sections (edges) of the supported membranes. This effect provides a new venue for controlling conformations of semiflexible polymers such as DNA by employing their interactions with specially designed biocompatible surfaces. We report the first experimental observation of semiflexible polymers unbinding transition in which DNA molecules unbind from one-dimensional manifolds (edges) while remaining bound to two-dimensional manifolds (cationic membranes).

Design of Perovskite Oxides as Anion-Intercalation-Type Electrodes for Supercapacitors: Cation Leaching Effect.

PubMed

Liu, Yu; Dinh, Jim; Tade, Moses O; Shao, Zongping

2016-09-14

Oxygen ions can be exploited as a charge carrier to effectively realize a new type of anion-intercalation supercapacitor. In this study, to get some useful guidelines for future materials development, we comparatively studied SrCoO3-δ (SC), Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF), and Co3O4 as electrodes in supercapacitors with aqueous alkaline electrolyte. The effect of interaction between the electrode materials with the alkaline solution was focused on the structure and specific surface area of the electrode material, and ultimately the electrochemical performance was emphasized. Both BSCF and SC were found to experience cation leaching in alkaline solution, resulting in an increase in the specific surface area of the material, but overleaching caused the damage of perovskite structure of BSCF. Barium leaching was more serious than strontium, and the cation leaching was component dependent. Although high initial capacitance was achieved for BSCF, it was not a good candidate as intercalation-type electrode for supercapacitor because of poor cycling stability from serious Ba(2+) and Sr(2+) leaching. Instead, SC was a favorable electrode candidate for practical use in supercapacitors due to its high capacity and proper cation leaching capacity, which brought beneficial effect on cycling stability. It is suggested that cation leaching effect should be seriously considered in the development of new perovskite materials as electrodes for supercapacitors.

Quantitative Characterization of Non-Classic Polarization of Cations on Clay Aggregate Stability

PubMed Central

Hu, Feinan; Li, Hang; Liu, Xinmin; Li, Song; Ding, Wuquan; Xu, Chenyang; Li, Yue; Zhu, Longhui

2015-01-01

Soil particle interactions are strongly influenced by the concentration, valence and ion species and the pH of the bulk solution, which will also affect aggregate stability and particle transport. In this study, we investigated clay aggregate stability in the presence of different alkali ions (Li+, Na+, K+, and Cs+) at concentrations from10−5 to 10−1 mol L−1. Strong specific ion effects on clay aggregate stability were observed, and showed the order Cs+>K+>Na+>Li+. We found that it was not the effects of ion size, hydration, and dispersion forces in the cation–surface interactions but strong non-classic polarization of adsorbed cations that resulted in these specific effects. In this study, the non-classic dipole moments of each cation species resulting from the non-classic polarization were estimated. By comparing non-classic dipole moments with classic values, the observed dipole moments of adsorbed cations were up to 104 times larger than the classic values for the same cation. The observed non-classic dipole moments sharply increased with decreasing electrolyte concentration. We conclude that strong non-classic polarization could significantly suppress the thickness of the diffuse layer, thereby weakening the electric field near the clay surface and resulting in improved clay aggregate stability. Even though we only demonstrated specific ion effects on aggregate stability with several alkali ions, our results indicate that these effects could be universally important in soil aggregate stability. PMID:25874864

Fullerene ion chemistry: a journey of discovery and achievement

PubMed Central

Böhme, Diethard K.

2016-01-01

An account is provided of the extraordinary features of buckminster fullerene cations and their chemistry that we discovered in our Ion Chemistry Laboratory at York University (Canada) during a ‘golden’ period of research in the early 1990s, just after C60 powder became available. We identified new chemical ways of C60 ionization and tracked novel chemistry of C60n+ as a function of charge state (n=1–3) with some 50 different reagent molecules. We found that multiple charges enhance reaction rates and diversify reaction products and mechanisms. Strong electrostatic interactions with reagent molecules were seen to reduce barriers to carbon surface bonding and charge-separation reactions, while intramolecular Coulomb repulsion appeared to localize charge on the surface or the substituent and so influence higher order chemistry, including ‘spindle’, ‘star’, ‘fuzzy ball’, ‘ball-and-chain’ and dimer ion formation. We introduced the notion of ‘apparent’ gas-phase acidity with measurements of proton-transfer reactions of multiply charged fullerene cations. We also explored the attachment of atomic metal cations to C60 and their subsequent reactions. All these findings were applied to the possible chemistry of fullerene cations in the interstellar medium with a focus on multiply charged fullerene ion formation and the intervention of fullerene cations in fullerene derivatization and molecular synthesis, with a view to their possible future detection. This article is part of the themed issue ‘Fullerenes: past, present and future, celebrating the 30th anniversary of Buckminster Fullerene’. PMID:27501972

Analysis of the sorption properties of different soils using water vapour adsorption and potentiometric titration methods

NASA Astrophysics Data System (ADS)

Skic, Kamil; Boguta, Patrycja; Sokołowska, Zofia

2016-07-01

Parameters of specific surface area as well as surface charge were used to determine and compare sorption properties of soils with different physicochemical characteristics. The gravimetric method was used to obtain water vapour isotherms and then specific surface areas, whereas surface charge was estimated from potentiometric titration curves. The specific surface area varied from 12.55 to 132.69 m2 g-1 for Haplic Cambisol and Mollic Gleysol soil, respectively, and generally decreased with pH (R=0.835; α = 0.05) and when bulk density (R=-0.736; α = 0.05) as well as ash content (R=-0.751; α = 0.05) increased. In the case of surface charge, the values ranged from 63.00 to 844.67 μmol g-1 Haplic Fluvisol and Mollic Gleysol, respecively. Organic matter gave significant contributions to the specific surface area and cation exchange capacity due to the large surface area and numerous surface functional groups, containing adsorption sites for water vapour molecules and for ions. The values of cation exchange capacity and specific surface area correlated linearly at the level of R=0.985; α = 0.05.

Mechanistic study of wettability alteration of oil-wet sandstone surface using different surfactants

NASA Astrophysics Data System (ADS)

Hou, Bao-feng; Wang, Ye-fei; Huang, Yong

2015-03-01

Different analytical methods including Fourier transform infrared (FTIR), atomic force microscopy (AFM), zeta potential measurements, contact angle measurements and spontaneous imbibition tests were utilized to make clear the mechanism for wettability alteration of oil-wet sandstone surface using different surfactants. Results show that among three types of surfactants including cationic surfactants, anionic surfactants and nonionic surfactants, the cationic surfactant CTAB demonstrates the best effect on the wettability alteration of oil-wet sandstone surface. The positively charged head groups of CTAB molecules and carboxylic acid groups from crude oil could interact to form ion pairs, which could be desorbed from the solid surface and solubilized into the micelle formed by CTAB. Thus, the water-wetness of the solid surface is improved. Nonionic surfactant TX-100 could be adsorbed on oil-wet sandstone surface through hydrogen bonds and hydrophobic interaction to alter the wettability of oil-wet solid surface. The wettability alteration of oil-wet sandstone surface using the anionic surfactant POE(1) is caused by hydrophobic interaction. Due to the electrostatic repulsion between the anionic surfactant and the negatively charged surface, POE(1) shows less effect on the wettability alteration of oil-wet sandstone surface.

Distance-Based Tear Lactoferrin Assay on Microfluidic Paper Device Using Interfacial Interactions on Surface-Modified Cellulose.

PubMed

Yamada, Kentaro; Henares, Terence G; Suzuki, Koji; Citterio, Daniel

2015-11-11

"Distance-based" detection motifs on microfluidic paper-based analytical devices (μPADs) allow quantitative analysis without using signal readout instruments in a similar manner to classical analogue thermometers. To realize a cost-effective and calibration-free distance-based assay of lactoferrin in human tear fluid on a μPAD not relying on antibodies or enzymes, we investigated the fluidic mobilities of the target protein and Tb(3+) cations used as the fluorescent detection reagent on surface-modified cellulosic filter papers. Chromatographic elution experiments in a tear-like sample matrix containing electrolytes and proteins revealed a collapse of attractive electrostatic interactions between lactoferrin or Tb(3+) and the cellulosic substrate, which was overcome by the modification of the paper surface with the sulfated polysaccharide ι-carrageenan. The resulting μPAD based on the fluorescence emission distance successfully analyzed 0-4 mg mL(-1) of lactoferrin in complex human tear matrix with a lower limit of detection of 0.1 mg mL(-1) by simple visual inspection. Assay results of 18 human tear samples including ocular disease patients and healthy volunteers showed good correlation to the reference ELISA method with a slope of 0.997 and a regression coefficient of 0.948. The distance-based quantitative signal and the good batch-to-batch fabrication reproducibility relying on printing methods enable quantitative analysis by simply reading out "concentration scale marks" printed on the μPAD without performing any calibration and using any signal readout instrument.

Impact of ionic liquids in aqueous solution on bacterial plasma membranes studied with molecular dynamics simulations.

PubMed

Lim, Geraldine S; Zidar, Jernej; Cheong, Daniel W; Jaenicke, Stephan; Klähn, Marco

2014-09-04

The impact of five different imidazolium-based ionic liquids (ILs) diluted in water on the properties of a bacterial plasma membrane is investigated using molecular dynamics (MD) simulations. Cations considered are 1-octyl-3-methylimidazolium (OMIM), 1-octyloxymethyl-3-methylimidazolium (OXMIM), and 1-tetradecyl-3-methylimidazolium (TDMIM), as well as the anions chloride and lactate. The atomistic model of the membrane bilayer is designed to reproduce the lipid composition of the plasma membrane of Gram-negative Escherichia coli. Spontaneous insertion of cations into the membrane is observed in all ILs. Substantially more insertions of OMIM than of OXMIM occur and the presence of chloride reduces cation insertions compared to lactate. In contrast, anions do not adsorb onto the membrane surface nor diffuse into the bilayer. Once inserted, cations are oriented in parallel to membrane lipids with cation alkyl tails embedded into the hydrophobic membrane core, while the imidazolium-ring remains mostly exposed to the solvent. Such inserted cations are strongly associated with one to two phospholipids in the membrane. The overall order of lipids decreased after OMIM and OXMIM insertions, while on the contrary the order of lipids in the vicinity of TDMIM increased. The short alkyl tails of OMIM and OXMIM generate voids in the bilayer that are filled by curling lipids. This cation induced lipid disorder also reduces the average membrane thickness. This effect is not observed after TDMIM insertions due to the similar length of cation alkyl chain and the fatty acids of the lipids. This lipid-mimicking behavior of inserted TDMIM indicates a high membrane affinity of this cation that could lead to an enhanced accumulation of cations in the membrane over time. Overall, the simulations reveal how cations are inserted into the bacterial membrane and how such insertions change its properties. Moreover, the different roles of cations and anions are highlighted and the fundamental importance of cation alkyl chain length and its functionalization is demonstrated.

Characterization of polylactic co-glycolic acid nanospheres modified with PVA and DDAB

NASA Astrophysics Data System (ADS)

Mulia, Kamarza; Satyapertiwi, Dwiantari; Devina, Ranee; Krisanti, Elsa

2017-02-01

The common treatment for diabetic retinopathy is corticosteroids intravitreal injection that sometimes lead to complications. Dexamethasone-loaded polylactic co-glycolic acid (PLGA) nanospheres, modified with dioctadecyldimethylammonium bromide (DDAB) as the cationic surfactant, is expected to prolong drug retention time. Zeta potential of the PLGA nanospheres prepared using non-ionic surfactant PVA and DDAB confirmed the cationic surfactant increase the surface charge of the PLGA nanospheres. The optimal formulation based on the particle size and high positive surface charge was the PLGA-DDAB nanospheres. SEM analysis showed spherical morphology of the nanospheres having diameter 626.9 ± 98.01 nm positive zeta potential of +22.5 mV.

Asp-Gly based peptides confined at the surface of cationic gemini surfactant aggregates.

PubMed

Brizard, Aurélie; Dolain, Christel; Huc, Ivan; Oda, Reiko

2006-04-11

Cationic gemini surfactants complexed with anionic oligoglycine-aspartate (called gemini peptides hereafter) were synthesized, and their aggregation behaviors were studied. The effects of the hydrophobic chain length (C10-C22) and the length of the oligoglycine (0-4) were investigated, and it was clearly shown by critical micellar concentration, Krafft temperature, and isothermal surface pressure measurements that the hydrophobic effect and interpeptidic interaction influence the aggregation behavior in a cooperative manner. Below their Krafft temperatures, some of them formed both hydro- and organogels with three-dimensional networks and the Fourier transform infrared measurements show the presence of interpeptidic hydrogen bonds.

Electrostatically driven resonance energy transfer in "cationic" biocompatible indium phosphide quantum dots.

PubMed

Devatha, Gayathri; Roy, Soumendu; Rao, Anish; Mallick, Abhik; Basu, Sudipta; Pillai, Pramod P

2017-05-01

Indium Phosphide Quantum Dots (InP QDs) have emerged as an alternative to toxic metal ion based QDs in nanobiotechnology. The ability to generate cationic surface charge, without compromising stability and biocompatibility, is essential in realizing the full potential of InP QDs in biological applications. We have addressed this challenge by developing a place exchange protocol for the preparation of cationic InP/ZnS QDs. The quaternary ammonium group provides the much required permanent positive charge and stability to InP/ZnS QDs in biofluids. The two important properties of QDs, namely bioimaging and light induced resonance energy transfer, are successfully demonstrated in cationic InP/ZnS QDs. The low cytotoxicity and stable photoluminescence of cationic InP/ZnS QDs inside cells make them ideal candidates as optical probes for cellular imaging. An efficient resonance energy transfer ( E ∼ 60%) is observed, under physiological conditions, between the cationic InP/ZnS QD donor and anionic dye acceptor. A large bimolecular quenching constant along with a linear Stern-Volmer plot confirms the formation of a strong ground state complex between the cationic InP/ZnS QDs and the anionic dye. Control experiments prove the role of electrostatic attraction in driving the light induced interactions, which can rightfully form the basis for future nano-bio studies between cationic InP/ZnS QDs and anionic biomolecules.

Adsorption Equilibrium and Kinetics at Goethite-Water and Related Interfaces

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

Katz, Lynn Ellen

This research study is an important component of a broader comprehensive project, “Geochemistry of Interfaces: From Surfaces to Interlayers to Clusters,” which sought to identify and evaluate the critical molecular phenomena at metal-oxide interfaces that control many geochemical and environmental processes. The primary goal of this research study was to better understand and predict adsorption of metal ions at mineral/water surfaces. Macroscopic data in traditional batch experiments was used to develop predictive models that characterize sorption in complex systems containing a wide range of background solution compositions. Our studies focused on systems involving alkaline earth metal (Mg 2+, Ca 2+,more » Sr 2+, Ba 2+) and heavy metal (Hg 2+, Co 2+, Cd 2+, Cu 2+, Zn 2+, Pb 2+) cations. The anions we selected for study included Cl -, NO 3 -, ClO 4 -, SO 4 2-, CO 3 2- and SeO 3 2- and the background electrolyte cations we examined included (Na +, K +, Rb + and Cs +) because these represent a range of ion sizes and have varying potentials for forming ion-pairs or ternary complexes with the metal ions studied. The research led to the development of a modified titration congruency approach for estimating site densities for mineral oxides such as goethite. The CD-MUSIC version of the surface complexation modeling approach was applied to potentiometric titration data and macroscopic adsorption data for single-solute heavy metals, oxyanions, alkaline earth metals and background electrolytes over a range of pH and ionic strength. The model was capable of predicting sorption in bi-solute systems containing multiple cations, cations and oxyanions, and transition metal cations and alkaline earth metal ions. Incorporation of ternary complexes was required for modeling Pb(II)-Se(IV) and Cd(II)-Se(IV) systems. -Both crystal face contributions and capacitance values were shown to be sensitive to varying specific surface area but were successfully accounted for in the modeling strategy. The insights gained from the macroscopic, spectroscopic and CD-MUSIC modeling developed in this study can be used to guide the implementation of less complex models which may be more applicable to field conditions. The findings of this research suggest that surface complexation models can be used as a predictive tool for fate and transport modeling of metal ions and oxyanions in fresh and saline systems typical of energy production waters and wastewaters.« less

Conformational sensitivity of conjugated poly(ethylene oxide)-poly(amidoamine) molecules to cations adducted upon electrospray ionization - a mass spectrometry, ion mobility and molecular modeling study.

PubMed

Tintaru, Aura; Chendo, Christophe; Wang, Qi; Viel, Stéphane; Quéléver, Gilles; Peng, Ling; Posocco, Paola; Pricl, Sabrina; Charles, Laurence

2014-01-15

Tandem mass spectrometry and ion mobility spectrometry experiments were performed on multiply charged molecules formed upon conjugation of a poly(amidoamine) (PAMAM) dendrimer with a poly(ethylene oxide) (PEO) linear polymer to evidence any conformational modification as a function of their charge state (2+ to 4+) and of the adducted cation (H(+)vs Li(+)). Experimental findings were rationalized by molecular dynamics simulations. The G0 PAMAM head-group could accommodate up to three protons, with protonated terminal amine group enclosed in a pseudo 18-crown-6 ring formed by the PEO segment. This particular conformation enabled a hydrogen bond network which allowed long-range proton transfer to occur during collisionally activated dissociation. In contrast, lithium adduction was found to mainly occur onto oxygen atoms of the polyether, each Li(+) cation being coordinated by a 12-crown-4 pseudo structure. As a result, for the studied polymeric segment (Mn=1500gmol(-1)), PEO-PAMAM hybrid molecules exhibited a more expanded shape when adducted to lithium as compared to proton. Copyright © 2013 Elsevier B.V. All rights reserved.

Impact of cationic surfactant on the self-assembly of sodium caseinate.

PubMed

Vinceković, Marko; Curlin, Marija; Jurašin, Darija

2014-08-27

The impact of a cationic surfactant, dodecylammonium chloride (DDACl), on the self-assembly of sodium caseinate (SC) has been investigated by light scattering, zeta potential, and rheological measurements as well as by microscopy (transmission electron and confocal laser scanning microscopy). In SC dilute solutions concentration-dependent self-assembly proceeds through the formation of spherical associates and their aggregation into elongated structures composed of connected spheres. DDACl interacts with SC via its hydrophilic and hydrophobic groups, inducing changes in SC self-assembled structures. These changes strongly depend on the surfactant aggregation states (monomeric or micellar) as well as concentration ratio of both components, leading to the formation of soluble and insoluble complexes of nano- to microdimensions. DDACl monomers interact with SC self-assembled entities in a different way compared to their micelles. Surfactant monomers form soluble complexes (similar to surfactant mixed micelles) at lower SC concentration but insoluble gelatinous complexes at higher SC concentration. At surfactant micellar concentration soluble complexes with casein chains wrapped around surfactant micelles are formed. This study suggests that the use of proper cationic surfactant concentration will allow modification and control of structural changes of SC self-assembled entities.

Modification of a cyclo-olefin surface by radio-sterilization: is there any effect on the interaction with drug solutions?

PubMed

Barakat, Hala; Saunier, Johanna; Aymes Chodur, Caroline; Aubert, Pascal; Vigneron, Jackie; Etcheberry, Arnaud; Yagoubi, Najet

2013-11-01

A cyclo-olefin copolymer was subjected to an e-beam ionizing treatment. Two doses were studied: one corresponding to the recommended dose for the sterilization of pharmaceutical packaging (25 kGy), and a greater one to enhance the modifications caused by the treatment (150 kGy). The surface modifications were studied by X-ray photoelectron spectroscopy (XPS), contact angle measurements and atomic force microscopy (AFM). The roughness and the wettability of the surface were enhanced by the treatment. The consequences of the surface modifications on the drug interaction with the polymer were studied. Copyright © 2013 Elsevier B.V. All rights reserved.

Laser-Based Surface Modification of Microstructure for Carbon Fiber-Reinforced Plastics

NASA Astrophysics Data System (ADS)

Yang, Wenfeng; Sun, Ting; Cao, Yu; Li, Shaolong; Liu, Chang; Tang, Qingru

2018-05-01

Bonding repair is a powerful feature of carbon fiber-reinforced plastics (CFRP). Based on the theory of interface bonding, the interface adhesion strength and reliability of the CFRP structure will be directly affected by the microscopic features of the CFRP surface, including the microstructure, physical, and chemical characteristics. In this paper, laser-based surface modification was compared to Peel-ply, grinding, and polishing to comparatively evaluate the surface microstructure of CFRP. The surface microstructure, morphology, fiber damage, height and space parameters were investigated by scanning electron microscopy (SEM) and laser confocal microscopy (LCM). Relative to the conventional grinding process, laser modification of the CFRP surface can result in more uniform resin removal and better processing control and repeatability. This decreases the adverse impact of surface fiber fractures and secondary damage. The surface properties were significantly optimized, which has been reflected such things as the obvious improvement of surface roughness, microstructure uniformity, and actual area. The improved surface microstructure based on laser modification is more conducive to interface bonding of CFRP structure repair. This can enhance the interfacial adhesion strength and reliability of repair.

Effect of plasticizer on surface of free films prepared from aqueous solutions of salts of cationic polymers with different plasticizers

NASA Astrophysics Data System (ADS)

Bajdik, János; Fehér, Máté; Pintye-Hódi, Klára

2007-06-01

Acquisition of a more detailed understanding of all technological processes is currently a relevant tendency in pharmaceutical technology and hence in industry. A knowledge of film formation from dispersion of polymers is very important during the coating of solid dosage forms. This process and the structure of the film can be influenced by different additives. In the present study, taste-masking films were prepared from aqueous citric acid solutions of a cationic polymer (Eudragit ® E PO) with various hydrophilic plasticizers (glycerol, propylene glycol and different poly(ethylene glycols)). The mechanical properties, film thickness, wetting properties and surface free energy of the free films were studied. The aim was to evaluate the properties of surface of free films to predict the arrangement of macromolecules in films formed from aqueous solutions of salts of cationic polymers. A high molecular weight of the plasticizer decreased the work of deformation. The surface free energy and the polarity were highest for the film without plasticizer; the hydrophilic additives decreased these parameters. The direction of the change in polarity (a hydrophilic component caused a decrease in the polarity) was unexpected. It can be explained by the change in orientation of the macromolecules, a hydrophobic surface being formed. Examination of the mechanical properties and film thickness can furnish additional results towards a knowledge of film formation by this not frequently applied type of polymer from aqueous solution.

Large-scale purification and in vitro characterization of the assembly of MreB from Leptospira interrogans.

PubMed

Barkó, Szilvia; Szatmári, Dávid; Bódis, Emőke; Türmer, Katalin; Ujfalusi, Zoltán; Popp, David; Robinson, Robert C; Nyitrai, Miklós

2016-09-01

Weil's syndrome is caused by Leptospira interrogans infections, a Gram negative bacterium with a distinct thin corkscrew cell shape. The molecular basis for this unusual morphology is unknown. In many bacteria, cell wall synthesis is orchestrated by the actin homolog, MreB. Here we have identified the MreB within the L. interrogans genome and expressed the His-tagged protein product of the synthesized gene (Li-MreB) in Escherichia coli. Li-MreB did not purify under standard nucleotide-free conditions used for MreBs from other species, requiring the continual presence of ATP to remain soluble. Covalent modification of Li-MreB free thiols with Alexa488 produced a fluorescent version of Li-MreB. We developed native and denaturing/refolding purification schemes for Li-MreB. The purified product was shown to assemble and disassemble in MgCl2 and KCl dependent manners, as monitored by light scattering and sedimentation studies. The fluorescence spectrum of labeled Li-MreB-Alexa488 showed cation-induced changes in line with an activation process followed by a polymerization phase. The resulting filaments appeared as bundles and sheets under the fluorescence microscope. Finally, since the Li-MreB polymerization was cation dependent, we developed a simple method to measure monovalent cation concentrations within a test case prokaryote, E. coli. We have identified and initially characterized the cation-dependent polymerization properties of a novel MreB from a non-rod shaped bacterium and developed a method to measure cation concentrations within prokaryotes. This initial characterization of Li-MreB will enable future structural determination of the MreB filament from this corkscrew-shaped bacterium. Copyright © 2016 Elsevier B.V. All rights reserved.

Strategies for generating peptide radical cations via ion/ion reactions.

PubMed

Gilbert, Joshua D; Fisher, Christine M; Bu, Jiexun; Prentice, Boone M; Redwine, James G; McLuckey, Scott A

2015-02-01

Several approaches for the generation of peptide radical cations using ion/ion reactions coupled with either collision induced dissociation (CID) or ultraviolet photo dissociation (UVPD) are described here. Ion/ion reactions are used to generate electrostatic or covalent complexes comprised of a peptide and a radical reagent. The radical site of the reagent can be generated multiple ways. Reagents containing a carbon-iodine (C-I) bond are subjected to UVPD with 266-nm photons, which selectively cleaves the C-I bond homolytically. Alternatively, reagents containing azo functionalities are collisionally activated to yield radical sites on either side of the azo group. Both of these methods generate an initial radical site on the reagent, which then abstracts a hydrogen from the peptide while the peptide and reagent are held together by either electrostatic interactions or a covalent linkage. These methods are demonstrated via ion/ion reactions between the model peptide RARARAA (doubly protonated) and various distonic anionic radical reagents. The radical site abstracts a hydrogen atom from the peptide, while the charge site abstracts a proton. The net result is the conversion of a doubly protonated peptide to a peptide radical cation. The peptide radical cations have been fragmented via CID and the resulting product ion mass spectra are compared to the control CID spectrum of the singly protonated, even-electron species. This work is then extended to bradykinin, a more broadly studied peptide, for comparison with other radical peptide generation methods. The work presented here provides novel methods for generating peptide radical cations in the gas phase through ion/ion reaction complexes that do not require modification of the peptide in solution or generation of non-covalent complexes in the electrospray process. Copyright © 2015 John Wiley & Sons, Ltd.

Infrared spectroscopy of the methanol cation and its methylene-oxonium isomer

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

Mosley, J. D.; Young, J. W.; Duncan, M. A., E-mail: mccoy@chemistry.ohio-state.edu, E-mail: maduncan@uga.edu

2015-03-21

The carbenium ion with nominal formula [C,H{sub 4},O]{sup +} is produced from methanol or ethylene glycol in a pulsed-discharge supersonic expansion source. The ion is mass selected, and its infrared spectrum is measured from 2000 to 4000 cm{sup −1} using laser photodissociation spectroscopy and the method of rare gas atom tagging. Computational chemistry predicts two isomers, the methanol and methylene-oxonium cations. Predicted vibrational spectra based on scaled harmonic and reduced dimensional treatments are compared to the experimental spectra. The methanol cation is the only isomer produced when methanol is used as a precursor. When ethylene glycol is used as themore » precursor, methylene-oxonium is produced in addition to the methanol cation. Theoretical results at the CCSD(T)/cc-pVTZ level show that methylene-oxonium is lower in energy than methanol cation by 6.4 kcal/mol, and is in fact the global minimum isomer on the [C,H{sub 4},O]{sup +} potential surface. Methanol cation is trapped behind an isomerization barrier in our source, providing a convenient method to produce and characterize this transient species. Analysis of the spectrum of the methanol cation provides evidence for strong CH stretch vibration/torsion coupling in this molecular ion.« less

Structure and short time degradation studies of sodium zirconium phosphate ceramics loaded with simulated fast breeder (FBR) waste

NASA Astrophysics Data System (ADS)

Ananthanarayanan, A.; Ambashta, R. D.; Sudarsan, V.; Ajithkumar, T.; Sen, D.; Mazumder, S.; Wattal, P. K.

2017-04-01

Sodium zirconium phosphate (NZP) ceramics have been prepared using conventional sintering and hot isostatic pressing (HIP) routes. The structure of NZP ceramics, prepared using the HIP route, has been compared with conventionally sintered NZP using a combination of X-ray diffraction (XRD) and (31P and 23Na) nuclear magnetic resonance (NMR) spectroscopy techniques. It is observed that NZP with no waste loading is aggressive toward the steel HIP-can during hot isostatic compaction and significant fraction of cations from the steel enter the ceramic material. Waste loaded NZP samples (10 wt% simulated FBR waste) show significantly low can-interaction and primary NZP phase is evident in this material. Upon exposure of can-interacted and waste loaded NZP to boiling water and steam, 31P NMR does not detect any major modifications in the network structure. However, the 23Na NMR spectra indicate migration of Na+ ions from the surface and possible re-crystallization. This is corroborated by Small-Angle Neutron Scattering (SANS) data and Scanning Electron Microscopy (SEM) measurements carried out on these samples.

A new approach to triggering mechanism of volcano landslides based on zeta potential and surface free energy balance

NASA Astrophysics Data System (ADS)

Plaza, I.; Ontiveros-Ortega, A.; Calero, J.; Romero, C.

2018-01-01

The layers of Almagre (iron-rich deposits) from Tenerife Island are the result of thermal metamorphism of soils in contact with lava flow (1073-1273 K). These layers of small thickness relative to the basaltic wash, are interesting for geotechnical study, because the stability of the deposits is determined by the weakest element, in this case Almagre, which acts as a sliding plane. The flow of maritime air over the hillsides of the volcanic islands increases the content of cations in ashes deposits. This modifies the superficial properties of material that composes the substratum. This modification affects the retention of water and the cohesion of material making up the deposit. The results show that the presence of sodium and magnesium increased the hydrophobicity of the material, which had a weak water retention capacity and strong cohesion at basic pH. When there is iron in solution, repulsion between the particles is greater than one obtained with other studied electrolytes. Hence, the deposit is less stable, and Almagre under saturated water conditions constitutes an ideal layer for landslides.

Electron beams in research and technology

NASA Astrophysics Data System (ADS)

Mehnert, R.

1995-11-01

Fast electrons lose their energy by inelastic collisions with electrons of target molecules forming secondary electrons and excited molecules. Coulomb interaction of secondary electrons with valence electrons of neighboring molecules leads to the formation of radical cations, thermalized electrons, excited molecular states and radicals. The primary reactive species initiate chemical reactions in the materials irradiated. Polymer modifications using accelerated electrons such as cross-linking of cable insulation, tubes, pipes and moldings, vulcanization of elastomers, grafting of polymer surfaces, processing of foamed plastics and heat shrinkable materials have gained wide industrial acceptance. A steadily growing electron beam technology is curing of paints, lacquers, printing inks and functional coatings. Electron beam processing offers high productivity, the possibility to treat the materials at normal temperature and pressure, excellent process control and clean production conditions. On an industrial scale the most important application of fast electrons is curing of 100% reactive monomer/prepolymer systems. Mainly acrylates and epoxides are used to formulate functional coatings on substrates such as paper, foil, wood, fibre board and high pressure laminates. A survey is given about the reaction mechanism of curing, the characterization of cured coatings, and of some industrial application.

Enhanced stability of solid oxide fuel cells by employing a modified cathode-interlayer interface with a dense La0.6Sr0.4Co0.2Fe0.8O3-δ thin film

NASA Astrophysics Data System (ADS)

De Vero, Jeffrey C.; Develos-Bagarinao, Katherine; Kishimoto, Haruo; Ishiyama, Tomohiro; Yamaji, Katsuhiko; Horita, Teruhisa; Yokokawa, Harumi

2018-02-01

In La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) cathode/Gd-doped ceria (GDC)/yttria-stabilized zirconia (YSZ)-electrolyte based solid oxide fuel cells (SOFCs), one of the key issues affecting performance and long-term stability is the apparent deactivation of LSCF cathode by the presence of secondary phases such as SrZrO3 at the interfaces. Herein, we report that by modifying the cathode-interlayer interface with a dense LSCF thin film, the severe cation interdiffusion is suppressed especially the fast gas or surface diffusion of Sr into adjacent GDC-interlayer/YSZ-electrolyte resulting in the significant reduction of SrZrO3 formation at the interfaces improving cell stability. In order to understand the present results, the interface chemistry is carefully considered and discussed. The results show that modification of cathode-interlayer interfaces is an important strategy for improving the lifetime of SOFCs.

Allylic ionic liquid electrolyte-assisted electrochemical surface passivation of LiCoO2 for advanced, safe lithium-ion batteries.

PubMed

Mun, Junyoung; Yim, Taeeun; Park, Jang Hoon; Ryu, Ji Heon; Lee, Sang Young; Kim, Young Gyu; Oh, Seung M

2014-08-29

Room-temperature ionic liquid (RTIL) electrolytes have attracted much attention for use in advanced, safe lithium-ion batteries (LIB) owing to their nonvolatility, high conductivity, and great thermal stability. However, LIBs containing RTIL-electrolytes exhibit poor cyclability because electrochemical side reactions cause problematic surface failures of the cathode. Here, we demonstrate that a thin, homogeneous surface film, which is electrochemically generated on LiCoO2 from an RTIL-electrolyte containing an unsaturated substituent on the cation (1-allyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide, AMPip-TFSI), can avert undesired side reactions. The derived surface film comprised of a high amount of organic species from the RTIL cations homogenously covered LiCoO2 with a <25 nm layer and helped suppress unfavorable thermal reactions as well as electrochemical side reactions. The superior performance of the cell containing the AMPip-TFSI electrolyte was further elucidated by surface, electrochemical, and thermal analyses.

Allylic ionic liquid electrolyte-assisted electrochemical surface passivation of LiCoO2 for advanced, safe lithium-ion batteries

NASA Astrophysics Data System (ADS)

Mun, Junyoung; Yim, Taeeun; Park, Jang Hoon; Ryu, Ji Heon; Lee, Sang Young; Kim, Young Gyu; Oh, Seung M.

2014-08-01

Room-temperature ionic liquid (RTIL) electrolytes have attracted much attention for use in advanced, safe lithium-ion batteries (LIB) owing to their nonvolatility, high conductivity, and great thermal stability. However, LIBs containing RTIL-electrolytes exhibit poor cyclability because electrochemical side reactions cause problematic surface failures of the cathode. Here, we demonstrate that a thin, homogeneous surface film, which is electrochemically generated on LiCoO2 from an RTIL-electrolyte containing an unsaturated substituent on the cation (1-allyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide, AMPip-TFSI), can avert undesired side reactions. The derived surface film comprised of a high amount of organic species from the RTIL cations homogenously covered LiCoO2 with a <25 nm layer and helped suppress unfavorable thermal reactions as well as electrochemical side reactions. The superior performance of the cell containing the AMPip-TFSI electrolyte was further elucidated by surface, electrochemical, and thermal analyses.

X-ray Reflectivity Characterization of Ion Distribution at Biomimetic Membrane Surfaces

NASA Astrophysics Data System (ADS)

Krüger, Peter; Pittler, Jens; Vaknin, David; Lösche, Mathias

2003-03-01

Ions at cell membrane surfaces may control the function and conformation of nearby biomolecules, thus playing an important role in inter- and intracellular transport as well as in biorecognition processes. Moreover, charge patterns at membrane surfaces may direct the growth of inorganic crystals in biomineralization. Langmuir monolayers are widely employed as model systems for studying charge distribution and growth processes at the organic/inorganic interface. We present a novel x-ray reflectivity technique that provides detailed information on ion distribution at biomembrane surfaces by using monochromatic x-rays at various energies at and away from the ion x-ray absorption edges. As a model, the interaction of Ba^2+ with DMPA^- (dimyristoyl phosphatidic acid) monolayers at the aqueous surface was studied. We find an unexpectedly large concentration of the cations near the interface where they form a Stern layer of bound ions. These studies have been complemented with conventional x-ray reflectivity measurements and extended to other anionic lipid species (DMPS, DMPG) and cations (Ca^2+).

Process for growing a film epitaxially upon an oxide surface and structures formed with the process

DOEpatents

McKee, Rodney Allen; Walker, Frederick Joseph

1998-01-01

A process and structure wherein a film comprised of a perovskite or a spinel is built epitaxially upon a surface, such as an alkaline earth oxide surface, involves the epitaxial build up of alternating constituent metal oxide planes of the perovskite or spinel. The first layer of metal oxide built upon the surface includes a metal element which provides a small cation in the crystalline structure of the perovskite or spinel, and the second layer of metal oxide built upon the surface includes a metal element which provides a large cation in the crystalline structure of the perovskite or spinel. The layering sequence involved in the film build up reduces problems which would otherwise result from the interfacial electrostatics at the first atomic layers, and these oxides can be stabilized as commensurate thin films at a unit cell thickness or grown with high crystal quality to thicknesses of 0.5-0.7 .mu.m for optical device applications.

Process for growing a film epitaxially upon an oxide surface and structures formed with the process

DOEpatents

McKee, Rodney A.; Walker, Frederick J.

1995-01-01

A process and structure wherein a film comprised of a perovskite or a spinel is built epitaxially upon a surface, such as an alkaline earth oxide surface, involves the epitaxial build up of alternating constituent metal oxide planes of the perovskite or spinel. The first layer of metal oxide built upon the surface includes a metal element which provides a small cation in the crystalline structure of the perovskite or spinel, and the second layer of metal oxide built upon the surface includes a metal element which provides a large cation in the crystalline structure of the perovskite or spinel. The layering sequence involved in the film build up reduces problems which would otherwise result from the interfacial electrostatics at the first atomic layers, and these oxides can be stabilized as commensurate thin films at a unit cell thickness or grown with high crystal quality to thicknesses of 0.5-0.7 .mu.m for optical device applications.

Allylic ionic liquid electrolyte-assisted electrochemical surface passivation of LiCoO2 for advanced, safe lithium-ion batteries

PubMed Central

Mun, Junyoung; Yim, Taeeun; Park, Jang Hoon; Ryu, Ji Heon; Lee, Sang Young; Kim, Young Gyu; Oh, Seung M.

2014-01-01

Room-temperature ionic liquid (RTIL) electrolytes have attracted much attention for use in advanced, safe lithium-ion batteries (LIB) owing to their nonvolatility, high conductivity, and great thermal stability. However, LIBs containing RTIL-electrolytes exhibit poor cyclability because electrochemical side reactions cause problematic surface failures of the cathode. Here, we demonstrate that a thin, homogeneous surface film, which is electrochemically generated on LiCoO2 from an RTIL-electrolyte containing an unsaturated substituent on the cation (1-allyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide, AMPip-TFSI), can avert undesired side reactions. The derived surface film comprised of a high amount of organic species from the RTIL cations homogenously covered LiCoO2 with a <25 nm layer and helped suppress unfavorable thermal reactions as well as electrochemical side reactions. The superior performance of the cell containing the AMPip-TFSI electrolyte was further elucidated by surface, electrochemical, and thermal analyses. PMID:25168309

Diphtheria toxin-induced channels in Vero cells selective for monovalent cations

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

Sandvig, K.; Olsnes, S.

1988-09-05

Ion fluxes associated with translocation of diphtheria toxin across the surface membrane of Vero cells were studied. When cells with surface-bound toxin were exposed to low pH to induce toxin entry, the cells became permeable to Na+, K+, H+, choline+, and glucosamine+. There was no increased permeability to Cl-, SO4(-2), glucose, or sucrose, whereas the uptake of /sup 45/Ca2+ was slightly increased. The influx of Ca2+, which appears to be different from that of monovalent cations, was reduced by several inhibitors of anion transport and by verapamil, Mn2+, Co2+, and Ca2+, but not by Mg2+. The toxin-induced fluxes of N+,more » K+, and protons were inhibited by Cd2+. Cd2+ also protected the cells against intoxication by diphtheria toxin, suggesting that the open cation-selective channel is required for toxin translocation. The involvement of the toxin receptor is discussed.« less

Efficient harvesting of marine Chlorella vulgaris microalgae utilizing cationic starch nanoparticles by response surface methodology.

PubMed

Bayat Tork, Mahya; Khalilzadeh, Rasoul; Kouchakzadeh, Hasan

2017-11-01

Harvesting involves nearly thirty percent of total production cost of microalgae that needs to be done efficiently. Utilizing inexpensive and highly available biopolymer-based flocculants can be a solution for reducing the harvest costs. Herein, flocculation process of Chlorella vulgaris microalgae using cationic starch nanoparticles (CSNPs) was evaluated and optimized through the response surface methodology (RSM). pH, microalgae and CSNPs concentrations were considered as the main independent variables. Under the optimum conditions of microalgae concentration 0.75gdry weight/L, CSNPs concentration 7.1mgdry weight/L and pH 11.8, the maximum flocculation efficiency (90%) achieved. Twenty percent increase in flocculation efficiency observed with the use of CSNPs instead of the non-particulate starch which can be due to the more electrostatic interactions between the cationic nanoparticles and the microalgae. Therefore, the synthesized CSNPs can be employed as a convenient and economical flocculants for efficient harvest of Chlorella vulgaris microalgae at large scale. Copyright © 2017 Elsevier Ltd. All rights reserved.

PES Surface Modification Using Green Chemistry: New Generation of Antifouling Membranes.

PubMed

Nady, Norhan

2016-04-18

A major limitation in using membrane-based separation processes is the loss of performance due to membrane fouling. This drawback can be addressed thanks to surface modification treatments. A new and promising surface modification using green chemistry has been recently investigated. This modification is carried out at room temperature and in aqueous medium using green catalyst (enzyme) and nontoxic modifier, which can be safely labelled "green surface modification". This modification can be considered as a nucleus of new generation of antifouling membranes and surfaces. In the current research, ferulic acid modifier and laccase bio-catalyst were used to make poly(ethersulfone) (PES) membrane less vulnerable to protein adsorption. The blank and modified PES membranes are evaluated based on e.g., their flux and protein repellence. Both the blank and the modified PES membranes (or laminated PES on silicon dioxide surface) are characterized using many techniques e.g., SEM, EDX, XPS and SPM, etc. The pure water flux of the most modified membranes was reduced by 10% on average relative to the blank membrane, and around a 94% reduction in protein adsorption was determined. In the conclusions section, a comparison between three modifiers-ferulic acid, and two other previously used modifiers (4-hydroxybenzoic acid and gallic acid)-is presented.

Sustainable environmental nanotechnology using nanoparticle surface modification.

EPA Science Inventory

Reactive nanomaterials used for environmental remediation require surface modification to make them mobile in the subsurface. Nanomaterials released into the environment inadvertently without an engineered surface coating will acquire one (e.g. adsorption of natural organic matt...

Spine interbody implants: material selection and modification, functionalization and bioactivation of surfaces to improve osseointegration.

PubMed

Rao, Prashanth J; Pelletier, Matthew H; Walsh, William R; Mobbs, Ralph J

2014-05-01

The clinical outcome of lumbar spinal fusion is correlated with achievement of bony fusion. Improving interbody implant bone on-growth and in-growth may enhance fusion, limiting pseudoarthrosis, stress shielding, subsidence and implant failure. Polyetheretherketone (PEEK) and titanium (Ti) are commonly selected for interbody spacer construction. Although these materials have desirable biocompatibility and mechanical properties, they require further modification to support osseointegration. Reports of extensive research on this topic are available in biomaterial-centric published reports; however, there are few clinical studies concerning surface modification of interbody spinal implants. The current article focuses on surface modifications aimed at fostering osseointegration from a clinician's point of view. Surface modification of Ti by creating rougher surfaces, modifying its surface topography (macro and nano), physical and chemical treatment and creating a porous material with high interconnectivity can improve its osseointegrative potential and bioactivity. Coating the surface with osteoconductive materials like hydroxyapatite (HA) can improve osseointegration. Because PEEK spacers are relatively inert, creating a composite by adding Ti or osteoconductive materials like HA can improve osseointegration. In addition, PEEK may be coated with Ti, effectively bio-activating the coating. © 2014 Chinese Orthopaedic Association and Wiley Publishing Asia Pty Ltd.

Crystal Nucleation Using Surface-Energy-Modified Glass Substrates.

PubMed

Nordquist, Kyle A; Schaab, Kevin M; Sha, Jierui; Bond, Andrew H

2017-08-02

Systematic surface energy modifications to glass substrates can induce nucleation and improve crystallization outcomes for small molecule active pharmaceutical ingredients (APIs) and proteins. A comparatively broad probe for function is presented in which various APIs, proteins, organic solvents, aqueous media, surface energy motifs, crystallization methods, form factors, and flat and convex surface energy modifications were examined. Replicate studies ( n ≥ 6) have demonstrated an average reduction in crystallization onset times of 52(4)% (alternatively 52 ± 4%) for acetylsalicylic acid from 91% isopropyl alcohol using two very different techniques: bulk cooling to 0 °C using flat surface energy modifications or microdomain cooling to 4 °C from the interior of a glass capillary having convex surface energy modifications that were immersed in the solution. For thaumatin and bovine pancreatic trypsin, a 32(2)% reduction in crystallization onset times was demonstrated in vapor diffusion experiments ( n ≥ 15). Nucleation site arrays have been engineered onto form factors frequently used in crystallization screening, including microscope slides, vials, and 96- and 384-well high-throughput screening plates. Nucleation using surface energy modifications on the vessels that contain the solutes to be crystallized adds a layer of useful variables to crystallization studies without requiring significant changes to workflows or instrumentation.

Surface modification of polymers for biocompatibility via exposure to extreme ultraviolet radiation.

PubMed

Inam Ul Ahad; Bartnik, Andrzej; Fiedorowicz, Henryk; Kostecki, Jerzy; Korczyc, Barbara; Ciach, Tomasz; Brabazon, Dermot

2014-09-01

Polymeric biomaterials are being widely used for the treatment of various traumata, diseases and defects in human beings due to ease in their synthesis. As biomaterials have direct interaction with the extracellular environment in the biological world, biocompatibility is a topic of great significance. The introduction or enhancement of biocompatibility in certain polymers is still a challenge to overcome. Polymer biocompatibility can be controlled by surface modification. Various physical and chemical methods (e.g., chemical and plasma treatment, ion implantation, and ultraviolet irradiation etc.) are in use or being developed for the modification of polymer surfaces. However an important limitation in their employment is the alteration of bulk material. Different surface and bulk properties of biomaterials are often desirable for biomedical applications. Because extreme ultraviolet (EUV) radiation penetration is quite limited even in low density mediums, it could be possible to use it for surface modification without influencing the bulk material. This article reviews the degree of biocompatibility of different polymeric biomaterials being currently employed in various biomedical applications, the surface properties required to be modified for biocompatibility control, plasma and laser ablation based surface modification techniques, and research studies indicating possible use of EUV for enhancing biocompatibility. © 2013 Wiley Periodicals, Inc.

Effect of chitosan and cationic starch on the surface chemistry properties of bagasse paper.

PubMed

Ashori, Alireza; Cordeiro, Nereida; Faria, Marisa; Hamzeh, Yahya

2013-07-01

The use of non-wood fibers in the paper industry has been an economical and environmental necessity. The application of dry-strength agents has been a successful method to enhance the strength properties of paper. The experimental results evidencing the potential of chitosan and cationic starch utilization in bagasse paper subjected to hot water pre-extraction has been presented in this paper. The research analyzes the surface properties alterations due to these dry-strength agents. Inverse gas chromatography was used to evaluate the properties of surface chemistry of the papers namely the surface energy, active sites, surface area as well as the acidic/basic character. The results of the study revealed that the handsheets process causes surface arrangement and orientation of chemical groups, which induce a more hydrophobic and basic surface. The acid-base surface characteristics after the addition of dry-strength agents were the same as the bagasse handsheets with and without hot water pre-extraction. The results showed that the dry-strength agent acts as a protecting film or glaze on the surfaces of bagasse paper handsheets. Copyright © 2013 Elsevier B.V. All rights reserved.

Surface modifications with Lissajous trajectories using atomic force microscopy

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

Cai, Wei; Yao, Nan, E-mail: nyao@princeton.edu

2015-09-14

In this paper, we report a method for atomic force microscopy surface modifications with single-tone and multiple-resolution Lissajous trajectories. The tip mechanical scratching experiments with two series of Lissajous trajectories were carried out on monolayer films. The scratching processes with two scan methods have been illustrated. As an application, the tip-based triboelectrification phenomenon on the silicon dioxide surface with Lissajous trajectories was investigated. The triboelectric charges generated within the tip rubbed area on the surface were characterized in-situ by scanning Kelvin force microscopy. This method would provide a promising and cost-effective approach for surface modifications and nanofabrication.

Surface modification of cellulose fibers: towards wood composites by biomimetics.

PubMed

Gradwell, Sheila E; Renneckar, Scott; Esker, Alan R; Heinze, Thomas; Gatenholm, Paul; Vaca-Garcia, Carlos; Glasser, Wolfgang

2004-01-01

A biomimetic approach was taken for studying the adsorption of a model copolymer (pullulan abietate, DS 0.027), representing the lignin-carbohydrate complex, to a model surface for cellulose fibers (Langmuir-Blodgett thin films of regenerated cellulose). Adsorption results were assayed using surface plasmon resonance spectroscopy (SPR) and atomic force microscopy (AFM). Rapid, spontaneous, and desorption-resistant surface modification resulted. This effort is viewed as a critical first step towards the permanent surface modification of cellulose fibers with a layer of molecules amenable to either enzymatic crosslinking for improved wood composites or thermoplastic consolidation.

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

NASA Astrophysics Data System (ADS)

Aumiller, William M.; Keating, Christine D.

2016-02-01

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

Simple and novel electrochemical sensor for the determination of tetracycline based on iron/zinc cations-exchanged montmorillonite catalyst.

PubMed

Gan, Tian; Shi, Zhaoxia; Sun, Junyong; Liu, Yanming

2014-04-01

A simple and novel electrochemical sensor for the determination of tetracycline (TC), a kind of antibiotic that may induce residue in the food chain, was developed by the modification of iron/zinc cation-exchanged montmorillonite (Fe/Zn-MMT) catalyst on glassy carbon electrode (GCE). The morphology and the structure of the Fe/Zn-MMT nanomaterial were characterized by scanning electron microscopy and X-ray diffraction, respectively. The results of electrochemical experiments demonstrated that the sensor exhibited excellent electrocatalytic activity to the oxidation of TC in the presence of sodium dodecyl sulfate. The sensor displayed a wide linear range from 0.30 to 52.0 μM and a low detection limit of 0.10 μM by using the derivative differential pulse voltammetry. Moreover, the electrochemical sensor was applied to the detection of TC in feedstuff and meat samples. Copyright © 2014 Elsevier B.V. All rights reserved.

Chitosan as cationic polyelectrolyte for the modification of electroosmotic flow and its utilization for the separation of inorganic anions by capillary zone electrophoresis.

PubMed

Takayanagi, Toshio; Motomizu, Shoji

2006-09-01

Cationic polyelectrolyte of chitosan was used for the reversal of electroosmotic flow in capillary zone electrophoresis. The chitosan was dissolved in acetic acid solution, and stable electroosmotic flow was obtained at the chitosan concentrations between 50 and 300 microg/mL. Separation of inorganic anions was carried out using the dynamically coated capillary by capillary zone electrophoresis. Nine kinds of anions were separated and detected with the capillary. The electrophoretic mobility of the analyte anions decreased with increasing concentrations of chitosan in the migrating solution through ion-ion interaction, but the migration order of the analyte anions was not changed in the concentration range of the chitosan examined. The signal shape for the analyte anions was developed by using field-enhanced sample stacking with 10 mM sodium sulfate.

Environmentally friendly cellulose-based polyelectrolytes in wastewater treatment.

PubMed

Grenda, Kinga; Arnold, Julien; Gamelas, José A F; Rasteiro, Maria G

2017-09-01

Natural-based polyelectrolytes (PELs), with all the advantages coming from being produced from renewable and biodegradable sources, are a potential solution for the removal of dyes from wastewater. In this work, surplus Eucalyptus bleached cellulose fibres from a paper mill were modified to increase the charge and solubility of cellulose. First, reactive aldehyde groups were introduced in the cellulose backbone by periodate oxidation of cellulose. Further modification with alkylammonium produced positively charged cellulose-based PELs. The final products were characterized by several analytical techniques. The PEL with the highest substitution degree of cationic groups was evaluated for its performance in decolouration processes, bentonite being used as aid. This was found to be effective for colour removal of either anionic or cationic dyes. Bio-PELs can thus be considered as very favourable eco-friendly flocculation agents for decolouration of harsh effluents from several industries, considering their biodegradable nature and thus the ability to produce less sludge.

High yield recombinant production of a self-assembling polycationic peptide for silica biomineralization.

PubMed

Zerfaß, Christian; Braukmann, Sandra; Nietzsche, Sandor; Hobe, Stephan; Paulsen, Harald

2015-04-01

We report the recombinant bacterial expression and purification at high yields of a polycationic oligopeptide, P5S3. The sequence of P5S3 was inspired by a diatom silaffin, a silica precipitating peptide. Like its native model, P5S3 exhibits silica biomineralizing activity, but furthermore has unusual self-assembling properties. P5S3 is efficiently expressed in Escherichia coli as fusion with ketosteroid isomerase (KSI), which causes deposition in inclusion bodies. After breaking the fusion by cyanogen bromide reaction, P5S3 was purified by cation exchange chromatography, taking advantage of the exceptionally high content of basic amino acids. The numerous cationic charges do not prevent, but may even promote counterion-independent self-assembly which in turn leads to silica precipitation. Enzymatic phosphorylation, a common modification in native silica biomineralizing peptides, can be used to modify the precipitation activity. Copyright © 2015 Elsevier Inc. All rights reserved.

Investigation of surface halide modification of nitrile butadiene rubber

NASA Astrophysics Data System (ADS)

Sukhareva, K. V.; Mikhailov, I. A.; Andriasyan, Yu O.; Mastalygina, E. E.; Popov, A. A.

2017-12-01

The investigation is devoted to the novel technology of surface halide modification of rubber samples based on nitrile butadiene rubber (NBR). 1,1,2-trifluoro-1,2,2-trichlorethane was used as halide modifier. The developed technology is characterized by production stages reduction to one by means of treating the rubber compound with a halide modifier. The surface halide modification of compounds based on nitrile butadiene rubber (NBR) was determined to result in increase of resistance to thermal oxidation and aggressive media. The conducted research revealed the influence of modification time on chemical resistance and physical-mechanical properties of rubbers under investigation.

Properties of Surface-Modification Layer Generated by Atomic Hydrogen Annealing on Poly(ethylene naphthalate) Substrate

NASA Astrophysics Data System (ADS)

Heya, Akira; Matsuo, Naoto

2008-01-01

The surface of a poly(ethylene naphthalate) (PEN) substrate was modified by atomic hydrogen annealing (AHA). In this method, a PEN substrate was exposed to atomic hydrogen generated by cracking hydrogen molecules on heated tungsten wire. The properties of the surface-modification layer by AHA were evaluated by spectroscopic ellipsometry. It is found that the thickness of the modified layer was 5 nm and that the modification layer has a low refractive index compared with the PEN substrate. The modification layer relates to the reduction reaction of the PEN substrate by AHA.

Reaction of Photochemically Generated Organic Cations with Colloidal Clays.

DTIC Science & Technology

1983-05-01

University of Notre Dame. IS. KEY WORDS (Continue on reverse aide if neceary end identify by block number) Chemistry of colloidal montmorillonite Absorption...Centlws m ftves n N mee.iy mi Identify by block number) Qi Organic radical cations will dimerize when adsorbed to the surface D of montmorillonite in...1 The Nature and Chemistry of Micelles .... 2 The Nature and Chemistry of Clay Minerals 5 Montmorillonite Catalyzed Color

Adsorption of weak polyelectrolytes on charged nanoparticles. Impact of salt valency, pH, and nanoparticle charge density. Monte Carlo simulations.

PubMed

Carnal, Fabrice; Stoll, Serge

2011-10-27

Complex formation between a weak flexible polyelectrolyte chain and one positively charged nanoparticle in presence of explicit counterions and salt particles is investigated using Monte Carlo simulations. The influence of parameters such as the nanoparticle surface charge density, salt valency, and solution property such as the pH on the chain protonation/deprotonation process and monomer adsorption at the nanoparticle surface are systematically investigated. It is shown that the nanoparticle presence significantly modifies chain acid/base and polyelectrolyte conformational properties. The importance of the attractive electrostatic interactions between the chain and the nanoparticle clearly promotes the chain deprotonation leading, at high pH and nanoparticle charge density, to fully wrapped polyelectrolyte at the nanoparticle surface. When the nanoparticle bare charge is overcompensated by the polyelectrolyte charges, counterions and salt particles condense at the surface of the polyelectrolyte-nanoparticle complex to compensate for the excess of charges providing from the adsorbed polyelectrolyte chain. It is also shown that the complex formation is significantly affected by the salt valency. Indeed, with the presence of trivalent salt cations, competition is observed between the nanoparticle and the trivalent cations. As a result, the amount of adsorbed monomers is less important than in the monovalent and divalent case and chain conformations are different due to the collapse of polyelectrolyte segments around trivalent cations out of the nanoparticle adsorption layer.

Removal of diphenhydramine from water by swelling clay minerals.

PubMed

Li, Zhaohui; Chang, Po-Hsiang; Jiang, Wei-Teh; Jean, Jiin-Shuh; Hong, Hanlie; Liao, Libing

2011-08-01

Frequent detection of pharmaceuticals in surface water and wastewater attracted renewed attention on studying interactions between pharmaceuticals and sludge or biosolids generated from wastewater treatment. Less attention was focused on studying interactions between pharmaceuticals and clay minerals, important soil and sediment components. This research targeted on investigating interactions between diphenhydramine (DPH), an important antihistamine drug, and a montmorillonite, a swelling clay, in aqueous solution. Stoichiometric desorption of exchangeable cations accompanying DPH adsorption confirmed that cation exchange was the most important mechanism of DPH uptake by the swelling clay. When the solution pH was below the pK(a) of DPH, its adsorption on the swelling clay was less affected by pH. Increasing solution pH above the pK(a) value resulted in a decrease in DPH adsorption by the clay. An increase in d(001) spacing at a high DPH loading level suggested interlayer adsorption, thus, intercalation of DPH. The results from this study showed that swelling clays are a good environmental sink for weak acidic drugs like DPH. In addition, the large cation exchange capacity and surface area make the clay a good candidate to remove cationic pharmaceuticals from the effluent of wastewater treatment facilities. Copyright © 2011 Elsevier Inc. All rights reserved.

Natural zeolite reactivity towards ozone: the role of compensating cations.

PubMed

Valdés, Héctor; Alejandro, Serguei; Zaror, Claudio A

2012-08-15

Among indoor pollutants, ozone is recognised to pose a threat to human health. Recently, low cost natural zeolites have been applied as alternative materials for ozone abatement. In this work, the effect of compensating cation content of natural zeolite on ozone removal is studied. A Chilean natural zeolite is used here as starting material. The amount of compensating cations in the zeolite framework was modified by ion exchange using an ammonium sulphate solution (0.1 mol L(-1)). Characterisation of natural and modified zeolites were performed by X-ray powder diffraction (XRD), nitrogen adsorption at 77K, elemental analysis, X-ray fluorescence (XRF), thermogravimetric analysis coupled with mass spectroscopy (TGA-MS), and temperature-programmed desorption of ammonia (NH(3)-TPD). Ozone adsorption and/or decomposition on natural and modified zeolites were studied by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Results show that the zeolite compensating cation content affects ozone interaction with zeolite active sites. Ammonium ion-exchange treatments followed by thermal out-gassing at 823 K, reduces ozone diffusion resistance inside the zeolite framework, increasing ozone abatement on zeolite surface active sites. Weak and strong Lewis acid sites of zeolite surface are identified here as the main active sites responsible of ozone removal. Copyright © 2012 Elsevier B.V. All rights reserved.

Molecular Dynamics Simulation of Resin Adsorption at Kaolinite Edge Sites: Effect of Surface Deprotonation on Interfacial Structure

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

Zeitler, T. R.; Greathouse, J. A.; Cygan, R. T.

Low-salinity water flooding, a method of enhanced oil recovery, consists of injecting low ionic strength fluids into an oil reservoir in order to detach oil from mineral surfaces in the underlying formation. Although highly successful in practice, the approach is not completely understood at the molecular scale. Molecular dynamics simulations have been used to investigate the effect of surface protonation on the adsorption of an anionic crude oil component on clay mineral edge surfaces. A set of interatomic potentials appropriate for edge simulations has been applied to the kaolinite (010) surface in contact with an aqueous nanopore. Decahydro-2-napthoic acid inmore » its deprotonated form (DHNA –) was used as a representative resin component of crude oil, with monovalent and divalent counterions, to test the observed trends in low-salinity water flooding experiments. Surface models include fully protonated (neutral) and deprotonated (negative) edge sites, which require implementation of a new deprotonation scheme. The surface adsorptive properties of the kaolinite edge under neutral and deprotonated conditions have been investigated for low and high DHNA – concentrations with Na + and Ca 2+ as counterions. The tendency of DHNA – ions to coordinate with divalent (Ca 2+) rather than monovalent (Na +) ions greatly influences adsorption tendencies of the anion. Additionally, the formation of net positively charged surface sites due to Ca 2+ at deprotonated sites results in increased DHNA – adsorption. Divalent cations such as Ca 2+ are able to efficiently bridge surface sites and organic anions. Replacing those cations with monovalent cations such as Na + diminishes the bridging mechanism, resulting in reduced adsorption of the organic species. As a result, a clear trend of decreased DHNA – adsorption is observed in the simulations as Ca 2+ is replaced by Na + for deprotonated surfaces, as would be expected for oil detachment from reservoir formations following a low-salinity flooding event.« less

Molecular Dynamics Simulation of Resin Adsorption at Kaolinite Edge Sites: Effect of Surface Deprotonation on Interfacial Structure

DOE PAGES

Zeitler, T. R.; Greathouse, J. A.; Cygan, R. T.; ...

2017-10-05

Low-salinity water flooding, a method of enhanced oil recovery, consists of injecting low ionic strength fluids into an oil reservoir in order to detach oil from mineral surfaces in the underlying formation. Although highly successful in practice, the approach is not completely understood at the molecular scale. Molecular dynamics simulations have been used to investigate the effect of surface protonation on the adsorption of an anionic crude oil component on clay mineral edge surfaces. A set of interatomic potentials appropriate for edge simulations has been applied to the kaolinite (010) surface in contact with an aqueous nanopore. Decahydro-2-napthoic acid inmore » its deprotonated form (DHNA –) was used as a representative resin component of crude oil, with monovalent and divalent counterions, to test the observed trends in low-salinity water flooding experiments. Surface models include fully protonated (neutral) and deprotonated (negative) edge sites, which require implementation of a new deprotonation scheme. The surface adsorptive properties of the kaolinite edge under neutral and deprotonated conditions have been investigated for low and high DHNA – concentrations with Na + and Ca 2+ as counterions. The tendency of DHNA – ions to coordinate with divalent (Ca 2+) rather than monovalent (Na +) ions greatly influences adsorption tendencies of the anion. Additionally, the formation of net positively charged surface sites due to Ca 2+ at deprotonated sites results in increased DHNA – adsorption. Divalent cations such as Ca 2+ are able to efficiently bridge surface sites and organic anions. Replacing those cations with monovalent cations such as Na + diminishes the bridging mechanism, resulting in reduced adsorption of the organic species. As a result, a clear trend of decreased DHNA – adsorption is observed in the simulations as Ca 2+ is replaced by Na + for deprotonated surfaces, as would be expected for oil detachment from reservoir formations following a low-salinity flooding event.« less

Texture Modification of the Shuttle Landing Facility Runway at Kennedy Space Center

NASA Technical Reports Server (NTRS)

Daugherty, Robert H.; Yager, Thomas J.

1997-01-01

This paper describes the test procedures and the criteria used in selecting an effective runway-surface-texture modification at the Kennedy Space Center (KSC) Shuttle Landing Facility (SLF) to reduce Orbiter tire wear. The new runway surface may ultimately result in an increase of allowable crosswinds for launch and landing operations. The modification allows launch and landing operations in 20-knot crosswinds, if desired. This 5-knot increase over the previous 15-knot limit drastically increases landing safety and the ability to make on-time launches to support missions in which Space Station rendezvous are planned. The paper presents the results of an initial (1988) texture modification to reduce tire spin-up wear and then describes a series of tests that use an instrumented ground-test vehicle to compare tire friction and wear characteristics, at small scale, of proposed texture modifications placed into the SLF runway surface itself. Based on these tests, three candidate surfaces were chosen to be tested at full-scale by using a highly modified and instrumented transport aircraft capable of duplicating full Orbiter landing profiles. The full-scale Orbiter tire testing revealed that tire wear could be reduced approximately by half with either of two candidates. The texture-modification technique using a Humble Equipment Company Skidabrader(trademark) shotpeening machine proved to be highly effective, and the entire SLF runway surface was modified in September 1994. The extensive testing and evaluation effort that preceded the selection of this particular surface-texture-modification technique is described herein.

Concurrent aggregation and transport of graphene oxide in saturated porous media: Roles of temperature, cation type, and electrolyte concentration.

PubMed

Wang, Mei; Gao, Bin; Tang, Deshan; Yu, Congrong

2018-04-01

Simultaneous aggregation and retention of nanoparticles can occur during their transport in porous media. In this work, the concurrent aggregation and transport of GO in saturated porous media were investigated under the conditions of different combinations of temperature, cation type (valence), and electrolyte concentration. Increasing temperature (6-24 °C) at a relatively high electrolyte concentration (i.e., 50 mM for Na + , 1 mM for Ca 2+ , 1.75 mM for Mg 2+ , and 0.03 and 0.05 mM for Al 3+ ) resulted in enhanced GO retention in the porous media. For instance, when the temperature increased from 6 to 24 °C, GO recovery rate decreased from 31.08% to 6.53% for 0.03 mM Al 3+ and from 27.11% to 0 for 0.05 mM Al 3+ . At the same temperature, increasing cation valence and electrolyte concentration also promoted GO retention. Although GO aggregation occurred in the electrolytes during the transport, the deposition mechanisms of GO retention in the media depended on cation type (valence). For 50 mM Na + , surface deposition via secondary minima was the dominant GO retention mechanism. For multivalent cation electrolytes, GO aggregation was rapid and thus other mechanisms such as physical straining and sedimentation also played important roles in controlling GO retention in the media. After passing through the columns, the GO particles in the effluents showed better stability with lower initial aggregation rates. This was probably because less stable GO particles with lower surface charge densities in the porewater were filtered by the porous media, resulting in more stable GO particle with higher surface charge densities in the effluents. An advection-dispersion-reaction model was applied to simulate GO breakthrough curves and the simulations matched all the experimental data well. Copyright © 2017 Elsevier Ltd. All rights reserved.

Mass spectrometry of analytical derivatives. 1. Cyanide cations in the spectra of N-alkyl-N-perfluoroacyl-α-amino acids and their methyl esters

PubMed Central

Todua, Nino G.; Tretyakov, Kirill V.; Mikaia, Anzor I.

2016-01-01

The central mission for the development of the National Institute of Standards and Technology/National Institutes of Health/Environmental Protection Agency Mass Spectral Library is the acquisition of reference gas chromatography–mass spectrometry data for important compounds and their chemical modification products. The addition of reliable reference data of various derivatives of amino acids to The Library, and the study of their behavior under electron ionization conditions may be useful for their identification, structure elucidation, and a better understanding of the data obtained when the same derivatives are subjected to other ionization methods. N-Alkyl-N-perfluoroacyl derivatives of amino acids readily produce previously unreported alkylnitrilium cations of composition [HC≡N-alkyl]+. Homologous [HC≡N-aryl]+ cations are typical for corresponding N-aryl analogs. The formation of other ions characteristic for these derivatives involves oxygen rearrangement giving rise to ions [CnF2n+1–C≡N+–CnH2n+1] and [CnF2n+1–C≡N+-aryl]. The introduction of an N-benzyl substituent in a molecule favors a process producing benzylidene iminium cations. l-Threonine and l-cysteine derivatives exhibit more fragmentation pathways not typical for other α-amino acids; additionally, the Nω-amino group in l-lysine directs the dissociation process and provides structural information on the substitution at the amino functions in the molecule. PMID:26307698

Peptides, polypeptides and peptide-polymer hybrids as nucleic acid carriers.

PubMed

Ahmed, Marya

2017-10-24

Cell penetrating peptides (CPPs), and protein transduction domains (PTDs) of viruses and other natural proteins serve as a template for the development of efficient peptide based gene delivery vectors. PTDs are sequences of acidic or basic amphipathic amino acids, with superior membrane trespassing efficacies. Gene delivery vectors derived from these natural, cationic and cationic amphipathic peptides, however, offer little flexibility in tailoring the physicochemical properties of single chain peptide based systems. Owing to significant advances in the field of peptide chemistry, synthetic mimics of natural peptides are often prepared and have been evaluated for their gene expression, as a function of amino acid functionalities, architecture and net cationic content of peptide chains. Moreover, chimeric single polypeptide chains are prepared by a combination of multiple small natural or synthetic peptides, which imparts distinct physiological properties to peptide based gene delivery therapeutics. In order to obtain multivalency and improve the gene delivery efficacies of low molecular weight cationic peptides, bioactive peptides are often incorporated into a polymeric architecture to obtain novel 'polymer-peptide hybrids' with improved gene delivery efficacies. Peptide modified polymers prepared by physical or chemical modifications exhibit enhanced endosomal escape, stimuli responsive degradation and targeting efficacies, as a function of physicochemical and biological activities of peptides attached onto a polymeric scaffold. The focus of this review is to provide comprehensive and step-wise progress in major natural and synthetic peptides, chimeric polypeptides, and peptide-polymer hybrids for nucleic acid delivery applications.

Virus Capsids as Targeted Nanoscale Delivery Vessels of Photoactive Compounds for Site-Specific Photodynamic Therapy

NASA Astrophysics Data System (ADS)

Cohen, Brian A.

The research presented in this work details the use of a viral capsid as an addressable delivery vessel of photoactive compounds for use in photodynamic therapy. Photodynamic therapy is a treatment that involves the interaction of light with a photosensitizing molecule to create singlet oxygen, a reactive oxygen species. Overproduction of singlet oxygen in cells can cause oxidative damage leading to cytotoxicity and eventually cell death. Challenges with the current generation of FDA-approved photosensitizers for photodynamic therapy primarily stem from their lack of tissue specificity. This work describes the packaging of photoactive cationic porphyrins inside the MS2 bacteriophage capsid, followed by external modification of the capsid with cancer cell-targeting G-quadruplex DNA aptamers to generate a tumor-specific photosensitizing agent. First, a cationic porphyrin is loaded into the capsids via nucleotide-driven packaging, a process that involves charge interaction between the porphyrin and the RNA inside the capsid. Results show that over 250 porphyrin molecules associate with the RNA within each MS2 capsid. Removal of RNA from the capsid severely inhibits the packaging of the cationic porphyrins. Porphyrin-virus constructs were then shown to photogenerate singlet oxygen, and cytotoxicity in non-targeted photodynamic treatment experiments. Next, each porphyrin-loaded capsid is externally modified with approximately 60 targeting DNA aptamers by employing a heterobifunctional crosslinking agent. The targeting aptamer is known to bind the protein nucleolin, a ubiquitous protein that is overexpressed on the cell surface by many cancer cell types. MCF-7 human breast carcinoma cells and MCF-10A human mammary epithelial cells were selected as an in vitro model for breast cancer and normal tissue, respectively. Fluorescently tagged virus-aptamer constructs are shown to selectively target MCF-7 cells versus MCF-10A cells. Finally, results are shown in which porphyrin-virus-aptamer constructs selectively target and kill cancer cells versus non-cancer cells. Specifically, the results show that MS2 is a viable candidate as an addressable nanodelivery vessel of photoactive compounds, and the implications are that the nucleotide-driven packaging approach for modifying MS2 can be used to impart new functionalities for a host of diagnostic or therapeutic applications.

Enhanced luminescence of Cu-In-S nanocrystals by surface modification.

PubMed

Kim, Young-Kuk; Cho, Young-Sang; Chung, Kookchae; Choi, Chul-Jin; Shin, Pyung-Woo

2012-04-01

We have synthesized highly luminescent Cu-In-S nanocrystals by heating the mixture of metal carboxylates and alkylthiol under inert atmosphere. We modified the surface of CIS nanocrystals with zinc carboxylate and subsequent injection of alkylthiol. As a result of the surface modification, highly luminescent CIS@ZnS core/shell nanocrystals were synthesized. The luminescence quantum yield (QY) of best CIS@ZnS nanocrystals was above 50%, which is more than 10 times higher than the initial QY of CIS nanocrystals before surface modification (QY = 3%). Detailed study on the luminescence mechanism implies that etching of the surface of nanocrystals by dissociated carboxylate group (CH3COO-) and formation of epitaxial shell by Zn with sulfur from alkylthiol efficiently removed the surface defects which are major non-radiative recombination sites in semiconductor nanocrystals. In this study, we developed a novel surface modification route for monodispersed highly luminescent Cu-In-S nanocrystals with less toxic and highly stable precursors.